Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801005293/tk6007sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801005293/tk6007Isup2.hkl |
CCDC reference: 165642
Key indicators
- Single-crystal X-ray study
- T = 150 K
- Mean (C-C) = 0.004 Å
- R factor = 0.034
- wR factor = 0.041
- Data-to-parameter ratio = 12.5
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry
Alert Level C:
GOODF_01 Alert C The least squares goodness of fit parameter lies outside the range 0.80 <> 2.00 Goodness of fit given = 3.021 General Notes
ABSTM_02 When printed, the submitted absorption T values will be replaced by the scaled T values. Since the ratio of scaled T's is identical to the ratio of reported T values, the scaling does not imply a change to the absorption corrections used in the study. Ratio of Tmax expected/reported 0.938 Tmax scaled 0.938 Tmin scaled 0.883 GOODF_01 _refine_ls_goodness_of_fit_obs is an old dataname which has been superseded by _refine_ls_goodness_of_fit_ref REFLE_01 _reflns_observed_criterion is an old dataname which has been superseded by _reflns_threshold_expression REFLG_01 _reflns_number_observed is an old dataname which has been superseded by _reflns_number_gt RFACG_01 _refine_ls_R_factor_obs is an old dataname which has been superseded by _refine_ls_R_factor_gt RFACR_01 _refine_ls_wR_factor_obs is an old dataname which has been superseded by _refine_ls_wR_factor_ref SHFSU_01 _refine_ls_shift/esd_max is an old dataname which has been superseded by _refine_ls_shift/su_max
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
1 Alert Level C = Please check
The title compound was prepared according to literature procedures (Teixidor et al., 1991). Crystals suitable for single-crystal X-ray diffraction studies were grown from a methanol solution at 269 K.
No reflections had unacceptable values for Δ(Fo—Fc)/σ(Fo) although 140 reflections had values of Δ(Fo—Fc)/σ(Fo) between 5 and 10, and 20 reflections had values Δ(fo—Fc)/σ(Fo) greater than 10. The large number of these reflections most probably account for the large goodness-of-fit value for the refined structure (3.02).
Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1988); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: TEXSAN (Molecular Structure Corporation, 1992); program(s) used to solve structure: SHELXS86 (Sheldrick, 1990); program(s) used to refine structure: TEXSAN; software used to prepare material for publication: TEXSAN.
