Polymorphism of methyl 4-amino-3-phenyl­iso­thia­zole-5-car­box­yl­ate: an experimental and theoretical study

Shishkina, S.V.; Konovalova, I.S.; Kovalenko, S.M.; Kravchenko, D.V.; Bunyatyan, N.D.

doi:10.1107/S2053229620016356

Polymorphism of methyl 4-amino-3-phenylisothiazole-5-carboxylate: an experimental and theoretical study

S. V. Shishkina, I. S. Konovalova, S. M. Kovalenko, D. V. Kravchenko and N. D. Bunyatyan

Being a close analogue of amflutizole, methyl 4-amino-3-phenylisothiazole-5-carboxylate (C₁₁H₁₀N₂O₂S) was assumed to be capable of forming polymorphic structures. Noncentrosymmetric and centrosymmetric polymorphs have been obtained by crystallization from a series of more volatile solvents and from denser tetrachloromethane, respectively. Identical conformations of the molecule are found in both structures. The two polymorphs differ mainly in the intermolecular interactions formed by the amino group and in the type of stacking interactions between the π-systems. The most effective method for revealing packing motifs in structures with intermolecular interactions of different types (hydrogen bonding, stacking, dispersion, etc.) is to study the pairwise interaction energies using quantum chemical calculations. Molecules form a column as the primary basic structural motif due to stacking interactions in both polymorphic structures under study. The character of a column (straight or zigzag) is determined by the orientations of the stacked molecules (in a `head-to-head' or `head-to-tail' manner). Columns bound by intermolecular N—H

O and N—H

N hydrogen bonds form a double column as the main structural motif in the noncentrosymmetric structure. Double columns in the noncentrosymmetric structure and columns in the centrosymmetric structure interact strongly within the ab crystallographic plane, forming a layer as a secondary basic structural motif. The noncentrosymmetric structure has a lower density and a lower (by 0.59 kJ mol⁻¹) lattice energy, calculated using periodic calculations, compared to the centrosymmetric structure.

Keywords: polymorphism; ester; isothiazole; crystal structure; pairwise interaction energies; periodic calculations; amflutizole analogue; quantum chemical calculations.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229620016356/vp3011sup1.cif Contains datablocks 1a, 1b, global
	Structure factor file (CIF format) https://doi.org/10.1107/S2053229620016356/vp30111asup2.hkl Contains datablock 1a
	Structure factor file (CIF format) https://doi.org/10.1107/S2053229620016356/vp30111bsup3.hkl Contains datablock 1b
	Portable Document Format (PDF) file https://doi.org/10.1107/S2053229620016356/vp3011sup4.pdf Supplementary material

CCDC references: 2039220; 2039221

Computing details top

For both structures, data collection: CrysAlis PRO (Rigaku OD, 2018); cell refinement: CrysAlis PRO (Rigaku OD, 2018); data reduction: CrysAlis PRO (Rigaku OD, 2018); program(s) used to solve structure: SHELXT2014 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2016 (Sheldrick, 2015b); molecular graphics: Mercury (Macrae et al., 2020); software used to prepare material for publication: SHELXL2016 (Sheldrick, 2015b).

Methyl 4-amino-3-phenylisothiazole-5-carboxylate (1a) top

Crystal data top

C₁₁H₁₀N₂O₂S	D_x = 1.459 Mg m⁻³
M_r = 234.27	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P2₁2₁2₁	Cell parameters from 1316 reflections
a = 3.9876 (5) Å	θ = 3.8–21.7°
b = 10.6511 (13) Å	µ = 0.29 mm⁻¹
c = 25.107 (2) Å	T = 293 K
V = 1066.3 (2) Å³	Plate, colorless
Z = 4	0.20 × 0.15 × 0.08 mm
F(000) = 488

Data collection top

Rigaku Xcalibur Sapphire3 diffractometer	1884 independent reflections
Radiation source: Enhance (Mo) X-ray Source	1448 reflections with I > 2σ(I)
Detector resolution: 16.1827 pixels mm^-1	R_int = 0.069
ω scans	θ_max = 25.0°, θ_min = 3.3°
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD, 2018)	h = −4→4
T_min = 0.108, T_max = 1.000	k = −12→10
7448 measured reflections	l = −25→29

