Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S010827010201123X/ob1066sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S010827010201123X/ob1066Isup2.hkl |
CCDC reference: 193407
Compound (I) was synthesized according to the reported procedure of Belakhov et al. (2000), and its purity was established by a combination of 1H NMR, 13C NMR, two-dimensional-COSY Please expand, and mass spectroscopic analyses. X-ray quality crystals of (I) were obtained by recrystallization from a methanol solution.
Because the crystal was a very small colourless plate, it was impossible to obtain an accurate measurement of the crystal faces. A little splitting was also found in some of the reflections and TWIN options (SHELXL97; Sheldrick, 1997) were used in the final refinement. Initially, the positions of the H atoms of the donor atoms were generated as idealized OH groups. During the refinement, the coordinates of atoms H2OA and H2OB were treated as riding on their parent atoms (O2A and O2B, respectively). Attempts to find the H atoms on atoms O3 and O7, using NFIX 81 or NFIX 147 options (SHELXL97), failed because, even in idealized positions, short contacts between donor and acceptor H atoms were found (H7A···H2OA 1.81 Å and H3B···H6OA 1.51 Å). The choice between which atoms were donors and which acceptors was based on measurement of the O—H···O angles. Short O···O distances involving atoms O3 or O7, except for those listed in Table 2, were 2.74 (2)–2.76 (2) Å for O3A···O2B(2 - x, y + 1/2, 2 - z) and O7B···O7A(2 - x, y + 1/2, 2 - z).
Data collection: COLLECT (Nonius, 2000); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: TEXSAN (Molecular Structure Corporation, 1999).
[Hg(CH3)(C9H15O7S)] | F(000) = 920 |
Mr = 482.89 | Dx = 2.213 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71070 Å |
a = 7.306 (1) Å | Cell parameters from 19347 reflections |
b = 15.247 (3) Å | θ = 1.2–25.4° |
c = 13.014 (2) Å | µ = 10.79 mm−1 |
β = 91.10 (3)° | T = 293 K |
V = 1449.4 (4) Å3 | Plate, colourless |
Z = 4 | 0.10 × 0.10 × 0.02 mm |
Nonius KappaCCD area-detector diffractometer | 5084 independent reflections |
Radiation source: fine-focus sealed tube | 4777 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.058 |
ϕ and ω scans | θmax = 25.1°, θmin = 2.7° |
Absorption correction: multi-scan (SORTAV; Blessing, 1995) | h = −8→8 |
Tmin = 0.388, Tmax = 0.806 | k = −18→18 |
11530 measured reflections | l = −15→15 |
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.064 | w = 1/[σ2(Fo2) + (0.0956P)2 + 11.7784P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.172 | (Δ/σ)max = 0.009 |
S = 1.06 | Δρmax = 4.38 e Å−3 |
5084 reflections | Δρmin = −1.78 e Å−3 |
349 parameters | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
