Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270111010328/sk3399sup1.cif | |
Rietveld powder data file (CIF format) https://doi.org/10.1107/S0108270111010328/sk3399Isup2.rtv | |
Rietveld powder data file (CIF format) https://doi.org/10.1107/S0108270111010328/sk3399IIsup3.rtv |
CCDC references: 829709; 829710
For related literature, see: Al-Ktaifani & Rukiah (2010); Altomare et al. (2004); Boultif & Louër (2004); Brandau et al. (1988); Chan et al. (1999); Chernyshev et al. (2003); Favre-Nicolin & Černý (2002); Finger et al. (1994); Guhlke et al. (1998); Hjelstuen et al. (1998); Huheey et al. (1993); Jones (2003); Kiang et al. (2003); Larson & Von Dreele (2004); Roisnel & Rodriguez-Carvajal (2001); Rukiah & Assaad (2010); Rukiah et al. (2004); Schneider et al. (1984); Shankland et al. (2001); Thompson et al. (1987); Toby (2001); Van Gog, Visser, Growising, Snow & van Dongen (1998); Van der Lee, Richez & Tapiero (2005); Von Dreele (1997); Xiuli et al. (2003).
Benzoyl chloride, mercaptoacetic acid, dicyclohexylcarbodiimide and N-hydroxysuccinimide were commercial samples and used as received. 1H and 13C{1H} NMR spectra were recorded on a Bruker Bio Spin 400 spectrometer. IR spectra were recorded on an FT–IR Jasco 300E. Microanalysis was performed using a EURO EA instrument. X-ray powder diffraction patterns were obtained using a Stoe STADI P diffractometer with monochromatic Cu Kα1 radiation (λ = 1.5406 Å) selected with an incident-beam curved-crystal Ge(111) monochromator, using Stoe transmission geometry (horizontal set-up) with a linear position-sensitive detector (PSD).
For the preparation of (I), benzoyl chloride (14.05 g, 0.10 mol) was added dropwise to a solution of NaOH (0.22 mol) and mercaptoacetic acid (9.2 g, 0.12 mol) at 273 K and the mixture stirred at room temperature overnight. The organic layer was separated off and washed with distilled water. The aqueous solutions were combined and acidified to pH = 1.5 by adding concentrated HCl to obtain a white precipitate, which was separated and washed with ether to afford a white powder. Further purification of the product was achieved by recrystallization from ethyl acetate at 263 K (yield 11.8 g, 60%; m.p. 377 K). Analytical data for C9H8O3S: found C 55.97, H 4.08, S 16.95%; required: C 55.09, H 4.11, S 16.34%. Spectroscopic analysis: IR (KBr, ν, cm-1): 1710, 1670 (C═O), 3400 (OH), 1450 (aromatic C≐C), 1200 (C—S—CO); 1H NMR (400 MHz, CDCl3, 298 K, δ, p.p.m.): 8.02 (m, aromatic, 2H), 7.63 (m, aromatic, 1H), 7.51 (m, aromatic, 2H), 3.95 (s, CH2, 2H), 9.58 (br, COOH, 1H); 13C{1H} NMR (100 MHz, CDCl3, 298 K, δ, p.p.m.): 31.1 (s, CH2), 127.52 (s, aromatic), 128.81 (s, aromatic), 134.04 (s, aromatic), 135.90 (s, aromatic), 174.58 (s, CO), 190.12 (s, COOH).
For the preparation of (II), a solution of dicyclohexylcarbodiimide (DCC; 6.02 g, 0.03 mol) in tetrahydrofuran (THF, 20 ml) was added dropwise over a period of 20 min to a solution of (I) (4.8 g, 0.02 mol) and N-hydroxysuccinimide (2.80 g, 0.02 mol) in THF (60 ml) at 268 K. The mixture was stirred at this temperature for 2 h and after that at room temperature overnight. Glacial acetic acid (1 ml) was added to the mixture, which was then stirred for a further hour. A red precipitate (N,N'-dicyclohexylurea) was filtered off and washed twice with boiling THF. The filtrates were combined and evaporated to give a crude product. Purification of the product was achieved by recrystallization from ethyl acetate at 268 K to give a white powder (yield 3.3 g, 55%; m.p. 408 K). Analytical data for C13H11O5NS: found C 54.20, H 4.15, S 11.70%; required: C 53.24, H 3.78, S 10.93%. Spectroscopic analysis: IR (KBr, ν, cm-1): 1550–1850 (C═O), 1450 (aromatic C≐ C), 1220 (C—S—CO); 1H NMR (400 MHz, CDCl3, 298 K, δ, p.p.m.): 8.01 (m, aromatic, 2H), 7.61 (m, aromatic, 1H), 7.51 (m, aromatic, 2H), 4.19 (s, CH2, 2H), 2.83 (s, CH2, 4H); 13C{1H} NMR (100 MHz, CDCl3, 298 K, δ, p.p.m.): 25.58 (s, CH2–ring), 28.28 (s, S—CH2), 127.62 (s, aromatic), 128.87 (s, aromatic), 134.20 (s, aromatic), 135.59 (s, aromatic), 164.80 (s, COS), 168.65 (s, CO–ring), 188.66 (s, COO).
