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Predicting the crystal habit of photoinitiator XBPO

and elucidating the solvent effect on crystal
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Cite this: CrystEngComm, 2019, 21,

2422 faces†
Pei Zhao,a Xiaohan Liu,a Liping Wang,a Zhenguo Gao,a Yang Yang,a
Hongxun Hao, a Chuang Xiea and Ying Bao *abc

The crystal habits of bisIJ2,4,6-trimethylbenzoyl)phenylphosphine oxide (XBPO) were predicted by consider-

ing solvent effects using a modified attachment energy model. The electrostatic potential (ESP) slices of
important crystal faces were determined to explore the surface features of the crystal. The hydrogen bond-
ing forming ability of solvents was investigated by the radial distribution function at the molecular level.
Besides, an affinity degree model was first introduced to elaborate the solvent effect on crystal faces. Re-
sults indicate that the different affinity degrees for solvent molecules at the face can lead to the dissimilarity
Received 14th December 2018, of the face in morphological importance. Meanwhile, the crystals were prepared in acetone and ethanol
Accepted 21st February 2019
solvents by adopting the slow solvent evaporation method. The experimental results were highly in accor-
dance with the simulated crystal morphology. Overall, this work could be helpful to better understand the
DOI: 10.1039/c8ce02114g
habits of crystals induced by solvents and to have clear guidance for screening solvents to acquire crystals
rsc.li/crystengcomm with desired morphologies in the crystallization process.

1. Introduction Molecular dynamics simulation has been developed for

decades which can establish the connections between molec-
Crystallization in solution is an important unit operation to ular interactions on the molecular scale and the appearance
purify and engineer various solid chemical products, in which of crystals on the mesoscopic and macroscopic scales.
the crystal morphology is a main target to be optimized in Through structural visualization, molecular dynamics simula-
industry. Crystal morphology could affect downstream pro- tion provides a convenient method to explore crystal growth
cessing, e.g. filtration and drying, as well as product qualities and solvent adsorption behavior on the molecular scale. In
like flowability, compressibility, and bulk density.1,2 The recent years, the effect of solvent on the crystal morphology
modification of crystal morphology in research and industry has been studied extensively by using molecular simulation
can be achieved by changing process parameters, such as methods.12–14
solvents,3–5 supersaturation,6,7 temperature,8 stirring rates, Chen et al.15 used a modified attachment energy model
and additives.9–11 Among these factors, solvent selection may considering both the solvent–surface adsorption interaction
be the most critical design decision in crystallization from so- and surface structures to explore the solvent effect on the
lution not only because solvent can provide an environment crystal habit of hexogen. Liu et al.16 studied the growth mor-
for crystal growth but also because the interactions between phology of 3,4-biIJ3nitrofurazan-4-yl)furoxan (DNTF) under vac-
the solvent and the crystal faces lead to various crystal mor- uum and solvent conditions through molecular dynamics
phologies. From an engineering perspective, to obtain the simulation. They found that the crystal morphology is an im-
optimum morphology, it is valuable to understand the effect portant factor for controlling the sensitivity of explosives.
of solvents on crystal habits. Kumar et al.17 investigated the impact of hydroxypropyl
methylcellulose (HPMC) concentration on the crystal habit of
a
State Key Laboratory of Chemical Engineering, School of Chemical Engineering
nifedipine and correlated important biopharmaceutical prop-
and Technology, Tianjin University, Tianjin 300072, P. R. China. erties with crystal habits through molecular dynamics and
E-mail: yingbao@tju.edu.cn; Fax: +86 22 27314971; Tel: +86 22 27405754 surface chemistry methods. Wang et al.18 predicted the mor-
b
Collaborative Innovation Center of Chemistry Science and Engineering, Tianjin phology of cefaclor dihydrate using a modified attachment
300072, P. R. China
c
energy model, and explored the effect of solvent and super-
Key Laboratory for Modern Drug Delivery and High Efficiency in Tianjin, P. R.
China
saturation on the crystal morphology. Meanwhile, the mecha-
† Electronic supplementary information (ESI) available. See DOI: 10.1039/ nism of solvent effects on different faces was elaborated by
c8ce02114g discussing the adsorption sites of solvent molecules. But a

