Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S010827010704694X/fa3119sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S010827010704694X/fa3119Isup2.hkl |
CCDC reference: 669155
Mercury(II) oxide (0.216 g, 1 mmol) was added to a solution of N-(2-methylphenyl) 4-nitrothiobenzamide (0.273 g, 1 mmol) at ambient temperature in chloroform (35 ml) and stirred for 130 min. The completion of the reaction was followed by thin-layer chromatography with CCl4–CH3OH (15:1 v/v) as eluent. The mixture was filtered through Celite to remove unreacted mercury(II) compounds. The pale-yellow crystals which formed by slow evaporation were separated, recrystallized from chloroform as fine pale-yellow crystals and dried in vacuo (yield 95%, m.p. 466–468 K). Analysis, calculated for C26H18N4O4S2Hg: C 45.28, H 2.96, N 7.55, Hg 26.95%; found: C 45.12, H 3.12, N 7.35, Hg 27.08%.
All H atoms were located in a difference map, idealized and treated as riding, with C—H = 0.95 Å and Uiso(H) = 1.2Ueq(C). The crystal was a non-merohedral twin and the overlap of inequivalent reflections was treated by ROTWIN (Pink & Young, 2000). The largest residual difference electron-density features lie 1.0–1.3 Å from Hg.
Data collection: COLLECT (Nonius, 1998); cell refinement: EVALCCD (Duisenberg et al., 2003); data reduction: EVALCCD (Duisenberg et al., 2003); program(s) used to solve structure: SHELXTL (Sheldrick, 2005); program(s) used to refine structure: SHELXTL (Sheldrick, 2005); molecular graphics: DIAMOND (Brandenburg, 2007); software used to prepare material for publication: SHELXTL (Sheldrick, 2005) and local programs.
Fig. 1. The molecular structure of (I), with the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii. |
[Hg(C13H9N2O2S)2] | F(000) = 1384 |
Mr = 715.15 | Dx = 1.906 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 204 reflections |
a = 9.7351 (8) Å | θ = 2.5–27.5° |
b = 14.3655 (14) Å | µ = 6.39 mm−1 |
c = 17.9804 (12) Å | T = 150 K |
β = 97.648 (6)° | Needle, pale yellow |
V = 2492.2 (4) Å3 | 0.57 × 0.19 × 0.15 mm |
Z = 4 |
Nonius KappaCCD area-detector diffractometer | 4332 independent reflections |
Radiation source: sealed tube | 3779 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.028 |
