Bis(2,2'-bi-1H-imidazole-κN,N)bis-(dimethyl sulfoxide-κO)copper(II) bis-(tetra-fluoridoborate).

In the title copper(II) salt, [Cu(C(6)H(6)N(4))(2)(C(2)H(6)OS)(2)](BF(4))(2), the Jahn-Teller distorted octa-hedral coordination sphere of copper is formed from four 2,2'-bi-1H-imidazole N atoms and two dimethyl sulfoxide O atoms. The Cu atom lies on a center of inversion. N-H⋯O and N-H⋯F hydrogen bonds give rise to a one-dimensional structure. The BF(4) (-) anion is disordered over two sites in a 0.671 (10):0.329 (10) ratio.

Related literature

Supra­molecular complexes containing H2biim (H2biim = 2,2′-biimidazole) have been applied widely in mol­ecular catalysis, photoelectric conversion materials and mol­ecular recognition, see: Ding et al. (2005 ▶). For the effect of the coordination bonds, inter­molecular hydrogen bonds and π–π packing inter­actions on the mol­ecular arrangement, see: Burrows (2004 ▶); Dai et al. (2009 ▶). For related structures, see: Jin et al. (2010 ▶); Aminou et al. (2004 ▶); Gruia et al. (2007 ▶); Yang et al. (2008 ▶). For Cu—O coordination bond lengths, see: Tao et al. (2002 ▶).

Experimental

Crystal data

[Cu(C6H6N4)2(C2H6OS)2](BF4)2

M = 661.71

Triclinic,

a = 7.059 (1) Å

b = 10.0721 (13) Å

c = 10.3669 (15) Å

α = 113.436 (2)°

β = 96.860 (1)°

γ = 92.000 (1)°

V = 668.68 (16) Å3

Z = 1

Mo Kα radiation

μ = 1.06 mm−1

T = 298 K

0.36 × 0.32 × 0.20 mm

Data collection

Bruker SMART CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2007 ▶) T min = 0.701, T max = 0.816

3418 measured reflections

2293 independent reflections

1885 reflections with I > 2σ(I)

R int = 0.023

Refinement

R[F 2 > 2σ(F 2)] = 0.040

wR(F 2) = 0.111

S = 1.03

2293 reflections

209 parameters

H-atom parameters constrained

Δρmax = 0.34 e Å−3

Δρmin = −0.32 e Å−3

Data collection: SMART (Bruker, 2007 ▶); cell refinement: SAINT-Plus (Bruker, 2007 ▶); data reduction: SAINT-Plus; 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.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810031922/ng5003sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810031922/ng5003Isup2.hkl

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

[Cu(C6H6N4)2(C2H6OS)2](BF4)2	Z = 1
Mr = 661.71	F(000) = 335
Triclinic, P1	Dx = 1.643 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.059 (1) Å	Cell parameters from 2039 reflections
b = 10.0721 (13) Å	θ = 2.2–27.1°
c = 10.3669 (15) Å	µ = 1.06 mm−1
α = 113.436 (2)°	T = 298 K
β = 96.860 (1)°	Block, green
γ = 92.000 (1)°	0.36 × 0.32 × 0.20 mm
V = 668.68 (16) Å3

Bruker SMART CCD area-detector diffractometer	2293 independent reflections
Radiation source: fine-focus sealed tube	1885 reflections with I > 2σ(I)
graphite	Rint = 0.023
phi and ω scans	θmax = 25.0°, θmin = 2.2°
Absorption correction: multi-scan SADABS	h = −8→8
Tmin = 0.701, Tmax = 0.816	k = −11→11
3418 measured reflections	l = −12→11

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.040	H-atom parameters constrained
wR(F2) = 0.111	w = 1/[σ2(Fo2) + (0.0545P)2 + 0.5099P] where P = (Fo2 + 2Fc2)/3
S = 1.03	(Δ/σ)max = 0.001
2293 reflections	Δρmax = 0.34 e Å−3
209 parameters	Δρmin = −0.32 e Å−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.048 (5)

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.

