metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890

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

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 CuII 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 ππ 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[Danan, A., Charon, D., Kirkiacharian, S., Bories, C. & Loiseau, P. M. (1997). Farmaco, 52, 227-229.]); Xu & Ye (2007[Xu, X.-B. & Ye, Q. (2007). Acta Cryst. E63, o4607.]). For the structure of a similar complex, see: Hang & Ye (2008[Hang, T. & Ye, Q. (2008). Acta Cryst. E64, m758.]).

[Scheme 1]

Experimental

Crystal data
  • [CuBr2(C8H6N4)2]

  • Mr = 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[Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan.]) Tmin = 0.702, Tmax = 1.000 (expected range = 0.359–0.511)

  • 4726 measured reflections

  • 2095 independent reflections

  • 1809 reflections with I > 2σ(I)

  • Rint = 0.037

Refinement
  • R[F2 > 2σ(F2)] = 0.067

  • wR(F2) = 0.218

  • S = 1.06

  • 2095 reflections

  • 124 parameters

  • H-atom parameters constrained

  • Δρmax = 3.13 e Å−3

  • Δρmin = −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 DA 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[Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan.]); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: SHELXTL.

Supporting information


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 CuII. CuII 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.

Refinement top

Positional parameters of all the H atoms were calculated geometrically and were allowed to ride on the C, O atoms to which they are bonded, with Uiso(H) = 1.2Ueq(C) or Uiso(H) = 1.5Ueq(O).

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
[Figure 1] Fig. 1. The molecular structure of the compound with the atomic numbering scheme. Displacement ellipsoids were drawn at the 30% probability level.
[Figure 2] 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
Mr = 539.70F(000) = 263
Triclinic, P1Dx = 1.961 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 7.9034 (16) ÅCell parameters from 4665 reflections
b = 8.1434 (16) Åθ = 6.2–57.6°
c = 8.7849 (18) ŵ = 5.59 mm1
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 tube1809 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.037
Detector resolution: 13.6612 pixels mm-1θmax = 27.5°, θmin = 3.1°
CCD_Profile_fitting scansh = 1010
Absorption correction: multi-scan
(CrystalClear; Rigaku, 2005)
k = 1010
Tmin = 0.702, Tmax = 1.000l = 1111
4726 measured reflections
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)] = 0.067Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.218H-atom parameters constrained
S = 1.06 w = 1/[σ2(Fo2) + (0.1128P)2 + 5.2279P]
where P = (Fo2 + 2Fc2)/3
2095 reflections(Δ/σ)max < 0.001
124 parametersΔρmax = 3.13 e Å3
0 restraintsΔρmin = 1.39 e Å3
Crystal data top
[CuBr2(C8H6N4)2]γ = 100.74 (3)°
Mr = 539.70V = 456.9 (3) Å3
Triclinic, P1Z = 1
a = 7.9034 (16) ÅMo Kα radiation
b = 8.1434 (16) ŵ = 5.59 mm1
c = 8.7849 (18) ÅT = 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)
Tmin = 0.702, Tmax = 1.000Rint = 0.037
4726 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0670 restraints
wR(F2) = 0.218H-atom parameters constrained
S = 1.06Δρmax = 3.13 e Å3
2095 reflectionsΔρmin = 1.39 e Å3
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
xyzUiso*/Ueq
Br10.13948 (13)0.20325 (12)0.56625 (11)0.0403 (3)
Cu10.00000.00000.50000.0170 (3)
C80.2130 (9)0.4022 (9)0.1349 (8)0.0175 (12)
N40.0651 (9)0.1575 (8)0.1166 (7)0.0240 (12)
N30.1103 (9)0.2050 (8)0.2291 (7)0.0222 (12)
N20.3749 (15)0.2480 (17)0.3869 (13)0.065 (3)
C70.1043 (11)0.3097 (11)0.2015 (9)0.0242 (14)
H7A0.09350.43080.28360.029*
H7B0.01280.20420.15260.029*
C60.3269 (10)0.6762 (10)0.1849 (9)0.0258 (14)
H6A0.33840.72580.30640.031*
N10.1353 (8)0.3207 (8)0.0490 (7)0.0210 (11)
C50.2293 (9)0.4777 (9)0.0471 (8)0.0181 (12)
C40.4036 (11)0.7908 (11)0.1270 (11)0.0316 (16)
H4A0.46750.92370.21190.038*
C30.2596 (12)0.2759 (12)0.3062 (10)0.0325 (17)
C20.3899 (11)0.7159 (11)0.0551 (11)0.0297 (15)
H2A0.44650.80020.08620.036*
C10.2947 (10)0.5205 (10)0.1897 (9)0.0239 (13)
H1A0.28600.47120.31030.029*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br10.0515 (6)0.0375 (5)0.0321 (5)0.0196 (4)0.0162 (4)0.0169 (4)
Cu10.0271 (6)0.0117 (5)0.0069 (5)0.0051 (4)0.0055 (4)0.0022 (4)
C80.025 (3)0.015 (3)0.008 (3)0.008 (2)0.003 (2)0.003 (2)
N40.038 (3)0.017 (3)0.011 (2)0.008 (2)0.008 (2)0.005 (2)
N30.038 (3)0.015 (3)0.011 (2)0.007 (2)0.008 (2)0.006 (2)
N20.075 (7)0.088 (8)0.037 (5)0.052 (6)0.018 (4)0.031 (5)
C70.039 (4)0.027 (3)0.017 (3)0.016 (3)0.018 (3)0.014 (3)
C60.029 (3)0.020 (3)0.012 (3)0.009 (3)0.004 (3)0.002 (2)
N10.035 (3)0.017 (2)0.010 (2)0.010 (2)0.009 (2)0.006 (2)
C50.021 (3)0.019 (3)0.013 (3)0.009 (2)0.006 (2)0.008 (2)
C40.030 (4)0.017 (3)0.032 (4)0.004 (3)0.006 (3)0.005 (3)
C30.049 (5)0.037 (4)0.014 (3)0.021 (4)0.015 (3)0.013 (3)
C20.028 (3)0.024 (4)0.033 (4)0.006 (3)0.010 (3)0.015 (3)
C10.029 (3)0.024 (3)0.018 (3)0.010 (3)0.009 (3)0.010 (3)
Geometric parameters (Å, º) top
Br1—Cu12.3385 (10)C7—H7B0.9700
Cu1—N32.012 (5)C6—C41.368 (11)
C8—N31.379 (8)C6—C51.407 (9)
C8—C11.387 (9)C6—H6A0.9300
C8—C51.395 (8)N1—C51.363 (9)
N4—N31.316 (8)C4—C21.402 (11)
N4—N11.333 (7)C4—H4A0.9300
N2—C31.118 (12)C2—C11.383 (10)
C7—N11.462 (8)C2—H2A0.9300
C7—C31.470 (10)C1—H1A0.9300
C7—H7A0.9700
N3—Cu1—Br189.46 (16)N4—N1—C5111.7 (5)
N3—C8—C1132.2 (6)N4—N1—C7118.6 (6)
N3—C8—C5106.6 (6)C5—N1—C7129.7 (6)
C1—C8—C5121.2 (6)N1—C5—C8104.5 (5)
N3—N4—N1107.1 (5)N1—C5—C6132.8 (6)
N4—N3—C8110.1 (5)C8—C5—C6122.7 (6)
N4—N3—Cu1118.1 (4)C6—C4—C2122.7 (7)
C8—N3—Cu1131.4 (4)C6—C4—H4A118.7
N1—C7—C3111.1 (6)C2—C4—H4A118.7
N1—C7—H7A109.4N2—C3—C7178.4 (10)
C3—C7—H7A109.4C1—C2—C4122.0 (7)
N1—C7—H7B109.4C1—C2—H2A119.0
C3—C7—H7B109.4C4—C2—H2A119.0
H7A—C7—H7B108.0C2—C1—C8116.3 (6)
C4—C6—C5115.1 (6)C2—C1—H1A121.9
C4—C6—H6A122.5C8—C1—H1A121.9
C5—C6—H6A122.5
N1—N4—N3—C80.5 (8)N4—N1—C5—C80.4 (7)
N1—N4—N3—Cu1172.6 (4)C7—N1—C5—C8179.9 (7)
C1—C8—N3—N4178.7 (7)N4—N1—C5—C6179.3 (7)
C5—C8—N3—N40.3 (8)C7—N1—C5—C60.5 (12)
C1—C8—N3—Cu19.4 (11)N3—C8—C5—N10.0 (7)
C5—C8—N3—Cu1171.6 (5)C1—C8—C5—N1179.2 (6)
N3i—Cu1—N3—N4167 (92)N3—C8—C5—C6179.7 (6)
Br1i—Cu1—N3—N459.4 (5)C1—C8—C5—C60.6 (10)
Br1—Cu1—N3—N4120.6 (5)C4—C6—C5—N1179.8 (7)
N3i—Cu1—N3—C84 (93)C4—C6—C5—C80.5 (10)
Br1i—Cu1—N3—C8129.2 (6)C5—C6—C4—C21.3 (11)
Br1—Cu1—N3—C850.8 (6)N1—C7—C3—N2150 (33)
N3—N4—N1—C50.5 (8)C6—C4—C2—C11.0 (12)
N3—N4—N1—C7179.7 (6)C4—C2—C1—C80.1 (11)
C3—C7—N1—N491.8 (8)N3—C8—C1—C2179.7 (7)
C3—C7—N1—C587.9 (9)C5—C8—C1—C20.9 (10)
Symmetry code: (i) x, y, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C7—H7A···Br1ii0.972.793.744 (7)168
C7—H7B···Br1iii0.972.913.421 (7)114
Symmetry codes: (ii) x, y1, z; (iii) x, y, z1.

