Supporting materials
On the origin of benzoic acid crystals morphology trimming
by surfaces through droplet evaporation
Piotr Cysewski1,3*, Maciej Przybyłek1, Tomasz Miernik1,
Mirosław Kobierski2, Dorota Ziółkowska3
1Department of Physical Chemistry, Collegium Medicum of Bydgoszcz, Nicolaus Copernicus University in Toruń, Kurpińskiego 5, 85-950 Bydgoszcz, Poland; ; 2University of Technology And Life Sciences in Bydgoszcz, Faculty of Agriculture and Biotechnology, Department of Land Reclamation and Agrometeorology, Bernardyńska 6, 85-029 Bydgoszcz, Poland; 3University of Technology and Life Sciences in Bydgoszcz, Faculty of Chemical Technology and Engineering, ul. Seminaryjna 3, 85-326 Bydgoszcz
Table S1. Structure of optimized benzoic acid crystals using periodic boundary conditions on PBE/DNP/ level including correction for dispersion interaction according DFT-D3 Grimme protocol.
a) a=5.52, b=5.14, c= 21.9, alpha= 90.0, beta=97.0, gamma=90.0
BENZAC form A / BENZAC form BO1 0.22955 0.24452 0.01165
O2 -0.08315 0.12910 0.06412
C1 0.09759 0.26811 0.05811
C2 0.18051 0.47579 0.10283
C7 0.38616 0.62952 0.09587
C6 0.45854 0.82485 0.13863
C5 0.32686 0.86730 0.18854
C4 0.12180 0.71409 0.19558
C3 0.04879 0.51936 0.15290
H6 0.48772 0.90362 0.55698
H5 0.61733 0.55582 0.63239
H4 0.38324 0.47877 0.72163
H3 0.01764 0.75203 0.73410
H2 -0.11139 1.10009 0.65727
H1 0.16433 1.40506 0.48310 / O2 0.20777 0.23546 0.01119
O1 -0.09214 0.13239 0.06897
C1 0.09899 0.27157 0.05716
C2 0.17552 0.47692 0.10316
C3 0.38214 0.62882 0.09609
C4 0.45672 0.82284 0.13899
C5 0.32610 0.86647 0.18906
C6 0.11977 0.71561 0.19609
C7 0.04469 0.52144 0.15337
H2 0.48230 0.90550 0.55691
H3 0.61631 0.55929 0.63293
H4 0.38464 0.48085 0.72231
H5 0.01618 0.74952 0.73465
H6 -0.11695 1.09469 0.65821
H1 -0.13181 1.50827 0.53594
b) a=5.51, b=5. 157, c=21.9730, alpha= 90.0, beta=97.41, gamma=90.0
BENZAC01 form A / BENZAC01 form BO1 0.22977 0.24467 0.01206
O2 -0.08157 0.12589 0.06419
C1 0.09883 0.26562 0.05844
C2 0.18223 0.47147 0.10351
C7 0.38839 0.62524 0.09724
C6 0.46118 0.81814 0.14045
C5 0.32944 0.85820 0.19012
C4 0.12384 0.70500 0.19645
C3 0.05048 0.51264 0.15335
H6 0.49018 0.59387 0.05858
H5 0.62044 0.93726 0.13478
H4 0.38616 1.01000 0.22361
H3 0.01996 0.73685 0.23482
H2 -0.11003 0.39321 0.15717
H1 0.16398 1.40365 0.48331 / O2 0.20740 0.23568 0.01160
O1 -0.09020 0.12835 0.06928
C1 0.10001 0.26901 0.05759
C2 0.17708 0.47264 0.10385
C3 0.38382 0.62481 0.09721
C4 0.45888 0.81718 0.14034
C5 0.32837 0.85923 0.19016
C6 0.12194 0.70807 0.19677
C7 0.04665 0.51526 0.15388
H2 0.48388 0.59152 0.05823
H3 0.61866 0.93516 0.13461
H4 0.38704 1.01088 0.22354
H5 0.01840 0.74177 0.23512
H6 -0.11509 0.39890 0.15836
H1 -0.13045 -0.01069 0.03609
c) a= 5.4996, b= 5.1283, c= 21.95, alpha= 90.0, beta= 97.37, gamma=90.0
BENZAC02 form A / BENZAC02 form BO1 0.23196 0.24348 0.01279
O2 -0.08165 0.12501 0.06454
C1 0.09993 0.26467 0.05905
C2 0.18330 0.47123 0.10432
C7 0.39082 0.62472 0.09834
C6 0.46311 0.81902 0.14155
C5 0.32983 0.86028 0.19101
C4 0.12311 0.70702 0.19709
C3 0.05010 0.51347 0.15394
H6 0.49392 0.59231 0.05986
H5 0.62292 0.93862 0.13595
H4 0.38616 1.01331 0.22447
H3 0.01789 0.73997 0.23526
H2 -0.11166 0.39449 0.15754
H1 0.16574 0.09531 -0.01627 / O2 0.20710 0.23729 0.01145
O1 -0.09147 0.13016 0.06918
C1 0.09952 0.27103 0.05750
C2 0.17762 0.47473 0.10397
C3 0.38606 0.62614 0.09762
C4 0.46321 0.81701 0.14129
C5 0.33327 0.85804 0.19140
C6 0.12476 0.70815 0.19761
C7 0.04723 0.51707 0.15414
H2 0.48573 0.59345 0.05844
H3 0.62469 0.93380 0.13589
H4 0.39443 1.00761 0.22536
H5 0.02186 0.74078 0.23620
H6 -0.11610 0.40181 0.15832
H1 -0.13195 1.50975 0.53600
Table S2 Energetically distinct contacts between benzoic acid molecules defining all possible pairs in crystals. All values of intermolecular interaction energies, ei, corresponds to M06-2X/ET-pVQZ computations.
pair / ni / ei [kJ/mol]1 / -x,-y,-z / 1 / -101.8±0.10
2 / x,1+y,z / 2 / -14.2±0.12
3 / 1-x,1-y,-z / 1 / -13.8±0.06
4 / -x,1-y,-z / 1 / -12.7±0.27
5 / -1+x,y,z / 2 / -9.4±0.06
6 / 1-x,1/2+y,1/2-z / 2 / -4.5±0.12
7 / -x,-1/2+y,1/2-z / 2 / -3.3±0.03
8 / 1+x,1+y,z / 2 / 3.5±0.01
9 / 1-x,-y,-z / 1 / -2.1±0.01
Elatt / -95.9±0.25
3