	x	y	z	Uiso*/Ueq	Occ. (<1)
Cu1	0.5000	0.5000	0.5000	0.0390 (2)
F1	0.7595 (5)	0.2780 (3)	0.7673 (4)	0.1074 (11)
F2	0.7494 (11)	0.2364 (7)	0.9569 (6)	0.133 (3)	0.671 (10)
F3	0.8593 (16)	0.0735 (12)	0.7739 (12)	0.131 (5)	0.671 (10)
F4	0.5500 (11)	0.1020 (9)	0.7667 (9)	0.111 (3)	0.671 (10)
F2'	0.676 (3)	0.0585 (13)	0.6485 (15)	0.153 (7)	0.329 (10)
F3'	0.577 (2)	0.1641 (18)	0.8495 (19)	0.114 (7)	0.329 (10)
F4'	0.873 (3)	0.121 (3)	0.844 (3)	0.137 (10)	0.329 (10)
N1	0.3310 (3)	0.6573 (3)	0.5939 (3)	0.0400 (6)
N2	0.0728 (4)	0.7101 (3)	0.6960 (3)	0.0487 (7)
H2	−0.0297	0.7002	0.7297	0.058*
N3	0.3261 (3)	0.3835 (3)	0.5650 (3)	0.0392 (6)
N4	0.0623 (4)	0.3776 (3)	0.6562 (3)	0.0472 (7)
H4	−0.0392	0.4047	0.6943	0.057*
O1	0.2552 (3)	0.4077 (3)	0.2573 (2)	0.0501 (6)
S1	0.37073 (11)	0.34825 (10)	0.13515 (8)	0.0454 (3)
B2	0.7268 (7)	0.1654 (5)	0.8039 (6)	0.0657 (13)
C1	0.1883 (4)	0.6060 (4)	0.6387 (3)	0.0378 (7)
C2	0.1466 (5)	0.8336 (4)	0.6911 (4)	0.0585 (10)
H2A	0.0972	0.9235	0.7252	0.070*
C3	0.3060 (5)	0.8018 (4)	0.6273 (4)	0.0526 (9)
H3	0.3849	0.8663	0.6093	0.063*
C4	0.1839 (4)	0.4588 (4)	0.6222 (3)	0.0377 (7)
C5	0.1283 (5)	0.2444 (5)	0.6198 (4)	0.0579 (10)
H5	0.0720	0.1651	0.6303	0.069*
C6	0.2919 (5)	0.2493 (4)	0.5652 (4)	0.0516 (9)
H6	0.3691	0.1732	0.5329	0.062*
C7	0.2567 (7)	0.3869 (5)	−0.0058 (4)	0.0692 (11)
H7A	0.1224	0.3562	−0.0226	0.104*
H7B	0.3121	0.3360	−0.0902	0.104*
H7C	0.2735	0.4895	0.0189	0.104*
C8	0.3115 (7)	0.1570 (5)	0.0606 (5)	0.0762 (13)
H8B	0.3505	0.1193	0.1304	0.114*
H8C	0.3765	0.1122	−0.0202	0.114*
H8A	0.1756	0.1363	0.0314	0.114*

	U11	U22	U33	U12	U13	U23
Cu1	0.0288 (3)	0.0399 (4)	0.0538 (4)	0.0093 (2)	0.0220 (2)	0.0197 (3)
F1	0.110 (2)	0.0760 (19)	0.165 (3)	0.0132 (16)	0.069 (2)	0.066 (2)
F2	0.163 (6)	0.137 (5)	0.080 (4)	−0.018 (4)	0.039 (4)	0.020 (3)
F3	0.130 (10)	0.099 (7)	0.197 (12)	0.083 (7)	0.096 (10)	0.067 (7)
F4	0.084 (4)	0.102 (6)	0.142 (7)	−0.037 (4)	−0.005 (5)	0.053 (5)
F2'	0.180 (15)	0.096 (9)	0.129 (11)	0.004 (8)	0.030 (10)	−0.013 (7)
F3'	0.095 (13)	0.124 (13)	0.143 (16)	0.020 (10)	0.085 (13)	0.056 (11)
F4'	0.098 (13)	0.120 (17)	0.18 (2)	0.012 (11)	−0.044 (14)	0.060 (15)
N1	0.0305 (13)	0.0407 (15)	0.0455 (15)	0.0044 (11)	0.0131 (11)	0.0119 (12)
N2	0.0365 (14)	0.0599 (19)	0.0431 (16)	0.0132 (13)	0.0190 (12)	0.0095 (14)
N3	0.0332 (13)	0.0446 (15)	0.0454 (15)	0.0063 (11)	0.0135 (11)	0.0217 (12)
N4	0.0333 (14)	0.066 (2)	0.0450 (16)	−0.0008 (13)	0.0155 (12)	0.0237 (14)
O1	0.0525 (14)	0.0504 (14)	0.0450 (13)	0.0066 (11)	0.0263 (11)	0.0113 (11)
S1	0.0382 (5)	0.0576 (6)	0.0371 (5)	0.0021 (4)	0.0142 (3)	0.0134 (4)
B2	0.051 (3)	0.052 (3)	0.105 (4)	0.009 (2)	0.034 (3)	0.037 (3)
C1	0.0261 (14)	0.0506 (19)	0.0314 (15)	0.0073 (13)	0.0100 (12)	0.0092 (14)
C2	0.056 (2)	0.048 (2)	0.059 (2)	0.0190 (18)	0.0190 (18)	0.0050 (18)
C3	0.050 (2)	0.042 (2)	0.064 (2)	0.0095 (15)	0.0198 (17)	0.0154 (17)
C4	0.0261 (14)	0.056 (2)	0.0328 (16)	0.0029 (13)	0.0103 (12)	0.0181 (14)
C5	0.055 (2)	0.065 (3)	0.065 (2)	−0.0041 (19)	0.0159 (18)	0.037 (2)
C6	0.050 (2)	0.051 (2)	0.063 (2)	0.0090 (16)	0.0183 (17)	0.0298 (18)
C7	0.089 (3)	0.070 (3)	0.053 (2)	0.015 (2)	0.015 (2)	0.026 (2)
C8	0.100 (3)	0.054 (3)	0.075 (3)	0.020 (2)	0.037 (3)	0.018 (2)