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full and comprehensive understanding of the relationship slowest growth rate. The relationship can be expressed as
between solvent molecules and crystal faces was rather lack- follows:
ing. To the best of our knowledge, none of the previous
studies have correlated quantitatively solvent molecules with Rhkl ∝ |Eatt| (1)
crystal faces to interpret the growth of crystal faces at the
molecular level. where Rhkl is the growth rate of the (h k l) face and Eatt is de-
Photoinitiators, which are essential components of photo- fined as the released energy by adding a growth slice to a
curing materials, can exert a decisive effect on photocuring growing crystal surface.29 Eatt is calculated as follows:
speed. They are substances that absorb radiant energy and
undergo photochemical changes upon excitation to produce Eatt = Elatt − Eslice (2)
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active intermediates (free radicals or cations) that initiate

polymerization. According to the difference in reactive inter- where Elatt is the lattice energy of the crystal and Eslice is the
mediates, photoinitiators can be divided into two types: free released energy when growing a slice with thickness dhkl.
radical photoinitiators and cationic photoinitiators.19 However, given the interaction between the solvent mole-
BisIJ2,4,6-trimethylbenzoyl)phenylphosphine oxide (XBPO) is a cules and the crystal faces, it is necessary to consider the re-
multifunctional UV photoinitiator for radical polymerization moval of the solvent molecules that are adsorbed on the sur-
of unsaturated resins, especially for pigmented formulations. face. This removal process will consume energy and result in
It is used as a photoinitiator for synthetic coatings for metals, a decrease in attachment energy. Therefore, we replace the
wood, plastics, paper, optical fibers and printing inks.20,21 classical attachment energy model with a modified attach-
XBPO has a higher initiation efficiency because it can decom- ment energy model that takes into account the effects of the
pose into more highly effective active radicals compared with solvent. On the basis of the AE model, the relationship of the
other photoinitiators.22 Therefore, research on bisacyl-  and the modified attachment energy
relative growth rate Rhkl
phosphine oxide photoinitiators is becoming more and more
 is given as follows:
Eatt
extensive in the field of photoinitiators. Wang et al.23 investi-
gated the solubilities of XBPO in different organic solvents
ranging from 295 K to 345 K by experimental and theoretical   Eatt
Rhkl  (3)
analyses. However, for a long time, the focus of XBPO re-
search has been solely on its synthesis and its performance  can be obtained by the following equation:
here, Eatt
in dental resin.24,25 Efforts to study its morphology have not
been reported.
  Eatt  Es
Eatt (4)
In this paper, the crystal habits of XBPO in acetone and
ethanol solvents were predicted via a modified attachment
energy (MAE) model and the interactions at the crystal– where Es describes the energy of the solvent binding on the
solvent interface were described. The growth of crystal faces crystal face (h k l) and it can be calculated using the following
was elaborated using a new affinity degree model considering formula:
solvent molecules and crystal surfaces. Moreover, recrystalli-
zation experiments in the two solvents were carried out for Es = Eint × Aacc/Abox (5)
verifying the simulation results. This article would provide a
fundamental understanding of crystal–solvent interactions where Abox is the total area of the crystal surface, Aacc repre-
and the basic information for the choice of solvent in the re- sents the area of the accessible solvent surface of the crystal
crystallization process of XBPO. surface in the unit cell,30 which can be obtained by calculat-
ing the Connolly surface, and Eint indicates the interaction
2. Theoretical background and energy between the solvent layer and the crystal face that can
be calculated using the following equation:
simulation details
2.1 Theoretical background Eint = Etot − (Esur + Esol) (6)
The first theoretical model for predicting the crystal mor-
phology is the Bravais–Friedel–Donnay–Harker (BFDH) here, Etot represents the total energy of the interface system
model, which generated some possible growth planes and including the crystal surface and solvent layer. Esur and Esol
their relative growth rates.13,26 To improve the prediction ac- stand for the energy of the crystal surface and solvents,
curacy, the BFDH model was further optimized through respectively.
considering the system's energy. Hartman and Bennema27,28
proposed the attachment energy (AE) model based on the 2.2 Simulation details
periodic bond chain (PBC) theory. The growth rate of the The crystal structure of XBPO (ref code FOQDIZ) was taken
crystal face is proportional to its attachment energy, mean- from the CSD (Cambridge Structural Database), which crys-
ing that the face with the lowest attachment energy has the tallized in the space group P21/c with lattice parameters a =

