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The title compound, [Cu(CN)(C10H9N3)]n, was prepared by the solvothermal treatment of CuCN with 2-[2-meth­yl(1H-benzo[d]imidazol-1-yl)]acetonitrile. The X-ray crystal structure shows that the title compound is a new cyano-bridged homometallic CuI coordination polymer in which the CuI atoms are linked by equally disordered CN groups, and are bonded to the N atom of the 2-[2-meth­yl(1H-benzo[d]imidazol-1-yl)]acetonitrile ligand. This ligand is alternately distributed along the zigzag chain. A three-dimensional structure is formed through a weak Cu—H inter­action and π–π stacking between neighbouring benzimidazole ring systems.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807059867/dn2273sup1.cif
Contains datablocks I, New_Global_Publ_Block

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807059867/dn2273Isup2.hkl
Contains datablock I

CCDC reference: 672733

Key indicators

  • Single-crystal X-ray study
  • T = 293 K
  • Mean [sigma](C-C) = 0.006 Å
  • Disorder in main residue
  • R factor = 0.059
  • wR factor = 0.120
  • Data-to-parameter ratio = 16.5

checkCIF/PLATON results

No syntax errors found



Alert level A PLAT480_ALERT_4_A Long H...A H-Bond Reported H3A .. CU1 .. 3.08 Ang.
Author Response: This distance is a relative short "intra" distances between two atoms with potential D/A contacts. PLATON suggests a weak C-H...Cu interaction.
PLAT481_ALERT_4_A Long D...A H-Bond Reported C3     ..  CU1     ..       3.83 Ang.
Author Response: This distance is a relative short "intra" distances between two atoms with potential D/A contacts. PLATON suggests a weak C-H...Cu interaction.

Alert level C RINTA01_ALERT_3_C The value of Rint is greater than 0.10 Rint given 0.114 PLAT020_ALERT_3_C The value of Rint is greater than 0.10 ......... 0.11 PLAT062_ALERT_4_C Rescale T(min) & T(max) by ..................... 0.98 PLAT301_ALERT_3_C Main Residue Disorder ......................... 8.00 Perc.
Alert level G PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature 293 K PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature . 293 K
2 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 4 ALERT level C = Check and explain 2 ALERT level G = General alerts; check 2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 3 ALERT type 3 Indicator that the structure quality may be low 3 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check

Comment top

Under hydrothermal or solvothermal conditions, some interesting reactions and compounds can be obtained, while It is worth noting that these products could not be synthesized using conventional solution techniques. (Qu et al.(2004)). In sealed tube, unstable copper (I) salt can exist under vacuums, and then interesting copper (I) coordination compound can be obtained. The title compound is obtained through solvothermal treatment of 2-(2-methyl(1H-benzol[d] imidazol-1-yl) acetonitrile and CuCN in methanol solvent at 80°C, colorless block crystals suitable for X-ray diffractions have been isolated.

The copper(I) is coordinated to two disordered cyano group and one nitrogen atom from benzolimidazole ligand in a trigonal environment (Fig 1). The cyano bridges link the molecules to form an homometallic CuI coordination polymer developping along the c axis. The 2-(2-methyl(1H- benzol[d] imidazol-1-yl) acetonitrile ligands are alternatively distributed along the polymeric zigzag chain (Fig. 1).

It is important to note that the bridging CN groups are statistically disoredered. This means that discrimination between the N and C atoms of the CN group linking the Cu (I) centre is impossible, and they are assumed to have 50% probability for each of the C and N designated as NC, in the structure refinement.

Two neighboring chains are interconnected through weak Cu—H interactions forming a two-dimensionnal layer (Table 1, Fig. 2). Futhermore, there are weak π-π stacking interactions between symetry related benzolimidazole rings (Table 2) resulting in a three dimensionnal ABAB sequence.

Related literature top

For solvothermal synthesis, see: Qu et al. (2004). For related structures, see: Mühle & Sheldrick (2003); Colacio et al. (2005).