The powders of (I) or (II) were ground and loaded between two Mylar foils and fixed in a sample holder with a mask of suitable internal diameter (0.7 mm). Data were collected at room temperature and pressure over the angular range 5–80° (2θ) with a step length for the PSD of 0.5° (2θ), and with a counting time of 360 s per step for (I) and 420 s for (II).
Indexing was carried out using DICVOL4.0, run with the default option (Boultif & Louër, 2004). Confidence factors were M(20) = 39.2 and F(20) = 69.9 for the (I), and M(20) = 77.6 and F(20) = 166.3 for (II). The most probable space group for (I) is P21/n, which was obtained using the program CHECK-CELL interfaced by WINPLOTR (Roisnel & Rodriguez-Carvajal, 2001), and the space group for (II) is P1. In order to accelerate the process of structure solution with the program FOX, the powder pattern was truncated to 45° in 2θ (Cu Kα1), corresponding to a real-space resolution of 2.0 Å. In the Rietveld refinement, carried out with the program GSAS (Larson & Von Dreele, 2004) interfaced by EXPGUI (Toby, 2001), the background was refined using a shifted Chebyshev polynomial with 23 coefficients. The Thompson–Cox–Hastings (Thompson et al., 1987) pseudo-Voigt profile function was used with an axial divergence asymmetry correction (Finger et al., 1994). The two asymmetry parameters of this function, S/L and D/L, were both fixed at 0.0225 during the Rietveld refinement. Geometric soft restraints were applied to the bond distances to guide them towards their normal values. Before the final refinement, the H atoms of the CH and CH2 groups were introduced from geometric arguments. The hydroxy H atom was located in a difference Fourier map. The coordinates of the H atoms were refined as riding. The final refinement cycles were performed using unrestrained isotropic displacement parameters for C and O [and H?] atoms and anisotropic displacement parameters for the S atom. No anomalous dispersion correction was applied. Intensities were corrected for absorption effects using a function for a flat-plate sample in transmission geometry with µd values which were determined experimentally for both compounds (µ is the absorption coefficient and d is the sample thickness). The preferred orientation was modelled using a spherical-harmonics description by Von Dreele (1997). The use of the preferred orientation correction leads to better molecular geometry with better agreement factors. The observed and calculated powder patterns for (I) and (II) are shown in Fig. 4.
For both compounds, data collection: WinXPOW (Stoe & Cie, 1999); cell refinement: GSAS (Larson & Von Dreele, 2004); data reduction: WinXPOW (Stoe & Cie, 1999); program(s) used to solve structure: FOX (Favre-Nicolin & Černý, 2002); program(s) used to refine structure: GSAS (Larson & Von Dreele, 2004); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: publCIF (Westrip, 2010).
C9H8O3S | F(000) = 408 |
Mr = 196.22 | Dx = 1.399 Mg m−3 |
Monoclinic, P21/n | Cu Kα1 radiation, λ = 1.54060 Å |
Hall symbol: -P 2yn | µ = 2.88 mm−1 |
a = 13.3928 (14) Å | T = 298 K |
b = 5.1432 (5) Å | Particle morphology: fine powder (visual estimate) |
c = 14.6577 (15) Å | white |
β = 112.6458 (6)° | flat sheet, 7.0 × 7.0 mm |
V = 931.81 (16) Å3 | Specimen preparation: Prepared at 298 K and 101.3 kPa |
Z = 4 |
Stoe STADI P transmission diffractometer | Scan method: step |