3 restraints | Extinction coefficient: 0.0040 (7) |
Primary atom site location: structure-invariant direct methods | Absolute structure: (Flack, 1983), 2408 Friedel pairs |
Secondary atom site location: difference Fourier map | Absolute structure parameter: 0.010 (19) |
[Hg(CH3)(C9H15O7S)] | V = 1449.4 (4) Å3 |
Mr = 482.89 | Z = 4 |
Monoclinic, P21 | Mo Kα radiation |
a = 7.306 (1) Å | µ = 10.79 mm−1 |
b = 15.247 (3) Å | T = 293 K |
c = 13.014 (2) Å | 0.10 × 0.10 × 0.02 mm |
β = 91.10 (3)° |
Nonius KappaCCD area-detector diffractometer | 5084 independent reflections |
Absorption correction: multi-scan (SORTAV; Blessing, 1995) | 4777 reflections with I > 2σ(I) |
Tmin = 0.388, Tmax = 0.806 | Rint = 0.058 |
11530 measured reflections |
R[F2 > 2σ(F2)] = 0.064 | H-atom parameters constrained |
wR(F2) = 0.172 | w = 1/[σ2(Fo2) + (0.0956P)2 + 11.7784P] where P = (Fo2 + 2Fc2)/3 |
S = 1.06 | Δρmax = 4.38 e Å−3 |
5084 reflections | Δρmin = −1.78 e Å−3 |
349 parameters | Absolute structure: (Flack, 1983), 2408 Friedel pairs |
3 restraints | Absolute structure parameter: 0.010 (19) |
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 | ||
Hg1A | 0.56409 (14) | 0.77997 (6) | 0.93025 (7) | 0.0592 (3) | |
S1A | 0.5106 (10) | 0.9311 (4) | 0.9450 (4) | 0.0553 (13) | |
O1A | 0.5247 (15) | 0.8934 (8) | 0.7470 (8) | 0.032 (2) | |
O2A | 0.5173 (19) | 1.1506 (8) | 0.6462 (10) | 0.047 (3) | |
H2OA | 0.5207 | 1.1739 | 0.5892 | 0.071* | |
O3A | 0.7418 (16) | 1.0038 (9) | 0.6214 (10) | 0.046 (3) | |
O4A | 0.1798 (19) | 0.8585 (10) | 0.7881 (13) | 0.054 (3) | |
O5A | 0.122 (3) | 0.9951 (16) | 0.8357 (15) | 0.085 (5) | |
O6A | 0.5667 (18) | 0.8438 (9) | 0.4772 (9) | 0.046 (3) | |
H6OA | 0.4635 | 0.8322 | 0.4695 | 0.069* | |
O7A | 0.582 (3) | 0.6715 (9) | 0.5669 (12) | 0.065 (4) | |
C1A | 0.226 (3) | 0.9403 (12) | 0.8101 (14) | 0.045 (4) | |
C2A | 0.432 (3) | 0.9536 (10) | 0.8159 (13) | 0.039 (4) | |
C3A | 0.484 (3) | 1.0467 (12) | 0.7901 (13) | 0.038 (4) | |
H3A2 | 0.6122 | 1.0561 | 0.8084 | 0.046* | |
H3A3 | 0.4116 | 1.0871 | 0.8299 | 0.046* | |
C4A | 0.454 (2) | 1.0656 (10) | 0.6735 (14) | 0.036 (4) | |
H4A | 0.3220 | 1.0627 | 0.6581 | 0.043* | |
C5A | 0.548 (2) | 0.9991 (12) | 0.6080 (11) | 0.034 (3) | |
H5A | 0.5156 | 1.0096 | 0.5356 | 0.041* | |
C6A | 0.483 (2) | 0.9069 (11) | 0.6391 (12) | 0.031 (3) | |
H6A | 0.3503 | 0.9019 | 0.6267 | 0.037* | |
C7A | 0.581 (3) | 0.8325 (11) | 0.5844 (12) | 0.038 (4) | |
H7A | 0.7107 | 0.8328 | 0.6053 | 0.046* | |
C8A | 0.496 (3) | 0.7460 (11) | 0.6148 (16) | 0.051 (5) | |
H8A1 | 0.5059 | 0.7396 | 0.6888 | 0.061* | |
H8A2 | 0.3672 | 0.7467 | 0.5959 | 0.061* | |
C9A | 0.613 (7) | 0.650 (2) | 0.906 (4) | 0.119 (15) | |
H91A | 0.5345 | 0.6293 | 0.8511 | 0.178* | |