ϕ and ω scans | θmax = 25.1°, θmin = 4.5° |
Absorption correction: numerical (SHELXTL; Sheldrick, 2005) | h = −11→11 |
Tmin = 0.088, Tmax = 0.414 | k = −17→17 |
27468 measured reflections | l = −21→21 |
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)] = 0.024 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.054 | H-atom parameters constrained |
S = 1.11 | w = 1/[σ2(Fo2) + (0.0152P)2 + 3.6857P] where P = (Fo2 + 2Fc2)/3 |
4332 reflections | (Δ/σ)max = 0.003 |
337 parameters | Δρmax = 1.07 e Å−3 |
0 restraints | Δρmin = −0.78 e Å−3 |
[Hg(C13H9N2O2S)2] | V = 2492.2 (4) Å3 |
Mr = 715.15 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 9.7351 (8) Å | µ = 6.39 mm−1 |
b = 14.3655 (14) Å | T = 150 K |
c = 17.9804 (12) Å | 0.57 × 0.19 × 0.15 mm |
β = 97.648 (6)° |
Nonius KappaCCD area-detector diffractometer | 4332 independent reflections |
Absorption correction: numerical (SHELXTL; Sheldrick, 2005) | 3779 reflections with I > 2σ(I) |
Tmin = 0.088, Tmax = 0.414 | Rint = 0.028 |
27468 measured reflections |
R[F2 > 2σ(F2)] = 0.024 | 0 restraints |
wR(F2) = 0.054 | H-atom parameters constrained |
S = 1.11 | Δρmax = 1.07 e Å−3 |
4332 reflections | Δρmin = −0.78 e Å−3 |
337 parameters |
x | y | z | Uiso*/Ueq | ||
Hg1 | 0.365692 (16) | 0.553143 (12) | 0.704857 (8) | 0.02291 (6) | |
S1 | 0.45050 (11) | 0.40043 (8) | 0.71002 (6) | 0.0262 (2) | |
C1 | 0.5596 (4) | 0.3923 (3) | 0.6390 (2) | 0.0193 (9) | |
C2 | 0.5843 (4) | 0.2943 (3) | 0.6155 (2) | 0.0204 (9) | |
C3 | 0.6984 (4) | 0.2753 (3) | 0.5782 (2) | 0.0219 (9) | |
H3 | 0.7602 | 0.3241 | 0.5695 | 0.026* | |
C4 | 0.7224 (5) | 0.1859 (3) | 0.5536 (2) | 0.0280 (10) | |
H4 | 0.8002 | 0.1739 | 0.5283 | 0.034* | |
C5 | 0.6340 (5) | 0.1147 (3) | 0.5658 (3) | 0.0385 (12) | |
H5 | 0.6489 | 0.0539 | 0.5478 | 0.046* | |
C6 | 0.5231 (5) | 0.1321 (3) | 0.6046 (3) | 0.0461 (14) | |
H6 | 0.4636 | 0.0825 | 0.6144 | 0.055* | |
C7 | 0.4979 (5) | 0.2214 (3) | 0.6293 (3) | 0.0352 (11) | |
H7 | 0.4212 | 0.2325 | 0.6558 | 0.042* | |
C8 | 0.6172 (4) | 0.5519 (3) | 0.6269 (2) | 0.0183 (8) | |
C9 | 0.5556 (4) | 0.6170 (3) | 0.5733 (2) | 0.0223 (9) | |
H9 | 0.5099 | 0.5958 | 0.5264 | 0.027* | |
C10 | 0.5616 (4) | 0.7109 (3) | 0.5891 (2) | 0.0234 (9) | |
