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The title compound, [Cu4Cl6O(C4H7NS)4], was obtained by the reaction of CuCl2·2H2O with 2-methyl-2-thia­zoline in methanol. The complex has twofold crystallographic symmetry and contains a tetrahedron of four CuII atoms coordinating a central [mu]4-O atom, with the six edges of the tetrahedron bridged by Cl atoms. Distance ranges are Cu-O 1.917 (4)-1.920 (4) and Cu-Cl 2.370 (2)-2.445 (2) Å.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270101016870/sk1502sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270101016870/sk1502Isup2.hkl
Contains datablock I

CCDC reference: 162864

Comment top

The magnetic properties and the presence to the active sites of biological systems of tetranuclear complexes of paramagnetic transition metal ions, have attracted the attention of inorganic and bioinorganic chemists for many years (Marsh et al., 1983; Halfen & Tolman, 1994). Among the ligands that allow the formation of tetranuclear copper(II) complexes are the thiazole derivatives, whose reaction products with CuCl2 have been extensively studied (Hodgson, 1984; Marsh et al., 1983, 1988). In contrast, relatively little information is known about the reaction of Cu(II) with thiazoline derivatives, which have an almost similar structure to that of thiazoles. The present study is part of a systematic investigation on the reaction products of CuCl2 and CuBr2 with thiazolines.

The molecular structure of the title compound (I), along with the atomic numbering scheme, is shown in Fig. 1, while selected bond lengths and angles are given in Table 1. Selected intramolecular contact distances are given in Table 2. The central unit Cu4OCl6 is of the same type as that found in many related complexes (Bertrand, 1967; Belford et al., 1972; Gill & Sterns, 1970; Guy et al., 1988). The four copper(II) atoms are arranged tetrahedrally around a central oxygen atom, being also bridged in pairs by chlorine atoms. Each copper atom is fivefold coordinated by three chlorine atoms, the central oxygen atom and the nitrogen atom from a 2-methyl-2-thiazoline ligand (2 m-2tzn hereafter), in an arrangement close to trigonal bipyramidal (TBP). The percentage trigonal distortion from the square pyramidal (SP) geometry of the atomic arrangements around the two independent copper atoms are τ = 77.5% and τ = 77.7% for Cu1 and Cu2, respectively [τ = 0% for ideal SP and τ = 100% for ideal TBP geometries (Addison et al., 1984)].

The cluster Cu4OCl6 has been reported to possess various point group symmetries, as for example 43m (Bertrand,1967), 2 (Belford et al.,1972) or 1 (Gill & Sterns, 1970). In the present case, it possesses the point group symmetry 2, with the twofold axis passing through Cl2, O and Cl3 (see Fig. 1). The observed bond lengths and angles in the cluster are in fair agreement with those observed in related complexes.

The two symmetrically independent 2 m-2tzn rings, being approximately perpendicular to each other [91.7 (3)°], have almost identical geometries, with most of the corresponding bond lengths and angles coinciding within the experimental error. The only significant differences appear between the bond lengths C3—S1 and C7—S2 [1.81 (1) Å and 1.73 (2) Å, respectively], and between the bond angles C2—C3—S1 and C6—C7—S2 [104.1 (6)° and 107.8 (8)°, respectively]. The two 2 m-2tzn rings differ also in the degree of planarity. Thus, while the ring attached to Cu(1) appears slightly puckered, the maximum atomic deviation from the mean plane being 0.18 (1) Å, (atom C2), the ring attached to Cu(2) is perfectly planar within the experimental error. The two bonds C1—N1 and C5—N2 of length 1.26 (1) Å and 1.28 (1) Å, respectively, are substantially shorter than the adjacent ones C2—N1 and C6–N2 of length 1.46 (1) Å and 1.45 (1) Å, respectively, indicating that the primary resonance structures in the two 2 m-2tzn rings have the double bond located between C1 and N1 and between C5 and N2, respectively. The nitrogen atoms N1 and N2 are pyramidally coordinated by C1, C2, Cu1 and C5, C6, Cu2, respectively, the corresponding deviations from their basal planes being 0.108 (8) Å and 0.07 (1) Å.

