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The structure of the title compound, [Co(C4H4N­OS2)2(CH4O)2], has been determined at 180 (2) K. The mol­ecule possesses \overline 1 point symmetry with the CoII 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.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801003737/ya6012sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536801003737/ya6012Isup2.hkl
Contains datablock I

CCDC reference: 162796

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


Yellow Alert 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

Comment top

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—Save = 2.377 (5) Å]; this may be attributed to a tetragonal Jahn–Teller distortion about the CoII 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—Save = 1.773 (9) Å and N—Oave = 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.

Experimental top

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.

Refinement top

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 top

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 top
[Figure 1] Fig. 1. The molecular unit in (I) showing displacement ellipsoids at the 50% probability level (XP; Sheldrick, 1993).
[Figure 2] Fig. 2. Chains of (I) linked via O—H···O interactions (CAMERON; Watkin et al., 1996).
[Figure 3] 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) top
Crystal data top
[Co(C4H4NOS2)2(CH4O)2]F(000) = 426
Mr = 415.42Dx = 1.692 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 5.0414 (4) ÅCell parameters from 9582 reflections
b = 18.878 (2) Åθ = 2.9–25.0°
c = 8.6814 (11) ŵ = 1.58 mm1
β = 99.349 (7)°T = 180 K
V = 815.23 (16) Å3Plate, red
Z = 20.13 × 0.08 × 0.02 mm
Data collection top
Nonius KappaCCD
diffractometer
1087 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.029
Graphite monochromatorθmax = 25.0°, θmin = 4.0°
Thin–slice ω and ϕ scansh = 55
2478 measured reflectionsk = 2022
1424 independent reflectionsl = 1010
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.034Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.078H atoms treated by a mixture of independent and constrained refinement
S = 1.01 w = 1/[σ2(Fo2) + (0.0359P)2]
where P = (Fo2 + 2Fc2)/3
1424 reflections(Δ/σ)max = 0.017
103 parametersΔρmax = 0.31 e Å3
0 restraintsΔρmin = 0.42 e Å3
Crystal data top
[Co(C4H4NOS2)2(CH4O)2]V = 815.23 (16) Å3
Mr = 415.42Z = 2
Monoclinic, P21/cMo Kα radiation
a = 5.0414 (4) ŵ = 1.58 mm1
b = 18.878 (2) ÅT = 180 K
c = 8.6814 (11) Å0.13 × 0.08 × 0.02 mm
β = 99.349 (7)°
Data collection top
Nonius KappaCCD
diffractometer
1087 reflections with I > 2σ(I)
2478 measured reflectionsRint = 0.029
1424 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0340 restraints
wR(F2) = 0.078H atoms treated by a mixture of independent and constrained refinement
S = 1.01Δρmax = 0.31 e Å3
1424 reflectionsΔρmin = 0.42 e Å3
103 parameters
Special details top

