Acta Cryst. (2007). E63, m1729 [ doi:10.1107/S1600536807024397 ]
In the title compound, [Cu(C16H14N3O)Cl], the CuII ion exhibits a distorted tetrahedral geometry. The coordination environment of the CuII ion is composed of one benzimidazole N atom, one imino N atom, one phenolato O atom and one Cl- anion. Intermolecular N-H
O hydrogen bonds play key roles in stabilizing the crystal packing.
All chemicals were of reagent grade and commercially available from the Beijing Chemical Reagents Company of China, and were used without further purification.
At room temperature, a methanol solution of CuCl2.2H2O (0.5 mmol, 5 ml) and a methanol solution of N-salicylidine-2-aminoethylbenzimidazole (0.5 mmol, 10 ml, Maurya et al., 2006) were mixed together. The mixture was stirred for about six hours and then filtered. The filtrate was allowed to evaporate at room temperature, affording the green crystal (I).
H atoms attached to C atoms were placed in geometrically idealized positions, with Csp3—H=0.970 Å and constrained to ride on their parent atoms, with Uiso(H) = 1.5Ueq(C), and with Csp2 = 0.930 Å, constrained to ride on their parent atoms, with Uiso(H) = 1.2Ueq(C). The H atom on N atom was located in a difference Fourier map and its position and isotropic displacement parameters were refined, with N—H distance was fixed at 0.86 Å.
Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2000); software used to prepare material for publication: SHELXTL.
![[Figure 1]](./wk2057fig1thm.gif)
| Fig. 1. The structure of the title compound in 30% probability ellipsoids. |
![[Figure 2]](./wk2057fig2thm.gif)
| Fig. 2. A packing diagram, viewed down the b axis. Hydrogen bonds are indicated by dashed lines. [Symmetry code: (A) x - 1, y, z] |
| [Cu(C16H14ON3)Cl] | Z = 2 |
| Mr = 363.29 | F(000) = 370 |
| Triclinic, P1 | Dx = 1.606 Mg m−3 |
| Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
| a = 8.009 (3) Å | Cell parameters from 1643 reflections |
| b = 9.303 (3) Å | θ = 2.2–26.6° |
| c = 10.192 (3) Å | µ = 1.64 mm−1 |
| α = 87.815 (4)° | T = 571 K |
| β = 87.548 (4)° | Block, green |
| γ = 82.267 (4)° | 0.20 × 0.20 × 0.10 mm |
| V = 751.3 (4) Å3 |
| Bruker SMART CCD diffractometer | 2599 independent reflections |
| Radiation source: fine-focus sealed tube | 2293 reflections with I > 2σ(I) |
| graphite | Rint = 0.020 |
| ω scans | θmax = 25.0°, θmin = 2.0° |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −8→9 |
| Tmin = 0.736, Tmax = 0.854 | k = −9→11 |
| 3708 measured reflections | l = −11→12 |
| 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)] = 0.047 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.096 | H-atom parameters constrained |
| S = 1.12 | w = 1/[σ2(Fo2) + (0.0324P)2 + 0.4537P] where P = (Fo2 + 2Fc2)/3 |
| 2599 reflections | (Δ/σ)max < 0.001 |
| 199 parameters | Δρmax = 0.42 e Å−3 |
| 0 restraints | Δρmin = −0.39 e Å−3 |
| [Cu(C16H14ON3)Cl] | γ = 82.267 (4)° |