H10 | 0.5192 | 0.7545 | 0.5535 | 0.028* | |
C11 | 0.6300 (4) | 0.7410 (3) | 0.6572 (2) | 0.0194 (9) | |
C12 | 0.6925 (4) | 0.6793 (3) | 0.7108 (2) | 0.0222 (9) | |
H12 | 0.7388 | 0.7017 | 0.7573 | 0.027* | |
C13 | 0.6861 (4) | 0.5842 (3) | 0.6956 (2) | 0.0223 (9) | |
H13 | 0.7284 | 0.5412 | 0.7317 | 0.027* | |
N1 | 0.6190 (3) | 0.4581 (2) | 0.60686 (18) | 0.0201 (7) | |
N2 | 0.6331 (4) | 0.8405 (3) | 0.6742 (2) | 0.0262 (8) | |
O1 | 0.6957 (3) | 0.8671 (2) | 0.73455 (18) | 0.0351 (8) | |
O2 | 0.5717 (4) | 0.8940 (2) | 0.6275 (2) | 0.0427 (9) | |
S2 | 0.27669 (11) | 0.70401 (8) | 0.71190 (6) | 0.0283 (3) | |
C14 | 0.1559 (4) | 0.7195 (3) | 0.6289 (2) | 0.0232 (9) | |
C15 | 0.1133 (4) | 0.8184 (3) | 0.6176 (2) | 0.0230 (9) | |
C16 | −0.0266 (4) | 0.8363 (3) | 0.5934 (2) | 0.0270 (10) | |
H16 | −0.0899 | 0.7861 | 0.5837 | 0.032* | |
C17 | −0.0730 (5) | 0.9272 (3) | 0.5837 (3) | 0.0379 (12) | |
H17 | −0.1685 | 0.9390 | 0.5680 | 0.045* | |
C18 | 0.0187 (5) | 1.0010 (3) | 0.5966 (3) | 0.0359 (11) | |
H18 | −0.0138 | 1.0632 | 0.5901 | 0.043* | |
C19 | 0.1571 (5) | 0.9837 (3) | 0.6188 (3) | 0.0321 (11) | |
H19 | 0.2203 | 1.0342 | 0.6265 | 0.038* | |
C20 | 0.2054 (5) | 0.8934 (3) | 0.6303 (2) | 0.0275 (10) | |
H20 | 0.3008 | 0.8823 | 0.6467 | 0.033* | |
C21 | 0.1093 (4) | 0.5626 (3) | 0.5915 (2) | 0.0232 (9) | |
C22 | 0.1784 (4) | 0.5074 (3) | 0.5436 (2) | 0.0255 (9) | |
H22 | 0.2284 | 0.5363 | 0.5079 | 0.031* | |
C23 | 0.1741 (5) | 0.4113 (3) | 0.5481 (2) | 0.0277 (10) | |
H23 | 0.2208 | 0.3740 | 0.5158 | 0.033* | |
C24 | 0.1010 (4) | 0.3701 (3) | 0.6004 (2) | 0.0268 (10) | |
C25 | 0.0322 (5) | 0.4226 (3) | 0.6485 (3) | 0.0317 (11) | |
H25 | −0.0178 | 0.3930 | 0.6838 | 0.038* | |
C26 | 0.0374 (4) | 0.5180 (3) | 0.6445 (3) | 0.0292 (10) | |
H26 | −0.0082 | 0.5544 | 0.6779 | 0.035* | |
N3 | 0.1004 (4) | 0.6585 (3) | 0.58198 (19) | 0.0260 (8) | |
N4 | 0.0957 (4) | 0.2685 (3) | 0.6056 (2) | 0.0377 (10) | |
O3 | 0.1700 (4) | 0.2228 (3) | 0.5688 (2) | 0.0496 (10) | |
O4 | 0.0177 (4) | 0.2327 (3) | 0.6465 (2) | 0.0488 (10) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Hg1 | 0.02093 (9) | 0.02133 (10) | 0.02660 (10) | 0.00489 (7) | 0.00359 (6) | −0.00331 (7) |
S1 | 0.0322 (6) | 0.0198 (6) | 0.0286 (6) | 0.0066 (5) | 0.0116 (4) | 0.0046 (4) |