Experimental details

Crystal data
Chemical formula[CuBr2(C8H6N4)2]
Mr539.70
Crystal system, space groupTriclinic, 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)
V3)456.9 (3)
Z1
Radiation typeMo Kα
µ (mm1)5.59
Crystal size (mm)0.20 × 0.12 × 0.12
Data collection
DiffractometerRigaku Mercury2
diffractometer
Absorption correctionMulti-scan
(CrystalClear; Rigaku, 2005)
Tmin, Tmax0.702, 1.000
No. of measured, independent and
observed [I > 2σ(I)] reflections
4726, 2095, 1809
Rint0.037
(sin θ/λ)max1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.067, 0.218, 1.06
No. of reflections2095
No. of parameters124
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)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—Cu12.3385 (10)Cu1—N32.012 (5)
N3—Cu1—Br189.46 (16)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C7—H7A···Br1i0.972.793.744 (7)168.0
C7—H7B···Br1ii0.972.913.421 (7)114.0
Symmetry codes: (i) x, y1, z; (ii) x, y, z1.
 

Acknowledgements

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

References

First citationDanan, A., Charon, D., Kirkiacharian, S., Bories, C. & Loiseau, P. M. (1997). Farmaco, 52, 227–229.  CAS PubMed Web of Science Google Scholar
First citationHang, T. & Ye, Q. (2008). Acta Cryst. E64, m758.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationRigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan.  Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationXu, X.-B. & Ye, Q. (2007). Acta Cryst. E63, o4607.  Web of Science CSD CrossRef IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Follow Acta Cryst. E
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds