research papers
A new copper(II) supramolecular coordination
ISSN 2053-2296
Received 22 November 2017
Accepted 11 February 2018
Edited by A. G. Oliver, University of Notre
Dame, USA
Keywords: supramolecular coordination
polymer; dinuclear compound; copper(II);
paddlewheel structure; synthesis; characteriza-
tion; dehydration–rehydration behaviour; crystal
structure.
CCDC references: 1823618; 1823617
Supporting information: this article has
supporting information at journals.iucr.org/c
# 2018 International Union of Crystallography
332 https://doi.org/10.1107/S2053229618002474
polymer and a dinuclear compound with multi-
functional 2-amino-5-sulfobenzoic acid and flexible
N-donor ligands: synthesis, structure and charac-
terization
Peng-Cheng Li and Kou-Lin Zhang*
School of Chemistry and Chemical Engineering, Yangzhou University, Yangzhou 225002, People’s Republic of China.
*Correspondence e-mail: koulinzhang2002@yahoo.com
Multifunctional 2-amino-5-sulfobenzoic acid (H2afsb) can exhibit a variety of
roles during the construction of supramolecular coordination polymers. The
pendant carboxylic acid, sulfonic acid and amino groups could not only play a
role in directing bonding but could also have the potential to act as hydrogen-
bond donors and acceptors, resulting in extended high-dimensional supramole-
cular networks. Two new CuII coordination compounds, namely catena-poly-
0
[[[diaquacopper(II)]--1,6-bis(1H-1,2,4-triazol-1-yl)hexane-2N4:N4 ] bis(3-amino-
4-carboxybenzenesulfonate) dihydrate], {[Cu(C10H16N6)2(H2O)2](C7H6NO5S)2-
2H2O}n or {[Cu(bth)2(H2O)2](Hafsb)22H2O}n, (1), and bis(-2-amino-5-sulfon-
0 0
atobenzoato-2O1:O1 )bis{-1,2-bis[(1H-imidazol-1-yl)methyl]benzene-2N3:N3 }-
bis[aquacopper(II)] trihydrate, [Cu2(C7H5NO5S)2(C14H14N4)2(H2O)2]3H2O or
[Cu2(afsb)2(obix)2(H2O)2]3H2O, (2), have been obtained through the assembly
between H2afsb and the CuII ion in the presence of the flexible N-donor ligands
1,6-bis(1H-1,2,4-triazol-1-yl)hexane (bth) and 1,2-bis[(1H-1,2,4-triazol-1-yl)methyl]-
benzene (obix), respectively. Compound (1) consists of a cationic coordination
polymeric chain and 3-amino-4-carboxybenzenesulfonate (Hafsb) anions.
Compound (2) exhibits an asymmetric dinuclear structure. There are
hydrogen-bonded networks within the lattices of (1) and (2). Interestingly,
both (1) and (2) exhibit reversible dehydration–rehydration behaviour.
1. Introduction
Recently, chemists have accorded much attention to the
rational design and construction of metal–organic coordina-
tion polymers (MOCPs) with differing dimensionality because
MOCPs incorporate the advantages of the inorganic metal
ions and the organic linkers, resulting in fascinating archi-
tectures (Leong & Vittal, 2011; Zhou, He et al., 2016) and
potential applications in gas sorption (He et al., 2015), catalysis
(Wei et al., 2014), drug delivery (Gao et al., 2013), electro-
chemistry (Nafady et al., 2014), magnetism (Hawes et al., 2015),
sensing (Lv et al., 2015) and as energetic materials (Zhang,
Yang et al., 2016; Shu et al., 2017). Supramolecular coordina-
tion polymers (SCPs) are assembled by noncovalent van der
Waals forces, such as hydrogen bonding and – stacking
interactions. SCPs have aroused interest because they often
share the characteristics of conventional covalent-bonded
polymers and the properties originating from noncovalent
interactions, such as dynamic behaviour and high degrees of
internal ordered supramolecular assemblies (Reger et al.,
2014; Zhang, Luo et al., 2011; Karthikeyan et al., 2016; Zhou,
Yan et al., 2016).
Acta Cryst. (2018). C74, 332–341

In the field of crystal engineering, organic linkers play an
indispensible role in controlling the structure and tuning the
functional properties of the coordination compounds (Zhou &
Kitagawa, 2014; Du et al., 2013). So far, many aromatic car-
boxylic acids have been rationally designed and successfully
applied in the construction of numerous complexes with novel
structures, as well as excellent functional properties (Lin et al.,
2017; Gong et al., 2017; Xu et al., 2015). It has also been shown
that N-donor ligands, such as bis(triazole) and bis(imidazole)
analogues, play significant roles in the construction of coor-
dination polymers (CPs) and have a crucial influence on the
assembly process (Yao et al., 2011; Shi et al., 2012; Chen et al.,
2016; Arici, 2017). So far, CPs with an aromatic sulfonic acid
or sulfonate derivative are relatively rare. The sulfonate group
can be regarded as a negative anion and is suitable for
constructing CPs without small anions. Furthermore, sulfonate
is a weak electron donor, thereby making it a good candidate
for forming flexible host structures (Zhang, Li et al., 2016). The
sulfonate group in many reported complexes exists in the form
of an anion and does not bind with the central metal ion
(Dalrymple & Shimizu, 2002; Zhang et al., 2015). During the
assembly process, the uncoordinated sulfonate anion may act
as the recognition site for hydrogen bonding, leading to the
formation of extended high-dimensional supramolecular
polymeric architectures.
Recently, we have paid special attention to the construction
of new SCPs based on multifunctional 2-amino-5-sulfobenzoic
acid (H2afsb). It is expected that H2afsb may exhibit a variety
of roles during the assembly process. The pendant carboxylic
acid, sulfonic acid and amino groups could not only play a role
in directing bonding but could also have the potential to act as
hydrogen-bond donors and acceptors, resulting in extended
high-dimensional supramolecular networks.
During the past decade, CuII coordination compounds have
attracted much interest due to their pleasing architectures and
interesting functional properties, such as fluorescence (Dhibar
et al., 2017), magnetism (Almáši et al., 2016), electrochemistry
(Wang, Luan, Lin et al., 2013) and photocatalysis (Hussain et
al., 2016).
On the basis of the aforementioned considerations, we
selected H2afsb to react with CuII in the presence of the
Acta Cryst. (2018). C74, 332–341 Li and Zhang
research papers
N-donor-flexible bis(triazole) and bis(imidazole) ligands 1,6-
bis(1H-1,2,4-triazol-1-yl)hexane (bth) and 1,2-bis[(1H-imid-
azol-1-yl)methyl]benzene (obix). As a result, two new CuII
complexes with interesting three-dimensional supramolecular
architectures and properties, namely {[Cu(bth)2(H2O)2](Hafsb)-
H2O}n, (1) (Scheme 1), and [Cu2(afsb)2(obix)2(H2O)2]3H2O,
(2) (Scheme 2), were obtained. Herein, their syntheses and
structures are described in detail. The thermal stabilities of (1)
and (2) were studied, the semiconductor properties of (1) and
(2) were explored and the dehydration and rehydration
behaviours of both compounds were investigated.
2. Experimental
2.1. Materials and characterization
The flexible N-donor nitrogeneous ligands bth and obix
were synthesized according to literature procedures (Yang et
al., 2008; Liu et al., 2012). All other reagents were purchased
commercially and used without further purification. Solid-
state UV–Vis–NIR diffuse reflectance spectra were recorded
on a finely ground sample with a Cary 5000 spectro-
photometer. Diffuse reflectivity was measured from 200 to
1600 nm using polytetrafluoroethylene as a standard with
100% reflectance. Thermogravimetric analysis (TGA) was
recorded on a NETZSCH STA 409 PG/PC instrument from
room temperature to 1273 K at a heating rate of 10 K min1
under an N2 atmosphere. Powder X-ray diffraction (PXRD)
data were collected on a computer-controlled Bruker D8
Advance XRD diffractometer equipped with Cu K radiation
( = 1.5418 Å) at a scanning rate of 0.02 s1 from 5 to 50 .
2.2. Synthesis and crystallization
2.2.1. Synthesis of (1). To a solution of H2afsb (0.044 g,
0.2 mmol) and NaOH (0.004 g, 0.1 mmol) in water (5 ml) was
added a solution of CuSO45H2O (0.024 g, 0.1 mmol) in water
(3 ml). To the resulting blue solution, aqueous bth (3 ml,
0.044 g, 0.2 mmol) was added and the solution filtered. The
filtrate was kept at room temperature for slow evaporation.
After about 3 d, blue crystals of (1) suitable for single-crystal
 A copper(II) coordination polymer and a dinuclear structure 333
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Table 1
Experimental details.
(1) (2)

Crystal data
Chemical formula [Cu(C10H16N6)2(H2O)2](C7H6NO5S)22H2O [Cu2(C7H5NO5S)2(C14H14N4)2(H2O)2]3H2O
Mr 1008.55 1124.10
Crystal system, space group Orthorhombic, Pba2 Monoclinic, P21/c
Temperature (K) 296 293
a, b, c (Å) 13.7110 (14), 19.1598 (19), 8.9327 (8) 18.787 (2), 12.0409 (12), 20.699 (2)
, , ( ) 90, 90, 90 90, 99.905 (4), 90
V (Å3) 2346.6 (4) 4612.6 (8)
Z 2 4
Radiation type Mo K Mo K
 (mm1) 0.63 1.09
Crystal size (mm) 0.3  0.25  0.2 0.26  0.25  0.22

Data collection
Diffractometer Bruker SMART CCD area detector Bruker SMART CCD area detector
Absorption correction Empirical (using intensity measurements) Empirical (using intensity measurements)
(SADABS; Bruker, 2008) (SADABS; Bruker, 2008)
Tmin, Tmax 0.828, 0.882 0.760, 0.786
No. of measured, independent and observed 20614, 5240, 4419 47208, 10554, 7450
[I > 2 (I)] reflections
Rint 0.026 0.040
(sin /)max (Å1) 0.650 0.650

Refinement
R[F 2 > 2 (F 2)], wR(F 2), S 0.034, 0.091, 1.03 0.045, 0.121, 1.03
No. of reflections 5240 10554
No. of parameters 296 640
No. of restraints 1 0
H-atom treatment H-atom parameters constrained H-atom parameters constrained

max,
min (e Å3) 0.30, 0.17 0.74, 0.79
Absolute structure Flack x determined using 1740 quotients –
[(I+)  (I)]/[(I+) + (I)] (Parsons et al., 2013)
Absolute structure parameter 0.003 (6) –
Computer programs: SMART (Bruker, 2008), SAINT (Bruker, 2008), SHELXS2017 (Sheldrick, 2015a), SHELXL2017 (Sheldrick, 2015b), DIAMOND (Brandenburg, 2005) and
Mercury (Macrae et al., 2008).

X-ray diffraction analysis were obtained (yield 62.2%, based 1.2Ueq(N,O). The H atoms of the water molecules were initi-
on H2afsb). FT–IR (KBr, , cm1): 3470 (s), 3355 (s), 3445 (m), ally located from a difference Fourier map, but were subse-
2933 (m), 1695 (s), 1609 (vs), 1532 (s), 1292 (s), 1234 (s), 1138 quently refined as riding, with O—H = 0.85 (1) Å, H  H =
(vs), 1033 (s), 688 (m), 582 (m). 1.39 (1) Å and Uiso(H) = 1.5Ueq(O).
2.2.2. Synthesis of (2). To an aqueous solution (6 ml) of
H2afsb (0.022 g, 0.1 mmol) and NaOH (0.004 g, 0.1 mmol) was
added a solution of CuSO45H2O (0.024 g, 0.1 mmol) in water 3. Results and discussion
(6 ml). To this mixed blue aqueous solution, a methanol 3.1. Syntheses of complexes (1) and (2)
solution (6 ml) of obix (0.0274 g, 0.1 mmol) was added and the
We should point out the differences in the syntheses of the
resulting solution filtered after about 4 h. The filtrate was kept
two title compounds, notably that for compound (1) only a
at room temperature for about 3 d, after which time blue
half equivalent of NaOH per H2asfb was used, while for
crystals were obtained (yield 43.2%, based on H2afsb). FT–IR
compound (2), there was one equivalent of NaOH. A poly-
(KBr, , cm1): 3448 (s), 3323 (s), 3141 (m), 1625 (vs), 1577
crystalline mixture was obtained if other molar ratios were
(m), 1481 (w), 1433 (s), 1337 (m), 1375 (w), 1270 (m), 1212 (s),
used.
1155 (s), 1106 (s), 1030 (s), 838 (m), 733 (m), 675 (s), 598 (s).