H92A | 0.5881 | 0.6178 | 0.9675 | 0.178* | |
H93A | 0.7383 | 0.6420 | 0.8879 | 0.178* | |
C10A | −0.011 (3) | 0.8422 (19) | 0.7757 (16) | 0.062 (6) | |
H10A | −0.0313 | 0.8034 | 0.7185 | 0.092* | |
H10B | −0.0737 | 0.8965 | 0.7633 | 0.092* | |
H10C | −0.0562 | 0.8155 | 0.8370 | 0.092* | |
Hg1B | 0.91891 (12) | 0.9919 | 1.04501 (6) | 0.0542 (3) | |
S1B | 0.9713 (8) | 0.8398 (3) | 1.0635 (4) | 0.0467 (11) | |
O1B | 0.9999 (16) | 0.8953 (7) | 1.2555 (9) | 0.033 (2) | |
O2B | 1.0271 (18) | 0.6442 (8) | 1.3804 (9) | 0.046 (3) | |
H2OB | 1.0495 | 0.6540 | 1.4417 | 0.070* | |
O3B | 1.2330 (16) | 0.7930 (9) | 1.3956 (10) | 0.044 (3) | |
O4B | 0.643 (2) | 0.9158 (9) | 1.2082 (11) | 0.048 (3) | |
O5B | 0.5970 (17) | 0.7741 (7) | 1.1971 (13) | 0.057 (4) | |
O6B | 1.069 (2) | 0.9635 (9) | 1.5213 (10) | 0.049 (3) | |
H6OB | 0.9523 | 0.9700 | 1.5502 | 0.073* | |
O7B | 1.053 (2) | 1.1305 (9) | 1.4146 (12) | 0.061 (4) | |
C1B | 0.702 (2) | 0.8351 (9) | 1.2046 (13) | 0.039 (4) | |
C2B | 0.908 (2) | 0.8275 (11) | 1.1997 (13) | 0.037 (4) | |
C3B | 0.973 (2) | 0.7356 (11) | 1.2356 (13) | 0.036 (4) | |
H31B | 0.9007 | 0.6907 | 1.2010 | 0.043* | |
H32B | 1.1002 | 0.7271 | 1.2185 | 0.043* | |
C4B | 0.950 (2) | 0.7282 (10) | 1.3515 (14) | 0.036 (4) | |
H4B | 0.8194 | 0.7284 | 1.3668 | 0.044* | |
C5B | 1.040 (2) | 0.8033 (11) | 1.4063 (12) | 0.035 (3) | |
H5B | 1.0106 | 0.8008 | 1.4794 | 0.042* | |
C6B | 0.978 (2) | 0.8880 (12) | 1.3632 (13) | 0.036 (4) | |
H6B | 0.8466 | 0.8928 | 1.3762 | 0.043* | |
C7B | 1.070 (2) | 0.9690 (11) | 1.4105 (13) | 0.039 (4) | |
H7B | 1.1981 | 0.9684 | 1.3898 | 0.046* | |
C8B | 0.986 (3) | 1.0525 (12) | 1.3708 (15) | 0.049 (5) | |
H81 | 1.0044 | 1.0551 | 1.2972 | 0.058* | |
H82 | 0.8551 | 1.0498 | 1.3814 | 0.058* | |
C9B | 0.889 (5) | 1.125 (2) | 1.032 (3) | 0.086 (9) | |
H91B | 0.7801 | 1.1378 | 0.9921 | 0.129* | |
H92B | 0.9933 | 1.1491 | 0.9982 | 0.129* | |
H93B | 0.8793 | 1.1504 | 1.0990 | 0.129* | |
C10B | 0.454 (3) | 0.928 (2) | 1.2173 (18) | 0.071 (7) | |
H101 | 0.4136 | 0.9729 | 1.1703 | 0.106* | |
H102 | 0.4274 | 0.9455 | 1.2863 | 0.106* | |
H103 | 0.3917 | 0.8742 | 1.2015 | 0.106* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Hg1A | 0.0847 (6) | 0.0389 (4) | 0.0537 (4) | −0.0061 (4) | −0.0062 (4) | 0.0069 (4) |
S1A | 0.093 (4) | 0.041 (3) | 0.032 (2) | −0.002 (3) | −0.006 (2) | 0.0000 (19) |
O1A | 0.041 (6) | 0.030 (6) | 0.027 (5) | −0.002 (5) | 0.003 (4) | −0.002 (4) |
O2A | 0.056 (8) | 0.031 (6) | 0.055 (8) | −0.001 (6) | 0.010 (6) | 0.008 (6) |
O3A | 0.043 (6) | 0.039 (7) | 0.056 (7) | −0.006 (5) | 0.011 (5) | −0.012 (6) |
O4A | 0.043 (7) | 0.054 (8) | 0.064 (9) | −0.007 (6) | 0.003 (6) | −0.004 (7) |
O5A | 0.079 (10) | 0.092 (14) | 0.084 (12) | 0.021 (11) | 0.036 (9) | 0.024 (12) |
