Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S010827010402150X/sq1169sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S010827010402150X/sq1169Iasup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S010827010402150X/sq1169Ibsup3.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S010827010402150X/sq1169Icsup4.hkl |
CCDC references: 257005; 257006; 257007
The title compound, (I), was synthesized by the reaction of 4-diethylaminobenzaldehyde with 2-cyanothioacetamide in the presence of a catalytic amount of morpholine in ethanol at room temperature. The precipitate was separated from the solution, and the structure and purity were investigated by NMR (m.p. 421–425 K, yield 83%). Probably, the reason for the large melting interval is the mixture of isomers present. After recrystallization from ethanol, only crystals of (Ia) (m.p. 424–425 K) were found. Crystals of (Ic) were obtained by slow isothermal evaporation from an acetonitrilic solution of (I). Compound (I) was used to synthesize a 2,4-disubstituted thiazole derivative, using DMF as a solvent. From one such reaction mixture were extracted two types of crystals with different shapes. X-ray analysis revealed that one of these forms was (Ia)? and another was a monoclinic modification, (Ib). All attempts to re-obtain polymorph (Ib), complex (Ic) and the literature polymorph (Id), using exactly the same conditions and variations of them, gave us only (Ia). Polymorph (Ia) is probably the most stable energetically. 1H NMR (CDCl3, 300 MHz): δ 8.65 (s, 1H, C7H), 7.96 (d, 2H, J = 9.2 Hz, C2, C6), 7.57 (br s, 1H, NH), 7.36 (br s, 1H, NH), 6.69 (d, 2H, J = 9.2 Hz, C3, C5), 3.47 (q, 4H, J = 7.1 Hz, 2CH2), 1.24 (t, 6H, J = 7.2 Hz, 2CH3). 13C NMR (CDCl3, 75 MHz): δ 193.6 (C=S), 158.1 (C7), 152.0 (C4), 134.9 (C2, C6), 119.3 (C1), 118.3 (C9), 111.3 (C3, C5), 98.7 (C8), 44.8 (2CH2), 12.5 (2CH3).
For all molecules of (Ia)–(Ic), H atoms were placed in calculated positions and included in the refinement using a riding model, with C—H or N—H distances of 0.93 Å for aromatic H atoms, 0.97 Å for CH2 atoms and 0.86 Å for NH2 atoms [Uiso(H) = 1.2Ueq(C,N)], and with C—H distances of 0.96 Å for CH3 groups [Uiso(H) = 1.5Ueq(C)]. The H atoms in the disordered acetonitrile molecule (which lies on a twofold axis) were found from a difference Fourier map and included using AFIX 33, with an occupancy of 0.5 and with C—H = 0.96 Å and Uiso(H) values of 1.5Ueq(C).
For all compounds, data collection: CAD-4 Software (Enraf–Nonuis, 1989); cell refinement: CAD-4 Software; data reduction: SHELXTL-Plus (Sheldrick, 1994); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL-Plus; software used to prepare material for publication: SHELXL97.
C14H17N3S | Z = 2 |
Mr = 259.38 | F(000) = 276 |
Triclinic, P1 | Dx = 1.220 Mg m−3 |
a = 8.753 (3) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 8.890 (3) Å | Cell parameters from 24 reflections |
c = 10.830 (4) Å | θ = 11–12° |
α = 85.44 (3)° | µ = 0.22 mm−1 |
β = 69.76 (2)° | T = 298 K |
γ = 63.65 (3)° | Plate, orange |
V = 705.8 (5) Å3 | 0.50 × 0.40 × 0.20 mm |
Enraf–Nonius CAD-4 diffractometer | Rint = 0.016 |
Radiation source: fine-focus sealed tube | θmax = 25.1°, θmin = 2.0° |
Graphite monochromator | h = 0→10 |
θ/2θ scans | k = −9→10 |
2639 measured reflections | l = −12→12 |
2465 independent reflections | 3 standard reflections every 97 reflections |
1811 reflections with I > 2σ(I) | intensity decay: 3% |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.035 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.098 | H-atom parameters constrained |
S = 1.00 | w = 1/[σ2(Fo2) + (0.06P)2] where P = (Fo2 + 2Fc2)/3 |
2465 reflections | (Δ/σ)max < 0.001 |
165 parameters | Δρmax = 0.15 e Å−3 |
0 restraints | Δρmin = −0.18 e Å−3 |
C14H17N3S | γ = 63.65 (3)° |
Mr = 259.38 | V = 705.8 (5) Å3 |
Triclinic, P1 | Z = 2 |
a = 8.753 (3) Å | Mo Kα radiation |
b = 8.890 (3) Å | µ = 0.22 mm−1 |
c = 10.830 (4) Å | T = 298 K |
α = 85.44 (3)° | 0.50 × 0.40 × 0.20 mm |
β = 69.76 (2)° |
Enraf–Nonius CAD-4 diffractometer | Rint = 0.016 |
2639 measured reflections | 3 standard reflections every 97 reflections |
2465 independent reflections | intensity decay: 3% |
1811 reflections with I > 2σ(I) |
R[F2 > 2σ(F2)] = 0.035 | 0 restraints |
wR(F2) = 0.098 | H-atom parameters constrained |
S = 1.00 | Δρmax = 0.15 e Å−3 |
2465 reflections | Δρmin = −0.18 e Å−3 |
165 parameters |
Experimental. 1H NMR (CDCl3, 300 MHz) δ 8.65 (s, 1H, C7H), 7.96 (d, 2H, J = 9.2 Hz, C2, C6), 7.57 (br s, 1H, NH), 7.36 (br s, 1H, NH), 6.69 (d, 2H, J = 9.2 Hz, C3, C5), 3.47 (q, 4H, J = 7.1 Hz, 2CH2), 1.24 (t, 6H, J = 7.2 Hz, 2CH3) p.p.m.. 13C NMR (CDCl3, 75 MHz) δ 193.6 (C=S), 158.1 (C7), 152.0 (C4), 134.9 (C2, C6), 119.3 (C1), 118.3 (C9), 111.3 (C3, C5), 98.7 (C8), 44.8 (2CH2), 12.5 (2CH3) p.p.m.. |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
S1 | 1.34596 (6) | 0.02000 (6) | 0.23115 (5) | 0.06403 (19) | |
N1 | 0.9459 (3) | 0.6025 (2) | 0.13473 (16) | 0.0829 (6) | |
N2 | 1.2768 (2) | 0.2136 (2) | 0.04250 (15) | 0.0717 (5) | |
H2A | 1.2133 | 0.3043 | 0.0136 | 0.086* | |
H2B | 1.3722 | 0.1349 | −0.0119 | 0.086* | |
N3 | 0.32237 (18) | 0.78661 (18) | 0.76587 (13) | 0.0560 (4) | |
C1 | 0.8086 (2) | 0.4485 (2) | 0.47908 (16) | 0.0489 (4) | |