Fig. 1. A view of the title molecule showing the atom-labelling scheme. Ellipsoids are at the 50% probability level (Johnson, 1976). |
C19H17NS2 | Z = 2 |
Mr = 323.47 | F(000) = 340 |
Triclinic, P1 | Dx = 1.307 Mg m−3 |
a = 10.165 (2) Å | Mo Kα radiation, λ = 0.7107 Å |
b = 10.365 (2) Å | Cell parameters from 25 reflections |
c = 9.053 (2) Å | θ = 45.2–49.9° |
α = 112.93 (1)° | µ = 0.32 mm−1 |
β = 100.12 (2)° | T = 150 K |
γ = 102.37 (1)° | Block, colourless |
V = 821.6 (3) Å3 | 0.3 × 0.3 × 0.2 mm |
Rigaku AFC-7S diffractometer | 2487 reflections with F > 2σ(F) |
Radiation source: X-ray tube | Rint = 0.01 |
Graphite monochromator | θmax = 25.0°, θmin = 2.1° |
ω/2θ scans | h = 0→12 |
Absorption correction: ψ scan (North et al., 1968) | k = −12→12 |
Tmin = 0.883, Tmax = 0.938 | l = −10→10 |
3073 measured reflections | 3 standard reflections every 150 reflections |
2894 independent reflections | intensity decay: −1.3% |
Refinement on F | 0 restraints |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.034 | Weighting scheme based on measured s.u.'s w = 1/[σ2(F) + 0.008|F|2] |
wR(F2) = 0.0407 | (Δ/σ)max < 0.001 |
2487 reflections | Δρmax = 0.25 e Å−3 |
199 parameters | Δρmin = −0.31 e Å−3 |
C19H17NS2 | γ = 102.37 (1)° |
Mr = 323.47 | V = 821.6 (3) Å3 |
Triclinic, P1 | Z = 2 |
a = 10.165 (2) Å | Mo Kα radiation |
b = 10.365 (2) Å | µ = 0.32 mm−1 |
c = 9.053 (2) Å | T = 150 K |
α = 112.93 (1)° | 0.3 × 0.3 × 0.2 mm |
β = 100.12 (2)° |
Rigaku AFC-7S diffractometer | 2487 reflections with F > 2σ(F) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.01 |
Tmin = 0.883, Tmax = 0.938 | 3 standard reflections every 150 reflections |
3073 measured reflections | intensity decay: −1.3% |
2894 independent reflections |
R[F2 > 2σ(F2)] = 0.034 | 0 restraints |
wR(F2) = 0.0407 | H-atom parameters constrained |
2487 reflections | Δρmax = 0.25 e Å−3 |
199 parameters | Δρmin = −0.31 e Å−3 |
x | y | z | Uiso*/Ueq | ||
S(1) | 0.56351 (6) | 0.65575 (6) | 0.34517 (7) | 0.0322 (2) | |
S(2) | 0.14211 (6) | 1.01495 (6) | 0.64662 (8) | 0.0377 (2) | |
N(1) | 0.4444 (2) | 0.9347 (2) | 0.6760 (2) | 0.0261 (4) | |
C(1) | 0.5986 (2) | 0.8310 (2) | 0.5255 (3) | 0.0292 (6) | |
C(2) | 0.5072 (2) | 0.8291 (2) | 0.6384 (2) | 0.0265 (5) | |
C(3) | 0.4910 (2) | 0.7260 (2) | 0.7034 (3) | 0.0326 (6) | |
C(4) | 0.4093 (2) | 0.7354 (2) | 0.8115 (3) | 0.0345 (6) | |