Radiation source: sealed X-ray tube, C-Tech | Absorption correction: for a cylinder mounted on the ϕ axis (GSAS; Larson & Von Dreele, 2004) |
Curved Ge(111) monochromator | Tmin = 0.268, Tmax = 0.303 |
Specimen mounting: powder loaded between two Mylar foils | 2θmin = 4.979°, 2θmax = 79.969°, 2θstep = 0.01° |
Data collection mode: transmission |
Least-squares matrix: full | Profile function: CW Profile function number 4 with 21 terms Pseudo-Voigt profile coefficients as parameterized in Thompson et al. (1987). Asymmetry correction of Finger et al. (1994). Microstrain broadening by Stephens (1999) #1(GU) = 0.000 #2(GV) = 0.000 #3(GW) = 8.875 #4(GP) = 0.000 #5(LX) = 0.997 #6(ptec) = 0.00 #7(trns) = 2.67 #8(shft) = 1.0898 #9(sfec) = 0.00 #10(S/L) = 0.0225 #11(H/L) = 0.0225 #12(eta) = 0.6000 #13(S400 ) = 2.7E-02 #14(S040 ) = 1.1E+00 #15(S004 ) = 1.2E-02 #16(S220 ) = -1.8E-03 #17(S202 ) = 1.7E-02 #18(S022 ) = 4.9E-02 #19(S301 ) = 1.1E-03 #20(S103 ) = 8.7E-03 #21(S121 ) = 8.8E-02 Peak tails are ignored where the intensity is below 0.0010 times the peak Aniso. broadening axis 0.0 0.0 1.0 |
Rp = 0.022 | 133 parameters |
Rwp = 0.028 | 13 restraints |
Rexp = 0.026 | H-atom parameters constrained |
R(F2) = 0.03399 | Weighting scheme based on measured s.u.'s |
χ2 = 1.210 | (Δ/σ)max = 0.04 |
7500 data points | Background function: GSAS Background function number 1 with 23 terms. Shifted Chebyshev function of 1st kind 1: 1268.82 2: -1180.75 3: 484.308 4: -94.8014 5: 1.00817 6: 24.6118 7: -21.3745 8: -6.45230 9: -6.78234 10: 34.6736 11: -41.4903 12: 16.6539 13: 9.04912 14: -13.7067 15: 10.9300 16: -0.511284 17: -9.05939 18: 11.5886 19: -2.56693 20: -8.44798 21: 2.93007 22: 5.08712 23: -7.59728 |
Excluded region(s): none | Preferred orientation correction: Spherical harmonics fonction |
C9H8O3S | V = 931.81 (16) Å3 |
Mr = 196.22 | Z = 4 |
Monoclinic, P21/n | Cu Kα1 radiation, λ = 1.54060 Å |
a = 13.3928 (14) Å | µ = 2.88 mm−1 |
b = 5.1432 (5) Å | T = 298 K |
c = 14.6577 (15) Å | flat sheet, 7.0 × 7.0 mm |
β = 112.6458 (6)° |
Stoe STADI P transmission diffractometer | Absorption correction: for a cylinder mounted on the ϕ axis (GSAS; Larson & Von Dreele, 2004) |
Specimen mounting: powder loaded between two Mylar foils | Tmin = 0.268, Tmax = 0.303 |
Data collection mode: transmission | 2θmin = 4.979°, 2θmax = 79.969°, 2θstep = 0.01° |
Scan method: step |
Rp = 0.022 | 7500 data points |
Rwp = 0.028 | 133 parameters |
Rexp = 0.026 | 13 restraints |
R(F2) = 0.03399 | H-atom parameters constrained |
χ2 = 1.210 |
Experimental. The sample was ground lightly in a mortar, loaded between two Mylar foils and fixed in the sample holder with a mask of 7.0 mm intrnal diameter. |
x | y | z | Uiso*/Ueq | ||
C1 | −0.1596 (4) | 1.0009 (9) | 0.2227 (2) | 0.078 (3)* | |
C2 | −0.1110 (4) | 1.0080 (9) | 0.32525 (16) | 0.104 (4)* | |
C3 | −0.0255 (4) | 0.8414 (9) | 0.3750 (3) | 0.093 (4)* | |
C4 | 0.0157 (4) | 0.6793 (9) | 0.3217 (3) | 0.071 (3)* | |
C5 | −0.0365 (4) | 0.6618 (9) | 0.21955 (14) | 0.102 (4)* | |
C6 | −0.1235 (4) | 0.8243 (9) | 0.16982 (19) | 0.092 (4)* | |
C7 | 0.1077 (6) | 0.5030 (13) | 0.3811 (5) | 0.086 (4)* | |
C8 | 0.2612 (4) | 0.1455 (9) | 0.3974 (3) | 0.105 (3)* | |
C9 | 0.3646 (6) | 0.2902 (14) | 0.4485 (6) | 0.110 (4)* | |
O1 | 0.1539 (5) | 0.5111 (10) | 0.4688 (5) | 0.109 (3)* | |
O2 | 0.4366 (4) | 0.2180 (10) | 0.5232 (5) | 0.105 (2)* | |
