Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270107049797/gd3156sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270107049797/gd3156Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270107049797/gd3156IIsup3.hkl |
CCDC references: 672537; 672538
For the synthesis of rac-(I), to a solution of trans-(±)-1,2-diaminocyclohexane (1.14 g, 10 mmol) in chloroform (15 ml) were added ethyl chlorooxoacetate (2.3 ml, 20 mmol) and triethylamine (2.8 ml, 20 mmol), and the mixture was kept at room temperature overnight. The reaction mixture was washed with water, diluted hydrochloric acid and saturated aqueous NaHCO3. The organic layer was dried (MgSO4) and then evaporated at reduced pressure. The resulting solid was recrystallized from chloroform–hexane to obtain 2.1 g of the product (m.p. 446–448 K). The above product (2.0 g, 6 mmol) was refluxed with Lawesson's reagent (2.86 g, 7.0 mmol) in toluene (50 ml) for 0.5 h. After removal of the solvent, the residue was purified by column chromatography on silica gel with chloroform–hexane (1:1) as an eluant to give rac-(I) as yellow prisms [needle in CIF?] [yield 1.45 g, 70%; m.p. 384–386 K (toluene–hexane)]. 1H NMR (CDCl3): δ 9.18 (s, NH, 2H), 4.63 (br s, 2H), 4.35 (m, 4H), 2.29 (br s, 2H), 1.89 (br s, 2H), 1.45 (d, J = 7.8 Hz, 4H), 1.39 (t, J = 7.1 Hz, 6H); nmax(KBr, cm-1): 3292, 1702, 1269, 1246. Analysis calculated for C14H22N2O4S2 (346.5): C 48.54, H 6.39, N 8.09, S 18.51%; found: C 48.54, H 6.28, N 8.02, S 18.68%.
For the synthesis of rac-(II), the oxamide (m.p. 464–466 K) prepared in an analogous way from (±)-1,2-diphenylethylenediamine (1.46 g, 3.5 mmol) was refluxed with Lawesson's reagent (1.43 g, 3.5 mmol) in toluene (50 ml) for 0.5 h. The reaction mixture was allowed to cool to room temperature and the yellow precipitate was removed by filtration to give rac-(II) [yield 1.2 g, 77%; m.p. 431–433 K (ethanol)]. 1H NMR (CDCl3): δ 9.67 (br s, NH, 2H), 7.31–7.24 (m, 10H), 6.19 (dd, J = 5.9 and 2.9 Hz, 2H), 4.37 (m, 4H), 1.39 (t, J = 7.1 Hz, 6H); nmax(KBr, cm-1): 3236, 1739, 1725, 1269. Analysis calculated for C22H24N2O4S2 (444.5): C 59.44, H 5.44, N 6.30, S 14.43%; found: C 59.19, H 5.44, N 6.27, S 14.51%.
All H atoms were placed at calculated positions (C—H = 0.95–1.00 Å and N—H = 0.88 Å) and were refined as riding on their carrier atoms [Uiso(H) = 1.2Ueq(C,N), with the exception of methyl groups, where Uiso(H) = 1.5Ueq(C)].
For both compounds, data collection: CrysAlis CCD (Oxford Diffraction, 2006); cell refinement: CrysAlis CCD (Oxford Diffraction, 2006); data reduction: CrysAlis RED (Oxford Diffraction, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: Stereochemical Workstation (Siemens, 1989) and Mercury (Version 1.4; Macrae et al., 2006); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).
C14H22N2O4S2 | Z = 2 |
Mr = 346.46 | F(000) = 368 |
Triclinic, P1 | Dx = 1.365 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 9.6438 (10) Å | Cell parameters from 1822 reflections |
b = 9.6656 (11) Å | θ = 2–25° |
c = 10.3316 (11) Å | µ = 0.33 mm−1 |
α = 85.068 (9)° | T = 120 K |
β = 63.887 (10)° | Needle, prism |
γ = 77.155 (9)° | 0.4 × 0.4 × 0.2 mm |
V = 843.02 (18) Å3 |
Kuma KM-4 CCD κ geometry diffractometer | 2957 independent reflections |
Radiation source: fine-focus sealed tube | 2587 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.016 |
ω scans | θmax = 25.0°, θmin = 4.2° |
Absorption correction: multi-scan (Blessing, 1995) | h = −11→9 |
Tmin = 0.840, Tmax = 0.935 | k = −11→11 |
6232 measured reflections | l = −12→12 |
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)] = 0.027 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.072 | H-atom parameters constrained |
S = 1.07 | w = 1/[σ2(Fo2) + (0.0368P)2 + 0.2571P] where P = (Fo2 + 2Fc2)/3 |
2957 reflections | (Δ/σ)max = 0.001 |