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18.205(3) Å, b = 15.055(2) Å, c = 8.6688(13) Å, and β = Table 1 The comparison of the experimental and optimized lattice pa-
rameters of XBPO
103.156IJ4)°. The molecular and unit cell structures of XBPO
are shown in Fig. 1. Lattice parameter a (Å) b (Å) c (Å) α (°) β (°) γ (°)
All computational simulations were performed using Ma-
Exp 18.205 15.055 8.669 90.00 103.156 90.00
terials Studio 6.0 (ref. 31) (Accelrys Inc., USA). Geometry opti- COMPASS 17.822 14.228 8.764 90.00 104.695 90.00
mization was carried out with the Forcite algorithm with Relative error (%) −2.10 −5.49 1.10 0 1.49 0
COMPASS force field (condensed phase optimized molecular
potentials for atomistic simulation studies).29,32–34 According
to Table 1, it was found that the COMPASS force field was calculated by employing an atom-based summation with a
suitable for the molecular dynamics (MD) simulation as the cut-off radius of 15.5 Å.
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relative errors were less than 6% compared with the experi-

mental results.16 3. Experimental section
The crystal habit of XBPO under vacuum was predicted 3.1 Materials
by the growth morphology method, which gave several pos-
sible crystal faces. The XBPO crystal was sliced parallel to Acetone and ethanol were of analytical grade, purchased from
the morphologically important surfaces (h k l) with a depth Tianjin Kewei Reagents Co., Ltd. (Tianjin, China), and used
of 2 × dhkl. A crystal segment was created as a periodic without further purification. XBPO (purity, 99%) was pro-
superstructure of 3 × 3 unit cells. A solvent layer containing vided by Tianjin Heowns-Opde Co., Ltd. (Tianjin, China). De-
200 molecules was constructed using the Amorphous Cell ionized water was used in this experiment.
tool. The dimensions of the amorphous cell were
predetermined by the crystal layer.35 The double-layer inter- 3.2 Recrystallization experiments
facial method was used for MD calculation to study the im- Based on XBPO solubility data,23 saturated solutions in ace-
pact of the solvent on the crystal shape. One part of this tone and ethanol at 25 °C were prepared, respectively. The
model was the crystal segment and the solvent layer occu- saturated solution was filtered into a crystallization vessel
pied the other. A vacuum layer with a thickness of 50 Å was and sealed with Parafilm. Afterwards, the solution was slowly
placed above the solvent layer to avoid the effect of addi- evaporated in an incubator at 25 °C. After 48 h, the XBPO
tional free boundaries. Subsequently, geometry and dynamic crystals were harvested and dried for further characterization.
optimizations of the structure were performed in the Forcite
module. An NVT (N = the constant number of particles, V = 3.3 Characterization of crystallized solid forms
constant volume, T = constant temperature) ensemble at The morphology of the recrystallization samples of XBPO was
298 K (500 ps with a time step of 1 fs, controlled with an detected using an optical microscope (Xige Photoelectric
Andersen33 thermostat) was employed for a steady state of Technology Co., Ltd., Tianjin). The crystal form of the sam-
the whole system. ples was recorded at room temperature on a powder X-ray
In the adsorption model, the likely adsorption sites and diffractometer (D/MAX-2500, Rigaku, Japan) with Cu Kα radi-
adsorption energies of solvent molecules on different crystal ation (λKα = 0.15406 nm) at 100 mA and 40 kV. The data were
faces were studied. Firstly, the solvent molecule was geomet- recorded over a 2θ scan range of 2° to 50° with a scanning
rically optimized, and periodic superstructures were rate of 8 degrees per minute.
constructed on cleaved faces. Then a vacuum was built and
the solute molecules of the supercell surface layer were 4. Results and discussion
constrained. Finally, 20 configurations were set, and the con-
figurations of a solvent molecule adsorbed at the crystal face 4.1 Prediction of the crystal morphology in a vacuum
were sampled by means of the Monte Carlo method36 com- The molecular interactions between XBPO molecules inside
bined with the annealing technique. the crystal are of great significance for studying the growth of
For the non-bonding interactions, the electrostatic interac- crystals. The interactions of molecules calculated by using
tions were calculated by the standard Ewald method with an Crystal Graph are displayed in Fig. 2. The blue lines
accuracy of 0.0001 kcal mol−1, and van der Waals forces were

Fig. 2 Intermolecular interactions for the XBPO crystal calculated

Fig. 1 Structures of the XBPO (a) molecule and (b) unit cell. using Crystal Graph.

