Bis­[3-hydroxy-4-methyl­-2(3H)-thia­zolethiol­ato-S²,O]bis­(methanol-O)cobalt(II)

The structure of the title compound, [Co(C₄H₄N­OS₂)₂(CH₄O)₂], has been determined at 180 (2) K. The mol­ecule possesses point symmetry with the Co^II atom adopting a Jahn–Teller-distorted octahedral geometry. The mol­ecules are linked into chains by O—H...O hydrogen-bond interactions involving the H atom of the coordinated methanol mol­ecules.

Key indicators

• Single-crystal X-ray study
• T = 180 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.034
• wR factor = 0.078
• Data-to-parameter ratio = 13.8

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


 Alert Level C:



ABSTM_02  Alert C The ratio of Tmax/Tmin expected RT(exp) is > 1.10
          Absorption corrections should be applied.
          Tmin and Tmax expected:      0.862     0.969
          RT(exp) =      1.124

PLAT_710  Alert C Delete 1-2-3 or 2-3-4 (CIF) Linear Torsion Angle #      5
                   S1  -CO1 -S1  -C1     88.00 70.00   3.565   1.555   1.555   1.555

PLAT_710  Alert C Delete 1-2-3 or 2-3-4 (CIF) Linear Torsion Angle #      6
                   O1  -CO1 -O1  -N1    -44.00100.00   3.565   1.555   1.555   1.555

PLAT_710  Alert C Delete 1-2-3 or 2-3-4 (CIF) Linear Torsion Angle #     13
                   O2  -CO1 -O2  -C5     51.00 65.00   3.565   1.555   1.555   1.555


 0 Alert Level A = Potentially serious problem

 0 Alert Level B = Potential problem

 4 Alert Level C = Please check

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S1. Comment

Cyclic thiohydroxamic acids, such as 1-hydroxypyridine-2(1H)-thione (pyrithione, HPT), find extensive use as fungicides (Paulus, 1993). It has been suggested that their mode of action is based predominantly on chelate complex formation (Albert, 1973). 3-Hydroxy-4-methylthiazole-2(3H)-thione (methylthiazolethione, HMTT) contains a chelating unit similar to that in pyrithione and might, therefore, be expected to exhibit similar antimicrobial properties. We are currently studying the solid-state chemistry of cyclic thiohydroxamic acids (Bond & Jones, 2000) and their complexes with first-row d-block elements, and report here the crystal structure of the chelate complex Co(MTT)₂(methanol)₂, (I) (Fig. 1).

In (I), the Co1 atom occupies a centre of symmetry and adopts octahedral coordination via two bidentate MTT ligands and two methanol molecules. The Co1—S1 distance [2.4590 (7) Å] is significantly greater than the Co—S distances in comparable complexes [see, for example, Kang et al. (1993); Co—S_ave = 2.377 (5) Å]; this may be attributed to a tetragonal Jahn–Teller distortion about the Co^II atom (d⁷). The C1—S1 and N1—O1 bond distances [1.699 (3) Å and 1.352 (3) Å, respectively] suggest that these bonds retain some multiple-bond character [cf. C—S_ave = 1.773 (9) Å and N—O_ave = 1.396 (12) Å; Alen et al., 1987].

The H atom of the coordinated methanol molecule is involved in a hydrogen-bond interaction with the O atom of an MTT ligand in an adjacent molecule [H1···O1ⁱ = 1.96 (4) Å, O2—H1···O1ⁱ = 171 (4)°; symmetry code: (i) 1 - x, 1 - y, -z], giving rise to extended chains running parallel to the a direction (Fig. 2). These chains pack in a herring-bone-type arrangement (Fig. 3). The vinylic H2 atom may be expected to be sufficiently acidic to become involved in a hydrogen-bond interaction. H2 makes its closest approach to an S atom in an MTT molecule of an adjacent chain [H2···S1ⁱⁱ = 2.82 Å and C2—H2···S1ⁱⁱ = 163.3°; symmetry code: (ii) 1 + x, 1/2 - y, 1/2 + z]. The approximate linear geometry of this interaction may be indicative of a C—H···S-type hydrogen bond.

S2. Experimental

HMTT was obtained from the Aldrich Chemical Co. and was recrystallized from CH₂Cl₂. The sodium salt hydrate Na(MTT).xH₂O was prepared by addition of 1 mol equivalent of NaOH to a suspension of HMTT in water, followed by evaporation of the solvent. The cobalt(II) complex was prepared initially as a monohydrate Co(MTT)₂·H₂O by combination of aqueous solutions of CoCl₂ and Na(MTT) in a 1:2 molar ratio at room temperature. The resulting pink precipitate was removed by filtration under gravity and dried in air at room temperature. Single crystals of (I) were grown by slow evaporation of a solution of Co(MTT)₂·H₂O in methanol at room temperature.

S3. Refinement

All H atoms except H1 were placed geometrically and allowed to ride during subsequent refinement. H1 was located in a difference Fourier map and refined freely with an isotropic displacement parameter.