199 parameters | Δρmax = 0.29 e Å−3 |
0 restraints | Δρmin = −0.25 e Å−3 |
C14H22N2O4S2 | γ = 77.155 (9)° |
Mr = 346.46 | V = 843.02 (18) Å3 |
Triclinic, P1 | Z = 2 |
a = 9.6438 (10) Å | Mo Kα radiation |
b = 9.6656 (11) Å | µ = 0.33 mm−1 |
c = 10.3316 (11) Å | T = 120 K |
α = 85.068 (9)° | 0.4 × 0.4 × 0.2 mm |
β = 63.887 (10)° |
Kuma KM-4 CCD κ geometry diffractometer | 2957 independent reflections |
Absorption correction: multi-scan (Blessing, 1995) | 2587 reflections with I > 2σ(I) |
Tmin = 0.840, Tmax = 0.935 | Rint = 0.016 |
6232 measured reflections |
R[F2 > 2σ(F2)] = 0.027 | 0 restraints |
wR(F2) = 0.072 | H-atom parameters constrained |
S = 1.07 | Δρmax = 0.29 e Å−3 |
2957 reflections | Δρmin = −0.25 e Å−3 |
199 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 | 0.35976 (4) | 0.69933 (4) | 0.46565 (4) | 0.02187 (12) | |
S2 | 1.19840 (4) | 0.53228 (4) | 0.29613 (4) | 0.02021 (11) | |
N1 | 0.62809 (13) | 0.69442 (12) | 0.48528 (13) | 0.0139 (3) | |
H1N | 0.6804 | 0.6847 | 0.5381 | 0.017* | |
N2 | 0.92356 (13) | 0.50755 (12) | 0.30340 (13) | 0.0135 (3) | |
H2N | 0.8554 | 0.4542 | 0.3170 | 0.016* | |
O1 | 0.47309 (11) | 0.72452 (11) | 0.77377 (11) | 0.0170 (2) | |
O2 | 0.30209 (12) | 0.59896 (12) | 0.77384 (12) | 0.0245 (3) | |
O3 | 1.02185 (11) | 0.22440 (10) | 0.27997 (11) | 0.0156 (2) | |
O4 | 1.12998 (13) | 0.23753 (11) | 0.43211 (12) | 0.0230 (3) | |
C1 | 0.71027 (16) | 0.71874 (15) | 0.33006 (15) | 0.0140 (3) | |
H1 | 0.6649 | 0.6720 | 0.2794 | 0.017* | |
C2 | 0.88775 (16) | 0.65738 (15) | 0.26827 (15) | 0.0133 (3) | |
H2 | 0.9352 | 0.7123 | 0.3101 | 0.016* | |
C3 | 0.96125 (17) | 0.67708 (15) | 0.10400 (16) | 0.0164 (3) | |
H3A | 1.0753 | 0.6338 | 0.0622 | 0.020* | |
H3B | 0.9109 | 0.6286 | 0.0610 | 0.020* | |
C4 | 0.93827 (18) | 0.83488 (16) | 0.06865 (16) | 0.0184 (3) | |
H4A | 0.9823 | 0.8462 | −0.0372 | 0.022* | |
H4B | 0.9964 | 0.8814 | 0.1047 | 0.022* | |
C5 | 0.76336 (18) | 0.90689 (16) | 0.13711 (17) | 0.0214 (3) | |
H5A | 0.7087 | 0.8712 | 0.0892 | 0.026* | |
H5B | 0.7531 | 1.0105 | 0.1215 | 0.026* | |
C6 | 0.68366 (17) | 0.87894 (15) | 0.29946 (17) | 0.0185 (3) | |
H6A | 0.5690 | 0.9190 | 0.3377 | 0.022* | |
H6B | 0.7271 | 0.9271 | 0.3496 | 0.022* | |
C7 | 0.47662 (16) | 0.68664 (15) | 0.54806 (16) | 0.0154 (3) | |
C8 | 0.40673 (16) | 0.66322 (15) | 0.71070 (16) | 0.0164 (3) | |
C9 | 0.42059 (18) | 0.69739 (17) | 0.92856 (16) | 0.0201 (3) | |
H9A | 0.4350 | 0.5940 | 0.9461 | 0.024* | |
H9B | 0.3074 | 0.7410 | 0.9824 | 0.024* | |
C10 | 0.51870 (19) | 0.7615 (2) | 0.97764 (18) | 0.0280 (4) | |
H10A | 0.4864 | 0.7447 | 1.0808 | 0.042* | |
H10B | 0.5030 | 0.8639 | 0.9604 | 0.042* | |
H10C | 0.6304 | 0.7176 | 0.9236 | 0.042* | |
C11 | 1.05620 (16) | 0.44974 (15) | 0.31527 (15) | 0.0150 (3) | |
C12 | 1.07415 (16) | 0.29256 (15) | 0.35109 (15) | 0.0151 (3) | |
C13 | 1.01111 (18) | 0.07662 (15) | 0.32092 (17) | 0.0191 (3) | |
H13A | 0.9368 | 0.0484 | 0.2910 | 0.023* | |
H13B | 0.9681 | 0.0694 | 0.4271 | 0.023* | |
C14 | 1.16926 (19) | −0.02452 (16) | 0.25308 (18) | 0.0234 (4) | |
H14A | 1.1562 | −0.1215 | 0.2833 | 0.035* | |
H14B | 1.2426 | 0.0016 | 0.2841 | 0.035* | |
H14C | 1.2114 | −0.0192 | 0.1479 | 0.035* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.01266 (19) | 0.0330 (2) | 0.0216 (2) | −0.00552 (16) | −0.00853 (16) | 0.00012 (17) |
S2 | 0.01332 (19) | 0.0207 (2) | 0.0287 (2) | −0.00356 (15) | −0.01048 (17) | −0.00263 (16) |
N1 | 0.0111 (6) | 0.0183 (6) | 0.0138 (6) | −0.0043 (5) | −0.0062 (5) | 0.0014 (5) |
N2 | 0.0113 (6) | 0.0139 (6) | 0.0158 (6) | −0.0040 (5) | −0.0059 (5) | 0.0011 (5) |
O1 | 0.0149 (5) | 0.0220 (6) | 0.0146 (5) | −0.0060 (4) | −0.0058 (4) | 0.0002 (4) |
O2 | 0.0206 (6) | 0.0333 (6) | 0.0191 (6) | −0.0156 (5) | −0.0034 (5) | −0.0003 (5) |
O3 | 0.0176 (5) | 0.0150 (5) | 0.0161 (5) | −0.0044 (4) | −0.0087 (4) | 0.0019 (4) |