O6A | 0.059 (7) | 0.049 (7) | 0.029 (6) | −0.014 (6) | −0.001 (5) | −0.004 (5) |
O7A | 0.104 (12) | 0.030 (7) | 0.060 (9) | 0.017 (7) | −0.007 (9) | −0.014 (6) |
C1A | 0.073 (12) | 0.030 (8) | 0.034 (8) | 0.010 (9) | 0.011 (8) | −0.001 (7) |
C2A | 0.054 (10) | 0.026 (7) | 0.036 (8) | 0.010 (7) | −0.008 (8) | −0.004 (6) |
C3A | 0.051 (10) | 0.039 (9) | 0.025 (7) | 0.000 (7) | 0.006 (6) | 0.004 (7) |
C4A | 0.042 (9) | 0.017 (7) | 0.048 (10) | −0.001 (6) | 0.001 (7) | 0.003 (7) |
C5A | 0.047 (8) | 0.031 (8) | 0.024 (6) | −0.001 (8) | 0.003 (6) | −0.001 (6) |
C6A | 0.037 (8) | 0.032 (8) | 0.024 (7) | 0.005 (6) | −0.003 (6) | −0.010 (6) |
C7A | 0.054 (10) | 0.036 (9) | 0.024 (7) | 0.004 (7) | −0.007 (7) | −0.008 (6) |
C8A | 0.086 (14) | 0.015 (7) | 0.050 (11) | −0.009 (8) | −0.007 (10) | −0.002 (7) |
C9A | 0.18 (4) | 0.046 (17) | 0.13 (3) | 0.01 (2) | −0.04 (3) | −0.006 (19) |
C10A | 0.067 (13) | 0.085 (17) | 0.033 (10) | −0.020 (12) | −0.002 (9) | −0.008 (10) |
Hg1B | 0.0732 (5) | 0.0374 (4) | 0.0521 (4) | −0.0051 (4) | 0.0059 (3) | 0.0066 (3) |
S1B | 0.069 (3) | 0.039 (3) | 0.032 (2) | 0.006 (2) | 0.001 (2) | −0.0010 (18) |
O1B | 0.045 (6) | 0.022 (5) | 0.034 (6) | −0.001 (4) | 0.005 (5) | −0.005 (4) |
O2B | 0.053 (7) | 0.032 (7) | 0.054 (8) | 0.015 (6) | 0.008 (6) | 0.012 (6) |
O3B | 0.037 (6) | 0.048 (7) | 0.047 (6) | −0.003 (5) | −0.003 (5) | −0.003 (6) |
O4B | 0.061 (8) | 0.033 (7) | 0.050 (8) | −0.001 (6) | 0.001 (6) | 0.007 (6) |
O5B | 0.057 (7) | 0.016 (5) | 0.098 (11) | −0.009 (6) | −0.011 (7) | 0.006 (7) |
O6B | 0.061 (8) | 0.051 (8) | 0.035 (6) | 0.008 (6) | −0.007 (6) | −0.011 (5) |
O7B | 0.091 (10) | 0.031 (7) | 0.059 (9) | −0.012 (7) | 0.004 (8) | −0.012 (6) |
C1B | 0.052 (9) | 0.032 (9) | 0.033 (8) | 0.001 (7) | 0.001 (7) | 0.003 (7) |
C2B | 0.047 (9) | 0.031 (8) | 0.034 (8) | −0.002 (7) | −0.003 (7) | −0.001 (6) |
C3B | 0.045 (9) | 0.029 (8) | 0.034 (8) | −0.006 (7) | 0.002 (7) | 0.001 (6) |
C4B | 0.039 (8) | 0.022 (8) | 0.048 (9) | 0.002 (6) | −0.002 (7) | 0.013 (7) |
C5B | 0.041 (8) | 0.036 (9) | 0.030 (7) | 0.005 (7) | 0.009 (6) | −0.003 (6) |
C6B | 0.044 (9) | 0.037 (10) | 0.026 (8) | −0.003 (7) | 0.009 (6) | −0.003 (7) |
C7B | 0.048 (9) | 0.038 (9) | 0.030 (7) | 0.002 (7) | 0.001 (7) | −0.010 (6) |
C8B | 0.086 (14) | 0.023 (8) | 0.037 (9) | −0.002 (8) | −0.006 (9) | 0.004 (7) |
C9B | 0.10 (2) | 0.061 (18) | 0.10 (2) | 0.000 (15) | 0.016 (18) | −0.011 (16) |
C10B | 0.044 (11) | 0.12 (2) | 0.048 (12) | 0.016 (12) | 0.004 (9) | 0.019 (13) |
Hg1A—C9A | 2.04 (3) | Hg1B—C9B | 2.05 (4) |
Hg1A—S1A | 2.346 (6) | Hg1B—S1B | 2.362 (5) |
S1A—C2A | 1.798 (17) | S1B—C2B | 1.850 (18) |
O1A—C6A | 1.446 (18) | O1B—C6B | 1.42 (2) |
O1A—C2A | 1.46 (2) | O1B—C2B | 1.42 (2) |
O2A—C4A | 1.42 (2) | O2B—C4B | 1.446 (18) |
