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
CCDC reference: 672733
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (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
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
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).
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).
(µ
2-Cyano)-2-[2-methyl(1
H-benzo[
d]imidazol-1-yl)acetonitrile]copper(I)
top
Crystal data top
[Cu(CN)(C10H9N3)] | F(000) = 528 |
Mr = 260.76 | Dx = 1.640 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 8475 reflections |
a = 13.267 (3) Å | θ = 3.3–27.5° |
b = 9.2456 (18) Å | µ = 2.04 mm−1 |
c = 9.1109 (18) Å | T = 293 K |
β = 109.11 (3)° | Block, colorless |
V = 1056.0 (4) Å3 | 0.22 × 0.18 × 0.12 mm |
Z = 4 | |
Data collection top
Mercury2 (2x2 bin mode) diffractometer | 2411 independent reflections |
Radiation source: fine-focus sealed tube | 1523 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.114 |
Detector resolution: 13.6612 pixels mm-1 | θmax = 27.5°, θmin = 3.2° |
CCD_Profile_fitting scans | h = −17→17 |
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005) | k = −11→12 |
Tmin = 0.645, Tmax = 0.796 | l = −11→11 |
10564 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)] = 0.059 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.121 | H-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 parameters | Δρmax = 0.40 e Å−3 |
0 restraints | Δρmin = −0.38 e Å−3 |
Crystal data top
[Cu(CN)(C10H9N3)] | V = 1056.0 (4) Å3 |
Mr = 260.76 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 13.267 (3) Å | µ = 2.04 mm−1 |
b = 9.2456 (18) Å | T = 293 K |
c = 9.1109 (18) Å | 0.22 × 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 = 0.796 | Rint = 0.114 |
10564 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.059 | 0 restraints |
wR(F2) = 0.121 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.40 e Å−3 |
2411 reflections | Δρmin = −0.38 e Å−3 |
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 | x | y | z | Uiso*/Ueq | Occ. (<1) |
C1 | 0.0444 (4) | 0.1630 (5) | −0.1163 (5) | 0.0452 (12) | |
H1 | −0.0019 | 0.1011 | −0.1875 | 0.054* | |
C2 | 0.0320 (4) | 0.3111 (5) | −0.1390 (5) | 0.0424 (12) | |
H2 | −0.0220 | 0.3459 | −0.2252 | 0.051* | |
C3 | 0.3109 (4) | 0.0462 (4) | 0.3248 (5) | 0.0391 (11) | |
H3A | 0.2589 | −0.0280 | 0.2768 | 0.047* | |
H3B | 0.3170 | 0.0516 | 0.4337 | 0.047* | |
C4 | 0.1235 (4) | 0.1043 (5) | 0.0093 (5) | 0.0421 (12) | |
H4 | 0.1325 | 0.0049 | 0.0234 | 0.051* | |
C5 | 0.4145 (4) | 0.0051 (5) | 0.3121 (5) | 0.0414 (12) | |
C6 | 0.0980 (3) | 0.4083 (5) | −0.0364 (5) | 0.0352 (11) | |
H6 | 0.0900 | 0.5075 | −0.0523 | 0.042* | |
C7 | 0.3085 (3) | 0.3196 (4) | 0.3065 (5) | 0.0281 (10) | |