3.2. Structural description of (1)

2.3. Refinement
Crystal data, data collection and structure refinement
details for (1) and (2) are summarized in Table 1. C-bound H
atoms were treated as riding atoms in geometrically idealized
positions, with aryl C—H = 0.93 Å and methylene C—H =
0.97 Å, and with Uiso(H) = 1.2Ueq(C). The amino/carboxyl
N/O-bound H atoms were also added geometrically, with
N—H = 0.86 Å and O—H = 0.82 Å, and Uiso(H) =
Complex (1) crystallizes in the orthorhombic space group
Pba2. In the asymmetric unit of (1), there is one bth ligand,
one Hafsb anion and one lattice water. The CuII atom and
the coordinated water molecules (O1W and O2W) are located
on the crystallographic twofold axis parallel to the c axis
(Fig. 1). The CuII atom is coordinated in an octahedral
geometry by two apical water molecules and by four bth N
atoms (N1, N1i, N6ii and N6iii; see Table 2 for symmetry codes)

334 Li and Zhang  A copper(II) coordination polymer and a dinuclear structure Acta Cryst. (2018). C74, 332–341
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Figure 1
The coordination environment of the CuII ion in (1). The H atoms, apart from those of the water molecules and amino group of the Hafsb anion, have
been omitted for clarity. Displacement ellipsoids are drawn at the 50% probability level. [Symmetry codes: (i) x, y + 2, z; (ii) x + 1, y + 2, z; (iii)
x  1, y, z; (vii) x + 1, y, z.]

Table 2 Table 3
Selected geometric parameters (Å,  ) for (1). Hydrogen-bond geometry (Å,  ) for (1).
Cu1—N1 2.010 (2) Cu1—O2W 2.315 (4) D—H  A D—H H  A D  A D—H  A
Cu1—N6ii 2.015 (2) Cu1—O1W 2.461 (4)
C8—H8B  N2iv 0.97 2.49 3.365 (5) 151
N1—Cu1—N1i 178.03 (18) N6ii—Cu1—O2W 90.74 (9) N7—H7C  O4v 0.86 2.52 3.344 (4) 160
N1—Cu1—N6ii 89.90 (9) N1—Cu1—O1W 89.02 (9) O3W—H3WB  O5v 0.85 1.90 2.737 (5) 170
N1i—Cu1—N6ii 90.08 (9) N6ii—Cu1—O1W 89.26 (9) O3W—H3WA  O1vi 0.84 2.07 2.740 (4) 136
N6ii—Cu1—N6iii 178.52 (18) O2W—Cu1—O1W 180.0 O2—H2A  O3W vii 0.82 1.79 2.603 (4) 172
N1—Cu1—O2W 90.98 (9) O2W—H2W  O4iii 0.84 2.16 2.981 (6) 163
O2W—H2W  O3iii 0.84 2.46 3.092 (4) 133
Symmetry codes: (i) x; y þ 2; z; (ii) x þ 1; y þ 2; z; (iii) x  1; y; z. O1W—H1W  O4viii 0.85 2.16 2.996 (6) 170
Symmetry codes: (iii) x  1; y; z; (iv) x þ 12; y þ 32; z; (v) x  12; y þ 32; z; (vi)
in the equatorial plane. Compound (1) displays a clear Jahn– x þ 1; y þ 1; z; (vii) x þ 1; y; z; (viii) x  1; y; z þ 1.

Teller distortion. The Cu—N bond lengths are in the range

2.010 (2)–2.015 (2) Å (Table 2), which are similar to those in
previously reported CuII complexes with the bth ligand, such
as Cu5(btx)4(PMoVI10MoV2O40) (btx = bth; Tian et al., 2008),
[CuII(bth)2( -Mo8O26)0.5]H2O (Du et al., 2011) and [Cu(CN)-
(bth)0.5]n (Xu et al., 2015). Two bth ligands link adjacent CuII
ions into a necklace-like polymeric cationic chain with
nanometer-sized elliptical rings [the Cu  Cu distance within
the ring is 13.7110 (14) Å] (Fig. 2). The Hafsb anion retains
the H atom of the carboxylic acid group and the sulfonic acid
group is deprotonated, providing charge balance.
The chains were further linked through C8—H8B  N2iv
hydrogen bonds (see Table 3 for details and symmetry codes),
leading to the formation of a two-dimensional supramolecular
cationic layer (Fig. 3). The hydrogen bonds between the water
molecules and the Hafsb anions, such as N7—H7C  O4v,

Figure 2
The one-dimensional necklace-like cationic chain of (1). The lattice Hafsb acts as a counter-anion and hydrogen bonds with the cationic chain.

Acta Cryst. (2018). C74, 332–341 Li and Zhang  A copper(II) coordination polymer and a dinuclear structure 335
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Figure 3
The two-dimensional supramolecular cationic network of (1), formed
through interchain C8—H8B  N2iv hydrogen bonds. The lattice Hafsb
anions and the lattice water molecules have been omitted for clarity.
O3W—H3WA  O1vi and O2—H2A  O3W vii (Table 3),
further link the Hafsb anions together, yielding a two-
dimensional supramolecular anionic layer (Fig. 4). The R22 (4)
hydrogen-bonded rings formed between two symmetric
sulfonate O4 atoms from two interstitial Hafsb anions and
two coordinated water molecules (O1W and O2W) from
adjacent two-dimensional cationic layers (O1W—H1W  
O4viii and O2W—H2W  O4iii; Table 3) result in the formation
of an interesting three-dimensional supramolecular network
in which the two-dimensional cationic layers and the anionic
layers are arrayed in an alternating fashion (Fig. 5).
3.3. Structural description of (2)
Complex (2) crystallizes in the monoclinic space group
P21/c and exhibits an asymmetric dinuclear paddlewheel
Figure 5
The three-dimensional supramolecular network of (1), showing the alternately arranged two-dimensional cationic layers and anionic layers.
336 Li and Zhang  A copper(II) coordination polymer and a dinuclear structure
Figure 4
The two-dimensional supramolecular anionic layer of (1), formed
through hydrogen bonds between the lattice Hafsb anions and water
molecules.
structure (Fig. 6). Within the asymmetric unit, there are two
crystallographically independent CuII ions, two bridging
afsb2 ligands, two bridging obix ligands, two coordinated
water molecules and three lattice water molecules. Both CuII
atoms are pentacoordinated by two obix N atoms (N1 and N6
for Cu1, and N4 and N9 for Cu2), two O atoms from two
afsb2 ligands (O1 and O6 for Cu1, and O2 and O7 for Cu2)
and one O atom from water (O1W for Cu1 and O2W for Cu2),
and exhibit a distorted trigonal biyramidal configuration. The
Cu—N bond lengths around the Cu1 and Cu2 ions are in the
range 1.957 (2)–1.974 (2) Å (Table 4), which are similar to
those in reported copper(II) complexes with the same obix
ligand, for example, [Cu2(L2)(1,2-bix)2(H2O)4]8H2O (H4L2 is
benzene-1,2,3,4-tetracarboxylic acid; Yang et al., 2008) and
{[Cu(-obix)2(H2O)2]2HCO2}n (Semerci et al., 2015). The
Acta Cryst. (2018). C74, 332–341
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Table 5
Hydrogen-bond geometry (Å,  ) for (2).
D—H  A D—H H  A D  A D—H  A

O5W—H5WB  O8 0.85 1.99 2.818 (3) 164

O5W—H5WA  O5i 0.85 2.27 3.084 (5) 160
O4W—H4WB  O3ii 0.84 2.11 2.914 (4) 158
O4W—H4WA  O4i 0.84 2.01 2.826 (4) 162
O3W—H3WB  O10iii 0.85 2.01 2.857 (3) 174
O3W—H3WA  O8iv 0.85 1.95 2.788 (3) 169
O2W—H2WB  O3W v 0.85 1.96 2.789 (3) 168
O2W—H2WA  O5i 0.84 1.95 2.786 (3) 170
O1W—H1WB  O5W vi 0.85 1.90 2.727 (3) 162
O1W—H1WA  O4W vi 0.86 1.96 2.732 (3) 149
N10—H10B  O10iii 0.86 2.13 2.976 (3) 168
N10—H10A  O6 0.86 2.08 2.705 (3) 129
N5—H5B  O2 0.86 2.06 2.693 (3) 130
C39—H39A  O4i 0.97 2.65 3.401 (4) 134
C31—H31  O4W vi 0.93 2.60 3.436 (4) 151
C29—H29  O6 0.93 2.36 2.845 (3) 112
Figure 6 C18—H18A  O9v 0.97 2.47 3.415 (4) 164
A view of the coordination environment of the CuII ion and the C11—H11B  O10vii 0.97 2.65 3.176 (4) 114
coordination modes of the afsb2 and obix ligands in complex (2). C9—H9  O3W iii 0.93 2.54 3.370 (4) 148
Displacement ellipsoids are drawn at the 50% probability level. C8—H8  O1 0.93 2.61 3.068 (3) 111
O1W—H1WA  O4W vi 0.86 1.96 2.732 (3) 149
O1W—H1WB  O5W vi 0.85 1.90 2.727 (3) 162
Table 4 O2W—H2WA  O5i 0.84 1.95 2.786 (3) 170
O2W—H2WB  O3W v 0.85 1.96 2.789 (3) 168
Selected geometric parameters (Å,  ) for (2).
N10—H10B  O10iii 0.86 2.13 2.976 (3) 168
Cu1—N1 1.957 (2) Cu2—N9 1.963 (2) O3W—H3WA  O8iv 0.85 1.95 2.788 (3) 169
Cu1—N6 1.974 (2) Cu2—N4 1.972 (2) O3W—H3WB  O10iii 0.85 2.01 2.857 (3) 174
Cu1—O6 1.9900 (18) Cu2—O2 1.9972 (19) O4W—H4WA  O4i 0.84 2.01 2.826 (4) 162
Cu1—O1W 2.076 (2) Cu2—O7 2.0458 (19) O4W—H4WB  O3ii 0.84 2.11 2.914 (4) 158
Cu1—O1 2.194 (2) Cu2—O2W 2.227 (2) O5W—H5WA  O5i 0.85 2.27 3.084 (5) 160
O5W—H5WB  O8 0.85 1.99 2.818 (3) 164
N1—Cu1—N6 177.19 (10) N9—Cu2—N4 177.69 (10) Symmetry codes: (i) x; y  1; z; (ii) x þ 2; y þ 2; z þ 2; (iii) x þ 1; y þ 12; z þ 32;
N1—Cu1—O6 88.93 (9) N9—Cu2—O2 92.40 (9) (iv) x; y þ 32; z  12; (v) x; y þ 32; z þ 12; (vi) x; y þ 1; z; (vii) x þ 1; y þ 2; z þ 2.
N6—Cu1—O6 89.05 (9) N4—Cu2—O2 89.91 (9)
N1—Cu1—O1W 89.17 (9) N9—Cu2—O7 89.98 (9)
N6—Cu1—O1W 90.99 (9) N4—Cu2—O7 88.01 (9) Hydrogen bonds play a significant role in the lattice
O6—Cu1—O1W 137.46 (9) O2—Cu2—O7 149.89 (9)
N1—Cu1—O1 90.63 (9) N9—Cu2—O2W 88.55 (9) (Table 5). The water molecules (O1W, O2W, O3W, O4W and
N6—Cu1—O1 92.17 (9) N4—Cu2—O2W 90.28 (9) O5W) and the uncoordinated sulfonate O atoms (O4, O5 and
O6—Cu1—O1 130.75 (8) O2—Cu2—O2W 121.16 (8) O8) form a hydrogen-bonded R67 (9) ring. There are two
O1W—Cu1—O1 91.77 (8) O7—Cu2—O2W 88.89 (8)
different hydrogen-bonded R44 (8) rings; one is formed between
the uncoordinated sulfonate O3 and O4 atoms, and two
Cu—O(carboxylate) bond lengths are in the range symmetric lattice O4W water molecules, while the other exists
1.9900 (18)–2.194 (2) Å, which are similar to those in reported between the uncoordinated sulfonate O8 and O10 atoms, and
CuII complexes with aromatic carboxylate ligands, such as two symmetric lattice O3W water molecules. These three
[Cu(3-dppa)(1,3,5-HBTC)] [3-dppa is N,N0 -di(3-pyridyl)pro- hydrogen-bonded rings share the edges O3W–O8 and O3–O4–
panediamide and 1,3,5-H3BTC is benzene-1,3,5-tricarboxylic O4W, respectively, and are thus arranged alternately in the
acid; Wang, Luan, Sui et al., 2013), [Cu(bibp)(1,2-bdc)]n [bibp sequence R67 (9)–R44 (8)–R67 (9)–R44 (8), resulting a one-dimen-
is 4,40 -bis(imidazol-1-yl)biphenyl and 1,2-bdc is benzene-1,2- sional hydrogen-bonded tape (Fig. 7), which links adjacent
dicarboxylic acid; Li et al., 2014]. asymmetric dinuclear units into a two-dimensional supra-

Figure 7
A perspective view of the one-dimensional hydrogen-bonded tape in (2), which links the dinuclear units.

Acta Cryst. (2018). C74, 332–341 Li and Zhang  A copper(II) coordination polymer and a dinuclear structure 337
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Figure 8
The two-dimensional supramolecular network in (2), formed through the
linkage of one-dimensional hydrogen-bonded tapes with adjacent
asymmetric dinuclear units.
molecular layer (Fig. 8). The two-dimensional layers are
further arranged into a three-dimensional supramolecular
Figure 9
A view of the three-dimensional supramolecular network in (2), formed
through interlayer hydrogen bonds (purple dashed lines).
338 Li and Zhang  A copper(II) coordination polymer and a dinuclear structure
Figure 10
The TGA curves of (1) and (2).
network (Fig. 9) via the interlayer N10—H10B  O10iii
hydrogen bond (Table 5).
3.4. Thermal stability
Thermogravimetric analyses (TGA) were performed in
order to investigate the thermal stabilities of both title
compounds (Fig. 10). Compound (1) loses the two coordinated
and two lattice water molecules (observed 7.2%, calculated
7.0%) in the temperature range 313–358 K. Compound (2)
showed a weight loss of ca 8.5% (calculated 8.1%) from 333 to
465 K, which corresponds to the removal of the two coordi-
nated and three lattice water molecules.
3.5. Reversible dehydration–rehydration behaviour
The phase purity of the bulk samples of (1) and (2) were
further confirmed by a powder X-ray diffraction (PXRD)
analysis at room temperature (Figs. 11 and 12). The experi-
Figure 11
The PXRD patterns for (1), showing the simulated XRD pattern
calculated from the single-crystal X-ray diffraction data with Mercury
(black; Macrae et al., 2008), the sample as-synthesized (red), after
removal of the water molecules at 373 K (green) and after exposure in
water vapour for ca 3 d at room temperature (blue).
Acta Cryst. (2018). C74, 332–341

Figure 12
The PXRD patterns for (2), showing the simulated XRD pattern
calculated from single-crystal X-ray diffraction data with Mercury (black;
Macrae et al., 2008), the sample as-synthesized (red), after removal of the
water molecules at 468 K (green) and after exposure in water vapour for
ca 3 d at room temperature (blue).
mental diffraction patterns of both bulk samples are consistent
with the simulated patterns calculated from the single-crystal
X-ray diffraction data with Mercury (Macrae et al., 2008),
indicating that the products are homogeneous pure phases.
The cyclic dehydration and rehydration behaviour of com-
plexes (1) and (2) were investigated via variable-temperature
PXRD in combination with the hydration process detailed
below. On heating the as-synthesized samples to 373 K for (1)
and 468 K for (2), the PXRD patterns of the dehydrated
samples of (1) (Fig. 11) and (2) (Fig. 12) show that the peak
patterns become broader, peak shifts occur and the diffraction
intensity becomes weaker. Thus, the structures of the dehy-
drated phases of (1) and (2) have changed. Both dehydrated
samples were cooled to room temperature and kept in water
vapour for about 3 d. Remarkably, the water-vapour-
Figure 13
The solid-state UV–Vis–NIR absorption spectra for H2afsb, bth, obix, (1)
and (2).
Acta Cryst. (2018). C74, 332–341 Li and Zhang
research papers
Figure 14
The diffuse reflectance UV–Vis–NIR spectrum of (Ahv)1/2 versus hv (eV)
of (1).
immersed samples show similar PXRD patterns to the related
simulated patterns of (1) and (2) calculated from the single-
crystal X-ray diffraction data. The results prove that the
dehydrated samples re-absorb water and revert to the original
structures. Therefore, the dehydration and rehydration beha-
viours of (1) and (2) are completely reversible and they can be
called ‘recoverable collapsing’ supramolecular networks. They
may serve as potential water-absorbent materials (Liu et al.,
2009; Shi et al., 2017).
3.6. Optical properties
It has been well documented that a common and convenient
method for determining whether a band gap is indirect or
direct is to use the UV–Vis absorption spectrum (Guo et al.,
2011). The UV–Vis–NIR absorption spectra of H2afsb, bth,
obix, (1) and (2) are shown in Fig. 13. In the spectra of the free
organic compounds, the bands around 228 and 262 nm for
obix, at 235 and 309 nm for bth, and at 234 and 283 nm for
H2afsb can be attributed to the –* transitions. In the spectra
of complexes (1) and (2), the –* transition bands were red-
Figure 15
The diffuse reflectance UV–Vis–NIR spectrum of (Ahv)1/2 versus hv (eV)
of (2).
 A copper(II) coordination polymer and a dinuclear structure 339
research papers
shifted to 254 and 335 nm, which may be attributed to the
coordination effect of the ligands. The broad absorption band
around 619 nm for (1) and 784 nm for (2) in the UV to NIR
region may be due to the d–d transition of the CuII ion with a
d9 configuration (Xu et al., 2013; Dai et al., 2014).
To further investigate the semiconductor properties of (1)
and (2), the experimental absorbance data were transformed
to a bandgap energy (Eg) according to the Kubelka–Munk
function: (Ahv)1/2 = B(hv  Eg), where B is a constant
corresponding to the material itself (Okubo et al., 2013; Zhang,
Du et al., 2011). The energy band gaps (Eg) obtained by
extrapolation of the linear portion of the absorption edges are
estimated to be 1.93 eV for (1) (Fig. 14) and 3.11 eV for (2)
(Fig. 15).
4. Conclusions
In summary, two copper(II) compounds based on the acid
H2afsb and N-donor-flexible ligands have been prepared
successfully and structurally characterized. Compound (1) is
an ionic one-dimensional coordination polymer, while com-
pound (2) is an asymmetric dinuclear complex. With the aid of
hydrogen bonding, (1) is extended into a three-dimensional
supramolecular network, which consists of alternately
arranged two-dimensional cationic and anionic layers. A one-
dimensional hydrogen-bonded tape in (2) links the dinuclear
species into a two-dimensional supramolecular layer, which is
further extended into a three-dimensional supramolecular
hydrogen-bonded network. In (1), the Hafsb anion does not
coordinate to the CuII ion, while in (2), the afsb2 anion acts as
a bidentate bridging ligand. The N-donor-flexible organic
linkers bth and obix have a big influence on the crystalline
architectures of (1) and (2). Both (1) and (2) may be used as
potential indirect band semiconductor materials. Most inter-
estingly, (1) and (2) show a recyclable dehydration–rehydra-
tion behaviour.
Funding information
Funding for this research was provided by: Natural Science
Foundation of Jiangsu Province (grant No. BK2012680);
Priority Academic Program Development of Jiangsu Higher
Education Institutions (PAPD).
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 A copper(II) coordination polymer and a dinuclear structure 341
 supporting information

supporting information

Acta Cryst. (2018). C74, 332-341 [https://doi.org/10.1107/S2053229618002474]

A new copper(II) supramolecular coordination polymer and a dinuclear

compound with multifunctional 2-amino-5-sulfobenzoic acid and flexible N-
donor ligands: synthesis, structure and characterization
Peng-Cheng Li and Kou-Lin Zhang

Computing details
For both structures, data collection: SMART (Bruker, 2008); cell refinement: SMART (Bruker, 2008); data reduction:
SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS2017 (Sheldrick, 2015a); program(s) used to refine
structure: SHELXL2017 (Sheldrick, 2015b); molecular graphics: DIAMOND (Brandenburg, 2005); software used to
prepare material for publication: Mercury (Macrae et al., 2008).

catena-Poly[[diaquacopper(II)-µ-1,6-bis(1H-1,2,4-triazol-1-yl)hexane-κ2N4:N4′] bis(3-amino-4-
carboxybenzenesulfonate) dihydrate] (001)

Crystal data
[Cu(C10H16N6)2(H2O)2](C7H6NO5S)2·2H2O Dx = 1.427 Mg m−3
Mr = 1008.55 Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pba2 Cell parameters from 9920 reflections
a = 13.7110 (14) Å θ = 2.6–27.4°
b = 19.1598 (19) Å µ = 0.63 mm−1
c = 8.9327 (8) Å T = 296 K
V = 2346.6 (4) Å3 Massive, blue
Z=2 0.3 × 0.25 × 0.2 mm
F(000) = 1054
Data collection
CCD area detector 5240 independent reflections
diffractometer 4419 reflections with I > 2σ(I)
phi and ω scans Rint = 0.026
Absorption correction: empirical (using θmax = 27.5°, θmin = 1.1°
intensity measurements) h = −13→17
(SADABS; Bruker, 2008) k = −24→24
Tmin = 0.828, Tmax = 0.882 l = −11→11
20614 measured reflections

Refinement
Refinement on F2 1 restraint
Least-squares matrix: full Hydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.034 H-atom parameters constrained
wR(F2) = 0.091 w = 1/[σ2(Fo2) + (0.0528P)2 + 0.1297P]
S = 1.03 where P = (Fo2 + 2Fc2)/3
5240 reflections (Δ/σ)max < 0.001
296 parameters Δρmax = 0.30 e Å−3

Acta Cryst. (2018). C74, 332-341 sup-1

 supporting information
Δρmin = −0.17 e Å−3 Absolute structure: Flack x determined using
1740 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et
al., 2013)
Absolute structure parameter: 0.003 (6)

Special details
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance
matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles;
correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate
(isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.
Refinement. Refined as a 2-component twin

