research papers
Two coordination polymers constructed by
ISSN 2053-2296
Received 4 September 2019
Accepted 29 October 2019
Edited by I. D. Williams, Hong Kong University
of Science and Technology, Hong Kong
Keywords: coordination polymer; cadmium;
manganese; crystal structure; tricarboxylic acid;
2,20 -bipyridine.
CCDC references: 1959290; 1959291
Supporting information: this article has
supporting information at journals.iucr.org/c
# 2019 International Union of Crystallography
1562 https://doi.org/10.1107/S2053229619014633
5-[(4-carboxyphenoxy)methyl]benzene-1,3-dicar-
boxylic acid and 2,20 -bipyridine: syntheses,
structures and luminescence properties
Yuan-Chun He,* Li-Yuan Xiao, Zi-Han Yuan, Jie Zhang, Yan Wang and Na Xu*
College of Chemistry and Chemical Engineering, Qufu Normal University, Qufu 273165, People’s Republic of China.
*Correspondence e-mail: heyc240@nenu.edu.cn, xunaqfnu@163.com
Coordination polymers (CPs) have attracted increasing interest in recent years.
In this work, two new CPs, namely poly[[aquabis(2,20 -bipyridine-2N,N0 ){3-5-
0
[(4-carboxylatophenoxy)methyl]benzene-1,3-dicarboxylato-4O1,O1 :O3:O5}(-
3
formato- O:O,O0 )dicadmium(II)] monohydrate], {[Cd2(C16H9O7)(HCO2)-
(C10H8N2)2(H2O)]H2O}n (1), and poly[[(2,20 -bipyridine-2N,N0 ){3-5-[(4-car-
0
boxylphenoxy)methyl]benzene-1,3-dicarboxylato-4O1,O1 :O3:O5}manganese(II)]
sesquihydrate], {[Mn(C16H10O7)(C10H8N2)]1.5H2O}n (2), have been prepared
using the tricarboxylic acid 5-[(4-carboxyphenoxy)methyl]benzene-1,3-dicarboxy-
lic acid and 2,20 -bipyridine under hydrothermal conditions. CP 1 displays a two-
dimensional layer structure which is further extended into a three-dimensional
(3D) supramolecular structure via intermolecular – interactions, while CP 2
shows a different 3D supramolecular structure extended from one-dimensional
ladder chains by intermolecular – interactions. In addition, the solid-state
luminescence spectra of 1 and 2 were studied at room temperature.
1. Introduction
In recent years, coordination complexes with one-dimensional
(1D), two-dimensional (2D) and three-dimensional (3D)
structures have been known as coordination polymers (CPs)
(Batten et al., 2013). Up to now, CPs have attracted increasing
attention for their interesting structures (Qin et al., 2017; He et
al., 2017a) and various applications, for example, luminescence
(Zhang et al., 2018a; Das & Mandal, 2018), catalysis (Li et al.,
2019; Zhang et al., 2018b), magnetism (Yang et al., 2019;
Huang et al., 2019), drug delivery (Wang et al., 2013), gas
adsorption and separation (Liu et al., 2016; Xue et al., 2019),
and so on. CPs are mainly composed of ligands and metals
linked by coordination bonds. In addition, there are several
weak interactions, such as hydrogen bonding, – stacking
and van der Waals. These weak interactions can effectively
stabilize the whole structure, while low-dimensional CPs can
be extended to form interesting high-dimensional supra-
molecular structures by weak interactions (Ghosh et al., 2019;
Khanpour et al., 2017; Liu et al., 2017). The – interaction is a
weak interaction between rigid rings, including benzene,
pyridine, imidazole and so on. Thus, some ligands with rigid
rings are beneficial to the formation of CPs with – inter-
actions.
In this work, we chose the tricarboxylic acid 5-[(4-carb-
oxyphenoxy)methyl]benzene-1,3-dicarboxylic acid (H3L) as
the main ligand and 2,20 -bipyridine (bpy) as an auxiliary
ligand. The benzene rings of H3L and the pyridine rings of bpy
can provide efficient recognition sites for – interactions to
Acta Cryst. (2019). C75, 1562–1568
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Table 1
Experimental details.
1 2

Crystal data
Chemical formula [Cd2(C16H9O7)(CHO2)(C10H8N2)2(H2O)]H2O [Mn2(C16H10O7)2(C10H8N2)2]3H2O
Mr 931.45 1104.77
Crystal system, space group Monoclinic, P21/c Triclinic, P1
Temperature (K) 150 150
a, b, c (Å) 13.8999 (7), 18.0445 (11), 14.4096 (8) 9.9758 (6), 10.5290 (7), 13.7445 (9)
, ,  ( ) 90, 99.568 (2), 90 91.623 (4), 108.250 (3), 116.694 (3)
V (Å3) 3563.9 (3) 1200.37 (14)
Z 4 1
Radiation type Mo K Mo K
 (mm1) 1.26 0.61
Crystal size (mm) 0.32  0.25  0.25 0.20  0.16  0.15

Data collection
Diffractometer Bruker D8 Venture Bruker D8 Venture
Absorption correction Multi-scan (SADABS; Bruker, 2016) Multi-scan (SADABS; Bruker, 2016)
Tmin, Tmax 0.692, 0.729 0.890, 0.913
No. of measured, independent and observed 82482, 6515, 5402 21405, 4370, 3522
[I > 2 (I)] reflections
Rint 0.055 0.044
(sin
/)max (Å1) 0.602 0.602

Refinement
R[F 2 > 2 (F 2)], wR(F 2), S 0.028, 0.064, 1.03 0.052, 0.160, 1.11
No. of reflections 6515 4370
No. of parameters 511 370
No. of restraints 11 15
H-atom treatment H atoms treated by a mixture of independent H atoms treated by a mixture of independent
and constrained refinement and constrained refinement

max,
min (e Å3) 0.51, 0.39 0.99, 0.41
Computer programs: APEX3 (Bruker, 2016), SAINT (Bruker, 2016), SHELXT2018 (Sheldrick, 2015a), SHELXL2018 (Sheldrick, 2015b), SHELXTL (Bruker, 2016), DIAMOND
(Brandenburg & Putz, 2005) and SHELXTL (Bruker, 2016).

form interesting structures. The three carboxylic acid groups
of H3L can adopt various coordination modes. In addition,
factors such as reaction temperature, pH values, solvents,
under hydrothermal conditions. Furthermore, these two
compounds have also been characterized by single-crystal
X-ray diffraction, IR spectroscopy, elemental analysis (EA),
powder X-ray diffraction (PXRD), fluorescence in the solid
state and thermogravimetric analysis (TGA).

2. Experimental
2.1. Materials and methods
The chemical reagents used were purchased and used
without further purification. PXRD patterns were recorded on
a MiniFlex600 X-ray diffractometer with graphite-mono-
chromatized Cu K radiation ( = 0.154 nm). The C, H and N
elemental analyses were measured on a PE 2400 elemental
analyzer. IR spectra were recorded on a Nicolet iS5 spectro-
meter. Thermogravimetric analyses were performed on a
HengJiu HCT-1 analyzer. The luminescence properties were
measured on a F-4600 fluorescence spectrometer.

2.2. Syntheses of 1 and 2

metal ions and organic ligands play important roles in the
construction of CPs (Ma et al., 2015; Wen & Xu, 2017; Meng et
al., 2012; Liu et al., 2011). Thus, we used these organic ligands
to react with different metal ions and two new CPs, namely
{[Cd2(L)(HCOO)(bpy)2(H2O)]H2O}n (1) (Scheme 1) and
{[Mn(HL)(bpy)]1.5H2O}n (2) (Scheme 2), were prepared
Cd(CH3COO)22H2O (0.1 mmol, 27 mg), H3L (0.1 mmol,
32 mg), bpy (0.1 mmol, 16 mg), dimethylformamide (DMF;
2 ml) and H2O (6 ml) were added to a 15 ml Teflon reactor.
After heating at 130  C for 3 d, colourless crystals were
obtained by filtration and washing with deionized water.
Finally, the product was dried at room temperature (yield

Acta Cryst. (2019). C75, 1562–1568 He et al.  Cd and Mn coordination polymers 1563
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63%). Analysis calculated (%) for C37H30Cd2N4O11: C 47.71, Table 2
H 3.25, N 6.01; found: C 47.55, H 3.48, N 5.89. IR (cm1): 3435 Selected geometric parameters (Å,  ) for 1.
(s), 2926 (m), 1605 (s), 1400 (s), 1166 (w), 854 (w), 770 (m). Cd1—O9i 2.232 (2) Cd2—O4 2.161 (2)
When Mn(CH3COO)24H2O (0.1 mmol, 25 mg) was used Cd1—O6ii 2.240 (2) Cd2—O1W 2.276 (2)
Cd1—O2 2.280 (2) Cd2—O9 2.2880 (19)
instead of Cd(CH3COO)22H2O, CP 2 was obtained by a Cd1—N1 2.367 (2) Cd2—N3 2.350 (3)
similar method (yield 47%). Analysis calculated (%) for Cd1—N2 2.394 (2) Cd2—N4 2.401 (3)
C26H21MnN2O8.5: C 56.53, H 3.83, N 5.07; found: C 56.37, H Cd1—O1 2.502 (2) Cd2—O8 2.571 (2)
4.12, N 5.19. IR (cm1): 3431 (s), 2925 (w), 1615 (s), 1406 (s), O9i—Cd1—O6ii 100.04 (8) O4—Cd2—O1W 96.27 (9)
1244 (m), 1169 (m), 1012 (w), 769 (w). O9i—Cd1—O2 139.57 (7) O4—Cd2—O9 130.07 (9)
O6ii—Cd1—O2 86.14 (7) O1W—Cd2—O9 85.86 (8)
O9i—Cd1—N1 85.95 (8) O4—Cd2—N3 95.78 (10)
O6ii—Cd1—N1 172.97 (8) O1W—Cd2—N3 165.17 (10)
O2—Cd1—N1 91.66 (8) O9—Cd2—N3 92.97 (8)
O9i—Cd1—N2 121.75 (8) O4—Cd2—N4 133.91 (9)
O6ii—Cd1—N2 102.09 (8) O1W—Cd2—N4 93.74 (9)
O2—Cd1—N2 95.21 (8) O9—Cd2—N4 95.41 (8)
N1—Cd1—N2 71.43 (8) N3—Cd2—N4 71.63 (10)
O9i—Cd1—O1 83.72 (7) O4—Cd2—O8 77.59 (9)
O6ii—Cd1—O1 96.14 (7) O1W—Cd2—O8 103.19 (9)
O2—Cd1—O1 55.85 (7) O9—Cd2—O8 53.72 (7)
N1—Cd1—O1 88.12 (8) N3—Cd2—O8 87.84 (9)
N2—Cd1—O1 144.65 (7) N4—Cd2—O8 142.58 (8)
Symmetry codes: (i) x  1; y; z; (ii) x; y þ 12; z þ 32.

unit (Fig. 1d), which can effectively stabilize the 2D structure.