C(5) | 0.3454 (2) | 0.8454 (2) | 0.8528 (3) | 0.0324 (6) | |
C(6) | 0.3654 (2) | 0.9426 (2) | 0.7816 (2) | 0.0270 (5) | |
C(7) | 0.2973 (2) | 1.0617 (2) | 0.8179 (3) | 0.0327 (6) | |
C(11) | 0.3996 (2) | 0.6303 (2) | 0.2137 (3) | 0.0279 (6) | |
C(12) | 0.3443 (2) | 0.4962 (2) | 0.0675 (3) | 0.0331 (6) | |
C(13) | 0.2199 (2) | 0.4682 (3) | −0.0478 (3) | 0.0399 (7) | |
C(14) | 0.1493 (2) | 0.5715 (3) | −0.0211 (3) | 0.0410 (7) | |
C(15) | 0.2020 (2) | 0.7031 (3) | 0.1256 (3) | 0.0386 (7) | |
C(16) | 0.3273 (2) | 0.7333 (2) | 0.2433 (3) | 0.0323 (6) | |
C(21) | 0.0296 (2) | 0.8583 (2) | 0.6482 (3) | 0.0317 (6) | |
C(22) | −0.0177 (3) | 0.8703 (3) | 0.7851 (3) | 0.0556 (8) | |
C(23) | −0.1078 (3) | 0.7483 (3) | 0.7833 (4) | 0.0580 (9) | |
C(24) | −0.1543 (2) | 0.6143 (3) | 0.6432 (3) | 0.0443 (7) | |
C(25) | −0.1095 (3) | 0.6032 (3) | 0.5060 (3) | 0.0476 (7) | |
C(26) | −0.0160 (2) | 0.7243 (3) | 0.5082 (3) | 0.0402 (7) | |
H(1a) | 0.5975 | 0.9140 | 0.4876 | 0.0598 | |
H(1b) | 0.6989 | 0.8442 | 0.5776 | 0.0598 | |
H(3) | 0.5480 | 0.6388 | 0.6717 | 0.0598 | |
H(4) | 0.3958 | 0.6620 | 0.8633 | 0.0598 | |
H(5) | 0.2788 | 0.8532 | 0.9248 | 0.0598 | |
H(7a) | 0.3671 | 1.1585 | 0.8297 | 0.0598 | |
H(7b) | 0.2732 | 1.0852 | 0.9335 | 0.0598 | |
H(12) | 0.3950 | 0.4161 | 0.0391 | 0.0598 | |
H(13) | 0.1886 | 0.3668 | −0.1610 | 0.0598 | |
H(14) | 0.0506 | 0.5415 | −0.1119 | 0.0598 | |
H(15) | 0.1511 | 0.7920 | 0.1619 | 0.0598 | |
H(16) | 0.3715 | 0.8334 | 0.3580 | 0.0598 | |
H(22) | 0.0000 | 0.9746 | 0.8789 | 0.0598 | |
H(23) | −0.1277 | 0.7579 | 0.8907 | 0.0598 | |
H(24) | −0.2276 | 0.5214 | 0.6390 | 0.0598 | |
H(25) | −0.1395 | 0.4988 | 0.4056 | 0.0598 | |
H(26) | 0.0244 | 0.7157 | 0.4129 | 0.0598 |
U11 | U22 | U33 | U12 | U13 | U23 | |
S(1) | 0.0385 (3) | 0.0253 (3) | 0.0326 (3) | 0.0132 (2) | 0.0067 (2) | 0.0125 (2) |
S(2) | 0.0358 (3) | 0.0361 (3) | 0.0475 (4) | 0.0099 (3) | 0.0088 (3) | 0.0268 (3) |
N(1) | 0.0284 (9) | 0.0199 (9) | 0.0248 (9) | 0.0021 (7) | 0.0019 (7) | 0.0101 (7) |
C(1) | 0.032 (1) | 0.022 (1) | 0.030 (1) | 0.0049 (9) | 0.0065 (9) | 0.0113 (9) |
C(2) | 0.027 (1) | 0.021 (1) | 0.025 (1) | 0.0009 (9) | 0.0006 (9) | 0.0098 (9) |
C(3) | 0.031 (1) | 0.028 (1) | 0.040 (1) | 0.0064 (9) | 0.006 (1) | 0.021 (1) |
C(4) | 0.033 (1) | 0.034 (1) | 0.042 (1) | 0.0056 (10) | 0.006 (1) | 0.027 (1) |
C(5) | 0.031 (1) | 0.033 (1) | 0.032 (1) | 0.0040 (10) | 0.0058 (10) | 0.018 (1) |
