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Acta Cryst. (2009). E65, m80-m81    [ doi:10.1107/S1600536808041202 ]

catena-Poly[[bis(nitrato-[kappa]2O,O')copper(II)]-[mu]-2,2'-(ethane-1,2-diyldithio)di-1,3,4-thiadiazole-[kappa]2N4:N4']

H.-M. Huang, F.-Y. Ju, J.-G. Wang and J.-H. Qin

Abstract top

In the title compound, [Cu(NO3)2(C6H6N4S4)]n, the CuII atom, occupying a crystallographic inversion centre, is six-coordinated by two N atoms of two 2,2'-[1,2-ethanediylbis(thio)]bis[1,3,4-thiadiazole] ligands in trans positions, and four O atoms from two symmetry-related opposite nitrate anions, which are asymmetrically bonded, resulting in a strong distorted octahedral geometry of the central atom. The ethane group is equally disordered over two sites via another inversion centre. The bridging bidentate 2,2'-[1,2-ethanediylbis(thio)]bis[1,3,4-thiadiazole] ligands link the CuII centres into a one-dimensional chain. The chains are interconnected via intermolecular S...O interactions [3.044 (4) and 3.084 (5) Å] and weak C-H...O hydrogen bonds, generating a three-dimensional supramolecular structure.

Comment top

As shown in Fig. 1, the copper atom is coordinated by four O atoms from two chelating nitrate anions and two N atoms from two Ci symmetry-related 2,2'-[1,2-ethanediylbis(thio)]bis[1,3,4-thiadiazole] ligands. The geometry around the Cu(II) atom appears to be strong distorted octahedral, which is shown with the angle O1—Cu1—O3 = 54.74 (14) °. The nitrate anions are asymmetrically bonded, with Cu1—O3 = 1.971 (3) Å and Cu1—O1 = 2.588 (4) Å (Table 1). Two examples of asymmetrically bonded carboxylate groups show the wide range of short and long Cu(II)–O distances: 1.989 (2) Å and 2.339 (3) Å (Youngme et al., 2007); 1.962 (3) Å and 2.706 Å were reported by Lee & Barboiu (2004).

The ethane group was disordered and the C3 atom was refined on split positions with occupancy (50:50). The 2,2'-[1,2-ethanediylbis(thio)]bis[1,3,4-thiadiazole] ligands adopt a N, N-bidentate bridging mode in trans configuration and bridge the copper atoms into one-dimensional infinite chains, with the bridged Cu-Cu distance of 11.2455 (12) Å (Fig. 2). The chains interact with neigboring molecules via intermolecular S···O interactions (the shortest distances found: O2···S1 = 3.084 (5) Å and O2···S2 = 3.044 (4) Å, with symmetry codes (1 - x, -1 - y, -z) and (1 - x, 1 - y, 1 - z), respectively, and weak intermolecular C—H···O hydrogen bonds (Bhogala et al. (2005), (Table 2). These chains are linked by the S···O interactions into two-dimensional layers (Fig. 3), which are further connected by weak intermolecular C—H···O hydrogen bonds to generate a a three-dimensional supramolecular structure (Fig. 4).

Related literature top

For related catena-poly Cu(II) complexes, see, for example: Wang et al. (2008). For elongated Cu—O bonds see, for example: Lee & Barboiu (2004); Youngme et al. (2007). For C—H···O hydrogen bonds, see: Bhogala et al. (2005);

Experimental top

The reaction of 2,2'-[1,2-ethanediyl-bis(thio)]bis(1,3,4- thiadiazole) (0.2 mmol) with Cu(NO3)2 (0.2 mmol) in MeOH(10 ml) for a few minutes afforded a light blue solid, which was filtered, washed with acetone, and dried on air. The single crystals suitable for X-ray analysis were obtained by slow diffusion of Et2O into the acetonitrile solution of the solid.

Refinement top

All hydrogen atoms were positioned geometrically and treated as riding, with C—H = 0.93 Å (CH) and Uĩso~(H) = 1.2Ueq(C), with C—H = 0.97 Å (CH2) and Uĩso~(H) = 1.2Ueq(C),