O2A—H2OA | 0.82 | O2B—H2OB | 0.83 |
O3A—C5A | 1.43 (2) | O3B—C5B | 1.43 (2) |
O4A—C1A | 1.32 (2) | O4B—C1B | 1.30 (2) |
O4A—C10A | 1.42 (3) | O4B—C10B | 1.40 (3) |
O5A—C1A | 1.19 (3) | O5B—C1B | 1.207 (9) |
O6A—C7A | 1.41 (2) | O6B—C7B | 1.44 (2) |
O6A—H6OA | 0.78 | O6B—H6OB | 0.94 |
O7A—C8A | 1.44 (3) | O7B—C8B | 1.40 (2) |
C1A—C2A | 1.51 (3) | C1B—C2B | 1.52 (2) |
C2A—C3A | 1.51 (2) | C2B—C3B | 1.55 (2) |
C3A—C4A | 1.56 (2) | C3B—C4B | 1.52 (3) |
C3A—H3A2 | 0.9700 | C3B—H31B | 0.9700 |
C3A—H3A3 | 0.9700 | C3B—H32B | 0.9700 |
C4A—C5A | 1.50 (2) | C4B—C5B | 1.49 (2) |
C4A—H4A | 0.9800 | C4B—H4B | 0.9800 |
C5A—C6A | 1.54 (2) | C5B—C6B | 1.48 (2) |
C5A—H5A | 0.9800 | C5B—H5B | 0.9800 |
C6A—C7A | 1.53 (2) | C6B—C7B | 1.53 (2) |
C6A—H6A | 0.9800 | C6B—H6B | 0.9800 |
C7A—C8A | 1.51 (2) | C7B—C8B | 1.50 (2) |
C7A—H7A | 0.9800 | C7B—H7B | 0.9800 |
C8A—H8A1 | 0.9700 | C8B—H81 | 0.9700 |
C8A—H8A2 | 0.9700 | C8B—H82 | 0.9700 |
C9A—H91A | 0.9600 | C9B—H91B | 0.9600 |
C9A—H92A | 0.9600 | C9B—H92B | 0.9600 |
C9A—H93A | 0.9600 | C9B—H93B | 0.9600 |
C10A—H10A | 0.9600 | C10B—H101 | 0.9600 |
C10A—H10B | 0.9600 | C10B—H102 | 0.9600 |
C10A—H10C | 0.9600 | C10B—H103 | 0.9600 |
C9A—Hg1A—S1A | 175.7 (15) | H10B—C10A—H10C | 109.5 |
C2A—S1A—Hg1A | 99.3 (6) | C9B—Hg1B—S1B | 176.7 (10) |
C6A—O1A—C2A | 114.5 (12) | C2B—S1B—Hg1B | 98.8 (6) |
C4A—O2A—H2OA | 129 | C6B—O1B—C2B | 112.7 (13) |
C1A—O4A—C10A | 115.9 (19) | C4B—O2B—H2OB | 99 |
C7A—O6A—H6OA | 99 | C1B—O4B—C10B | 116.8 (19) |
O5A—C1A—O4A | 124 (2) | C7B—O6B—H6OB | 115 |
O5A—C1A—C2A | 122 (2) | O5B—C1B—O4B | 121.6 (16) |
O4A—C1A—C2A | 112.9 (15) | O5B—C1B—C2B | 124.6 (16) |
O1A—C2A—C1A | 110.9 (13) | O4B—C1B—C2B | 113.6 (12) |
O1A—C2A—C3A | 109.2 (15) | O1B—C2B—C1B | 112.4 (14) |
C1A—C2A—C3A | 111.8 (14) | O1B—C2B—C3B | 111.5 (12) |
O1A—C2A—S1A | 108.0 (10) | C1B—C2B—C3B | 110.7 (14) |
C1A—C2A—S1A | 108.8 (14) | O1B—C2B—S1B | 107.0 (11) |
C3A—C2A—S1A | 108.0 (12) | C1B—C2B—S1B | 107.4 (12) |
C2A—C3A—C4A | 111.0 (14) | C3B—C2B—S1B | 107.5 (12) |
C2A—C3A—H3A2 | 109.4 | C4B—C3B—C2B | 109.1 (14) |
C4A—C3A—H3A2 | 109.4 | C4B—C3B—H31B | 109.9 |
C2A—C3A—H3A3 | 109.4 | C2B—C3B—H31B | 109.9 |
C4A—C3A—H3A3 | 109.4 | C4B—C3B—H32B | 109.9 |
H3A2—C3A—H3A3 | 108.0 | C2B—C3B—H32B | 109.9 |
O2A—C4A—C5A | 108.5 (15) | H31B—C3B—H32B | 108.3 |
O2A—C4A—C3A | 111.6 (14) | O2B—C4B—C5B | 112.9 (13) |
C5A—C4A—C3A | 111.7 (13) | O2B—C4B—C3B | 105.9 (15) |
O2A—C4A—H4A | 108.3 | C5B—C4B—C3B | 111.1 (14) |
C5A—C4A—H4A | 108.3 | O2B—C4B—H4B | 108.9 |
C3A—C4A—H4A | 108.3 | C5B—C4B—H4B | 108.9 |
O3A—C5A—C4A | 111.3 (13) | C3B—C4B—H4B | 108.9 |
O3A—C5A—C6A | 109.0 (13) | O3B—C5B—C6B | 110.9 (14) |
C4A—C5A—C6A | 108.6 (13) | O3B—C5B—C4B | 107.2 (13) |
O3A—C5A—H5A | 109.3 | C6B—C5B—C4B | 111.0 (14) |