O3 | 0.3770 (4) | 0.5113 (10) | 0.4065 (4) | 0.112 (2)* | |
S1 | 0.1540 (2) | 0.3105 (4) | 0.3027 (3) | 0.12159 | |
H1 | −0.21745 | 1.12637 | 0.18708 | 0.093 (4)* | |
H2 | −0.13489 | 1.13731 | 0.36266 | 0.125 (5)* | |
H3 | 0.00314 | 0.8303 | 0.44804 | 0.112 (4)* | |
H5 | −0.01557 | 0.52442 | 0.18289 | 0.123 (4)* | |
H6 | −0.16322 | 0.80569 | 0.09755 | 0.110 (5)* | |
H8A | 0.23536 | 0.08947 | 0.44828 | 0.126 (4)* | |
H8B | 0.27805 | −0.01078 | 0.36775 | 0.126 (4)* | |
H3o | 0.42096 | 0.60542 | 0.44808 | 0.137 (4)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.141 (4) | 0.097 (3) | 0.128 (5) | 0.020 (3) | 0.054 (3) | −0.012 (3) |
C1—C2 | 1.390 (3) | C6—H6 | 0.990 |
C1—C6 | 1.396 (6) | C4—C7 | 1.507 (9) |
C1—H1 | 0.989 | C7—O1 | 1.195 (5) |
C2—C3 | 1.391 (7) | C7—S1 | 1.798 (5) |
C2—H2 | 0.990 | C8—C9 | 1.495 (5) |
C3—C4 | 1.394 (4) | C8—S1 | 1.781 (4) |
C3—H3 | 0.991 | C8—H8A | 0.979 |
C4—C5 | 1.390 (4) | C8—H8B | 0.980 |
C5—C6 | 1.391 (6) | C9—O2 | 1.205 (5) |
C5—H5 | 0.992 | C9—O3 | 1.334 (5) |
C2—C1—C6 | 120.0 (4) | C1—C6—H6 | 119.9 |
C2—C1—H1 | 120.0 | C5—C6—H6 | 119.9 |
C6—C1—H1 | 120.0 | C4—C7—O1 | 124.8 (5) |
C1—C2—C3 | 119.9 (4) | C4—C7—S1 | 111.6 (4) |
C1—C2—H2 | 120.0 | O1—C7—S1 | 123.0 (6) |
C3—C2—H2 | 120.0 | C9—C8—S1 | 117.8 (4) |
C2—C3—C4 | 119.9 (4) | C9—C8—H8A | 107.2 |
C2—C3—H3 | 120.0 | C9—C8—H8B | 107.7 |
C4—C3—H3 | 120.0 | S1—C8—H8A | 108.6 |
C3—C4—C5 | 119.9 (5) | S1—C8—H8B | 107.4 |
C3—C4—C7 | 116.6 (3) | H8A—C8—H8B | 107.8 |
C5—C4—C7 | 122.9 (3) | C8—C9—O2 | 124.4 (7) |
C4—C5—C6 | 119.9 (4) | C8—C9—O3 | 116.7 (5) |
C4—C5—H5 | 120.0 | O2—C9—O3 | 118.9 (7) |
C6—C5—H5 | 120.0 | C9—O3—H3o | 109.9 |
C1—C6—C5 | 120.0 (2) | C7—S1—C8 | 97.9 (3) |
C7—S1—C8—C9 | −78.3 (5) | C5—C4—C7—S1 | 9.4 (8) |
C8—S1—C7—O1 | 6.8 (7) | C5—C4—C7—O1 | −179.5 (7) |
C8—S1—C7—C4 | 178.1 (5) | C3—C4—C7—S1 | −178.9 (4) |
C2—C1—C6—C5 | −2.2 (8) | C3—C4—C5—C6 | 6.2 (8) |
C6—C1—C2—C3 | 0.8 (8) | C7—C4—C5—C6 | 177.6 (5) |
C1—C2—C3—C4 | 4.0 (8) | C4—C5—C6—C1 | −1.3 (8) |
C2—C3—C4—C5 | −7.6 (8) | S1—C8—C9—O2 | 167.9 (7) |
C2—C3—C4—C7 | −179.5 (5) | S1—C8—C9—O3 | −13.2 (9) |
C3—C4—C7—O1 | −7.8 (10) |
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3O···O2i | 0.82 | 2.01 | 2.693 (8) | 141 |
C5—H5···O2ii | 0.99 | 2.51 | 3.381 (7) | 147 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x−1/2, −y+1/2, z−1/2. |
C13H11NO5S | Z = 2 |
Mr = 293.30 | F(000) = 304.0 |
Triclinic, P1 | Dx = 1.473 Mg m−3 |
Hall symbol: -p 1 | Cu Kα1 radiation, λ = 1.5406 Å |
a = 6.51605 (7) Å | µ = 2.37 mm−1 |
b = 8.52612 (9) Å | T = 298 K |
c = 12.91910 (11) Å | Particle morphology: fine powder (visual estimate) |
α = 84.3274 (6)° | white |
β = 80.5788 (6)° | flat sheet, 7.0 × 7.0 mm |
γ = 69.1900 (4)° | Specimen preparation: Prepared at 298 K and 101.3 kPa |
V = 661.23 (1) Å3 |
Stoe STADI P transmission diffractometer | Scan method: step |
Radiation source: sealed X-ray tube, C-Tech | Absorption correction: for a cylinder mounted on the ϕ axis (GSAS; Larson & Von Dreele, 2004) |
Curved Ge(111) monochromator | Tmin = 0.327, Tmax = 0.358 |
Specimen mounting: powder loaded between two Mylar foils | 2θmin = 4.975°, 2θmax = 79.965°, 2θstep = 0.01° |
Data collection mode: transmission |
Least-squares matrix: full | Profile function: CW Profile function number 4 with 21 terms
Pseudo-Voigt profile coefficients as parameterized in
Thompson et al. (1987). Asymmetry correction of Finger et
al. (1994).