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELX97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. A view of the local coordination of the Cu(II) cation in the title compound. Displacement ellipsoids are drawn at the 30% probability level. The disordered ethane group was omitted for clarity. Symmetry codes: (A) (-x, -y, -z); (B) (1 - x, 1 - y, 1 - z); (C) (-1 + x, -1 + y, -1 + z).
[Figure 2] Fig. 2. A view of the polymeric chain in the title compound.
[Figure 3] Fig. 3. A view of the two-dimensional network, indicating the S···O interactions by dashed lines.
[Figure 4] Fig. 4. A view of the compound packing down the b axis.
catena-Poly[[bis(nitrato-κ2O,O')copper(II)]-µ- 2,2'-(ethane-1,2-diyldithio)di-1,3,4-thiadiazole-κ2N4:N4'] top
Crystal data top
[Cu(NO3)2(C6H6N4S4)]Z = 1
Mr = 449.95F(000) = 225
Triclinic, P1Dx = 2.031 Mg m−3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 5.2143 (8) ÅCell parameters from 1855 reflections
b = 7.0214 (10) Åθ = 3.0–29.2°
c = 10.6476 (16) ŵ = 2.09 mm−1
α = 105.144 (2)°T = 296 K
β = 100.000 (2)°Plate, colorless
γ = 93.958 (2)°0.48 × 0.29 × 0.04 mm
V = 367.88 (9) Å3
Data collection top
Bruker SMART CCD area-detector
diffractometer		1336 independent reflections
Radiation source: fine-focus sealed tube1273 reflections with I > 2σ(I)
graphiteRint = 0.020
phi and ω scansθmax = 25.5°, θmin = 3.0°
Absorption correction: multi-scan
(SADABS; Bruker, 1997)		h = −6→3
Tmin = 0.432, Tmax = 0.924k = −8→8
1983 measured reflectionsl = −11→12
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)] = 0.058Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.173H-atom parameters constrained
S = 1.05 w = 1/[σ2(Fo2) + (0.1363P)2 + 0.4692P]
where P = (Fo2 + 2Fc2)/3
1336 reflections(Δ/σ)max < 0.001
110 parametersΔρmax = 1.86 e Å−3
1 restraintΔρmin = −0.50 e Å−3
Crystal data top
[Cu(NO3)2(C6H6N4S4)]γ = 93.958 (2)°
Mr = 449.95V = 367.88 (9) Å3
Triclinic, P1Z = 1
a = 5.2143 (8) ÅMo Kα radiation
b = 7.0214 (10) ŵ = 2.09 mm−1
c = 10.6476 (16) ÅT = 296 K
α = 105.144 (2)°0.48 × 0.29 × 0.04 mm
β = 100.000 (2)°
Data collection top
Bruker SMART CCD area-detector
diffractometer		1336 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 1997)		1273 reflections with I > 2σ(I)
Tmin = 0.432, Tmax = 0.924Rint = 0.020
1983 measured reflectionsθmax = 25.5°
Refinement top
R[F2 > 2σ(F2)] = 0.058H-atom parameters constrained
wR(F2) = 0.173Δρmax = 1.86 e Å−3
S = 1.05Δρmin = −0.50 e Å−3
1336 reflectionsAbsolute structure: ?
110 parametersFlack parameter: ?
1 restraintRogers parameter: ?
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
C30.6301 (17)0.4878 (11)0.4823 (9)0.0366 (14)0.499 (9)
H3A0.76020.59210.54220.044*0.499 (9)
H3B0.62430.49720.39260.044*0.499 (9)
C3'0.4746 (17)0.4163 (12)0.5298 (9)0.0366 (14)0.501 (9)
H3B'0.29880.34850.49170.044*0.501 (9)
H3A'0.48900.46800.62490.044*0.501 (9)
Cu10.00000.00000.00000.0312 (3)
S10.6997 (3)−0.12017 (17)0.26648 (12)0.0406 (4)
S20.7207 (3)0.23982 (18)0.49437 (12)0.0455 (4)
O1−0.2024 (8)−0.3668 (6)−0.0576 (4)0.0546 (10)
O2−0.0393 (10)−0.5352 (6)−0.2188 (4)0.0650 (12)
O30.1101 (7)−0.2255 (5)−0.1244 (3)0.0417 (8)
N1−0.0491 (8)−0.3829 (5)−0.1353 (4)0.0385 (9)
N20.3011 (8)−0.0167 (6)0.1409 (4)0.0345 (8)
N30.3672 (7)0.1312 (5)0.2605 (4)0.0370 (9)
C10.4554 (9)−0.1563 (6)0.1321 (4)0.0355 (10)
H1A0.4330−0.26630.05830.043*
C20.5716 (9)0.0958 (6)0.3353 (4)0.0347 (10)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C30.036 (4)0.032 (3)0.038 (3)0.005 (2)0.007 (3)0.004 (3)