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

x y z Uiso*/Ueq
C1 0.1624 (3) 0.90465 (19) 0.8446 (4) 0.0601 (9)
H1 0.129851 0.895428 0.933794 0.072*
C2 0.1950 (2) 0.94757 (17) 0.6347 (4) 0.0505 (7)
H2 0.192804 0.973160 0.546285 0.061*
C3 0.3511 (3) 0.8832 (2) 0.5886 (5) 0.0666 (10)
H3A 0.356550 0.912201 0.499975 0.080*
H3B 0.343067 0.835253 0.556156 0.080*
C4 0.4439 (3) 0.8893 (2) 0.6792 (5) 0.0674 (10)
H4A 0.442899 0.855455 0.760020 0.081*
H4B 0.448043 0.935517 0.722990 0.081*
C5 0.5326 (3) 0.8764 (3) 0.5797 (5) 0.0781 (12)
H5A 0.538042 0.913901 0.507339 0.094*
H5B 0.523451 0.833124 0.524951 0.094*
C6 0.6274 (3) 0.8719 (2) 0.6706 (5) 0.0674 (10)
H6A 0.681578 0.884956 0.606605 0.081*
H6B 0.624328 0.905346 0.751917 0.081*
C7 0.6469 (2) 0.80038 (17) 0.7348 (5) 0.0614 (8)
H7A 0.662471 0.768751 0.653450 0.074*
H7B 0.587773 0.783484 0.782248 0.074*
C8 0.7292 (2) 0.79852 (18) 0.8482 (4) 0.0552 (8)
H8A 0.708689 0.822491 0.938550 0.066*
H8B 0.743115 0.750396 0.874260 0.066*
C9 0.9413 (3) 0.84857 (16) 0.6597 (5) 0.0594 (9)
H9 0.991834 0.842399 0.591617 0.071*
C10 0.8497 (2) 0.89557 (16) 0.8173 (4) 0.0482 (7)
H10 0.820187 0.927118 0.882163 0.058*
C11 0.8215 (2) 0.68972 (15) 0.2055 (4) 0.0468 (7)
C12 0.7237 (2) 0.67469 (14) 0.2423 (4) 0.0503 (7)
C13 0.6631 (2) 0.73038 (18) 0.2821 (4) 0.0579 (9)
H13 0.597941 0.721760 0.304079 0.070*
C14 0.6975 (2) 0.79707 (17) 0.2893 (4) 0.0539 (8)
H14 0.656068 0.833097 0.317896 0.065*
C15 0.7950 (2) 0.81165 (14) 0.2539 (4) 0.0453 (7)
C16 0.8551 (2) 0.75859 (14) 0.2110 (4) 0.0448 (7)

Acta Cryst. (2018). C74, 332-341 sup-2

 supporting information
H16 0.919317 0.768350 0.184899 0.054*
C17 0.8904 (3) 0.63429 (18) 0.1629 (5) 0.0608 (9)
Cu1 0.000000 1.000000 0.73657 (8) 0.04232 (14)
N1 0.12802 (15) 0.94891 (11) 0.7404 (3) 0.0455 (5)
N2 0.2454 (2) 0.87580 (18) 0.8094 (4) 0.0687 (9)
N3 0.26582 (19) 0.90431 (14) 0.6733 (3) 0.0522 (7)
N4 0.81759 (18) 0.83127 (13) 0.7908 (3) 0.0482 (6)
N5 0.8757 (2) 0.80055 (14) 0.6880 (4) 0.0635 (8)
N6 0.92825 (15) 0.90826 (11) 0.7395 (3) 0.0462 (5)
N7 0.6852 (2) 0.60838 (14) 0.2410 (5) 0.0675 (8)
H7C 0.625113 0.601875 0.264899 0.081*
H7D 0.721213 0.573465 0.216698 0.081*
O1 0.8713 (2) 0.57288 (13) 0.1721 (5) 0.0995 (12)
O2 0.9758 (2) 0.65620 (14) 0.1184 (4) 0.0811 (9)
H2A 1.010637 0.622503 0.099914 0.122*
O3 0.8047 (3) 0.92748 (15) 0.4013 (3) 0.0897 (10)
O4 0.94143 (19) 0.89604 (12) 0.2459 (7) 0.1211 (17)
O5 0.7917 (3) 0.93515 (14) 0.1366 (3) 0.0781 (8)
O1W 0.000000 1.000000 1.0120 (5) 0.0684 (13)
H1W −0.023600 0.971200 1.074324 0.103*
O2W 0.000000 1.000000 0.4774 (5) 0.0692 (13)
H2W −0.026300 0.968500 0.424974 0.104*
O3W 0.0996 (3) 0.55755 (15) 0.0546 (4) 0.0913 (10)
H3WA 0.088797 0.514210 0.049020 0.137*
H3WB 0.158097 0.565110 0.080710 0.137*
S1 0.83731 (6) 0.89868 (4) 0.26184 (11) 0.0558 (2)

Atomic displacement parameters (Å2)

U11 U22 U33 U12 U13 U23

C1 0.056 (2) 0.060 (2) 0.064 (2) 0.0082 (16) 0.0095 (16) 0.0184 (18)
C2 0.0434 (16) 0.0521 (18) 0.0560 (19) 0.0068 (13) −0.0012 (14) 0.0096 (15)
C3 0.0509 (19) 0.079 (2) 0.070 (2) 0.0161 (17) 0.0007 (17) −0.004 (2)
C4 0.0470 (19) 0.089 (3) 0.066 (2) 0.0105 (17) 0.0013 (16) −0.0049 (19)
C5 0.051 (2) 0.114 (3) 0.069 (3) 0.014 (2) 0.0084 (19) 0.007 (2)
C6 0.0437 (18) 0.081 (2) 0.077 (2) 0.0014 (17) 0.0042 (17) 0.000 (2)
C7 0.0504 (16) 0.0588 (18) 0.075 (2) −0.0131 (13) 0.0014 (19) −0.005 (2)
C8 0.0530 (18) 0.0469 (18) 0.066 (2) −0.0142 (14) 0.0022 (15) 0.0044 (16)
C9 0.0512 (19) 0.0419 (17) 0.085 (2) 0.0019 (14) 0.0109 (16) −0.0081 (17)
C10 0.0464 (16) 0.0438 (17) 0.0545 (19) −0.0070 (12) 0.0015 (14) −0.0059 (14)
C11 0.0517 (16) 0.0384 (14) 0.0502 (18) −0.0059 (11) −0.0038 (13) −0.0002 (13)
C12 0.0558 (16) 0.0437 (14) 0.0513 (17) −0.0146 (12) −0.0071 (17) 0.0011 (17)
C13 0.0458 (16) 0.061 (2) 0.067 (2) −0.0135 (14) 0.0058 (15) 0.0020 (18)
C14 0.0480 (16) 0.0501 (17) 0.064 (2) −0.0044 (13) 0.0089 (14) −0.0090 (16)
C15 0.0508 (14) 0.0375 (13) 0.0477 (17) −0.0085 (11) 0.0015 (14) −0.0055 (15)
C16 0.0435 (14) 0.0429 (15) 0.0480 (19) −0.0084 (11) −0.0015 (13) −0.0022 (14)
C17 0.060 (2) 0.0460 (18) 0.077 (2) −0.0038 (15) −0.0021 (18) −0.0017 (17)
Cu1 0.0338 (2) 0.0362 (2) 0.0571 (3) −0.00195 (16) 0.000 0.000

Acta Cryst. (2018). C74, 332-341 sup-3

 supporting information
N1 0.0376 (10) 0.0406 (11) 0.0582 (14) 0.0006 (9) −0.0012 (13) 0.0062 (14)
N2 0.0607 (19) 0.072 (2) 0.073 (2) 0.0187 (15) 0.0065 (16) 0.0218 (17)
N3 0.0412 (14) 0.0548 (16) 0.0605 (16) 0.0092 (11) 0.0004 (12) 0.0039 (13)
N4 0.0460 (13) 0.0379 (12) 0.0605 (16) −0.0065 (10) −0.0037 (12) 0.0004 (12)
N5 0.0618 (17) 0.0387 (13) 0.090 (2) −0.0017 (12) 0.0112 (15) −0.0098 (14)
N6 0.0402 (11) 0.0411 (12) 0.0573 (14) −0.0026 (9) −0.0015 (13) −0.0017 (13)
N7 0.0647 (17) 0.0470 (14) 0.091 (2) −0.0210 (11) 0.002 (2) −0.001 (2)
O1 0.088 (2) 0.0361 (13) 0.174 (4) −0.0072 (12) 0.026 (2) −0.0093 (17)
O2 0.0645 (16) 0.0448 (14) 0.134 (3) 0.0034 (11) 0.0197 (17) 0.0005 (16)
O3 0.146 (3) 0.0552 (16) 0.0676 (17) −0.0180 (17) 0.0059 (18) −0.0221 (14)
O4 0.0528 (14) 0.0509 (14) 0.260 (5) −0.0154 (11) 0.014 (3) −0.013 (3)
O5 0.114 (2) 0.0502 (15) 0.0701 (17) −0.0101 (14) 0.0084 (16) 0.0074 (14)
O1W 0.075 (3) 0.076 (3) 0.054 (2) −0.0265 (18) 0.000 0.000
O2W 0.065 (3) 0.090 (4) 0.053 (2) −0.0332 (19) 0.000 0.000
O3W 0.091 (2) 0.0529 (15) 0.130 (3) 0.0140 (14) 0.021 (2) 0.0144 (18)
S1 0.0580 (4) 0.0375 (4) 0.0720 (6) −0.0098 (3) 0.0069 (4) −0.0083 (4)

Geometric parameters (Å, º)

C1—N2 1.303 (5) C11—C17 1.471 (5)

C1—N1 1.344 (4) C12—N7 1.376 (4)
C1—H1 0.9300 C12—C13 1.398 (5)
C2—N1 1.318 (4) C13—C14 1.364 (5)
C2—N3 1.322 (4) C13—H13 0.9300
C2—H2 0.9300 C14—C15 1.402 (4)
C3—N3 1.450 (5) C14—H14 0.9300
C3—C4 1.512 (5) C15—C16 1.363 (4)
C3—H3A 0.9700 C15—S1 1.767 (3)
C3—H3B 0.9700 C16—H16 0.9300
C4—C5 1.527 (6) C17—O1 1.208 (4)
C4—H4A 0.9700 C17—O2 1.307 (5)
C4—H4B 0.9700 Cu1—N1 2.010 (2)
C5—C6 1.535 (6) Cu1—N1i 2.010 (2)
C5—H5A 0.9700 Cu1—N6ii 2.015 (2)
C5—H5B 0.9700 Cu1—N6iii 2.015 (2)
C6—C7 1.509 (6) Cu1—O2W 2.315 (4)
C6—H6A 0.9700 Cu1—O1W 2.461 (4)
C6—H6B 0.9700 N2—N3 1.362 (4)
C7—C8 1.517 (5) N4—N5 1.351 (4)
C7—H7A 0.9700 N7—H7C 0.8603
C7—H7B 0.9700 N7—H7D 0.8591
C8—N4 1.458 (4) O2—H2A 0.8197
C8—H8A 0.9700 O3—S1 1.434 (3)
C8—H8B 0.9700 O4—S1 1.436 (3)
C9—N5 1.311 (4) O5—S1 1.460 (3)
C9—N6 1.359 (4) O1W—H1W 0.8479
C9—H9 0.9300 O1W—H1Wi 0.8479
C10—N6 1.305 (4) O2W—H2W 0.8446

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C10—N4 1.329 (4) O2W—H2Wi 0.8446
C10—H10 0.9300 O3W—H3WA 0.8450
C11—C16 1.398 (4) O3W—H3WB 0.8478
C11—C12 1.411 (4)