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correspond to strong interactions and the red lines corre- Table 2 The crystal habit parameters of XBPO crystals in a vacuum pre-
dicted using the AE model
spond to weak interactions. Previous studies indicated an
increase of the growth rate of the crystal surface that had a (h k l) Multiplicity dhkl (Å) Total Eatt (kcal mol−1) Area (%)
stronger intermolecular interaction.37 Therefore, the fastest
(1 0 0) 2 17.24 −33.59 46.12
growth rate of the crystal surface would be present in the (1 1 0) 4 10.97 −63.39 28.41
direction that contains the strongest bond, which means that (0 1 1) 4 7.28 −97.32 12.52
XBPO molecules grow faster along the blue line direction (1 1 −1) 4 7.30 −97.38 12.95
than those along the red line direction. The crystal surfaces
that have a fast growth rate will vanish and the crystal sur-
faces with a slow growth rate will appear in the final tional groups exposed on the exterior of the four crystal faces
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morphology. are methyl groups and aromatic rings which belong to non-
For the above reasons, the crystal morphology of XBPO in polar groups. Therefore, these four faces can be classified as
a vacuum is composed of different faces. The crystal mor- non-polar surfaces which facilitate the adsorption of non-
phology predicted using the AE model under vacuum is polar solvent molecules.
shown in Fig. 3, and the morphologically dominant faces of The electrostatic potential (ESP) map which illustrates the
XBPO are listed in Table 2. The results indicated that (1 0 0), electrostatic potential distribution of molecules is a very use-
(1 1 0), (0 1 1), and (1 1 −1) are the important surfaces. The ful tool. It can help us to understand the properties of mole-
most important growth surface is the (1 0 0) surface that oc- cules and further comprehend the interaction between mole-
cupies more than 46% surface area. The attachment energy cules. In the Dmol3 module, the PBE39,40 of the generalized
consists of van der Waals forces and electrostatic interac- gradient approximation (GGA) density functional with the
tions; correspondingly, the Eatt of the (1 0 0) face (−33.59 kcal DNP basis set was used to perform electrostatic potential cal-
mol−1) is composed of the van der Waals force (−30.63 kcal culations on solute molecule, solvent molecules, and impor-
mol−1) and the electrostatic interaction (−2.96 kcal mol−1), as tant crystal faces. Fig. 5 shows the ESP maps and partial ESP
shown in Table S1 of the ESI.† The (0 1 1) and (1 1 −1) faces changes on the O/P/H atoms of molecules. The ESP maps of
show similar attachment energies (−97.32 kcal mol−1 and important crystal faces are depicted in Fig. S1 of the ESI.†
−97.38 kcal mol−1), which are much smaller than the attach- The ESPs of different surface areas are displayed in different
ment energy of the (1 0 0) face (−33.59 kcal mol−1). The colors. The negative electrostatic potential corresponding to a
higher the absolute value of Eatt, the stronger the ability to high electron density (negative charge accumulation region)
adsorb XBPO molecules onto the crystal face.38 Therefore, the is represented by a red hue colored region, and the positive
growth rates of the (0 1 1) and (1 1 −1) faces are faster among electrostatic potential corresponding to a low electron density
the dominant growth faces, and these faces have lower mor- (positive charge accumulation region) is represented by a
phological importance. blue hue colored region.
O atoms in both acetone and ethanol are very negative
due to the existence of lone pairs and the ESPs of O atoms
4.2 The molecular arrangement and the electrostatic are −0.507 and −0.630, respectively. The remaining areas of
potential of the crystal faces the molecules are surrounded by positive potentials. The
There are various molecular orientations outside each face of strong hydrogen bond between the ethanol molecule and the
a crystal owing to the different structures of the face.38 As XBPO molecule on the crystal face should be attributed to
shown in Fig. 4, the molecular arrangements of morphologi- the highest electronegativity at the O atom. The central re-
cally dominant habit faces are dissimilar. The XBPO mole- gions of the XBPO molecule with two benzoyl groups and one
cules on the (1 0 0) face are arranged perpendicular to the phosphono group show negative charge accumulation (the
crystal plane, resulting in a relatively flat face. And the mole- presence of lone pairs) while the peripheral areas show the
cules on the (1 1 0), (0 1 1) and (1 1 −1) faces are at an angle
to the crystal plane causing the faces to be uneven. In addi-
tion, the arrangement of the molecules shows that the func-

Fig. 3 The predicted morphology of XBPO in a vacuum using the AE Fig. 4 Surface structure of the dominant crystal faces of the XPBO
model. crystal.