C(6) | 0.027 (1) | 0.023 (1) | 0.023 (1) | 0.0012 (9) | 0.0013 (9) | 0.0091 (9) |
C(7) | 0.035 (1) | 0.026 (1) | 0.032 (1) | 0.0046 (9) | 0.0058 (10) | 0.0118 (10) |
C(11) | 0.032 (1) | 0.025 (1) | 0.030 (1) | 0.0052 (9) | 0.0098 (9) | 0.0174 (9) |
C(12) | 0.040 (1) | 0.028 (1) | 0.030 (1) | 0.0050 (10) | 0.013 (1) | 0.0129 (10) |
C(13) | 0.040 (1) | 0.040 (1) | 0.031 (1) | −0.001 (1) | 0.009 (1) | 0.015 (1) |
C(14) | 0.031 (1) | 0.054 (2) | 0.036 (1) | 0.002 (1) | 0.007 (1) | 0.025 (1) |
C(15) | 0.035 (1) | 0.044 (1) | 0.046 (1) | 0.012 (1) | 0.013 (1) | 0.028 (1) |
C(16) | 0.035 (1) | 0.028 (1) | 0.036 (1) | 0.0086 (10) | 0.009 (1) | 0.0176 (10) |
C(21) | 0.028 (1) | 0.032 (1) | 0.039 (1) | 0.0100 (9) | 0.0076 (10) | 0.020 (1) |
C(22) | 0.066 (2) | 0.040 (2) | 0.050 (2) | 0.002 (1) | 0.031 (1) | 0.010 (1) |
C(23) | 0.063 (2) | 0.060 (2) | 0.055 (2) | 0.008 (1) | 0.032 (2) | 0.029 (2) |
C(24) | 0.033 (1) | 0.042 (1) | 0.061 (2) | 0.005 (1) | 0.009 (1) | 0.031 (1) |
C(25) | 0.047 (2) | 0.036 (1) | 0.047 (2) | 0.002 (1) | 0.002 (1) | 0.016 (1) |
C(26) | 0.041 (1) | 0.041 (1) | 0.034 (1) | 0.007 (1) | 0.007 (1) | 0.018 (1) |
S(1)—C(1) | 1.816 (2) | C(11)—C(12) | 1.403 (3) |
S(1)—C(11) | 1.770 (2) | C(11)—C(16) | 1.390 (3) |
S(2)—C(7) | 1.832 (2) | C(12)—C(13) | 1.384 (3) |
S(2)—C(21) | 1.781 (2) | C(13)—C(14) | 1.382 (3) |
N(1)—C(2) | 1.344 (3) | C(14)—C(15) | 1.391 (3) |
N(1)—C(6) | 1.343 (3) | C(15)—C(16) | 1.395 (3) |
C(1)—C(2) | 1.500 (3) | C(21)—C(22) | 1.378 (3) |
C(2)—C(3) | 1.401 (3) | C(21)—C(26) | 1.377 (3) |
C(3)—C(4) | 1.379 (3) | C(22)—C(23) | 1.385 (3) |
C(4)—C(5) | 1.390 (3) | C(23)—C(24) | 1.377 (4) |
C(5)—C(6) | 1.391 (3) | C(24)—C(25) | 1.369 (3) |
C(6)—C(7) | 1.497 (3) | C(25)—C(26) | 1.393 (3) |
C(1)—S(1)—C(11) | 104.13 (10) | S(1)—C(11)—C(16) | 125.0 (2) |
C(7)—S(2)—C(21) | 100.90 (10) | C(12)—C(11)—C(16) | 119.6 (2) |
C(2)—N(1)—C(6) | 118.5 (2) | C(11)—C(12)—C(13) | 120.0 (2) |
S(1)—C(1)—C(2) | 115.1 (1) | C(12)—C(13)—C(14) | 120.6 (2) |
N(1)—C(2)—C(1) | 115.6 (2) | C(13)—C(14)—C(15) | 119.5 (2) |
N(1)—C(2)—C(3) | 122.3 (2) | C(14)—C(15)—C(16) | 120.7 (2) |
C(1)—C(2)—C(3) | 122.1 (2) | C(11)—C(16)—C(15) | 119.5 (2) |
C(2)—C(3)—C(4) | 118.5 (2) | S(2)—C(21)—C(22) | 121.0 (2) |
C(3)—C(4)—C(5) | 119.7 (2) | S(2)—C(21)—C(26) | 119.8 (2) |
C(4)—C(5)—C(6) | 118.3 (2) | C(22)—C(21)—C(26) | 119.2 (2) |
N(1)—C(6)—C(5) | 122.6 (2) | C(21)—C(22)—C(23) | 120.4 (2) |