O4 | 0.0284 (6) | 0.0215 (6) | 0.0239 (6) | 0.0012 (5) | −0.0182 (5) | −0.0015 (5) |
C1 | 0.0129 (7) | 0.0165 (7) | 0.0139 (7) | −0.0045 (6) | −0.0065 (6) | 0.0016 (6) |
C2 | 0.0127 (7) | 0.0133 (7) | 0.0151 (8) | −0.0040 (6) | −0.0066 (6) | 0.0018 (6) |
C3 | 0.0151 (7) | 0.0193 (8) | 0.0143 (8) | −0.0050 (6) | −0.0054 (6) | 0.0001 (6) |
C4 | 0.0232 (8) | 0.0189 (8) | 0.0135 (8) | −0.0080 (6) | −0.0071 (6) | 0.0031 (6) |
C5 | 0.0251 (8) | 0.0179 (8) | 0.0237 (9) | −0.0062 (6) | −0.0130 (7) | 0.0066 (7) |
C6 | 0.0160 (7) | 0.0164 (8) | 0.0216 (8) | −0.0025 (6) | −0.0074 (6) | 0.0016 (6) |
C7 | 0.0129 (7) | 0.0125 (7) | 0.0191 (8) | −0.0028 (6) | −0.0052 (6) | −0.0014 (6) |
C8 | 0.0122 (7) | 0.0155 (7) | 0.0200 (8) | −0.0004 (6) | −0.0064 (6) | −0.0021 (6) |
C9 | 0.0190 (8) | 0.0254 (8) | 0.0142 (8) | −0.0039 (6) | −0.0060 (6) | 0.0011 (6) |
C10 | 0.0214 (8) | 0.0410 (10) | 0.0212 (9) | −0.0041 (7) | −0.0085 (7) | −0.0076 (8) |
C11 | 0.0136 (7) | 0.0184 (8) | 0.0118 (7) | −0.0013 (6) | −0.0048 (6) | −0.0031 (6) |
C12 | 0.0113 (7) | 0.0185 (7) | 0.0132 (7) | −0.0011 (6) | −0.0037 (6) | −0.0023 (6) |
C13 | 0.0230 (8) | 0.0147 (7) | 0.0208 (8) | −0.0073 (6) | −0.0097 (7) | 0.0040 (6) |
C14 | 0.0273 (9) | 0.0179 (8) | 0.0225 (9) | −0.0015 (7) | −0.0099 (7) | 0.0001 (7) |
S1—C7 | 1.6659 (15) | C4—C5 | 1.531 (2) |
S2—C11 | 1.6664 (14) | C4—H4A | 0.9900 |
N1—C7 | 1.3291 (18) | C4—H4B | 0.9900 |
N1—C1 | 1.4678 (18) | C5—C6 | 1.535 (2) |
N1—H1N | 0.8800 | C5—H5A | 0.9900 |
N2—C11 | 1.3312 (18) | C5—H5B | 0.9900 |
N2—C2 | 1.4648 (18) | C6—H6A | 0.9900 |
N2—H2N | 0.8800 | C6—H6B | 0.9900 |
O1—C8 | 1.3368 (18) | C7—C8 | 1.528 (2) |
O1—C9 | 1.4686 (18) | C9—C10 | 1.508 (2) |
O2—C8 | 1.2080 (18) | C9—H9A | 0.9900 |
O3—C12 | 1.3362 (17) | C9—H9B | 0.9900 |
O3—C13 | 1.4674 (17) | C10—H10A | 0.9800 |
O4—C12 | 1.2110 (17) | C10—H10B | 0.9800 |
C1—C2 | 1.5300 (19) | C10—H10C | 0.9800 |
C1—C6 | 1.541 (2) | C11—C12 | 1.522 (2) |
C1—H1 | 1.0000 | C13—C14 | 1.512 (2) |
C2—C3 | 1.538 (2) | C13—H13A | 0.9900 |
C2—H2 | 1.0000 | C13—H13B | 0.9900 |
C3—C4 | 1.528 (2) | C14—H14A | 0.9800 |
C3—H3A | 0.9900 | C14—H14B | 0.9800 |
C3—H3B | 0.9900 | C14—H14C | 0.9800 |
C7—N1—C1 | 121.67 (12) | C1—C6—H6A | 109.4 |
C7—N1—H1N | 119.2 | C5—C6—H6B | 109.4 |
C1—N1—H1N | 119.2 | C1—C6—H6B | 109.4 |
C11—N2—C2 | 121.92 (12) | H6A—C6—H6B | 108.0 |
C11—N2—H2N | 119.0 | N1—C7—C8 | 115.68 (12) |
C2—N2—H2N | 119.0 | N1—C7—S1 | 126.01 (12) |
C8—O1—C9 | 115.03 (11) | C8—C7—S1 | 118.31 (10) |
C12—O3—C13 | 116.13 (11) | O2—C8—O1 | 124.61 (14) |
N1—C1—C2 | 112.62 (11) | O2—C8—C7 | 123.49 (13) |
N1—C1—C6 | 110.12 (12) | O1—C8—C7 | 111.89 (12) |
C2—C1—C6 | 109.01 (11) | O1—C9—C10 | 107.65 (12) |
N1—C1—H1 | 108.3 | O1—C9—H9A | 110.2 |
C2—C1—H1 | 108.3 | C10—C9—H9A | 110.2 |
C6—C1—H1 | 108.3 | O1—C9—H9B | 110.2 |
N2—C2—C1 | 112.54 (11) | C10—C9—H9B | 110.2 |
N2—C2—C3 | 110.48 (11) | H9A—C9—H9B | 108.5 |
C1—C2—C3 | 108.87 (11) | C9—C10—H10A | 109.5 |
N2—C2—H2 | 108.3 | C9—C10—H10B | 109.5 |
C1—C2—H2 | 108.3 | H10A—C10—H10B | 109.5 |
C3—C2—H2 | 108.3 | C9—C10—H10C | 109.5 |
C4—C3—C2 | 110.10 (12) | H10A—C10—H10C | 109.5 |
C4—C3—H3A | 109.6 | H10B—C10—H10C | 109.5 |
C2—C3—H3A | 109.6 | N2—C11—C12 | 114.68 (12) |
C4—C3—H3B | 109.6 | N2—C11—S2 | 126.56 (11) |
C2—C3—H3B | 109.6 | C12—C11—S2 | 118.76 (10) |
H3A—C3—H3B | 108.2 | O4—C12—O3 | 125.05 (13) |
C3—C4—C5 | 111.16 (12) | O4—C12—C11 | 124.11 (13) |
C3—C4—H4A | 109.4 | O3—C12—C11 | 110.83 (12) |
C5—C4—H4A | 109.4 | O3—C13—C14 | 112.42 (12) |
C3—C4—H4B | 109.4 | O3—C13—H13A | 109.1 |
C5—C4—H4B | 109.4 | C14—C13—H13A | 109.1 |
H4A—C4—H4B | 108.0 | O3—C13—H13B | 109.1 |
C4—C5—C6 | 111.90 (12) | C14—C13—H13B | 109.1 |
C4—C5—H5A | 109.2 | H13A—C13—H13B | 107.9 |
C6—C5—H5A | 109.2 | C13—C14—H14A | 109.5 |
C4—C5—H5B | 109.2 | C13—C14—H14B | 109.5 |
C6—C5—H5B | 109.2 | H14A—C14—H14B | 109.5 |