Cu1—N1	2.016 (2)	N4—H4	0.8600
Cu1—N1i	2.016 (2)	N4—C4	1.335 (4)
Cu1—N3i	2.016 (2)	N4—C5	1.357 (5)
Cu1—N3	2.016 (2)	O1—S1	1.519 (2)
Cu1—O1	2.678 (2)	S1—C7	1.769 (4)
F1—B2	1.351 (5)	S1—C8	1.779 (4)
F2—B2	1.443 (8)	C1—C4	1.422 (5)
F3—B2	1.316 (9)	C2—H2A	0.9300
F4—B2	1.322 (8)	C2—C3	1.356 (5)
F2'—B2	1.529 (14)	C3—H3	0.9300
F3'—B2	1.213 (13)	C5—H5	0.9300
F4'—B2	1.23 (2)	C5—C6	1.353 (5)
N1—C1	1.328 (4)	C6—H6	0.9300
N1—C3	1.378 (4)	C7—H7A	0.9600
N2—H2	0.8600	C7—H7B	0.9600
N2—C1	1.340 (4)	C7—H7C	0.9600
N2—C2	1.353 (5)	C8—H8B	0.9600
N3—C4	1.331 (4)	C8—H8C	0.9600
N3—C6	1.365 (4)	C8—H8A	0.9600
F1—B2—F2	102.1 (5)	N3—C6—H6	125.3
F1—B2—F2'	92.2 (7)	N4—C4—C1	132.0 (3)
F2—B2—F2'	165.0 (7)	N4—C5—H5	126.6
F3—B2—F1	113.0 (7)	O1—S1—C7	107.35 (18)
F3—B2—F2	106.0 (7)	O1—S1—C8	104.93 (18)
F3—B2—F4	113.7 (8)	S1—O1—Cu1	107.75 (12)
F3—B2—F2'	71.8 (8)	S1—C7—H7A	109.5
F4—B2—F1	115.9 (6)	S1—C7—H7B	109.5
F4—B2—F2	104.4 (6)	S1—C7—H7C	109.5
F4—B2—F2'	64.6 (8)	S1—C8—H8B	109.5
F3'—B2—F1	114.3 (9)	S1—C8—H8C	109.5
F3'—B2—F2	67.7 (10)	S1—C8—H8A	109.5
F3'—B2—F3	132.6 (11)	C1—N1—Cu1	111.0 (2)
F3'—B2—F4	37.9 (7)	C1—N1—C3	106.2 (3)
F3'—B2—F2'	102.4 (11)	C1—N2—H2	126.1
F3'—B2—F4'	123.6 (18)	C1—N2—C2	107.7 (3)
F4'—B2—F1	114.2 (15)	C2—N2—H2	126.1
F4'—B2—F2	75.5 (12)	C2—C3—N1	108.3 (3)
F4'—B2—F3	31.1 (11)	C2—C3—H3	125.9
F4'—B2—F4	128.6 (14)	C3—N1—Cu1	142.8 (2)
F4'—B2—F2'	102.9 (11)	C3—C2—H2A	126.3
N1—Cu1—N1i	180.00 (16)	C4—N3—Cu1	111.3 (2)
N1i—Cu1—N3i	82.24 (10)	C4—N3—C6	105.6 (3)
N1i—Cu1—N3	97.76 (10)	C4—N4—H4	126.3
N1—Cu1—N3i	97.76 (10)	C4—N4—C5	107.5 (3)
N1—Cu1—N3	82.24 (10)	C5—N4—H4	126.3
N1—Cu1—O1	90.17 (9)	C5—C6—N3	109.4 (3)
N1i—Cu1—O1	89.83 (9)	C5—C6—H6	125.3
N1—C1—N2	110.5 (3)	C6—N3—Cu1	143.0 (2)
N1—C1—C4	118.0 (3)	C6—C5—N4	106.7 (3)
N1—C3—H3	125.9	C6—C5—H5	126.6