C1 | 0.018 (2) | 0.018 (2) | 0.020 (2) | 0.0030 (17) | −0.0028 (15) | −0.0008 (16) |
C2 | 0.020 (2) | 0.020 (2) | 0.020 (2) | 0.0021 (18) | −0.0007 (15) | 0.0007 (16) |
C3 | 0.025 (2) | 0.018 (2) | 0.021 (2) | 0.0041 (18) | −0.0012 (16) | 0.0013 (16) |
C4 | 0.030 (2) | 0.026 (3) | 0.028 (2) | 0.008 (2) | 0.0027 (18) | −0.0015 (18) |
C5 | 0.039 (3) | 0.017 (3) | 0.058 (3) | 0.009 (2) | 0.000 (2) | −0.011 (2) |
C6 | 0.035 (3) | 0.017 (3) | 0.087 (4) | −0.006 (2) | 0.013 (3) | −0.001 (3) |
C7 | 0.029 (2) | 0.017 (2) | 0.061 (3) | 0.001 (2) | 0.013 (2) | 0.002 (2) |
C8 | 0.021 (2) | 0.017 (2) | 0.018 (2) | −0.0007 (17) | 0.0057 (15) | −0.0015 (16) |
C9 | 0.028 (2) | 0.022 (2) | 0.016 (2) | −0.0005 (18) | 0.0000 (16) | −0.0035 (16) |
C10 | 0.025 (2) | 0.016 (2) | 0.028 (2) | 0.0024 (18) | 0.0011 (17) | 0.0021 (17) |
C11 | 0.017 (2) | 0.014 (2) | 0.028 (2) | 0.0005 (16) | 0.0041 (16) | −0.0041 (16) |
C12 | 0.021 (2) | 0.021 (2) | 0.022 (2) | −0.0018 (17) | −0.0021 (16) | −0.0082 (17) |
C13 | 0.020 (2) | 0.024 (2) | 0.022 (2) | 0.0024 (17) | 0.0002 (16) | 0.0021 (17) |
N1 | 0.0242 (18) | 0.0140 (19) | 0.0222 (19) | 0.0017 (14) | 0.0034 (13) | −0.0017 (14) |
N2 | 0.0250 (19) | 0.0149 (19) | 0.039 (2) | −0.0017 (16) | 0.0055 (16) | −0.0031 (16) |
O1 | 0.0412 (19) | 0.0214 (18) | 0.041 (2) | −0.0061 (14) | −0.0011 (14) | −0.0130 (14) |
O2 | 0.048 (2) | 0.0167 (18) | 0.060 (2) | 0.0031 (16) | −0.0056 (17) | −0.0002 (16) |
S2 | 0.0291 (6) | 0.0234 (6) | 0.0307 (6) | 0.0100 (5) | −0.0030 (4) | −0.0095 (4) |
C14 | 0.020 (2) | 0.027 (3) | 0.024 (2) | 0.0046 (18) | 0.0051 (16) | −0.0012 (18) |
C15 | 0.029 (2) | 0.025 (2) | 0.016 (2) | 0.0065 (19) | 0.0060 (16) | −0.0033 (17) |
C16 | 0.029 (2) | 0.023 (2) | 0.028 (2) | 0.001 (2) | −0.0001 (18) | 0.0020 (18) |
C17 | 0.036 (3) | 0.033 (3) | 0.043 (3) | 0.011 (2) | −0.003 (2) | 0.007 (2) |
C18 | 0.054 (3) | 0.021 (3) | 0.034 (3) | 0.004 (2) | 0.008 (2) | 0.005 (2) |
C19 | 0.043 (3) | 0.022 (2) | 0.033 (3) | −0.006 (2) | 0.013 (2) | −0.0033 (19) |
C20 | 0.025 (2) | 0.028 (3) | 0.031 (3) | 0.001 (2) | 0.0089 (18) | −0.0052 (19) |
C21 | 0.022 (2) | 0.019 (2) | 0.027 (2) | −0.0006 (18) | −0.0041 (16) | −0.0031 (17) |