In the crystal structure of the studied compound no unusual intermolecular contact distances are observed, so that the molecular packing may be attributed to normal van der Waals interactions.

Experimental top

The title compound was synthesized by mixing a solution of copper(II) chloride dihydrate (1 mmol) in methanol (10 ml) with a solution of the ligand 2-methyl-2-thiazoline (4 mmol) in methanol (5 ml), the reaction being at 291 K. The light brown solution, was left overnight at 291 K, forming brown rhombic crystals.

Refinement top

For one atom, C(7), the ratio of maximum/minimum principal r.m.s. atomic displacements was found fairly large (5.54), indicating possible disorder. An attempt, however, to refine C7 as a split atom proved unsuccessful. Hence, its anisotropic displacement parameters were retained, since the refinement converged smoothly, leading to chemically reasonable positions for all atoms. The H atoms were placed geometrically at their ideal positions and allowed to ride with isotropic displacement parameters equal to 1.2 Ueq of the parent atoms. An extinction correction was deemed as not necessary. Some geometrical calculations were performed with the Xtal 3.2 package (Hall et al., 1992).

Computing details top

Data collection: DIF4 (Stoe & Cie, 1988); cell refinement: DIF4; data reduction: REDU4 (Stoe & Cie, 1988); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Bergerhoff, 1996); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. DIAMOND (Bergerhoff, 1996) plot of the molecule of Cu4OCl6(C4H7NS)4 with the atomic numbering scheme. Atomic thermal ellipsoids are at 30% probability level. Symmetry operation: (i) -x, y, -z + 1/2.
µ4-oxo-hexa-µ-chloro-tetrakis[(2-methyl-2-thiazoline)copper(II)] top
Crystal data top
C16H28Cl6Cu4N4OS4F(000) = 1768
Mr = 887.52Dx = 1.872 Mg m3
Dm = 1.87 Mg m3
Dm measured by flotation in a mixture of CCl4/CH3I
Orthorhombic, PbcnMo Kα radiation, λ = 0.71070 Å
Hall symbol: -P 2n 2abCell parameters from 15 reflections
a = 10.3705 (18) Åθ = 8.2–11.5°
b = 14.903 (2) ŵ = 3.46 mm1
c = 20.375 (4) ÅT = 293 K
V = 3148.9 (9) Å3Plate, brown
Z = 40.23 × 0.13 × 0.04 mm
Data collection top
Upgraded Philips PW1100
diffractometer
1273 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.101
Graphite monochromatorθmax = 25.0°, θmin = 2.4°
θ/2θ scansh = 1212
Absorption correction: ψ-scan
EMPIR (Stoe & Cie, 1988)
k = 1717
Tmin = 0.448, Tmax = 0.652l = 024
5588 measured reflections3 standard reflections every 120 min
2775 independent reflections intensity decay: 10%
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)] = 0.064Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.127H-atom parameters constrained