Refinement top

Refinement on F²	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.055	w = 1/[σ²(F_o²) + (0.0835P)²] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.161	(Δ/σ)_max = 0.001
S = 1.08	Δρ_max = 0.32 e Å⁻³
1884 reflections	Δρ_min = −0.27 e Å⁻³
154 parameters	Absolute structure: Flack x determined using 447 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
0 restraints	Absolute structure parameter: −0.05 (12)

Special details top

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

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

	x	y	z	U_iso*/U_eq
S1	0.2394 (4)	0.35815 (11)	0.54763 (5)	0.0668 (5)
O1	0.5651 (12)	0.5782 (4)	0.43313 (14)	0.0764 (12)
O2	0.2700 (12)	0.3981 (3)	0.43330 (12)	0.0717 (10)
N1	0.3181 (13)	0.4133 (4)	0.60720 (15)	0.0676 (12)
N2	0.6782 (13)	0.6802 (4)	0.5394 (2)	0.0659 (12)
H2NA	0.751 (17)	0.690 (6)	0.510 (2)	0.09 (2)*
H2NB	0.829 (16)	0.719 (6)	0.562 (2)	0.080 (19)*
C1	0.4647 (13)	0.5246 (5)	0.60441 (19)	0.0585 (12)
C2	0.5288 (12)	0.5695 (5)	0.55133 (19)	0.0562 (11)
C3	0.4080 (13)	0.4835 (5)	0.51442 (18)	0.0584 (13)
C4	0.4257 (13)	0.4936 (5)	0.4571 (2)	0.0616 (12)
C5	0.277 (2)	0.3949 (6)	0.37640 (19)	0.0851 (18)
H5A	0.182862	0.471159	0.362582	0.128*
H5B	0.148297	0.324580	0.363958	0.128*
H5C	0.504661	0.386723	0.364444	0.128*
C6	0.5616 (13)	0.5909 (5)	0.65374 (18)	0.0599 (13)
C7	0.7137 (16)	0.5273 (5)	0.69520 (19)	0.0707 (14)
H7	0.760580	0.442141	0.691773	0.085*
C8	0.7962 (19)	0.5891 (6)	0.74152 (19)	0.0802 (17)
H8	0.895947	0.544633	0.769183	0.096*
C9	0.7354 (18)	0.7131 (6)	0.74764 (19)	0.0799 (16)
H9	0.794107	0.753853	0.779057	0.096*
C10	0.5842 (16)	0.7788 (6)	0.7064 (2)	0.0811 (17)
H10	0.540439	0.864097	0.710404	0.097*
C11	0.4979 (17)	0.7193 (5)	0.6596 (2)	0.0706 (15)
H11	0.397894	0.764232	0.632133	0.085*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0790 (9)	0.0541 (8)	0.0673 (8)	−0.0041 (8)	0.0023 (8)	0.0014 (5)
O1	0.101 (3)	0.062 (2)	0.066 (2)	−0.006 (2)	0.013 (2)	0.0047 (19)
O2	0.092 (3)	0.064 (2)	0.0594 (18)	−0.004 (2)	−0.0054 (19)	−0.0047 (16)
N1	0.086 (3)	0.054 (3)	0.063 (2)	−0.002 (2)	0.007 (2)	0.0063 (19)
N2	0.075 (3)	0.054 (3)	0.068 (3)	−0.010 (2)	0.001 (2)	0.003 (2)
C1	0.063 (3)	0.051 (3)	0.062 (3)	0.008 (2)	0.000 (2)	0.004 (2)
C2	0.053 (3)	0.051 (3)	0.064 (3)	0.003 (2)	0.000 (2)	0.005 (2)
C3	0.063 (3)	0.055 (3)	0.057 (3)	0.004 (2)	0.001 (2)	0.000 (2)
C4	0.068 (3)	0.057 (3)	0.059 (3)	0.007 (2)	0.002 (2)	−0.001 (2)
C5	0.106 (5)	0.090 (4)	0.059 (3)	0.004 (4)	−0.010 (3)	−0.006 (3)
C6	0.058 (3)	0.061 (3)	0.061 (3)	−0.003 (2)	−0.001 (2)	0.002 (2)
C7	0.076 (4)	0.072 (4)	0.064 (3)	0.000 (3)	−0.003 (3)	0.009 (2)
C8	0.089 (4)	0.092 (5)	0.059 (3)	−0.006 (4)	−0.009 (3)	0.000 (3)
C9	0.089 (4)	0.092 (5)	0.059 (3)	−0.018 (4)	−0.005 (3)	−0.008 (3)
C10	0.099 (4)	0.065 (4)	0.079 (3)	−0.011 (3)	0.009 (3)	−0.009 (3)
C11	0.086 (4)	0.060 (4)	0.066 (3)	0.009 (3)	0.001 (3)	0.001 (2)