C4A—C5A—H5A | 109.3 | O3B—C5B—H5B | 109.2 |
C6A—C5A—H5A | 109.3 | C6B—C5B—H5B | 109.2 |
O1A—C6A—C7A | 104.7 (12) | C4B—C5B—H5B | 109.2 |
O1A—C6A—C5A | 108.9 (12) | O1B—C6B—C5B | 113.8 (14) |
C7A—C6A—C5A | 113.8 (14) | O1B—C6B—C7B | 106.1 (13) |
O1A—C6A—H6A | 109.8 | C5B—C6B—C7B | 115.0 (14) |
C7A—C6A—H6A | 109.8 | O1B—C6B—H6B | 107.2 |
C5A—C6A—H6A | 109.8 | C5B—C6B—H6B | 107.2 |
O6A—C7A—C8A | 110.0 (14) | C7B—C6B—H6B | 107.2 |
O6A—C7A—C6A | 110.1 (14) | O6B—C7B—C8B | 112.5 (15) |
C8A—C7A—C6A | 109.0 (16) | O6B—C7B—C6B | 110.2 (14) |
O6A—C7A—H7A | 109.2 | C8B—C7B—C6B | 111.9 (14) |
C8A—C7A—H7A | 109.2 | O6B—C7B—H7B | 107.3 |
C6A—C7A—H7A | 109.2 | C8B—C7B—H7B | 107.3 |
O7A—C8A—C7A | 113.0 (19) | C6B—C7B—H7B | 107.3 |
O7A—C8A—H8A1 | 109.0 | O7B—C8B—C7B | 116.3 (16) |
C7A—C8A—H8A1 | 109.0 | O7B—C8B—H81 | 108.2 |
O7A—C8A—H8A2 | 109.0 | C7B—C8B—H81 | 108.2 |
C7A—C8A—H8A2 | 109.0 | O7B—C8B—H82 | 108.2 |
H8A1—C8A—H8A2 | 107.8 | C7B—C8B—H82 | 108.2 |
Hg1A—C9A—H91A | 109.5 | H81—C8B—H82 | 107.4 |
Hg1A—C9A—H92A | 109.5 | Hg1B—C9B—H91B | 109.5 |
H91A—C9A—H92A | 109.5 | Hg1B—C9B—H92B | 109.5 |
Hg1A—C9A—H93A | 109.5 | H91B—C9B—H92B | 109.5 |
H91A—C9A—H93A | 109.5 | Hg1B—C9B—H93B | 109.5 |
H92A—C9A—H93A | 109.5 | H91B—C9B—H93B | 109.5 |
O4A—C10A—H10A | 109.5 | H92B—C9B—H93B | 109.5 |
O4A—C10A—H10B | 109.5 | O4B—C10B—H101 | 109.5 |
H10A—C10A—H10B | 109.5 | O4B—C10B—H102 | 109.5 |
O4A—C10A—H10C | 109.5 | O4B—C10B—H103 | 109.5 |
H10A—C10A—H10C | 109.5 |
D—H···A | D—H | H···A | D···A | D—H···A |
O2A—H2OA···O7Ai | 0.82 | 2.15 | 2.87 (2) | 146 |
O6A—H6OA···O3Bii | 0.78 | 2.01 | 2.75 (2) | 158 |
O2B—H2OB···O7Biii | 0.83 | 2.06 | 2.75 (2) | 141 |
O6B—H6OB···O3Aiv | 0.94 | 1.88 | 2.81 (2) | 168 |
Symmetry codes: (i) −x+1, y+1/2, −z+1; (ii) x−1, y, z−1; (iii) −x+2, y−1/2, −z+3; (iv) x, y, z+1. |
Experimental details
Crystal data | |
Chemical formula | [Hg(CH3)(C9H15O7S)] |
Mr | 482.89 |
Crystal system, space group | Monoclinic, P21 |
Temperature (K) | 293 |
a, b, c (Å) | 7.306 (1), 15.247 (3), 13.014 (2) |
β (°) | 91.10 (3) |
V (Å3) | 1449.4 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 10.79 |
Crystal size (mm) | 0.10 × 0.10 × 0.02 |
Data collection | |
Diffractometer | Nonius KappaCCD area-detector diffractometer |
Absorption correction | Multi-scan (SORTAV; Blessing, 1995) |
Tmin, Tmax | 0.388, 0.806 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 11530, 5084, 4777 |
Rint | 0.058 |
(sin θ/λ)max (Å−1) | 0.596 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.064, 0.172, 1.06 |
No. of reflections | 5084 |
No. of parameters | 349 |
No. of restraints | 3 |
H-atom treatment | H-atom parameters constrained |
w = 1/[σ2(Fo2) + (0.0956P)2 + 11.7784P] where P = (Fo2 + 2Fc2)/3 | |
Δρmax, Δρmin (e Å−3) | 4.38, −1.78 |
