catena-Poly[[bis­(nitrato-κ² O,O′)copper(II)]-μ-2,2′-(ethane-1,2-diyldithio)di-1,3,4-thia­diazole-κ² N ⁴:N ^4′]

Abstract

In the title compound, [Cu(NO₃)₂(C₆H₆N₄S₄)]_n, the Cu^II 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 Cu^II 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.

Related literature

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

Crystal data

• [Cu(NO₃)₂(C₆H₆N₄S₄)]

• M _r = 449.95

• Triclinic,

• a = 5.2143 (8) Å

• b = 7.0214 (10) Å

• c = 10.6476 (16) Å

• α = 105.144 (2)°

• β = 100.000 (2)°

• γ = 93.958 (2)°

• V = 367.88 (9) ų

• Z = 1

• Mo Kα radiation

• μ = 2.09 mm⁻¹

• T = 296 (2) K

• 0.48 × 0.29 × 0.04 mm

Data collection

• Bruker SMART CCD area-detector diffractometer

• Absorption correction: multi-scan (SADABS; Bruker, 1997 ▶) T _min = 0.432, T _max = 0.924

• 1983 measured reflections

• 1336 independent reflections

• 1273 reflections with I > 2σ(I)

• R _int = 0.020

Refinement

• R[F ² > 2σ(F ²)] = 0.058

• wR(F ²) = 0.173

• S = 1.05

• 1336 reflections

• 110 parameters

• 1 restraint

• H-atom parameters constrained

• Δρ_max = 1.86 e Å⁻³

• Δρ_min = −0.50 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: SHELX97 (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

Table 1. Selected geometric parameters (Å, °).

Cu1—O1	2.588 (4)
Cu1—O3	1.971 (3)
Cu1—N2	2.007 (4)

O1—Cu1—O3	54.74 (14)
N2—Cu1—O3	89.02 (15)
O1—Cu1—O3i	125.26 (14)

Symmetry code: (i) .

Table 2. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1A⋯O1ii	0.93	2.49	3.083 (6)	122

Symmetry code: (ii) .

supplementary crystallographic information

Comment

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 C_i 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).

Experimental

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

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),

Figures

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).

Fig. 2.

A view of the polymeric chain in the title compound.

Fig. 3.

A view of the two-dimensional network, indicating the S···O interactions by dashed lines.

Fig. 4.

A view of the compound packing down the b axis.

Crystal data

[Cu(NO3)2(C6H6N4S4)]	Z = 1
Mr = 449.95	F(000) = 225
Triclinic, P1	Dx = 2.031 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 5.2143 (8) Å	Cell parameters from 1855 reflections
b = 7.0214 (10) Å	θ = 3.0–29.2°
c = 10.6476 (16) Å	µ = 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

Bruker SMART CCD area-detector diffractometer	1336 independent reflections
Radiation source: fine-focus sealed tube	1273 reflections with I > 2σ(I)
graphite	Rint = 0.020
phi and ω scans	θmax = 25.5°, θmin = 3.0°
Absorption correction: multi-scan (SADABS; Bruker, 1997)	h = −6→3
Tmin = 0.432, Tmax = 0.924	k = −8→8
1983 measured reflections	l = −11→12

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)] = 0.058	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.173	H-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 parameters	Δρmax = 1.86 e Å−3
1 restraint	Δρmin = −0.50 e Å−3

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
C3	0.6301 (17)	0.4878 (11)	0.4823 (9)	0.0366 (14)	0.499 (9)
H3A	0.7602	0.5921	0.5422	0.044*	0.499 (9)
H3B	0.6243	0.4972	0.3926	0.044*	0.499 (9)
C3'	0.4746 (17)	0.4163 (12)	0.5298 (9)	0.0366 (14)	0.501 (9)
H3B'	0.2988	0.3485	0.4917	0.044*	0.501 (9)
H3A'	0.4890	0.4680	0.6249	0.044*	0.501 (9)
Cu1	0.0000	0.0000	0.0000	0.0312 (3)
S1	0.6997 (3)	−0.12017 (17)	0.26648 (12)	0.0406 (4)
S2	0.7207 (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)
O3	0.1101 (7)	−0.2255 (5)	−0.1244 (3)	0.0417 (8)
N1	−0.0491 (8)	−0.3829 (5)	−0.1353 (4)	0.0385 (9)
N2	0.3011 (8)	−0.0167 (6)	0.1409 (4)	0.0345 (8)
N3	0.3672 (7)	0.1312 (5)	0.2605 (4)	0.0370 (9)
C1	0.4554 (9)	−0.1563 (6)	0.1321 (4)	0.0355 (10)
H1A	0.4330	−0.2663	0.0583	0.043*
C2	0.5716 (9)	0.0958 (6)	0.3353 (4)	0.0347 (10)