Microstrain broadening by Stephens (1999) Peak tails are ignored where the intensity is below 0.0010 times the peak Aniso. broadening axis 0.0 0.0 1.0 |
Rp = 0.021 | 228 parameters |
Rwp = 0.028 | 21 restraints |
Rexp = 0.024 | H-atom parameters constrained |
R(F2) = 0.01729 | Weighting scheme based on measured s.u.'s |
χ2 = 1.440 | (Δ/σ)max = 0.02 |
7500 data points | Background function: GSAS Background function number 1 with 23 terms. Shifted Chebyshev function of 1st kind 1: 1389.05 2: -1379.93 3: 634.132 4: -160.988 5: 9.65051 6: 41.8787 7: -30.4073 8: 7.11085 9: -19.2380 10: 29.6885 11: -23.7756 12: 4.99938 13: 9.25658 14: -4.99727 15: 4.30644 16: 2.37093 17: -0.767448 18: 6.26228 19: -3.29348 20: -4.19448 21: 4.52422 22: 3.02424 23: -2.02919 |
Excluded region(s): none | Preferred orientation correction: Spherical harmonics function |
C13H11NO5S | γ = 69.1900 (4)° |
Mr = 293.30 | V = 661.23 (1) Å3 |
Triclinic, P1 | Z = 2 |
a = 6.51605 (7) Å | Cu Kα1 radiation, λ = 1.5406 Å |
b = 8.52612 (9) Å | µ = 2.37 mm−1 |
c = 12.91910 (11) Å | T = 298 K |
α = 84.3274 (6)° | flat sheet, 7.0 × 7.0 mm |
β = 80.5788 (6)° |
Stoe STADI P transmission diffractometer | Absorption correction: for a cylinder mounted on the ϕ axis (GSAS; Larson & Von Dreele, 2004) |
Specimen mounting: powder loaded between two Mylar foils | Tmin = 0.327, Tmax = 0.358 |
Data collection mode: transmission | 2θmin = 4.975°, 2θmax = 79.965°, 2θstep = 0.01° |
Scan method: step |
Rp = 0.021 | 7500 data points |
Rwp = 0.028 | 228 parameters |
Rexp = 0.024 | 21 restraints |
R(F2) = 0.01729 | H-atom parameters constrained |
χ2 = 1.440 |
Experimental. The sample was ground lightly in a mortar, loaded between two Mylar foils and fixed in the sample holder with a mask of 7.0 mm intrnal diameter. |
x | y | z | Uiso*/Ueq | ||
S1 | −0.3864 (4) | 0.2635 (5) | 0.1330 (2) | 0.05595 | |
C1 | 0.1937 (9) | 0.3650 (10) | −0.1818 (5) | 0.050 (4)* | |
C2 | 0.3267 (8) | 0.2412 (11) | −0.1199 (6) | 0.074 (5)* | |
C3 | 0.2285 (10) | 0.1835 (11) | −0.0270 (5) | 0.062 (4)* | |
C4 | 0.0037 (11) | 0.2471 (11) | 0.0037 (6) | 0.034 (3)* | |
C5 | −0.1232 (8) | 0.3729 (9) | −0.0595 (5) | 0.045 (4)* | |
C6 | −0.0264 (9) | 0.4328 (10) | −0.1519 (5) | 0.056 (4)* | |
C7 | −0.0989 (9) | 0.1823 (12) | 0.1039 (6) | 0.035 (3)* | |
C8 | −0.4242 (7) | 0.1510 (6) | 0.2555 (4) | 0.048 (4)* | |
C9 | −0.3759 (14) | 0.2304 (10) | 0.3402 (7) | 0.059 (4)* | |
C10 | −0.0199 (15) | 0.2515 (11) | 0.4773 (5) | 0.068 (4)* | |
C11 | −0.3121 (13) | 0.1868 (12) | 0.5904 (6) | 0.056 (4)* | |
C12 | −0.0242 (8) | 0.3007 (6) | 0.5866 (5) | 0.084 (5)* | |
C13 | −0.1950 (8) | 0.2493 (6) | 0.6586 (4) | 0.048 (4)* | |
N1 | −0.1871 (13) | 0.1848 (10) | 0.4916 (6) | 0.044 (3)* | |
O1 | 0.0234 (11) | 0.0882 (10) | 0.1652 (5) | 0.068 (3)* | |
O2 | −0.4307 (12) | 0.3719 (10) | 0.3656 (6) | 0.072 (3)* | |
O3 | −0.2361 (10) | 0.1169 (8) | 0.4081 (5) | 0.044 (3)* | |
O4 | 0.0782 (12) | 0.2739 (9) | 0.3933 (5) | 0.071 (3)* | |
O5 | −0.4601 (11) | 0.1339 (9) | 0.6087 (5) | 0.056 (3)* | |
H1 | 0.26291 | 0.40697 | −0.24741 | 0.060 (4)* | |
H2 | 0.4885 | 0.19243 | −0.14223 | 0.088 (6)* | |
H3 | 0.32241 | 0.09219 | 0.01639 | 0.075 (5)* | |
H5 | −0.28534 | 0.42173 | −0.03813 | 0.054 (5)* | |
H6 | −0.12023 | 0.52333 | −0.19586 | 0.067 (5)* | |
H8A | −0.32392 | 0.03414 | 0.25101 | 0.057 (4)* | |
H8B | −0.57767 | 0.15329 | 0.27126 | 0.057 (4)* | |
H12A | 0.11988 | 0.24449 | 0.61106 | 0.067 (5)* | |
H12B | −0.0633 | 0.42271 | 0.58684 | 0.067 (5)* | |
H13A | −0.29887 | 0.34601 | 0.69732 | 0.057 (4)* | |
H13B | −0.12351 | 0.15867 | 0.70779 | 0.057 (4)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.028 (3) | 0.065 (4) | 0.064 (3) | −0.009 (3) | −0.007 (2) | 0.021 (3) |