2.3. X-ray crystallography
Crystal data, data collection and structure refinement
details are summarized in Table 1. H atoms were placed in
idealized positions and allowed to ride on the parent C atoms.
H atoms of water molecules were located in difference Fourier
maps and refined as riding in their as-found positions. The H
atoms of the water molecules in 1 were treated as disordered
and split over three sites with a total occupancy of 1.
The face-to-face, centroid-to-centroid and slippage distances
between pyridine rings N2/C17–C21 and N4/C27–C31 are
3.701, 3.487 and 1.241 Å, respectively, and the corresponding
distances between the other two pyridine rings (N1/C22–C26
and N3/C32–C36) are 3.883, 3.561 and 1.548 Å, respectively. In
addition, there are two kinds of intermolecular – inter-
actions between the bpy ligands of adjacent asymmetric units
(Fig. 1e). The face-to-face, centroid-to-centroid and slippage
distances between pyridine rings N2/C17–C21 and N1/C22–
C26 are 3.621, 3.363 and 1.343 Å, respectively, and the
corresponding distances between the other two pyridine rings
(N4/C27–C31 and N3/C32–C36) are 3.671, 3.376 and 1.443 Å,
respectively. The 2D layers can be extended into a 3D
supramolecular structure by these intermolecular – inter-
actions (Fig. 1f).

3. Results and discussion 3.2. Structure analysis of 2

3.1. Structure analysis of 1 When the CdII ion is replaced by an MnII ion, CP 2, with a
Single-crystal X-ray diffraction analysis reveals that there different configuration, is obtained. Single-crystal X-ray
are two CdII cations, an L3 anion, two bpy ligands, a formate diffraction analysis reveals that there is an MnII cation, a HL2
ion, a coordinated water molecule and a lattice water molecule
in the asymmetric unit of CP 1 (Fig. 1a). The formate ion is
Table 3
from the decomposition of DMF. Atoms Cd1 and Cd2 are Selected geometric parameters (Å,  ) for 2.
both six-coordinated in distorted octahedral geometries. Cd1
Mn1—O6i 2.194 (2) Mn1—N1 2.247 (3)
is coordinated with two L3 cations (O1, O2 and O6ii; Table 2), Mn1—O1 2.200 (3) Mn1—O4ii 2.306 (3)
a formate ion (O9i) and a bpy ligand (N1 and N2), while Cd2 is Mn1—N2 2.247 (3) Mn1—O3ii 2.370 (2)
coordinated by an L3 anion (O4), a formate ion (O8 and O9),
O6i—Mn1—O1 99.28 (9) N2—Mn1—O4ii 95.83 (10)
a bpy ligand (N3 and N4) and a water molecule (O1W). Atoms O6i—Mn1—N2 165.44 (10) N1—Mn1—O4ii 137.06 (9)
Cd1 and Cd2 are bridged by O9 to form a binuclear unit, and O1—Mn1—N2 91.55 (10) O6i—Mn1—O3ii 87.96 (9)
adjacent binuclear cadmium units are linked by the L3 anion O6i—Mn1—N1 92.45 (10) O1—Mn1—O3ii 136.46 (9)
O1—Mn1—N1 139.26 (10) N2—Mn1—O3ii 90.88 (10)
to form a 1D infinite chain (Fig. 1b). Furthermore, the 1D N2—Mn1—N1 73.02 (11) N1—Mn1—O3ii 82.43 (9)
chains are connected by Cd1—O6 bonds to form a 2D layer O6i—Mn1—O4ii 95.51 (10) O4ii—Mn1—O3ii 55.86 (8)
(Fig. 1c). Interestingly, there are two kinds of intramolecular O1—Mn1—O4ii 80.65 (9)
– interactions between the bpy ligands in the asymmetric Symmetry codes: (i) x þ 1; y þ 2; z þ 2; (ii) x þ 1; y; z.

1564 He et al.  Cd and Mn coordination polymers Acta Cryst. (2019). C75, 1562–1568

anion, a bpy ligand and one and a half lattice water molecules
in the asymmetric unit (Fig. 2a). Atom Mn1 is six-coordinated
by four O atoms from three HL2 anions (O1, O3ii, O4ii and
O6i; Table 3) and two N atoms from a bpy ligand (N1 and N2)
in a distorted octahedral geometry. In this way, a ladder chain
is formed and the bpy ligands are located on both sides of the
ladder (Fig. 2b). There are two kinds of intermolecular –
interactions between bpy ligands of adjacent asymmetric units
(Fig. 2c). The face-to-face, centroid-to-centroid and slippage
distances between six-membered rings C10–C15 and N2/C22–
C26 are 3.677, 3.305 and 1.612 Å, respectively, and the
corresponding distances between the other six-membered
rings (N1/C17–C21 and N2/C22–C26) are 3.634, 3.293 and
1.537 Å, respectively. The 1D ladder chains are extended into
research papers
a 3D supramolecular structure by intermolecular – inter-
actions (Fig. 2d).
3.3. Powder X-ray diffraction (PXRD) and thermogravimetric
analysis (TGA)
CPs 1 and 2 have been characterized by PXRD and TGA.
As shown in Fig. 3, the experimental and simulated patterns
are identical. The results reveal that the purity of the powder
sample is good.
The thermal stability properties of 1 and 2 were tested from
room temperature to 800  C. As shown in Fig. 4(a), for 1, the
first loss (observed 3.92%, calculated 3.86%) from room
temperature to 170  C can be attributed to a water molecule,

Figure 1
Views of (a) the coordination environments of the CdII cations of CP 1, with H atoms omitted for clarity, (b) the 1D chain, (c) the 2D layer, (d) the
intramolecular – interactions, (e) the intermolecular – interactions and (f) the 3D supramolecular structure. The symmetry codes are as in Table 2.

Acta Cryst. (2019). C75, 1562–1568 He et al.  Cd and Mn coordination polymers 1565
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Figure 2
Views of (a) the coordination environment of the MnII cation of CP 2, with H atoms omitted for clarity, (b) the 1D chain, (c) the intermolecular –
interactions and (d) the 3D supramolecular structure. The symmetry codes are as in Table 3.

and the organic component decomposes at 260  C. For 2, the

first loss (observed 3.86%, calculated 4.88%) from room
temperature to 150  C can be attributed to the loss of a water
molecule, and the organic component decomposes at 230  C
(Fig. 4b).

3.4. Luminescence properties

Luminescence is a common phenomenon in nature and
materials with luminescence properties have important
applications in sensing and lighting. Many luminescent com-
pounds have been studied (Cui et al., 2012; Wang et al., 2016;
Zhang et al., 2012; Zhou et al., 2013). In this work, the solid-
state luminescence spectra of 1 and 2 were measured at room
temperature. As shown in Fig. 5, CP 1 shows a broad emission
band at max = 465 nm upon excitation at 360 nm, while the
maximum emission peak of CP 2 is observed at about 470 nm,
with the excitation peak at 360 nm. As reported previously,
free H3L displays an emission peak with a maximum at 442 nm
Figure 3
PXRD patterns (red is as-synthesized and black is simulated) for (a) CP 1 (ex = 360 nm) (He et al., 2017b). This emission peak of H3L
and (b) CP 2. may be assigned to the *!n or *! transitions. Compared

1566 He et al.  Cd and Mn coordination polymers Acta Cryst. (2019). C75, 1562–1568

Figure 4
TGA curves of (a) CP 1 and (b) CP 2.
with free H3L, the emission bands of 1 and 2 are red-shifted by
23 and 28 nm, respectively. This may be because the *!n or
*! gaps of H3L decrease after the replacement of the
hydrogen proton by a metal ion (Zhang et al., 2009, 2010).
4. Conclusions
We have prepared two new CPs based on a tricarboxylic acid
and 2,20 -bipyridine. Structure analysis reveals that CPs 1 and 2
show different configurations. CP 1 displays a 3D supra-
molecular structure extended from 2D layers by inter-
molecular – interactions. When CdII is replaced by MnII, CP
2 shows a different 3D supramolecular structure extended
from 1D ladder chains by intermolecular – interactions. The
results suggest that the metal ion and – interactions play
important roles in the design and construction of various CPs.
In addition, the solid-state luminescence spectra of 1 and 2
were studied at room temperature.
Funding information
Funding for this research was provided by: National Natural
Science Foundation of China (grant No. 21601104); Natural
Science Foundation of Shandong Province (grant No.
ZR2016BQ19).
Acta Cryst. (2019). C75, 1562–1568
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Figure 5
Solid-state excitation (black) and emission (blue) spectra of (a) CP 1 and
(b) CP 2.
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 supporting information

supporting information

Acta Cryst. (2019). C75, 1562-1568 [https://doi.org/10.1107/S2053229619014633]

Two coordination polymers constructed by 5-[(4-carboxyphenoxy)methyl]-

benzene-1,3-dicarboxylic acid and 2,2′-bipyridine: syntheses, structures and
luminescence properties
Yuan-Chun He, Li-Yuan Xiao, Zi-Han Yuan, Jie Zhang, Yan Wang and Na Xu

Computing details
For both structures, data collection: APEX3 (Bruker, 2016); cell refinement: SAINT (Bruker, 2016); data reduction:
SAINT (Bruker, 2016); program(s) used to solve structure: SHELXT2018 (Sheldrick, 2015a); program(s) used to refine
structure: SHELXL2018 (Sheldrick, 2015b); molecular graphics: SHELXTL (Bruker, 2016) and DIAMOND (Brandenburg
& Putz, 2005); software used to prepare material for publication: SHELXTL (Bruker, 2016).