N2—C1—N1 114.0 (3) C13—C14—H14 119.8

N2—C1—H1 123.0 C15—C14—H14 119.8
N1—C1—H1 123.0 C16—C15—C14 119.4 (3)
N1—C2—N3 109.7 (3) C16—C15—S1 121.1 (2)
N1—C2—H2 125.2 C14—C15—S1 119.5 (2)
N3—C2—H2 125.2 C15—C16—C11 121.0 (3)
N3—C3—C4 112.2 (3) C15—C16—H16 119.5
N3—C3—H3A 109.2 C11—C16—H16 119.5
C4—C3—H3A 109.2 O1—C17—O2 121.9 (3)
N3—C3—H3B 109.2 O1—C17—C11 123.1 (3)
C4—C3—H3B 109.2 O2—C17—C11 115.0 (3)
H3A—C3—H3B 107.9 N1—Cu1—N1i 178.03 (18)
C3—C4—C5 110.2 (4) N1—Cu1—N6ii 89.90 (9)
C3—C4—H4A 109.6 N1i—Cu1—N6ii 90.08 (9)
C5—C4—H4A 109.6 N1—Cu1—N6iii 90.08 (9)
C3—C4—H4B 109.6 N1i—Cu1—N6iii 89.90 (9)
C5—C4—H4B 109.6 N6ii—Cu1—N6iii 178.52 (18)
H4A—C4—H4B 108.1 N1—Cu1—O2W 90.98 (9)
C4—C5—C6 112.1 (4) N1i—Cu1—O2W 90.98 (9)
C4—C5—H5A 109.2 N6ii—Cu1—O2W 90.74 (9)
C6—C5—H5A 109.2 N6iii—Cu1—O2W 90.74 (9)
C4—C5—H5B 109.2 N1—Cu1—O1W 89.02 (9)
C6—C5—H5B 109.2 N1i—Cu1—O1W 89.02 (9)
H5A—C5—H5B 107.9 N6ii—Cu1—O1W 89.26 (9)
C7—C6—C5 113.7 (4) N6iii—Cu1—O1W 89.26 (9)
C7—C6—H6A 108.8 O2W—Cu1—O1W 180.0
C5—C6—H6A 108.8 C2—N1—C1 103.9 (3)
C7—C6—H6B 108.8 C2—N1—Cu1 127.3 (2)
C5—C6—H6B 108.8 C1—N1—Cu1 128.7 (2)
H6A—C6—H6B 107.7 C1—N2—N3 103.0 (3)
C6—C7—C8 114.0 (3) C2—N3—N2 109.5 (3)
C6—C7—H7A 108.8 C2—N3—C3 129.1 (3)
C8—C7—H7A 108.8 N2—N3—C3 121.3 (3)
C6—C7—H7B 108.8 C10—N4—N5 109.2 (3)
C8—C7—H7B 108.8 C10—N4—C8 127.7 (3)
H7A—C7—H7B 107.6 N5—N4—C8 122.8 (2)
N4—C8—C7 111.9 (3) C9—N5—N4 103.3 (3)
N4—C8—H8A 109.2 C10—N6—C9 103.3 (2)
C7—C8—H8A 109.2 C10—N6—Cu1iv 124.9 (2)
N4—C8—H8B 109.2 C9—N6—Cu1iv 131.5 (2)
C7—C8—H8B 109.2 C12—N7—H7C 119.9
H8A—C8—H8B 107.9 C12—N7—H7D 120.1
N5—C9—N6 113.6 (3) H7C—N7—H7D 120.0

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N5—C9—H9 123.2 C17—O2—H2A 109.3
N6—C9—H9 123.2 Cu1—O1W—H1W 131.0
N6—C10—N4 110.6 (3) Cu1—O1W—H1Wi 131.024 (4)
N6—C10—H10 124.7 H1W—O1W—H1Wi 98.0
N4—C10—H10 124.7 Cu1—O2W—H2W 123.7
C16—C11—C12 119.8 (3) Cu1—O2W—H2Wi 123.655 (3)
C16—C11—C17 118.6 (3) H2W—O2W—H2Wi 112.7
C12—C11—C17 121.5 (3) H3WA—O3W—H3WB 110.5
N7—C12—C13 118.7 (3) O3—S1—O4 114.2 (3)
N7—C12—C11 123.4 (3) O3—S1—O5 110.4 (2)
C13—C12—C11 117.9 (3) O4—S1—O5 111.5 (3)
C14—C13—C12 121.5 (3) O3—S1—C15 107.19 (18)
C14—C13—H13 119.3 O4—S1—C15 106.80 (14)
C12—C13—H13 119.3 O5—S1—C15 106.30 (16)
C13—C14—C15 120.4 (3)

Symmetry codes: (i) −x, −y+2, z; (ii) −x+1, −y+2, z; (iii) x−1, y, z; (iv) x+1, y, z.

Hydrogen-bond geometry (Å, º)

D—H···A D—H H···A D···A D—H···A

v
C8—H8B···N2 0.97 2.49 3.365 (5) 151
N7—H7C···O4vi 0.86 2.52 3.344 (4) 160
O3W—H3WB···O5vi 0.85 1.90 2.737 (5) 170
O3W—H3WA···O1vii 0.84 2.07 2.740 (4) 136
O2—H2A···O3Wiv 0.82 1.79 2.603 (4) 172
O2W—H2W···O4iii 0.84 2.16 2.981 (6) 163
O2W—H2W···O3iii 0.84 2.46 3.092 (4) 133
O1W—H1W···O4viii 0.85 2.16 2.996 (6) 170

Symmetry codes: (iii) x−1, y, z; (iv) x+1, y, z; (v) x+1/2, −y+3/2, z; (vi) x−1/2, −y+3/2, z; (vii) −x+1, −y+1, z; (viii) x−1, y, z+1.

Bis(µ-2-amino-5-sulfonatobenzoato-κ2O1:O1′)bis{µ-1,2-bis[(1H-imidazol-1-yl)methyl]benzene-
κ2N3:N3′}bis[aquacopper(II)] trihydrate (002)

Crystal data
[Cu2(C7H5NO5S)2(C14H14N4)2(H2O)2]·3H2O F(000) = 2320
Mr = 1124.10 Dx = 1.619 Mg m−3
Monoclinic, P21/c Mo Kα radiation, λ = 0.71073 Å
a = 18.787 (2) Å Cell parameters from 9870 reflections
b = 12.0409 (12) Å θ = 2.2–27.4°
c = 20.699 (2) Å µ = 1.09 mm−1
β = 99.905 (4)° T = 293 K
V = 4612.6 (8) Å3 Massive, green
Z=4 0.26 × 0.25 × 0.22 mm

Data collection
CCD area detector Absorption correction: empirical (using
diffractometer intensity measurements)
phi and ω scans (SADABS; Bruker, 2008)
Tmin = 0.760, Tmax = 0.786

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47208 measured reflections θmax = 27.5°, θmin = 2.0°
10554 independent reflections h = −24→22
7450 reflections with I > 2σ(I) k = −15→15
Rint = 0.040 l = −22→26

Refinement
Refinement on F2 Hydrogen site location: mixed
Least-squares matrix: full H-atom parameters constrained
R[F2 > 2σ(F2)] = 0.045 w = 1/[σ2(Fo2) + (0.0587P)2 + 3.4892P]
wR(F2) = 0.121 where P = (Fo2 + 2Fc2)/3
S = 1.03 (Δ/σ)max = 0.002
10554 reflections Δρmax = 0.74 e Å−3
640 parameters Δρmin = −0.78 e Å−3
0 restraints

Special details
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance
matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles;
correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate
(isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

x y z Uiso*/Ueq
C1 0.86921 (13) 1.1781 (2) 1.12680 (13) 0.0255 (6)
C2 0.89216 (15) 1.1639 (2) 1.19508 (14) 0.0310 (6)
C3 0.91954 (17) 1.2574 (2) 1.23217 (14) 0.0370 (7)
H3 0.935213 1.249487 1.277055 0.044*
C4 0.92371 (16) 1.3593 (2) 1.20401 (14) 0.0352 (7)
H4 0.941930 1.419394 1.229870 0.042*
C5 0.90099 (14) 1.3737 (2) 1.13720 (14) 0.0289 (6)
C6 0.87424 (14) 1.2832 (2) 1.09968 (13) 0.0268 (6)
H6 0.859071 1.292770 1.054837 0.032*
C7 0.83654 (14) 1.0871 (2) 1.08145 (14) 0.0276 (6)
C8 0.67367 (15) 1.2209 (2) 1.00930 (14) 0.0304 (6)
H8 0.713774 1.232767 1.041736 0.037*
C9 0.56369 (16) 1.2236 (3) 0.95644 (16) 0.0411 (8)
H9 0.514309 1.236385 0.944954 0.049*
C10 0.60638 (16) 1.1720 (3) 0.91948 (16) 0.0409 (8)
H10 0.591092 1.142680 0.877843 0.049*
C11 0.58234 (17) 1.3181 (3) 1.06622 (15) 0.0404 (7)
H11A 0.537096 1.287362 1.074633 0.049*
H11B 0.573178 1.393930 1.051223 0.049*
C12 0.63549 (15) 1.3194 (2) 1.12894 (14) 0.0311 (6)
C13 0.63425 (15) 1.2414 (2) 1.17913 (14) 0.0299 (6)
C14 0.68443 (17) 1.2496 (3) 1.23635 (15) 0.0399 (7)
H14 0.683355 1.198565 1.269894 0.048*
C15 0.73598 (18) 1.3323 (3) 1.24437 (17) 0.0478 (9)
H15 0.769723 1.336213 1.282854 0.057*
C16 0.73737 (18) 1.4086 (3) 1.19554 (18) 0.0478 (9)

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H16 0.772209 1.464242 1.200826 0.057*
C17 0.68722 (17) 1.4030 (2) 1.13858 (17) 0.0410 (8)
H17 0.688020 1.456112 1.106068 0.049*
C18 0.58280 (17) 1.1449 (2) 1.17130 (16) 0.0374 (7)
H18A 0.580889 1.112848 1.213962 0.045*
H18B 0.534708 1.170705 1.152758 0.045*
C19 0.67366 (15) 1.0339 (2) 1.12209 (14) 0.0305 (6)
H19 0.714405 1.067703 1.145944 0.037*
C20 0.60505 (18) 0.9284 (3) 1.05549 (19) 0.0530 (9)
H20 0.589058 0.874851 1.023952 0.064*
C21 0.56216 (18) 0.9921 (3) 1.0862 (2) 0.0534 (10)
H21 0.511952 0.990316 1.079787 0.064*
C22 0.62813 (13) 0.8210 (2) 0.85464 (12) 0.0226 (5)
C23 0.59604 (13) 0.8469 (2) 0.78963 (13) 0.0251 (6)
C24 0.55254 (15) 0.7649 (2) 0.75305 (14) 0.0306 (6)
H24 0.529988 0.781028 0.710493 0.037*
C25 0.54288 (15) 0.6625 (2) 0.77875 (14) 0.0311 (6)
H25 0.514751 0.609797 0.753280 0.037*
C26 0.57492 (14) 0.6365 (2) 0.84301 (13) 0.0238 (6)
C27 0.61649 (13) 0.7152 (2) 0.87949 (12) 0.0240 (6)
H27 0.637769 0.698064 0.922273 0.029*
C28 0.67575 (13) 0.8989 (2) 0.89909 (13) 0.0254 (6)
C29 0.83651 (16) 0.9462 (2) 0.85162 (14) 0.0338 (7)
H29 0.794516 0.904689 0.840112 0.041*
C30 0.94817 (17) 1.0011 (3) 0.85936 (17) 0.0450 (8)
H30 0.996583 1.005622 0.855163 0.054*
C31 0.91083 (17) 1.0739 (3) 0.89097 (16) 0.0424 (8)
H31 0.929891 1.137976 0.912397 0.051*
C32 0.91608 (19) 0.8209 (3) 0.79701 (17) 0.0466 (8)
H32A 0.960500 0.786786 0.818919 0.056*
H32B 0.923278 0.844160 0.753724 0.056*
C33 0.85592 (17) 0.7372 (2) 0.79038 (15) 0.0367 (7)
C34 0.85259 (18) 0.6550 (2) 0.83744 (15) 0.0387 (7)
C35 0.7930 (2) 0.5842 (3) 0.8290 (2) 0.0570 (11)
H35 0.790228 0.528318 0.859442 0.068*
C36 0.7379 (2) 0.5962 (3) 0.7756 (2) 0.0629 (12)
H36 0.697933 0.549467 0.770907 0.075*
C37 0.7423 (2) 0.6761 (4) 0.7303 (2) 0.0623 (11)
H37 0.705318 0.683986 0.694401 0.075*
C38 0.8008 (2) 0.7447 (3) 0.73715 (16) 0.0512 (9)
H38 0.803566 0.798028 0.705169 0.061*
C39 0.9083 (2) 0.6439 (3) 0.89827 (17) 0.0543 (10)
H39A 0.905487 0.570026 0.916394 0.065*
H39B 0.956022 0.652921 0.887137 0.065*
C40 0.83550 (17) 0.7487 (3) 0.96783 (15) 0.0388 (7)
H40 0.792528 0.711141 0.953130 0.047*
C41 0.91219 (18) 0.8623 (4) 1.01778 (19) 0.0591 (10)
H41 0.933123 0.919071 1.045063 0.071*