Experimental top

A mixture of 2-(2-methyl(1H-benzol[d] imidazol-1-yl) acetonitrile (20 mg, 0.2 mmol), CuCN (17.9 mg,0.2 mmol), and methanol (2 ml) sealed in a glass tube were maintained at 80 °C. Crystals suitable for X-ray analysis were obtained after 5 days

Refinement top

All H atoms were fixed geometrically and treated as riding with C—H = 0.93 Å (aromatic), 0.97 Å (methylene) or 0.96Å (methyl) with Uiso(H) = 1.2Ueq(Caromatic, Cmethylene) or Uiso(H) = 1.5Ueq(Cmethyl).

The large difference in the isotropic thermal parameters within the cyano bridge indicates the occurrence of a statistical distribution C—N or N—C for the cyano bridge. This disorder was treated with the tools available in SHELXL97 (Sheldrick, 1997).

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, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003) and XP from SHELXTL/PC (Sheldrick, 1998); software used to prepare material for publication: SHELXTL/PC (Sheldrick, 1998).

Figures top
[Figure 1] Fig. 1. A view of the asymmetric unit of the title compoud with atomic numbering scheme. Displacement ellipsoids were drawn at the 30% probability level. [Symmetry codes: (i) x, 3/2 - y, -1/2 + z; (ii) x, 3/2 - y, 1/2 + z].
[Figure 2] Fig. 2. The two-dimensionnal layer structure of the title compound formed by weak C—H···Cu hydrogen bonding interaction. Hydrogen bonds are shown as dashed lines. H atoms not involved in hydrogen bonding have been omitted for clarity.
[Figure 3] Fig. 3. The crystal packing of the title compound viewed along the c axis.
2-Cyano)-2-[2-methyl(1H-benzo[d]imidazol-1-yl)acetonitrile]copper(I) top
Crystal data top
[Cu(CN)(C10H9N3)]F(000) = 528
Mr = 260.76Dx = 1.640 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 8475 reflections
a = 13.267 (3) Åθ = 3.3–27.5°
b = 9.2456 (18) ŵ = 2.04 mm1
c = 9.1109 (18) ÅT = 293 K
β = 109.11 (3)°Block, colorless
V = 1056.0 (4) Å30.22 × 0.18 × 0.12 mm
Z = 4
Data collection top
Mercury2 (2x2 bin mode)
diffractometer
2411 independent reflections
Radiation source: fine-focus sealed tube1523 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.114
Detector resolution: 13.6612 pixels mm-1θmax = 27.5°, θmin = 3.2°
CCD_Profile_fitting scansh = 1717
Absorption correction: multi-scan
(CrystalClear; Rigaku, 2005)
k = 1112
Tmin = 0.645, Tmax = 0.796l = 1111
10564 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)] = 0.059Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.121H-atom parameters constrained
S = 1.03 w = 1/[σ2(Fo2) + (0.0403P)2]
where P = (Fo2 + 2Fc2)/3
2411 reflections(Δ/σ)max < 0.001
146 parametersΔρmax = 0.40 e Å3
0 restraintsΔρmin = 0.38 e Å3
Crystal data top
[Cu(CN)(C10H9N3)]V = 1056.0 (4) Å3
Mr = 260.76Z = 4
Monoclinic, P21/cMo Kα radiation
a = 13.267 (3) ŵ = 2.04 mm1
b = 9.2456 (18) ÅT = 293 K
c = 9.1109 (18) Å0.22 × 0.18 × 0.12 mm
β = 109.11 (3)°
Data collection top
Mercury2 (2x2 bin mode)
diffractometer
2411 independent reflections
Absorption correction: multi-scan
(CrystalClear; Rigaku, 2005)
1523 reflections with I > 2σ(I)
Tmin = 0.645, Tmax = 0.796Rint = 0.114
10564 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0590 restraints
wR(F2) = 0.121H-atom parameters constrained
S = 1.03Δρmax = 0.40 e Å3
2411 reflectionsΔρmin = 0.38 e Å3
146 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 > 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
C10.0444 (4)0.1630 (5)0.1163 (5)0.0452 (12)
H10.00190.10110.18750.054*
C20.0320 (4)0.3111 (5)0.1390 (5)0.0424 (12)
H20.02200.34590.22520.051*