Poly[[aquabis(2,2′-bipyridine-κ2N,N′){µ3-5-[(4-carboxylatophenoxy)methyl]benzene-1,3-dicarboxylato-
κ4O1,O1′:O3:O5}(µ-formato-κ3O:O,O′)dicadmium(II)] monohydrate] (Cd)

Crystal data
[Cd2(C16H9O7)(CHO2)(C10H8N2)2(H2O)]·H2O F(000) = 1856
Mr = 931.45 Dx = 1.736 Mg m−3
Monoclinic, P21/c Mo Kα radiation, λ = 0.71073 Å
a = 13.8999 (7) Å Cell parameters from 9802 reflections
b = 18.0445 (11) Å θ = 2.5–27.1°
c = 14.4096 (8) Å µ = 1.26 mm−1
β = 99.568 (2)° T = 150 K
V = 3563.9 (3) Å3 Block, colorless
Z=4 0.32 × 0.25 × 0.25 mm

Data collection
Bruker D8 Venture 6515 independent reflections
diffractometer 5402 reflections with I > 2σ(I)
Radiation source: sealed tube Rint = 0.055
ω scans θmax = 25.4°, θmin = 2.2°
Absorption correction: multi-scan h = −16→16
(SADABS; Bruker, 2016) k = −21→21
Tmin = 0.692, Tmax = 0.729 l = −17→17
82482 measured reflections
Refinement
Refinement on F2 11 restraints
Least-squares matrix: full Primary atom site location: structure-invariant
R[F2 > 2σ(F2)] = 0.028 direct methods
wR(F2) = 0.064 Hydrogen site location: mixed
S = 1.03 H atoms treated by a mixture of independent
6515 reflections and constrained refinement
511 parameters

Acta Cryst. (2019). C75, 1562-1568 sup-1

 supporting information
w = 1/[σ2(Fo2) + (0.024P)2 + 4.307P] Δρmax = 0.51 e Å−3
where P = (Fo2 + 2Fc2)/3 Δρmin = −0.39 e Å−3
(Δ/σ)max = 0.002
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. Experiments were carried out at 150 K with Mo Kα radiation using a Bruker D8 Venture diffractometer.
Absorption was corrected for by multi-scan methods (SADABS; Bruker, 2016). The non-hydrogen atoms were refined
with anisotropic displacement parameters, while the

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

x y z Uiso*/Ueq Occ. (<1)

Cd1 −0.14081 (2) 0.67805 (2) 0.90033 (2) 0.02893 (6)
Cd2 0.55809 (2) 0.66916 (2) 0.83917 (2) 0.03633 (7)
C1 0.0037 (2) 0.68198 (15) 0.7954 (2) 0.0298 (6)
C2 0.0868 (2) 0.68415 (15) 0.7423 (2) 0.0299 (6)
C3 0.0730 (2) 0.68330 (16) 0.6406 (2) 0.0312 (6)
H3 0.008418 0.683022 0.606331 0.037*
C4 0.1494 (2) 0.68288 (15) 0.5917 (2) 0.0311 (6)
C5 0.2401 (2) 0.68517 (16) 0.6452 (2) 0.0350 (7)
H5 0.295436 0.685743 0.614403 0.042*
C6 0.2556 (2) 0.68678 (16) 0.7476 (2) 0.0341 (7)
C7 0.1781 (2) 0.68545 (16) 0.7948 (2) 0.0316 (6)
H7 0.187384 0.685425 0.861593 0.038*
C8 0.3547 (2) 0.68764 (18) 0.8026 (3) 0.0430 (8)
C9 0.1369 (2) 0.67638 (17) 0.4820 (2) 0.0375 (7)
H9A 0.070243 0.658430 0.457198 0.045*
H9B 0.144398 0.726038 0.454887 0.045*
C10 0.2008 (2) 0.55397 (17) 0.4780 (2) 0.0361 (7)
C11 0.1256 (2) 0.52318 (18) 0.5146 (2) 0.0397 (7)
H11 0.074419 0.553505 0.529436 0.048*
C12 0.1245 (2) 0.44751 (17) 0.5301 (2) 0.0397 (8)
H12 0.071598 0.426857 0.555511 0.048*
C13 0.1960 (2) 0.40154 (16) 0.5106 (2) 0.0330 (7)
C14 0.2722 (2) 0.43367 (18) 0.4767 (2) 0.0375 (7)
H14 0.324273 0.403414 0.463557 0.045*
C15 0.2753 (2) 0.50940 (17) 0.4610 (2) 0.0377 (7)
H15 0.329632 0.530381 0.438218 0.045*
C16 0.1877 (2) 0.31987 (16) 0.5260 (2) 0.0317 (6)
C17 −0.1028 (2) 0.65693 (17) 1.1357 (2) 0.0351 (7)
H17 −0.109186 0.709352 1.133955 0.042*
C18 −0.0770 (2) 0.62301 (18) 1.2248 (2) 0.0399 (7)
H18 −0.068331 0.651343 1.281161 0.048*
C19 −0.0649 (3) 0.54672 (19) 1.2267 (2) 0.0438 (8)
H19 −0.045225 0.521441 1.284545 0.053*

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C20 −0.0827 (2) 0.50706 (17) 1.1402 (2) 0.0379 (7)
H20 −0.076011 0.454657 1.140538 0.045*
C21 −0.1102 (2) 0.54486 (16) 1.0536 (2) 0.0310 (6)
C22 −0.1333 (2) 0.50581 (16) 0.9577 (2) 0.0314 (7)
C23 −0.1331 (2) 0.42834 (17) 0.9514 (2) 0.0355 (7)
H23 −0.117364 0.398488 1.006073 0.043*
C24 −0.1572 (2) 0.39567 (18) 0.8607 (2) 0.0408 (8)
H24 −0.157510 0.343207 0.855135 0.049*
C25 −0.1805 (2) 0.43937 (18) 0.7787 (2) 0.0408 (8)
H25 −0.197440 0.417645 0.718174 0.049*
C26 −0.1775 (2) 0.51560 (18) 0.7912 (2) 0.0398 (7)
H26 −0.191638 0.546515 0.737243 0.048*
C27 0.6286 (2) 0.6424 (2) 1.0725 (2) 0.0444 (8)
H27 0.621048 0.694660 1.073867 0.053*
C28 0.6619 (3) 0.6056 (2) 1.1587 (3) 0.0508 (9)
H28 0.676518 0.632414 1.216028 0.061*
C29 0.6725 (3) 0.5300 (2) 1.1566 (3) 0.0540 (10)
H29 0.695090 0.503004 1.212567 0.065*
C30 0.6491 (2) 0.4933 (2) 1.0690 (3) 0.0487 (9)
H30 0.655734 0.441007 1.066542 0.058*
C31 0.6158 (2) 0.53289 (17) 0.9846 (2) 0.0393 (8)
C32 0.5883 (2) 0.49631 (18) 0.8878 (3) 0.0422 (8)
C33 0.5911 (3) 0.4194 (2) 0.8762 (3) 0.0537 (10)
H33 0.610671 0.387664 0.928591 0.064*
C34 0.5640 (3) 0.3899 (2) 0.7845 (3) 0.0642 (12)
H34 0.565397 0.337761 0.775752 0.077*
C35 0.5352 (3) 0.4357 (2) 0.7064 (3) 0.0666 (12)
H35 0.517174 0.415696 0.644997 0.080*
C36 0.5340 (3) 0.5116 (2) 0.7226 (3) 0.0562 (10)
H36 0.514611 0.544104 0.671050 0.067*
C37 0.6897 (2) 0.69144 (18) 0.7182 (2) 0.0383 (7)
H37 0.740544 0.699254 0.682678 0.046*
N1 −0.15480 (18) 0.54826 (14) 0.87812 (17) 0.0331 (6)
N2 −0.11921 (17) 0.61950 (13) 1.05150 (17) 0.0297 (5)
N3 0.5601 (2) 0.54090 (16) 0.8112 (2) 0.0442 (7)
N4 0.60638 (18) 0.60729 (14) 0.98712 (19) 0.0373 (6)
O1 −0.07848 (14) 0.68556 (12) 0.74743 (15) 0.0357 (5)
O2 0.02038 (14) 0.67557 (11) 0.88713 (14) 0.0344 (5)
O3 0.36871 (17) 0.68538 (13) 0.89355 (18) 0.0508 (6)
O4 0.41925 (16) 0.68948 (15) 0.7506 (2) 0.0563 (7)
O5 0.24904 (15) 0.27632 (11) 0.50414 (15) 0.0375 (5)
O6 0.11702 (15) 0.29771 (12) 0.56125 (16) 0.0390 (5)
O7 0.20617 (16) 0.62719 (11) 0.45336 (15) 0.0404 (5)
O8 0.60713 (17) 0.68812 (15) 0.67644 (17) 0.0531 (6)
O9 0.71322 (14) 0.68498 (12) 0.80885 (14) 0.0348 (5)
H2A 0.461 (9) 0.816 (6) 1.0786 (15) 0.052* 0.3
H2B 0.419 (9) 0.768 (3) 0.993 (7) 0.052* 0.3
H2C 0.458 (9) 0.8592 (19) 1.027 (7) 0.052* 0.3

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H2D 0.451 (10) 0.779 (4) 1.064 (5) 0.052* 0.3
H2F 0.486 (5) 0.844 (4) 1.003 (5) 0.052* 0.4
H2E 0.400 (5) 0.790 (4) 0.972 (4) 0.052* 0.4
O1W 0.57509 (16) 0.78436 (13) 0.9041 (2) 0.0489 (6)
H1A 0.6321 (16) 0.790 (2) 0.941 (2) 0.073*
H1B 0.534 (2) 0.795 (2) 0.943 (2) 0.073*
O2W 0.4422 (2) 0.8117 (2) 1.0163 (2) 0.0710 (9)

Atomic displacement parameters (Å2)