Geometric parameters (Å, º) top

S1—N1	1.637 (4)	C5—H5B	0.9600
S1—C3	1.711 (5)	C5—H5C	0.9600
O1—C4	1.219 (6)	C6—C7	1.382 (7)
O2—C4	1.334 (6)	C6—C11	1.399 (7)
O2—C5	1.429 (6)	C7—C8	1.376 (7)
N1—C1	1.323 (6)	C7—H7	0.9300
N2—C2	1.354 (7)	C8—C9	1.352 (9)
N2—H2NA	0.80 (6)	C8—H8	0.9300
N2—H2NB	0.92 (7)	C9—C10	1.387 (8)
C1—C2	1.439 (6)	C9—H9	0.9300
C1—C6	1.477 (7)	C10—C11	1.379 (7)
C2—C3	1.390 (7)	C10—H10	0.9300
C3—C4	1.444 (7)	C11—H11	0.9300
C5—H5A	0.9600

N1—S1—C3	95.1 (2)	O2—C5—H5C	109.5
C4—O2—C5	117.2 (4)	H5A—C5—H5C	109.5
C1—N1—S1	111.0 (3)	H5B—C5—H5C	109.5
C2—N2—H2NA	119 (5)	C7—C6—C11	118.6 (5)
C2—N2—H2NB	123 (4)	C7—C6—C1	120.8 (5)
H2NA—N2—H2NB	105 (6)	C11—C6—C1	120.6 (5)
N1—C1—C2	115.2 (4)	C8—C7—C6	120.5 (6)
N1—C1—C6	119.9 (4)	C8—C7—H7	119.8
C2—C1—C6	124.8 (5)	C6—C7—H7	119.8
N2—C2—C3	125.4 (5)	C9—C8—C7	121.4 (6)
N2—C2—C1	124.9 (5)	C9—C8—H8	119.3
C3—C2—C1	109.7 (5)	C7—C8—H8	119.3
C2—C3—C4	126.7 (5)	C8—C9—C10	119.1 (5)
C2—C3—S1	109.0 (4)	C8—C9—H9	120.5
C4—C3—S1	124.2 (4)	C10—C9—H9	120.5
O1—C4—O2	123.7 (5)	C11—C10—C9	120.8 (6)
O1—C4—C3	124.8 (5)	C11—C10—H10	119.6
O2—C4—C3	111.6 (5)	C9—C10—H10	119.6
O2—C5—H5A	109.5	C10—C11—C6	119.7 (5)
O2—C5—H5B	109.5	C10—C11—H11	120.2
H5A—C5—H5B	109.5	C6—C11—H11	120.2