S1—C7 | 1.740 (5) | C8—H8B | 0.981 |
S1—C8 | 1.796 (4) | C9—O2 | 1.194 (11) |
C1—C2 | 1.384 (11) | C9—O3 | 1.415 (11) |
C1—C6 | 1.347 (5) | C10—C12 | 1.506 (5) |
C1—H1 | 0.990 | C10—N1 | 1.377 (13) |
C2—C3 | 1.395 (5) | C10—O4 | 1.200 (5) |
C2—H2 | 0.990 | C11—C13 | 1.498 (5) |
C3—C4 | 1.373 (11) | C11—N1 | 1.396 (11) |
C3—H3 | 0.991 | C11—O5 | 1.184 (12) |
C4—C5 | 1.385 (11) | C12—C10 | 1.506 (5) |
C4—C7 | 1.505 (11) | C12—C13 | 1.492 (5) |
C5—C6 | 1.395 (5) | C12—H12A | 0.979 |
C5—H5 | 0.990 | C12—H12B | 0.979 |
C6—H6 | 0.991 | C13—H13A | 0.981 |
C7—O1 | 1.238 (11) | C13—H13B | 0.980 |
C8—C9 | 1.471 (5) | N1—O3 | 1.403 (5) |
C8—H8A | 0.980 | ||
C7—S1—C8 | 100.0 (3) | H8A—C8—H8B | 109.1 |
C2—C1—C6 | 120.9 (4) | C8—C9—O2 | 133.9 (8) |
C2—C1—H1 | 119.2 | C8—C9—O3 | 114.5 (7) |
C6—C1—H1 | 119.8 | O2—C9—O3 | 111.5 (8) |
C1—C2—C3 | 118.9 (4) | C12—C10—N1 | 101.9 (6) |
C1—C2—H2 | 120.4 | C12—C10—O4 | 133.3 (8) |
C3—C2—H2 | 120.7 | N1—C10—O4 | 124.3 (8) |
C2—C3—C4 | 121.3 (5) | C13—C11—N1 | 103.1 (6) |
C2—C3—H3 | 119.2 | C13—C11—O5 | 133.0 (8) |
C4—C3—H3 | 119.4 | N1—C11—O5 | 123.6 (8) |
C3—C4—C5 | 118.0 (6) | C10—C12—C13 | 108.5 (5) |
C3—C4—C7 | 120.4 (5) | C10—C12—H12A | 110.9 |
C5—C4—C7 | 121.6 (6) | C10—C12—H12B | 109.3 |
C4—C5—C6 | 121.2 (5) | C13—C12—H12A | 108.7 |
C4—C5—H5 | 119.2 | C13—C12—H12B | 109.4 |
C6—C5—H5 | 119.6 | H12A—C12—H12B | 110.0 |
C1—C6—C5 | 119.6 (4) | C11—C13—C12 | 106.3 (4) |
C1—C6—H6 | 120.5 | C11—C13—H13A | 110.8 |
C5—C6—H6 | 119.9 | C11—C13—H13B | 109.7 |
S1—C7—C4 | 117.1 (5) | C12—C13—H13A | 109.8 |
S1—C7—O1 | 123.5 (6) | C12—C13—H13B | 110.0 |
C4—C7—O1 | 119.1 (6) | H13A—C13—H13B | 110.1 |
S1—C8—C9 | 109.4 (5) | C10—N1—C11 | 119.5 (7) |
S1—C8—H8A | 109.5 | C10—N1—O3 | 121.1 (7) |
S1—C8—H8B | 110.1 | C11—N1—O3 | 119.3 (7) |
C9—C8—H8A | 109.7 | C9—O3—N1 | 117.2 (7) |
C9—C8—H8B | 109.0 | ||
C8—S1—C7—O1 | −6.9 (9) | C1—C2—C3—C4 | 0.1 (12) |
C8—S1—C7—C4 | −179.8 (6) | C2—C3—C4—C7 | 179.6 (8) |
C7—S1—C8—C9 | 79.2 (6) | C2—C3—C4—C5 | −1.1 (12) |
C9—O3—N1—C10 | −83.2 (10) | C7—C4—C5—C6 | 179.6 (7) |
C9—O3—N1—C11 | 95.9 (10) | C3—C4—C5—C6 | 0.4 (11) |
N1—O3—C9—C8 | −178.9 (7) | C3—C4—C7—S1 | −177.0 (7) |
N1—O3—C9—O2 | 0.5 (12) | C5—C4—C7—O1 | −169.5 (8) |
C11—N1—C10—O4 | −170.6 (9) | C3—C4—C7—O1 | 9.7 (13) |
O3—N1—C10—C12 | −177.9 (7) | C5—C4—C7—S1 | 3.8 (11) |
O3—N1—C10—O4 | 8.5 (14) | C4—C5—C6—C1 | 1.5 (11) |
C10—N1—C11—O5 | 179.1 (9) | S1—C8—C9—O3 | −132.8 (6) |
O3—N1—C11—C13 | 173.9 (7) | S1—C8—C9—O2 | 48.0 (13) |
C11—N1—C10—C12 | 3.0 (10) | O4—C10—C12—C13 | 175.2 (10) |
O3—N1—C11—O5 | −0.1 (14) | N1—C10—C12—C13 | 2.5 (8) |
C10—N1—C11—C13 | −7.0 (11) | O5—C11—C13—C12 | −179.2 (10) |
C6—C1—C2—C3 | 1.8 (12) | N1—C11—C13—C12 | 7.6 (8) |
C2—C1—C6—C5 | −2.6 (11) | C10—C12—C13—C11 | −6.4 (7) |
D—H···A | D—H | H···A | D···A | D—H···A |
C8—H8B···O4i | 0.98 | 2.47 | 3.293 (9) | 141 |
C12—H12A···O5ii | 0.98 | 2.55 | 3.488 (9) | 159 |
C12—H12B···O4iii | 0.98 | 2.59 | 3.549 (9) | 166 |
C13—H13A···O2iv | 0.98 | 2.57 | 3.307 (9) | 132 |
C13—H13B···O1v | 0.98 | 2.50 | 3.458 (9) | 166 |
Symmetry codes: (i) x−1, y, z; (ii) x+1, y, z; (iii) −x, −y+1, −z−1; (iv) −x+1, −y+1, −z−1; (v) −x, −y+2, −z−1. |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | C9H8O3S | C13H11NO5S |
Mr | 196.22 | 293.30 |
Crystal system, space group | Monoclinic, P21/n | Triclinic, P1 |
Temperature (K) | 298 | 298 |
a, b, c (Å) | 13.3928 (14), 5.1432 (5), 14.6577 (15) | 6.51605 (7), 8.52612 (9), 12.91910 (11) |
α, β, γ (°) | 90, 112.6458 (6), 90 | 84.3274 (6), 80.5788 (6), 69.1900 (4) |
V (Å3) | 931.81 (16) | 661.23 (1) |
Z | 4 | 2 |
Radiation type | Cu Kα1, λ = 1.54060 Å | Cu Kα1, λ = 1.5406 Å |