U11 U22 U33 U12 U13 U23

Cd1 0.02627 (11) 0.02783 (11) 0.03295 (12) 0.00050 (8) 0.00571 (9) 0.00148 (9)
Cd2 0.02465 (12) 0.03839 (13) 0.04597 (14) −0.00090 (9) 0.00595 (10) 0.00310 (10)
C1 0.0275 (15) 0.0230 (14) 0.0403 (17) 0.0014 (12) 0.0096 (13) −0.0003 (12)
C2 0.0280 (15) 0.0255 (15) 0.0362 (16) 0.0019 (12) 0.0053 (12) −0.0008 (12)
C3 0.0253 (14) 0.0282 (15) 0.0390 (16) 0.0000 (12) 0.0023 (12) 0.0014 (13)
C4 0.0340 (16) 0.0240 (14) 0.0362 (16) 0.0026 (12) 0.0083 (13) 0.0032 (12)
C5 0.0273 (15) 0.0309 (16) 0.0487 (19) −0.0019 (12) 0.0118 (14) 0.0015 (14)
C6 0.0219 (14) 0.0269 (15) 0.0526 (19) −0.0004 (12) 0.0032 (13) −0.0066 (14)
C7 0.0283 (15) 0.0281 (15) 0.0374 (16) 0.0028 (12) 0.0026 (12) −0.0016 (13)
C8 0.0301 (17) 0.0302 (17) 0.067 (2) −0.0046 (13) 0.0038 (16) −0.0007 (16)
C9 0.0419 (18) 0.0302 (16) 0.0426 (18) 0.0053 (14) 0.0133 (14) 0.0036 (14)
C10 0.0406 (18) 0.0333 (17) 0.0357 (17) −0.0003 (14) 0.0101 (14) 0.0015 (13)
C11 0.0345 (17) 0.0327 (17) 0.054 (2) 0.0004 (13) 0.0149 (15) −0.0008 (15)
C12 0.0381 (18) 0.0352 (17) 0.048 (2) −0.0029 (14) 0.0147 (15) 0.0012 (14)
C13 0.0343 (16) 0.0306 (16) 0.0345 (17) −0.0020 (13) 0.0065 (13) −0.0016 (13)
C14 0.0322 (16) 0.0368 (17) 0.0450 (19) 0.0034 (13) 0.0104 (14) 0.0006 (14)
C15 0.0362 (17) 0.0369 (17) 0.0424 (18) −0.0023 (14) 0.0138 (14) 0.0025 (14)
C16 0.0295 (15) 0.0329 (16) 0.0307 (15) −0.0024 (13) −0.0010 (12) −0.0012 (13)
C17 0.0326 (16) 0.0326 (16) 0.0405 (17) 0.0008 (13) 0.0067 (14) −0.0011 (13)
C18 0.0437 (19) 0.0398 (18) 0.0357 (18) 0.0033 (14) 0.0049 (15) −0.0059 (14)
C19 0.055 (2) 0.0416 (19) 0.0337 (18) 0.0078 (16) 0.0026 (16) 0.0067 (14)
C20 0.0442 (18) 0.0300 (16) 0.0389 (17) 0.0043 (14) 0.0051 (14) 0.0018 (13)
C21 0.0258 (15) 0.0307 (16) 0.0373 (16) 0.0009 (12) 0.0076 (13) 0.0020 (13)
C22 0.0255 (15) 0.0314 (16) 0.0375 (17) 0.0025 (12) 0.0057 (13) 0.0011 (13)
C23 0.0371 (17) 0.0319 (16) 0.0370 (18) −0.0003 (13) 0.0045 (14) 0.0030 (13)
C24 0.0440 (19) 0.0288 (16) 0.0472 (19) 0.0004 (14) 0.0007 (15) 0.0003 (14)
C25 0.049 (2) 0.0352 (17) 0.0371 (18) −0.0004 (15) 0.0046 (15) −0.0074 (14)
C26 0.0482 (19) 0.0354 (17) 0.0347 (17) 0.0026 (15) 0.0034 (15) 0.0033 (14)
C27 0.0392 (18) 0.0444 (19) 0.050 (2) −0.0053 (15) 0.0101 (16) 0.0022 (16)
C28 0.044 (2) 0.059 (2) 0.050 (2) −0.0098 (17) 0.0068 (17) 0.0047 (18)
C29 0.045 (2) 0.062 (3) 0.054 (2) −0.0004 (18) 0.0064 (18) 0.0215 (19)
C30 0.043 (2) 0.0399 (19) 0.065 (2) 0.0013 (15) 0.0145 (18) 0.0111 (17)
C31 0.0273 (16) 0.0345 (17) 0.058 (2) −0.0026 (13) 0.0129 (15) 0.0049 (15)
C32 0.0320 (17) 0.0375 (18) 0.060 (2) −0.0037 (14) 0.0166 (16) −0.0031 (16)
C33 0.042 (2) 0.041 (2) 0.081 (3) −0.0007 (16) 0.018 (2) −0.0057 (19)
C34 0.058 (3) 0.043 (2) 0.097 (3) −0.0111 (19) 0.027 (2) −0.017 (2)
C35 0.067 (3) 0.065 (3) 0.073 (3) −0.026 (2) 0.025 (2) −0.026 (2)

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C36 0.061 (2) 0.053 (2) 0.058 (2) −0.0163 (19) 0.0181 (19) −0.0072 (19)
C37 0.0307 (17) 0.0436 (19) 0.0419 (19) −0.0025 (14) 0.0094 (14) 0.0056 (15)
N1 0.0325 (13) 0.0314 (13) 0.0350 (14) −0.0001 (10) 0.0044 (11) 0.0007 (11)
N2 0.0261 (12) 0.0277 (13) 0.0350 (14) 0.0012 (10) 0.0041 (10) 0.0003 (10)
N3 0.0391 (16) 0.0441 (16) 0.0509 (17) −0.0094 (13) 0.0118 (13) −0.0055 (14)
N4 0.0254 (13) 0.0351 (15) 0.0521 (17) −0.0031 (11) 0.0081 (12) 0.0017 (12)
O1 0.0228 (10) 0.0448 (13) 0.0399 (12) 0.0023 (9) 0.0068 (9) 0.0072 (10)
O2 0.0312 (11) 0.0350 (11) 0.0379 (12) 0.0041 (9) 0.0082 (9) 0.0008 (9)
O3 0.0360 (13) 0.0478 (14) 0.0620 (17) −0.0076 (11) −0.0116 (11) 0.0073 (12)
O4 0.0246 (12) 0.0648 (17) 0.0782 (18) 0.0000 (11) 0.0044 (12) 0.0033 (14)
O5 0.0332 (12) 0.0310 (11) 0.0479 (13) 0.0010 (9) 0.0058 (10) −0.0034 (10)
O6 0.0365 (12) 0.0320 (11) 0.0502 (13) −0.0027 (9) 0.0120 (10) 0.0033 (10)
O7 0.0479 (13) 0.0313 (12) 0.0460 (13) 0.0008 (10) 0.0195 (11) 0.0023 (10)
O8 0.0308 (13) 0.0764 (18) 0.0498 (14) −0.0044 (12) −0.0002 (11) 0.0131 (13)
O9 0.0257 (10) 0.0433 (12) 0.0356 (12) −0.0008 (9) 0.0055 (9) −0.0001 (9)
O1W 0.0291 (12) 0.0382 (13) 0.0765 (19) 0.0010 (10) 0.0005 (12) −0.0028 (12)
O2W 0.0506 (18) 0.099 (3) 0.0606 (18) 0.0130 (19) 0.0016 (15) −0.0184 (18)

Geometric parameters (Å, º)

Cd1—O9i 2.232 (2) C18—C19 1.387 (5)

Cd1—O6ii 2.240 (2) C18—H18 0.9500
Cd1—O2 2.280 (2) C19—C20 1.422 (4)
Cd1—N1 2.367 (2) C19—H19 0.9500
Cd1—N2 2.394 (2) C20—C21 1.419 (4)
Cd1—O1 2.502 (2) C20—H20 0.9500
Cd1—C1 2.708 (3) C21—N2 1.353 (4)
Cd2—O4 2.161 (2) C21—C22 1.536 (4)
Cd2—O1W 2.276 (2) C22—N1 1.371 (4)
Cd2—O9 2.2880 (19) C22—C23 1.401 (4)
Cd2—N3 2.350 (3) C23—C24 1.421 (4)
Cd2—N4 2.401 (3) C23—H23 0.9500
Cd2—O8 2.571 (2) C24—C25 1.412 (5)
Cd2—C37 2.757 (3) C24—H24 0.9500
C1—O1 1.235 (3) C25—C26 1.387 (4)
C1—O2 1.308 (4) C25—H25 0.9500
C1—C2 1.488 (4) C26—N1 1.373 (4)
C2—C7 1.365 (4) C26—H26 0.9500
C2—C3 1.447 (4) C27—N4 1.372 (4)
C3—C4 1.368 (4) C27—C28 1.416 (5)
C3—H3 0.9500 C27—H27 0.9500
C4—C5 1.365 (4) C28—C29 1.373 (5)
C4—C9 1.565 (4) C28—H28 0.9500
C5—C6 1.455 (4) C29—C30 1.415 (5)
C5—H5 0.9500 C29—H29 0.9500
C6—C7 1.366 (4) C30—C31 1.419 (5)
C6—C8 1.472 (4) C30—H30 0.9500
C7—H7 0.9500 C31—N4 1.350 (4)

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C8—O4 1.261 (4) C31—C32 1.533 (5)
C8—O3 1.293 (4) C32—N3 1.370 (4)
C9—O7 1.421 (4) C32—C33 1.400 (5)
C9—H9A 0.9900 C33—C34 1.416 (6)
C9—H9B 0.9900 C33—H33 0.9500
C10—C11 1.365 (4) C34—C35 1.399 (6)
C10—C15 1.365 (4) C34—H34 0.9500
C10—O7 1.373 (4) C35—C36 1.391 (6)
C11—C12 1.384 (4) C35—H35 0.9500
C11—H11 0.9500 C36—N3 1.373 (5)
C12—C13 1.360 (4) C36—H36 0.9500
C12—H12 0.9500 C37—O8 1.205 (4)
C13—C14 1.367 (4) C37—O9 1.298 (4)
C13—C16 1.498 (4) C37—H37 0.9500
C14—C15 1.387 (4) O1W—H1A 0.884 (10)
C14—H14 0.9500 O1W—H1B 0.887 (10)
C15—H15 0.9500 O2W—H2A 0.896 (10)
C16—O5 1.238 (4) O2W—H2B 0.897 (10)
C16—O6 1.245 (4) O2W—H2C 0.893 (11)
C17—N2 1.375 (4) O2W—H2D 0.895 (10)
C17—C18 1.413 (4) O2W—H2F 0.887 (10)
C17—H17 0.9500 O2W—H2E 0.885 (10)