C3—S1—N1—C1	0.8 (4)	S1—C3—C4—O1	−174.8 (4)
S1—N1—C1—C2	−1.6 (6)	C2—C3—C4—O2	−176.6 (5)
S1—N1—C1—C6	−179.3 (4)	S1—C3—C4—O2	5.1 (7)
N1—C1—C2—N2	−179.5 (5)	N1—C1—C6—C7	43.4 (8)
C6—C1—C2—N2	−1.9 (8)	C2—C1—C6—C7	−134.1 (6)
N1—C1—C2—C3	1.7 (7)	N1—C1—C6—C11	−135.9 (6)
C6—C1—C2—C3	179.3 (5)	C2—C1—C6—C11	46.6 (8)
N2—C2—C3—C4	1.7 (9)	C11—C6—C7—C8	0.9 (9)
C1—C2—C3—C4	−179.5 (5)	C1—C6—C7—C8	−178.5 (6)
N2—C2—C3—S1	−179.8 (5)	C6—C7—C8—C9	−0.8 (11)
C1—C2—C3—S1	−1.1 (5)	C7—C8—C9—C10	0.5 (11)
N1—S1—C3—C2	0.2 (4)	C8—C9—C10—C11	−0.3 (11)
N1—S1—C3—C4	178.7 (5)	C9—C10—C11—C6	0.4 (10)
C5—O2—C4—O1	1.6 (8)	C7—C6—C11—C10	−0.7 (9)
C5—O2—C4—C3	−178.3 (5)	C1—C6—C11—C10	178.7 (5)
C2—C3—C4—O1	3.4 (9)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2NA···O1	0.80 (6)	2.39 (6)	2.917 (6)	124 (6)
N2—H2NA···N2ⁱ	0.80 (6)	2.52 (6)	3.179 (8)	141 (6)
N2—H2NB···O1ⁱ	0.92 (7)	2.36 (7)	3.078 (6)	135 (5)

Symmetry code: (i) x+1/2, −y+3/2, −z+1.

Methyl 4-amino-3-phenylisothiazole-5-carboxylate (1b) top

Crystal data top

C₁₁H₁₀N₂O₂S	D_x = 1.466 Mg m⁻³
M_r = 234.27	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbca	Cell parameters from 1207 reflections
a = 6.9210 (9) Å	θ = 4.1–23.2°
b = 7.2371 (17) Å	µ = 0.29 mm⁻¹
c = 42.396 (8) Å	T = 293 K
V = 2123.5 (7) Å³	Stick, colourless
Z = 8	0.20 × 0.05 × 0.05 mm
F(000) = 976

Data collection top

Rigaku Xcalibur Sapphire3 diffractometer	1868 independent reflections
Radiation source: Enhance (Mo) X-ray Source	1262 reflections with I > 2σ(I)
Detector resolution: 16.1827 pixels mm^-1	R_int = 0.105
ω scans	θ_max = 25.0°, θ_min = 3.1°
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD, 2018)	h = −8→7
T_min = 0.373, T_max = 1.000	k = −8→8
13405 measured reflections	l = −50→46

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.056	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.146	w = 1/[σ²(F_o²) + (0.063P)²] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max = 0.001
1868 reflections	Δρ_max = 0.26 e Å⁻³
154 parameters	Δρ_min = −0.32 e Å⁻³