C30.3109 (4)0.0462 (4)0.3248 (5)0.0391 (11)
H3A0.25890.02800.27680.047*
H3B0.31700.05160.43370.047*
C40.1235 (4)0.1043 (5)0.0093 (5)0.0421 (12)
H40.13250.00490.02340.051*
C50.4145 (4)0.0051 (5)0.3121 (5)0.0414 (12)
C60.0980 (3)0.4083 (5)0.0364 (5)0.0352 (11)
H60.09000.50750.05230.042*
C70.3085 (3)0.3196 (4)0.3065 (5)0.0281 (10)
C80.1884 (3)0.2021 (4)0.1124 (5)0.0287 (10)
C90.3986 (4)0.3413 (5)0.4509 (5)0.0405 (12)
H9A0.46420.32000.43260.061*
H9B0.39080.27820.53020.061*
H9C0.39940.44000.48420.061*
N1B0.2695 (4)0.7159 (4)0.4355 (5)0.0471 (12)0.50
C10A0.2695 (4)0.7159 (4)0.4355 (5)0.0471 (12)0.50
C110.1765 (3)0.3518 (4)0.0908 (4)0.0268 (9)
Cu10.26730 (5)0.64111 (6)0.23978 (6)0.0411 (2)
N1A0.2663 (4)0.7661 (4)0.5510 (5)0.0431 (11)0.50
C10B0.2663 (4)0.7661 (4)0.5510 (5)0.0431 (11)0.50
N20.4948 (4)0.0270 (5)0.3056 (5)0.0694 (14)
N30.2733 (3)0.1842 (3)0.2514 (4)0.0295 (8)
N40.2535 (3)0.4221 (4)0.2148 (3)0.0286 (8)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.046 (3)0.045 (3)0.041 (3)0.010 (2)0.010 (2)0.012 (2)
C20.037 (3)0.056 (3)0.030 (2)0.000 (2)0.005 (2)0.002 (2)
C30.049 (3)0.023 (2)0.049 (3)0.005 (2)0.021 (3)0.010 (2)
C40.048 (3)0.028 (3)0.053 (3)0.006 (2)0.019 (3)0.012 (2)
C50.052 (3)0.044 (3)0.027 (2)0.016 (3)0.011 (3)0.004 (2)
C60.034 (3)0.036 (2)0.033 (2)0.005 (2)0.009 (2)0.003 (2)
C70.029 (2)0.030 (2)0.027 (2)0.0079 (19)0.012 (2)0.0002 (18)
C80.029 (2)0.024 (2)0.035 (2)0.0012 (19)0.012 (2)0.0028 (18)
C90.039 (3)0.047 (3)0.030 (2)0.008 (2)0.004 (2)0.003 (2)
N1B0.078 (4)0.025 (2)0.036 (2)0.002 (2)0.014 (2)0.0061 (19)
C10A0.078 (4)0.025 (2)0.036 (2)0.002 (2)0.014 (2)0.0061 (19)
C110.030 (2)0.025 (2)0.028 (2)0.0035 (19)0.0136 (19)0.0041 (18)
Cu10.0608 (4)0.0280 (3)0.0326 (3)0.0038 (3)0.0126 (3)0.0023 (2)
N1A0.074 (3)0.025 (2)0.030 (2)0.003 (2)0.017 (2)0.0009 (17)
C10B0.074 (3)0.025 (2)0.030 (2)0.003 (2)0.017 (2)0.0009 (17)
N20.064 (3)0.094 (4)0.047 (3)0.035 (3)0.015 (3)0.002 (2)
N30.033 (2)0.0245 (18)0.0291 (19)0.0012 (16)0.0081 (17)0.0043 (14)
N40.035 (2)0.0226 (18)0.0268 (19)0.0010 (16)0.0083 (17)0.0016 (14)
Geometric parameters (Å, º) top
C1—C41.385 (6)C7—N31.372 (5)
C1—C21.387 (6)C7—C91.473 (6)
C1—H10.9300C8—C111.400 (5)
C2—C61.382 (6)C8—N31.401 (5)
C2—H20.9300C9—H9A0.9600
C3—N31.451 (5)C9—H9B0.9600
C3—C51.467 (7)C9—H9C0.9600
C3—H3A0.9700N1B—N1A1.164 (5)
C3—H3B0.9700N1B—Cu11.904 (4)
C4—C81.383 (6)C11—N41.409 (5)
C4—H40.9300Cu1—C10Bi1.918 (4)
C5—N21.126 (6)Cu1—N1Ai1.918 (4)
C6—C111.381 (5)Cu1—N42.039 (3)
C6—H60.9300N1A—Cu1ii1.918 (4)
C7—N41.315 (5)
C4—C1—C2122.1 (4)C11—C8—N3105.3 (3)
C4—C1—H1119.0C7—C9—H9A109.5
C2—C1—H1119.0C7—C9—H9B109.5
C6—C2—C1121.5 (4)H9A—C9—H9B109.5
C6—C2—H2119.3C7—C9—H9C109.5
C1—C2—H2119.2H9A—C9—H9C109.5
N3—C3—C5112.4 (4)H9B—C9—H9C109.5
N3—C3—H3A109.1N1A—N1B—Cu1176.4 (4)
C5—C3—H3A109.1C6—C11—C8120.7 (4)
N3—C3—H3B109.1C6—C11—N4130.4 (4)
C5—C3—H3B109.1C8—C11—N4108.9 (3)
H3A—C3—H3B107.9N1B—Cu1—C10Bi132.14 (17)
C8—C4—C1116.1 (4)N1B—Cu1—N1Ai132.14 (17)
C8—C4—H4121.9C10Bi—Cu1—N1Ai0.0 (2)
C1—C4—H4121.9N1B—Cu1—N4116.01 (14)
N2—C5—C3178.5 (5)C10Bi—Cu1—N4111.72 (14)
C11—C6—C2117.3 (4)N1Ai—Cu1—N4111.72 (14)
C11—C6—H6121.4N1B—N1A—Cu1ii176.2 (4)
C2—C6—H6121.4C7—N3—C8107.4 (3)
N4—C7—N3111.9 (4)C7—N3—C3127.5 (4)
N4—C7—C9126.1 (4)C8—N3—C3125.0 (3)
N3—C7—C9122.0 (4)C7—N4—C11106.5 (3)
C4—C8—C11122.3 (4)C7—N4—Cu1129.3 (3)
C4—C8—N3132.4 (4)C11—N4—Cu1124.2 (3)
Symmetry codes: (i) x, y+3/2, z1/2; (ii) x, y+3/2, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C3—H3A···Cu1iii0.973.083.830 (4)135
Symmetry code: (iii) x, y1, z.