H5A—C5—H5B | 107.9 | C13—C14—H14C | 109.5 |
C5—C6—C1 | 111.12 (12) | H14A—C14—H14C | 109.5 |
C5—C6—H6A | 109.4 | H14B—C14—H14C | 109.5 |
C7—N1—C1—C2 | −153.12 (13) | C9—O1—C8—O2 | 5.7 (2) |
C7—N1—C1—C6 | 84.98 (16) | C9—O1—C8—C7 | −175.52 (11) |
C11—N2—C2—C1 | −151.70 (13) | N1—C7—C8—O2 | −148.80 (14) |
C11—N2—C2—C3 | 86.37 (15) | S1—C7—C8—O2 | 30.94 (19) |
N1—C1—C2—N2 | 52.61 (15) | N1—C7—C8—O1 | 32.43 (17) |
C6—C1—C2—N2 | 175.14 (11) | S1—C7—C8—O1 | −147.83 (10) |
N1—C1—C2—C3 | 175.44 (11) | C8—O1—C9—C10 | 174.37 (12) |
C6—C1—C2—C3 | −62.03 (14) | C2—N2—C11—C12 | −179.51 (12) |
N2—C2—C3—C4 | −174.06 (11) | C2—N2—C11—S2 | 1.0 (2) |
C1—C2—C3—C4 | 61.88 (14) | C13—O3—C12—O4 | 9.3 (2) |
C2—C3—C4—C5 | −56.87 (16) | C13—O3—C12—C11 | −171.39 (11) |
C3—C4—C5—C6 | 52.72 (17) | N2—C11—C12—O4 | −141.38 (14) |
C4—C5—C6—C1 | −53.51 (16) | S2—C11—C12—O4 | 38.18 (19) |
N1—C1—C6—C5 | −177.87 (11) | N2—C11—C12—O3 | 39.32 (17) |
C2—C1—C6—C5 | 58.11 (15) | S2—C11—C12—O3 | −141.12 (11) |
C1—N1—C7—C8 | −179.09 (12) | C12—O3—C13—C14 | −79.71 (16) |
C1—N1—C7—S1 | 1.2 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N···O4i | 0.88 | 2.27 | 3.0226 (16) | 144 |
N1—H1N···S2i | 0.88 | 2.96 | 3.6806 (13) | 141 |
N2—H2N···O2ii | 0.88 | 2.27 | 3.0163 (16) | 143 |
N2—H2N···S1ii | 0.88 | 2.87 | 3.6093 (13) | 143 |
C1—H1···O2ii | 1.00 | 2.64 | 3.3820 (18) | 131 |
C2—H2···O4i | 1.00 | 2.52 | 3.2620 (18) | 131 |
Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) −x+1, −y+1, −z+1. |
C22H24N2O4S2 | F(000) = 936 |
Mr = 444.55 | Dx = 1.304 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 4659 reflections |
a = 9.2414 (4) Å | θ = 4–25° |
b = 21.7781 (10) Å | µ = 0.27 mm−1 |
c = 11.4322 (6) Å | T = 110 K |
β = 100.273 (4)° | Plate, orange |
V = 2263.96 (19) Å3 | 0.30 × 0.30 × 0.08 mm |
Z = 4 |
Kuma KM-4 CCD κ geometry diffractometer | 4613 independent reflections |
Radiation source: fine-focus sealed tube | 3649 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.026 |
ω scans | θmax = 26.4°, θmin = 4.1° |
Absorption correction: multi-scan (Blessing, 1995) | h = −11→11 |
Tmin = 0.906, Tmax = 0.979 | k = −25→27 |
16375 measured reflections | l = −14→14 |
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)] = 0.032 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.084 | H-atom parameters constrained |
S = 1.08 | w = 1/[\s^2^(Fo^2^) + (0.0469P)^2^ + 0.1761P]
where P = (Fo^2^ + 2Fc^2^)/3' |
4613 reflections | (Δ/σ)max = 0.003 |
271 parameters | Δρmax = 0.26 e Å−3 |
0 restraints | Δρmin = −0.24 e Å−3 |
C22H24N2O4S2 | V = 2263.96 (19) Å3 |
Mr = 444.55 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 9.2414 (4) Å | µ = 0.27 mm−1 |
b = 21.7781 (10) Å | T = 110 K |
c = 11.4322 (6) Å | 0.30 × 0.30 × 0.08 mm |
β = 100.273 (4)° |
Kuma KM-4 CCD κ geometry diffractometer | 4613 independent reflections |
Absorption correction: multi-scan (Blessing, 1995) | 3649 reflections with I > 2σ(I) |
Tmin = 0.906, Tmax = 0.979 | Rint = 0.026 |
16375 measured reflections |
R[F2 > 2σ(F2)] = 0.032 | 0 restraints |
wR(F2) = 0.084 | H-atom parameters constrained |
S = 1.08 | Δρmax = 0.26 e Å−3 |
4613 reflections | Δρmin = −0.24 e Å−3 |
271 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 | 1.10727 (4) | 0.577807 (18) | 0.44121 (3) | 0.02186 (11) | |
S2 | 0.40946 (4) | 0.559452 (17) | 0.65132 (3) | 0.02230 (11) | |
O1 | 0.96788 (11) | 0.47620 (5) | 0.25722 (10) | 0.0263 (3) | |
O2 | 0.49931 (11) | 0.42075 (5) | 0.67245 (10) | 0.0254 (3) | |
O3 | 0.79147 (10) | 0.54746 (4) | 0.19994 (8) | 0.0195 (2) | |
O4 | 0.70910 (10) | 0.45238 (4) | 0.78833 (9) | 0.0189 (2) | |
N1 | 0.81645 (12) | 0.57864 (5) | 0.43173 (10) | 0.0162 (3) | |
H1N | 0.7291 | 0.5644 | 0.4002 | 0.019* | |
N2 | 0.69531 (12) | 0.55176 (5) | 0.64079 (10) | 0.0159 (3) | |
H2N | 0.7769 | 0.5300 | 0.6522 | 0.019* | |
C1 | 0.82927 (15) | 0.62231 (6) | 0.53043 (12) | 0.0164 (3) | |