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ecules on each crystal face. The alternating appearance of

positive and negative charge regions on the crystal face is
more conducive to the attachment of external molecules to
the crystal faces.41 As seen from the slice (1 0 0), the distribu-
tion of the surface charge is relatively simple and it has a
small electrostatic interaction. Thus, the external molecules
have less influence on it. However, the ESP distributions of
the (0 1 1), (1 1 0) and (1 1 −1) surfaces are complicated on
the charge distribution, and the XBPO molecules on these
crystal faces will have more chance to interact with solute or
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solvent molecules in the external environment.

The diversity of the molecular arrangements of the crystal
faces and the ESP distribution of the crystal faces are respon-
sible for the difference in the solvent molecule effect on the
crystal growth surface.
Fig. 5 Electrostatic potential (ESP) maps and partial ESP changes on
the O/P/H atoms of molecules. 4.3 Prediction of the crystal morphology in solvent systems
To investigate the interaction between the solvent molecules
and four different crystal faces of XBPO, a parameter S is in-
positive charge accumulation. The solvent molecule would troduced to quantitatively describe the roughness of the crys-
adopt the optimal orientation to match the potential distribu- tal surface. The S is calculated using the following formula:
tion of the XBPO molecule, for example, the hydroxyl group
of the ethanol solvent molecule would interact with the S = Aacc/Ahkl (7)
positive-potential area of the XBPO molecule. Alternatively,
the negative charge region in the XBPO molecule can electro- where Aacc is the solvent-accessible area and Ahkl is the sur-
statically interact with the positive charge region in the face area of the (h k l) face.42 Oblique views of the XBPO
solvent. habit faces represented by the Connolly surface are illus-
In order to further study the electrostatic potential distri- trated in Fig. 7. The red grid on surface of XBPO represents
bution of each dominant face of the XBPO crystal, a slice was the Connolly surface (solvent accessible area). It can be seen
added to the ESP model, in which the distributions of the that the solvent accessible areas are not the same, which is
ESP on every crystal face can be analyzed by the difference in due to the different molecular packing structures of the
the planar hue. As shown in Fig. 6, the slice diagrams of the XBPO faces. Table 3 lists the S values for the different habit
dominant crystal faces indicate the variations of the distribu- faces of XBPO. It can be noted that the (1 0 0) face has a min-
tions of the ESP caused by the different arrangements of mol- imum S value of 1.44, which verifies the morphological
smoothness of the (1 0 0) face, and thus it is difficult for the
solute molecules to enter this face. Hence, the (1 0 0) grows
very slowly and has a larger crystal morphology face. For
the (0 1 1) and (1 1 0) faces, the S values are quite large,

Fig. 7 Oblique views of the XBPO habit faces represented by the

Fig. 6 Slice diagrams of the dominant crystal faces generated from Connolly surface. The red grid on the XBPO crystal face denotes the
ESP maps. solvent accessible area.

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Table 3 The parameter S values for the dominant crystal faces of the
XBPO crystal

(h k l) Aacc (Å2) Ahkl (Å2) Abox (Å2) S

(1 0 0) 179.63 124.69 1122.21 1.44
(1 1 0) 349.10 195.89 1763.01 1.78
(0 1 1) 501.50 295.17 2656.53 1.70
(1 1 −1) 464.74 294.33 2648.97 1.58

indicating the rough topography of the crystal surface, which

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makes the adsorption behaviors more favorable.