C2 | 0.7254 (2) | 0.3960 (2) | 0.59772 (16) | 0.0564 (5) | |
H2C | 0.7800 | 0.2832 | 0.6133 | 0.068* | |
C3 | 0.5674 (2) | 0.5034 (2) | 0.69165 (17) | 0.0569 (5) | |
H3A | 0.5167 | 0.4618 | 0.7683 | 0.068* | |
C4 | 0.4797 (2) | 0.6764 (2) | 0.67435 (16) | 0.0495 (4) | |
C5 | 0.5639 (2) | 0.7303 (2) | 0.55641 (17) | 0.0597 (5) | |
H5A | 0.5117 | 0.8435 | 0.5415 | 0.072* | |
C6 | 0.7201 (2) | 0.6210 (2) | 0.46323 (17) | 0.0594 (5) | |
H6A | 0.7702 | 0.6621 | 0.3860 | 0.071* | |
C7 | 0.9722 (2) | 0.3269 (2) | 0.38408 (16) | 0.0488 (4) | |
H7A | 1.0257 | 0.2232 | 0.4158 | 0.059* | |
C8 | 1.0623 (2) | 0.33738 (19) | 0.25591 (16) | 0.0479 (4) | |
C9 | 0.9949 (2) | 0.4865 (2) | 0.19119 (17) | 0.0571 (5) | |
C10 | 1.2277 (2) | 0.1950 (2) | 0.17130 (17) | 0.0520 (4) | |
C11 | 0.2325 (2) | 0.7332 (2) | 0.88957 (17) | 0.0617 (5) | |
H11A | 0.2518 | 0.6191 | 0.8740 | 0.074* | |
H11B | 0.1027 | 0.8058 | 0.9182 | 0.074* | |
C12 | 0.3009 (3) | 0.7389 (3) | 0.9972 (2) | 0.0857 (7) | |
H12A | 0.2410 | 0.6992 | 1.0751 | 0.129* | |
H12B | 0.2760 | 0.8528 | 1.0166 | 0.129* | |
H12C | 0.4297 | 0.6684 | 0.9691 | 0.129* | |
C13 | 0.2428 (2) | 0.9689 (2) | 0.75219 (18) | 0.0582 (5) | |
H13A | 0.3404 | 1.0009 | 0.7109 | 0.070* | |
H13B | 0.1739 | 1.0286 | 0.8395 | 0.070* | |
C14 | 0.1208 (3) | 1.0228 (3) | 0.6723 (2) | 0.0759 (6) | |
H14A | 0.0712 | 1.1428 | 0.6688 | 0.114* | |
H14D | 0.0237 | 0.9917 | 0.7125 | 0.114* | |
H14C | 0.1893 | 0.9684 | 0.5843 | 0.114* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0421 (3) | 0.0609 (3) | 0.0601 (3) | 0.0007 (2) | −0.0123 (2) | −0.0145 (2) |
N1 | 0.0969 (14) | 0.0565 (10) | 0.0507 (9) | −0.0111 (9) | −0.0042 (9) | −0.0041 (8) |
N2 | 0.0513 (9) | 0.0687 (10) | 0.0508 (9) | −0.0015 (7) | 0.0020 (7) | −0.0105 (7) |
N3 | 0.0417 (7) | 0.0525 (8) | 0.0479 (8) | −0.0096 (6) | 0.0014 (6) | −0.0083 (6) |
C1 | 0.0400 (8) | 0.0450 (9) | 0.0461 (9) | −0.0103 (7) | −0.0066 (7) | −0.0076 (7) |
C2 | 0.0529 (10) | 0.0447 (9) | 0.0489 (10) | −0.0072 (8) | −0.0107 (8) | 0.0015 (7) |
C3 | 0.0528 (10) | 0.0532 (10) | 0.0417 (9) | −0.0132 (8) | −0.0036 (7) | 0.0017 (7) |
C4 | 0.0407 (8) | 0.0487 (9) | 0.0434 (9) | −0.0116 (7) | −0.0053 (7) | −0.0079 (7) |
C5 | 0.0544 (10) | 0.0389 (9) | 0.0559 (10) | −0.0102 (8) | 0.0019 (8) | −0.0021 (7) |
C6 | 0.0551 (10) | 0.0444 (9) | 0.0499 (10) | −0.0152 (8) | 0.0068 (8) | −0.0039 (7) |
C7 | 0.0394 (8) | 0.0432 (9) | 0.0499 (9) | −0.0085 (7) | −0.0109 (7) | −0.0063 (7) |
C8 | 0.0366 (8) | 0.0432 (9) | 0.0503 (9) | −0.0108 (7) | −0.0059 (7) | −0.0106 (7) |
C9 | 0.0557 (10) | 0.0503 (11) | 0.0425 (9) | −0.0142 (9) | −0.0004 (8) | −0.0117 (8) |
C10 | 0.0365 (8) | 0.0554 (10) | 0.0528 (10) | −0.0151 (7) | −0.0059 (7) | −0.0126 (8) |
C11 | 0.0430 (9) | 0.0698 (12) | 0.0511 (10) | −0.0187 (9) | 0.0028 (8) | −0.0109 (8) |
C12 | 0.0824 (15) | 0.1120 (18) | 0.0547 (12) | −0.0428 (14) | −0.0137 (11) | −0.0009 (12) |
C13 | 0.0421 (9) | 0.0508 (10) | 0.0594 (11) | −0.0098 (8) | −0.0024 (8) | −0.0165 (8) |
C14 | 0.0633 (12) | 0.0589 (12) | 0.0972 (16) | −0.0174 (10) | −0.0305 (12) | 0.0014 (10) |
S1—C10 | 1.669 (2) | C6—H6A | 0.9300 |
N1—C9 | 1.145 (2) | C7—C8 | 1.358 (2) |
N2—C10 | 1.330 (2) | C7—H7A | 0.9300 |
N2—H2A | 0.8600 | C8—C9 | 1.428 (3) |
N2—H2B | 0.8600 | C8—C10 | 1.476 (2) |
N3—C4 | 1.361 (2) | C11—C12 | 1.497 (3) |
N3—C11 | 1.463 (2) | C11—H11A | 0.9700 |
N3—C13 | 1.471 (2) | C11—H11B | 0.9700 |
C1—C2 | 1.399 (3) | C12—H12A | 0.9600 |
C1—C6 | 1.406 (3) | C12—H12B | 0.9600 |
C1—C7 | 1.435 (2) | C12—H12C | 0.9600 |
C2—C3 | 1.367 (3) | C13—C14 | 1.496 (3) |
C2—H2C | 0.9300 | C13—H13A | 0.9700 |
C3—C4 | 1.412 (3) | C13—H13B | 0.9700 |
C3—H3A | 0.9300 | C14—H14A | 0.9600 |
C4—C5 | 1.403 (3) | C14—H14D | 0.9600 |
C5—C6 | 1.361 (3) | C14—H14C | 0.9600 |
C5—H5A | 0.9300 | ||
C10—N2—H2A | 120.0 | C9—C8—C10 | 115.16 (15) |
C10—N2—H2B | 120.0 | N1—C9—C8 | 177.31 (18) |
H2A—N2—H2B | 120.0 | N2—C10—C8 | 115.65 (16) |
C4—N3—C11 | 121.94 (16) | N2—C10—S1 | 121.47 (13) |
C4—N3—C13 | 121.80 (15) | C8—C10—S1 | 122.88 (14) |
C11—N3—C13 | 115.99 (14) | N3—C11—C12 | 112.69 (16) |
C2—C1—C6 | 115.45 (15) | N3—C11—H11A | 109.1 |
C2—C1—C7 | 119.34 (16) | C12—C11—H11A | 109.1 |
C6—C1—C7 | 125.21 (16) | N3—C11—H11B | 109.1 |
C3—C2—C1 | 122.77 (17) | C12—C11—H11B | 109.1 |
C3—C2—H2C | 118.6 | H11A—C11—H11B | 107.8 |
C1—C2—H2C | 118.6 | C11—C12—H12A | 109.5 |
C2—C3—C4 | 121.18 (17) | C11—C12—H12B | 109.5 |
C2—C3—H3A | 119.4 | H12A—C12—H12B | 109.5 |
C4—C3—H3A | 119.4 | C11—C12—H12C | 109.5 |
N3—C4—C5 | 121.03 (16) | H12A—C12—H12C | 109.5 |
N3—C4—C3 | 122.66 (16) | H12B—C12—H12C | 109.5 |
C5—C4—C3 | 116.32 (15) | N3—C13—C14 | 113.52 (16) |
C6—C5—C4 | 121.66 (17) | N3—C13—H13A | 108.9 |
C6—C5—H5A | 119.2 | C14—C13—H13A | 108.9 |
C4—C5—H5A | 119.2 | N3—C13—H13B | 108.9 |
C5—C6—C1 | 122.61 (17) | C14—C13—H13B | 108.9 |
C5—C6—H6A | 118.7 | H13A—C13—H13B | 107.7 |
C1—C6—H6A | 118.7 | C13—C14—H14A | 109.5 |
C8—C7—C1 | 131.08 (16) | C13—C14—H14D | 109.5 |
C8—C7—H7A | 114.5 | H14A—C14—H14D | 109.5 |
C1—C7—H7A | 114.5 | C13—C14—H14C | 109.5 |
C7—C8—C9 | 121.42 (14) | H14A—C14—H14C | 109.5 |
C7—C8—C10 | 123.31 (16) | H14D—C14—H14C | 109.5 |
C6—C1—C2—C3 | 1.0 (3) | C7—C1—C6—C5 | 179.34 (17) |
C7—C1—C2—C3 | −178.50 (16) | C2—C1—C7—C8 | 167.98 (17) |