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C42 0.94700 (18) 0.7993 (4) 0.97891 (18) 0.0591 (11)
H42 0.995299 0.804840 0.974474 0.071*
Cu1 0.75935 (2) 1.10477 (3) 0.92216 (2) 0.02946 (10)
Cu2 0.76041 (2) 0.89423 (3) 1.04557 (2) 0.03086 (10)
N1 0.67600 (12) 1.16985 (19) 0.95330 (11) 0.0303 (5)
N2 0.60666 (12) 1.25333 (18) 1.01373 (11) 0.0280 (5)
N3 0.60573 (12) 1.05910 (19) 1.12809 (12) 0.0308 (5)
N4 0.67560 (12) 0.95488 (19) 1.07792 (12) 0.0315 (5)
N5 0.89258 (17) 1.0633 (2) 1.22539 (13) 0.0556 (8)
H5A 0.909419 1.057533 1.266594 0.083*
H5B 0.876020 1.005605 1.203290 0.083*
N6 0.84047 (12) 1.03843 (19) 0.88643 (11) 0.0300 (5)
N7 0.89982 (13) 0.91953 (19) 0.83485 (12) 0.0331 (5)
N8 0.89774 (14) 0.7268 (2) 0.94779 (12) 0.0394 (6)
N9 0.84222 (13) 0.8300 (2) 1.01092 (12) 0.0352 (6)
N10 0.60322 (15) 0.9475 (2) 0.76169 (13) 0.0438 (7)
H10A 0.628242 0.998879 0.783815 0.066*
H10B 0.582729 0.959763 0.721891 0.066*
O1 0.82157 (12) 1.10717 (17) 1.02207 (10) 0.0412 (5)
O2 0.82486 (10) 0.99374 (16) 1.10700 (10) 0.0338 (5)
O3 0.95690 (18) 1.5696 (2) 1.14177 (14) 0.0776 (9)
O4 0.92283 (17) 1.4881 (2) 1.03698 (13) 0.0711 (8)
O5 0.83108 (16) 1.5489 (2) 1.0933 (2) 0.1032 (13)
O6 0.69428 (10) 0.98941 (15) 0.87518 (10) 0.0325 (5)
O7 0.69515 (11) 0.86864 (17) 0.95701 (10) 0.0389 (5)
O8 0.60268 (11) 0.50267 (16) 0.94180 (10) 0.0367 (5)
O9 0.59960 (13) 0.42735 (17) 0.83275 (11) 0.0458 (6)
O10 0.48886 (10) 0.48052 (17) 0.86896 (10) 0.0365 (5)
O1W 0.79382 (11) 1.26356 (16) 0.90347 (11) 0.0423 (5)
H1WA 0.835856 1.281786 0.896402 0.064*
H1WB 0.774556 1.323006 0.914712 0.064*
O2W 0.73288 (11) 0.72419 (17) 1.07575 (11) 0.0450 (6)
H2WA 0.765890 0.676170 1.078457 0.067*
H2WB 0.691840 0.694270 1.073588 0.067*
O3W 0.59312 (11) 0.86211 (18) 0.54928 (11) 0.0443 (5)
H3WA 0.593378 0.896440 0.513372 0.067*
H3WB 0.567508 0.900150 0.571012 0.067*
O4W 0.92969 (14) 0.3521 (2) 0.92691 (17) 0.0766 (9)
H4WA 0.936966 0.396368 0.958965 0.115*
H4WB 0.957416 0.361618 0.899315 0.115*
O5W 0.75022 (13) 0.4449 (2) 0.96529 (13) 0.0649 (7)
H5WA 0.778876 0.480819 0.993893 0.097*
H5WB 0.707926 0.471069 0.964603 0.097*
S1 0.90347 (4) 1.50651 (6) 1.10037 (4) 0.03859 (19)
S2 0.56619 (4) 0.50074 (5) 0.87364 (3) 0.02652 (15)

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Atomic displacement parameters (Å2)

U11 U22 U33 U12 U13 U23

C1 0.0207 (13) 0.0282 (14) 0.0275 (14) 0.0004 (11) 0.0042 (11) −0.0021 (11)
C2 0.0343 (16) 0.0310 (16) 0.0282 (15) −0.0025 (12) 0.0068 (12) 0.0004 (12)
C3 0.0491 (19) 0.0368 (17) 0.0242 (15) −0.0037 (14) 0.0035 (13) −0.0055 (13)
C4 0.0416 (17) 0.0296 (16) 0.0338 (17) −0.0037 (13) 0.0047 (13) −0.0089 (13)
C5 0.0262 (14) 0.0240 (14) 0.0371 (17) −0.0007 (11) 0.0075 (12) 0.0004 (12)
C6 0.0243 (14) 0.0297 (15) 0.0266 (14) 0.0015 (11) 0.0046 (11) 0.0016 (11)
C7 0.0188 (13) 0.0286 (15) 0.0350 (17) 0.0017 (11) 0.0031 (11) −0.0074 (12)
C8 0.0265 (15) 0.0319 (15) 0.0321 (16) 0.0009 (12) 0.0027 (12) −0.0023 (12)
C9 0.0269 (16) 0.0422 (18) 0.052 (2) 0.0030 (13) 0.0003 (14) −0.0053 (15)
C10 0.0340 (17) 0.0453 (19) 0.0402 (18) 0.0025 (14) −0.0026 (14) −0.0114 (15)
C11 0.0394 (17) 0.0425 (18) 0.0419 (18) 0.0144 (14) 0.0140 (14) 0.0018 (14)
C12 0.0342 (16) 0.0291 (15) 0.0328 (16) 0.0074 (12) 0.0135 (12) −0.0026 (12)
C13 0.0329 (15) 0.0263 (15) 0.0340 (16) 0.0031 (11) 0.0152 (13) −0.0044 (12)
C14 0.050 (2) 0.0414 (18) 0.0297 (16) 0.0048 (15) 0.0106 (14) −0.0007 (14)
C15 0.0432 (19) 0.060 (2) 0.0393 (19) 0.0004 (17) 0.0044 (15) −0.0160 (17)
C16 0.0411 (19) 0.045 (2) 0.062 (2) −0.0107 (15) 0.0208 (17) −0.0182 (17)
C17 0.0487 (19) 0.0283 (16) 0.052 (2) 0.0007 (14) 0.0245 (16) 0.0007 (14)
C18 0.0410 (18) 0.0338 (16) 0.0423 (18) 0.0005 (13) 0.0206 (14) −0.0040 (13)
C19 0.0302 (15) 0.0300 (15) 0.0312 (16) −0.0015 (12) 0.0050 (12) −0.0031 (12)
C20 0.0376 (19) 0.050 (2) 0.071 (3) −0.0089 (16) 0.0070 (17) −0.0299 (19)
C21 0.0290 (17) 0.048 (2) 0.082 (3) −0.0086 (15) 0.0076 (17) −0.0230 (19)
C22 0.0221 (13) 0.0220 (13) 0.0234 (14) −0.0007 (10) 0.0031 (10) −0.0033 (10)
C23 0.0226 (13) 0.0261 (14) 0.0264 (14) −0.0018 (11) 0.0037 (11) −0.0004 (11)
C24 0.0351 (16) 0.0315 (15) 0.0229 (14) −0.0023 (12) −0.0013 (12) −0.0002 (12)
C25 0.0326 (15) 0.0287 (15) 0.0302 (16) −0.0066 (12) 0.0005 (12) −0.0066 (12)
C26 0.0265 (14) 0.0206 (13) 0.0244 (14) −0.0024 (10) 0.0052 (11) −0.0008 (10)
C27 0.0251 (13) 0.0259 (14) 0.0199 (13) −0.0005 (11) 0.0007 (10) −0.0021 (11)
C28 0.0199 (13) 0.0248 (14) 0.0315 (16) −0.0002 (11) 0.0044 (11) −0.0086 (12)
C29 0.0327 (16) 0.0329 (16) 0.0358 (17) −0.0027 (13) 0.0055 (13) −0.0047 (13)
C30 0.0334 (17) 0.048 (2) 0.053 (2) −0.0028 (15) 0.0077 (15) −0.0066 (16)
C31 0.0348 (17) 0.0418 (18) 0.048 (2) −0.0013 (14) 0.0002 (14) −0.0127 (15)
C32 0.055 (2) 0.0400 (19) 0.051 (2) 0.0001 (15) 0.0270 (17) −0.0104 (15)
C33 0.0500 (19) 0.0273 (15) 0.0353 (17) 0.0052 (13) 0.0147 (14) −0.0090 (13)
C34 0.055 (2) 0.0279 (16) 0.0376 (18) 0.0099 (14) 0.0193 (15) −0.0053 (13)
C35 0.086 (3) 0.0355 (19) 0.062 (3) −0.0043 (18) 0.047 (2) −0.0078 (17)
C36 0.059 (2) 0.063 (3) 0.073 (3) −0.019 (2) 0.028 (2) −0.037 (2)
C37 0.063 (3) 0.069 (3) 0.052 (2) 0.000 (2) 0.0006 (19) −0.024 (2)
C38 0.075 (3) 0.045 (2) 0.0327 (18) 0.0037 (18) 0.0080 (17) −0.0064 (15)
C39 0.070 (2) 0.052 (2) 0.043 (2) 0.0326 (19) 0.0159 (18) 0.0020 (17)
C40 0.0409 (18) 0.0384 (18) 0.0379 (18) 0.0023 (14) 0.0089 (14) −0.0045 (14)
C41 0.0330 (19) 0.079 (3) 0.062 (2) 0.0029 (18) −0.0015 (17) −0.026 (2)
C42 0.0308 (18) 0.086 (3) 0.060 (2) 0.0115 (18) 0.0043 (16) −0.016 (2)
Cu1 0.02727 (19) 0.02813 (19) 0.0329 (2) −0.00299 (14) 0.00486 (14) −0.00800 (14)
Cu2 0.02895 (19) 0.0310 (2) 0.0318 (2) −0.00243 (14) 0.00273 (14) −0.01002 (15)
N1 0.0291 (12) 0.0287 (13) 0.0334 (13) −0.0015 (10) 0.0062 (10) −0.0058 (10)