µ (mm−1) | 2.88 | 2.37 |
Specimen shape, size (mm) | Flat sheet, 7.0 × 7.0 | Flat sheet, 7.0 × 7.0 |
Data collection | ||
Diffractometer | Stoe STADI P transmission diffractometer | Stoe STADI P transmission diffractometer |
Specimen mounting | Powder loaded between two Mylar foils | Powder loaded between two Mylar foils |
Data collection mode | Transmission | Transmission |
Scan method | Step | Step |
Absorption correction | For a cylinder mounted on the ϕ axis (GSAS; Larson & Von Dreele, 2004) | – |
Tmin, Tmax | 0.268, 0.303 | – |
2θ values (°) | 2θmin = 4.979 2θmax = 79.969 2θstep = 0.01 | 2θmin = 4.975 2θmax = 79.965 2θstep = 0.01 |
Refinement | ||
R factors and goodness of fit | Rp = 0.022, Rwp = 0.028, Rexp = 0.026, R(F2) = 0.03399, χ2 = 1.210 | Rp = 0.021, Rwp = 0.028, Rexp = 0.024, R(F2) = 0.01729, χ2 = 1.440 |
No. of data points | 7500 | 7500 |
No. of parameters | 133 | 228 |
No. of restraints | 13 | 21 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Computer programs: WinXPOW (Stoe & Cie, 1999), GSAS (Larson & Von Dreele, 2004), FOX (Favre-Nicolin & Černý, 2002), ORTEP-3 (Farrugia, 1997), publCIF (Westrip, 2010).
C7—S1 | 1.798 (5) | C8—S1 | 1.781 (4) |
O1—C7—S1 | 123.0 (6) | C7—S1—C8 | 97.9 (3) |
C9—C8—S1 | 117.8 (4) | ||
C7—S1—C8—C9 | −78.3 (5) | S1—C8—C9—O3 | −13.2 (9) |
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3O···O2i | 0.82 | 2.01 | 2.693 (8) | 141 |
C5—H5···O2ii | 0.99 | 2.51 | 3.381 (7) | 147 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x−1/2, −y+1/2, z−1/2. |
S1—C7 | 1.740 (5) | C11—N1 | 1.396 (11) |
S1—C8 | 1.796 (4) | C11—O5 | 1.184 (12) |
C10—N1 | 1.377 (13) | N1—O3 | 1.403 (5) |
C10—O4 | 1.200 (5) | ||
C7—S1—C8 | 100.0 (3) | C10—N1—O3 | 121.1 (7) |
N1—C10—O4 | 124.3 (8) | C11—N1—O3 | 119.3 (7) |
C10—N1—C11 | 119.5 (7) |
D—H···A | D—H | H···A | D···A | D—H···A |
C8—H8B···O4i | 0.98 | 2.47 | 3.293 (9) | 141 |
C12—H12A···O5ii | 0.98 | 2.55 | 3.488 (9) | 159 |
C12—H12B···O4iii | 0.98 | 2.59 | 3.549 (9) | 166 |
C13—H13A···O2iv | 0.98 | 2.57 | 3.307 (9) | 132 |
C13—H13B···O1v | 0.98 | 2.50 | 3.458 (9) | 166 |
Symmetry codes: (i) x−1, y, z; (ii) x+1, y, z; (iii) −x, −y+1, −z−1; (iv) −x+1, −y+1, −z−1; (v) −x, −y+2, −z−1. |
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S-Benzoyl mercaptoacetictriglycine (S-Bz-MAG3) is widely used in radiopharmaceutical applications in nuclear medicine after labelling with 99mTc or 188Re for kidney imaging (Guhlke et al., 1998; Van Gog et al., 1998; Hjelstuen et al., 1998). As part of our interest in preparing S-benzoyl mercaptoacetictriglycine (S-Bz-MAG3) for pharmaceutical applications according to literature methods (Brandau et al., 1988; Schneider et al., 1984; Xiuli et al., 2003), and during the course of these preparations, the two title precursors of Bz-MAG3, 2-(benzoylsulfanyl)acetic acid, (I), and 2,5-dioxopyrrolidin-1-yl 2-(benzoylsulfanyl)acetate, (II), were isolated. These two compounds have a tendency to crystallize in the form of a very fine white powder. No single crystal of sufficient thickness and quality could be obtained to perform a single-crystal analysis. In this work, laboratory powder X-ray diffraction was used to solve and refine their crystal structures. This involves a 13-atom (non-H) problem for (I) and a 20-atom (non-H) problem for (II). Crystal structures of a number of pharmaceutical compounds have been determined from X-ray powder data as a last resort in the absence of single crystals of sufficient quality (Chan et al., 1999; Shankland et al., 2001; Chernyshev et al., 2003; Kiang et al., 2003; Rukiah et al., 2004; Van der Lee et al., 2005; Rukiah & Assaad, 2010; Al-Ktaifani & Rukiah, 2010).