Computing details

Data collection: COLLECT (Nonius, 1998); cell refinement: HKL SCALEPACK (Otwinowski & Minor, 1997); data reduction: HKL DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. The molecular unit in (I) showing displacement ellipsoids at the 50% probability level (XP; Sheldrick, 1993).
	Fig. 2. Chains of (I) linked via O—H···O interactions (CAMERON; Watkin et al., 1996).
	Fig. 3. Projection onto (100) showing chains of (I) packed in a herring-bone-type arrangement. Close H···S contacts are indicated by dotted lines (CAMERON; Watkin et al., 1996).

Bis[3-hydroxy-4-methylthiazole-2(3H)-thiolato-S²,O]bis(methanol-O)- cobalt(II)

Crystal data

[Co(C4H4NOS2)2(CH4O)2]	F(000) = 426
Mr = 415.42	Dx = 1.692 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 5.0414 (4) Å	Cell parameters from 9582 reflections
b = 18.878 (2) Å	θ = 2.9–25.0°
c = 8.6814 (11) Å	µ = 1.58 mm^−1
β = 99.349 (7)°	T = 180 K
V = 815.23 (16) Å^3	Plate, red
Z = 2	0.13 × 0.08 × 0.02 mm

Data collection

Nonius KappaCCD diffractometer	1087 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.029
Graphite monochromator	θmax = 25.0°, θmin = 4.0°
Thin–slice ω and ϕ scans	h = −5→5
2478 measured reflections	k = −20→22
1424 independent reflections	l = −10→10

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.078	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	w = 1/[σ^2(Fo^2) + (0.0359P)^2] where P = (Fo^2 + 2Fc^2)/3
1424 reflections	(Δ/σ)max = 0.017
103 parameters	Δρmax = 0.31 e Å^−3
0 restraints	Δρmin = −0.42 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.

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.

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

	x	y	z	Uiso*/Ueq
Co1	0.0000	0.5000	0.0000	0.0228 (2)
S1	−0.19352 (14)	0.38022 (4)	−0.02754 (9)	0.0299 (2)
S2	0.09944 (16)	0.25946 (4)	0.15912 (10)	0.0412 (3)
O1	0.2694 (3)	0.45657 (10)	0.1764 (2)	0.0258 (5)
H1	0.385 (8)	0.4983 (19)	−0.163 (4)	0.049 (13)*
O2	0.2661 (4)	0.47558 (12)	−0.1582 (2)	0.0307 (5)
N1	0.2553 (4)	0.38537 (12)	0.1892 (2)	0.0238 (6)
C1	0.0599 (5)	0.34690 (15)	0.1057 (3)	0.0255 (7)
C2	0.3815 (6)	0.27863 (18)	0.2935 (4)	0.0413 (8)
H2	0.4829	0.2442	0.3578	0.050*
C3	0.4403 (5)	0.34770 (16)	0.2964 (3)	0.0303 (7)
C4	0.6625 (6)	0.38600 (18)	0.3956 (4)	0.0378 (8)
H4A	0.7561	0.3536	0.4745	0.045*
H4B	0.5889	0.4258	0.4474	0.045*
H4C	0.7893	0.4038	0.3303	0.045*
C5	0.2171 (6)	0.43229 (18)	−0.2938 (4)	0.0422 (9)
H5A	0.0743	0.3982	−0.2836	0.051*
H5B	0.3818	0.4067	−0.3055	0.051*
H5C	0.1616	0.4621	−0.3858	0.051*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.0191 (3)	0.0204 (4)	0.0276 (4)	0.0001 (2)	0.0001 (2)	0.0020 (2)
S1	0.0272 (4)	0.0246 (5)	0.0353 (5)	−0.0039 (3)	−0.0026 (3)	0.0020 (3)
S2	0.0464 (5)	0.0230 (5)	0.0511 (6)	0.0011 (3)	−0.0009 (4)	0.0063 (4)
O1	0.0263 (10)	0.0187 (12)	0.0316 (12)	−0.0012 (8)	0.0020 (9)	0.0021 (9)
O2	0.0235 (12)	0.0357 (14)	0.0331 (13)	−0.0060 (10)	0.0052 (10)	−0.0071 (11)
N1	0.0229 (13)	0.0224 (15)	0.0259 (14)	0.0025 (10)	0.0037 (10)	0.0034 (11)
C1	0.0264 (16)	0.0189 (17)	0.0325 (17)	0.0004 (12)	0.0087 (13)	0.0022 (13)
C2	0.0437 (19)	0.032 (2)	0.046 (2)	0.0051 (15)	0.0006 (16)	0.0125 (17)
C3	0.0257 (16)	0.038 (2)	0.0280 (17)	0.0070 (13)	0.0071 (13)	0.0108 (15)
C4	0.0318 (18)	0.043 (2)	0.036 (2)	0.0089 (14)	−0.0022 (15)	0.0104 (16)
C5	0.0435 (19)	0.046 (2)	0.038 (2)	−0.0074 (15)	0.0077 (16)	−0.0085 (17)