H1 | 0.9221 | 0.6131 | 0.5874 | 0.020* | |
C2 | 0.69867 (15) | 0.61482 (6) | 0.59676 (12) | 0.0163 (3) | |
H2 | 0.6056 | 0.6225 | 0.5392 | 0.020* | |
C3 | 0.93355 (15) | 0.56004 (6) | 0.38864 (12) | 0.0169 (3) | |
C4 | 0.57279 (15) | 0.52636 (6) | 0.66405 (12) | 0.0165 (3) | |
C5 | 0.90036 (15) | 0.52134 (7) | 0.27626 (13) | 0.0189 (3) | |
C6 | 0.58841 (15) | 0.46044 (7) | 0.70675 (12) | 0.0171 (3) | |
C7 | 0.75031 (17) | 0.51735 (7) | 0.08505 (13) | 0.0247 (3) | |
H7A | 0.7053 | 0.4768 | 0.0946 | 0.030* | |
H7B | 0.8379 | 0.5112 | 0.0476 | 0.030* | |
C8 | 0.73393 (16) | 0.38900 (7) | 0.82938 (15) | 0.0253 (3) | |
H8A | 0.7317 | 0.3612 | 0.7605 | 0.030* | |
H8B | 0.6557 | 0.3762 | 0.8731 | 0.030* | |
C9 | 0.64184 (19) | 0.55885 (8) | 0.01005 (14) | 0.0316 (4) | |
H9A | 0.6114 | 0.5405 | −0.0688 | 0.047* | |
H9B | 0.6877 | 0.5988 | 0.0020 | 0.047* | |
H9C | 0.5556 | 0.5643 | 0.0480 | 0.047* | |
C10 | 0.88098 (17) | 0.38546 (8) | 0.90941 (15) | 0.0300 (4) | |
H10A | 0.8988 | 0.3433 | 0.9383 | 0.045* | |
H10B | 0.8824 | 0.4132 | 0.9771 | 0.045* | |
H10C | 0.9579 | 0.3976 | 0.8651 | 0.045* | |
C11 | 0.83808 (15) | 0.68767 (6) | 0.48626 (12) | 0.0174 (3) | |
C12 | 0.73369 (17) | 0.71090 (7) | 0.39422 (13) | 0.0246 (3) | |
H12A | 0.6558 | 0.6854 | 0.3563 | 0.030* | |
C13 | 0.74327 (19) | 0.77137 (8) | 0.35763 (15) | 0.0315 (4) | |
H13A | 0.6718 | 0.7871 | 0.2946 | 0.038* | |
C14 | 0.85608 (19) | 0.80885 (7) | 0.41222 (15) | 0.0310 (4) | |
H14A | 0.8623 | 0.8501 | 0.3865 | 0.037* | |
C15 | 0.95956 (18) | 0.78618 (7) | 0.50409 (15) | 0.0288 (4) | |
H15A | 1.0367 | 0.8119 | 0.5424 | 0.035* | |
C16 | 0.95072 (16) | 0.72572 (7) | 0.54045 (13) | 0.0227 (3) | |
H16A | 1.0227 | 0.7102 | 0.6033 | 0.027* | |
C17 | 0.70980 (15) | 0.66189 (6) | 0.69635 (12) | 0.0164 (3) | |
C18 | 0.82724 (16) | 0.66136 (7) | 0.79099 (13) | 0.0229 (3) | |
H18A | 0.8979 | 0.6293 | 0.7975 | 0.028* | |
C19 | 0.84170 (17) | 0.70749 (7) | 0.87609 (14) | 0.0276 (4) | |
H19A | 0.9230 | 0.7072 | 0.9400 | 0.033* | |
C20 | 0.73777 (17) | 0.75398 (7) | 0.86819 (14) | 0.0261 (3) | |
H20A | 0.7484 | 0.7857 | 0.9260 | 0.031* | |
C21 | 0.61919 (16) | 0.75392 (7) | 0.77623 (14) | 0.0243 (3) | |
H21A | 0.5467 | 0.7852 | 0.7716 | 0.029* | |
C22 | 0.60529 (15) | 0.70818 (7) | 0.69025 (13) | 0.0204 (3) | |
H22A | 0.5236 | 0.7086 | 0.6267 | 0.024* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.01436 (18) | 0.0280 (2) | 0.0234 (2) | 0.00108 (15) | 0.00388 (14) | 0.00000 (16) |
S2 | 0.01411 (18) | 0.0219 (2) | 0.0309 (2) | 0.00173 (15) | 0.00417 (15) | 0.00474 (16) |
O1 | 0.0281 (6) | 0.0220 (6) | 0.0293 (6) | 0.0089 (5) | 0.0066 (5) | −0.0017 (5) |
O2 | 0.0211 (5) | 0.0182 (6) | 0.0354 (6) | −0.0041 (4) | 0.0011 (5) | 0.0002 (5) |
O3 | 0.0200 (5) | 0.0191 (6) | 0.0190 (5) | 0.0032 (4) | 0.0023 (4) | −0.0025 (4) |
O4 | 0.0198 (5) | 0.0149 (5) | 0.0214 (5) | 0.0022 (4) | 0.0021 (4) | 0.0029 (4) |
N1 | 0.0146 (6) | 0.0146 (6) | 0.0198 (6) | −0.0013 (5) | 0.0036 (5) | −0.0021 (5) |
N2 | 0.0136 (6) | 0.0141 (6) | 0.0206 (6) | 0.0019 (4) | 0.0045 (5) | 0.0030 (5) |
C1 | 0.0150 (7) | 0.0177 (8) | 0.0162 (7) | −0.0003 (5) | 0.0020 (5) | −0.0006 (6) |
C2 | 0.0153 (7) | 0.0149 (7) | 0.0191 (7) | 0.0014 (5) | 0.0041 (6) | 0.0027 (6) |
C3 | 0.0189 (7) | 0.0133 (7) | 0.0188 (7) | 0.0028 (6) | 0.0042 (6) | 0.0046 (6) |
C4 | 0.0174 (7) | 0.0171 (8) | 0.0145 (7) | −0.0015 (6) | 0.0013 (5) | −0.0013 (6) |
C5 | 0.0156 (7) | 0.0187 (8) | 0.0234 (8) | −0.0005 (6) | 0.0065 (6) | 0.0031 (6) |
C6 | 0.0167 (7) | 0.0180 (8) | 0.0178 (7) | 0.0009 (6) | 0.0063 (6) | −0.0002 (6) |
C7 | 0.0277 (8) | 0.0234 (9) | 0.0224 (8) | 0.0022 (6) | 0.0031 (6) | −0.0072 (6) |
C8 | 0.0263 (8) | 0.0170 (8) | 0.0332 (9) | 0.0047 (6) | 0.0070 (7) | 0.0089 (7) |
C9 | 0.0395 (10) | 0.0318 (10) | 0.0210 (8) | 0.0068 (8) | −0.0008 (7) | −0.0043 (7) |