C22 | 0.029 (2) | 0.028 (3) | 0.020 (2) | −0.0011 (19) | 0.0037 (17) | −0.0022 (18) |
C23 | 0.031 (2) | 0.024 (2) | 0.027 (2) | 0.0031 (19) | −0.0015 (18) | −0.0065 (18) |
C24 | 0.026 (2) | 0.016 (2) | 0.035 (3) | −0.0016 (18) | −0.0101 (18) | 0.0000 (18) |
C25 | 0.029 (2) | 0.033 (3) | 0.033 (3) | −0.009 (2) | 0.0042 (19) | 0.003 (2) |
C26 | 0.024 (2) | 0.032 (3) | 0.032 (3) | −0.001 (2) | 0.0062 (18) | −0.0026 (19) |
N3 | 0.030 (2) | 0.019 (2) | 0.029 (2) | 0.0014 (16) | 0.0004 (15) | −0.0040 (15) |
N4 | 0.035 (2) | 0.027 (2) | 0.045 (3) | −0.003 (2) | −0.0199 (19) | −0.0037 (19) |
O3 | 0.061 (2) | 0.028 (2) | 0.055 (2) | 0.0067 (18) | −0.0110 (19) | −0.0059 (17) |
O4 | 0.046 (2) | 0.033 (2) | 0.063 (3) | −0.0171 (17) | −0.0126 (18) | 0.0139 (18) |
Hg1—S1 | 2.3415 (11) | N2—O2 | 1.233 (5) |
Hg1—S2 | 2.3438 (11) | S2—C14 | 1.787 (4) |
S1—C1 | 1.770 (4) | C14—C15 | 1.486 (6) |
C1—C2 | 1.499 (6) | C14—N3 | 1.284 (5) |
C1—N1 | 1.285 (5) | C15—C16 | 1.397 (6) |
C2—C3 | 1.399 (6) | C15—C20 | 1.400 (6) |
C2—C7 | 1.386 (6) | C16—H16 | 0.950 |
C3—H3 | 0.950 | C16—C17 | 1.386 (6) |
C3—C4 | 1.388 (6) | C17—H17 | 0.950 |
C4—H4 | 0.950 | C17—C18 | 1.385 (7) |
C4—C5 | 1.373 (7) | C18—H18 | 0.950 |
C5—H5 | 0.950 | C18—C19 | 1.377 (7) |
C5—C6 | 1.383 (7) | C19—H19 | 0.950 |
C6—H6 | 0.950 | C19—C20 | 1.386 (7) |
C6—C7 | 1.390 (7) | C20—H20 | 0.950 |
C7—H7 | 0.950 | C21—C22 | 1.406 (6) |
C8—C9 | 1.418 (6) | C21—C26 | 1.410 (6) |
C8—C13 | 1.403 (6) | C21—N3 | 1.390 (6) |
C8—N1 | 1.395 (5) | C22—H22 | 0.950 |
C9—H9 | 0.950 | C22—C23 | 1.384 (6) |
C9—C10 | 1.377 (6) | C23—H23 | 0.950 |
C10—H10 | 0.950 | C23—C24 | 1.385 (6) |
C10—C11 | 1.382 (6) | C24—C25 | 1.384 (7) |
C11—C12 | 1.389 (6) | C24—N4 | 1.464 (6) |
C11—N2 | 1.462 (5) | C25—H25 | 0.950 |
C12—H12 | 0.950 | C25—C26 | 1.374 (7) |
C12—C13 | 1.393 (6) | C26—H26 | 0.950 |
C13—H13 | 0.950 | N4—O3 | 1.233 (6) |
N2—O1 | 1.232 (5) | N4—O4 | 1.237 (6) |
S1—Hg1—S2 | 174.37 (4) | Hg1—S2—C14 | 106.10 (15) |
Hg1—S1—C1 | 105.98 (14) | S2—C14—C15 | 112.0 (3) |
S1—C1—C2 | 113.6 (3) | S2—C14—N3 | 129.5 (3) |
S1—C1—N1 | 128.7 (3) | C15—C14—N3 | 118.5 (4) |
C2—C1—N1 | 117.8 (4) | C14—C15—C16 | 117.5 (4) |
C1—C2—C3 | 119.1 (4) | C14—C15—C20 | 123.5 (4) |
C1—C2—C7 | 122.3 (4) | C16—C15—C20 | 119.1 (4) |