O9i—Cd1—O6ii 100.04 (8) O6—C16—C13 117.5 (3)

O9i—Cd1—O2 139.57 (7) N2—C17—C18 124.7 (3)
O6ii—Cd1—O2 86.14 (7) N2—C17—H17 117.7
O9i—Cd1—N1 85.95 (8) C18—C17—H17 117.7
O6ii—Cd1—N1 172.97 (8) C19—C18—C17 117.3 (3)
O2—Cd1—N1 91.66 (8) C19—C18—H18 121.3
O9i—Cd1—N2 121.75 (8) C17—C18—H18 121.3
O6ii—Cd1—N2 102.09 (8) C18—C19—C20 118.7 (3)
O2—Cd1—N2 95.21 (8) C18—C19—H19 120.7
N1—Cd1—N2 71.43 (8) C20—C19—H19 120.7
O9i—Cd1—O1 83.72 (7) C21—C20—C19 120.7 (3)
O6ii—Cd1—O1 96.14 (7) C21—C20—H20 119.6
O2—Cd1—O1 55.85 (7) C19—C20—H20 119.6
N1—Cd1—O1 88.12 (8) N2—C21—C20 120.6 (3)
N2—Cd1—O1 144.65 (7) N2—C21—C22 115.6 (3)
O9i—Cd1—C1 110.77 (8) C20—C21—C22 123.8 (3)
O6ii—Cd1—C1 91.14 (8) N1—C22—C23 120.4 (3)
O2—Cd1—C1 28.80 (8) N1—C22—C21 118.7 (2)
N1—Cd1—C1 90.13 (8) C23—C22—C21 121.0 (3)
N2—Cd1—C1 121.79 (8) C22—C23—C24 118.1 (3)
O1—Cd1—C1 27.05 (8) C22—C23—H23 120.9
O4—Cd2—O1W 96.27 (9) C24—C23—H23 120.9
O4—Cd2—O9 130.07 (9) C25—C24—C23 121.5 (3)
O1W—Cd2—O9 85.86 (8) C25—C24—H24 119.2
O4—Cd2—N3 95.78 (10) C23—C24—H24 119.2

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O1W—Cd2—N3 165.17 (10) C26—C25—C24 116.6 (3)
O9—Cd2—N3 92.97 (8) C26—C25—H25 121.7
O4—Cd2—N4 133.91 (9) C24—C25—H25 121.7
O1W—Cd2—N4 93.74 (9) N1—C26—C25 122.7 (3)
O9—Cd2—N4 95.41 (8) N1—C26—H26 118.6
N3—Cd2—N4 71.63 (10) C25—C26—H26 118.6
O4—Cd2—O8 77.59 (9) N4—C27—C28 124.2 (3)
O1W—Cd2—O8 103.19 (9) N4—C27—H27 117.9
O9—Cd2—O8 53.72 (7) C28—C27—H27 117.9
N3—Cd2—O8 87.84 (9) C29—C28—C27 117.8 (4)
N4—Cd2—O8 142.58 (8) C29—C28—H28 121.1
O4—Cd2—C37 102.90 (10) C27—C28—H28 121.1
O1W—Cd2—C37 95.29 (9) C28—C29—C30 118.3 (3)
O9—Cd2—C37 27.87 (8) C28—C29—H29 120.8
N3—Cd2—C37 90.42 (9) C30—C29—H29 120.8
N4—Cd2—C37 120.80 (9) C29—C30—C31 121.5 (3)
O8—Cd2—C37 25.84 (8) C29—C30—H30 119.2
O1—C1—O2 124.3 (3) C31—C30—H30 119.2
O1—C1—C2 115.8 (3) N4—C31—C30 119.7 (3)
O2—C1—C2 120.0 (3) N4—C31—C32 116.3 (3)
O1—C1—Cd1 67.13 (15) C30—C31—C32 124.0 (3)
O2—C1—Cd1 57.14 (13) N3—C32—C33 119.8 (3)
C2—C1—Cd1 177.1 (2) N3—C32—C31 118.4 (3)
C7—C2—C3 121.0 (3) C33—C32—C31 121.9 (3)
C7—C2—C1 116.4 (3) C32—C33—C34 118.4 (4)
C3—C2—C1 122.6 (3) C32—C33—H33 120.8
C4—C3—C2 122.6 (3) C34—C33—H33 120.8
C4—C3—H3 118.7 C35—C34—C33 121.7 (4)
C2—C3—H3 118.7 C35—C34—H34 119.2
C5—C4—C3 115.6 (3) C33—C34—H34 119.2
C5—C4—C9 120.7 (3) C36—C35—C34 117.1 (4)
C3—C4—C9 123.7 (3) C36—C35—H35 121.4
C4—C5—C6 122.7 (3) C34—C35—H35 121.4
C4—C5—H5 118.6 N3—C36—C35 121.8 (4)
C6—C5—H5 118.6 N3—C36—H36 119.1
C7—C6—C5 120.6 (3) C35—C36—H36 119.1
C7—C6—C8 118.5 (3) O8—C37—O9 123.9 (3)
C5—C6—C8 120.9 (3) O8—C37—Cd2 68.42 (18)
C2—C7—C6 117.5 (3) O9—C37—Cd2 55.51 (14)
C2—C7—H7 121.2 O8—C37—H37 118.0
C6—C7—H7 121.2 O9—C37—H37 118.0
O4—C8—O3 126.9 (3) Cd2—C37—H37 173.5
O4—C8—C6 112.0 (3) C22—N1—C26 120.6 (3)
O3—C8—C6 121.0 (3) C22—N1—Cd1 115.99 (19)
O7—C9—C4 111.9 (2) C26—N1—Cd1 123.3 (2)
O7—C9—H9A 109.2 C21—N2—C17 117.9 (3)
C4—C9—H9A 109.2 C21—N2—Cd1 117.16 (19)
O7—C9—H9B 109.2 C17—N2—Cd1 124.32 (19)

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C4—C9—H9B 109.2 C32—N3—C36 121.3 (3)
H9A—C9—H9B 107.9 C32—N3—Cd2 116.8 (2)
C11—C10—C15 118.8 (3) C36—N3—Cd2 122.0 (2)
C11—C10—O7 124.7 (3) C31—N4—C27 118.3 (3)
C15—C10—O7 116.4 (3) C31—N4—Cd2 116.9 (2)
C10—C11—C12 119.6 (3) C27—N4—Cd2 124.7 (2)
C10—C11—H11 120.2 C1—O1—Cd1 85.82 (17)
C12—C11—H11 120.2 C1—O2—Cd1 94.05 (16)
C13—C12—C11 122.7 (3) C8—O4—Cd2 107.4 (2)
C13—C12—H12 118.7 C16—O6—Cd1iii 108.45 (19)
C11—C12—H12 118.7 C10—O7—C9 117.2 (2)
C12—C13—C14 116.9 (3) C37—O8—Cd2 85.7 (2)
C12—C13—C16 119.5 (3) C37—O9—Cd1iv 130.69 (18)
C14—C13—C16 123.6 (3) C37—O9—Cd2 96.62 (17)
C13—C14—C15 121.5 (3) Cd1iv—O9—Cd2 132.32 (9)
C13—C14—H14 119.2 Cd2—O1W—H1A 112 (3)
C15—C14—H14 119.2 Cd2—O1W—H1B 115 (3)
C10—C15—C14 120.4 (3) H1A—O1W—H1B 102 (4)
C10—C15—H15 119.8 H2A—O2W—H2B 119 (2)
C14—C15—H15 119.8 H2C—O2W—H2D 120 (2)
O5—C16—O6 121.6 (3) H2F—O2W—H2E 123 (2)
O5—C16—C13 120.9 (3)

O1—C1—C2—C7 175.6 (3) C28—C29—C30—C31 0.3 (5)

O2—C1—C2—C7 −5.3 (4) C29—C30—C31—N4 0.3 (5)
O1—C1—C2—C3 −5.8 (4) C29—C30—C31—C32 −179.4 (3)
O2—C1—C2—C3 173.3 (3) N4—C31—C32—N3 2.3 (4)
C7—C2—C3—C4 0.8 (4) C30—C31—C32—N3 −178.0 (3)
C1—C2—C3—C4 −177.8 (3) N4—C31—C32—C33 −177.4 (3)
C2—C3—C4—C5 −1.6 (4) C30—C31—C32—C33 2.3 (5)
C2—C3—C4—C9 175.6 (3) N3—C32—C33—C34 −0.2 (5)
C3—C4—C5—C6 0.9 (4) C31—C32—C33—C34 179.6 (3)
C9—C4—C5—C6 −176.3 (3) C32—C33—C34—C35 0.2 (6)
C4—C5—C6—C7 0.5 (5) C33—C34—C35—C36 −0.1 (6)
C4—C5—C6—C8 178.7 (3) C34—C35—C36—N3 0.1 (6)
C3—C2—C7—C6 0.7 (4) C23—C22—N1—C26 0.7 (4)
C1—C2—C7—C6 179.4 (3) C21—C22—N1—C26 −179.0 (3)
C5—C6—C7—C2 −1.3 (4) C23—C22—N1—Cd1 −175.7 (2)
C8—C6—C7—C2 −179.6 (3) C21—C22—N1—Cd1 4.5 (3)
C7—C6—C8—O4 −179.4 (3) C25—C26—N1—C22 0.4 (5)
C5—C6—C8—O4 2.4 (4) C25—C26—N1—Cd1 176.6 (2)
C7—C6—C8—O3 1.6 (4) C20—C21—N2—C17 −1.2 (4)
C5—C6—C8—O3 −176.6 (3) C22—C21—N2—C17 177.7 (2)
C5—C4—C9—O7 39.6 (4) C20—C21—N2—Cd1 170.5 (2)
C3—C4—C9—O7 −137.3 (3) C22—C21—N2—Cd1 −10.6 (3)
C15—C10—C11—C12 −2.6 (5) C18—C17—N2—C21 0.0 (4)
O7—C10—C11—C12 175.1 (3) C18—C17—N2—Cd1 −171.1 (2)
C10—C11—C12—C13 0.2 (5) C33—C32—N3—C36 0.2 (5)

