metal-organic compounds
Poly[(2,2′-bipyridine-κ2N,N′)[μ4-2,2′-(1,3-phenylene)bis(imidazol-1-yl)-κ4N:N′:N′′:N′′′]dicopper(I)]
aDepartment of Inoganic Chemistry and Physical Chemistry, College of Pharmacy, Guangxi Medical University, Nanning 530021, People's Republic of China
*Correspondence e-mail: xuehuali_100@163.com
Two CuI atoms are present in the of the polymeric title complex, [Cu2(C20H12N4)(C10H8N2)]n. One of the cations is located on an inversion centre and is linearly coordinated by the N atoms of benzimidazolyl moieties of the 1,2-bis(2-benzimidazolium)benzene ligand, whereas the second cation is located on a twofold rotation axis and is tetrahedrally coordinated by two N atoms of a chelating 2,2′-bipyridine ligand and two other N atoms of the benzimidazolyl moieties. The bridging character of the 1,2-bis(2-benzimidazolyl)benzene leads to the formation of a three-dimensional framework structure.
CCDC reference: 1471071
Structure description
Copper complexes have attracted significant attention because of their biological activities. Apart from a low toxicity, copper complexes can potentially inhibit cellular proteasomal activity, enhance apoptosis and DNA binding activities (Gopalakrishnan et al., 2014). Benzimidazole and its derivatives exhibit anticancer (Rodríguez-Solano et al., 2011), antifungal (Coyle et al., 2004), anti-inflammatory (Sączewski et al., 2006), anti-rheumatism (Rowan et al., 2009) or insect-repellent activities (Rowan et al., 2009), and are widely used in metal-organic chemistry. In the current project we have combined copper and a benzimidazole derivative together with 2,2′-bipyridine as a co-ligand to yield the title complex, [Cu2(C20H12N4)(C10H8N2)]n.
As shown in Fig. 1, the contains two CuI ions. The Cu1 site is linearly coordinated by the N1 atoms from symmetry-related benzimidazolium moieties at a distance of 1.887 (2) Å. The Cu2 site shows a tetrahedral coordination by the other two N atoms of the benzimidazolyl moieties and the N atoms of the 2,2′-bipyridine ligand. The small bite angle of the latter [N—Cu—N 79.01 (13)°] causes a considerable distortion of the coordination sphere [angular range 79.01 (13) − 117.21 (8)°]. The dihedral angle between two benzimidazolyl rings is 37.00 (9)°, in good agreement with those of other Cu complexes containing benzimidazolyl ligands (Lin et al., 2015). The dihedral angle of 15.07 (15)° between the two pyridinyl rings in the 2,2′-bipyridine ligand indicates considerable twisting. The bridging character of the organic anion leads to the formation of a three-dimensional polymeric structure (Fig. 2).
Synthesis and crystallization
1,2-Bis(2-benzimidazolyl)benzene was synthesized according to a reported procedure (Deng et al., 2012). 1,2-bis(2-benzimidazolyl)benzene (0.1 mmol, 0.0312 g), 2,2′-bipyridine (0.1 mmol, 0.0156 g) and CuCl2 (0.1 mmol, 0.0170 g) were added to 15 ml aqueous NH3 and stirred for 30 s. Then the solution was placed in a 23 ml Teflon-lined stainless-steel vessel and heated at 466 K for 3 d, then cooled to room temperature at 5 K h−1. Dark-red block-like crystals were obtained directly from the reaction mixture. IR (KBr, cm−1): 3444.6 (s), 1605.7 (m), 1439.3 (m), 1372.6 (s), 1283.0 (s), 860.5 (w), 747.0 (w), 699.0 (w).
Refinement
Crystal data, data collection and structure .