C8 | 0.1884 (3) | 0.2021 (4) | 0.1124 (5) | 0.0287 (10) | |
C9 | 0.3986 (4) | 0.3413 (5) | 0.4509 (5) | 0.0405 (12) | |
H9A | 0.4642 | 0.3200 | 0.4326 | 0.061* | |
H9B | 0.3908 | 0.2782 | 0.5302 | 0.061* | |
H9C | 0.3994 | 0.4400 | 0.4842 | 0.061* | |
N1B | 0.2695 (4) | 0.7159 (4) | 0.4355 (5) | 0.0471 (12) | 0.50 |
C10A | 0.2695 (4) | 0.7159 (4) | 0.4355 (5) | 0.0471 (12) | 0.50 |
C11 | 0.1765 (3) | 0.3518 (4) | 0.0908 (4) | 0.0268 (9) | |
Cu1 | 0.26730 (5) | 0.64111 (6) | 0.23978 (6) | 0.0411 (2) | |
N1A | 0.2663 (4) | 0.7661 (4) | 0.5510 (5) | 0.0431 (11) | 0.50 |
C10B | 0.2663 (4) | 0.7661 (4) | 0.5510 (5) | 0.0431 (11) | 0.50 |
N2 | 0.4948 (4) | −0.0270 (5) | 0.3056 (5) | 0.0694 (14) | |
N3 | 0.2733 (3) | 0.1842 (3) | 0.2514 (4) | 0.0295 (8) | |
N4 | 0.2535 (3) | 0.4221 (4) | 0.2148 (3) | 0.0286 (8) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.046 (3) | 0.045 (3) | 0.041 (3) | −0.010 (2) | 0.010 (2) | −0.012 (2) |
C2 | 0.037 (3) | 0.056 (3) | 0.030 (2) | 0.000 (2) | 0.005 (2) | −0.002 (2) |
C3 | 0.049 (3) | 0.023 (2) | 0.049 (3) | 0.005 (2) | 0.021 (3) | 0.010 (2) |
C4 | 0.048 (3) | 0.028 (3) | 0.053 (3) | −0.006 (2) | 0.019 (3) | −0.012 (2) |
C5 | 0.052 (3) | 0.044 (3) | 0.027 (2) | 0.016 (3) | 0.011 (3) | 0.004 (2) |
C6 | 0.034 (3) | 0.036 (2) | 0.033 (2) | 0.005 (2) | 0.009 (2) | 0.003 (2) |
C7 | 0.029 (2) | 0.030 (2) | 0.027 (2) | −0.0079 (19) | 0.012 (2) | −0.0002 (18) |
C8 | 0.029 (2) | 0.024 (2) | 0.035 (2) | 0.0012 (19) | 0.012 (2) | −0.0028 (18) |
C9 | 0.039 (3) | 0.047 (3) | 0.030 (2) | −0.008 (2) | 0.004 (2) | 0.003 (2) |
N1B | 0.078 (4) | 0.025 (2) | 0.036 (2) | −0.002 (2) | 0.014 (2) | 0.0061 (19) |
C10A | 0.078 (4) | 0.025 (2) | 0.036 (2) | −0.002 (2) | 0.014 (2) | 0.0061 (19) |
C11 | 0.030 (2) | 0.025 (2) | 0.028 (2) | −0.0035 (19) | 0.0136 (19) | −0.0041 (18) |
Cu1 | 0.0608 (4) | 0.0280 (3) | 0.0326 (3) | −0.0038 (3) | 0.0126 (3) | −0.0023 (2) |
N1A | 0.074 (3) | 0.025 (2) | 0.030 (2) | −0.003 (2) | 0.017 (2) | −0.0009 (17) |
C10B | 0.074 (3) | 0.025 (2) | 0.030 (2) | −0.003 (2) | 0.017 (2) | −0.0009 (17) |
N2 | 0.064 (3) | 0.094 (4) | 0.047 (3) | 0.035 (3) | 0.015 (3) | 0.002 (2) |
N3 | 0.033 (2) | 0.0245 (18) | 0.0291 (19) | 0.0012 (16) | 0.0081 (17) | 0.0043 (14) |
N4 | 0.035 (2) | 0.0226 (18) | 0.0268 (19) | −0.0010 (16) | 0.0083 (17) | 0.0016 (14) |
Geometric parameters (Å, º) top
C1—C4 | 1.385 (6) | C7—N3 | 1.372 (5) |
C1—C2 | 1.387 (6) | C7—C9 | 1.473 (6) |
C1—H1 | 0.9300 | C8—C11 | 1.400 (5) |
C2—C6 | 1.382 (6) | C8—N3 | 1.401 (5) |
C2—H2 | 0.9300 | C9—H9A | 0.9600 |
C3—N3 | 1.451 (5) | C9—H9B | 0.9600 |
C3—C5 | 1.467 (7) | C9—H9C | 0.9600 |
C3—H3A | 0.9700 | N1B—N1A | 1.164 (5) |