C3—C2—C7 | 118.6 (4) | C15—C16—H16 | 120.0 |
C2—C3—H3 | 119.7 | C15—C16—C17 | 120.1 (4) |
C2—C3—C4 | 120.7 (4) | H16—C16—C17 | 120.0 |
H3—C3—C4 | 119.7 | C16—C17—H17 | 119.7 |
C3—C4—H4 | 119.9 | C16—C17—C18 | 120.5 (4) |
C3—C4—C5 | 120.2 (4) | H17—C17—C18 | 119.7 |
H4—C4—C5 | 119.9 | C17—C18—H18 | 120.2 |
C4—C5—H5 | 120.2 | C17—C18—C19 | 119.6 (5) |
C4—C5—C6 | 119.6 (4) | H18—C18—C19 | 120.2 |
H5—C5—C6 | 120.2 | C18—C19—H19 | 119.6 |
C5—C6—H6 | 119.6 | C18—C19—C20 | 120.8 (4) |
C5—C6—C7 | 120.7 (5) | H19—C19—C20 | 119.6 |
H6—C6—C7 | 119.6 | C15—C20—C19 | 119.9 (4) |
C2—C7—C6 | 120.1 (4) | C15—C20—H20 | 120.1 |
C2—C7—H7 | 120.0 | C19—C20—H20 | 120.1 |
C6—C7—H7 | 120.0 | C22—C21—C26 | 118.6 (4) |
C9—C8—C13 | 119.3 (4) | C22—C21—N3 | 120.8 (4) |
C9—C8—N1 | 118.7 (3) | C26—C21—N3 | 120.3 (4) |
C13—C8—N1 | 121.7 (4) | C21—C22—H22 | 119.8 |
C8—C9—H9 | 119.9 | C21—C22—C23 | 120.4 (4) |
C8—C9—C10 | 120.2 (4) | H22—C22—C23 | 119.8 |
H9—C9—C10 | 119.9 | C22—C23—H23 | 120.4 |
C9—C10—H10 | 120.3 | C22—C23—C24 | 119.2 (4) |
C9—C10—C11 | 119.4 (4) | H23—C23—C24 | 120.4 |
H10—C10—C11 | 120.3 | C23—C24—C25 | 121.8 (4) |
C10—C11—C12 | 122.0 (4) | C23—C24—N4 | 119.7 (4) |
C10—C11—N2 | 119.1 (4) | C25—C24—N4 | 118.6 (4) |
C12—C11—N2 | 118.9 (4) | C24—C25—H25 | 120.5 |
C11—C12—H12 | 120.5 | C24—C25—C26 | 119.1 (4) |
C11—C12—C13 | 119.0 (4) | H25—C25—C26 | 120.5 |
H12—C12—C13 | 120.5 | C21—C26—C25 | 121.0 (4) |
C8—C13—C12 | 120.1 (4) | C21—C26—H26 | 119.5 |
C8—C13—H13 | 120.0 | C25—C26—H26 | 119.5 |
C12—C13—H13 | 120.0 | C14—N3—C21 | 125.6 (4) |
C1—N1—C8 | 124.9 (3) | C24—N4—O3 | 117.9 (4) |
C11—N2—O1 | 118.8 (4) | C24—N4—O4 | 118.9 (4) |
C11—N2—O2 | 118.2 (4) | O3—N4—O4 | 123.2 (4) |
O1—N2—O2 | 123.1 (4) | ||
Hg1—S1—C1—C2 | −160.0 (2) | Hg1—S2—C14—C15 | −167.9 (2) |
Hg1—S1—C1—N1 | 20.8 (4) | Hg1—S2—C14—N3 | 15.0 (4) |
S1—C1—C2—C3 | −160.6 (3) | S2—C14—C15—C16 | −138.5 (3) |
S1—C1—C2—C7 | 19.5 (5) | S2—C14—C15—C20 | 41.1 (5) |
N1—C1—C2—C3 | 18.8 (5) | N3—C14—C15—C16 | 39.0 (5) |
N1—C1—C2—C7 | −161.2 (4) | N3—C14—C15—C20 | −141.4 (4) |
C1—C2—C3—C4 | −178.1 (4) | C14—C15—C16—C17 | 178.4 (4) |
C7—C2—C3—C4 | 1.8 (6) | C20—C15—C16—C17 | −1.2 (6) |
C2—C3—C4—C5 | −0.1 (6) | C15—C16—C17—C18 | 1.0 (7) |
