Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801001179/tk6003sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801001179/tk6003Isup2.hkl |
CCDC reference: 159709
Oxidation of 4-methylthiazol-2-thione [prepared by reacting 4-methylthiazol-2-yllithium with suldur at 195 K and then water, Gundermann et al. (1985)] at 306 K in 0.2 M phosphate buffer (pH 7.6) with an NaI/I2 solution (2:1, w/w) yields di-4-methylthiazole 2-disulfide (Doerr et al., 1961). A solution of di-4-methylthiazolyl 2-disulfide in THF (20% excess) was added to W(CO)5(thf) [obtained by UV-irradiation of W(CO)6 in THF as described by Werner et al. (1969)] and stirred for 1 h. Stripping of solvent in vacuo followed by flash chromatography (258 K, 8:5 diethyl ether/hexane eluent) afforded orange microcrystalline (I). Single crystals formed from a concentrated diethyl ether solution layered with pentane at 253 K.
The positions of the H atoms could be identified from difference density maps, however, they were calculated geometrically and constrained to ride on the atoms to which they were attached. Their isotropic displacement parameters were fixed at 1.2 or 1.5 (for methyl groups) times the equivalent isotropic displacement parameters of their parent atoms. The highest peak and deepest hole in the final difference density map were 0.92 Å from W1 and 1.08 Å from W1, respectively.
Data collection: PWPC (Gomm, 1998); cell refinement: PWPC; data reduction: Xtal3.4 (Hall et al., 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97.
Fig. 1. The molecular configuration of the title compound. Ellipsoids are shown at the 50% probability level (Farrugia, 1997). |
[W(C4H4NS2)2(CO)3] | F(000) = 1000 |
Mr = 528.28 | Dx = 2.202 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 9.6233 (9) Å | Cell parameters from 46 reflections |
b = 10.2686 (8) Å | θ = 4.5–17.7° |
c = 16.272 (2) Å | µ = 7.78 mm−1 |
β = 97.672 (11)° | T = 293 K |
V = 1593.5 (3) Å3 | Plate, orange-red |
Z = 4 | 0.25 × 0.23 × 0.10 mm |
Philips PW1100 diffractometer | 2259 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.069 |
Graphite monochromator | θmax = 25.0°, θmin = 3.1° |
ω–2θ scans | h = 0→11 |
Absorption correction: ψ scan (North et al., 1968) | k = 0→12 |
Tmin = 0.160, Tmax = 0.459 | l = −19→19 |
2993 measured reflections | 3 standard reflections every 50 reflections |
2817 independent reflections | intensity decay: none |
Refinement on F2 | Primary atom site location: heavy-atom method |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.036 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.119 | H-atom parameters constrained |
S = 1.07 | w = 1/[σ2(Fo2) + (0.0809P)2 + 1.9916P] where P = (Fo2 + 2Fc2)/3 |
2817 reflections | (Δ/σ)max < 0.001 |