| Mr = 363.29 | V = 751.3 (4) Å3 |
| Triclinic, P1 | Z = 2 |
| a = 8.009 (3) Å | Mo Kα radiation |
| b = 9.303 (3) Å | µ = 1.64 mm−1 |
| c = 10.192 (3) Å | T = 571 K |
| α = 87.815 (4)° | 0.20 × 0.20 × 0.10 mm |
| β = 87.548 (4)° |
| Bruker SMART CCD diffractometer | 2599 independent reflections |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2293 reflections with I > 2σ(I) |
| Tmin = 0.736, Tmax = 0.854 | Rint = 0.020 |
| 3708 measured reflections | θmax = 25.0° |
| R[F2 > 2σ(F2)] = 0.047 | H-atom parameters constrained |
| wR(F2) = 0.096 | Δρmax = 0.42 e Å−3 |
| S = 1.12 | Δρmin = −0.39 e Å−3 |
| 2599 reflections | Absolute structure: ? |
| 199 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
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 | ||
| Cu1 | 0.32075 (6) | 0.15770 (6) | 0.09550 (4) | 0.03379 (17) | |
| Cl1 | 0.45923 (12) | 0.15497 (12) | −0.09963 (9) | 0.0441 (3) | |
| O1 | 0.4966 (3) | 0.2340 (3) | 0.1815 (2) | 0.0364 (7) | |
| N1 | 0.2375 (4) | 0.0735 (3) | 0.2598 (3) | 0.0310 (7) | |
| N2 | −0.1942 (4) | 0.2427 (4) | 0.0546 (3) | 0.0371 (8) | |
| H16 | −0.2948 | 0.2365 | 0.0852 | 0.045* | |
| N3 | 0.0840 (4) | 0.2006 (3) | 0.0333 (3) | 0.0319 (7) | |
| C1 | 0.5099 (4) | 0.2481 (4) | 0.3089 (4) | 0.0323 (9) | |
| C2 | 0.6238 (5) | 0.3345 (5) | 0.3519 (4) | 0.0398 (10) | |
| H2 | 0.6862 | 0.3832 | 0.2901 | 0.048* | |
| C3 | 0.6470 (5) | 0.3500 (5) | 0.4830 (4) | 0.0464 (11) | |
| H3 | 0.7257 | 0.4076 | 0.5081 | 0.056* | |
| C4 | 0.5554 (5) | 0.2816 (5) | 0.5775 (4) | 0.0486 (11) | |
| H4 | 0.5720 | 0.2921 | 0.6662 | 0.058* | |
| C5 | 0.4401 (5) | 0.1984 (4) | 0.5393 (4) | 0.0412 (10) | |
| H5 | 0.3776 | 0.1526 | 0.6032 | 0.049* | |
| C6 | 0.4126 (4) | 0.1795 (4) | 0.4062 (4) | 0.0310 (9) | |
| C7 | 0.2891 (5) | 0.0901 (4) | 0.3741 (4) | 0.0339 (9) | |
| H7 | 0.2419 | 0.0391 | 0.4433 | 0.041* | |
| C8 | 0.1105 (5) | −0.0237 (4) | 0.2442 (4) | 0.0385 (10) | |
| H8A | 0.0996 | −0.0822 | 0.3242 | 0.046* | |
| H8B | 0.1461 | −0.0886 | 0.1731 | 0.046* | |
| C9 | −0.0580 (5) | 0.0634 (5) | 0.2148 (4) | 0.0385 (10) | |
| H9A | −0.1376 | −0.0032 | 0.1986 | 0.046* | |
| H9B | −0.0996 | 0.1173 | 0.2919 | 0.046* | |
| C10 | −0.0531 (4) | 0.1680 (4) | 0.0993 (4) | 0.0326 (9) | |
| C11 | −0.1515 (4) | 0.3313 (4) | −0.0485 (4) | 0.0335 (9) | |
| C12 | −0.2493 (5) | 0.4289 (4) | −0.1289 (4) | 0.0414 (10) | |
| H12 | −0.3660 | 0.4461 | −0.1172 | 0.050* | |
| C13 | −0.1657 (5) | 0.4988 (5) | −0.2260 (4) | 0.0459 (11) | |
| H13 | −0.2267 | 0.5662 | −0.2814 | 0.055* | |
| C14 | 0.0094 (5) | 0.4713 (5) | −0.2444 (4) | 0.0462 (11) | |
| H14 | 0.0618 | 0.5184 | −0.3135 | 0.055* | |
| C15 | 0.1063 (5) | 0.3762 (5) | −0.1626 (4) | 0.0412 (10) | |
| H15 | 0.2231 | 0.3608 | −0.1735 | 0.049* | |
| C16 | 0.0237 (4) | 0.3041 (4) | −0.0634 (4) | 0.0324 (9) |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Cu1 | 0.0250 (3) | 0.0526 (3) | 0.0254 (3) | −0.0124 (2) | 0.00124 (19) | 0.0014 (2) |