N2—C1—C4	131.6 (3)	C7—S1—C8	98.8 (2)
N2—C2—H2A	126.3	H7A—C7—H7B	109.5
N2—C2—C3	107.3 (3)	H7A—C7—H7C	109.5
N3i—Cu1—N3	180.0	H7B—C7—H7C	109.5
N3—Cu1—O1	87.32 (9)	H8B—C8—H8C	109.5
N3i—Cu1—O1	92.68 (9)	H8B—C8—H8A	109.5
N3—C4—N4	110.9 (3)	H8C—C8—H8A	109.5
N3—C4—C1	117.1 (3)
Cu1—N1—C1—N2	−177.6 (2)	N3—Cu1—N1—C3	176.9 (4)
Cu1—N1—C1—C4	3.6 (3)	N3i—Cu1—N1—C3	−3.1 (4)
Cu1—N1—C3—C2	177.8 (3)	N3i—Cu1—N3—C4	−68 (100)
Cu1—N3—C4—N4	175.87 (19)	N3i—Cu1—N3—C6	107 (100)
Cu1—N3—C4—C1	−5.3 (3)	N3—Cu1—O1—S1	−129.93 (14)
Cu1—N3—C6—C5	−173.6 (3)	N3i—Cu1—O1—S1	50.07 (14)
Cu1—O1—S1—C7	−146.23 (18)	N4—C5—C6—N3	−1.1 (4)
Cu1—O1—S1—C8	109.39 (19)	O1—Cu1—N1—C1	82.3 (2)
N1i—Cu1—N1—C1	−142 (100)	O1—Cu1—N1—C3	−95.8 (4)
N1i—Cu1—N1—C3	40 (100)	O1—Cu1—N3—C4	−85.0 (2)
N1i—Cu1—N3—C4	−174.5 (2)	O1—Cu1—N3—C6	89.6 (4)
N1—Cu1—N3—C4	5.5 (2)	C1—N1—C3—C2	−0.4 (4)
N1i—Cu1—N3—C6	0.1 (4)	C1—N2—C2—C3	1.3 (4)
N1—Cu1—N3—C6	−179.9 (4)	C2—N2—C1—N1	−1.6 (4)
N1—Cu1—O1—S1	147.85 (14)	C2—N2—C1—C4	177.0 (3)
N1i—Cu1—O1—S1	−32.15 (14)	C3—N1—C1—N2	1.2 (4)
N1—C1—C4—N3	1.2 (4)	C3—N1—C1—C4	−177.6 (3)
N1—C1—C4—N4	179.7 (3)	C4—N3—C6—C5	1.2 (4)
N2—C1—C4—N3	−177.3 (3)	C4—N4—C5—C6	0.7 (4)
N2—C1—C4—N4	1.3 (6)	C5—N4—C4—N3	0.0 (4)
N2—C2—C3—N1	−0.5 (4)	C5—N4—C4—C1	−178.6 (3)
N3i—Cu1—N1—C1	175.1 (2)	C6—N3—C4—N4	−0.7 (4)
N3—Cu1—N1—C1	−4.9 (2)	C6—N3—C4—C1	178.1 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O1ii	0.86	1.94	2.745 (4)	155.
N4—H4···F1iii	0.86	2.26	2.874 (4)	128.
N4—H4···O1ii	0.86	2.40	3.127 (4)	142.

Table 1

Selected bond lengths (Å)

Cu1—N1	2.016 (2)
Cu1—N3	2.016 (2)
Cu1—O1	2.678 (2)

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯O1ii	0.86	1.94	2.745 (4)	155
N4—H4⋯F1iii	0.86	2.26	2.874 (4)	128
N4—H4⋯O1ii	0.86	2.40	3.127 (4)	142

Symmetry codes: (ii) ; (iii) .