S = 0.90 w = 1/[σ2(Fo2) + (0.054P)2]
where P = (Fo2 + 2Fc2)/3
2775 reflections(Δ/σ)max = 0.020
162 parametersΔρmax = 0.71 e Å3
0 restraintsΔρmin = 0.60 e Å3
Crystal data top
C16H28Cl6Cu4N4OS4V = 3148.9 (9) Å3
Mr = 887.52Z = 4
Orthorhombic, PbcnMo Kα radiation
a = 10.3705 (18) ŵ = 3.46 mm1
b = 14.903 (2) ÅT = 293 K
c = 20.375 (4) Å0.23 × 0.13 × 0.04 mm
Data collection top
Upgraded Philips PW1100
diffractometer
1273 reflections with I > 2σ(I)
Absorption correction: ψ-scan
EMPIR (Stoe & Cie, 1988)
Rint = 0.101
Tmin = 0.448, Tmax = 0.6523 standard reflections every 120 min
5588 measured reflections intensity decay: 10%
2775 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0640 restraints
wR(F2) = 0.127H-atom parameters constrained
S = 0.90Δρmax = 0.71 e Å3
2775 reflectionsΔρmin = 0.60 e Å3
162 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
C10.2640 (8)0.3495 (6)0.4212 (4)0.035 (2)
C20.2378 (9)0.4632 (6)0.3483 (5)0.050 (3)
H2A0.16110.49640.33600.060*
H2B0.29250.45810.30990.060*
C30.3096 (9)0.5138 (6)0.4023 (4)0.054 (3)
H3A0.25160.55280.42640.064*
H3B0.37890.54970.38400.064*
C40.2571 (9)0.2591 (7)0.4518 (5)0.054 (3)
H4A0.16890.24470.46140.081*
H4B0.30620.25890.49180.081*
H4C0.29180.21530.42210.081*
C50.3496 (10)0.1194 (9)0.1237 (5)0.063 (3)
C60.2292 (11)0.0072 (7)0.1350 (5)0.078 (4)
H6A0.14470.01360.11520.094*
H6B0.23170.04400.17420.094*
C70.3324 (15)0.0392 (9)0.0868 (6)0.122 (6)
H7A0.29250.05910.04630.147*
H7B0.38020.08890.10550.147*
C80.3933 (9)0.2119 (10)0.1308 (6)0.099 (5)
H8A0.31990.25100.13400.149*
H8B0.44390.22850.09320.149*
H8C0.44480.21730.16970.149*
Cl10.2729 (2)0.20436 (17)0.28580 (12)0.0534 (7)
Cl20.00000.4174 (2)0.25000.0549 (10)
Cl30.00000.0296 (2)0.25000.0483 (9)
Cl40.0481 (2)0.22807 (16)0.10777 (11)0.0457 (6)
N10.2014 (6)0.3738 (4)0.3710 (3)0.0338 (18)
N20.2508 (8)0.0859 (6)0.1524 (3)0.051 (2)
O10.00000.2263 (5)0.25000.0222 (17)
S10.3727 (2)0.42602 (17)0.45479 (13)0.0548 (7)
S20.4347 (4)0.0500 (3)0.07156 (19)0.1196 (16)
Cu10.09508 (9)0.29778 (6)0.31167 (5)0.0324 (3)
Cu20.12283 (9)0.15368 (7)0.20396 (5)0.0371 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.031 (5)0.042 (5)0.032 (5)0.008 (5)0.007 (5)0.009 (5)
C20.049 (6)0.045 (6)0.057 (7)0.008 (5)0.004 (6)0.003 (5)
C30.066 (7)0.052 (7)0.044 (7)0.013 (6)0.005 (6)0.015 (5)
C40.043 (6)0.062 (7)0.056 (7)0.005 (5)0.021 (6)0.001 (5)
C50.029 (6)0.114 (10)0.046 (7)0.029 (6)0.005 (6)0.010 (7)
C60.106 (10)0.067 (8)0.062 (8)0.048 (7)0.016 (8)0.015 (6)
C70.190 (16)0.116 (11)0.062 (9)0.133 (12)0.014 (10)0.031 (9)
C80.026 (6)0.190 (16)0.082 (10)0.022 (8)0.015 (6)0.017 (10)
Cl10.0275 (12)0.0781 (18)0.0546 (16)0.0097 (13)0.0077 (11)0.0240 (14)
Cl20.078 (3)0.0347 (19)0.052 (2)0.0000.025 (2)0.000