N(1)—C(6)—C(7) | 116.2 (2) | C(22)—C(23)—C(24) | 120.6 (2) |
C(5)—C(6)—C(7) | 121.2 (2) | C(23)—C(24)—C(25) | 119.0 (2) |
S(2)—C(7)—C(6) | 112.3 (1) | C(24)—C(25)—C(26) | 120.9 (2) |
S(1)—C(11)—C(12) | 115.4 (2) | C(21)—C(26)—C(25) | 120.0 (2) |
S(1)—C(1)—C(2)—N(1) | −129.1 (2) | C(3)—C(2)—N(1)—C(6) | 1.1 (2) |
S(1)—C(1)—C(2)—C(3) | 52.3 (2) | C(3)—C(4)—C(5)—C(6) | 0.5 (2) |
S(1)—C(11)—C(12)—C(13) | −176.9 (2) | C(4)—C(5)—C(6)—C(7) | 178.7 (2) |
S(1)—C(11)—C(12)—C(13) | −176.9 (2) | C(6)—C(7)—S(2)—C(21) | 63.8 (2) |
S(2)—C(7)—C(6)—N(1) | 77.4 (2) | C(7)—S(2)—C(21)—C(22) | 63.3 (2) |
S(2)—C(7)—C(6)—C(5) | −101.9 (2) | C(7)—S(2)—C(21)—C(26) | −119.5 (2) |
S(2)—C(21)—C(22)—C(23) | 178.5 (2) | C(11)—C(12)—C(13)—C(14) | 0.3 (4) |
S(2)—C(21)—C(26)—C(25) | −176.9 (2) | C(11)—C(16)—C(15)—C(14) | −0.3 (5) |
N(1)—C(2)—C(3)—C(4) | −1.0 (2) | C(12)—C(11)—C(16)—C(15) | −1.2 (4) |
N(1)—C(6)—C(5)—C(4) | −0.4 (2) | C(12)—C(13)—C(14)—C(15) | −1.9 (4) |
C(1)—S(1)—C(11)—C(12) | −176.5 (2) | C(13)—C(12)—C(11)—C(16) | 1.2 (4) |
C(1)—S(1)—C(11)—C(16) | 5.5 (4) | C(13)—C(14)—C(15)—C(16) | 1.9 (5) |
C(1)—C(2)—N(1)—C(6) | −177.5 (1) | C(21)—C(22)—C(23)—C(24) | −1.7 (4) |
C(1)—C(2)—C(3)—C(4) | 177.5 (1) | C(21)—C(26)—C(25)—C(24) | −1.7 (5) |
C(2)—N(1)—C(6)—C(5) | −0.4 (2) | C(22)—C(21)—C(26)—C(25) | 0.4 (4) |
C(2)—N(1)—C(6)—C(7) | −179.6 (1) | C(22)—C(23)—C(24)—C(25) | 0.4 (5) |
Experimental details
Crystal data | |
Chemical formula | C19H17NS2 |
Mr | 323.47 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 150 |
a, b, c (Å) | 10.165 (2), 10.365 (2), 9.053 (2) |
α, β, γ (°) | 112.93 (1), 100.12 (2), 102.37 (1) |
V (Å3) | 821.6 (3) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.32 |
Crystal size (mm) | 0.3 × 0.3 × 0.2 |
Data collection | |
Diffractometer | Rigaku AFC-7S diffractometer |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.883, 0.938 |
No. of measured, independent and observed [F > 2σ(F)] reflections | 3073, 2894, 2487 |
Rint | 0.01 |
(sin θ/λ)max (Å−1) | 0.594 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.034, 0.0407, ? |
No. of reflections | 2487 |
No. of parameters | 199 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.25, −0.31 |
Computer programs: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1988), MSC/AFC Diffractometer Control Software, TEXSAN (Molecular Structure Corporation, 1992), SHELXS86 (Sheldrick, 1990), TEXSAN.