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C11—C12—C13—C14 1.8 (5) C31—C32—N3—C36 −179.6 (3)
C11—C12—C13—C16 −177.8 (3) C33—C32—N3—Cd2 180.0 (2)
C12—C13—C14—C15 −1.4 (5) C31—C32—N3—Cd2 0.2 (3)
C16—C13—C14—C15 178.1 (3) C35—C36—N3—C32 −0.1 (5)
C11—C10—C15—C14 2.9 (5) C35—C36—N3—Cd2 −179.9 (3)
O7—C10—C15—C14 −174.9 (3) C30—C31—N4—C27 −0.8 (4)
C13—C14—C15—C10 −0.9 (5) C32—C31—N4—C27 178.9 (3)
C12—C13—C16—O5 176.2 (3) C30—C31—N4—Cd2 176.7 (2)
C14—C13—C16—O5 −3.3 (5) C32—C31—N4—Cd2 −3.6 (3)
C12—C13—C16—O6 −3.7 (4) C28—C27—N4—C31 0.7 (5)
C14—C13—C16—O6 176.8 (3) C28—C27—N4—Cd2 −176.5 (2)
N2—C17—C18—C19 1.9 (5) O2—C1—O1—Cd1 1.2 (3)
C17—C18—C19—C20 −2.4 (5) C2—C1—O1—Cd1 −179.8 (2)
C18—C19—C20—C21 1.3 (5) O1—C1—O2—Cd1 −1.3 (3)
C19—C20—C21—N2 0.6 (5) C2—C1—O2—Cd1 179.7 (2)
C19—C20—C21—C22 −178.2 (3) O3—C8—O4—Cd2 9.6 (4)
N2—C21—C22—N1 4.1 (4) C6—C8—O4—Cd2 −169.2 (2)
C20—C21—C22—N1 −177.0 (3) O5—C16—O6—Cd1iii 10.6 (3)
N2—C21—C22—C23 −175.6 (3) C13—C16—O6—Cd1iii −169.5 (2)
C20—C21—C22—C23 3.2 (4) C11—C10—O7—C9 10.6 (5)
N1—C22—C23—C24 −1.0 (4) C15—C10—O7—C9 −171.6 (3)
C21—C22—C23—C24 178.7 (3) C4—C9—O7—C10 64.3 (3)
C22—C23—C24—C25 0.2 (5) O9—C37—O8—Cd2 0.3 (3)
C23—C24—C25—C26 0.9 (5) O8—C37—O9—Cd1iv 173.3 (2)
C24—C25—C26—N1 −1.1 (5) Cd2—C37—O9—Cd1iv 173.6 (3)
N4—C27—C28—C29 −0.2 (5) O8—C37—O9—Cd2 −0.3 (4)
C27—C28—C29—C30 −0.4 (5)

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

Hydrogen-bond geometry (Å, º)

D—H···A D—H H···A D···A D—H···A

C9—H9B···O2v 0.99 2.55 3.300 (4) 132
C17—H17···O1vi 0.95 2.49 3.256 (4) 137
C18—H18···O6vii 0.95 2.64 3.525 (4) 155
C20—H20···O2vii 0.95 2.53 3.447 (4) 163
C23—H23···O2vii 0.95 2.30 3.190 (4) 156
C25—H25···O7viii 0.95 2.58 3.515 (4) 167
C27—H27···O8vi 0.95 2.61 3.440 (4) 147
C30—H30···O3ix 0.95 2.39 3.286 (4) 157
C37—H37···O1iv 0.95 2.55 3.182 (4) 125
O2W—H2A···O4vi 0.90 (1) 2.64 (6) 3.445 (4) 150 (11)
O2W—H2A···O8vi 0.90 (1) 2.28 (10) 2.971 (4) 134 (11)
O2W—H2B···O3 0.90 (1) 2.10 (4) 2.960 (4) 160 (9)

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O1W—H1A···O5x 0.88 (1) 1.73 (2) 2.583 (3) 162 (4)
O1W—H1B···O2W 0.89 (1) 1.81 (1) 2.695 (4) 176 (4)
Symmetry codes: (iv) x+1, y, z; (v) x, −y+3/2, z−1/2; (vi) x, −y+3/2, z+1/2; (vii) −x, −y+1, −z+2; (viii) −x, −y+1, −z+1; (ix) −x+1, −y+1, −z+2; (x) −x+1,
y+1/2, −z+3/2.

Poly[[(2,2′-bipyridine-κ2N,N′){µ3-5-[(4-carboxyphenoxy)methyl]benzene-1,3-dicarboxylato-
κ4O1,O1′:O3:O5}manganese(II)] sesquihydrate] (Mn)

Crystal data
[Mn2(C16H10O7)2(C10H8N2)2]·3H2O Z=1
Mr = 1104.77 F(000) = 568
Triclinic, P1 Dx = 1.528 Mg m−3
a = 9.9758 (6) Å Mo Kα radiation, λ = 0.71073 Å
b = 10.5290 (7) Å Cell parameters from 7534 reflections
c = 13.7445 (9) Å θ = 2.2–26.4°
α = 91.623 (4)° µ = 0.61 mm−1
β = 108.250 (3)° T = 150 K
γ = 116.694 (3)° Block, colorless
V = 1200.37 (14) Å3 0.20 × 0.16 × 0.15 mm

Data collection
Bruker D8 Venture 4370 independent reflections
diffractometer 3522 reflections with I > 2σ(I)
Radiation source: sealed tube Rint = 0.044
φ and ω scans θmax = 25.3°, θmin = 2.4°
Absorption correction: multi-scan h = −12→12
(SADABS; Bruker, 2016) k = −12→12
Tmin = 0.890, Tmax = 0.913 l = −16→16
21405 measured reflections
Refinement
Refinement on F2 Primary atom site location: structure-invariant
Least-squares matrix: full direct methods
R[F2 > 2σ(F2)] = 0.052 Hydrogen site location: mixed
wR(F2) = 0.160 H atoms treated by a mixture of independent
S = 1.11 and constrained refinement
4370 reflections w = 1/[σ2(Fo2) + (0.0862P)2 + 1.1197P]
370 parameters where P = (Fo2 + 2Fc2)/3
15 restraints (Δ/σ)max = 0.001
Δρmax = 0.99 e Å−3
Δρmin = −0.41 e Å−3
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. Experiments were carried out at 150 K with Mo Kα radiation using a Bruker D8 Venture diffractometer.
Absorption was corrected for by multi-scan methods (SADABS; Bruker, 2016). The non-hydrogen atoms were refined
with anisotropic displacement parameters, while the

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

x y z Uiso*/Ueq Occ. (<1)

Mn1 0.36356 (6) 0.37989 (6) 0.66887 (4) 0.03265 (19)
C1 0.1642 (4) 0.4256 (4) 0.7397 (3) 0.0347 (8)
C2 0.0871 (4) 0.4874 (4) 0.7909 (3) 0.0323 (7)
C3 −0.0723 (4) 0.4554 (4) 0.7419 (3) 0.0317 (7)
H3 −0.133554 0.396362 0.673831 0.038*
C4 −0.1426 (4) 0.5096 (4) 0.7921 (3) 0.0317 (7)
C5 −0.3182 (4) 0.4654 (4) 0.7453 (3) 0.0333 (7)
C6 −0.0507 (4) 0.5995 (4) 0.8902 (3) 0.0336 (7)
H6 −0.098024 0.637896 0.924139 0.040*
C7 0.1093 (4) 0.6341 (4) 0.9392 (3) 0.0328 (7)
C8 0.1770 (4) 0.5771 (4) 0.8898 (3) 0.0336 (7)
H8 0.286063 0.599296 0.923466 0.040*
C9 0.2048 (4) 0.7247 (4) 1.0482 (3) 0.0371 (8)
H9A 0.133875 0.702798 1.089070 0.045*
H9B 0.292060 0.702109 1.083861 0.045*
C10 0.3481 (4) 0.9713 (4) 1.1341 (3) 0.0393 (8)
C11 0.3772 (4) 0.9354 (4) 1.2319 (3) 0.0375 (8)
H11 0.345422 0.837336 1.238412 0.045*
C12 0.4533 (4) 1.0439 (4) 1.3203 (3) 0.0369 (8)
H12 0.473440 1.019712 1.387579 0.044*
C13 0.5005 (4) 1.1881 (4) 1.3116 (3) 0.0363 (8)
C14 0.4727 (5) 1.2227 (4) 1.2128 (3) 0.0406 (8)
H14 0.505318 1.320796 1.206206 0.049*
C15 0.3982 (5) 1.1160 (4) 1.1244 (3) 0.0437 (9)
H15 0.381028 1.140525 1.057247 0.052*
C16 0.5685 (4) 1.3024 (4) 1.4047 (3) 0.0371 (8)
C17 0.2284 (4) 0.2751 (4) 0.4214 (3) 0.0384 (8)
H17 0.258286 0.374521 0.421912 0.046*
C18 0.1695 (5) 0.1841 (4) 0.3273 (3) 0.0434 (9)
H18 0.161178 0.220356 0.264389 0.052*
C19 0.1226 (4) 0.0387 (4) 0.3258 (3) 0.0430 (9)
H19 0.079146 −0.027076 0.261572 0.052*
C20 0.1398 (4) −0.0095 (4) 0.4190 (3) 0.0403 (8)
H20 0.108767 −0.108953 0.419546 0.048*
C21 0.2031 (4) 0.0886 (4) 0.5124 (3) 0.0334 (7)
C22 0.2261 (4) 0.0463 (4) 0.6155 (3) 0.0332 (7)
C23 0.1785 (5) −0.0966 (4) 0.6263 (3) 0.0411 (8)
H23 0.131278 −0.171424 0.566608 0.049*
C24 0.2009 (5) −0.1285 (4) 0.7253 (3) 0.0478 (10)
H24 0.168865 −0.225747 0.734209 0.057*
C25 0.2702 (5) −0.0182 (4) 0.8110 (3) 0.0456 (9)
H25 0.287178 −0.037579 0.879610 0.055*
C26 0.3139 (5) 0.1209 (4) 0.7940 (3) 0.0419 (9)
H26 0.360888 0.196991 0.852693 0.050*
N1 0.2455 (3) 0.2303 (3) 0.5124 (2) 0.0338 (6)