Experimental details

Crystal data
Chemical formula[Cu(CN)(C10H9N3)]
Mr260.76
Crystal system, space groupMonoclinic, P21/c
Temperature (K)293
a, b, c (Å)13.267 (3), 9.2456 (18), 9.1109 (18)
β (°) 109.11 (3)
V3)1056.0 (4)
Z4
Radiation typeMo Kα
µ (mm1)2.04
Crystal size (mm)0.22 × 0.18 × 0.12
Data collection
DiffractometerMercury2 (2x2 bin mode)
diffractometer
Absorption correctionMulti-scan
(CrystalClear; Rigaku, 2005)
Tmin, Tmax0.645, 0.796
No. of measured, independent and
observed [I > 2σ(I)] reflections
10564, 2411, 1523
Rint0.114
(sin θ/λ)max1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.059, 0.121, 1.03
No. of reflections2411
No. of parameters146
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.40, 0.38

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2003) and XP from SHELXTL/PC (Sheldrick, 1998), SHELXTL/PC (Sheldrick, 1998).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C3—H3A···Cu1i0.973.083.830 (4)134.9
Symmetry code: (i) x, y1, z.
π-π interaction in (I).
α is dihedral angle between the planes, DCC is the length of the CC vector (centroid to centroid), τ is the angle(s) subtended by the plane normal(s) to CC. Cg1 is the centroid of ring N3, C7, N4, C11, C8, Cg2 of ring C1 C2 C4 C6 C8 C11.
top
Group 1Group 2αDCC /Åτ
Cg1Cg2i1.483.639 (3)14.9
Symmetry codes: (i) x, 1/2-y, 1/2+z
 

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