C10 | 0.0341 (9) | 0.0256 (9) | 0.0294 (9) | 0.0095 (7) | 0.0028 (7) | 0.0060 (7) |
C11 | 0.0196 (7) | 0.0160 (8) | 0.0184 (7) | 0.0002 (6) | 0.0087 (6) | −0.0013 (6) |
C12 | 0.0276 (8) | 0.0226 (8) | 0.0229 (8) | 0.0004 (7) | 0.0027 (6) | 0.0015 (6) |
C13 | 0.0417 (10) | 0.0263 (9) | 0.0267 (9) | 0.0083 (8) | 0.0063 (7) | 0.0064 (7) |
C14 | 0.0459 (10) | 0.0155 (8) | 0.0373 (9) | 0.0011 (7) | 0.0228 (8) | 0.0019 (7) |
C15 | 0.0327 (9) | 0.0217 (9) | 0.0358 (9) | −0.0072 (7) | 0.0158 (8) | −0.0068 (7) |
C16 | 0.0232 (8) | 0.0227 (8) | 0.0226 (8) | −0.0028 (6) | 0.0056 (6) | −0.0026 (6) |
C17 | 0.0188 (7) | 0.0135 (7) | 0.0185 (7) | −0.0023 (6) | 0.0076 (6) | 0.0024 (6) |
C18 | 0.0235 (8) | 0.0219 (8) | 0.0233 (8) | 0.0054 (6) | 0.0039 (6) | 0.0018 (6) |
C19 | 0.0294 (8) | 0.0296 (9) | 0.0232 (8) | 0.0014 (7) | 0.0030 (7) | −0.0018 (7) |
C20 | 0.0348 (9) | 0.0213 (8) | 0.0245 (8) | −0.0020 (7) | 0.0114 (7) | −0.0053 (7) |
C21 | 0.0261 (8) | 0.0175 (8) | 0.0319 (9) | 0.0036 (6) | 0.0125 (7) | 0.0020 (7) |
C22 | 0.0190 (7) | 0.0189 (8) | 0.0243 (8) | 0.0002 (6) | 0.0069 (6) | 0.0034 (6) |
S1—C3 | 1.6565 (14) | C9—H9B | 0.9800 |
S2—C4 | 1.6554 (14) | C9—H9C | 0.9800 |
O1—C5 | 1.2048 (17) | C10—H10A | 0.9800 |
O2—C6 | 1.2097 (17) | C10—H10B | 0.9800 |
O3—C5 | 1.3358 (17) | C10—H10C | 0.9800 |
O3—C7 | 1.4566 (17) | C11—C16 | 1.387 (2) |
O4—C6 | 1.3318 (16) | C11—C12 | 1.390 (2) |
O4—C8 | 1.4626 (17) | C12—C13 | 1.389 (2) |
N1—C3 | 1.3296 (17) | C12—H12A | 0.9500 |
N1—C1 | 1.4642 (17) | C13—C14 | 1.382 (2) |
N1—H1N | 0.8800 | C13—H13A | 0.9500 |
N2—C4 | 1.3290 (17) | C14—C15 | 1.379 (2) |
N2—C2 | 1.4648 (18) | C14—H14A | 0.9500 |
N2—H2N | 0.8800 | C15—C16 | 1.388 (2) |
C1—C11 | 1.517 (2) | C15—H15A | 0.9500 |
C1—C2 | 1.5443 (18) | C16—H16A | 0.9500 |
C1—H1 | 1.0000 | C17—C22 | 1.3892 (19) |
C2—C17 | 1.5219 (19) | C17—C18 | 1.389 (2) |
C2—H2 | 1.0000 | C18—C19 | 1.388 (2) |
C3—C5 | 1.521 (2) | C18—H18A | 0.9500 |
C4—C6 | 1.515 (2) | C19—C20 | 1.387 (2) |
C7—C9 | 1.500 (2) | C19—H19A | 0.9500 |
C7—H7A | 0.9900 | C20—C21 | 1.377 (2) |
C7—H7B | 0.9900 | C20—H20A | 0.9500 |
C8—C10 | 1.499 (2) | C21—C22 | 1.389 (2) |
C8—H8A | 0.9900 | C21—H21A | 0.9500 |
C8—H8B | 0.9900 | C22—H22A | 0.9500 |
C9—H9A | 0.9800 | ||
C5—O3—C7 | 116.25 (11) | H9A—C9—H9B | 109.5 |
C6—O4—C8 | 114.39 (11) | C7—C9—H9C | 109.5 |
C3—N1—C1 | 121.60 (12) | H9A—C9—H9C | 109.5 |
C3—N1—H1N | 119.2 | H9B—C9—H9C | 109.5 |
C1—N1—H1N | 119.2 | C8—C10—H10A | 109.5 |
C4—N2—C2 | 122.01 (11) | C8—C10—H10B | 109.5 |
C4—N2—H2N | 119.0 | H10A—C10—H10B | 109.5 |
C2—N2—H2N | 119.0 | C8—C10—H10C | 109.5 |
N1—C1—C11 | 110.77 (11) | H10A—C10—H10C | 109.5 |
N1—C1—C2 | 110.30 (11) | H10B—C10—H10C | 109.5 |
C11—C1—C2 | 110.82 (11) | C16—C11—C12 | 119.01 (14) |
N1—C1—H1 | 108.3 | C16—C11—C1 | 119.49 (13) |
C11—C1—H1 | 108.3 | C12—C11—C1 | 121.48 (13) |
C2—C1—H1 | 108.3 | C13—C12—C11 | 120.01 (15) |
N2—C2—C17 | 112.16 (11) | C13—C12—H12A | 120.0 |
N2—C2—C1 | 109.51 (11) | C11—C12—H12A | 120.0 |
C17—C2—C1 | 109.99 (11) | C14—C13—C12 | 120.48 (15) |
N2—C2—H2 | 108.4 | C14—C13—H13A | 119.8 |
C17—C2—H2 | 108.4 | C12—C13—H13A | 119.8 |
C1—C2—H2 | 108.4 | C15—C14—C13 | 119.81 (15) |
N1—C3—C5 | 115.26 (12) | C15—C14—H14A | 120.1 |
N1—C3—S1 | 126.49 (11) | C13—C14—H14A | 120.1 |
C5—C3—S1 | 118.17 (10) | C14—C15—C16 | 119.86 (15) |
N2—C4—C6 | 115.05 (12) | C14—C15—H15A | 120.1 |
N2—C4—S2 | 126.67 (11) | C16—C15—H15A | 120.1 |
C6—C4—S2 | 118.28 (10) | C11—C16—C15 | 120.84 (14) |
O1—C5—O3 | 125.70 (13) | C11—C16—H16A | 119.6 |
O1—C5—C3 | 124.87 (13) | C15—C16—H16A | 119.6 |
O3—C5—C3 | 109.30 (11) | C22—C17—C18 | 119.00 (13) |
O2—C6—O4 | 124.71 (14) | C22—C17—C2 | 119.84 (13) |
O2—C6—C4 | 123.53 (13) | C18—C17—C2 | 121.08 (12) |
O4—C6—C4 | 111.74 (12) | C19—C18—C17 | 120.26 (14) |
O3—C7—C9 | 106.53 (12) | C19—C18—H18A | 119.9 |
O3—C7—H7A | 110.4 | C17—C18—H18A | 119.9 |