C1—C2—C3—C4 | −0.9 (3) | C6—C1—C7—C8 | −11.4 (3) |
C11—N3—C4—C5 | −179.88 (16) | C1—C7—C8—C9 | −1.9 (3) |
C13—N3—C4—C5 | −6.1 (3) | C1—C7—C8—C10 | −177.86 (16) |
C11—N3—C4—C3 | 0.1 (3) | C7—C8—C10—N2 | 166.16 (17) |
C13—N3—C4—C3 | 173.85 (16) | C9—C8—C10—N2 | −10.0 (2) |
C2—C3—C4—N3 | 179.99 (17) | C7—C8—C10—S1 | −13.1 (2) |
C2—C3—C4—C5 | 0.0 (3) | C9—C8—C10—S1 | 170.72 (13) |
N3—C4—C5—C6 | −179.14 (17) | C4—N3—C11—C12 | 87.8 (2) |
C3—C4—C5—C6 | 0.9 (3) | C13—N3—C11—C12 | −86.3 (2) |
C4—C5—C6—C1 | −0.8 (3) | C4—N3—C13—C14 | 86.9 (2) |
C2—C1—C6—C5 | −0.1 (3) | C11—N3—C13—C14 | −99.00 (19) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2A···N1i | 0.86 | 2.35 | 3.069 (2) | 141 |
N2—H2B···S1ii | 0.86 | 2.66 | 3.481 (2) | 160 |
Symmetry codes: (i) −x+2, −y+1, −z; (ii) −x+3, −y, −z. |
C14H17N3S | F(000) = 552 |
Mr = 259.38 | Dx = 1.189 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 9.1670 (18) Å | Cell parameters from 24 reflections |
b = 13.023 (3) Å | θ = 11–12° |
c = 12.172 (2) Å | µ = 0.21 mm−1 |
β = 93.97 (3)° | T = 295 K |
V = 1449.6 (5) Å3 | Prism, red |
Z = 4 | 0.50 × 0.35 × 0.25 mm |
Enraf–Nonius CAD-4 diffractometer | Rint = 0.027 |
Radiation source: fine-focus sealed tube | θmax = 27.0°, θmin = 2.3° |
Graphite monochromator | h = 0→11 |
θ/2θ scans | k = 0→16 |
3307 measured reflections | l = −15→15 |
3114 independent reflections | 3 standard reflections every 97 reflections |
2316 reflections with I > 2σ(I) | intensity decay: 3% |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.038 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.113 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.06P)2 + 0.25P] where P = (Fo2 + 2Fc2)/3 |
3114 reflections | (Δ/σ)max < 0.001 |
165 parameters | Δρmax = 0.21 e Å−3 |
0 restraints | Δρmin = −0.15 e Å−3 |
C14H17N3S | V = 1449.6 (5) Å3 |
Mr = 259.38 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 9.1670 (18) Å | µ = 0.21 mm−1 |
b = 13.023 (3) Å | T = 295 K |
c = 12.172 (2) Å | 0.50 × 0.35 × 0.25 mm |
β = 93.97 (3)° |
Enraf–Nonius CAD-4 diffractometer | Rint = 0.027 |
3307 measured reflections | 3 standard reflections every 97 reflections |
3114 independent reflections | intensity decay: 3% |
2316 reflections with I > 2σ(I) |
R[F2 > 2σ(F2)] = 0.038 | 0 restraints |
wR(F2) = 0.113 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.21 e Å−3 |
3114 reflections | Δρmin = −0.15 e Å−3 |
165 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
S1 | 0.08338 (5) | 0.35087 (3) | 0.92865 (3) | 0.05656 (16) | |
N1 | 0.3091 (2) | 0.24156 (11) | 0.72955 (14) | 0.0679 (4) | |
N2 | 0.09034 (18) | 0.54174 (10) | 0.85958 (12) | 0.0574 (4) | |
H2A | 0.1106 | 0.5882 | 0.8128 | 0.069* | |
H2B | 0.0495 | 0.5585 | 0.9185 | 0.069* | |
N3 | 0.38319 (17) | 0.47951 (11) | 0.22219 (12) | 0.0568 (4) | |
C1 | 0.24136 (19) | 0.47803 (12) | 0.54408 (14) | 0.0505 (4) | |
C2 | 0.1954 (2) | 0.55290 (14) | 0.46559 (15) | 0.0671 (5) | |
H2C | 0.1327 | 0.6046 | 0.4861 | 0.080* | |
C3 | 0.2390 (2) | 0.55270 (15) | 0.36095 (16) | 0.0687 (5) | |
H3A | 0.2024 | 0.6022 | 0.3113 | 0.082* | |
C4 | 0.33829 (19) | 0.47901 (12) | 0.32654 (14) | 0.0514 (4) | |
C5 | 0.38953 (19) | 0.40580 (12) | 0.40595 (13) | 0.0523 (4) | |
H5A | 0.4574 | 0.3570 | 0.3869 | 0.063* | |
C6 | 0.34196 (19) | 0.40492 (12) | 0.50953 (14) | 0.0508 (4) | |
H6A | 0.3769 | 0.3547 | 0.5589 | 0.061* | |
C7 | 0.18521 (18) | 0.48488 (12) | 0.65037 (14) | 0.0490 (4) | |
H7A | 0.1342 | 0.5453 | 0.6615 | 0.059* | |
C8 | 0.19161 (17) | 0.42019 (11) | 0.73893 (13) | 0.0438 (3) | |
C9 | 0.25688 (18) | 0.32041 (11) | 0.73484 (13) | 0.0490 (4) | |
C10 | 0.12203 (17) | 0.44415 (11) | 0.84082 (12) | 0.0440 (3) | |
C11 | 0.3110 (2) | 0.54304 (15) | 0.13463 (15) | 0.0634 (5) | |
H11A | 0.2101 | 0.5542 | 0.1508 | 0.076* | |
H11B | 0.3106 | 0.5061 | 0.0654 | 0.076* | |
C12 | 0.3839 (3) | 0.64552 (18) | 0.1218 (2) | 0.0909 (7) | |
H12A | 0.3321 | 0.6836 | 0.0638 | 0.136* | |
H12B | 0.4831 | 0.6351 | 0.1038 | 0.136* | |
H12C | 0.3828 | 0.6832 | 0.1895 | 0.136* | |
C13 | 0.4912 (2) | 0.40610 (13) | 0.18761 (15) | 0.0568 (4) | |
H13A | 0.5624 | 0.3930 | 0.2487 | 0.068* | |
H13B | 0.5425 | 0.4357 | 0.1282 | 0.068* | |
C14 | 0.4224 (3) | 0.30572 (15) | 0.14940 (18) | 0.0750 (6) | |
H14D | 0.4960 | 0.2616 | 0.1227 | 0.112* | |
H14A | 0.3484 | 0.3187 | 0.0913 | 0.112* | |
H14B | 0.3790 | 0.2731 | 0.2099 | 0.112* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0813 (3) | 0.0369 (2) | 0.0531 (2) | −0.00360 (19) | 0.0160 (2) | 0.00204 (16) |
N1 | 0.0897 (11) | 0.0407 (7) | 0.0758 (10) | 0.0093 (7) | 0.0235 (8) | 0.0005 (7) |
N2 | 0.0842 (10) | 0.0332 (6) | 0.0579 (8) | −0.0029 (6) | 0.0275 (7) | −0.0029 (6) |
N3 | 0.0666 (9) | 0.0524 (8) | 0.0528 (8) | 0.0088 (7) | 0.0133 (7) | 0.0043 (6) |
C1 | 0.0582 (9) | 0.0391 (8) | 0.0552 (9) | 0.0051 (7) | 0.0117 (7) | 0.0026 (6) |
C2 | 0.0844 (13) | 0.0523 (10) | 0.0674 (11) | 0.0285 (9) | 0.0260 (10) | 0.0134 (8) |
C3 | 0.0871 (14) | 0.0573 (10) | 0.0643 (11) | 0.0273 (10) | 0.0227 (10) | 0.0202 (9) |
C4 | 0.0578 (10) | 0.0449 (8) | 0.0523 (9) | 0.0052 (7) | 0.0106 (7) | 0.0034 (7) |
C5 | 0.0601 (10) | 0.0418 (8) | 0.0560 (9) | 0.0114 (7) | 0.0111 (8) | −0.0008 (7) |
C6 | 0.0608 (9) | 0.0409 (8) | 0.0511 (8) | 0.0097 (7) | 0.0068 (7) | 0.0043 (6) |