Cl30.045 (2)0.0370 (19)0.063 (2)0.0000.0043 (19)0.000
Cl40.0431 (14)0.0592 (15)0.0348 (14)0.0112 (12)0.0090 (12)0.0010 (12)
N10.039 (5)0.033 (4)0.029 (5)0.006 (4)0.001 (4)0.005 (3)
N20.043 (5)0.076 (7)0.034 (5)0.030 (5)0.004 (5)0.013 (4)
O10.018 (4)0.037 (4)0.011 (4)0.0000.009 (3)0.000
S10.0498 (18)0.0566 (16)0.0579 (17)0.0109 (13)0.0131 (15)0.0107 (13)
S20.091 (3)0.196 (4)0.071 (3)0.082 (3)0.019 (2)0.019 (3)
Cu10.0304 (6)0.0361 (6)0.0308 (6)0.0037 (5)0.0005 (5)0.0018 (5)
Cu20.0306 (6)0.0451 (6)0.0355 (6)0.0074 (5)0.0023 (5)0.0064 (5)
Geometric parameters (Å, º) top
C1—N11.264 (10)C7—H7A0.9700
C1—C41.487 (11)C7—H7B0.9700
C1—S11.743 (8)C8—H8A0.9600
C2—N11.460 (10)C8—H8B0.9600
C2—C31.527 (11)C8—H8C0.9600
C2—H2A0.9700Cl1—Cu12.370 (2)
C2—H2B0.9700Cl1—Cu22.402 (2)
C3—S11.812 (10)Cl2—Cu1i2.393 (2)
C3—H3A0.9700Cl2—Cu12.393 (2)
C3—H3B0.9700Cl3—Cu2i2.434 (3)
C4—H4A0.9600Cl3—Cu22.434 (3)
C4—H4B0.9600Cl4—Cu22.381 (3)
C4—H4C0.9600Cl4—Cu1i2.445 (2)
C5—N21.282 (12)N1—Cu11.991 (7)
C5—C81.458 (16)N2—Cu21.972 (7)
C5—S21.726 (11)O1—Cu2i1.917 (4)
C6—N21.448 (12)O1—Cu21.917 (4)
C6—C71.528 (14)O1—Cu11.920 (4)
C6—H6A0.9700O1—Cu1i1.920 (4)
C6—H6B0.9700Cu1—Cl4i2.445 (2)
C7—S21.728 (16)
Cu1···Cu23.083 (1)Cu1···Cu2i3.133 (1)
Cu1···Cu1i3.195 (1)Cu2···Cu2i3.164 (1)
N1—C1—C4125.0 (8)H8A—C8—H8C109.5
N1—C1—S1117.6 (7)H8B—C8—H8C109.5
C4—C1—S1117.3 (6)Cu1—Cl1—Cu280.51 (8)
N1—C2—C3110.4 (8)Cu1i—Cl2—Cu183.73 (11)
N1—C2—H2A109.6Cu2i—Cl3—Cu281.08 (10)
C3—C2—H2A109.6Cu2—Cl4—Cu1i80.96 (8)
N1—C2—H2B109.6C1—N1—C2112.6 (7)
C3—C2—H2B109.6C1—N1—Cu1127.8 (6)
H2A—C2—H2B108.1C2—N1—Cu1118.0 (5)
C2—C3—S1104.1 (6)C5—N2—C6112.7 (9)
C2—C3—H3A110.9C5—N2—Cu2125.5 (8)
S1—C3—H3A110.9C6—N2—Cu2121.2 (7)
C2—C3—H3B110.9Cu2i—O1—Cu2111.2 (3)
S1—C3—H3B110.9Cu2i—O1—Cu1109.53 (4)
H3A—C3—H3B108.9Cu2—O1—Cu1106.99 (4)
C1—C4—H4A109.5Cu2i—O1—Cu1i106.99 (4)
C1—C4—H4B109.5Cu2—O1—Cu1i109.53 (4)
H4A—C4—H4B109.5Cu1—O1—Cu1i112.6 (3)
C1—C4—H4C109.5C1—S1—C390.4 (4)
H4A—C4—H4C109.5C5—S2—C792.1 (6)
H4B—C4—H4C109.5O1—Cu1—N1176.4 (2)
N2—C5—C8124.9 (10)O1—Cu1—Cl185.88 (13)
N2—C5—S2117.1 (10)N1—Cu1—Cl192.2 (2)
C8—C5—S2118.0 (9)O1—Cu1—Cl281.83 (18)
N2—C6—C7110.4 (10)N1—Cu1—Cl297.1 (2)
N2—C6—H6A109.6Cl1—Cu1—Cl2129.89 (8)
C7—C6—H6A109.6O1—Cu1—Cl4i83.78 (10)
N2—C6—H6B109.6N1—Cu1—Cl4i99.8 (2)
C7—C6—H6B109.6Cl1—Cu1—Cl4i111.86 (10)
H6A—C6—H6B108.1Cl2—Cu1—Cl4i114.74 (7)
C6—C7—S2107.8 (8)O1—Cu2—N2176.1 (3)
C6—C7—H7A110.2O1—Cu2—Cl485.62 (11)
S2—C7—H7A110.2N2—Cu2—Cl491.1 (2)
C6—C7—H7B110.2O1—Cu2—Cl185.02 (8)
S2—C7—H7B110.2N2—Cu2—Cl195.5 (2)
H7A—C7—H7B108.5Cl4—Cu2—Cl1129.46 (10)
C5—C8—H8A109.5O1—Cu2—Cl383.85 (18)
C5—C8—H8B109.5N2—Cu2—Cl399.7 (3)
H8A—C8—H8B109.5Cl4—Cu2—Cl3120.05 (7)
C5—C8—H8C109.5Cl1—Cu2—Cl3108.08 (7)
Symmetry code: (i) x, y, z+1/2.