Special details top

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

	x	y	z	U_iso*/U_eq
S1	0.42918 (11)	0.59107 (14)	0.57558 (2)	0.0505 (3)
O1	0.9859 (3)	0.6044 (3)	0.55881 (6)	0.0570 (7)
O2	0.7258 (3)	0.6860 (4)	0.53025 (5)	0.0567 (7)
N1	0.3778 (4)	0.5226 (4)	0.61153 (6)	0.0466 (7)
N2	0.8945 (4)	0.4892 (5)	0.62263 (8)	0.0507 (8)
H2NA	1.005 (6)	0.504 (6)	0.6095 (11)	0.087 (14)*
H2NB	0.906 (5)	0.447 (4)	0.6411 (9)	0.050 (11)*
C1	0.5377 (4)	0.4890 (4)	0.62771 (8)	0.0383 (8)
C2	0.7147 (4)	0.5166 (4)	0.61061 (7)	0.0376 (8)
C3	0.6725 (4)	0.5760 (4)	0.58047 (7)	0.0395 (8)
C4	0.8140 (5)	0.6202 (5)	0.55628 (8)	0.0444 (8)
C5	0.8505 (6)	0.7393 (5)	0.50457 (9)	0.0676 (12)
H5A	0.918208	0.632711	0.496880	0.101*
H5B	0.941971	0.829417	0.511872	0.101*
H5C	0.774296	0.791444	0.487871	0.101*
C6	0.5208 (4)	0.4307 (4)	0.66074 (8)	0.0392 (8)
C7	0.3810 (5)	0.3026 (4)	0.66978 (9)	0.0487 (9)
H7	0.297328	0.253813	0.654777	0.058*
C8	0.3661 (6)	0.2480 (5)	0.70069 (9)	0.0529 (9)
H8	0.271709	0.162904	0.706452	0.063*
C9	0.4882 (6)	0.3172 (5)	0.72311 (9)	0.0575 (10)
H9	0.478398	0.277382	0.743911	0.069*
C10	0.6267 (5)	0.4466 (5)	0.71482 (9)	0.0514 (9)
H10	0.708180	0.496064	0.730091	0.062*
C11	0.6431 (5)	0.5016 (4)	0.68392 (8)	0.0447 (8)
H11	0.737122	0.587405	0.678373	0.054*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0392 (5)	0.0746 (7)	0.0378 (6)	0.0036 (4)	0.0012 (4)	0.0091 (5)
O1	0.0384 (13)	0.0772 (17)	0.0553 (18)	0.0025 (13)	0.0042 (12)	0.0094 (13)
O2	0.0476 (13)	0.0870 (19)	0.0354 (14)	0.0057 (13)	0.0112 (11)	0.0155 (13)
N1	0.0425 (16)	0.0628 (18)	0.0344 (17)	0.0012 (14)	0.0019 (13)	0.0047 (15)
N2	0.0399 (18)	0.074 (2)	0.038 (2)	−0.0018 (17)	−0.0002 (15)	0.0025 (18)
C1	0.0399 (19)	0.0397 (17)	0.035 (2)	0.0024 (15)	0.0020 (14)	0.0002 (16)
C2	0.0371 (17)	0.0383 (17)	0.0374 (19)	−0.0015 (15)	−0.0007 (15)	−0.0054 (15)
C3	0.0411 (18)	0.0488 (19)	0.0285 (18)	0.0028 (16)	0.0010 (14)	0.0009 (15)
C4	0.043 (2)	0.050 (2)	0.040 (2)	−0.0011 (17)	0.0048 (16)	0.0000 (16)
C5	0.067 (2)	0.092 (3)	0.044 (2)	0.003 (2)	0.023 (2)	0.023 (2)
C6	0.0440 (18)	0.0403 (17)	0.033 (2)	0.0053 (16)	0.0019 (15)	−0.0003 (15)
C7	0.0491 (19)	0.052 (2)	0.045 (2)	−0.0077 (18)	0.0061 (16)	−0.0009 (17)
C8	0.061 (2)	0.054 (2)	0.044 (2)	−0.0070 (18)	0.0157 (19)	0.0036 (18)
C9	0.074 (3)	0.060 (2)	0.038 (3)	0.013 (2)	0.011 (2)	0.006 (2)
C10	0.058 (2)	0.056 (2)	0.040 (2)	0.0051 (19)	−0.0040 (17)	−0.0039 (18)
C11	0.0473 (19)	0.0484 (19)	0.038 (2)	−0.0044 (17)	0.0044 (16)	−0.0001 (17)

Geometric parameters (Å, º) top

S1—N1	1.642 (3)	C5—H5B	0.9600
S1—C3	1.701 (3)	C5—H5C	0.9600
O1—C4	1.200 (4)	C6—C7	1.394 (4)
O2—C4	1.348 (4)	C6—C11	1.395 (5)
O2—C5	1.442 (4)	C7—C8	1.373 (5)
N1—C1	1.324 (4)	C7—H7	0.9300
N2—C2	1.360 (4)	C8—C9	1.367 (5)
N2—H2NA	0.95 (5)	C8—H8	0.9300
N2—H2NB	0.85 (4)	C9—C10	1.386 (5)
C1—C2	1.438 (4)	C9—H9	0.9300
C1—C6	1.467 (5)	C10—C11	1.374 (4)
C2—C3	1.379 (4)	C10—H10	0.9300
C3—C4	1.453 (4)	C11—H11	0.9300
C5—H5A	0.9600