C7 | 0.0551 (9) | 0.0368 (7) | 0.0560 (9) | 0.0043 (6) | 0.0114 (7) | −0.0020 (6) |
C8 | 0.0495 (8) | 0.0326 (7) | 0.0497 (8) | −0.0021 (6) | 0.0064 (6) | −0.0048 (6) |
C9 | 0.0581 (9) | 0.0374 (7) | 0.0522 (9) | −0.0015 (7) | 0.0090 (7) | −0.0029 (6) |
C10 | 0.0493 (8) | 0.0350 (7) | 0.0480 (8) | −0.0050 (6) | 0.0056 (6) | −0.0039 (6) |
C11 | 0.0676 (11) | 0.0690 (12) | 0.0534 (10) | 0.0006 (9) | 0.0037 (8) | 0.0052 (8) |
C12 | 0.1061 (18) | 0.0754 (15) | 0.0913 (16) | −0.0014 (13) | 0.0082 (14) | 0.0262 (12) |
C13 | 0.0612 (10) | 0.0569 (10) | 0.0536 (9) | 0.0009 (8) | 0.0124 (8) | −0.0054 (8) |
C14 | 0.0894 (14) | 0.0589 (11) | 0.0749 (13) | −0.0013 (10) | −0.0065 (11) | −0.0130 (10) |
S1—C10 | 1.6723 (15) | C6—H6A | 0.9300 |
N1—C9 | 1.137 (2) | C7—C8 | 1.366 (2) |
N2—C10 | 1.3270 (19) | C7—H7A | 0.9300 |
N2—H2A | 0.8600 | C8—C9 | 1.433 (2) |
N2—H2B | 0.8600 | C8—C10 | 1.467 (2) |
N3—C4 | 1.362 (2) | C11—C12 | 1.505 (3) |
N3—C13 | 1.459 (2) | C11—H11A | 0.9700 |
N3—C11 | 1.470 (2) | C11—H11B | 0.9700 |
C1—C2 | 1.409 (2) | C12—H12A | 0.9600 |
C1—C6 | 1.410 (2) | C12—H12B | 0.9600 |
C1—C7 | 1.428 (2) | C12—H12C | 0.9600 |
C2—C3 | 1.361 (3) | C13—C14 | 1.511 (3) |
C2—H2C | 0.9300 | C13—H13A | 0.9700 |
C3—C4 | 1.406 (2) | C13—H13B | 0.9700 |
C3—H3A | 0.9300 | C14—H14D | 0.9600 |
C4—C5 | 1.415 (2) | C14—H14A | 0.9600 |
C5—C6 | 1.362 (2) | C14—H14B | 0.9600 |
C5—H5A | 0.9300 | ||
C10—N2—H2A | 120.0 | C9—C8—C10 | 115.42 (13) |
C10—N2—H2B | 120.0 | N1—C9—C8 | 178.70 (18) |
H2A—N2—H2B | 120.0 | N2—C10—C8 | 117.54 (13) |
C4—N3—C13 | 121.38 (14) | N2—C10—S1 | 121.81 (12) |
C4—N3—C11 | 121.92 (15) | C8—C10—S1 | 120.65 (11) |
C13—N3—C11 | 116.11 (14) | N3—C11—C12 | 113.17 (18) |
C2—C1—C6 | 115.86 (15) | N3—C11—H11A | 108.9 |
C2—C1—C7 | 117.48 (15) | C12—C11—H11A | 108.9 |
C6—C1—C7 | 126.64 (15) | N3—C11—H11B | 108.9 |
C3—C2—C1 | 122.68 (16) | C12—C11—H11B | 108.9 |
C3—C2—H2C | 118.7 | H11A—C11—H11B | 107.8 |
C1—C2—H2C | 118.7 | C11—C12—H12A | 109.5 |
C2—C3—C4 | 121.20 (16) | C11—C12—H12B | 109.5 |
C2—C3—H3A | 119.4 | H12A—C12—H12B | 109.5 |
C4—C3—H3A | 119.4 | C11—C12—H12C | 109.5 |
N3—C4—C3 | 121.21 (15) | H12A—C12—H12C | 109.5 |
N3—C4—C5 | 122.20 (15) | H12B—C12—H12C | 109.5 |
C3—C4—C5 | 116.59 (15) | N3—C13—C14 | 112.25 (16) |
C6—C5—C4 | 121.71 (15) | N3—C13—H13A | 109.2 |
C6—C5—H5A | 119.1 | C14—C13—H13A | 109.2 |
C4—C5—H5A | 119.1 | N3—C13—H13B | 109.2 |
C5—C6—C1 | 121.89 (15) | C14—C13—H13B | 109.2 |
C5—C6—H6A | 119.1 | H13A—C13—H13B | 107.9 |
C1—C6—H6A | 119.1 | C13—C14—H14D | 109.5 |
C8—C7—C1 | 132.68 (14) | C13—C14—H14A | 109.5 |
C8—C7—H7A | 113.7 | H14D—C14—H14A | 109.5 |
C1—C7—H7A | 113.7 | C13—C14—H14B | 109.5 |
C7—C8—C9 | 121.81 (14) | H14D—C14—H14B | 109.5 |
C7—C8—C10 | 122.58 (13) | H14A—C14—H14B | 109.5 |
C6—C1—C2—C3 | 3.1 (3) | C7—C1—C6—C5 | −179.46 (17) |
C7—C1—C2—C3 | −178.4 (2) | C2—C1—C7—C8 | 170.58 (19) |
C1—C2—C3—C4 | −2.6 (4) | C6—C1—C7—C8 | −11.1 (3) |
C13—N3—C4—C3 | 177.21 (18) | C1—C7—C8—C9 | −4.3 (3) |
C11—N3—C4—C3 | −11.9 (3) | C1—C7—C8—C10 | −179.09 (17) |
C13—N3—C4—C5 | −2.1 (3) | C7—C8—C10—N2 | −20.1 (2) |
C11—N3—C4—C5 | 168.79 (17) | C9—C8—C10—N2 | 164.83 (16) |
C2—C3—C4—N3 | −179.2 (2) | C7—C8—C10—S1 | 159.37 (13) |
C2—C3—C4—C5 | 0.1 (3) | C9—C8—C10—S1 | −15.7 (2) |
N3—C4—C5—C6 | −178.85 (17) | C4—N3—C11—C12 | 94.3 (2) |
C3—C4—C5—C6 | 1.8 (3) | C13—N3—C11—C12 | −94.4 (2) |
C4—C5—C6—C1 | −1.3 (3) | C4—N3—C13—C14 | 85.6 (2) |
C2—C1—C6—C5 | −1.1 (3) | C11—N3—C13—C14 | −85.8 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2A···N1i | 0.86 | 2.20 | 2.989 (2) | 152 |
N2—H2B···S1ii | 0.86 | 2.58 | 3.421 (2) | 167 |
Symmetry codes: (i) −x+1/2, y+1/2, −z+3/2; (ii) −x, −y+1, −z+2. |
C14H17N3S·0.25C2H3N | F(000) = 2296 |
Mr = 269.64 | Dx = 1.225 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 39.370 (8) Å | Cell parameters from 24 reflections |
b = 8.8800 (18) Å | θ = 10–11° |
c = 17.056 (3) Å | µ = 0.21 mm−1 |
β = 101.19 (3)° | T = 298 K |
V = 5850 (2) Å3 | Plate, orange |
Z = 16 | 0.50 × 0.40 × 0.20 mm |
Enraf–Nonius CAD-4 diffractometer | Rint = 0.050 |
Radiation source: fine-focus sealed tube | θmax = 25.5°, θmin = 1.1° |
Graphite monochromator | h = 0→47 |
θ/2θ scans | k = 0→10 |
5506 measured reflections | l = −20→20 |
5423 independent reflections | 3 standard reflections every 97 reflections |
2754 reflections with I > 2σ(I) | intensity decay: 3% |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.050 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.149 | H-atom parameters constrained |
S = 0.99 | w = 1/[σ2(Fo2) + (0.075P)2] where P = (Fo2 + 2Fc2)/3 |
5423 reflections | (Δ/σ)max < 0.001 |
344 parameters | Δρmax = 0.38 e Å−3 |
0 restraints | Δρmin = −0.24 e Å−3 |
C14H17N3S·0.25C2H3N | V = 5850 (2) Å3 |
Mr = 269.64 | Z = 16 |
Monoclinic, C2/c | Mo Kα radiation |
a = 39.370 (8) Å | µ = 0.21 mm−1 |
b = 8.8800 (18) Å | T = 298 K |
c = 17.056 (3) Å | 0.50 × 0.40 × 0.20 mm |
β = 101.19 (3)° |
Enraf–Nonius CAD-4 diffractometer | Rint = 0.050 |
5506 measured reflections | 3 standard reflections every 97 reflections |
5423 independent reflections | intensity decay: 3% |
2754 reflections with I > 2σ(I) |
R[F2 > 2σ(F2)] = 0.050 | 0 restraints |
wR(F2) = 0.149 | H-atom parameters constrained |
S = 0.99 | Δρmax = 0.38 e Å−3 |