C3'0.036 (4)0.032 (3)0.038 (3)0.005 (2)0.007 (3)0.004 (3)
Cu10.0330 (5)0.0269 (5)0.0289 (5)0.0069 (3)0.0028 (3)0.0009 (3)
S10.0423 (7)0.0364 (7)0.0419 (7)0.0170 (5)0.0040 (5)0.0086 (5)
S20.0479 (8)0.0415 (7)0.0367 (7)0.0153 (5)−0.0092 (5)0.0016 (5)
O10.062 (2)0.049 (2)0.059 (2)0.0151 (17)0.020 (2)0.0183 (17)
O20.088 (3)0.0380 (19)0.053 (2)0.024 (2)−0.002 (2)−0.0102 (17)
O30.0405 (18)0.0406 (17)0.0388 (17)0.0109 (14)0.0058 (14)0.0017 (14)
N10.049 (2)0.0291 (17)0.0304 (18)0.0149 (16)−0.0031 (17)0.0004 (14)
N20.0384 (19)0.0289 (17)0.0321 (19)0.0068 (15)0.0039 (15)0.0025 (14)
N30.039 (2)0.0306 (19)0.035 (2)0.0102 (17)−0.0015 (17)0.0016 (16)
C10.039 (2)0.032 (2)0.033 (2)0.0098 (18)0.0062 (18)0.0034 (17)
C20.037 (2)0.0291 (19)0.035 (2)0.0078 (18)0.0048 (19)0.0054 (17)
Geometric parameters (Å, °) top
C3—C3i1.479 (17)Cu1—N2ii2.007 (4)
C3—S21.866 (7)S1—C11.693 (5)
C3—H3A0.9700S1—C21.735 (4)
C3—H3B0.9700S2—C21.743 (4)
C3'—C3'i1.504 (17)O1—N11.237 (6)
C3'—S21.863 (7)O2—N11.209 (5)
C3'—H3B'0.9700O3—N11.303 (5)
C3'—H3A'0.9700N2—C11.305 (6)
Cu1—O12.588 (4)N2—N31.389 (5)
Cu1—O3ii1.971 (3)N3—C21.295 (6)
Cu1—O31.971 (3)C1—H1A0.9300
Cu1—N22.007 (4)
C3i—C3—S2108.9 (7)C2—S2—C3'100.6 (3)
C3i—C3—H3A109.9C2—S2—C399.5 (3)
S2—C3—H3A109.9N1—O3—Cu1107.4 (2)
C3i—C3—H3B109.9O2—N1—O1123.7 (5)
S2—C3—H3B109.9O2—N1—O3119.2 (4)
H3A—C3—H3B108.3O1—N1—O3117.1 (4)
C3'i—C3'—S2108.5 (7)O1—Cu1—O354.74 (14)
C3'i—C3'—H3B'110.0N2—Cu1—O389.02 (15)
S2—C3'—H3B'110.0O1—Cu1—O3ii125.26 (14)
C3'i—C3'—H3A'110.0C1—N2—N3113.3 (4)
S2—C3'—H3A'110.0C1—N2—Cu1126.2 (3)
H3B'—C3'—H3A'108.4N3—N2—Cu1120.5 (3)
O3ii—Cu1—O3180.0C2—N3—N2110.7 (4)
O3ii—Cu1—N290.98 (15)N2—C1—S1114.2 (3)
O3—Cu1—N289.02 (15)N2—C1—H1A122.9
O3ii—Cu1—N2ii89.02 (15)S1—C1—H1A122.9
O3—Cu1—N2ii90.98 (15)N3—C2—S1114.8 (3)
N2—Cu1—N2ii180.0N3—C2—S2126.5 (3)
C1—S1—C287.1 (2)S1—C2—S2118.7 (3)
C3'i—C3'—S2—C2−83.9 (9)Cu1—N2—N3—C2−177.8 (3)
C3'i—C3'—S2—C37.8 (7)N3—N2—C1—S1−1.2 (5)
C3i—C3—S2—C287.1 (9)Cu1—N2—C1—S1177.3 (2)
C3i—C3—S2—C3'−7.9 (7)C2—S1—C1—N20.9 (4)
N2—Cu1—O3—N1103.2 (3)N2—N3—C2—S1−0.1 (5)
N2ii—Cu1—O3—N1−76.8 (3)N2—N3—C2—S2−179.2 (3)
Cu1—O3—N1—O2171.2 (4)C1—S1—C2—N3−0.4 (4)
Cu1—O3—N1—O1−9.2 (4)C1—S1—C2—S2178.7 (3)
O3ii—Cu1—N2—C1171.9 (4)C3'—S2—C2—N39.6 (5)
O3—Cu1—N2—C1−8.1 (4)C3—S2—C2—N3−27.8 (5)
O3ii—Cu1—N2—N3−9.7 (3)C3'—S2—C2—S1−169.5 (4)
O3—Cu1—N2—N3170.3 (3)C3—S2—C2—S1153.1 (3)
C1—N2—N3—C20.8 (6)
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x, −y, −z.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C1—H1A···O1iii0.932.493.083 (6)122
Symmetry codes: (iii) x+1, y, z.
Table 1
Selected geometric parameters (Å, °) top
Cu1—O12.588 (4)Cu1—N22.007 (4)
Cu1—O31.971 (3)
O1—Cu1—O354.74 (14)O1—Cu1—O3i125.26 (14)
N2—Cu1—O389.02 (15)
Symmetry codes: (i) −x, −y, −z.
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C1—H1A···O1ii0.932.493.083 (6)122
Symmetry codes: (ii) x+1, y, z.
Acknowledgements top

The authors thank Luo Yang Normal University for supporting this work.

references
References top

Bhogala, B. R., Basavoju, S. & Nangia, A. (2005). Cryst. Growth Des. 5, 1683–1686.

Bruker (1997). SMART, SAINT and SADABS. Bruker AXS Inc., Madison,Wisconsin, USA.

Lee, A. & Barboiu, M. (2004). Acta Cryst. C60, m156–m158.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Wang, J. G., Qin, J. H., Hu, P. Z. & Zhao, B. T. (2008). Z. Kristallogr. New Cryst. Struct. 223, 225–227.

Youngme, S., Chotkhun, T. & Chaichit, N. N. (2007). Acta Cryst. C63, m59–m61.