192 parameters | Δρmax = 1.20 e Å−3 |
0 restraints | Δρmin = −2.28 e Å−3 |
[W(C4H4NS2)2(CO)3] | V = 1593.5 (3) Å3 |
Mr = 528.28 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 9.6233 (9) Å | µ = 7.78 mm−1 |
b = 10.2686 (8) Å | T = 293 K |
c = 16.272 (2) Å | 0.25 × 0.23 × 0.10 mm |
β = 97.672 (11)° |
Philips PW1100 diffractometer | 2259 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.069 |
Tmin = 0.160, Tmax = 0.459 | 3 standard reflections every 50 reflections |
2993 measured reflections | intensity decay: none |
2817 independent reflections |
R[F2 > 2σ(F2)] = 0.036 | 0 restraints |
wR(F2) = 0.119 | H-atom parameters constrained |
S = 1.07 | Δρmax = 1.20 e Å−3 |
2817 reflections | Δρmin = −2.28 e Å−3 |
192 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. Equation of least-squares plane through W1, S1, C4, N1, S2, C5, C6 and C7: 6.1182 (0.0158) x - 4.1342 (0.0175) y + 9.2389 (0.0191) z = 5.0933 (0.0182) Deviations of atoms from least-squares plane (* indicates atom used to define plane) * -0.0781 (0.0030) W1 * 0.0956 (0.0041) S1 * -0.0019 (0.0070) C4 * -0.0069 (0.0060) N1 * -0.0439 (0.0040) S2 * -0.0243 (0.0069) C5 * -0.0047 (0.0079) C6 * 0.0643 (0.0065) C7 Rms deviation of fitted atoms = 0.0524 Equation of least-squares plane through W1, S3, C8, N2, S4, C9, C10 and C11: - 3.3446 (0.0166) x + 6.9412 (0.0161) y + 11.2342 (0.0200) z = 3.6125 (0.0142) Angle to previous plane (with approximate e.s.d.) = 86.29 (0.12) Deviations of atoms from least-squares plane (* indicates included in calculation) * 0.0456 (0.0033) W1 * 0.0116 (0.0040) S3 * -0.0520 (0.0076) C8 * -0.0650 (0.0062) N2 * 0.0384 (0.0045) S4 * 0.0268 (0.0077) C9 * -0.0227 (0.0079) C10 * 0.0174 (0.0062) C11 Rms deviation of fitted atoms = 0.0390 |
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. |
x | y | z | Uiso*/Ueq | ||
W1 | 0.77064 (3) | 0.49051 (3) | 0.251981 (18) | 0.03869 (17) | |
S1 | 0.9670 (2) | 0.5556 (2) | 0.16984 (16) | 0.0556 (6) | |
S2 | 0.9807 (3) | 0.3314 (3) | 0.04536 (14) | 0.0596 (6) | |
S3 | 0.5427 (2) | 0.3713 (3) | 0.25474 (15) | 0.0573 (6) | |
S4 | 0.3383 (3) | 0.5057 (3) | 0.11324 (19) | 0.0667 (8) | |
O1 | 0.7009 (13) | 0.5300 (10) | 0.4311 (5) | 0.109 (4) | |
O2 | 1.0234 (7) | 0.3820 (7) | 0.3731 (5) | 0.072 (2) | |
O3 | 0.7901 (8) | 0.7905 (7) | 0.2826 (5) | 0.083 (2) | |
N1 | 0.8226 (7) | 0.3411 (6) | 0.1584 (4) | 0.0387 (14) | |
N2 | 0.5983 (7) | 0.5501 (7) | 0.1540 (4) | 0.0390 (14) | |
C1 | 0.7224 (14) | 0.5151 (11) | 0.3636 (6) | 0.069 (3) | |
C2 | 0.9311 (9) | 0.4205 (9) | 0.3271 (6) | 0.050 (2) | |
C3 | 0.7821 (9) | 0.6805 (10) | 0.2734 (6) | 0.056 (2) | |
C4 | 0.9179 (9) | 0.4073 (8) | 0.1255 (5) | 0.0448 (19) | |
