Bis[2-(1H-benzotriazol-1-yl)acetonitrile-κN3]dibromidocopper(II)

Wang, W.

doi:10.1107/S1600536808019260

metal-organic compounds

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Volume 64| Part 8| August 2008| Page m998

doi:10.1107/S1600536808019260

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Bis[2-(1H-benzotriazol-1-yl)acetonitrile-κN³]dibromidocopper(II)

Wei Wang ^a ^*

^aOrdered Matter Science Research Center, Southeast University, Nanjing 210096, People's Republic of China
^*Correspondence e-mail: seuwangwei@gmail.com

(Received 18 June 2008; accepted 25 June 2008; online 5 July 2008)

In the title complex, [CuBr₂(C₈H₆N₄)₂], the Cu^II atom is located on an inversion centre and the asymmetric unit comprises one half-molecule. The Cu atom is coordinated by two Br ions and two N atoms in approximately square-planar geometry. In the crystal structure, intermolecular C—H⋯Br hydrogen bonds and π–π interactions between benzotriazole rings (centroid–centroid distance = 3.651 Å) generate a three-dimensional network.

Related literature

For the synthesis of the organic ligand, see: Danan et al. (1997 ); Xu & Ye (2007 ). For the structure of a similar complex, see: Hang & Ye (2008 ).

Experimental

Crystal data

[CuBr₂(C₈H₆N₄)₂]
M_r = 539.70
Triclinic, $[P \overline 1]$
a = 7.9034 (16) Å
b = 8.1434 (16) Å
c = 8.7849 (18) Å
α = 116.04 (3)°
β = 105.86 (3)°
γ = 100.74 (3)°
V = 456.9 (3) Å³
Z = 1
Mo Kα radiation
μ = 5.59 mm⁻¹
T = 293 (2) K
0.20 × 0.12 × 0.12 mm

Data collection

Rigaku Mercury2 diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.702, T_max = 1.000 (expected range = 0.359–0.511)
4726 measured reflections
2095 independent reflections
1809 reflections with I > 2σ(I)
R_int = 0.037

Refinement

R[F² > 2σ(F²)] = 0.067
wR(F²) = 0.218
S = 1.06
2095 reflections
124 parameters
H-atom parameters constrained
Δρ_max = 3.13 e Å⁻³
Δρ_min = −1.39 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

Br1—Cu1	2.3385 (10)
Cu1—N3	2.012 (5)

N3—Cu1—Br1	89.46 (16)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C7—H7A⋯Br1ⁱ	0.97	2.79	3.744 (7)	168
C7—H7B⋯Br1ⁱⁱ	0.97	2.91	3.421 (7)	114
Symmetry codes: (i) -x, -y-1, -z; (ii) x, y, z-1.

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear; data reduction: CrystalClear; 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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808019260/kp2178sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808019260/kp2178Isup2.hkl

checkCIF report

Comment top

Recently, the crystal structure of 2-(1H-benzo[d][1,2,3] triazol-1-yl)acetonitrile (Xu et al. (2007)) and its Zn complex [Hang et al. (2008)] have been reported successively. Though adopting the same ligand, the structure of the title complex is quite different from the Zn analogue due to the different synthesis route. The precipitate of the title compound is obtained by mixing the ethanol solution of ligand and a water solution of CuBr₂. Under this condition, the cyano group in the title compound does not hydrolyse nor coordinate to Cu^II. Cu^II is coordinated by two nitrogen atoms from the benzotriazole rings and two terminal bromide anions in an almost square planar geometry (Fig. 1). The intermolecular C—H···Br hydrogen bonding interactions and π···π stacking between benzotriazole rings generate the three-dimensional network (Fig. 2); Cg···Cgⁱ distance is 3.651 Å, (symmetry code: -1-x,-1-y,-z; –x,-1-y,-z).

Related literature top

For the synthesis of the organic ligand, see: Danan et al. (1997); Xu & Ye (2007). For the synthesis of a similar complex, see: Hang & Ye (2008).