N1—S1—C3	94.70 (14)	O2—C5—H5C	109.5
C4—O2—C5	116.2 (3)	H5A—C5—H5C	109.5
C1—N1—S1	110.8 (2)	H5B—C5—H5C	109.5
C2—N2—H2NA	120 (3)	C7—C6—C11	118.2 (3)
C2—N2—H2NB	119 (2)	C7—C6—C1	120.6 (3)
H2NA—N2—H2NB	121 (4)	C11—C6—C1	121.2 (3)
N1—C1—C2	115.2 (3)	C8—C7—C6	120.4 (3)
N1—C1—C6	118.7 (3)	C8—C7—H7	119.8
C2—C1—C6	126.1 (3)	C6—C7—H7	119.8
N2—C2—C3	125.9 (3)	C9—C8—C7	120.8 (3)
N2—C2—C1	124.8 (3)	C9—C8—H8	119.6
C3—C2—C1	109.3 (3)	C7—C8—H8	119.6
C2—C3—C4	125.4 (3)	C8—C9—C10	119.9 (4)
C2—C3—S1	110.0 (2)	C8—C9—H9	120.0
C4—C3—S1	124.6 (2)	C10—C9—H9	120.0
O1—C4—O2	123.8 (3)	C11—C10—C9	119.6 (3)
O1—C4—C3	125.7 (3)	C11—C10—H10	120.2
O2—C4—C3	110.5 (3)	C9—C10—H10	120.2
O2—C5—H5A	109.5	C10—C11—C6	121.0 (3)
O2—C5—H5B	109.5	C10—C11—H11	119.5
H5A—C5—H5B	109.5	C6—C11—H11	119.5

C3—S1—N1—C1	0.4 (3)	S1—C3—C4—O1	−177.2 (3)
S1—N1—C1—C2	−0.8 (4)	C2—C3—C4—O2	−175.8 (3)
S1—N1—C1—C6	178.5 (2)	S1—C3—C4—O2	4.0 (4)
N1—C1—C2—N2	−179.6 (3)	N1—C1—C6—C7	42.1 (4)
C6—C1—C2—N2	1.2 (5)	C2—C1—C6—C7	−138.8 (3)
N1—C1—C2—C3	0.8 (4)	N1—C1—C6—C11	−137.7 (3)
C6—C1—C2—C3	−178.4 (3)	C2—C1—C6—C11	41.4 (5)
N2—C2—C3—C4	−0.2 (5)	C11—C6—C7—C8	−0.3 (5)
C1—C2—C3—C4	179.4 (3)	C1—C6—C7—C8	179.8 (3)
N2—C2—C3—S1	−180.0 (3)	C6—C7—C8—C9	−0.3 (5)
C1—C2—C3—S1	−0.4 (3)	C7—C8—C9—C10	1.2 (6)
N1—S1—C3—C2	0.0 (2)	C8—C9—C10—C11	−1.4 (5)
N1—S1—C3—C4	−179.8 (3)	C9—C10—C11—C6	0.8 (5)
C5—O2—C4—O1	−0.2 (5)	C7—C6—C11—C10	0.1 (5)
C5—O2—C4—C3	178.6 (3)	C1—C6—C11—C10	180.0 (3)
C2—C3—C4—O1	3.0 (6)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2NA···O1	0.95 (5)	2.27 (5)	2.901 (5)	123 (3)
N2—H2NA···N1ⁱ	0.95 (5)	2.58 (4)	3.386 (4)	142 (4)

Symmetry code: (i) x+1, y, z.