5423 reflections | Δρmin = −0.24 e Å−3 |
344 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
S1A | 0.30718 (2) | 0.24174 (11) | 0.27209 (5) | 0.0478 (3) | |
N1A | 0.32656 (7) | 0.2712 (4) | −0.01178 (18) | 0.0536 (8) | |
N2A | 0.35114 (7) | 0.3122 (3) | 0.18127 (16) | 0.0512 (8) | |
H2AA | 0.3580 | 0.3148 | 0.1363 | 0.061* | |
H2AB | 0.3637 | 0.3513 | 0.2232 | 0.061* | |
N3A | 0.18347 (7) | −0.2138 (3) | −0.13861 (16) | 0.0453 (7) | |
C1A | 0.25282 (7) | 0.0149 (3) | 0.04174 (17) | 0.0338 (7) | |
C2A | 0.22709 (8) | −0.0820 (4) | 0.05954 (19) | 0.0419 (8) | |
H2AC | 0.2253 | −0.0953 | 0.1127 | 0.050* | |
C3A | 0.20450 (8) | −0.1576 (4) | 0.00131 (19) | 0.0419 (8) | |
H3AA | 0.1878 | −0.2201 | 0.0159 | 0.050* | |
C4A | 0.20615 (8) | −0.1424 (3) | −0.0792 (2) | 0.0394 (8) | |
C5A | 0.23241 (8) | −0.0470 (4) | −0.09762 (18) | 0.0425 (8) | |
H5AA | 0.2345 | −0.0352 | −0.1507 | 0.051* | |
C6A | 0.25474 (8) | 0.0280 (4) | −0.03933 (18) | 0.0398 (8) | |
H6AA | 0.2717 | 0.0893 | −0.0537 | 0.048* | |
C7A | 0.27457 (8) | 0.0913 (3) | 0.10672 (17) | 0.0351 (7) | |
H7AA | 0.2687 | 0.0735 | 0.1562 | 0.042* | |
C8A | 0.30202 (7) | 0.1846 (3) | 0.10968 (17) | 0.0318 (7) | |
C9A | 0.31473 (7) | 0.2292 (4) | 0.04067 (19) | 0.0366 (8) | |
C10A | 0.32134 (8) | 0.2480 (3) | 0.18593 (17) | 0.0351 (7) | |
C11A | 0.15694 (9) | −0.3130 (4) | −0.1196 (2) | 0.0538 (10) | |
H11B | 0.1664 | −0.3695 | −0.0717 | 0.065* | |
H11C | 0.1503 | −0.3844 | −0.1629 | 0.065* | |
C12A | 0.12486 (9) | −0.2282 (5) | −0.1065 (3) | 0.0697 (12) | |
H12A | 0.1078 | −0.2988 | −0.0959 | 0.105* | |
H12B | 0.1155 | −0.1710 | −0.1535 | 0.105* | |
H12C | 0.1310 | −0.1613 | −0.0617 | 0.105* | |
C13A | 0.18095 (9) | −0.1790 (4) | −0.2231 (2) | 0.0517 (9) | |
H13A | 0.1881 | −0.0756 | −0.2281 | 0.062* | |
H13B | 0.1569 | −0.1871 | −0.2498 | 0.062* | |
C14A | 0.20243 (10) | −0.2797 (5) | −0.2647 (2) | 0.0678 (12) | |
H14B | 0.1995 | −0.2507 | −0.3198 | 0.102* | |
H14C | 0.1951 | −0.3822 | −0.2613 | 0.102* | |
H14D | 0.2264 | −0.2705 | −0.2396 | 0.102* | |
S1B | 0.41456 (2) | 0.47668 (11) | 0.30624 (5) | 0.0500 (3) | |
N1B | 0.40596 (8) | 0.6653 (4) | 0.58260 (19) | 0.0717 (11) | |
N2B | 0.37145 (7) | 0.5157 (3) | 0.40298 (16) | 0.0463 (7) | |
H2BA | 0.3660 | 0.5484 | 0.4464 | 0.056* | |
H2BB | 0.3564 | 0.4690 | 0.3683 | 0.056* | |
N3B | 0.57131 (7) | 0.9542 (3) | 0.63859 (16) | 0.0446 (7) | |
C1B | 0.48736 (8) | 0.7335 (3) | 0.49443 (18) | 0.0364 (7) | |
C2B | 0.52112 (8) | 0.7223 (4) | 0.4801 (2) | 0.0445 (8) | |
H2BC | 0.5250 | 0.6643 | 0.4372 | 0.053* | |
C3B | 0.54872 (8) | 0.7935 (4) | 0.5268 (2) | 0.0456 (9) | |
H3BA | 0.5708 | 0.7806 | 0.5159 | 0.055* | |
C4B | 0.54420 (8) | 0.8859 (4) | 0.59123 (18) | 0.0383 (8) | |
C5B | 0.50987 (8) | 0.9042 (4) | 0.60238 (18) | 0.0407 (8) | |
H5BA | 0.5055 | 0.9691 | 0.6421 | 0.049* | |
C6B | 0.48296 (8) | 0.8299 (4) | 0.55692 (18) | 0.0400 (8) | |
H6BA | 0.4609 | 0.8432 | 0.5675 | 0.048* | |
C7B | 0.46041 (8) | 0.6522 (3) | 0.44399 (18) | 0.0368 (8) | |
H7BA | 0.4663 | 0.6158 | 0.3973 | 0.044* | |
C8B | 0.42750 (8) | 0.6185 (3) | 0.45210 (18) | 0.0348 (7) | |
C9B | 0.41600 (8) | 0.6480 (4) | 0.5246 (2) | 0.0427 (8) | |
C10B | 0.40321 (8) | 0.5375 (3) | 0.38965 (18) | 0.0357 (7) | |
C11B | 0.60725 (8) | 0.9184 (4) | 0.6357 (2) | 0.0531 (10) | |
H11A | 0.6084 | 0.8152 | 0.6179 | 0.064* | |
H11D | 0.6210 | 0.9252 | 0.6893 | 0.064* | |
C12B | 0.62301 (10) | 1.0190 (5) | 0.5817 (3) | 0.0750 (13) | |
H12D | 0.6464 | 0.9877 | 0.5821 | 0.113* | |
H12E | 0.6230 | 1.1211 | 0.6002 | 0.113* | |
H12F | 0.6098 | 1.0126 | 0.5283 | 0.113* | |
C13B | 0.56671 (9) | 1.0554 (4) | 0.7037 (2) | 0.0514 (9) | |
H13C | 0.5458 | 1.1141 | 0.6868 | 0.062* | |
H13D | 0.5861 | 1.1249 | 0.7146 | 0.062* | |
C14B | 0.56427 (11) | 0.9718 (5) | 0.7793 (2) | 0.0748 (13) | |
H14A | 0.5613 | 1.0425 | 0.8200 | 0.112* | |
H14E | 0.5851 | 0.9151 | 0.7969 | 0.112* | |
H14F | 0.5448 | 0.9045 | 0.7692 | 0.112* | |
N1S | 0.5000 | 0.7142 (8) | 0.2500 | 0.110 (2) | |
C1S | 0.5000 | 0.5886 (9) | 0.2500 | 0.0738 (18) | |
C2S | 0.5000 | 0.4252 (8) | 0.2500 | 0.130 (3) | |
H2SA | 0.5178 | 0.3891 | 0.2925 | 0.195* | 0.50 |
H2SB | 0.5043 | 0.3891 | 0.1998 | 0.195* | 0.50 |
H2SC | 0.4779 | 0.3891 | 0.2577 | 0.195* | 0.50 |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1A | 0.0487 (5) | 0.0586 (6) | 0.0382 (5) | −0.0023 (5) | 0.0134 (4) | −0.0077 (4) |
N1A | 0.0501 (18) | 0.062 (2) | 0.0504 (18) | −0.0092 (16) | 0.0147 (15) | −0.0046 (16) |
N2A | 0.0421 (16) | 0.072 (2) | 0.0395 (16) | −0.0167 (16) | 0.0074 (13) | −0.0171 (15) |
N3A | 0.0458 (16) | 0.0388 (17) | 0.0479 (17) | −0.0098 (14) | 0.0009 (13) | −0.0044 (14) |
C1A | 0.0325 (17) | 0.0321 (18) | 0.0349 (18) | 0.0000 (15) | 0.0016 (13) | 0.0021 (15) |
C2A | 0.045 (2) | 0.042 (2) | 0.0380 (18) | −0.0014 (17) | 0.0060 (15) | 0.0076 (16) |
C3A | 0.0388 (19) | 0.036 (2) | 0.049 (2) | −0.0070 (16) | 0.0047 (16) | 0.0044 (16) |
C4A | 0.0378 (18) | 0.0293 (18) | 0.048 (2) | 0.0005 (15) | −0.0003 (15) | −0.0012 (15) |
C5A | 0.046 (2) | 0.042 (2) | 0.0362 (18) | −0.0026 (17) | 0.0015 (15) | 0.0008 (16) |
C6A | 0.0393 (18) | 0.0347 (19) | 0.044 (2) | −0.0043 (16) | 0.0044 (15) | 0.0012 (16) |
C7A | 0.0363 (18) | 0.0352 (19) | 0.0335 (17) | 0.0080 (15) | 0.0058 (14) | 0.0022 (15) |
