Poly[[tris­[μ-2,2′-(butane-1,4-diyl­dithio)bis­(1,3,4-thia­diazole)-κ² N ⁴:N ^4′]copper(II)] bis­(perchlorate)]

Abstract

In the title compound, {[Cu(C₈H₁₀N₄S₄)₃](ClO₄)₂}_n, the Cu^II atom is located on a threefold inversion axis coordinated by six N atoms of symmetry-equivalent 2,2′-(butane-1,4-diyl­dithio)bis­(1,3,4-thia­diazole) ligands in a slightly distorted octa­hedral geometry. Adjacent Cu^II atoms are linked by the bridging bidentate thia­diazole ligands, which are situated about inversion centers. This leads to the formation of a three-dimensional network structure.

Related literature

For copper(II) complexes involving the same ligand, see: Huang et al. (2009 ▶); Wang et al. (2008 ▶).

Experimental

Crystal data

• [Cu(C₈H₁₀N₄S₄)₃](ClO₄)₂

• M _r = 1133.76

• Trigonal,

• a = 10.5455 (6) Å

• c = 33.728 (4) Å

• V = 3248.3 (5) ų

• Z = 3

• Mo Kα radiation

• μ = 1.27 mm⁻¹

• T = 291 K

• 0.28 × 0.21 × 0.14 mm

Data collection

• Bruker SMART CCD area-detector diffractometer

• Absorption correction: multi-scan (SADABS; Bruker, 1997 ▶) T _min = 0.717, T _max = 0.839

• 9432 measured reflections

• 1673 independent reflections

• 1320 reflections with I > 2σ(I)

• R _int = 0.028

Refinement

• R[F ² > 2σ(F ²)] = 0.047

• wR(F ²) = 0.133

• S = 1.05

• 1673 reflections

• 90 parameters

• H-atom parameters constrained

• Δρ_max = 0.82 e Å⁻³

• Δρ_min = −0.51 e Å⁻³

Data collection: SMART (Bruker, 1997 ▶); cell refinement: SAINT (Bruker, 1997 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

supplementary crystallographic information

Comment

The asymmetric unit of the title compound consists of one sixth of a Cu^II atom, which is located on a three-fold inversion axis, half a 2,2'-(butane-1,4-diyldithio)bis(1,3,4-thiadiazole) ligand which possesses an inversion center, and one third of a perchlorate ion, which is situated on a three-fold rotation axis. As depicted in Fig. 1, the Cu^II atom is coordinated by six N atoms from six symmetry equivalent 2,2'-(butane-1,4-diyldithio)bis(1,3,4-thiadiazole) ligands, in a slightly distorted octahedral geometry of the central atom. The Cu—N bond distance is 2.149 (3) Å, within the range expected for such coordination bonds (Huang et al., 2009; Wang et al., 2008). The centrosymmetric 2,2'-(butane-1,4-diyldithio)bis(1,3,4-thiadiazole) ligand adopts a N,N'-bidentate bridging mode in a trans configuration and links the Cu^II atoms to form a three-dimensional network. The bridging Cu···Cu distance is 12.7854 (12) Å (Fig. 2).

Experimental

The reaction of 2,2'-(butane-1,4-diyldithio)bis(1,3,4-thiadiazole) (0.3 mmol) with Cu(ClO₄)₂ (0.1 mmol) in MeOH(10 ml) for a few minutes gave a light blue solid, which was filtered off, washed with acetone, and dried in air. Single crystals, suitable for X-ray analysis, were obtained by slow diffusion of Et₂O into an acetonitrile solution of the solid.

Refinement

The H-atoms were positioned geometrically and treated as riding: C—H = 0.93 - 0.97 Å and U_iso(H) = 1.2U_eq(parent C-atom).

Figures

Fig. 1.

A view of the coordination around the CuII atom in the cation of the title compound. Displacement ellipsoids are drawn at the 30% probability level. The H atoms and perchlorate ion were omitted for clarity.

Fig. 2.

A view down the b axis of the crystal packing of the title compound.