Some characteristics of the solvents used for crystallization of compound 1 top

Solvent	Boiling point (°C)	Density (Mg m^-3)	Dipole moment (D)
Isopropanol	82.4	0.785	1.66
Methanol	64.7	0.792	1.65
Ethylacetate	77.1	0.902	1.78
Tetrahydrofuran	66.0	0.888	1.63
Acetonitrile	81.3	0.786	3.92
Tetrachloromethane	76.7	1.587	0

Selected geometric parameters for molecule 1 in polymorphic crystals 1a and 1b top

Parameter	Polymorph 1a	Polymorph 1r
Bond length (Å)
N1—C1	1.324 (7)	1.325 (4)
C2—C3	1.389 (7)	1.379 (4)
C1—C2	1.439 (7)	1.437 (4)
C3—C4	1.445 (7)	1.454 (4)
C2—N2	1.355 (7)	1.359 (4)
C4—O1	1.218 (7)	1.200 (4)
C1—C6	1.477 (7)	1.467 (5)
ΣN2 (deg)	348	359

Torsion angle (°)
C2—C3—C4—O1	3.4 (9)	3.0 (5)
C2—C1—C6—C11	46.6 (8)	41.4 (5)
O1—C4—O2—C5	1.6 (8)	-0.2 (5)

N2—H···O1 intramolecular hydrogen bond
H···O (Å)	2.39 (6)	2.27 (5)
N—H···O (°)	125 (5)	123 (3)

Short intramolecular contacts (Å)
C11···N2	3.130 (7)	3.128 (5)
C11···H2Nb	2.78 (5)	2.60 (4)
H11···H2Nb		2.21

Geometric characteristics (Å, °) of the intermolecular hydrogen bonds and stacking interactions in the different polymorphic crystals of compound 1 top

Interaction	Symmetry operation	Geometric characteristics
		H···A	D—H···A
Polymorph 1a
N2—H2NA···N2(lp)	x+1/2, -y+3/2, -z+1	2.52 (6)	140 (5)
N2—H2NB···O1	x+1/2, -y+3/2, -z+1	2.36 (6)	134 (5)
Stacking isothiazole–isothiazole	x+1, y, z	Distance between mean planes is 3.56 Å Plane-to-plane shift is 1.806 Å
Stacking phenyl–phenyl	x+1, y, z	Distance between mean planes is 3.59 Å Plane-to-plane shift is 1.735 Å

Polymorph 1b
N2—H2NA···N1	x+1, y, z	2.59 (4)	142 (3)
Stacking isothiazole–isothiazole	x+1, y, z	Distance between mean planes is 3.45 Å Plane-to-plane shift is 1.194 Å

Symmetry codes, interaction energies of the basic unit with neighbouring ones (E_int, kJ mol^-1) with the highest values (more than 5% of the total interaction energy) and the contribution of this energy to the total interaction energy (%) in polymorphic crystals 1a (for the full list of dimers, see Tables S1 in the supporting information) top

Dimer	Symmetry operation	E_int	Contribution to the total interaction energy	Type of interaction
d1	x-1, y, z	-53.09	20.0	Stacking
d2	x+1, y, z	-53.09	20.0	Stacking
d3	x+1/2, -y+3/2, -z+1	-30.73	11.6	N—H···O/N—H···N
d4	x-1/2, -y+3/2, -z+1	-30.73	11.6	N—H···O/N—H···N
d5	x+1/2, -y+1/2, -z+1	-20.14	7.6	Dispersion
d6	x-1/2, -y+1/2, -z+1	-20.14	7.6	Dispersion

Symmetry codes, interaction energies of the basic molecule with neighbouring ones (E_int, kJ mol^-1) with the highest values (more than 5% of the total interaction energy) and the contribution of this energy to the total interaction energy (%) in polymorphic crystals 1b (for the full list of dimers, see Tables S2 in the supporting information) top

Dimer	Symmetry operation	E_int	Contribution to the total interaction energy	Type of interaction
d1	-x+3/2, y-1/2, z	-53.97	21.2	Stacking
d2	-x+3/2, y+1/2, z	-53.97	21.2	Stacking
d3	-x+1/2, y+1/2, z	-22.69	8.9	Dispersion
d4	-x+1/2, y-1/2, z	-22.69	8.9	Dispersion
d5	x+1, y, z	-20.05	7.9	N—H···N
d6	x-1, y, z	-20.05	7.9	N—H···N

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Polymorphism of methyl 4-amino-3-phenyl­iso­thia­zole-5-car­box­yl­ate: an experimental and theoretical study

Supporting information

Polymorphism of methyl 4-amino-3-phenylisothiazole-5-carboxylate: an experimental and theoretical study