C9—C7—H7A | 110.4 | C20—C19—C18 | 120.23 (15) |
O3—C7—H7B | 110.4 | C20—C19—H19A | 119.9 |
C9—C7—H7B | 110.4 | C18—C19—H19A | 119.9 |
H7A—C7—H7B | 108.6 | C21—C20—C19 | 119.78 (15) |
O4—C8—C10 | 108.53 (12) | C21—C20—H20A | 120.1 |
O4—C8—H8A | 110.0 | C19—C20—H20A | 120.1 |
C10—C8—H8A | 110.0 | C20—C21—C22 | 120.10 (14) |
O4—C8—H8B | 110.0 | C20—C21—H21A | 119.9 |
C10—C8—H8B | 110.0 | C22—C21—H21A | 119.9 |
H8A—C8—H8B | 108.4 | C21—C22—C17 | 120.60 (14) |
C7—C9—H9A | 109.5 | C21—C22—H22A | 119.7 |
C7—C9—H9B | 109.5 | C17—C22—H22A | 119.7 |
C3—N1—C1—C11 | 81.42 (15) | C6—O4—C8—C10 | 173.51 (12) |
C3—N1—C1—C2 | −155.52 (12) | N1—C1—C11—C16 | −128.69 (13) |
C4—N2—C2—C17 | 81.00 (16) | C2—C1—C11—C16 | 108.54 (14) |
C4—N2—C2—C1 | −156.60 (12) | N1—C1—C11—C12 | 52.81 (17) |
N1—C1—C2—N2 | 58.36 (14) | C2—C1—C11—C12 | −69.96 (17) |
C11—C1—C2—N2 | −178.60 (11) | C16—C11—C12—C13 | 0.1 (2) |
N1—C1—C2—C17 | −177.95 (11) | C1—C11—C12—C13 | 178.63 (14) |
C11—C1—C2—C17 | −54.91 (15) | C11—C12—C13—C14 | −0.1 (2) |
C1—N1—C3—C5 | −172.35 (12) | C12—C13—C14—C15 | −0.3 (2) |
C1—N1—C3—S1 | 4.36 (19) | C13—C14—C15—C16 | 0.6 (2) |
C2—N2—C4—C6 | 178.93 (12) | C12—C11—C16—C15 | 0.2 (2) |
C2—N2—C4—S2 | −1.3 (2) | C1—C11—C16—C15 | −178.34 (13) |
C7—O3—C5—O1 | 1.4 (2) | C14—C15—C16—C11 | −0.6 (2) |
C7—O3—C5—C3 | 177.46 (11) | N2—C2—C17—C22 | −124.30 (13) |
N1—C3—C5—O1 | −138.24 (15) | C1—C2—C17—C22 | 113.57 (14) |
S1—C3—C5—O1 | 44.77 (19) | N2—C2—C17—C18 | 58.99 (17) |
N1—C3—C5—O3 | 45.63 (16) | C1—C2—C17—C18 | −63.14 (16) |
S1—C3—C5—O3 | −131.37 (11) | C22—C17—C18—C19 | −1.8 (2) |
C8—O4—C6—O2 | 4.37 (19) | C2—C17—C18—C19 | 174.90 (13) |
C8—O4—C6—C4 | −177.43 (11) | C17—C18—C19—C20 | 0.9 (2) |
N2—C4—C6—O2 | −137.14 (14) | C18—C19—C20—C21 | 0.7 (2) |
S2—C4—C6—O2 | 43.06 (18) | C19—C20—C21—C22 | −1.4 (2) |
N2—C4—C6—O4 | 44.63 (16) | C20—C21—C22—C17 | 0.5 (2) |
S2—C4—C6—O4 | −135.16 (10) | C18—C17—C22—C21 | 1.1 (2) |
C5—O3—C7—C9 | −172.71 (12) | C2—C17—C22—C21 | −175.63 (13) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2N···O1i | 0.88 | 2.40 | 3.1819 (15) | 147 |
N2—H2N···S1i | 0.88 | 2.87 | 3.5749 (12) | 139 |
N1—H1N···O2ii | 0.88 | 2.15 | 2.9487 (15) | 151 |
N1—H1N···S2ii | 0.88 | 3.00 | 3.6875 (12) | 137 |
C1—H1···O1i | 1.00 | 2.71 | 3.5195 (17) | 139 |
C2—H2···O2ii | 1.00 | 2.62 | 3.3781 (18) | 133 |
Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) −x+1, −y+1, −z+1. |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | C14H22N2O4S2 | C22H24N2O4S2 |
Mr | 346.46 | 444.55 |
Crystal system, space group | Triclinic, P1 | Monoclinic, P21/n |
Temperature (K) | 120 | 110 |
a, b, c (Å) | 9.6438 (10), 9.6656 (11), 10.3316 (11) | 9.2414 (4), 21.7781 (10), 11.4322 (6) |
α, β, γ (°) | 85.068 (9), 63.887 (10), 77.155 (9) | 90, 100.273 (4), 90 |
V (Å3) | 843.02 (18) | 2263.96 (19) |
Z | 2 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.33 | 0.27 |
Crystal size (mm) | 0.4 × 0.4 × 0.2 | 0.30 × 0.30 × 0.08 |
Data collection | ||
Diffractometer | Kuma KM-4 CCD κ geometry diffractometer | Kuma KM-4 CCD κ geometry diffractometer |
Absorption correction | Multi-scan (Blessing, 1995) | Multi-scan (Blessing, 1995) |
Tmin, Tmax | 0.840, 0.935 | 0.906, 0.979 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6232, 2957, 2587 | 16375, 4613, 3649 |
Rint | 0.016 | 0.026 |
(sin θ/λ)max (Å−1) | 0.595 | 0.625 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.027, 0.072, 1.07 | 0.032, 0.084, 1.08 |
No. of reflections | 2957 | 4613 |
No. of parameters | 199 | 271 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.29, −0.25 | 0.26, −0.24 |
Computer programs: CrysAlis CCD (Oxford Diffraction, 2006), CrysAlis RED (Oxford Diffraction, 2006), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), Stereochemical Workstation (Siemens, 1989) and Mercury (Version 1.4; Macrae et al., 2006).