For success in a structure determination from powder diffraction data, the method is long and difficult before the final refinement step. This final step is commonly realised using the Rietveld method. Initial attempts to solve the structures of (I) and (II) by direct methods with the program EXPO2004 (Altomare et al., 2004) failed. The structures were solved with Monte Carlo simulated annealing (parallel tempering algorithm) from powder patterns in direct space using the program FOX (Favre-Nicolin & Černý, 2002). FOX solves structures by altering the positions, orientations and conformations of the molecule(s) in the unit cell according to the constraints of the space-group symmetry, until a good match is obtained between the calculated and observed intensities. One molecule was introduced randomly into the unit cell, which was calculated by Le Bail refinement. The H atoms can be ignored during the structure-solution process because they do not contribute significantly to the powder diffraction pattern, due to their low X-ray scattering power. During the parallel tempering calculations, the molecule had the possibility of translating, rotating around its centre of mass and modifying its torsion angles. The molecule of (I) has four independent torsion angles, and there are then ten degrees of freedom for determination of the starting model by FOX. On the other hand, the molecule of (II) has six independent torsion angles, which indicates that there are 12 degrees of freedom for determining the starting model.
Compound (I) crystallizes with one molecule in the asymmetric unit in the space group P21/n (Fig. 1a). In (I), atoms C7, S1 and O1 of the C6H5–CO–S fragment lie almost in the same plane, which is that of the benzene ring. Atoms C8, C9, O2 and O3 of the C–COOH fragment are coplanar and roughly perpendicular to the plane of the C6H5–CO–S fragment and the C6H5 ring. The C—S—C bond angle [97.9 (3)°] is smaller than the normal value [Normal value is ? Standard reference?]. This observation indicates more p character in the bonding orbitals of the S atom in (I) (causing a reduced C—S—C bond angle), according to Bent's rule (Huheey et al., 1993).
As shown in Fig. 2, the crystal structure of (I) is stabilized by hydrogen bonds (Table 2). The molecules are joined into hydrogen-bonded dimers across an inversion centre. The dimers are joined by weak aromatic C—H···O hydrogen bonds into a two-dimensional network parallel to (101).
Compound (II) crystallizes with one molecule in the asymmetric unit in the space group P1 (Fig. 1b). Its structure is similar to that of (I), except that the H atom in the COOH group of (I) is replaced by a five-membered N(COCH2)2 ring in (II). This five-membered N(COCH2)2 ring is effectively planar, with a maximum deviation of -0.044 (6) Å for atom C13 (average C—C bond distance = 1.499 Å and [average?] C—C—C bond angle = 107.4°). A major point in the structure dimensions is that each pair of chemically equivalent N—C and C═O bonds in the five-membered ring has significantly different bond lengths (Table 3). Similar observations were reported for the parent molecule, N-hydroxysuccinmide (Jones, 2003). This could be attributed to delocalization resulting from conjugation between the N non-bonding pair (the tricoordinate N atom is planar and the sum of the angles around it is 359.5°) and one of the carbonyl groups (specifically, C10—O4), which increases the C═O bond length (reduces the double-bond character) and decreases the N—C bond lengths (increases the double-bond character). It is noteworthy that the C—S—C bond angle of 100.0 (3)° in (II) is larger than its counterpart in (I) [97.9 (3)°]; this gives an indication that the S atom of (II) has less p character in the bonding orbitals than that in (I), according to Bent's rule.
The crystal structure of (II) is stabilized by non-standard hydrogen contacts (Fig. 3), each pair of molecules held together in the unit cell by two non-standard C—H···O hydrogen bonds formed between the CH2 group of one molecule and the O centre of an adjacent molecule. This hydrogen bond forms a dimer (Table 4).