Crystal data

[Cu(C8H10N4S4)3](ClO4)2	Dx = 1.739 Mg m−3
Mr = 1133.76	Mo Kα radiation, λ = 0.71073 Å
Trigonal, R3	Cell parameters from 2638 reflections
Hall symbol: -R 3	θ = 2.3–24.5°
a = 10.5455 (6) Å	µ = 1.27 mm−1
c = 33.728 (4) Å	T = 291 K
V = 3248.3 (5) Å3	Block, blue
Z = 3	0.28 × 0.21 × 0.14 mm
F(000) = 1731

Data collection

Bruker SMART CCD area-detector diffractometer	1673 independent reflections
Radiation source: fine-focus sealed tube	1320 reflections with I > 2σ(I)
graphite	Rint = 0.028
φ and ω scans	θmax = 27.5°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 1997)	h = −13→13
Tmin = 0.717, Tmax = 0.839	k = −13→13
9432 measured reflections	l = −43→43

Refinement

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.133	H-atom parameters constrained
S = 1.05	w = 1/[σ2(Fo2) + (0.0617P)2 + 10.9603P] where P = (Fo2 + 2Fc2)/3
1673 reflections	(Δ/σ)max < 0.001
90 parameters	Δρmax = 0.82 e Å−3
0 restraints	Δρmin = −0.51 e Å−3

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

	x	y	z	Uiso*/Ueq
Cu1	1.0000	1.0000	0.5000	0.0338 (2)
Cl1	0.3333	0.6667	0.45984 (7)	0.0692 (5)
S1	0.94592 (14)	0.59055 (13)	0.43361 (3)	0.0702 (4)
S2	0.71904 (11)	0.56831 (12)	0.37580 (3)	0.0608 (3)
O1	0.3599 (4)	0.8063 (4)	0.47130 (14)	0.1084 (13)
O2	0.3333	0.6667	0.4165 (2)	0.124 (3)
N1	0.8519 (3)	0.7722 (3)	0.43379 (8)	0.0500 (7)
N2	0.9537 (3)	0.8133 (3)	0.46412 (8)	0.0461 (6)
C1	1.0099 (4)	0.7300 (4)	0.46704 (11)	0.0578 (9)
H1	1.0802	0.7448	0.4860	0.069*
C2	0.8366 (4)	0.6570 (4)	0.41560 (10)	0.0501 (8)
C3	0.6329 (4)	0.6782 (5)	0.36973 (12)	0.0615 (9)
H3A	0.5323	0.6158	0.3613	0.074*
H3B	0.6313	0.7208	0.3951	0.074*
C4	0.7119 (5)	0.8003 (5)	0.33947 (13)	0.0679 (11)
H4A	0.8032	0.8758	0.3508	0.082*
H4B	0.7351	0.7613	0.3163	0.082*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Cu1	0.0332 (3)	0.0332 (3)	0.0350 (4)	0.01660 (15)	0.000	0.000
Cl1	0.0537 (6)	0.0537 (6)	0.1003 (14)	0.0269 (3)	0.000	0.000
S1	0.0854 (8)	0.0764 (7)	0.0679 (7)	0.0548 (6)	−0.0153 (5)	−0.0153 (5)
S2	0.0585 (6)	0.0671 (6)	0.0537 (6)	0.0292 (5)	−0.0048 (4)	−0.0096 (4)
O1	0.101 (3)	0.073 (2)	0.152 (4)	0.045 (2)	0.015 (3)	−0.023 (2)
O2	0.140 (4)	0.140 (4)	0.090 (5)	0.070 (2)	0.000	0.000
N1	0.0441 (15)	0.0547 (17)	0.0504 (16)	0.0242 (13)	−0.0014 (12)	−0.0007 (13)
N2	0.0424 (14)	0.0526 (16)	0.0430 (14)	0.0237 (12)	0.0009 (11)	0.0021 (12)
C1	0.063 (2)	0.067 (2)	0.053 (2)	0.040 (2)	−0.0060 (17)	−0.0057 (17)
C2	0.0449 (17)	0.059 (2)	0.0434 (17)	0.0241 (16)	0.0067 (13)	0.0052 (15)
C3	0.051 (2)	0.068 (2)	0.062 (2)	0.0271 (19)	−0.0115 (17)	−0.0019 (19)
C4	0.060 (2)	0.073 (3)	0.075 (3)	0.036 (2)	−0.004 (2)	−0.001 (2)

Geometric parameters (Å, °)