C8A | 0.0311 (16) | 0.0285 (17) | 0.0357 (17) | 0.0049 (14) | 0.0065 (13) | −0.0031 (14) |
C9A | 0.0307 (17) | 0.0345 (19) | 0.0425 (19) | 0.0004 (15) | 0.0020 (15) | −0.0100 (16) |
C10A | 0.0354 (17) | 0.0305 (17) | 0.0390 (18) | 0.0044 (15) | 0.0063 (13) | −0.0034 (15) |
C11A | 0.053 (2) | 0.045 (2) | 0.059 (2) | −0.0105 (19) | 0.0020 (18) | −0.0079 (19) |
C12A | 0.053 (2) | 0.077 (3) | 0.078 (3) | −0.005 (2) | 0.008 (2) | −0.012 (2) |
C13A | 0.052 (2) | 0.045 (2) | 0.052 (2) | −0.0050 (18) | −0.0037 (18) | −0.0031 (18) |
C14A | 0.083 (3) | 0.064 (3) | 0.054 (2) | 0.003 (2) | 0.007 (2) | −0.004 (2) |
S1B | 0.0437 (5) | 0.0612 (6) | 0.0456 (5) | −0.0129 (5) | 0.0098 (4) | −0.0153 (5) |
N1B | 0.056 (2) | 0.107 (3) | 0.056 (2) | −0.028 (2) | 0.0208 (17) | −0.022 (2) |
N2B | 0.0386 (16) | 0.0543 (19) | 0.0455 (16) | −0.0096 (14) | 0.0072 (12) | −0.0101 (14) |
N3B | 0.0406 (16) | 0.0371 (16) | 0.0520 (17) | −0.0047 (14) | −0.0012 (13) | −0.0032 (14) |
C1B | 0.0372 (17) | 0.0312 (18) | 0.0400 (18) | −0.0016 (15) | 0.0054 (14) | −0.0017 (15) |
C2B | 0.0408 (19) | 0.044 (2) | 0.049 (2) | −0.0027 (17) | 0.0105 (16) | −0.0077 (17) |
C3B | 0.0345 (18) | 0.042 (2) | 0.061 (2) | −0.0035 (16) | 0.0118 (17) | −0.0035 (18) |
C4B | 0.0382 (18) | 0.0311 (18) | 0.0439 (19) | −0.0045 (15) | 0.0033 (15) | 0.0037 (16) |
C5B | 0.0395 (19) | 0.039 (2) | 0.0432 (19) | −0.0051 (16) | 0.0071 (15) | −0.0074 (16) |
C6B | 0.0353 (17) | 0.040 (2) | 0.0444 (19) | −0.0032 (16) | 0.0072 (15) | −0.0022 (16) |
C7B | 0.0439 (19) | 0.0305 (19) | 0.0347 (17) | 0.0037 (15) | 0.0045 (15) | −0.0001 (14) |
C8B | 0.0345 (17) | 0.0324 (18) | 0.0378 (18) | −0.0013 (15) | 0.0074 (14) | −0.0017 (15) |
C9B | 0.0344 (18) | 0.048 (2) | 0.044 (2) | −0.0106 (16) | 0.0021 (16) | −0.0048 (17) |
C10B | 0.0342 (17) | 0.0295 (18) | 0.0422 (18) | 0.0005 (14) | 0.0042 (14) | 0.0086 (15) |
C11B | 0.041 (2) | 0.038 (2) | 0.075 (3) | −0.0047 (17) | −0.0037 (18) | 0.0073 (19) |
C12B | 0.058 (3) | 0.061 (3) | 0.111 (4) | −0.010 (2) | 0.029 (2) | 0.012 (3) |
C13B | 0.051 (2) | 0.042 (2) | 0.057 (2) | −0.0123 (18) | 0.0014 (17) | −0.0069 (19) |
C14B | 0.087 (3) | 0.078 (3) | 0.057 (2) | −0.015 (3) | 0.006 (2) | 0.003 (2) |
N1S | 0.142 (6) | 0.074 (4) | 0.134 (6) | 0.000 | 0.079 (5) | 0.000 |
C1S | 0.073 (4) | 0.081 (5) | 0.080 (4) | 0.000 | 0.045 (3) | 0.000 |
C2S | 0.149 (8) | 0.060 (5) | 0.212 (10) | 0.000 | 0.107 (7) | 0.000 |
S1A—C10A | 1.671 (3) | N2B—H2BA | 0.8600 |
N1A—C9A | 1.148 (4) | N2B—H2BB | 0.8600 |
N2A—C10A | 1.320 (4) | N3B—C4B | 1.351 (4) |
N2A—H2AA | 0.8600 | N3B—C11B | 1.460 (4) |
N2A—H2AB | 0.8600 | N3B—C13B | 1.467 (4) |
N3A—C4A | 1.369 (4) | C1B—C2B | 1.401 (4) |
N3A—C11A | 1.451 (4) | C1B—C6B | 1.404 (4) |
N3A—C13A | 1.458 (4) | C1B—C7B | 1.426 (4) |
C1A—C6A | 1.404 (4) | C2B—C3B | 1.371 (4) |
C1A—C2A | 1.406 (4) | C2B—H2BC | 0.9300 |
C1A—C7A | 1.433 (4) | C3B—C4B | 1.410 (4) |
C2A—C3A | 1.373 (4) | C3B—H3BA | 0.9300 |
C2A—H2AC | 0.9300 | C4B—C5B | 1.410 (4) |
C3A—C4A | 1.394 (4) | C5B—C6B | 1.356 (4) |
C3A—H3AA | 0.9300 | C5B—H5BA | 0.9300 |
C4A—C5A | 1.418 (4) | C6B—H6BA | 0.9300 |
C5A—C6A | 1.366 (4) | C7B—C8B | 1.363 (4) |
C5A—H5AA | 0.9300 | C7B—H7BA | 0.9300 |
C6A—H6AA | 0.9300 | C8B—C9B | 1.422 (4) |
C7A—C8A | 1.355 (4) | C8B—C10B | 1.473 (4) |
C7A—H7AA | 0.9300 | C11B—C12B | 1.500 (5) |
C8A—C9A | 1.422 (4) | C11B—H11A | 0.9700 |
C8A—C10A | 1.484 (4) | C11B—H11D | 0.9700 |
C11A—C12A | 1.524 (5) | C12B—H12D | 0.9600 |
C11A—H11B | 0.9700 | C12B—H12E | 0.9600 |
C11A—H11C | 0.9700 | C12B—H12F | 0.9600 |
C12A—H12A | 0.9600 | C13B—C14B | 1.508 (5) |
C12A—H12B | 0.9600 | C13B—H13C | 0.9700 |
C12A—H12C | 0.9600 | C13B—H13D | 0.9700 |
C13A—C14A | 1.500 (5) | C14B—H14A | 0.9600 |
C13A—H13A | 0.9700 | C14B—H14E | 0.9600 |
C13A—H13B | 0.9700 | C14B—H14F | 0.9600 |
C14A—H14B | 0.9600 | N1S—C1S | 1.116 (8) |
C14A—H14C | 0.9600 | C1S—C2S | 1.451 (10) |
C14A—H14D | 0.9600 | C2S—H2SA | 0.9600 |
S1B—C10B | 1.662 (3) | C2S—H2SB | 0.9600 |
N1B—C9B | 1.144 (4) | C2S—H2SC | 0.9600 |
N2B—C10B | 1.328 (4) | ||
C10A—N2A—H2AA | 120.0 | C4B—N3B—C13B | 121.9 (3) |
C10A—N2A—H2AB | 120.0 | C11B—N3B—C13B | 114.9 (3) |
H2AA—N2A—H2AB | 120.0 | C2B—C1B—C6B | 115.9 (3) |
C4A—N3A—C11A | 120.7 (3) | C2B—C1B—C7B | 118.6 (3) |
C4A—N3A—C13A | 122.9 (3) | C6B—C1B—C7B | 125.4 (3) |
C11A—N3A—C13A | 115.8 (3) | C3B—C2B—C1B | 122.5 (3) |
C6A—C1A—C2A | 116.2 (3) | C3B—C2B—H2BC | 118.8 |
C6A—C1A—C7A | 125.7 (3) | C1B—C2B—H2BC | 118.8 |
C2A—C1A—C7A | 118.0 (3) | C2B—C3B—C4B | 121.1 (3) |
C3A—C2A—C1A | 122.4 (3) | C2B—C3B—H3BA | 119.5 |
C3A—C2A—H2AC | 118.8 | C4B—C3B—H3BA | 119.5 |
C1A—C2A—H2AC | 118.8 | N3B—C4B—C3B | 121.5 (3) |
C2A—C3A—C4A | 121.2 (3) | N3B—C4B—C5B | 122.3 (3) |
C2A—C3A—H3AA | 119.4 | C3B—C4B—C5B | 116.2 (3) |
C4A—C3A—H3AA | 119.4 | C6B—C5B—C4B | 122.0 (3) |
N3A—C4A—C3A | 122.4 (3) | C6B—C5B—H5BA | 119.0 |
N3A—C4A—C5A | 120.8 (3) | C4B—C5B—H5BA | 119.0 |
C3A—C4A—C5A | 116.8 (3) | C5B—C6B—C1B | 122.2 (3) |
C6A—C5A—C4A | 121.6 (3) | C5B—C6B—H6BA | 118.9 |
C6A—C5A—H5AA | 119.2 | C1B—C6B—H6BA | 118.9 |
C4A—C5A—H5AA | 119.2 | C8B—C7B—C1B | 131.4 (3) |
C5A—C6A—C1A | 121.8 (3) | C8B—C7B—H7BA | 114.3 |
C5A—C6A—H6AA | 119.1 | C1B—C7B—H7BA | 114.3 |
C1A—C6A—H6AA | 119.1 | C7B—C8B—C9B | 121.2 (3) |