C7—N1—C1—C2 | −153.12 (13) | N1—C1—C2—N2 | 52.61 (15) |
C7—N1—C1—C6 | 84.98 (16) | S1—C7—C8—O2 | 30.94 (19) |
C11—N2—C2—C1 | −151.70 (13) | S2—C11—C12—O4 | 38.18 (19) |
C11—N2—C2—C3 | 86.37 (15) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N···O4i | 0.88 | 2.27 | 3.0226 (16) | 144 |
N1—H1N···S2i | 0.88 | 2.96 | 3.6806 (13) | 141 |
N2—H2N···O2ii | 0.88 | 2.27 | 3.0163 (16) | 143 |
N2—H2N···S1ii | 0.88 | 2.87 | 3.6093 (13) | 143 |
C1—H1···O2ii | 1.00 | 2.64 | 3.3820 (18) | 131 |
C2—H2···O4i | 1.00 | 2.52 | 3.2620 (18) | 131 |
Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) −x+1, −y+1, −z+1. |
C3—N1—C1—C11 | 81.42 (15) | N1—C1—C2—N2 | 58.36 (14) |
C3—N1—C1—C2 | −155.52 (12) | S1—C3—C5—O1 | 44.77 (19) |
C4—N2—C2—C17 | 81.00 (16) | S2—C4—C6—O2 | 43.06 (18) |
C4—N2—C2—C1 | −156.60 (12) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2N···O1i | 0.88 | 2.40 | 3.1819 (15) | 147 |
N2—H2N···S1i | 0.88 | 2.87 | 3.5749 (12) | 139 |
N1—H1N···O2ii | 0.88 | 2.15 | 2.9487 (15) | 151 |
N1—H1N···S2ii | 0.88 | 3.00 | 3.6875 (12) | 137 |
C1—H1···O1i | 1.00 | 2.71 | 3.5195 (17) | 139 |
C2—H2···O2ii | 1.00 | 2.62 | 3.3781 (18) | 133 |
Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) −x+1, −y+1, −z+1. |
The self-complementary oxamic acid ester functionality is considered as a good supramolecular building block and it is expected to form the R22 (10) hydrogen-bond motif by the interaction of two amide H atoms with two ester carbonyl groups (Blay et al., 2003). However, a survey of the structures collected in the Cambridge Structural Database (Allen, 2002; CSD version 5.8 plus three updates) showed that during the self-assembly process the C(4) chain motif involving only the amide units competes with the cyclic R22(10) motif (Piotrkowska et al., 2007). As the structural data of oxalamic acid esters are scarce, any generalizations about the robustness of their supramolecular synthons seem to be premature, and definitely more information about their supramolecular structures is needed. We focused our interest on bisthionooxamide esters expecting that, on the one hand, replacement of the amide carbonyl O atom by sulfur should enhance the acidity of the amide H atom, making it a stronger hydrogen-bond donor. On the other hand, this modification should promote hydrogen bonding to the ester carbonyl group, and thus also promote the cyclic R22 (10) motif, because the thiocarbonyl group is a weaker hydrogen-bond acceptor than the carbonyl group. Very recently, we have reported the crystal structures of four bisthionooxamide esters (Piotrkowska et al., 2007); in the crystal structures of the homochiral compounds derived from (1S, 2S)-1,2-diaminocyclohexane, S-(I), and (1R,2R)-1,2-diphenylethylenediamine, R-(II), the molecules assembled via the R22 (10) motif, forming right-handed helices and discrete dimeric assemblies, respectively.
In order to compare the self-assembly mode of enantiopure and racemic bisthionooxamide esters the racemic compounds, rac-(I) and rac-(II), were synthesized and their crystal structures were determined (Figs. 1 and 2). In the crystal structures, these symmetrical and conformationally flexible molecules are located at general positions; however, they adopt conformations that do not deviate much from C2 symmetry. In both molecules, the torsion angles N1—C1—C2—N2, C(3,7)—N1—C1—C2 and C1—C2—N2—C(4,11), determining to a large extent the molecular conformation, have similar values (Tables 1 and 3, and Figs. 1 and 2). The last two torsions are responsible for the orientation of the thioamide units relative to the plane of the –CH—CH– spacer. In rac-(II), the orientation of these groups is close to that observed in the homochiral crystals; the two torsion angles are 155.52 (12) and 156.60 (12)° in the racemic form, whereas in R-(II) they are in the range 155.8 (4)–166.4 (4)°. The difference is more pronounced in (I), where the C3—N1—C1—C2 and C1—C2—N2—C4 torsion angles are -151.70 (13) and -153.12 (13)° in rac-(I), whereas in the homochiral crystal S-(I) these angles are -94.5 (2)°, resulting in a nearly perpendicular orientation of the thioamide group relative to the mean cyclohexane ring plane. In the racemic and enantiopure forms of (I) and (II), the thionooxamide groups are significantly twisted, with a dihedral angle between the thioamide and ester parts in the range 23.01 (6)–45.72 (6)°. Surprisingly, in the homochiral crystals these groups were found in the s-trans conformation, whereas in the racemic forms they are always in the s-cis conformation, as indicated by the values of the S═ C—C═O torsion angles (Tables 1 and 3).
As mentioned earlier, in the homochiral crystals of (I) and (II) (Piotrkowska et al., 2007) the hydrogen-bonded assemblies of molecules are formed via the R22 (10) hydrogen-bond motif. However, in the crystal structures of the racemic compounds, the molecules form one-dimensional polymeric structures via two antiparallel C(5) motifs generated by N—H···O interactions between molecules of the opposite chirality (Figs. 3a and 4a). The supramolecular assemblies in the racemic crystals of the two studied compounds are very similar. The N—H···O hydrogen bond is part of a three-center interaction, because each thioamide H atom forms, in addition to a short contact with the carbonyl O atom, a short contact to the thiocarbonyl S atom of the same thionooxamide unit (Tables 2 and 4, and Figs. 3 and 4). The aggregate of the (S,S) and (R,R) enantiomeric molecules is further stabilized by a C—H···O interaction between the carbonyl O atom and the methine CH group of the cyclohexane ring that is located on the same side of the ring as the N—H group. All of these attractive intermolecular interactions between the molecules of different chirality are optimized by a twisting of the thionooxamide groups.
To summarize, in the homo- and heterochiral crystals of symmetrical bis-thionooxalamic acid esters derived from trans-1,2-diaminocyclohexane or 1,2-diphenylethylenediamine, the thioamide H atom is involved in hydrogen bonding to the best acceptor, viz. the ester carbonyl O atom. In the enantiopure crystals this interaction leads to the expected cyclic R22 (10) motif, but in the case of racemic crystals, it generates a C(5) motif, assembling molecules into an achiral one-dimensional polymeric structure.