Cu1—N2i	2.149 (3)	S2—C2	1.748 (4)
Cu1—N2	2.149 (3)	S2—C3	1.807 (4)
Cu1—N2ii	2.149 (3)	N1—C2	1.298 (4)
Cu1—N2iii	2.149 (3)	N1—N2	1.386 (4)
Cu1—N2iv	2.149 (3)	N2—C1	1.286 (4)
Cu1—N2v	2.149 (3)	C1—H1	0.9300
Cl1—O1	1.409 (4)	C3—C4	1.523 (6)
Cl1—O1vi	1.409 (4)	C3—H3A	0.9700
Cl1—O1vii	1.409 (4)	C3—H3B	0.9700
Cl1—O2	1.463 (8)	C4—C4viii	1.494 (8)
S1—C1	1.702 (4)	C4—H4A	0.9700
S1—C2	1.731 (4)	C4—H4B	0.9700
N2i—Cu1—N2	91.39 (10)	C2—N1—N2	110.8 (3)
N2i—Cu1—N2ii	91.40 (10)	C1—N2—N1	113.1 (3)
N2—Cu1—N2ii	91.39 (10)	C1—N2—Cu1	127.7 (2)
N2i—Cu1—N2iii	88.61 (10)	N1—N2—Cu1	119.2 (2)
N2—Cu1—N2iii	88.61 (10)	N2—C1—S1	114.9 (3)
N2ii—Cu1—N2iii	179.998 (1)	N2—C1—H1	122.6
N2i—Cu1—N2iv	88.61 (10)	S1—C1—H1	122.6
N2—Cu1—N2iv	179.999 (2)	N1—C2—S1	114.7 (3)
N2ii—Cu1—N2iv	88.61 (10)	N1—C2—S2	125.9 (3)
N2iii—Cu1—N2iv	91.39 (10)	S1—C2—S2	119.4 (2)
N2i—Cu1—N2v	179.999 (1)	C4—C3—S2	112.3 (3)
N2—Cu1—N2v	88.61 (10)	C4—C3—H3A	109.1
N2ii—Cu1—N2v	88.60 (10)	S2—C3—H3A	109.1
N2iii—Cu1—N2v	91.39 (10)	C4—C3—H3B	109.1
N2iv—Cu1—N2v	91.39 (10)	S2—C3—H3B	109.1
O1—Cl1—O1vi	112.77 (18)	H3A—C3—H3B	107.9
O1—Cl1—O1vii	112.77 (18)	C4viii—C4—C3	111.9 (4)
O1vi—Cl1—O1vii	112.77 (18)	C4viii—C4—H4A	109.2
O1—Cl1—O2	105.9 (2)	C3—C4—H4A	109.2
O1vi—Cl1—O2	105.9 (2)	C4viii—C4—H4B	109.2
O1vii—Cl1—O2	105.9 (2)	C3—C4—H4B	109.2
C1—S1—C2	86.55 (18)	H4A—C4—H4B	107.9
C2—S2—C3	101.18 (18)
C2—N1—N2—C1	0.6 (4)	Cu1—N2—C1—S1	179.51 (16)
C2—N1—N2—Cu1	−179.3 (2)	C2—S1—C1—N2	0.1 (3)
N2i—Cu1—N2—C1	84.4 (4)	N2—N1—C2—S1	−0.6 (4)
N2ii—Cu1—N2—C1	175.8 (3)	N2—N1—C2—S2	179.7 (2)
N2iii—Cu1—N2—C1	−4.2 (3)	C1—S1—C2—N1	0.3 (3)
N2v—Cu1—N2—C1	−95.6 (4)	C1—S1—C2—S2	−179.9 (2)
N2i—Cu1—N2—N1	−95.76 (17)	C3—S2—C2—N1	−0.8 (4)
N2ii—Cu1—N2—N1	−4.3 (2)	C3—S2—C2—S1	179.4 (2)
N2iii—Cu1—N2—N1	175.7 (2)	C2—S2—C3—C4	93.0 (3)
N2v—Cu1—N2—N1	84.24 (17)	S2—C3—C4—C4viii	165.9 (4)
N1—N2—C1—S1	−0.4 (4)

Symmetry codes: (i) −y+2, x−y+1, z; (ii) −x+y+1, −x+2, z; (iii) x−y+1, x, −z+1; (iv) −x+2, −y+2, −z+1; (v) y, −x+y+1, −z+1; (vi) −x+y, −x+1, z; (vii) −y+1, x−y+1, z; (viii) −x+4/3, −y+5/3, −z+2/3.