C3—H3B | 0.9700 | N1B—Cu1 | 1.904 (4) |
C4—C8 | 1.383 (6) | C11—N4 | 1.409 (5) |
C4—H4 | 0.9300 | Cu1—C10Bi | 1.918 (4) |
C5—N2 | 1.126 (6) | Cu1—N1Ai | 1.918 (4) |
C6—C11 | 1.381 (5) | Cu1—N4 | 2.039 (3) |
C6—H6 | 0.9300 | N1A—Cu1ii | 1.918 (4) |
C7—N4 | 1.315 (5) | | |
| | | |
C4—C1—C2 | 122.1 (4) | C11—C8—N3 | 105.3 (3) |
C4—C1—H1 | 119.0 | C7—C9—H9A | 109.5 |
C2—C1—H1 | 119.0 | C7—C9—H9B | 109.5 |
C6—C2—C1 | 121.5 (4) | H9A—C9—H9B | 109.5 |
C6—C2—H2 | 119.3 | C7—C9—H9C | 109.5 |
C1—C2—H2 | 119.2 | H9A—C9—H9C | 109.5 |
N3—C3—C5 | 112.4 (4) | H9B—C9—H9C | 109.5 |
N3—C3—H3A | 109.1 | N1A—N1B—Cu1 | 176.4 (4) |
C5—C3—H3A | 109.1 | C6—C11—C8 | 120.7 (4) |
N3—C3—H3B | 109.1 | C6—C11—N4 | 130.4 (4) |
C5—C3—H3B | 109.1 | C8—C11—N4 | 108.9 (3) |
H3A—C3—H3B | 107.9 | N1B—Cu1—C10Bi | 132.14 (17) |
C8—C4—C1 | 116.1 (4) | N1B—Cu1—N1Ai | 132.14 (17) |
C8—C4—H4 | 121.9 | C10Bi—Cu1—N1Ai | 0.0 (2) |
C1—C4—H4 | 121.9 | N1B—Cu1—N4 | 116.01 (14) |
N2—C5—C3 | 178.5 (5) | C10Bi—Cu1—N4 | 111.72 (14) |
C11—C6—C2 | 117.3 (4) | N1Ai—Cu1—N4 | 111.72 (14) |
C11—C6—H6 | 121.4 | N1B—N1A—Cu1ii | 176.2 (4) |
C2—C6—H6 | 121.4 | C7—N3—C8 | 107.4 (3) |
N4—C7—N3 | 111.9 (4) | C7—N3—C3 | 127.5 (4) |
N4—C7—C9 | 126.1 (4) | C8—N3—C3 | 125.0 (3) |
N3—C7—C9 | 122.0 (4) | C7—N4—C11 | 106.5 (3) |
C4—C8—C11 | 122.3 (4) | C7—N4—Cu1 | 129.3 (3) |
C4—C8—N3 | 132.4 (4) | C11—N4—Cu1 | 124.2 (3) |
Symmetry codes: (i) x, −y+3/2, z−1/2; (ii) x, −y+3/2, z+1/2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3A···Cu1iii | 0.97 | 3.08 | 3.830 (4) | 135 |
Symmetry code: (iii) x, y−1, z. |
Experimental details
Crystal data |
Chemical formula | [Cu(CN)(C10H9N3)] |
Mr | 260.76 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 13.267 (3), 9.2456 (18), 9.1109 (18) |
β (°) | 109.11 (3) |
V (Å3) | 1056.0 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 2.04 |
Crystal size (mm) | 0.22 × 0.18 × 0.12 |
|
Data collection |
Diffractometer | Mercury2 (2x2 bin mode) diffractometer |
Absorption correction | Multi-scan (CrystalClear; Rigaku, 2005) |
Tmin, Tmax | 0.645, 0.796 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 10564, 2411, 1523 |
Rint | 0.114 |
(sin θ/λ)max (Å−1) | 0.649 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.059, 0.121, 1.03 |
No. of reflections | 2411 |
No. of parameters | 146 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.40, −0.38 |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3A···Cu1i | 0.97 | 3.08 | 3.830 (4) | 134.9 |
Symmetry code: (i) x, y−1, 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. topGroup 1 | Group 2 | α /° | DCC /Å | τ /° |
Cg1 | Cg2i | 1.48 | 3.639 (3) | 14.9 |
Symmetry codes: (i) x, 1/2-y, 1/2+z |
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.