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
C3	0.036 (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)
Cu1	0.0330 (5)	0.0269 (5)	0.0289 (5)	0.0069 (3)	0.0028 (3)	0.0009 (3)
S1	0.0423 (7)	0.0364 (7)	0.0419 (7)	0.0170 (5)	0.0040 (5)	0.0086 (5)
S2	0.0479 (8)	0.0415 (7)	0.0367 (7)	0.0153 (5)	−0.0092 (5)	0.0016 (5)
O1	0.062 (2)	0.049 (2)	0.059 (2)	0.0151 (17)	0.020 (2)	0.0183 (17)
O2	0.088 (3)	0.0380 (19)	0.053 (2)	0.024 (2)	−0.002 (2)	−0.0102 (17)
O3	0.0405 (18)	0.0406 (17)	0.0388 (17)	0.0109 (14)	0.0058 (14)	0.0017 (14)
N1	0.049 (2)	0.0291 (17)	0.0304 (18)	0.0149 (16)	−0.0031 (17)	0.0004 (14)
N2	0.0384 (19)	0.0289 (17)	0.0321 (19)	0.0068 (15)	0.0039 (15)	0.0025 (14)
N3	0.039 (2)	0.0306 (19)	0.035 (2)	0.0102 (17)	−0.0015 (17)	0.0016 (16)
C1	0.039 (2)	0.032 (2)	0.033 (2)	0.0098 (18)	0.0062 (18)	0.0034 (17)
C2	0.037 (2)	0.0291 (19)	0.035 (2)	0.0078 (18)	0.0048 (19)	0.0054 (17)

Geometric parameters (Å, °)

C3—C3i	1.479 (17)	Cu1—N2ii	2.007 (4)
C3—S2	1.866 (7)	S1—C1	1.693 (5)
C3—H3A	0.9700	S1—C2	1.735 (4)
C3—H3B	0.9700	S2—C2	1.743 (4)
C3'—C3'i	1.504 (17)	O1—N1	1.237 (6)
C3'—S2	1.863 (7)	O2—N1	1.209 (5)
C3'—H3B'	0.9700	O3—N1	1.303 (5)
C3'—H3A'	0.9700	N2—C1	1.305 (6)
Cu1—O1	2.588 (4)	N2—N3	1.389 (5)
Cu1—O3ii	1.971 (3)	N3—C2	1.295 (6)
Cu1—O3	1.971 (3)	C1—H1A	0.9300
Cu1—N2	2.007 (4)
C3i—C3—S2	108.9 (7)	C2—S2—C3'	100.6 (3)
C3i—C3—H3A	109.9	C2—S2—C3	99.5 (3)
S2—C3—H3A	109.9	N1—O3—Cu1	107.4 (2)
C3i—C3—H3B	109.9	O2—N1—O1	123.7 (5)
S2—C3—H3B	109.9	O2—N1—O3	119.2 (4)
H3A—C3—H3B	108.3	O1—N1—O3	117.1 (4)
C3'i—C3'—S2	108.5 (7)	O1—Cu1—O3	54.74 (14)
C3'i—C3'—H3B'	110.0	N2—Cu1—O3	89.02 (15)
S2—C3'—H3B'	110.0	O1—Cu1—O3ii	125.26 (14)
C3'i—C3'—H3A'	110.0	C1—N2—N3	113.3 (4)
S2—C3'—H3A'	110.0	C1—N2—Cu1	126.2 (3)
H3B'—C3'—H3A'	108.4	N3—N2—Cu1	120.5 (3)
O3ii—Cu1—O3	180.0	C2—N3—N2	110.7 (4)
O3ii—Cu1—N2	90.98 (15)	N2—C1—S1	114.2 (3)
O3—Cu1—N2	89.02 (15)	N2—C1—H1A	122.9
O3ii—Cu1—N2ii	89.02 (15)	S1—C1—H1A	122.9
O3—Cu1—N2ii	90.98 (15)	N3—C2—S1	114.8 (3)
N2—Cu1—N2ii	180.0	N3—C2—S2	126.5 (3)
C1—S1—C2	87.1 (2)	S1—C2—S2	118.7 (3)
C3'i—C3'—S2—C2	−83.9 (9)	Cu1—N2—N3—C2	−177.8 (3)
C3'i—C3'—S2—C3	7.8 (7)	N3—N2—C1—S1	−1.2 (5)
C3i—C3—S2—C2	87.1 (9)	Cu1—N2—C1—S1	177.3 (2)
C3i—C3—S2—C3'	−7.9 (7)	C2—S1—C1—N2	0.9 (4)
N2—Cu1—O3—N1	103.2 (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—O2	171.2 (4)	C1—S1—C2—N3	−0.4 (4)
Cu1—O3—N1—O1	−9.2 (4)	C1—S1—C2—S2	178.7 (3)
O3ii—Cu1—N2—C1	171.9 (4)	C3'—S2—C2—N3	9.6 (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—N3	170.3 (3)	C3—S2—C2—S1	153.1 (3)
C1—N2—N3—C2	0.8 (6)

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x, −y, −z.

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1A···O1iii	0.93	2.49	3.083 (6)	122

Symmetry codes: (iii) x+1, y, z.