Absolute structure | (Flack, 1983), 2408 Friedel pairs |
Absolute structure parameter | 0.010 (19) |
Computer programs: COLLECT (Nonius, 2000), DENZO-SMN (Otwinowski & Minor, 1997), DENZO-SMN, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), TEXSAN (Molecular Structure Corporation, 1999).
D—H···A | D—H | H···A | D···A | D—H···A |
O2A—H2OA···O7Ai | 0.82 | 2.15 | 2.87 (2) | 146 |
O6A—H6OA···O3Bii | 0.78 | 2.01 | 2.75 (2) | 158 |
O2B—H2OB···O7Biii | 0.83 | 2.06 | 2.75 (2) | 141 |
O6B—H6OB···O3Aiv | 0.94 | 1.88 | 2.81 (2) | 168 |
Symmetry codes: (i) −x+1, y+1/2, −z+1; (ii) x−1, y, z−1; (iii) −x+2, y−1/2, −z+3; (iv) x, y, z+1. |
A | B | |
Hg-C9 | 2.04 (3) | 2.05 (4) |
Hg-S | 2.346 (6) | 2.362 (5) |
S-C2 | 1.798 (17) | 1.850 (18) |
S-Hg-C9 | 175.7 (15) | 176.7 (10) |
Hg-S-C2 | 99.3 (6) | 98.8 (6) |
S-C2-C3 | 108.0 (11) | 107.5 (12) |
S-C2-O1 | 108.0 (10) | 107.0 (11) |
C1-C2-S-Hg | 88.7 (11) | 73.0 (10) |
C3-C2-S-Hg | -149.8 (11) | -167.9 (9) |
O1-C2-S-Hg | -31.8 (12) | -47.9 (11) |
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For structure-function studies of glycosidases, we have recently reported on the synthesis of a series of mono- and disaccharides, in which methylmercury or phenylmercury is covalently attached to anomeric thioglycosides (Belakhov et al., 2000). It was predicted that the examination of these compounds, in the form of stable binary complexes with appropriate enzymes, should provide both the specific binding and the heavy-atom derivative for complete X-ray analysis. Indeed, the similar thiomercuric analogues of sialic acid were used to determine the crystallographic phases for pertussis toxin (Shigeta et al., 1994), and 9-O-acetylsialic acid esterase (Fitz et al., 1996) from influenza C virus. The title thiomercuric derivative, (I), was designed as a model compound for a structure-function study of enzymes involved in the biosynthetic formation and utilization of 3-deoxy-D-manno-2-octulosonic acid (Kdo). This unique eight-carbon sugar is a specific constituent of the lipopolysaccharides of most Gram-negative bacteria, and is required by them for growth and virulence (Unger, 1981; Unger & Anderson, 1983). Several groups have therefore pursued inhibition of Kdo metabolism as a strategy for the development of novel antibacterial drugs (Hammond et al., 1987; Goldman et al., 1987; Baasov & Kohen, 1995; Liang et al., 1998; Du et al., 1999). As part of this program, the crystal structure of the title compound, (I), has been determined. \sch