Experimental details

Crystal data
Chemical formulaC16H28Cl6Cu4N4OS4
Mr887.52
Crystal system, space groupOrthorhombic, Pbcn
Temperature (K)293
a, b, c (Å)10.3705 (18), 14.903 (2), 20.375 (4)
V3)3148.9 (9)
Z4
Radiation typeMo Kα
µ (mm1)3.46
Crystal size (mm)0.23 × 0.13 × 0.04
Data collection
DiffractometerUpgraded Philips PW1100
diffractometer
Absorption correctionψ-scan
EMPIR (Stoe & Cie, 1988)
Tmin, Tmax0.448, 0.652
No. of measured, independent and
observed [I > 2σ(I)] reflections
5588, 2775, 1273
Rint0.101
(sin θ/λ)max1)0.594
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.064, 0.127, 0.90
No. of reflections2775
No. of parameters162
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.71, 0.60

Computer programs: DIF4 (Stoe & Cie, 1988), DIF4, REDU4 (Stoe & Cie, 1988), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), DIAMOND (Bergerhoff, 1996), SHELXL97.

Selected geometric parameters (Å, º) top
Cl1—Cu12.370 (2)Cl4—Cu1i2.445 (2)
Cl1—Cu22.402 (2)N1—Cu11.991 (7)
Cl2—Cu12.393 (2)N2—Cu21.972 (7)
Cl3—Cu22.434 (3)O1—Cu21.917 (4)
Cl4—Cu22.381 (3)O1—Cu11.920 (4)
Cu1···Cu23.083 (1)Cu1···Cu2i3.133 (1)
Cu1···Cu1i3.195 (1)Cu2···Cu2i3.164 (1)
Cu1—Cl1—Cu280.51 (8)Cl1—Cu1—Cl2129.89 (8)
Cu1i—Cl2—Cu183.73 (11)O1—Cu1—Cl4i83.78 (10)
Cu2i—Cl3—Cu281.08 (10)N1—Cu1—Cl4i99.8 (2)
Cu2—Cl4—Cu1i80.96 (8)Cl1—Cu1—Cl4i111.86 (10)
Cu2i—O1—Cu2111.2 (3)Cl2—Cu1—Cl4i114.74 (7)
Cu2i—O1—Cu1109.53 (4)O1—Cu2—N2176.1 (3)
Cu2—O1—Cu1106.99 (4)O1—Cu2—Cl485.62 (11)
Cu2i—O1—Cu1i106.99 (4)N2—Cu2—Cl491.1 (2)
Cu2—O1—Cu1i109.53 (4)O1—Cu2—Cl185.02 (8)
Cu1—O1—Cu1i112.6 (3)N2—Cu2—Cl195.5 (2)
O1—Cu1—N1176.4 (2)Cl4—Cu2—Cl1129.46 (10)
O1—Cu1—Cl185.88 (13)O1—Cu2—Cl383.85 (18)
N1—Cu1—Cl192.2 (2)N2—Cu2—Cl399.7 (3)
O1—Cu1—Cl281.83 (18)Cl4—Cu2—Cl3120.05 (7)
N1—Cu1—Cl297.1 (2)Cl1—Cu2—Cl3108.08 (7)
Symmetry code: (i) x, y, z+1/2.
 

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