C5 | 0.8752 (10) | 0.2031 (9) | 0.0599 (5) | 0.055 (2) | |
H5 | 0.8720 | 0.1278 | 0.0281 | 0.065* | |
C6 | 0.7975 (9) | 0.2199 (8) | 0.1210 (5) | 0.0438 (18) | |
C7 | 0.6995 (12) | 0.1248 (9) | 0.1508 (7) | 0.077 (3) | |
H7A | 0.7284 | 0.1066 | 0.2084 | 0.115* | |
H7B | 0.7003 | 0.0456 | 0.1195 | 0.115* | |
H7C | 0.6065 | 0.1604 | 0.1438 | 0.115* | |
C8 | 0.4967 (10) | 0.4719 (9) | 0.1732 (6) | 0.047 (2) | |
C9 | 0.4191 (10) | 0.6244 (11) | 0.0629 (6) | 0.061 (3) | |
H9 | 0.3731 | 0.6749 | 0.0203 | 0.074* | |
C10 | 0.5558 (9) | 0.6370 (8) | 0.0914 (5) | 0.0426 (18) | |
C11 | 0.6554 (11) | 0.7337 (11) | 0.0649 (7) | 0.071 (3) | |
H11A | 0.7327 | 0.6891 | 0.0457 | 0.106* | |
H11B | 0.6898 | 0.7885 | 0.1110 | 0.106* | |
H11C | 0.6084 | 0.7861 | 0.0209 | 0.106* |
U11 | U22 | U33 | U12 | U13 | U23 | |
W1 | 0.0334 (2) | 0.0424 (2) | 0.0399 (2) | 0.00635 (13) | 0.00322 (14) | −0.00361 (13) |
S1 | 0.0446 (13) | 0.0429 (12) | 0.0818 (17) | −0.0065 (10) | 0.0172 (11) | −0.0041 (11) |
S2 | 0.0550 (14) | 0.0776 (17) | 0.0488 (13) | 0.0063 (12) | 0.0161 (10) | −0.0084 (12) |
S3 | 0.0423 (12) | 0.0674 (15) | 0.0643 (14) | −0.0018 (11) | 0.0147 (10) | 0.0191 (12) |
S4 | 0.0353 (13) | 0.093 (2) | 0.0693 (16) | −0.0069 (12) | −0.0028 (11) | 0.0131 (13) |
O1 | 0.135 (10) | 0.143 (8) | 0.054 (5) | 0.058 (7) | 0.025 (5) | −0.002 (5) |
O2 | 0.059 (4) | 0.065 (4) | 0.085 (5) | 0.020 (4) | −0.015 (4) | 0.002 (4) |
O3 | 0.080 (5) | 0.047 (4) | 0.114 (6) | 0.021 (4) | −0.015 (4) | −0.021 (4) |
N1 | 0.033 (3) | 0.041 (4) | 0.043 (3) | −0.002 (3) | 0.007 (3) | 0.000 (3) |
N2 | 0.034 (4) | 0.037 (3) | 0.045 (4) | −0.002 (3) | 0.003 (3) | −0.005 (3) |
C1 | 0.078 (8) | 0.085 (8) | 0.043 (5) | 0.037 (6) | 0.009 (5) | 0.002 (5) |
C2 | 0.042 (5) | 0.049 (5) | 0.058 (5) | 0.016 (4) | 0.004 (4) | −0.002 (4) |
C3 | 0.041 (5) | 0.056 (6) | 0.064 (5) | 0.026 (4) | −0.015 (4) | 0.005 (4) |
C4 | 0.038 (4) | 0.051 (5) | 0.047 (4) | 0.006 (4) | 0.010 (4) | 0.000 (4) |
C5 | 0.063 (6) | 0.044 (5) | 0.054 (5) | 0.000 (4) | 0.000 (4) | −0.020 (4) |
C6 | 0.049 (5) | 0.033 (4) | 0.047 (4) | −0.002 (4) | −0.001 (4) | −0.006 (3) |
C7 | 0.087 (8) | 0.035 (5) | 0.109 (9) | −0.019 (5) | 0.010 (7) | −0.017 (5) |
C8 | 0.034 (5) | 0.057 (5) | 0.052 (5) | 0.004 (4) | 0.011 (4) | 0.007 (4) |
C9 | 0.049 (6) | 0.075 (7) | 0.058 (6) | −0.005 (5) | −0.003 (4) | 0.011 (5) |
C10 | 0.044 (5) | 0.037 (4) | 0.046 (4) | 0.003 (4) | 0.004 (3) | 0.009 (3) |
C11 | 0.070 (7) | 0.073 (7) | 0.069 (6) | −0.009 (6) | 0.008 (5) | 0.021 (5) |
W1—C1 | 1.950 (10) | N1—C4 | 1.311 (10) |
W1—C3 | 1.982 (10) | N1—C6 | 1.392 (10) |
W1—C2 | 1.973 (9) | N2—C8 | 1.334 (11) |
W1—N2 | 2.227 (7) | N2—C10 | 1.374 (10) |
W1—N1 | 2.264 (6) | C5—C6 | 1.332 (12) |
W1—S3 | 2.517 (2) | C5—H5 | 0.9300 |