| Cl1 | 0.0364 (6) | 0.0643 (7) | 0.0292 (6) | −0.0022 (5) | 0.0072 (4) | 0.0041 (5) |
| O1 | 0.0271 (14) | 0.0581 (19) | 0.0260 (15) | −0.0135 (13) | 0.0011 (11) | −0.0011 (13) |
| N1 | 0.0277 (17) | 0.0395 (19) | 0.0265 (18) | −0.0078 (14) | 0.0012 (14) | 0.0013 (14) |
| N2 | 0.0208 (16) | 0.054 (2) | 0.037 (2) | −0.0087 (15) | 0.0039 (14) | −0.0036 (17) |
| N3 | 0.0222 (16) | 0.044 (2) | 0.0303 (18) | −0.0092 (14) | −0.0028 (14) | 0.0037 (15) |
| C1 | 0.0231 (19) | 0.041 (2) | 0.031 (2) | 0.0026 (17) | −0.0003 (16) | −0.0013 (18) |
| C2 | 0.037 (2) | 0.050 (3) | 0.034 (2) | −0.0128 (19) | 0.0034 (19) | −0.0034 (19) |
| C3 | 0.044 (3) | 0.056 (3) | 0.042 (3) | −0.014 (2) | −0.009 (2) | −0.009 (2) |
| C4 | 0.058 (3) | 0.064 (3) | 0.025 (2) | −0.012 (2) | −0.006 (2) | −0.004 (2) |
| C5 | 0.047 (3) | 0.046 (3) | 0.029 (2) | −0.008 (2) | −0.002 (2) | 0.0062 (19) |
| C6 | 0.030 (2) | 0.035 (2) | 0.028 (2) | −0.0023 (17) | −0.0016 (17) | 0.0015 (17) |
| C7 | 0.032 (2) | 0.037 (2) | 0.031 (2) | −0.0021 (17) | 0.0067 (17) | 0.0044 (17) |
| C8 | 0.040 (2) | 0.042 (2) | 0.036 (2) | −0.0136 (19) | 0.0014 (19) | 0.0020 (19) |
| C9 | 0.029 (2) | 0.054 (3) | 0.035 (2) | −0.0156 (19) | 0.0030 (18) | 0.0022 (19) |
| C10 | 0.026 (2) | 0.049 (3) | 0.024 (2) | −0.0129 (18) | 0.0025 (16) | −0.0055 (17) |
| C11 | 0.027 (2) | 0.040 (2) | 0.035 (2) | −0.0071 (17) | −0.0018 (17) | −0.0057 (18) |
| C12 | 0.030 (2) | 0.045 (3) | 0.049 (3) | −0.0022 (19) | −0.008 (2) | −0.007 (2) |
| C13 | 0.046 (3) | 0.042 (3) | 0.049 (3) | −0.004 (2) | −0.014 (2) | 0.004 (2) |
| C14 | 0.041 (2) | 0.050 (3) | 0.050 (3) | −0.015 (2) | −0.007 (2) | 0.013 (2) |
| C15 | 0.028 (2) | 0.053 (3) | 0.045 (3) | −0.0143 (19) | −0.0027 (19) | 0.008 (2) |
| C16 | 0.027 (2) | 0.038 (2) | 0.034 (2) | −0.0082 (17) | −0.0031 (17) | −0.0045 (18) |
| Cu1—O1 | 1.918 (3) | C5—C6 | 1.404 (5) |
| Cu1—N1 | 1.951 (3) | C5—H5 | 0.9300 |
| Cu1—N3 | 2.009 (3) | C6—C7 | 1.431 (5) |
| Cu1—Cl1 | 2.2347 (12) | C7—H7 | 0.9300 |
| O1—C1 | 1.321 (4) | C8—C9 | 1.514 (5) |
| N1—C7 | 1.274 (5) | C8—H8A | 0.9700 |
| N1—C8 | 1.466 (5) | C8—H8B | 0.9700 |
| N2—C10 | 1.333 (5) | C9—C10 | 1.501 (5) |
| N2—C11 | 1.371 (5) | C9—H9A | 0.9700 |
| N2—H16 | 0.8600 | C9—H9B | 0.9700 |
| N3—C10 | 1.327 (4) | C11—C12 | 1.384 (5) |
| N3—C16 | 1.406 (5) | C11—C16 | 1.395 (5) |
| C1—C2 | 1.389 (5) | C12—C13 | 1.365 (6) |
| C1—C6 | 1.420 (5) | C12—H12 | 0.9300 |
| C2—C3 | 1.372 (6) | C13—C14 | 1.397 (6) |
| C2—H2 | 0.9300 | C13—H13 | 0.9300 |
| C3—C4 | 1.375 (6) | C14—C15 | 1.376 (5) |
| C3—H3 | 0.9300 | C14—H14 | 0.9300 |
| C4—C5 | 1.360 (6) | C15—C16 | 1.385 (5) |
| C4—H4 | 0.9300 | C15—H15 | 0.9300 |
| O1—Cu1—N1 | 92.21 (12) | N1—C7—H7 | 116.9 |
| O1—Cu1—N3 | 145.14 (13) | C6—C7—H7 | 116.9 |
| N1—Cu1—N3 | 90.28 (12) | N1—C8—C9 | 110.3 (3) |
| O1—Cu1—Cl1 | 93.09 (8) | N1—C8—H8A | 109.6 |
| N1—Cu1—Cl1 | 155.59 (10) | C9—C8—H8A | 109.6 |