C8A—C7A—C1A | 132.1 (3) | C7B—C8B—C10B | 122.0 (3) |
C8A—C7A—H7AA | 113.9 | C9B—C8B—C10B | 116.6 (3) |
C1A—C7A—H7AA | 113.9 | N1B—C9B—C8B | 176.8 (4) |
C7A—C8A—C9A | 123.1 (3) | N2B—C10B—C8B | 116.6 (3) |
C7A—C8A—C10A | 122.3 (3) | N2B—C10B—S1B | 121.2 (2) |
C9A—C8A—C10A | 114.6 (3) | C8B—C10B—S1B | 122.2 (2) |
N1A—C9A—C8A | 175.4 (3) | N3B—C11B—C12B | 114.2 (3) |
N2A—C10A—C8A | 114.9 (3) | N3B—C11B—H11A | 108.7 |
N2A—C10A—S1A | 121.3 (2) | C12B—C11B—H11A | 108.7 |
C8A—C10A—S1A | 123.8 (2) | N3B—C11B—H11D | 108.7 |
N3A—C11A—C12A | 112.7 (3) | C12B—C11B—H11D | 108.7 |
N3A—C11A—H11B | 109.1 | H11A—C11B—H11D | 107.6 |
C12A—C11A—H11B | 109.1 | C11B—C12B—H12D | 109.5 |
N3A—C11A—H11C | 109.1 | C11B—C12B—H12E | 109.5 |
C12A—C11A—H11C | 109.1 | H12D—C12B—H12E | 109.5 |
H11B—C11A—H11C | 107.8 | C11B—C12B—H12F | 109.5 |
C11A—C12A—H12A | 109.5 | H12D—C12B—H12F | 109.5 |
C11A—C12A—H12B | 109.5 | H12E—C12B—H12F | 109.5 |
H12A—C12A—H12B | 109.5 | N3B—C13B—C14B | 112.5 (3) |
C11A—C12A—H12C | 109.5 | N3B—C13B—H13C | 109.1 |
H12A—C12A—H12C | 109.5 | C14B—C13B—H13C | 109.1 |
H12B—C12A—H12C | 109.5 | N3B—C13B—H13D | 109.1 |
N3A—C13A—C14A | 113.9 (3) | C14B—C13B—H13D | 109.1 |
N3A—C13A—H13A | 108.8 | H13C—C13B—H13D | 107.8 |
C14A—C13A—H13A | 108.8 | C13B—C14B—H14A | 109.5 |
N3A—C13A—H13B | 108.8 | C13B—C14B—H14E | 109.5 |
C14A—C13A—H13B | 108.8 | H14A—C14B—H14E | 109.5 |
H13A—C13A—H13B | 107.7 | C13B—C14B—H14F | 109.5 |
C13A—C14A—H14B | 109.5 | H14A—C14B—H14F | 109.5 |
C13A—C14A—H14C | 109.5 | H14E—C14B—H14F | 109.5 |
H14B—C14A—H14C | 109.5 | N1S—C1S—C2S | 180.000 (3) |
C13A—C14A—H14D | 109.5 | C1S—C2S—H2SA | 109.5 |
H14B—C14A—H14D | 109.5 | C1S—C2S—H2SB | 109.5 |
H14C—C14A—H14D | 109.5 | H2SA—C2S—H2SB | 109.5 |
C10B—N2B—H2BA | 120.0 | C1S—C2S—H2SC | 109.5 |
C10B—N2B—H2BB | 120.0 | H2SA—C2S—H2SC | 109.5 |
H2BA—N2B—H2BB | 120.0 | H2SB—C2S—H2SC | 109.5 |
C4B—N3B—C11B | 122.7 (3) | ||
C6A—C1A—C2A—C3A | −1.4 (5) | C6B—C1B—C2B—C3B | 3.7 (5) |
C7A—C1A—C2A—C3A | 178.5 (3) | C7B—C1B—C2B—C3B | −178.3 (3) |
C1A—C2A—C3A—C4A | 0.4 (5) | C1B—C2B—C3B—C4B | −1.7 (5) |
C11A—N3A—C4A—C3A | −1.7 (5) | C11B—N3B—C4B—C3B | −10.5 (5) |
C13A—N3A—C4A—C3A | 169.0 (3) | C13B—N3B—C4B—C3B | 177.4 (3) |
C11A—N3A—C4A—C5A | 179.1 (3) | C11B—N3B—C4B—C5B | 170.3 (3) |
C13A—N3A—C4A—C5A | −10.2 (5) | C13B—N3B—C4B—C5B | −1.7 (5) |
C2A—C3A—C4A—N3A | −178.5 (3) | C2B—C3B—C4B—N3B | 178.7 (3) |
C2A—C3A—C4A—C5A | 0.7 (5) | C2B—C3B—C4B—C5B | −2.1 (5) |
N3A—C4A—C5A—C6A | 178.4 (3) | N3B—C4B—C5B—C6B | −176.9 (3) |
C3A—C4A—C5A—C6A | −0.8 (5) | C3B—C4B—C5B—C6B | 3.9 (5) |
C4A—C5A—C6A—C1A | −0.2 (5) | C4B—C5B—C6B—C1B | −1.9 (5) |
C2A—C1A—C6A—C5A | 1.3 (5) | C2B—C1B—C6B—C5B | −1.9 (5) |
C7A—C1A—C6A—C5A | −178.6 (3) | C7B—C1B—C6B—C5B | −179.8 (3) |
C6A—C1A—C7A—C8A | −3.4 (5) | C2B—C1B—C7B—C8B | 165.7 (3) |
C2A—C1A—C7A—C8A | 176.7 (3) | C6B—C1B—C7B—C8B | −16.5 (6) |
C1A—C7A—C8A—C9A | 1.4 (5) | C1B—C7B—C8B—C9B | −8.6 (5) |
C1A—C7A—C8A—C10A | −178.3 (3) | C1B—C7B—C8B—C10B | 177.1 (3) |
C7A—C8A—C10A—N2A | 167.4 (3) | C7B—C8B—C10B—N2B | −177.6 (3) |
C9A—C8A—C10A—N2A | −12.4 (4) | C9B—C8B—C10B—N2B | 7.9 (4) |
C7A—C8A—C10A—S1A | −13.0 (4) | C7B—C8B—C10B—S1B | 2.0 (4) |
C9A—C8A—C10A—S1A | 167.3 (2) | C9B—C8B—C10B—S1B | −172.5 (2) |
C4A—N3A—C11A—C12A | 83.2 (4) | C4B—N3B—C11B—C12B | 93.8 (4) |
C13A—N3A—C11A—C12A | −88.2 (4) | C13B—N3B—C11B—C12B | −93.7 (4) |
C4A—N3A—C13A—C14A | 94.4 (4) | C4B—N3B—C13B—C14B | 83.7 (4) |
C11A—N3A—C13A—C14A | −94.5 (4) | C11B—N3B—C13B—C14B | −88.9 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2A—H2AA···N1Bi | 0.86 | 2.26 | 2.990 (4) | 143 |
N2A—H2AB···S1B | 0.86 | 2.48 | 3.293 (4) | 158 |
N2B—H2BA···N1Aii | 0.86 | 2.43 | 3.133 (4) | 139 |
Symmetry codes: (i) x, −y+1, z−1/2; (ii) x, −y+1, z+1/2. |
Experimental details
(Ia) | (Ib) | (Ic) | |
Crystal data | |||
Chemical formula | C14H17N3S | C14H17N3S | C14H17N3S·0.25C2H3N |
Mr | 259.38 | 259.38 | 269.64 |
Crystal system, space group | Triclinic, P1 | Monoclinic, P21/n | Monoclinic, C2/c |
Temperature (K) | 298 | 295 | 298 |
a, b, c (Å) | 8.753 (3), 8.890 (3), 10.830 (4) | 9.1670 (18), 13.023 (3), 12.172 (2) | 39.370 (8), 8.8800 (18), 17.056 (3) |
α, β, γ (°) | 85.44 (3), 69.76 (2), 63.65 (3) | 90, 93.97 (3), 90 | 90, 101.19 (3), 90 |
V (Å3) | 705.8 (5) | 1449.6 (5) | 5850 (2) |
Z | 2 | 4 | 16 |
Radiation type | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.22 | 0.21 | 0.21 |
Crystal size (mm) | 0.50 × 0.40 × 0.20 | 0.50 × 0.35 × 0.25 | 0.50 × 0.40 × 0.20 |
Data collection | |||
Diffractometer | Enraf–Nonius CAD-4 diffractometer | Enraf–Nonius CAD-4 diffractometer | Enraf–Nonius CAD-4 diffractometer |
Absorption correction | – | – | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2639, 2465, 1811 | 3307, 3114, 2316 | 5506, 5423, 2754 |
Rint | 0.016 | 0.027 | 0.050 |
(sin θ/λ)max (Å−1) | 0.596 | 0.638 | 0.605 |
Refinement | |||
R[F2 > 2σ(F2)], wR(F2), S | 0.035, 0.098, 1.00 | 0.038, 0.113, 1.03 | 0.050, 0.149, 0.99 |
No. of reflections | 2465 | 3114 | 5423 |
No. of parameters | 165 | 165 | 344 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.15, −0.18 | 0.21, −0.15 | 0.38, −0.24 |
Computer programs: CAD-4 Software (Enraf–Nonuis, 1989), CAD-4 Software, SHELXTL-Plus (Sheldrick, 1994), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), SHELXTL-Plus, SHELXL97.