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N2 0.2936 (3) 0.1543 (3) 0.6992 (2) 0.0346 (6)
O1 0.2975 (3) 0.4351 (3) 0.7961 (2) 0.0394 (6)
O2 0.0998 (3) 0.3708 (3) 0.6443 (2) 0.0420 (6)
O3 −0.3992 (3) 0.4013 (3) 0.65041 (19) 0.0387 (6)
O4 −0.3863 (3) 0.4898 (3) 0.8013 (2) 0.0403 (6)
O5 0.5886 (3) 1.2548 (3) 1.4928 (2) 0.0437 (6)
H5 0.627448 1.323648 1.543166 0.065*
O6 0.5989 (3) 1.4288 (3) 1.4022 (2) 0.0391 (6)
O7 0.2717 (3) 0.8738 (3) 1.0416 (2) 0.0457 (7)
O1W −0.0303 (8) 0.8879 (13) 1.0657 (7) 0.154 (4) 0.69
H1A −0.131 (8) 0.819 (13) 1.053 (10) 0.231* 0.69
H1B 0.011 (14) 0.901 (17) 1.016 (7) 0.231* 0.69
O2W 0.0452 (17) 0.5770 (10) 0.5449 (8) 0.061 (4) 0.25
H2A −0.03 (2) 0.489 (8) 0.507 (13) 0.092* 0.25
H2B 0.06 (2) 0.656 (11) 0.520 (13) 0.092* 0.25
O3W 0.3383 (6) 0.3517 (4) 0.9967 (3) 0.0308 (9) 0.56
H3A 0.430 (3) 0.413 (6) 0.994 (5) 0.046* 0.56
H3B 0.246 (3) 0.346 (7) 0.966 (5) 0.046* 0.56

Atomic displacement parameters (Å2)

U11 U22 U33 U12 U13 U23

Mn1 0.0314 (3) 0.0321 (3) 0.0334 (3) 0.0154 (2) 0.0105 (2) 0.0045 (2)
C1 0.0355 (18) 0.0302 (18) 0.041 (2) 0.0160 (15) 0.0173 (16) 0.0097 (15)
C2 0.0332 (17) 0.0314 (18) 0.0343 (18) 0.0158 (14) 0.0143 (14) 0.0089 (14)
C3 0.0322 (17) 0.0304 (17) 0.0323 (18) 0.0145 (14) 0.0121 (14) 0.0069 (14)
C4 0.0317 (17) 0.0314 (17) 0.0310 (17) 0.0147 (14) 0.0106 (14) 0.0086 (14)
C5 0.0341 (18) 0.0312 (17) 0.0338 (18) 0.0159 (15) 0.0110 (15) 0.0084 (14)
C6 0.0374 (18) 0.0311 (18) 0.0334 (18) 0.0170 (15) 0.0134 (15) 0.0064 (14)
C7 0.0340 (17) 0.0294 (17) 0.0330 (18) 0.0140 (14) 0.0119 (14) 0.0056 (14)
C8 0.0294 (17) 0.0309 (18) 0.0374 (19) 0.0131 (14) 0.0105 (14) 0.0076 (14)
C9 0.0362 (18) 0.0355 (19) 0.0348 (19) 0.0160 (16) 0.0091 (15) 0.0056 (15)
C10 0.0400 (19) 0.035 (2) 0.0364 (19) 0.0158 (16) 0.0106 (16) 0.0006 (15)
C11 0.0397 (19) 0.0308 (18) 0.041 (2) 0.0170 (15) 0.0135 (16) 0.0067 (15)
C12 0.0361 (18) 0.039 (2) 0.0348 (19) 0.0188 (16) 0.0114 (15) 0.0068 (15)
C13 0.0343 (18) 0.0348 (19) 0.040 (2) 0.0172 (15) 0.0129 (15) 0.0061 (15)
C14 0.045 (2) 0.0332 (19) 0.038 (2) 0.0168 (16) 0.0117 (16) 0.0054 (16)
C15 0.057 (2) 0.035 (2) 0.0342 (19) 0.0201 (18) 0.0134 (17) 0.0101 (16)
C16 0.0339 (18) 0.039 (2) 0.038 (2) 0.0177 (16) 0.0126 (15) 0.0077 (16)
C17 0.0379 (19) 0.038 (2) 0.037 (2) 0.0170 (16) 0.0131 (15) 0.0092 (16)
C18 0.040 (2) 0.051 (2) 0.036 (2) 0.0199 (18) 0.0139 (16) 0.0102 (17)
C19 0.0376 (19) 0.050 (2) 0.036 (2) 0.0197 (18) 0.0098 (16) −0.0014 (17)
C20 0.0381 (19) 0.0350 (19) 0.045 (2) 0.0152 (16) 0.0157 (16) 0.0020 (16)
C21 0.0278 (16) 0.0327 (18) 0.0406 (19) 0.0146 (14) 0.0136 (14) 0.0051 (15)
C22 0.0297 (17) 0.0319 (18) 0.0387 (19) 0.0154 (14) 0.0125 (14) 0.0063 (15)
C23 0.043 (2) 0.038 (2) 0.046 (2) 0.0222 (17) 0.0175 (17) 0.0095 (17)
C24 0.047 (2) 0.042 (2) 0.062 (3) 0.0229 (18) 0.025 (2) 0.022 (2)
C25 0.051 (2) 0.050 (2) 0.044 (2) 0.028 (2) 0.0200 (18) 0.0219 (19)

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C26 0.041 (2) 0.049 (2) 0.038 (2) 0.0232 (18) 0.0145 (16) 0.0091 (17)
N1 0.0305 (14) 0.0328 (15) 0.0360 (16) 0.0143 (12) 0.0110 (12) 0.0054 (12)
N2 0.0336 (15) 0.0373 (16) 0.0354 (16) 0.0187 (13) 0.0129 (12) 0.0100 (13)
O1 0.0355 (13) 0.0424 (14) 0.0435 (14) 0.0215 (11) 0.0146 (11) 0.0049 (11)
O2 0.0502 (15) 0.0490 (16) 0.0353 (14) 0.0296 (13) 0.0175 (12) 0.0070 (12)
O3 0.0320 (12) 0.0440 (14) 0.0350 (14) 0.0161 (11) 0.0100 (11) 0.0021 (11)
O4 0.0347 (13) 0.0484 (15) 0.0398 (14) 0.0221 (12) 0.0136 (11) 0.0030 (12)
O5 0.0556 (16) 0.0398 (14) 0.0326 (14) 0.0237 (13) 0.0113 (12) 0.0064 (11)
O6 0.0428 (14) 0.0318 (14) 0.0433 (15) 0.0183 (11) 0.0158 (11) 0.0072 (11)
O7 0.0597 (17) 0.0319 (13) 0.0336 (14) 0.0160 (12) 0.0121 (12) 0.0037 (11)
O1W 0.060 (4) 0.204 (10) 0.124 (6) 0.018 (5) 0.023 (4) −0.083 (6)
O2W 0.107 (9) 0.016 (5) 0.025 (5) 0.031 (6) −0.022 (5) −0.004 (4)
O3W 0.064 (3) 0.022 (2) 0.0130 (17) 0.029 (2) 0.0083 (18) 0.0059 (15)

Geometric parameters (Å, º)

Mn1—O6i 2.194 (2) C14—C15 1.377 (5)

Mn1—O1 2.200 (3) C14—H14 0.9500
Mn1—N2 2.247 (3) C15—H15 0.9500
Mn1—N1 2.247 (3) C16—O6 1.229 (4)
Mn1—O4ii 2.306 (3) C16—O5 1.316 (4)
Mn1—O3ii 2.370 (2) C17—N1 1.337 (5)
Mn1—O2 2.502 (3) C17—C18 1.373 (5)
C1—O2 1.250 (4) C17—H17 0.9500
C1—O1 1.269 (4) C18—C19 1.383 (6)
C1—C2 1.507 (5) C18—H18 0.9500
C2—C3 1.390 (5) C19—C20 1.381 (5)
C2—C8 1.396 (5) C19—H19 0.9500
C3—C4 1.391 (5) C20—C21 1.394 (5)
C3—H3 0.9500 C20—H20 0.9500
C4—C6 1.388 (5) C21—N1 1.355 (4)
C4—C5 1.498 (5) C21—C22 1.478 (5)
C5—O4 1.262 (4) C22—N2 1.350 (5)
C5—O3 1.269 (4) C22—C23 1.388 (5)
C6—C7 1.388 (5) C23—C24 1.385 (6)
C6—H6 0.9500 C23—H23 0.9500
C7—C8 1.381 (5) C24—C25 1.380 (6)
C7—C9 1.506 (5) C24—H24 0.9500
C8—H8 0.9500 C25—C26 1.378 (6)
C9—O7 1.422 (4) C25—H25 0.9500
C9—H9A 0.9900 C26—N2 1.337 (5)
C9—H9B 0.9900 C26—H26 0.9500
C10—O7 1.366 (4) O5—H5 0.8400
C10—C11 1.385 (5) O1W—H1A 0.893 (11)
C10—C15 1.399 (5) O1W—H1B 0.891 (11)
C11—C12 1.386 (5) O2W—O2Wiii 1.685 (18)
C11—H11 0.9500 O2W—H2A 0.890 (11)
C12—C13 1.395 (5) O2W—H2B 0.887 (11)

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C12—H12 0.9500 O2W—H2Aiii 0.90 (16)
C13—C14 1.392 (5) O3W—H3A 0.863 (11)
C13—C16 1.477 (5) O3W—H3B 0.861 (10)

O6i—Mn1—O1 99.28 (9) C12—C13—C16 121.0 (3)