The simulation results of the XBPO crystal morphology in
the two solvent systems are summarized in Table 4. The neg-
ative interaction energies between the solvents and the XBPO
crystal faces imply that the adsorptions of the solvent mole-
cules are exothermic processes. As indicated in Table 4, the
changes in the attachment energy (|Es|) of each crystal Fig. 8 The crystal habits of XBPO: (a) predicted and (b) experimental
results in acetone; (c) predicted and (d) experimental results in ethanol.
face are different because solvent molecules have different
interactions with different crystal faces. In the acetone sol-
vent, the (1 1 −1) face has the largest change in attachment
energy and the (1 0 0) face change is the smallest. The rank can be found that the crystal habits are significantly diverse
order of the change in attachment energy with different faces in different solvents. The morphology appears as a hexagonal
is (1 1 −1) > (0 1 1) > (1 1 0) > (1 0 0). In the ethanol solvent, block in acetone, whereas it displays a plate-like structure in
the (1 1 −1) face has the maximum change in attachment ethanol. Compared with the ethanol solvent, the crystal mor-
energy while the (1 1 0) face has the minimum value. Eatt phology in acetone is preferred, since the hexagonal block
changes can be listed in the order (1 1 −1) > (0 1 1) > (1 0 0) shape not only can benefit the downstream processing, such
> (1 1 0). The simulation results indicated that the (1 1 −1) as filtration and drying, but also can improve product
surface has the strongest interaction with the two solvents. flowability. The total area of the (1 1 −1) face is remarkably
Besides, the weakest adsorption surface is (1 0 0) in acetone increased in both solvents. It can be observed that the pre-
and (1 1 0) in ethanol. dicted results of the crystal morphology are in good agree-
The modified attachment energies ( Eatt ) of the XBPO ment with the observed experimental results.
habit faces are in the following sequence: (1 0 0) > (1 1 0) >
(1 1 −1) > (0 1 1) and (1 0 0) > (1 1 −1) > (0 1 1) > (1 1 0) 4.4 The interactions at the crystal–solvent interface
in acetone and ethanol solvents, respectively. Therefore, the 4.4.1 The hydrogen bonding forming ability. The hydrogen
(1 0 0) face has the slowest growth rate and has the largest bonding forming ability of solvent molecules on different
morphological importance in the acetone and ethanol sys- crystal faces has a significant impact on the crystal morphol-
tems. The (1 1 0) face has morphological importance in ace- ogy. Therefore, the radial distribution function (RDF) was
tone as it has a relatively slower growth rate, while it disap- employed to analyze the interactions between the solvents
pears in ethanol owing to its fastest growth rate. and the crystal growth interface. The RDF is a characteristic
The crystal habits of the XBPO crystals predicted using the physical quantity that reflects the microstructure of mate-
MAE model in acetone and ethanol solvents as well as the rials, which is widely used in studying specific interactions
corresponding experimental results are shown in Fig. 8. It such as hydrogen bonds and van der Waals forces. It is used

Table 4 Modified attachment energies and relative growth rates of the XBPO crystal habit faces in acetone and ethanola


Eatt 
Rhkl
Solvent (h k l) Etot Esurf Esol Eint Es Area (%)
Acetone (1 0 0) −3594.77 −386.23 −3135.58 −72.96 −11.68 −21.91 1.00 44.58
(1 1 0) −3376.56 −160.06 −3111.99 −104.51 −20.69 −42.70 1.95 19.80
(0 1 1) −3021.39 167.65 −2957.95 −231.09 −43.63 −53.69 2.45 —
(1 1 −1) −2921.55 458.61 −3073.82 −306.34 −53.74 −43.64 1.99 35.62
Ethanol (1 0 0) −2571.03 −386.23 −2040.17 −144.63 −23.15 −10.44 1.00 59.30
(1 1 0) −2226.51 −160.06 −2011.43 −55.02 −10.89 −52.50 5.03 —
(0 1 1) −2074.60 167.65 −1934.24 −308.01 −58.15 −39.17 3.75 —
(1 1 −1) −1823.81 458.61 −1900.78 −381.64 −66.96 −30.42 2.91 40.70
a
All energies are in kcal mol−1.