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 supporting information
N2 0.0286 (12) 0.0249 (12) 0.0312 (13) 0.0032 (9) 0.0071 (10) 0.0021 (10)
N3 0.0304 (13) 0.0256 (12) 0.0384 (14) −0.0046 (10) 0.0114 (11) −0.0028 (10)
N4 0.0315 (13) 0.0263 (12) 0.0362 (14) −0.0008 (10) 0.0045 (10) −0.0040 (10)
N5 0.093 (2) 0.0365 (16) 0.0312 (15) −0.0182 (15) −0.0053 (15) 0.0069 (13)
N6 0.0313 (13) 0.0273 (12) 0.0310 (13) −0.0003 (10) 0.0037 (10) −0.0045 (10)
N7 0.0339 (13) 0.0293 (13) 0.0376 (14) 0.0000 (10) 0.0106 (11) −0.0040 (11)
N8 0.0411 (15) 0.0438 (15) 0.0343 (14) 0.0155 (12) 0.0089 (12) 0.0016 (12)
N9 0.0331 (14) 0.0389 (14) 0.0334 (14) 0.0021 (11) 0.0048 (11) −0.0055 (11)
N10 0.0593 (18) 0.0314 (14) 0.0350 (15) −0.0130 (12) −0.0081 (12) 0.0091 (12)
O1 0.0485 (13) 0.0407 (12) 0.0288 (12) 0.0030 (10) −0.0085 (10) −0.0052 (9)
O2 0.0360 (11) 0.0279 (11) 0.0365 (11) −0.0091 (8) 0.0037 (9) −0.0071 (9)
O3 0.115 (2) 0.0479 (16) 0.0631 (18) −0.0438 (16) −0.0038 (16) 0.0023 (14)
O4 0.119 (2) 0.0461 (15) 0.0514 (16) −0.0130 (15) 0.0235 (16) 0.0113 (12)
O5 0.0651 (19) 0.0551 (18) 0.203 (4) 0.0305 (15) 0.063 (2) 0.062 (2)
O6 0.0333 (11) 0.0239 (10) 0.0396 (12) −0.0084 (8) 0.0043 (9) −0.0069 (8)
O7 0.0428 (12) 0.0390 (12) 0.0293 (12) −0.0060 (9) −0.0099 (9) −0.0067 (9)
O8 0.0459 (12) 0.0323 (11) 0.0292 (11) −0.0011 (9) −0.0010 (9) 0.0036 (9)
O9 0.0651 (15) 0.0294 (11) 0.0496 (14) 0.0044 (10) 0.0285 (12) −0.0065 (10)
O10 0.0345 (11) 0.0374 (12) 0.0381 (12) −0.0108 (9) 0.0075 (9) 0.0014 (9)
O1W 0.0405 (12) 0.0263 (11) 0.0638 (15) −0.0040 (9) 0.0191 (11) 0.0002 (10)
O2W 0.0388 (12) 0.0294 (11) 0.0664 (16) 0.0031 (9) 0.0083 (11) 0.0099 (11)
O3W 0.0471 (13) 0.0387 (12) 0.0506 (14) 0.0072 (10) 0.0179 (11) 0.0019 (10)
O4W 0.0516 (16) 0.0498 (16) 0.129 (3) −0.0148 (13) 0.0174 (16) −0.0197 (17)
O5W 0.0490 (15) 0.0685 (18) 0.0744 (18) 0.0122 (13) 0.0023 (13) −0.0154 (15)
S1 0.0394 (4) 0.0249 (4) 0.0533 (5) −0.0010 (3) 0.0132 (4) 0.0048 (3)
S2 0.0332 (4) 0.0214 (3) 0.0258 (3) −0.0034 (3) 0.0073 (3) −0.0025 (3)

Geometric parameters (Å, º)

C1—C6 1.394 (4) C29—N7 1.334 (4)

C1—C2 1.415 (4) C29—H29 0.9300
C1—C7 1.504 (4) C30—C31 1.359 (4)
C2—N5 1.364 (4) C30—N7 1.375 (4)
C2—C3 1.409 (4) C30—H30 0.9300
C3—C4 1.366 (4) C31—N6 1.377 (4)
C3—H3 0.9300 C31—H31 0.9300
C4—C5 1.386 (4) C32—N7 1.483 (4)
C4—H4 0.9300 C32—C33 1.503 (4)
C5—C6 1.381 (4) C32—H32A 0.9700
C5—S1 1.776 (3) C32—H32B 0.9700
C6—H6 0.9300 C33—C38 1.379 (5)
C7—O1 1.237 (3) C33—C34 1.397 (4)
C7—O2 1.277 (3) C34—C35 1.394 (5)
C8—N1 1.319 (4) C34—C39 1.498 (5)
C8—N2 1.336 (3) C35—C36 1.385 (6)
C8—H8 0.9300 C35—H35 0.9300
C9—C10 1.351 (4) C36—C37 1.357 (6)
C9—N2 1.363 (4) C36—H36 0.9300

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C9—H9 0.9300 C37—C38 1.363 (5)
C10—N1 1.373 (4) C37—H37 0.9300
C10—H10 0.9300 C38—H38 0.9300
C11—N2 1.473 (4) C39—N8 1.468 (4)
C11—C12 1.496 (4) C39—H39A 0.9700
C11—H11A 0.9700 C39—H39B 0.9700
C11—H11B 0.9700 C40—N9 1.316 (4)
C12—C17 1.390 (4) C40—N8 1.333 (4)
C12—C13 1.404 (4) C40—H40 0.9300
C13—C14 1.385 (4) C41—C42 1.353 (5)
C13—C18 1.502 (4) C41—N9 1.355 (4)
C14—C15 1.379 (5) C41—H41 0.9300
C14—H14 0.9300 C42—N8 1.352 (5)
C15—C16 1.369 (5) C42—H42 0.9300
C15—H15 0.9300 Cu1—N1 1.957 (2)
C16—C17 1.379 (5) Cu1—N6 1.974 (2)
C16—H16 0.9300 Cu1—O6 1.9900 (18)
C17—H17 0.9300 Cu1—O1W 2.076 (2)
C18—N3 1.478 (4) Cu1—O1 2.194 (2)
C18—H18A 0.9700 Cu2—N9 1.963 (2)
C18—H18B 0.9700 Cu2—N4 1.972 (2)
C19—N4 1.325 (4) Cu2—O2 1.9972 (19)
C19—N3 1.338 (3) Cu2—O7 2.0458 (19)
C19—H19 0.9300 Cu2—O2W 2.227 (2)
C20—C21 1.348 (5) N5—H5A 0.8600
C20—N4 1.365 (4) N5—H5B 0.8600
C20—H20 0.9300 N10—H10A 0.8600
C21—N3 1.352 (4) N10—H10B 0.8600
C21—H21 0.9300 O3—S1 1.422 (3)
C22—C27 1.404 (4) O4—S1 1.438 (3)
C22—C23 1.412 (4) O5—S1 1.436 (3)
C22—C28 1.498 (4) O8—S2 1.459 (2)
C23—N10 1.359 (4) O9—S2 1.440 (2)
C23—C24 1.415 (4) O10—S2 1.460 (2)
C24—C25 1.367 (4) O1W—H1WA 0.8562
C24—H24 0.9300 O1W—H1WB 0.8523
C25—C26 1.398 (4) O2W—H2WA 0.8427
C25—H25 0.9300 O2W—H2WB 0.8452
C26—C27 1.370 (4) O3W—H3WA 0.8513
C26—S2 1.771 (3) O3W—H3WB 0.8474
C27—H27 0.9300 O4W—H4WA 0.8438
C28—O7 1.246 (3) O4W—H4WB 0.8444
C28—O6 1.271 (3) O5W—H5WA 0.8471
C29—N6 1.318 (4) O5W—H5WB 0.8525

C6—C1—C2 118.8 (2) C34—C33—C32 122.3 (3)

C6—C1—C7 117.3 (2) C35—C34—C33 118.5 (3)
C2—C1—C7 123.8 (2) C35—C34—C39 118.7 (3)

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N5—C2—C3 119.1 (3) C33—C34—C39 122.7 (3)
N5—C2—C1 122.9 (3) C36—C35—C34 120.7 (3)
C3—C2—C1 117.9 (3) C36—C35—H35 119.7
C4—C3—C2 121.8 (3) C34—C35—H35 119.7
C4—C3—H3 119.1 C37—C36—C35 120.0 (4)
C2—C3—H3 119.1 C37—C36—H36 120.0
C3—C4—C5 120.5 (3) C35—C36—H36 120.0
C3—C4—H4 119.7 C36—C37—C38 120.1 (4)
C5—C4—H4 119.7 C36—C37—H37 120.0
C6—C5—C4 118.8 (3) C38—C37—H37 120.0
C6—C5—S1 120.2 (2) C37—C38—C33 121.7 (4)
C4—C5—S1 121.0 (2) C37—C38—H38 119.2
C5—C6—C1 122.2 (3) C33—C38—H38 119.2
C5—C6—H6 118.9 N8—C39—C34 111.6 (3)
C1—C6—H6 118.9 N8—C39—H39A 109.3
O1—C7—O2 123.9 (3) C34—C39—H39A 109.3
O1—C7—C1 118.4 (3) N8—C39—H39B 109.3
O2—C7—C1 117.6 (2) C34—C39—H39B 109.3
N1—C8—N2 111.8 (2) H39A—C39—H39B 108.0
N1—C8—H8 124.1 N9—C40—N8 111.8 (3)
N2—C8—H8 124.1 N9—C40—H40 124.1
C10—C9—N2 107.0 (3) N8—C40—H40 124.1
C10—C9—H9 126.5 C42—C41—N9 109.7 (3)
N2—C9—H9 126.5 C42—C41—H41 125.2
C9—C10—N1 109.0 (3) N9—C41—H41 125.2
C9—C10—H10 125.5 N8—C42—C41 106.5 (3)
N1—C10—H10 125.5 N8—C42—H42 126.8
N2—C11—C12 113.6 (2) C41—C42—H42 126.8
N2—C11—H11A 108.8 N1—Cu1—N6 177.19 (10)
C12—C11—H11A 108.8 N1—Cu1—O6 88.93 (9)
N2—C11—H11B 108.8 N6—Cu1—O6 89.05 (9)
C12—C11—H11B 108.8 N1—Cu1—O1W 89.17 (9)
H11A—C11—H11B 107.7 N6—Cu1—O1W 90.99 (9)
C17—C12—C13 118.6 (3) O6—Cu1—O1W 137.46 (9)
C17—C12—C11 118.6 (3) N1—Cu1—O1 90.63 (9)
C13—C12—C11 122.8 (3) N6—Cu1—O1 92.17 (9)
C14—C13—C12 119.3 (3) O6—Cu1—O1 130.75 (8)
C14—C13—C18 118.6 (3) O1W—Cu1—O1 91.77 (8)
C12—C13—C18 122.0 (3) N9—Cu2—N4 177.69 (10)
C15—C14—C13 121.0 (3) N9—Cu2—O2 92.40 (9)
C15—C14—H14 119.5 N4—Cu2—O2 89.91 (9)
C13—C14—H14 119.5 N9—Cu2—O7 89.98 (9)
C16—C15—C14 119.8 (3) N4—Cu2—O7 88.01 (9)
C16—C15—H15 120.1 O2—Cu2—O7 149.89 (9)
C14—C15—H15 120.1 N9—Cu2—O2W 88.55 (9)
C15—C16—C17 120.1 (3) N4—Cu2—O2W 90.28 (9)
C15—C16—H16 119.9 O2—Cu2—O2W 121.16 (8)
C17—C16—H16 119.9 O7—Cu2—O2W 88.89 (8)

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C16—C17—C12 121.1 (3) C8—N1—C10 105.5 (2)
C16—C17—H17 119.5 C8—N1—Cu1 128.70 (19)
C12—C17—H17 119.5 C10—N1—Cu1 125.8 (2)
N3—C18—C13 110.9 (2) C8—N2—C9 106.7 (2)
N3—C18—H18A 109.5 C8—N2—C11 128.4 (2)
C13—C18—H18A 109.5 C9—N2—C11 124.7 (2)
N3—C18—H18B 109.5 C19—N3—C21 106.7 (2)
C13—C18—H18B 109.5 C19—N3—C18 126.6 (2)
H18A—C18—H18B 108.0 C21—N3—C18 126.7 (3)
N4—C19—N3 111.5 (2) C19—N4—C20 105.2 (2)
N4—C19—H19 124.2 C19—N4—Cu2 128.3 (2)
N3—C19—H19 124.2 C20—N4—Cu2 126.3 (2)
C21—C20—N4 109.3 (3) C2—N5—H5A 120.0
C21—C20—H20 125.3 C2—N5—H5B 120.0
N4—C20—H20 125.3 H5A—N5—H5B 120.0
C20—C21—N3 107.3 (3) C29—N6—C31 105.2 (2)
C20—C21—H21 126.4 C29—N6—Cu1 124.81 (19)
N3—C21—H21 126.4 C31—N6—Cu1 130.0 (2)
C27—C22—C23 118.8 (2) C29—N7—C30 107.1 (2)
C27—C22—C28 117.2 (2) C29—N7—C32 127.2 (3)
C23—C22—C28 124.0 (2) C30—N7—C32 125.7 (3)
N10—C23—C22 123.0 (2) C40—N8—C42 106.8 (3)
N10—C23—C24 119.0 (2) C40—N8—C39 125.7 (3)
C22—C23—C24 117.9 (2) C42—N8—C39 127.5 (3)
C25—C24—C23 121.6 (3) C40—N9—C41 105.2 (3)
C25—C24—H24 119.2 C40—N9—Cu2 123.4 (2)
C23—C24—H24 119.2 C41—N9—Cu2 131.0 (2)
C24—C25—C26 120.6 (2) C23—N10—H10A 120.0
C24—C25—H25 119.7 C23—N10—H10B 120.0
C26—C25—H25 119.7 H10A—N10—H10B 120.0
C27—C26—C25 118.7 (2) C7—O1—Cu1 158.1 (2)
C27—C26—S2 121.4 (2) C7—O2—Cu2 113.13 (18)
C25—C26—S2 119.8 (2) C28—O6—Cu1 126.52 (18)
C26—C27—C22 122.4 (2) C28—O7—Cu2 148.13 (19)
C26—C27—H27 118.8 Cu1—O1W—H1WA 126.5
C22—C27—H27 118.8 Cu1—O1W—H1WB 124.2
O7—C28—O6 124.8 (2) H1WA—O1W—H1WB 106.2
O7—C28—C22 116.9 (2) Cu2—O2W—H2WA 116.5
O6—C28—C22 118.2 (2) Cu2—O2W—H2WB 129.1
N6—C29—N7 112.1 (3) H2WA—O2W—H2WB 111.4
N6—C29—H29 124.0 H3WA—O3W—H3WB 106.9
N7—C29—H29 124.0 H4WA—O4W—H4WB 114.3
C31—C30—N7 106.0 (3) H5WA—O5W—H5WB 107.6
C31—C30—H30 127.0 O3—S1—O5 115.4 (2)
N7—C30—H30 127.0 O3—S1—O4 111.66 (18)
C30—C31—N6 109.6 (3) O5—S1—O4 110.2 (2)
C30—C31—H31 125.2 O3—S1—C5 106.87 (15)
N6—C31—H31 125.2 O5—S1—C5 105.64 (15)