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 (Å2) top
xyzUiso*/Ueq
Co10.00000.50000.00000.0228 (2)
S10.19352 (14)0.38022 (4)0.02754 (9)0.0299 (2)
S20.09944 (16)0.25946 (4)0.15912 (10)0.0412 (3)
O10.2694 (3)0.45657 (10)0.1764 (2)0.0258 (5)
H10.385 (8)0.4983 (19)0.163 (4)0.049 (13)*
O20.2661 (4)0.47558 (12)0.1582 (2)0.0307 (5)
N10.2553 (4)0.38537 (12)0.1892 (2)0.0238 (6)
C10.0599 (5)0.34690 (15)0.1057 (3)0.0255 (7)
C20.3815 (6)0.27863 (18)0.2935 (4)0.0413 (8)
H20.48290.24420.35780.050*
C30.4403 (5)0.34770 (16)0.2964 (3)0.0303 (7)
C40.6625 (6)0.38600 (18)0.3956 (4)0.0378 (8)
H4A0.75610.35360.47450.045*
H4B0.58890.42580.44740.045*
H4C0.78930.40380.33030.045*
C50.2171 (6)0.43229 (18)0.2938 (4)0.0422 (9)
H5A0.07430.39820.28360.051*
H5B0.38180.40670.30550.051*
H5C0.16160.46210.38580.051*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Co10.0191 (3)0.0204 (4)0.0276 (4)0.0001 (2)0.0001 (2)0.0020 (2)
S10.0272 (4)0.0246 (5)0.0353 (5)0.0039 (3)0.0026 (3)0.0020 (3)
S20.0464 (5)0.0230 (5)0.0511 (6)0.0011 (3)0.0009 (4)0.0063 (4)
O10.0263 (10)0.0187 (12)0.0316 (12)0.0012 (8)0.0020 (9)0.0021 (9)
O20.0235 (12)0.0357 (14)0.0331 (13)0.0060 (10)0.0052 (10)0.0071 (11)
N10.0229 (13)0.0224 (15)0.0259 (14)0.0025 (10)0.0037 (10)0.0034 (11)
C10.0264 (16)0.0189 (17)0.0325 (17)0.0004 (12)0.0087 (13)0.0022 (13)
C20.0437 (19)0.032 (2)0.046 (2)0.0051 (15)0.0006 (16)0.0125 (17)
C30.0257 (16)0.038 (2)0.0280 (17)0.0070 (13)0.0071 (13)0.0108 (15)
C40.0318 (18)0.043 (2)0.036 (2)0.0089 (14)0.0022 (15)0.0104 (16)
C50.0435 (19)0.046 (2)0.038 (2)0.0074 (15)0.0077 (16)0.0085 (17)
Geometric parameters (Å, º) top
Co1—O12.0459 (17)N1—C11.339 (3)
Co1—O1i2.0459 (17)N1—C31.400 (3)
Co1—O2i2.121 (2)C2—C31.336 (4)
Co1—O22.121 (2)C2—H20.9500
Co1—S1i2.4590 (7)C3—C41.485 (4)
Co1—S12.4590 (7)C4—H4A0.9800
S1—C11.699 (3)C4—H4B0.9800
S2—C11.717 (3)C4—H4C0.9800
S2—C21.725 (3)C5—H5A0.9800
O1—N11.352 (3)C5—H5B0.9800
O2—C51.421 (4)C5—H5C0.9800
O2—H10.75 (4)
O1—Co1—O1i180.00 (9)O1—N1—C3121.5 (2)
O1—Co1—O2i90.88 (8)N1—C1—S1125.0 (2)
O1i—Co1—O2i89.12 (8)N1—C1—S2109.4 (2)
O1—Co1—O289.12 (8)S1—C1—S2125.54 (17)
O1i—Co1—O290.88 (8)C3—C2—S2111.9 (2)
O2i—Co1—O2180.00 (12)C3—C2—H2124.0
O1—Co1—S1i95.22 (5)S2—C2—H2124.0
O1i—Co1—S1i84.78 (5)C2—C3—N1111.2 (3)
O2i—Co1—S1i91.14 (6)C2—C3—C4129.0 (3)
O2—Co1—S1i88.86 (6)N1—C3—C4119.8 (3)
O1—Co1—S184.78 (5)C3—C4—H4A109.5
O1i—Co1—S195.22 (5)C3—C4—H4B109.5
O2i—Co1—S188.86 (6)H4A—C4—H4B109.5
O2—Co1—S191.14 (6)C3—C4—H4C109.5
S1i—Co1—S1180.0H4A—C4—H4C109.5
C1—S1—Co191.82 (10)H4B—C4—H4C109.5
C1—S2—C291.59 (14)O2—C5—H5A109.5
N1—O1—Co1115.02 (14)O2—C5—H5B109.5
C5—O2—Co1128.20 (18)H5A—C5—H5B109.5
C5—O2—H1109 (3)O2—C5—H5C109.5
Co1—O2—H1121 (3)H5A—C5—H5C109.5
C1—N1—O1122.6 (2)H5B—C5—H5C109.5
C1—N1—C3115.9 (2)
O1—Co1—S1—C16.19 (11)Co1—O1—N1—C3174.97 (18)
O1i—Co1—S1—C1173.81 (11)O1—N1—C1—S10.6 (4)
O2i—Co1—S1—C197.18 (11)C3—N1—C1—S1178.09 (19)
O2—Co1—S1—C182.82 (11)O1—N1—C1—S2177.41 (17)
S1i—Co1—S1—C188 (70)C3—N1—C1—S20.1 (3)
O1i—Co1—O1—N144 (100)Co1—S1—C1—N15.1 (2)
O2i—Co1—O1—N196.91 (16)Co1—S1—C1—S2177.21 (17)
O2—Co1—O1—N183.09 (16)C2—S2—C1—N10.0 (2)
S1i—Co1—O1—N1171.87 (14)C2—S2—C1—S1178.0 (2)
S1—Co1—O1—N18.13 (14)C1—S2—C2—C30.1 (3)
O1—Co1—O2—C5120.9 (3)S2—C2—C3—N10.1 (3)
O1i—Co1—O2—C559.1 (3)S2—C2—C3—C4179.2 (3)
O2i—Co1—O2—C551 (65)C1—N1—C3—C20.1 (3)
S1i—Co1—O2—C5143.8 (2)O1—N1—C3—C2177.4 (2)
S1—Co1—O2—C536.2 (2)C1—N1—C3—C4179.3 (3)
Co1—O1—N1—C17.7 (3)O1—N1—C3—C41.8 (4)
Symmetry code: (i) x, y+1, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2—H1···O1ii0.75 (4)1.96 (4)2.696 (3)171 (4)
Symmetry code: (ii) x+1, y+1, z.

Experimental details

Crystal data
Chemical formula[Co(C4H4NOS2)2(CH4O)2]
Mr415.42
Crystal system, space groupMonoclinic, P21/c
Temperature (K)180
a, b, c (Å)5.0414 (4), 18.878 (2), 8.6814 (11)
β (°) 99.349 (7)
V3)815.23 (16)
Z2
Radiation typeMo Kα
µ (mm1)1.58
Crystal size (mm)0.13 × 0.08 × 0.02
Data collection
DiffractometerNonius KappaCCD
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
2478, 1424, 1087
Rint0.029
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.034, 0.078, 1.01
No. of reflections1424
No. of parameters103
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.31, 0.42

Computer programs: COLLECT (Nonius, 1998), HKL SCALEPACK (Otwinowski & Minor, 1997), HKL DENZO and SCALEPACK (Otwinowski & Minor, 1997), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXL97.

Selected bond lengths (Å) top
Co1—O12.0459 (17)S2—C21.725 (3)
Co1—O22.121 (2)O1—N11.352 (3)
Co1—S12.4590 (7)N1—C11.339 (3)
S1—C11.699 (3)N1—C31.400 (3)
S2—C11.717 (3)C2—C31.336 (4)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2—H1···O1i0.75 (4)1.96 (4)2.696 (3)171 (4)
Symmetry code: (i) x+1, y+1, z.
 

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