O6i—Mn1—N2 165.44 (10) C15—C14—C13 120.6 (4)
O1—Mn1—N2 91.55 (10) C15—C14—H14 119.7
O6i—Mn1—N1 92.45 (10) C13—C14—H14 119.7
O1—Mn1—N1 139.26 (10) C14—C15—C10 119.7 (4)
N2—Mn1—N1 73.02 (11) C14—C15—H15 120.2
O6i—Mn1—O4ii 95.51 (10) C10—C15—H15 120.2
O1—Mn1—O4ii 80.65 (9) O6—C16—O5 122.0 (3)
N2—Mn1—O4ii 95.83 (10) O6—C16—C13 124.7 (3)
N1—Mn1—O4ii 137.06 (9) O5—C16—C13 113.2 (3)
O6i—Mn1—O3ii 87.96 (9) N1—C17—C18 123.0 (4)
O1—Mn1—O3ii 136.46 (9) N1—C17—H17 118.5
N2—Mn1—O3ii 90.88 (10) C18—C17—H17 118.5
N1—Mn1—O3ii 82.43 (9) C17—C18—C19 118.8 (4)
O4ii—Mn1—O3ii 55.86 (8) C17—C18—H18 120.6
O6i—Mn1—O2 81.64 (9) C19—C18—H18 120.6
O1—Mn1—O2 55.38 (9) C20—C19—C18 119.0 (4)
N2—Mn1—O2 96.80 (10) C20—C19—H19 120.5
N1—Mn1—O2 88.52 (9) C18—C19—H19 120.5
O4ii—Mn1—O2 134.38 (9) C19—C20—C21 119.6 (4)
O3ii—Mn1—O2 165.91 (9) C19—C20—H20 120.2
O2—C1—O1 121.8 (3) C21—C20—H20 120.2
O2—C1—C2 120.4 (3) N1—C21—C20 120.7 (3)
O1—C1—C2 117.7 (3) N1—C21—C22 116.2 (3)
C3—C2—C8 119.4 (3) C20—C21—C22 123.1 (3)
C3—C2—C1 121.3 (3) N2—C22—C23 121.6 (3)
C8—C2—C1 119.4 (3) N2—C22—C21 116.2 (3)
C2—C3—C4 120.2 (3) C23—C22—C21 122.2 (3)
C2—C3—H3 119.9 C24—C23—C22 119.0 (4)
C4—C3—H3 119.9 C24—C23—H23 120.5
C6—C4—C3 119.4 (3) C22—C23—H23 120.5
C6—C4—C5 119.3 (3) C25—C24—C23 119.6 (4)
C3—C4—C5 121.1 (3) C25—C24—H24 120.2
O4—C5—O3 120.0 (3) C23—C24—H24 120.2
O4—C5—C4 119.7 (3) C26—C25—C24 118.0 (4)
O3—C5—C4 120.3 (3) C26—C25—H25 121.0
C7—C6—C4 120.9 (3) C24—C25—H25 121.0
C7—C6—H6 119.6 N2—C26—C25 123.5 (4)
C4—C6—H6 119.6 N2—C26—H26 118.3
C8—C7—C6 119.3 (3) C25—C26—H26 118.3
C8—C7—C9 120.3 (3) C17—N1—C21 118.9 (3)
C6—C7—C9 120.3 (3) C17—N1—Mn1 123.8 (2)
C7—C8—C2 120.8 (3) C21—N1—Mn1 117.0 (2)
C7—C8—H8 119.6 C26—N2—C22 118.4 (3)

Acta Cryst. (2019). C75, 1562-1568 sup-14

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C2—C8—H8 119.6 C26—N2—Mn1 124.3 (3)
O7—C9—C7 108.8 (3) C22—N2—Mn1 117.3 (2)
O7—C9—H9A 109.9 C1—O1—Mn1 97.5 (2)
C7—C9—H9A 109.9 C1—O2—Mn1 84.1 (2)
O7—C9—H9B 109.9 C5—O3—Mn1iv 90.5 (2)
C7—C9—H9B 109.9 C5—O4—Mn1iv 93.6 (2)
H9A—C9—H9B 108.3 C16—O5—H5 109.5
O7—C10—C11 124.7 (3) C16—O6—Mn1i 156.0 (2)
O7—C10—C15 114.9 (3) C10—O7—C9 116.4 (3)
C11—C10—C15 120.4 (3) H1A—O1W—H1B 121 (2)
C10—C11—C12 119.4 (3) O2Wiii—O2W—H2A 20 (10)
C10—C11—H11 120.3 O2Wiii—O2W—H2B 116 (10)
C12—C11—H11 120.3 H2A—O2W—H2B 121 (2)
C11—C12—C13 120.7 (3) O2Wiii—O2W—H2Aiii 20 (10)
C11—C12—H12 119.6 H2A—O2W—H2Aiii 39 (10)
C13—C12—H12 119.6 H2B—O2W—H2Aiii 107 (10)
C14—C13—C12 119.2 (3) H3A—O3W—H3B 128 (2)
C14—C13—C16 119.6 (3)

O2—C1—C2—C3 15.6 (5) C18—C19—C20—C21 0.3 (5)

O1—C1—C2—C3 −166.3 (3) C19—C20—C21—N1 1.0 (5)
O2—C1—C2—C8 −165.1 (3) C19—C20—C21—C22 −179.8 (3)
O1—C1—C2—C8 13.0 (5) N1—C21—C22—N2 −2.9 (4)
C8—C2—C3—C4 −1.5 (5) C20—C21—C22—N2 177.9 (3)
C1—C2—C3—C4 177.7 (3) N1—C21—C22—C23 175.9 (3)
C2—C3—C4—C6 2.0 (5) C20—C21—C22—C23 −3.3 (5)
C2—C3—C4—C5 −174.2 (3) N2—C22—C23—C24 0.1 (5)
C6—C4—C5—O4 −11.5 (5) C21—C22—C23—C24 −178.7 (3)
C3—C4—C5—O4 164.6 (3) C22—C23—C24—C25 −0.2 (6)
C6—C4—C5—O3 169.7 (3) C23—C24—C25—C26 0.3 (6)
C3—C4—C5—O3 −14.1 (5) C24—C25—C26—N2 −0.4 (6)
C3—C4—C6—C7 −1.0 (5) C18—C17—N1—C21 0.0 (5)
C5—C4—C6—C7 175.2 (3) C18—C17—N1—Mn1 173.8 (3)
C4—C6—C7—C8 −0.5 (5) C20—C21—N1—C17 −1.2 (5)
C4—C6—C7—C9 −176.5 (3) C22—C21—N1—C17 179.6 (3)
C6—C7—C8—C2 0.9 (5) C20—C21—N1—Mn1 −175.4 (2)
C9—C7—C8—C2 176.9 (3) C22—C21—N1—Mn1 5.3 (4)
C3—C2—C8—C7 0.1 (5) C25—C26—N2—C22 0.3 (5)
C1—C2—C8—C7 −179.2 (3) C25—C26—N2—Mn1 180.0 (3)
C8—C7—C9—O7 97.8 (4) C23—C22—N2—C26 −0.1 (5)
C6—C7—C9—O7 −86.3 (4) C21—C22—N2—C26 178.7 (3)
O7—C10—C11—C12 −178.7 (3) C23—C22—N2—Mn1 −179.8 (3)
C15—C10—C11—C12 1.5 (6) C21—C22—N2—Mn1 −1.0 (4)
C10—C11—C12—C13 0.0 (5) O2—C1—O1—Mn1 11.7 (4)
C11—C12—C13—C14 −1.0 (5) C2—C1—O1—Mn1 −166.4 (3)
C11—C12—C13—C16 174.6 (3) O1—C1—O2—Mn1 −10.2 (3)
C12—C13—C14—C15 0.5 (6) C2—C1—O2—Mn1 167.8 (3)
C16—C13—C14—C15 −175.1 (3) O4—C5—O3—Mn1iv −1.1 (3)

Acta Cryst. (2019). C75, 1562-1568 sup-15

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C13—C14—C15—C10 0.9 (6) C4—C5—O3—Mn1iv 177.7 (3)
O7—C10—C15—C14 178.3 (4) O3—C5—O4—Mn1iv 1.2 (3)
C11—C10—C15—C14 −2.0 (6) C4—C5—O4—Mn1iv −177.6 (3)
C14—C13—C16—O6 2.6 (5) O5—C16—O6—Mn1i 170.1 (4)
C12—C13—C16—O6 −173.0 (3) C13—C16—O6—Mn1i −12.7 (8)
C14—C13—C16—O5 −180.0 (3) C11—C10—O7—C9 6.4 (5)
C12—C13—C16—O5 4.4 (5) C15—C10—O7—C9 −173.8 (3)
N1—C17—C18—C19 1.3 (6) C7—C9—O7—C10 173.3 (3)
C17—C18—C19—C20 −1.4 (6)

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

Hydrogen-bond geometry (Å, º)

D—H···A D—H H···A D···A D—H···A

v
C15—H15···O3W 0.95 2.56 3.243 (5) 129
C17—H17···O3iii 0.95 2.56 3.393 (4) 146
C17—H17···O6i 0.95 2.66 3.270 (4) 123
C20—H20···O2vi 0.95 2.50 3.358 (5) 150
C23—H23···O2Wvii 0.95 2.37 3.094 (10) 133
C25—H25···O7vii 0.95 2.46 3.396 (5) 168
C26—H26···O3W 0.95 2.65 3.520 (5) 152
O5—H5···O3viii 0.84 1.81 2.561 (4) 148
O1W—H1A···O3Wix 0.89 (1) 1.92 (4) 2.793 (9) 167 (13)
O1W—H1B···O7 0.89 (1) 2.66 (14) 3.199 (8) 120 (12)
O1W—H1B···O1Wx 0.89 (1) 2.48 (15) 2.97 (3) 116 (14)
O2W—H2A···O2Wiii 0.89 (1) 0.90 (16) 1.685 (18) 141 (29)
O2W—H2B···O2iii 0.89 (1) 2.23 (15) 2.756 (9) 118 (13)
O3W—H3A···O3Wxi 0.86 (1) 2.48 (3) 3.304 (9) 160 (6)
O3W—H3B···O1Wix 0.86 (1) 2.34 (6) 2.793 (9) 113 (5)

Symmetry codes: (i) −x+1, −y+2, −z+2; (iii) −x, −y+1, −z+1; (v) x, y+1, z; (vi) −x, −y, −z+1; (vii) x, y−1, z; (viii) x+1, y+1, z+1; (ix) −x, −y+1, −z+2; (x)
−x, −y+2, −z+2; (xi) −x+1, −y+1, −z+2.

Acta Cryst. (2019). C75, 1562-1568 sup-16