Experimental top

The ligand, 2-(1H-benzo[d][1,2,3]triazol-1-yl)acetonitrile, was synthesized by the reaction of benzotriazole and bromoacetonitrile according to the procedure described in the literature [Danan et al. (1997)].

2-(1H-benzotriazol-1-yl)acetonitrile (0.32 g,2 mmol) was dissolved in 5 mL ethanol, added into a solution of CuBr₂(0.22 g,1 mmol) which was dissolved in 5 mL water, the mixture was filtered. Crystals suitable for X-ray analysis were obtained after standing the filtrate for 3 days at the room temperature.

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); 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 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the compound with the atomic numbering scheme. Displacement ellipsoids were drawn at the 30% probability level.
	Fig. 2. The crystal packing along b axis with π···π stacking.

Bis[2-(1H-benzotriazol-1-yl)acetonitrile-κN³]dibromidocopper(II) top

Crystal data top

[CuBr₂(C₈H₆N₄)₂]	Z = 1
M_r = 539.70	F(000) = 263
Triclinic, P1	D_x = 1.961 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.9034 (16) Å	Cell parameters from 4665 reflections
b = 8.1434 (16) Å	θ = 6.2–57.6°
c = 8.7849 (18) Å	µ = 5.59 mm⁻¹
α = 116.04 (3)°	T = 293 K
β = 105.86 (3)°	Block, red
γ = 100.74 (3)°	0.20 × 0.12 × 0.12 mm
V = 456.9 (3) Å³

Data collection top

Rigaku Mercury2 diffractometer	2095 independent reflections
Radiation source: fine-focus sealed tube	1809 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.037
Detector resolution: 13.6612 pixels mm^-1	θ_max = 27.5°, θ_min = 3.1°
CCD_Profile_fitting scans	h = −10→10
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −10→10
T_min = 0.702, T_max = 1.000	l = −11→11
4726 measured reflections

Refinement top

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)] = 0.067	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.218	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.1128P)² + 5.2279P] where P = (F_o² + 2F_c²)/3
2095 reflections	(Δ/σ)_max < 0.001
124 parameters	Δρ_max = 3.13 e Å⁻³
0 restraints	Δρ_min = −1.39 e Å⁻³

Crystal data top

[CuBr₂(C₈H₆N₄)₂]	γ = 100.74 (3)°
M_r = 539.70	V = 456.9 (3) Å³
Triclinic, P1	Z = 1
a = 7.9034 (16) Å	Mo Kα radiation
b = 8.1434 (16) Å	µ = 5.59 mm⁻¹
c = 8.7849 (18) Å	T = 293 K
α = 116.04 (3)°	0.20 × 0.12 × 0.12 mm
β = 105.86 (3)°

Data collection top

Rigaku Mercury2 diffractometer	2095 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	1809 reflections with I > 2σ(I)
T_min = 0.702, T_max = 1.000	R_int = 0.037
4726 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.067	0 restraints
wR(F²) = 0.218	H-atom parameters constrained
S = 1.06	Δρ_max = 3.13 e Å⁻³
2095 reflections	Δρ_min = −1.39 e Å⁻³
124 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 > 2σ(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