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to measure the probability density of another particle face can be also observed in the range of 3.1–5.0 Å and above
appearing at a distance around the reference particle. In gen- 5.0 Å representing the presence of strong vdW interactions
eral, the effective range of intermolecular short-range interac- and Coulomb interactions.
tions that include hydrogen bonding and van der Waals in- Hence, it can be concluded that the hydrogen bond-
teractions is considered to be within 3.1 Å and 3.1–5.0 Å, forming ability of solvents can affect the XBPO habits
respectively. Intermolecular long-range interactions usually through the (1 1 −1) face in depth. Further, the solvents with
refer to electrostatic interactions, which exhibit a large dis- a strong hydrogen bond formation ability can lead to a great
tance range of above 5.0 Å.43 The outermost layer of each area of the (1 1 −1) face.
dominant face of the XBPO crystal was chosen to plot the 4.4.2 The affinity degree model. The surface interfacial
RDF graphs because it is very close to the solvent molecules. roughness, as well as the diffusion capacity of solvent mole-
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Fig. 9 shows the RDF curves of the (1 1 −1) surface in the two cules on crystal surfaces, can strongly influence the growth
solvent systems, which consist of H and O atoms in the sol- mechanism and growth rates of crystal surfaces.18,37,47 In
vent and the XBPO molecules. The RDF results of the other other words, the crystal morphology is closely related to the
surfaces are illustrated in Fig. S2 of the ESI.† It should be relationship between solvent molecules and crystal faces.
noted that the first peak of acetone (H)-XBPO (O) appears at Therefore, an affinity degree model was proposed to quantita-
about 2.63 Å for the dominant crystal faces, which indicates tively describe the relationship between solvent molecules
that the hydrogen bond formed between the acetone mole- and the crystal surface. The affinity degree model is illus-
cule and the XBPO molecule is C–H⋯O, which belongs to a trated in Fig. 10. It not only considers the roughness and the
weak hydrogen bond.44 In contrast, the first sharp peak of attachment energy of the crystal face, but also takes into ac-
ethanol (H)-XBPO (O) is roughly present at 1.80 Å for differ- count the solvent factors such as the diffusion ability, adsorp-
ent crystal faces, which demonstrates that the existence of tion energy and number of adsorption sites. At a high affinity
strong hydrogen bonds is based on the protic properties of degree the crystal face has a large morphological importance,
ethanol. From the above results, the hydrogen bonding where the solvent inhibits the adsorption of the solute mole-
forming ability of ethanol molecules is stronger compared cule that results in the slow growth rate. At a lower affinity
with that of acetone molecules. This is well consistent with degree the crystal face grows fast and becomes less morpho-
the fact that the α value (the hydrogen bond donor capacity) logically important. The affinity degree can be calculated
of ethanol is 0.86, which is much larger than that of acetone using the following formula:
(0.08).45,46
Moreover, it is quite obvious that the peak representing ε = ϕSnAhklEads/AboxEatt (8)
strong hydrogen bonds between ethanol solvents and the (1 1
−1) face is sharper compared to the other crystal faces, which where ϕ is the diffusion factor of solvent molecules on differ-
can be attributed to the fact that the hydrogen bonding ent crystal faces, which is obtained from the diffusion coeffi-
forming ability of solvent molecules has a greater effect on cient (see Table S2 of the ESI† for details). S denotes the
the (1 1 −1) surface. Thus, the area proportion of the (1 1 −1) roughness of the crystal faces. n is the number of adsorption
face is remarkably increased in both solvents than that in a sites of solvent molecules, which is approximately equal to
vacuum. The difference is that there are strong hydrogen the number of XBPO molecules in the supercell surface layer.
bonds in ethanol and weak hydrogen bonds in acetone. The Eads stands for the adsorption energy of the single solvent
dissimilar hydrogen bond formation abilities lead to different molecule estimated from the energy value of high density ad-
proportions of the (1 1 −1) face, i.e., the face area of (1 1 −1) sorption sites.
is 35.62% in acetone and 40.70% in ethanol (Table 4). In the The field of adsorption sites on different crystal faces
acetone and ethanol solvents, the sharp peaks for the (1 1 −1) obtained using the adsorption locator module is exhibited in

Fig. 9 The RDF analysis of the solvent molecules and the (1 1 –1) surface of the XBPO crystal (a) corresponding to the acetone solvent and (b)
corresponding to the ethanol solvent.

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Fig. 10 The schematic diagram of the affinity degree model.

Published on 22 February 2019. Downloaded by Tianjin University on 6/17/2023 2:23:30 PM.