Geometric parameters (Å, º)

Co1—O1	2.0459 (17)	N1—C1	1.339 (3)
Co1—O1^i	2.0459 (17)	N1—C3	1.400 (3)
Co1—O2^i	2.121 (2)	C2—C3	1.336 (4)
Co1—O2	2.121 (2)	C2—H2	0.9500
Co1—S1^i	2.4590 (7)	C3—C4	1.485 (4)
Co1—S1	2.4590 (7)	C4—H4A	0.9800
S1—C1	1.699 (3)	C4—H4B	0.9800
S2—C1	1.717 (3)	C4—H4C	0.9800
S2—C2	1.725 (3)	C5—H5A	0.9800
O1—N1	1.352 (3)	C5—H5B	0.9800
O2—C5	1.421 (4)	C5—H5C	0.9800
O2—H1	0.75 (4)
O1—Co1—O1^i	180.00 (9)	O1—N1—C3	121.5 (2)
O1—Co1—O2^i	90.88 (8)	N1—C1—S1	125.0 (2)
O1^i—Co1—O2^i	89.12 (8)	N1—C1—S2	109.4 (2)
O1—Co1—O2	89.12 (8)	S1—C1—S2	125.54 (17)
O1^i—Co1—O2	90.88 (8)	C3—C2—S2	111.9 (2)
O2^i—Co1—O2	180.00 (12)	C3—C2—H2	124.0
O1—Co1—S1^i	95.22 (5)	S2—C2—H2	124.0
O1^i—Co1—S1^i	84.78 (5)	C2—C3—N1	111.2 (3)
O2^i—Co1—S1^i	91.14 (6)	C2—C3—C4	129.0 (3)
O2—Co1—S1^i	88.86 (6)	N1—C3—C4	119.8 (3)
O1—Co1—S1	84.78 (5)	C3—C4—H4A	109.5
O1^i—Co1—S1	95.22 (5)	C3—C4—H4B	109.5
O2^i—Co1—S1	88.86 (6)	H4A—C4—H4B	109.5
O2—Co1—S1	91.14 (6)	C3—C4—H4C	109.5
S1^i—Co1—S1	180.0	H4A—C4—H4C	109.5
C1—S1—Co1	91.82 (10)	H4B—C4—H4C	109.5
C1—S2—C2	91.59 (14)	O2—C5—H5A	109.5
N1—O1—Co1	115.02 (14)	O2—C5—H5B	109.5
C5—O2—Co1	128.20 (18)	H5A—C5—H5B	109.5
C5—O2—H1	109 (3)	O2—C5—H5C	109.5
Co1—O2—H1	121 (3)	H5A—C5—H5C	109.5
C1—N1—O1	122.6 (2)	H5B—C5—H5C	109.5
C1—N1—C3	115.9 (2)
O1—Co1—S1—C1	−6.19 (11)	Co1—O1—N1—C3	174.97 (18)
O1^i—Co1—S1—C1	173.81 (11)	O1—N1—C1—S1	0.6 (4)
O2^i—Co1—S1—C1	−97.18 (11)	C3—N1—C1—S1	178.09 (19)
O2—Co1—S1—C1	82.82 (11)	O1—N1—C1—S2	−177.41 (17)
S1^i—Co1—S1—C1	88 (70)	C3—N1—C1—S2	0.1 (3)
O1^i—Co1—O1—N1	−44 (100)	Co1—S1—C1—N1	5.1 (2)
O2^i—Co1—O1—N1	96.91 (16)	Co1—S1—C1—S2	−177.21 (17)
O2—Co1—O1—N1	−83.09 (16)	C2—S2—C1—N1	0.0 (2)
S1^i—Co1—O1—N1	−171.87 (14)	C2—S2—C1—S1	−178.0 (2)
S1—Co1—O1—N1	8.13 (14)	C1—S2—C2—C3	−0.1 (3)
O1—Co1—O2—C5	120.9 (3)	S2—C2—C3—N1	0.1 (3)
O1^i—Co1—O2—C5	−59.1 (3)	S2—C2—C3—C4	179.2 (3)
O2^i—Co1—O2—C5	51 (65)	C1—N1—C3—C2	−0.1 (3)
S1^i—Co1—O2—C5	−143.8 (2)	O1—N1—C3—C2	177.4 (2)
S1—Co1—O2—C5	36.2 (2)	C1—N1—C3—C4	−179.3 (3)
Co1—O1—N1—C1	−7.7 (3)	O1—N1—C3—C4	−1.8 (4)

Symmetry code: (i) −x, −y+1, −z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H1···O1^ii	0.75 (4)	1.96 (4)	2.696 (3)	171 (4)

Symmetry code: (ii) −x+1, −y+1, −z.