W1—S1 | 2.545 (2) | C6—C7 | 1.484 (12) |
S1—C4 | 1.724 (9) | C7—H7A | 0.9600 |
S2—C4 | 1.698 (8) | C7—H7B | 0.9600 |
S2—C5 | 1.699 (10) | C7—H7C | 0.9600 |
S3—C8 | 1.692 (9) | C9—C10 | 1.341 (12) |
S4—C9 | 1.712 (10) | C9—H9 | 0.9300 |
S4—C8 | 1.732 (10) | C10—C11 | 1.484 (12) |
O1—C1 | 1.154 (12) | C11—H11A | 0.9600 |
O2—C2 | 1.152 (10) | C11—H11B | 0.9600 |
O3—C3 | 1.140 (12) | C11—H11C | 0.9600 |
C1—W1—C3 | 74.0 (4) | O2—C2—W1 | 177.7 (8) |
C1—W1—C2 | 74.6 (4) | O3—C3—W1 | 177.2 (9) |
C3—W1—C2 | 103.3 (4) | N1—C4—S2 | 114.6 (7) |
C1—W1—N2 | 112.6 (4) | N1—C4—S1 | 117.0 (6) |
C3—W1—N2 | 82.8 (3) | S2—C4—S1 | 128.4 (5) |
C2—W1—N2 | 171.9 (3) | C6—C5—S2 | 114.2 (6) |
C1—W1—N1 | 144.6 (4) | C6—C5—H5 | 122.9 |
C3—W1—N1 | 140.6 (3) | S2—C5—H5 | 122.9 |
C2—W1—N1 | 86.8 (3) | C5—C6—N1 | 111.1 (7) |
N2—W1—N1 | 85.1 (2) | C5—C6—C7 | 127.1 (8) |
C1—W1—S3 | 74.3 (4) | N1—C6—C7 | 121.8 (8) |
C3—W1—S3 | 120.2 (3) | C6—C7—H7A | 109.5 |
C2—W1—S3 | 115.1 (3) | C6—C7—H7B | 109.5 |
N2—W1—S3 | 65.09 (18) | H7A—C7—H7B | 109.5 |
N1—W1—S3 | 87.35 (17) | C6—C7—H7C | 109.5 |
C1—W1—S1 | 137.8 (4) | H7A—C7—H7C | 109.5 |
C3—W1—S1 | 78.8 (3) | H7B—C7—H7C | 109.5 |
C2—W1—S1 | 81.2 (3) | N2—C8—S3 | 115.3 (7) |
N2—W1—S1 | 94.95 (18) | N2—C8—S4 | 111.3 (6) |
N1—W1—S1 | 65.07 (16) | S3—C8—S4 | 133.1 (6) |
S3—W1—S1 | 147.86 (8) | C10—C9—S4 | 113.0 (7) |
C4—S1—W1 | 78.8 (3) | C10—C9—H9 | 123.5 |
C4—S2—C5 | 88.1 (4) | S4—C9—H9 | 123.5 |
C8—S3—W1 | 80.0 (3) | C9—C10—N2 | 112.0 (8) |
C9—S4—C8 | 89.5 (4) | C9—C10—C11 | 127.3 (8) |
C4—N1—C6 | 112.0 (7) | N2—C10—C11 | 120.7 (7) |
C4—N1—W1 | 98.8 (5) | C10—C11—H11A | 109.5 |
C6—N1—W1 | 149.2 (5) | C10—C11—H11B | 109.5 |
C8—N2—C10 | 114.2 (7) | H11A—C11—H11B | 109.5 |
C8—N2—W1 | 99.5 (5) | C10—C11—H11C | 109.5 |
C10—N2—W1 | 145.9 (5) | H11A—C11—H11C | 109.5 |
O1—C1—W1 | 176.6 (12) | H11B—C11—H11C | 109.5 |
Experimental details
Crystal data | |
Chemical formula | [W(C4H4NS2)2(CO)3] |
Mr | 528.28 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 9.6233 (9), 10.2686 (8), 16.272 (2) |
β (°) | 97.672 (11) |
V (Å3) | 1593.5 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 7.78 |
Crystal size (mm) | 0.25 × 0.23 × 0.10 |
Data collection | |
Diffractometer | Philips PW1100 diffractometer |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.160, 0.459 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2993, 2817, 2259 |
Rint | 0.069 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.036, 0.119, 1.07 |
No. of reflections | 2817 |
No. of parameters | 192 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.20, −2.28 |
Computer programs: PWPC (Gomm, 1998), PWPC, Xtal3.4 (Hall et al., 1995), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997), SHELXL97.