S1—C10 | 1.669 (2) | C7—C8 | 1.358 (2) |
N1—C9 | 1.145 (2) | C8—C9 | 1.428 (3) |
N2—C10 | 1.330 (2) | C8—C10 | 1.476 (2) |
N3—C4 | 1.361 (2) | ||
C8—C7—C1 | 131.08 (16) | N1—C9—C8 | 177.31 (18) |
C2—C1—C7—C8 | 167.98 (17) | C9—C8—C10—N2 | −10.0 (2) |
C1—C7—C8—C10 | −177.86 (16) | C7—C8—C10—S1 | −13.1 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2A···N1i | 0.86 | 2.35 | 3.069 (2) | 141 |
N2—H2B···S1ii | 0.86 | 2.66 | 3.481 (2) | 160 |
Symmetry codes: (i) −x+2, −y+1, −z; (ii) −x+3, −y, −z. |
S1—C10 | 1.6723 (15) | C7—C8 | 1.366 (2) |
N1—C9 | 1.137 (2) | C8—C9 | 1.433 (2) |
N2—C10 | 1.3270 (19) | C8—C10 | 1.467 (2) |
N3—C4 | 1.362 (2) | ||
C8—C7—C1 | 132.68 (14) | N1—C9—C8 | 178.70 (18) |
C2—C1—C7—C8 | 170.58 (19) | C9—C8—C10—N2 | 164.83 (16) |
C1—C7—C8—C10 | −179.09 (17) | C7—C8—C10—S1 | 159.37 (13) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2A···N1i | 0.86 | 2.20 | 2.989 (2) | 152 |
N2—H2B···S1ii | 0.86 | 2.58 | 3.421 (2) | 167 |
Symmetry codes: (i) −x+1/2, y+1/2, −z+3/2; (ii) −x, −y+1, −z+2. |
S1A—C10A | 1.671 (3) | S1B—C10B | 1.662 (3) |
N1A—C9A | 1.148 (4) | N1B—C9B | 1.144 (4) |
N2A—C10A | 1.320 (4) | N2B—C10B | 1.328 (4) |
N3A—C4A | 1.369 (4) | N3B—C4B | 1.351 (4) |
C7A—C8A | 1.355 (4) | C7B—C8B | 1.363 (4) |
C8A—C9A | 1.422 (4) | C8B—C9B | 1.422 (4) |
C8A—C10A | 1.484 (4) | C8B—C10B | 1.473 (4) |
C8A—C7A—C1A | 132.1 (3) | C8B—C7B—C1B | 131.4 (3) |
N1A—C9A—C8A | 175.4 (3) | N1B—C9B—C8B | 176.8 (4) |
C2A—C1A—C7A—C8A | 176.7 (3) | C2B—C1B—C7B—C8B | 165.7 (3) |
C1A—C7A—C8A—C10A | −178.3 (3) | C1B—C7B—C8B—C10B | 177.1 (3) |
C9A—C8A—C10A—N2A | −12.4 (4) | C9B—C8B—C10B—N2B | 7.9 (4) |
C7A—C8A—C10A—S1A | −13.0 (4) | C7B—C8B—C10B—S1B | 2.0 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2A—H2AA···N1Bi | 0.86 | 2.26 | 2.990 (4) | 143 |
N2A—H2AB···S1B | 0.86 | 2.48 | 3.293 (4) | 158 |
N2B—H2BA···N1Aii | 0.86 | 2.43 | 3.133 (4) | 139 |
Symmetry codes: (i) x, −y+1, z−1/2; (ii) x, −y+1, z+1/2. |
The present investigation is a continuation of a project that includes the syntheses and structural studies of polar conjugated organic compounds that crystallize in non-centrosymmetric space groups (Antipin et al., 1998; V. N. Nesterov et al., 1998, 2000; V. V. Nesterov et al., 2004a,2004b). These compounds may find application in nonlinear optical materials (Zyss et al., 1994; Kuzyk & Dirk, 1998) and in the syntheses of heterocyclic compounds (Brunskill et al., 1984; Nesterov et al., 2002). Moreover, related compounds have found application as potential antitumor drugs (Hutchinson et al., 2001; Thacher et al., 2001; Wermuth, 2004). During thorough and systematic work, we have found many compounds that crystallize in different space groups and reveal polymorphism (Timofeeva et al., 2000, 2003a, 2003b; Wang et al., 2001). Thus, cocrystallization of such compounds with chiral molecules can build acentric crystalline structures or polymorphs (Timofeeva et al., 2000), and polymorphism is a very important phenomenon in the pharmaceutical industry (Davey et al., 1997; Bernstein, 2002).
In this paper, we present interesting results that were obtained working with compound (I). X-ray structural investigations have been carried out for two polymorphs, viz. orange triclinic (Ia) and red monoclinic (Ib) (Figs. 1 and 2), and for a complex, (Ic) (Fig. 3), of (I) with acetonitrile. In an attempt to find other crystalline forms, crystals of (I) have been grown from several solvents, including ethanol, propane-2-ol, acetonitrile, toluene, chloroform and their mixtures. In almost all cases, we obtained crystals of the (Ia) modification, and only from acetonitrile did we obtain complex (Ic). Starting with (I), we have synthesized several thiazole derivative compounds, using dimethylformamide (DMF) as a solvent. In one case, from the reaction mixture were separated crystals with different shapes, viz. red prisms (several crystals) and orange plates. The first crystals were another monoclinic modification, (Ib), of the starting material, while the second crystals were the thiazole product. According to the Cambridge Structural Database (CSD; Allen, 2003), the structure of another monoclinic modification, (Id), of (I) has been investigated (Brunskill et al., 1984). All our attempts to obtain complexes of (I) with L-proline and L-tartaric acid, using different solvents and different crystallization conditions, gave only good crystals of polymorph (Ia).
As seen in Figs. 1 and 2, the main distinction between (Ia) and (Ib) is the different orientation of the thioamide group relative to the CN substituent (two rotamers). ?In accordance with the results of Brunskill et al. (1984), in these cases we obtained two forms with s-cis and s-trans geometry of the C=C—C=S fragment. Although conformer (Id) has a structure similar to that of (Ib), the values of the C7—C8—C10—S1 torsion angles are different [159.4 (1)° in (Ib) and −158.5° in (Id)]. In both independent molecules, A and B, of (Ic), the orientation of this substituent is similar to that in (Ia) (Fig. 3), but compounds (Ic) and (Ia) also have different dihedral angles (see below). The rotatation of the thioamide group about the C8—C10 single bond is a possible reason for the existence of the three modifications.
Most of the geometric parameters in the investigated molecules (Ia)–(Ic) are very similar. The molecular skeleton of each molecule is slightly non-planar; the dihedral angles between the conjugated linkage (C=C—CN) and the phenyl ring, and between this linkage and the thioamide group, are 13.4 (2) and 12.0 (2)° in (Ia), 14.0 (2) and 18.2 (2) in (Ib), and 2.3 (3)/23.2 (3) and 12.7 (4)/8.1 (4)° in (Ic) for the two independent molecules A and B, respectively. Such slight non-planarity is not sufficient to preclude conjugation between aryl and CN groups via a C=C-bridged fragment. Really, because of the strong conjugation between donor and acceptor parts in these molecules, the substituted phenyl rings have a noticeably quinoid character (Tables 1, 3 and 5). Moreover, the dihedral angles between the trigonal diethylamine substituent [in all structures the sum of bond angles around the N atom is 359.5 (2)°] and the phenyl ring are small [5.6 (2)° in (Ia), 10.7 (2)° in (Ib), and 10.6 (4) and 10.4 (4)° in molecules A and B of (Ic)]. In all compounds, the N3—C4 bond length [range 1.351 (4)–1.369 (4) Å] is comparable to the average conjugated C—N single bond (1.370 Å) and is distinctly shorter than the average non-conjugated C—N single bond (1.430 Å) found in the CSD. Furthermore, the C1—C7 and C7=C8 bond lengths also have noticeable differences in comparison with standard distances (Allen et al., 1987).
As seen in Tables 1, 3 and 5, all of the molecules possess a strong conjugation in the thioamide fragment. The C=S bond lengths are distinctly elongated, while the C—N bonds have a partly double-bond character. In our previous work (Nesterov et al., 1986), we have analyzed such conjugation in the thioamide fragments. As mentioned above, the deviations of the thioamide groups in (Ia)–(Ic) from the bridged plane are not significant, but the C8—C10 bond lengths are equal or slightly elongated compared with the conjugated C—C bond (1.470 Å; Allen et al., 1987).
The planarity of the molecules leads to the existence of shortened H···C/H intramolecular contacts [H6A···C9 = 2.38 Å and H2A···C9 = 2.28 Å in (Ia); H6A···C9 = 2.52 Å and H7A···H2A = 1.95 Å in (Ib); and H6AA···C9A = 2.44 Å and H2AA···C9A = 2.25 Å, and H6BA···C9B 2.48 Å and H2BA···C9B 2.33 Å, in molecules A and B of (Ic), respectively]. In (Ib) there exists a very strong steric H···H interaction between the bridging and thioamide parts of the molecule. The same short steric contact is also found in the monoclinic form (Id) at 2.04 Å. Probably, the presence of such short contacts indicates that polymorphs (Ib) and (Id) are energetically less stable than (Ia). This is perhaps the reason that we were unable to obtain polymorphs (Ib) and (Id) again in our work. Such intramolecular interactions are the reason for the elongation of the C8—C10 bond lengths.
The crystal packings of (Ia) and (Ib) are different. In (Ia), intermolecular N—H···N and N—H···S hydrogen bonds link molecules in two centrosymmetric dimmers to build infinite tapes along the [1–10] direction (Fig. 4 and Table 2). However, in (Ib), such hydrogen bonds link molecules into infinite planes (101) (Fig. 5 and Table 4). In the case of (Ic), intermolecular N—H···N hydrogen bonds link molecules A and B into dimers, which are connected via N—H···S hydrogen bonds and form infinite chains along the c direction (Fig. 6 and Table 6). In molecule B, one atom of the NH2 group (H2BB) does not participate in hydrogen bonding. The intermolecular distance between atoms H2BB and S1A of molecules A and B (3.05 Å) is greater than the sum of van der Waals radii of the atoms (Rowland & Taylor, 1996).
According to the foregoing results, previously studied compounds (Nesterov et al., 2003) having 4-diethylamine substituents that occupy different positions relative to the phenyl ring (two CH3 groups above a plane or disordered) might also yield polymorphic forms.