Fig. S3 and S4 of the ESI.† The more likely adsorption areas

are shown in green and the less likely sites appear red (the
Fig. 12 PXRD patterns of XBPO crystals. (a) The raw material, (b)
pink part indicates the constrained supercell surface layer). crystals in acetone, and (c) crystals in ethanol.
The results of the affinity degree calculation are depicted in
Fig. 11. The calculation details are displayed in Table S3 of
the ESI.† It can be seen that the affinity degree of the (1 0 0)
face is the largest in the two solvents. Therefore, the relation- the characteristic peaks of XBPO remain unchanged with re-
ship between solvent molecules and the (1 0 0) face is the spect to all solid forms. Furthermore, the PXRD patterns of
closest, resulting in the embedding of the solute molecule be- these crystals demonstrated similar diffraction peaks to the
ing hindered. This face eventually has the largest morpholog- simulated pattern of the XBPO (Fig. S5†). The changes in the
ical importance. Besides, the ε values of the faces decrease in intensity of some characteristic peaks can be attributed to
the order of (1 0 0) > (1 1 0) > (1 1 −1) > (0 1 1) in the ace- the higher crystal perfection or the different preferred orien-
 in
tone solvent, which correlates well with the order of Rhkl tations for the crystallized solid forms.50 Thus, the possibility
of any other polymorphs can be ruled out through the PXRD
Table 4. In the ethanol solvent, the (1 1 0) and (0 1 1) faces
analysis. The results suggested merely that habit modifica-
with smaller affinity degrees disappeared in the final growth
tions occurred when the XBPO crystals were recrystallized
morphology.
from acetone and ethanol, respectively.
From the above analysis, the affinity degree model includ-
ing the solvent molecules and crystal surfaces was found to
match well with the experimental results, which provided 5. Conclusion
new ideas for analyzing the solvent effect on crystal faces.
In this paper, we successfully predicted the crystal habits of
XBPO in acetone and ethanol solvent systems using a modi-
4.5 Solvent effects on crystal polymorphs fied attachment energy model. The molecular arrangement
Generally, the alterations in the crystal morphology may be and the ESP distribution of the dominant crystal faces
indicative of polymorphic transformation.48,49 Hence, to ex- resulted in different effects of solvent molecules on crystal
amine the crystal polymorphism, the samples were character- faces.
ized by PXRD. In the PXRD patterns as illustrated in Fig. 12, The (1 0 0) face is the most dominant morphological face
because its smooth surface can hinder embedding of external
molecules. The hydrogen bond-forming ability of solvents
plays the critical role between the solvents and the (1 1 −1)
face of the XBPO crystal, which results in the different mor-
phological importance of the (1 1 −1) face. A new affinity de-
gree model was proposed to deal with crystal morphologies
influenced by solvents, which offered support for the growth
of crystal faces.
In addition, the crystal habits of XBPO harvested in both
solvents are highly consistent with the predicted results. The
XBPO crystals in acetone have a preferred habit compared
with its habit in ethanol. The presence of any polymorphs
can be eliminated according to the PXRD characterization.
Thus, this study may guide solvent selection to obtain crys-
tals of desired morphologies and provide insight into the
mechanism responsible in solvent-induced crystal habit
Fig. 11 The results of the affinity degree of dominant crystal faces. modifications.

This journal is © The Royal Society of Chemistry 2019 CrystEngComm, 2019, 21, 2422–2430 | 2429
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Paper CrystEngComm

Conflicts of interest 20 C. Dursun, M. Degirmenci, Y. Yagci, S. Jockusch and N. J.

Turro, Polymer, 2003, 44, 7389–7396.
There are no conflicts to declare. 21 J. A. Deverell, T. Rodemann, J. A. Smith, A. J. Canty and
R. M. Guijt, Sens. Actuators, B, 2011, 155, 388–396.
Acknowledgements 22 Y. Lin and J. W. Stansbury, Polymer, 2003, 44, 4781–4789.
23 Z. Wang, Q. Yu, Y. Liu, J. Zhao, Z. Lü and J. Sun, J. Chem.
The authors acknowledge the financial support from the Na- Eng. Data, 2012, 57, 3340–3343.
tional Natural Science Foundation of China (No. 21776203 and 24 P. P. Albuquerque, A. D. Moreira, R. R. Moraes, L. M.
21576187) and the Natural Science Foundation of Tianjin Munic- Cavalcante and L. F. Schneider, J. Dent., 2013, 41(Suppl 3),
ipal Science and Technology Commission (No. 18JCYBJC21100). e67–e72.
Published on 22 February 2019. Downloaded by Tianjin University on 6/17/2023 2:23:30 PM.

25 C. T. Meereis, F. B. Leal, G. S. Lima, R. V. de Carvalho, E.

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