W1—C1 | 1.950 (10) | W1—N1 | 2.264 (6) |
W1—C3 | 1.982 (10) | W1—S3 | 2.517 (2) |
W1—C2 | 1.973 (9) | W1—S1 | 2.545 (2) |
W1—N2 | 2.227 (7) | ||
C1—W1—C3 | 74.0 (4) | N1—W1—S3 | 87.35 (17) |
C1—W1—C2 | 74.6 (4) | N2—W1—S1 | 94.95 (18) |
C3—W1—C2 | 103.3 (4) | N1—W1—S1 | 65.07 (16) |
N2—W1—N1 | 85.1 (2) | S3—W1—S1 | 147.86 (8) |
N2—W1—S3 | 65.09 (18) |
The title compound, (I), represents the first seven-coordinate WII complex synthesized from a neutral W0 complex and a thiazolyl disulfide. In this process, the disulfide oxidatively substitutes the metal carbonyl, and the N atom of the thiazole moiety coordinates to the metal, as seen in Fig, 1. Similar complexes containing pyridine-2-thionate (Deeming et al., 1990), pyrimidine-2-thionate (Baker et al., 1995) and pyridine-2-selenate (Kienitz et al., 1996) have been obtained previously, but not via the same preparative route.
The coordination sphere of the W atom can be described as a 4:3 piano-stool arrangement, with the three carbonyl ligands forming the legs of the stool (Dreyer et al., 1979). The other four atoms bonded to the W atom form the distorted square base of the piano-stool. Alternatively, the coordination sphere can be viewed as a distorted monocapped trigonal prism, with the C1—O1 carbonyl group in the capping position. The two methylthiazole sulfide ligands are planar [maximum deviations from planarity for the two ligands are 0.096 (4) Å for S1 and -0.065 (6) Å for N2, respectively]. The angle between the two planes is 86.26 (12)°.
There is some evidence for a small difference between the two W—N bond lengths [W1—N2 2.227 (7) Å and W1—N1 2.264 (6) Å], despite the relatively large standard deviations. This observation is similar to the structure of tricarbonylbis(pyrimidine-2-thionato-S,N)tungsten(II) (Baker et al., 1995), where the difference in W—N bond lengths may be attributed to greater trans effect of the two noncapping carbonyl ligands C2—O2 and C3—O3 as opposed to that of the capping carbonyl ligand C1—O1. A similar effect was observed in the structure of dicarbonyldimethylphenylphosphinebis(pyridine-2-thionato-S,N)tungsten(II) (Deeming et al., 1990), where the difference in W—N bond lengths is a result of the trans ligands [P(CH3)2(C6H5) and CO] having different trans influences. The W—S [W1—S3 2.515 (2) Å and W1—S1 2.546 (2) Å] bond lengths also differ, in contrast to the two comparable thionate structures, where the difference in W—S bond lengths is less than 0.02 Å. This is as a result of the constraints of the four-membered W—N—C—S rings, where the differing W—N bond lengths result in differing W—S bond lengths. The three W—C(carbonyl) bond lengths are the same within experimental error. The bond angles around the tungsten do not differ significantly from those observed in the comparable tricarbonylbis(pyrimidine-2-thionato-N,S)tungsten(II) (Baker et al., 1995).
No significant intermolecular interactions were observed.