| N3—Cu1—Cl1 | 98.78 (9) | N1—C8—H8B | 109.6 |
| C1—O1—Cu1 | 127.4 (2) | C9—C8—H8B | 109.6 |
| C7—N1—C8 | 119.2 (3) | H8A—C8—H8B | 108.1 |
| C7—N1—Cu1 | 126.2 (3) | C10—C9—C8 | 114.3 (3) |
| C8—N1—Cu1 | 114.5 (2) | C10—C9—H9A | 108.7 |
| C10—N2—C11 | 108.3 (3) | C8—C9—H9A | 108.7 |
| C10—N2—H16 | 125.8 | C10—C9—H9B | 108.7 |
| C11—N2—H16 | 125.8 | C8—C9—H9B | 108.7 |
| C10—N3—C16 | 104.9 (3) | H9A—C9—H9B | 107.6 |
| C10—N3—Cu1 | 125.4 (2) | N3—C10—N2 | 112.6 (3) |
| C16—N3—Cu1 | 127.2 (2) | N3—C10—C9 | 126.3 (3) |
| O1—C1—C2 | 119.2 (3) | N2—C10—C9 | 121.1 (3) |
| O1—C1—C6 | 123.4 (4) | N2—C11—C12 | 131.5 (3) |
| C2—C1—C6 | 117.4 (4) | N2—C11—C16 | 105.6 (3) |
| C3—C2—C1 | 121.9 (4) | C12—C11—C16 | 122.9 (4) |
| C3—C2—H2 | 119.0 | C13—C12—C11 | 116.6 (4) |
| C1—C2—H2 | 119.0 | C13—C12—H12 | 121.7 |
| C2—C3—C4 | 120.9 (4) | C11—C12—H12 | 121.7 |
| C2—C3—H3 | 119.6 | C12—C13—C14 | 121.6 (4) |
| C4—C3—H3 | 119.6 | C12—C13—H13 | 119.2 |
| C5—C4—C3 | 118.9 (4) | C14—C13—H13 | 119.2 |
| C5—C4—H4 | 120.5 | C15—C14—C13 | 121.6 (4) |
| C3—C4—H4 | 120.5 | C15—C14—H14 | 119.2 |
| C4—C5—C6 | 122.0 (4) | C13—C14—H14 | 119.2 |
| C4—C5—H5 | 119.0 | C14—C15—C16 | 117.7 (4) |
| C6—C5—H5 | 119.0 | C14—C15—H15 | 121.2 |
| C5—C6—C1 | 118.8 (4) | C16—C15—H15 | 121.2 |
| C5—C6—C7 | 118.6 (3) | C15—C16—C11 | 119.7 (4) |
| C1—C6—C7 | 122.6 (3) | C15—C16—N3 | 131.7 (3) |
| N1—C7—C6 | 126.3 (3) | C11—C16—N3 | 108.6 (3) |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N2—H16···O1i | 0.86 | 1.90 | 2.753 (4) | 170 |
| Symmetry codes: (i) x−1, y, z. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N2—H16···O1i | 0.86 | 1.90 | 2.753 (4) | 170 |
| Symmetry codes: (i) x−1, y, z. |
We appreciate the financial support of the National Natural Science Foundation of China (No. 30470408).
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The aggregation of the amyloid-beta peptide to form senile plaques is a key event in Alzheimer's disease (Masters et al., 1985). Complexation of copper and zinc with the amyloid-beta peptide induces aggregation of the peptide (Atwood et al., 1998; Bush et al., 1994; Syme et al., 2004). Detailed knowledge of the metal- Amyloid-beta coordination environment could aid in the development of compounds with more effective and specific metal chelating properties as eventual treatments in Alzheimer's disease. As our efforts to develop model complexes as mimics of the metal site, we report a novel copper complex in this paper.
A displacement ellipsoid drawing of (I) is shown in Fig. 1. Selected bond lengths and angles are listed in Table 1. Cu(II) ion exhibits a distorted tetrahedral geometry. The coordination sphere of Cu(II) ion is composed of one benzoimidazole N atom, one imino N atom, one phenolato O atom and one Cl anion. As shown in Fig. 2, intermolecular N—H···O hydrogen bonds play key roles in stabilizing the crystal packing. The detailed hydrogen bond information is listed in Table 2.