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N7—C32—C33 111.4 (2) O4—S1—C5 106.38 (14)
N7—C32—H32A 109.3 O9—S2—O8 113.47 (14)
C33—C32—H32A 109.3 O9—S2—O10 112.84 (13)
N7—C32—H32B 109.3 O8—S2—O10 111.32 (12)
C33—C32—H32B 109.3 O9—S2—C26 106.21 (12)
H32A—C32—H32B 108.0 O8—S2—C26 105.93 (12)
C38—C33—C34 119.1 (3) O10—S2—C26 106.42 (12)
C38—C33—C32 118.6 (3)

C6—C1—C2—N5 −176.7 (3) C32—C33—C38—C37 −175.8 (3)

C7—C1—C2—N5 5.9 (4) C35—C34—C39—N8 −98.9 (4)
C6—C1—C2—C3 −0.4 (4) C33—C34—C39—N8 77.7 (4)
C7—C1—C2—C3 −177.8 (3) N9—C41—C42—N8 −0.2 (5)
N5—C2—C3—C4 176.9 (3) N2—C8—N1—C10 1.2 (3)
C1—C2—C3—C4 0.5 (4) N2—C8—N1—Cu1 −179.29 (18)
C2—C3—C4—C5 −0.2 (5) C9—C10—N1—C8 −0.6 (4)
C3—C4—C5—C6 −0.1 (4) C9—C10—N1—Cu1 180.0 (2)
C3—C4—C5—S1 178.0 (2) N1—C8—N2—C9 −1.5 (3)
C4—C5—C6—C1 0.1 (4) N1—C8—N2—C11 −176.0 (3)
S1—C5—C6—C1 −178.0 (2) C10—C9—N2—C8 1.0 (3)
C2—C1—C6—C5 0.2 (4) C10—C9—N2—C11 175.9 (3)
C7—C1—C6—C5 177.7 (2) C12—C11—N2—C8 −18.2 (4)
C6—C1—C7—O1 6.0 (4) C12—C11—N2—C9 168.1 (3)
C2—C1—C7—O1 −176.6 (3) N4—C19—N3—C21 0.6 (3)
C6—C1—C7—O2 −172.9 (2) N4—C19—N3—C18 −178.4 (3)
C2—C1—C7—O2 4.5 (4) C20—C21—N3—C19 −0.4 (4)
N2—C9—C10—N1 −0.3 (4) C20—C21—N3—C18 178.6 (3)
N2—C11—C12—C17 90.0 (3) C13—C18—N3—C19 32.3 (4)
N2—C11—C12—C13 −91.6 (3) C13—C18—N3—C21 −146.5 (3)
C17—C12—C13—C14 −0.2 (4) N3—C19—N4—C20 −0.6 (3)
C11—C12—C13—C14 −178.7 (3) N3—C19—N4—Cu2 175.34 (19)
C17—C12—C13—C18 −176.6 (3) C21—C20—N4—C19 0.3 (4)
C11—C12—C13—C18 4.9 (4) C21—C20—N4—Cu2 −175.7 (3)
C12—C13—C14—C15 −0.8 (4) N7—C29—N6—C31 1.3 (3)
C18—C13—C14—C15 175.7 (3) N7—C29—N6—Cu1 −178.83 (19)
C13—C14—C15—C16 0.8 (5) C30—C31—N6—C29 −0.8 (4)
C14—C15—C16—C17 0.2 (5) C30—C31—N6—Cu1 179.3 (2)
C15—C16—C17—C12 −1.3 (5) N6—C29—N7—C30 −1.2 (3)
C13—C12—C17—C16 1.2 (4) N6—C29—N7—C32 178.8 (3)
C11—C12—C17—C16 179.8 (3) C31—C30—N7—C29 0.6 (4)
C14—C13—C18—N3 −102.0 (3) C31—C30—N7—C32 −179.3 (3)
C12—C13—C18—N3 74.4 (3) C33—C32—N7—C29 −12.1 (5)
N4—C20—C21—N3 0.1 (4) C33—C32—N7—C30 167.8 (3)
C27—C22—C23—N10 178.9 (3) N9—C40—N8—C42 −1.1 (4)
C28—C22—C23—N10 −2.5 (4) N9—C40—N8—C39 −177.7 (3)
C27—C22—C23—C24 1.0 (4) C41—C42—N8—C40 0.8 (4)
C28—C22—C23—C24 179.6 (2) C41—C42—N8—C39 177.3 (3)
N10—C23—C24—C25 −179.5 (3) C34—C39—N8—C40 49.2 (4)

Acta Cryst. (2018). C74, 332-341 sup-15

 supporting information
C22—C23—C24—C25 −1.5 (4) C34—C39—N8—C42 −126.7 (4)
C23—C24—C25—C26 1.2 (4) N8—C40—N9—C41 0.9 (4)
C24—C25—C26—C27 −0.4 (4) N8—C40—N9—Cu2 174.4 (2)
C24—C25—C26—S2 −176.2 (2) C42—C41—N9—C40 −0.4 (4)
C25—C26—C27—C22 −0.1 (4) C42—C41—N9—Cu2 −173.2 (3)
S2—C26—C27—C22 175.6 (2) O2—C7—O1—Cu1 39.2 (7)
C23—C22—C27—C26 −0.2 (4) C1—C7—O1—Cu1 −139.6 (4)
C28—C22—C27—C26 −178.9 (2) O1—C7—O2—Cu2 −12.9 (3)
C27—C22—C28—O7 −7.5 (3) C1—C7—O2—Cu2 165.91 (17)
C23—C22—C28—O7 173.9 (2) O7—C28—O6—Cu1 1.0 (4)
C27—C22—C28—O6 171.4 (2) C22—C28—O6—Cu1 −177.83 (16)
C23—C22—C28—O6 −7.2 (4) O6—C28—O7—Cu2 −9.6 (5)
N7—C30—C31—N6 0.1 (4) C22—C28—O7—Cu2 169.3 (3)
N7—C32—C33—C38 90.0 (4) C6—C5—S1—O3 −157.6 (2)
N7—C32—C33—C34 −87.5 (4) C4—C5—S1—O3 24.3 (3)
C38—C33—C34—C35 −0.6 (4) C6—C5—S1—O5 79.0 (3)
C32—C33—C34—C35 176.9 (3) C4—C5—S1—O5 −99.1 (3)
C38—C33—C34—C39 −177.2 (3) C6—C5—S1—O4 −38.2 (3)
C32—C33—C34—C39 0.3 (4) C4—C5—S1—O4 143.7 (3)
C33—C34—C35—C36 −0.9 (5) C27—C26—S2—O9 −114.4 (2)
C39—C34—C35—C36 175.8 (3) C25—C26—S2—O9 61.3 (3)
C34—C35—C36—C37 1.3 (5) C27—C26—S2—O8 6.6 (3)
C35—C36—C37—C38 −0.1 (6) C25—C26—S2—O8 −177.7 (2)
C36—C37—C38—C33 −1.4 (6) C27—C26—S2—O10 125.1 (2)
C34—C33—C38—C37 1.8 (5) C25—C26—S2—O10 −59.2 (2)

Hydrogen-bond geometry (Å, º)

D—H···A D—H H···A D···A D—H···A

O5W—H5WB···S2 0.85 3.01 3.708 (3) 141
O5W—H5WB···O8 0.85 1.99 2.818 (3) 164
O5W—H5WA···S1i 0.85 2.94 3.727 (3) 155
O5W—H5WA···O5i 0.85 2.27 3.084 (5) 160
O4W—H4WB···O3ii 0.84 2.11 2.914 (4) 158
O4W—H4WA···O4i 0.84 2.01 2.826 (4) 162
O3W—H3WB···O10iii 0.85 2.01 2.857 (3) 174
O3W—H3WA···O8iv 0.85 1.95 2.788 (3) 169
O2W—H2WB···O3Wv 0.85 1.96 2.789 (3) 168
O2W—H2WA···O5i 0.84 1.95 2.786 (3) 170
O1W—H1WB···O5Wvi 0.85 1.90 2.727 (3) 162
O1W—H1WA···O4Wvi 0.86 1.96 2.732 (3) 149
N10—H10B···O10iii 0.86 2.13 2.976 (3) 168
N10—H10A···O6 0.86 2.08 2.705 (3) 129
N5—H5B···O2 0.86 2.06 2.693 (3) 130
C39—H39A···O4i 0.97 2.65 3.401 (4) 134
C31—H31···O4Wvi 0.93 2.60 3.436 (4) 151
C29—H29···O6 0.93 2.36 2.845 (3) 112
C18—H18A···O9v 0.97 2.47 3.415 (4) 164

Acta Cryst. (2018). C74, 332-341 sup-16

 supporting information
C11—H11B···O10vii 0.97 2.65 3.176 (4) 114
C9—H9···O3Wiii 0.93 2.54 3.370 (4) 148
C8—H8···O1 0.93 2.61 3.068 (3) 111
O1W—H1WA···O4Wvi 0.86 1.96 2.732 (3) 149
O1W—H1WB···O5Wvi 0.85 1.90 2.727 (3) 162
O2W—H2WA···O5i 0.84 1.95 2.786 (3) 170
O2W—H2WB···O3Wv 0.85 1.96 2.789 (3) 168
N10—H10B···O10iii 0.86 2.13 2.976 (3) 168
O3W—H3WA···O8iv 0.85 1.95 2.788 (3) 169
O3W—H3WB···O10iii 0.85 2.01 2.857 (3) 174
O4W—H4WA···O4i 0.84 2.01 2.826 (4) 162
O4W—H4WB···O3ii 0.84 2.11 2.914 (4) 158
O5W—H5WA···O5i 0.85 2.27 3.084 (5) 160
O5W—H5WB···O8 0.85 1.99 2.818 (3) 164

Symmetry codes: (i) x, y−1, z; (ii) −x+2, −y+2, −z+2; (iii) −x+1, y+1/2, −z+3/2; (iv) x, −y+3/2, z−1/2; (v) x, −y+3/2, z+1/2; (vi) x, y+1, z; (vii) −x+1, −y+2,
−z+2.

Acta Cryst. (2018). C74, 332-341 sup-17