C3—C4—C5—C6 | −1.8 (7) | C16—C17—C18—C19 | 0.3 (7) |
C4—C5—C6—C7 | 1.9 (8) | C17—C18—C19—C20 | −1.6 (7) |
C1—C2—C7—C6 | 178.2 (4) | C18—C19—C20—C15 | 1.4 (6) |
C3—C2—C7—C6 | −1.7 (7) | C14—C15—C20—C19 | −179.6 (4) |
C5—C6—C7—C2 | −0.2 (8) | C16—C15—C20—C19 | 0.0 (6) |
C13—C8—C9—C10 | −0.9 (6) | C26—C21—C22—C23 | 0.8 (6) |
N1—C8—C9—C10 | −174.8 (4) | N3—C21—C22—C23 | −173.0 (4) |
C8—C9—C10—C11 | 0.9 (6) | C21—C22—C23—C24 | 0.0 (6) |
C9—C10—C11—C12 | −0.5 (6) | C22—C23—C24—C25 | −0.2 (6) |
C9—C10—C11—N2 | −178.5 (4) | C22—C23—C24—N4 | 180.0 (4) |
C10—C11—C12—C13 | 0.1 (6) | C23—C24—C25—C26 | −0.3 (7) |
N2—C11—C12—C13 | 178.1 (4) | N4—C24—C25—C26 | 179.5 (4) |
C11—C12—C13—C8 | −0.1 (6) | C24—C25—C26—C21 | 1.1 (7) |
C9—C8—C13—C12 | 0.5 (6) | C22—C21—C26—C25 | −1.3 (6) |
N1—C8—C13—C12 | 174.2 (4) | N3—C21—C26—C25 | 172.4 (4) |
S1—C1—N1—C8 | 5.4 (6) | S2—C14—N3—C21 | 9.1 (7) |
C2—C1—N1—C8 | −173.8 (3) | C15—C14—N3—C21 | −167.8 (4) |
C9—C8—N1—C1 | −118.3 (4) | C22—C21—N3—C14 | −115.0 (5) |
C13—C8—N1—C1 | 68.0 (5) | C26—C21—N3—C14 | 71.4 (6) |
C10—C11—N2—O1 | −179.0 (4) | C23—C24—N4—O3 | 8.0 (6) |
C10—C11—N2—O2 | 1.4 (6) | C23—C24—N4—O4 | −172.0 (4) |
C12—C11—N2—O1 | 2.9 (6) | C25—C24—N4—O3 | −171.8 (4) |
C12—C11—N2—O2 | −176.7 (4) | C25—C24—N4—O4 | 8.2 (6) |
Experimental details
Crystal data | |
Chemical formula | [Hg(C13H9N2O2S)2] |
Mr | 715.15 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 150 |
a, b, c (Å) | 9.7351 (8), 14.3655 (14), 17.9804 (12) |
β (°) | 97.648 (6) |
V (Å3) | 2492.2 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 6.39 |
Crystal size (mm) | 0.57 × 0.19 × 0.15 |
Data collection | |
Diffractometer | Nonius KappaCCD area-detector diffractometer |
Absorption correction | Numerical (SHELXTL; Sheldrick, 2005) |
Tmin, Tmax | 0.088, 0.414 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 27468, 4332, 3779 |
Rint | 0.028 |
(sin θ/λ)max (Å−1) | 0.596 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.024, 0.054, 1.11 |
No. of reflections | 4332 |
No. of parameters | 337 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.07, −0.78 |
Computer programs: COLLECT (Nonius, 1998), EVALCCD (Duisenberg et al., 2003), DIAMOND (Brandenburg, 2007), SHELXTL (Sheldrick, 2005) and local programs.