S(1)—C(1) | 1.816 (2) | S(2)—C(21) | 1.781 (2) |
S(1)—C(11) | 1.770 (2) | N(1)—C(2) | 1.344 (3) |
S(2)—C(7) | 1.832 (2) | N(1)—C(6) | 1.343 (3) |
C(1)—S(1)—C(11) | 104.13 (10) | N(1)—C(2)—C(1) | 115.6 (2) |
C(7)—S(2)—C(21) | 100.90 (10) | N(1)—C(2)—C(3) | 122.3 (2) |
C(2)—N(1)—C(6) | 118.5 (2) | S(2)—C(7)—C(6) | 112.3 (1) |
S(1)—C(1)—C(2) | 115.1 (1) | ||
S(1)—C(1)—C(2)—N(1) | −129.1 (2) | C(1)—S(1)—C(11)—C(16) | 5.5 (4) |
S(1)—C(1)—C(2)—C(3) | 52.3 (2) | C(1)—C(2)—N(1)—C(6) | −177.5 (1) |
S(1)—C(11)—C(12)—C(13) | −176.9 (2) | C(1)—C(2)—C(3)—C(4) | 177.5 (1) |
S(1)—C(11)—C(12)—C(13) | −176.9 (2) | C(2)—N(1)—C(6)—C(7) | −179.6 (1) |
S(2)—C(7)—C(6)—N(1) | 77.4 (2) | C(4)—C(5)—C(6)—C(7) | 178.7 (2) |
S(2)—C(7)—C(6)—C(5) | −101.9 (2) | C(6)—C(7)—S(2)—C(21) | 63.8 (2) |
S(2)—C(21)—C(22)—C(23) | 178.5 (2) | C(7)—S(2)—C(21)—C(22) | 63.3 (2) |
S(2)—C(21)—C(26)—C(25) | −176.9 (2) | C(7)—S(2)—C(21)—C(26) | −119.5 (2) |
C(1)—S(1)—C(11)—C(12) | −176.5 (2) |
Compounds that have both nitrogen and sulfur centres available for coordination to metals are becoming topical with respect to their role in enzyme mimicry, where the N-donor fragments somewhat resemble the imidazole fragment of histidine and the S-donor fragments model the amino acid cysteine. Interest in the structure of such ligands comes from the desire to understand how the preferred conformation of the uncoordinated compound affects the coordination mode of the ligand when coordinated to a metal centre or metal centres, and how the ligand may best be modified to achieve a desired coordination mode. In the course of our work on transition metal halide complexes of mixed-donor N/S ligands (Ball et al., 2001), we isolated the title compound, (I), as colourless blocks from methanol. This ligand has previously been complexed with inorganic metal compounds (Teixidor et al., 1989, 1991; Vinãs et al., 1998). Until now, it has not been possible to compare the structure of the uncoordinated ligand with the ligand incorporated into such complexes.
An ORTEP drawing of (I) is shown in Fig. 1. The bond distances and angles are comparable with those of 2,6-bis(p-nitrophenylthiomethyl)pyridine (Sillanpää et al., 1994), which posesses deactivating nitro groups at the para position of the phenyl rings. The difference in structure between the two compounds arises in the position of the thiolate groups with respect to the plane of the pyridyl ring. Compound (I) has both phenyl thiolate moieties syn with respect to the pyridyl ring [S—C—C—N torsion angles -129.1 (2) and 77.4 (2)°], whereas the nitro-substituted compound has one thiolate S-centre almost in the plane of the pyridyl ring [S—C—C—N angle 6.8 (5)°] with the other directed away from the pyridyl ring plane [S—C—C—N -112.0 (4)°] (Sillanpää et al., 1994). The lone pairs of electrons on the two sulfur centres in (I) are directed away from each other [C—C—S—CPh 71.1 (3) and 63.8 (2)°]. We have observed, however, that the conformation of (I) can adjust so as to act as a bidentate or tridentate ligand toward metal centres (Ball et al., 2001). The phenyl substituents are orientated in such a way so that one is almost perpendicular to the plane of the pyridyl ring while the other tends towards the plane of the pyridyl ring.