Interestingly, an analysis of the crystallographic data reveals that (I) exists as two symmetry-independent molecules, A and B, within the unit cell. A view of conformer A of the molecule of (I) together with the atomic numbering scheme is shown in Fig. 1. The geometry observed for the pyranose ring is a 4C1 chair, while the thiomercuryl moiety is oriented cis to the hydroxyl groups at positions C4 and C5, indicating the β-anomeric configuration. The Hg atom has an almost linear stereochemistry, with normal Hg—S and Hg—C distances and S—Hg—C angles of 175.7 (15) and 176.7 (10)° for the two conformers OK? (Table 1). These values are in agreement with those found for CH3—Hg—S moieties in the Cambridge Structural Database (CSD, April 2001 release; Allen & Kennard, 1993).
As illustrated in Fig. 2, while most of the bond distances and angles in conformers A and B are very similar, marked differences exist at the thiomethylmercury side-chain conformation. This is clearly seen by comparing three torsion angles, C1—C2—S—Hg, C3—C2—S—Hg and O1—C2—S—Hg, showing differences of 15.7 (11), 18.1 (10) and 16.1 (10)°, respectively (Table 1).
The presence of two similar independent structures, A and B, has also been reported for other thiomercury derivatives (Kuz'mina & Struchkov, 1984; Tasende et al., 1990; Zukerman-Schpector et al., 1991; Varela et al., 1993; Bravo et al., 1985; Castano et al., 1991; Hutton et al., 1980). This phenomenon was attributed to a low residual Lewis acidity of Hg in these complexes, leading to the formation of `secondary bonds' that are intermediate in strength between covalent and van der Waals bonds (Kuz'mina & Struchkov, 1984). Indeed, the intramolecular Hg···O1 distances in molecules A and B of (I) were found to be 2.955 (11) and 3.155 (11) Å, respectively. These distances are smaller than the sum of the van der Waals radii for the atoms concerned, confirming the presence of a secondary interaction in this part of the molecule, similar to that observed in (2-mercaptobenzothiazolato)methylmercury(II) (Bravo et al., 1985) and in (2-mercaptobenzooxazolato)methylmercury(II) (Castano et al., 1991).
It is of note that, in the latter compound, in addition to an intramolecular Hg···N interaction, an additional intermolecular Hg···O interaction was also observed. In compound (I), however, if we take the values of 3.35 and 3.10 Å for Hg···S and Hg···O, as the sums of the van der Waals radii of Hg and S and Hg and O, respectively (Kuz'mina & Struchkov, 1984), no additional secondary interactions through the Hg atom are observed. This may be due to the presence of an intermolecular hydrogen-bonding network (Table 2). There are rather strong hydrogen bonds both between the molecules of each conformer [O2A—H···O7A and O2B—H···O7B], and between the two different conformers [O6A—H···O3B and O6B—H···O3A]. Because of the presence of these hydrogen bonds, the crystal can be regarded as made up ofa three-dimensional network.