	x	y	z	U_iso*/U_eq
Br1	0.13948 (13)	−0.20325 (12)	0.56625 (11)	0.0403 (3)
Cu1	0.0000	0.0000	0.5000	0.0170 (3)
C8	−0.2130 (9)	−0.4022 (9)	0.1349 (8)	0.0175 (12)
N4	−0.0651 (9)	−0.1575 (8)	0.1166 (7)	0.0240 (12)
N3	−0.1103 (9)	−0.2050 (8)	0.2291 (7)	0.0222 (12)
N2	−0.3749 (15)	−0.2480 (17)	−0.3869 (13)	0.065 (3)
C7	−0.1043 (11)	−0.3097 (11)	−0.2015 (9)	0.0242 (14)
H7A	−0.0935	−0.4308	−0.2836	0.029*
H7B	0.0128	−0.2042	−0.1526	0.029*
C6	−0.3269 (10)	−0.6762 (10)	−0.1849 (9)	0.0258 (14)
H6A	−0.3384	−0.7258	−0.3064	0.031*
N1	−0.1353 (8)	−0.3207 (8)	−0.0490 (7)	0.0210 (11)
C5	−0.2293 (9)	−0.4777 (9)	−0.0471 (8)	0.0181 (12)
C4	−0.4036 (11)	−0.7908 (11)	−0.1270 (11)	0.0316 (16)
H4A	−0.4675	−0.9237	−0.2119	0.038*
C3	−0.2596 (12)	−0.2759 (12)	−0.3062 (10)	0.0325 (17)
C2	−0.3899 (11)	−0.7159 (11)	0.0551 (11)	0.0297 (15)
H2A	−0.4465	−0.8002	0.0862	0.036*
C1	−0.2947 (10)	−0.5205 (10)	0.1897 (9)	0.0239 (13)
H1A	−0.2860	−0.4712	0.3103	0.029*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0515 (6)	0.0375 (5)	0.0321 (5)	0.0196 (4)	0.0162 (4)	0.0169 (4)
Cu1	0.0271 (6)	0.0117 (5)	0.0069 (5)	0.0051 (4)	0.0055 (4)	0.0022 (4)
C8	0.025 (3)	0.015 (3)	0.008 (3)	0.008 (2)	0.003 (2)	0.003 (2)
N4	0.038 (3)	0.017 (3)	0.011 (2)	0.008 (2)	0.008 (2)	0.005 (2)
N3	0.038 (3)	0.015 (3)	0.011 (2)	0.007 (2)	0.008 (2)	0.006 (2)
N2	0.075 (7)	0.088 (8)	0.037 (5)	0.052 (6)	0.018 (4)	0.031 (5)
C7	0.039 (4)	0.027 (3)	0.017 (3)	0.016 (3)	0.018 (3)	0.014 (3)
C6	0.029 (3)	0.020 (3)	0.012 (3)	0.009 (3)	0.004 (3)	−0.002 (2)
N1	0.035 (3)	0.017 (2)	0.010 (2)	0.010 (2)	0.009 (2)	0.006 (2)
C5	0.021 (3)	0.019 (3)	0.013 (3)	0.009 (2)	0.006 (2)	0.008 (2)
C4	0.030 (4)	0.017 (3)	0.032 (4)	0.004 (3)	0.006 (3)	0.005 (3)
C3	0.049 (5)	0.037 (4)	0.014 (3)	0.021 (4)	0.015 (3)	0.013 (3)
C2	0.028 (3)	0.024 (4)	0.033 (4)	0.006 (3)	0.010 (3)	0.015 (3)
C1	0.029 (3)	0.024 (3)	0.018 (3)	0.010 (3)	0.009 (3)	0.010 (3)

Geometric parameters (Å, º) top

Br1—Cu1	2.3385 (10)	C7—H7B	0.9700
Cu1—N3	2.012 (5)	C6—C4	1.368 (11)
C8—N3	1.379 (8)	C6—C5	1.407 (9)
C8—C1	1.387 (9)	C6—H6A	0.9300
C8—C5	1.395 (8)	N1—C5	1.363 (9)
N4—N3	1.316 (8)	C4—C2	1.402 (11)
N4—N1	1.333 (7)	C4—H4A	0.9300
N2—C3	1.118 (12)	C2—C1	1.383 (10)
C7—N1	1.462 (8)	C2—H2A	0.9300
C7—C3	1.470 (10)	C1—H1A	0.9300
C7—H7A	0.9700

N3—Cu1—Br1	89.46 (16)	N4—N1—C5	111.7 (5)
N3—C8—C1	132.2 (6)	N4—N1—C7	118.6 (6)
N3—C8—C5	106.6 (6)	C5—N1—C7	129.7 (6)
C1—C8—C5	121.2 (6)	N1—C5—C8	104.5 (5)
N3—N4—N1	107.1 (5)	N1—C5—C6	132.8 (6)
N4—N3—C8	110.1 (5)	C8—C5—C6	122.7 (6)
N4—N3—Cu1	118.1 (4)	C6—C4—C2	122.7 (7)
C8—N3—Cu1	131.4 (4)	C6—C4—H4A	118.7
N1—C7—C3	111.1 (6)	C2—C4—H4A	118.7
N1—C7—H7A	109.4	N2—C3—C7	178.4 (10)
C3—C7—H7A	109.4	C1—C2—C4	122.0 (7)
N1—C7—H7B	109.4	C1—C2—H2A	119.0
C3—C7—H7B	109.4	C4—C2—H2A	119.0
H7A—C7—H7B	108.0	C2—C1—C8	116.3 (6)
C4—C6—C5	115.1 (6)	C2—C1—H1A	121.9
C4—C6—H6A	122.5	C8—C1—H1A	121.9
C5—C6—H6A	122.5

