Tri­carbonyl­bis(4-methyl-1,3-thia­zole-2(3H)-thionato-N,S²)­tungsten(II)

The title compound, [W(C₄H₄NS₂)₂(CO)₃], consists of a seven-coordinate tungsten centre with three carbonyl ligands and two planar methyl­thia­zole sulfide ligands, both coordinating bidentately to the W atom through the N and sulfide S atoms. The two 4-methyl­thi­azole sulfide ligands are twisted at an angle of 86.98 (15)° with respect to each other.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.013 Å
• R factor = 0.036
• wR factor = 0.119
• Data-to-parameter ratio = 14.7

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


 Alert Level C:



PLAT_320  Alert C Check Hybridisation of  S(2)   in main residue          ?

PLAT_320  Alert C Check Hybridisation of  S(4)   in main residue          ?


 0 Alert Level A = Potentially serious problem

 0 Alert Level B = Potential problem

 2 Alert Level C = Please check

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S1. Comment

The title compound, (I), represents the first seven-coordinate W^II 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.

S2. Experimental

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.

S3. Refinement

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.

Computing details

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.

Figures

Fig. 1. The molecular configuration of the title compound. Ellipsoids are shown at the 50% probability level (Farrugia, 1997).

Tricarbonylbis(4-methyl-1,3-thiazole-2(3H)-thionato-N,S²)tungsten(II)

Crystal data

[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) Å^3	Plate, orange-red
Z = 4	0.25 × 0.23 × 0.10 mm

Data collection

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

Refinement on F^2	Primary atom site location: heavy-atom method
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.119	H-atom parameters constrained
S = 1.07	w = 1/[σ^2(Fo^2) + (0.0809P)^2 + 1.9916P] where P = (Fo^2 + 2Fc^2)/3
2817 reflections	(Δ/σ)max < 0.001
192 parameters	Δρmax = 1.20 e Å^−3
0 restraints	Δρmin = −2.28 e Å^−3

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	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*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Geometric parameters (Å, º)

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