Hg1—S1 | 2.3415 (11) | C1—N1 | 1.285 (5) |
Hg1—S2 | 2.3438 (11) | S2—C14 | 1.787 (4) |
S1—C1 | 1.770 (4) | C14—N3 | 1.284 (5) |
S1—Hg1—S2 | 174.37 (4) | Hg1—S2—C14 | 106.10 (15) |
Hg1—S1—C1 | 105.98 (14) | S2—C14—C15 | 112.0 (3) |
S1—C1—C2 | 113.6 (3) | S2—C14—N3 | 129.5 (3) |
S1—C1—N1 | 128.7 (3) | C15—C14—N3 | 118.5 (4) |
C2—C1—N1 | 117.8 (4) | C14—N3—C21 | 125.6 (4) |
C1—N1—C8 | 124.9 (3) |
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The fact that mercury(II) ions interact with many biological molecules through coordination with deprotonated thiol, imidazole, disulfide, thioether, amino or carboxylate groups is well known, and a great deal of effort has been devoted to the characterization of these interactions in model molecules and in proteins (Popovic et al., 2000; Kajdan et al., 2000). Interest in the structural chemistry of mercury(II) complexes with ligands containing S-donor atoms, such as thioamides, is related not only to the toxicological behaviour of the metal and to the detoxification of mercury, but also to their industrial applications, especially in semiconductors or in photovoltaic devices (Hadjikakou et al., 2003). Consequently, a number of attempts have been made to explore the coordination chemistry of mercury(II) with diverse sulfur-containing ligands, such as aromatic thiolates (Bell, Branston et al., 2001; Bell, Coles et al., 2001; Bell et al., 2004; Blower & Dilworth, 1987). Extensive use of thionates as bridging ligands stems from the presence of the thioamide NCS group. Parent ligands adopt the thione form in the solid but may exist, at least in part, as the thiol form in solution, particularly in non-polar solvents (Cotton & Walton, 1993). This work describes the synthesis and crystal structure of a mercury(II) complex of such a ligand, the title compound, (I), which is only the second example to be crystallographically characterized.
The molecular structure of (I) is shown in Fig. 1. The molecule has no crystallographic symmetry, but the molecular symmetry is close to C2, with approximately linear coordination of Hg. The Hg—S distances (Table 1) agree well with those in similar mercury(II) complexes, e.g. 2.344 (3)–2.351 (3) Å (Bell, Coles et al., 2001) and 2.338 (3)–2.345 (3) Å (Popovic et al., 2002); the mean value for Hg—S distances in HgII arenethionate complexes in the compilation of Orpen et al. (1989) is 2.362 Å. The S—C distances are indicative of single bonds, also in reasonable agreement with the mean value of 1.761 Å reported for related systems by Orpen et al. (1989).
The phenyl and nitrophenyl rings make dihedral angles of 19.2 (2) and 68.51 (8)°, respectively, with the SC(N)C thionate unit in the S1 ligand, and the corresponding angles in the S2 ligand are 40.71 (15) and 75.21 (9)°. The dihedral angles between the two aromatic rings within each ligand are 86.75 (12) and 65.28 (12)°, and the nitro group is essentially coplanar with its parent benzene ring in each case, with dihedral angles of 3.0 (2) and 8.3 (3)°. The C—S···S···C pseudo-torsion angle indicating the relative twist of the two ligands in their coordination of Hg is 70.5 (2)°.
The most closely related previous mercury(II) complex to be crystallographically characterized has two thioacetanilide ligands (Avalos et al., 1997). It is much less symmetrical, having a weak π coordination of the phenyl ring of one ligand to Hg, while the other is oriented well away from the metal. In the title complex, both nitrophenyl groups lie in orientations such that the shortest Hg···C distance is close to 3 Å [Hg1···C8 = 2.979 (4) and Hg1···C21 = 3.008 (4) Å] and this Hg···C vector is approximately perpendicular to the ring. The most significant intermolecular interactions include a short S2···O4(1/2 − x, 1/2 + y, 3/2 − z) contact of 3.050 (4) Å, some C—H···π interactions with H···ring-centroid distances < 3 Å, and a slipped π-stacking interaction between centrosymmetrically related nitrophenyl rings (C21–C26), with a centroid-to-centroid distance of 3.906 (2) Å and a perpendicular interplanar distance of 3.466 Å, the lateral slippage being 1.802 Å.