N1—N4—N3—C8	−0.5 (8)	N4—N1—C5—C8	−0.4 (7)
N1—N4—N3—Cu1	172.6 (4)	C7—N1—C5—C8	179.9 (7)
C1—C8—N3—N4	−178.7 (7)	N4—N1—C5—C6	179.3 (7)
C5—C8—N3—N4	0.3 (8)	C7—N1—C5—C6	−0.5 (12)
C1—C8—N3—Cu1	9.4 (11)	N3—C8—C5—N1	0.0 (7)
C5—C8—N3—Cu1	−171.6 (5)	C1—C8—C5—N1	179.2 (6)
N3ⁱ—Cu1—N3—N4	−167 (92)	N3—C8—C5—C6	−179.7 (6)
Br1ⁱ—Cu1—N3—N4	59.4 (5)	C1—C8—C5—C6	−0.6 (10)
Br1—Cu1—N3—N4	−120.6 (5)	C4—C6—C5—N1	179.8 (7)
N3ⁱ—Cu1—N3—C8	4 (93)	C4—C6—C5—C8	−0.5 (10)
Br1ⁱ—Cu1—N3—C8	−129.2 (6)	C5—C6—C4—C2	1.3 (11)
Br1—Cu1—N3—C8	50.8 (6)	N1—C7—C3—N2	150 (33)
N3—N4—N1—C5	0.5 (8)	C6—C4—C2—C1	−1.0 (12)
N3—N4—N1—C7	−179.7 (6)	C4—C2—C1—C8	−0.1 (11)
C3—C7—N1—N4	−91.8 (8)	N3—C8—C1—C2	179.7 (7)
C3—C7—N1—C5	87.9 (9)	C5—C8—C1—C2	0.9 (10)

Symmetry code: (i) −x, −y, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7A···Br1ⁱⁱ	0.97	2.79	3.744 (7)	168
C7—H7B···Br1ⁱⁱⁱ	0.97	2.91	3.421 (7)	114

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

Experimental details

Crystal data
Chemical formula	[CuBr₂(C₈H₆N₄)₂]
M_r	539.70
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	7.9034 (16), 8.1434 (16), 8.7849 (18)
α, β, γ (°)	116.04 (3), 105.86 (3), 100.74 (3)
V (Å³)	456.9 (3)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	5.59
Crystal size (mm)	0.20 × 0.12 × 0.12

Data collection
Diffractometer	Rigaku Mercury2 diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.702, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	4726, 2095, 1809
R_int	0.037
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.067, 0.218, 1.06
No. of reflections	2095
No. of parameters	124
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	3.13, −1.39

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected geometric parameters (Å, º) top

Br1—Cu1	2.3385 (10)	Cu1—N3	2.012 (5)

N3—Cu1—Br1	89.46 (16)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7A···Br1ⁱ	0.97	2.79	3.744 (7)	168.0
C7—H7B···Br1ⁱⁱ	0.97	2.91	3.421 (7)	114.0

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

Acknowledgements

The author is grateful to the Starter Fund of Southeast University for financial support to buy the CCD X-ray diffractometer.

References

Danan, A., Charon, D., Kirkiacharian, S., Bories, C. & Loiseau, P. M. (1997). Farmaco, 52, 227–229. CAS PubMed Web of Science Google Scholar
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Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Xu, X.-B. & Ye, Q. (2007). Acta Cryst. E63, o4607. Web of Science CSD CrossRef IUCr Journals Google Scholar