details are summarized in Table 1Structural data
CCDC reference: 1471071
10.1107/S2414314616010075/wm5300sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S2414314616010075/wm5300Isup2.hkl
Data collection: APEX2 (Bruker, 2013); cell
SAINT (Bruker, 2013); data reduction: SAINT (Bruker, 2013); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).[Cu2(C20H12N4)(C10H8N2)] | Dx = 1.651 Mg m−3 |
Mr = 591.60 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Fddd | Cell parameters from 4559 reflections |
a = 10.857 (3) Å | θ = 3.0–26.7° |
b = 26.523 (8) Å | µ = 1.82 mm−1 |
c = 33.064 (10) Å | T = 298 K |
V = 9521 (5) Å3 | Block, dark red |
Z = 16 | 0.3 × 0.2 × 0.1 mm |
F(000) = 4800 |
Bruker APEXII CCD diffractometer | 1969 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.042 |
phi and ω scans | θmax = 26.4°, θmin = 2.7° |
Absorption correction: multi-scan (SADABS; Bruker, 2013) | h = −13→13 |
Tmin = 0.752, Tmax = 0.940 | k = −33→32 |
17682 measured reflections | l = −40→41 |
2438 independent reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.035 | H-atom parameters constrained |
wR(F2) = 0.084 | w = 1/[σ2(Fo2) + (0.0421P)2 + 18.4382P] where P = (Fo2 + 2Fc2)/3 |
S = 1.09 | (Δ/σ)max < 0.001 |
2438 reflections | Δρmax = 0.43 e Å−3 |
175 parameters | Δρmin = −0.24 e Å−3 |
0 restraints |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
x | y | z | Uiso*/Ueq | ||
Cu1 | 1.0000 | 0.5000 | 0.5000 | 0.02680 (14) | |
Cu2 | 0.6250 | 0.6250 | 0.41384 (2) | 0.02941 (14) | |
N1 | 0.89614 (18) | 0.55364 (8) | 0.48437 (6) | 0.0240 (4) | |
N2 | 0.77124 (18) | 0.60678 (8) | 0.44890 (6) | 0.0238 (5) | |
N3 | 0.5862 (2) | 0.57785 (8) | 0.36543 (6) | 0.0313 (5) | |
C8 | 0.8571 (2) | 0.53486 (9) | 0.41133 (7) | 0.0207 (5) | |
C9 | 0.8750 | 0.56041 (12) | 0.3750 | 0.0202 (7) | |
H9 | 0.8750 | 0.5955 | 0.3750 | 0.024* | |
C1 | 0.8628 (2) | 0.59333 (10) | 0.50958 (7) | 0.0255 (5) | |
C7 | 0.8393 (2) | 0.56451 (9) | 0.44871 (7) | 0.0203 (5) | |
C10 | 0.8574 (2) | 0.48240 (9) | 0.41092 (7) | 0.0287 (6) | |
H10 | 0.8456 | 0.4646 | 0.4349 | 0.034* | |
C6 | 0.7865 (2) | 0.62607 (10) | 0.48737 (7) | 0.0250 (5) | |
C11 | 0.8750 | 0.45660 (14) | 0.3750 | 0.0348 (9) | |
H11 | 0.8750 | 0.4215 | 0.3750 | 0.042* | |
C2 | 0.8954 (3) | 0.60438 (11) | 0.54960 (8) | 0.0364 (7) | |
H2 | 0.9454 | 0.5828 | 0.5645 | 0.044* | |
C5 | 0.7417 (3) | 0.67038 (11) | 0.50444 (8) | 0.0366 (7) | |
H5 | 0.6910 | 0.6920 | 0.4899 | 0.044* | |
C16 | 0.5963 (2) | 0.59969 (11) | 0.32881 (8) | 0.0319 (6) | |
C3 | 0.8506 (3) | 0.64837 (13) | 0.56591 (9) | 0.0454 (8) | |
H3 | 0.8709 | 0.6567 | 0.5924 | 0.054* | |
C4 | 0.7754 (3) | 0.68100 (12) | 0.54375 (10) | 0.0470 (8) | |
H4 | 0.7474 | 0.7105 | 0.5558 | 0.056* | |
C15 | 0.5544 (3) | 0.57578 (15) | 0.29392 (10) | 0.0520 (9) | |
H15 | 0.5602 | 0.5917 | 0.2689 | 0.062* | |
C12 | 0.5399 (3) | 0.53138 (12) | 0.36714 (11) | 0.0497 (8) | |
H12 | 0.5348 | 0.5157 | 0.3923 | 0.060* | |
C13 | 0.4992 (3) | 0.50542 (15) | 0.33384 (15) | 0.0662 (12) | |
H13 | 0.4687 | 0.4728 | 0.3364 | 0.079* | |
C14 | 0.5042 (3) | 0.52832 (17) | 0.29698 (14) | 0.0680 (13) | |
H14 | 0.4741 | 0.5120 | 0.2741 | 0.082* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.0312 (2) | 0.0276 (2) | 0.0215 (2) | 0.00712 (19) | −0.00507 (18) | 0.00262 (18) |
Cu2 | 0.0312 (3) | 0.0374 (3) | 0.0196 (2) | 0.0108 (2) | 0.000 | 0.000 |
N1 | 0.0285 (11) | 0.0256 (11) | 0.0179 (10) | 0.0025 (9) | −0.0015 (8) | 0.0018 (9) |
N2 | 0.0250 (10) | 0.0262 (11) | 0.0203 (10) | 0.0049 (9) | −0.0026 (8) | −0.0021 (8) |
N3 | 0.0301 (12) | 0.0331 (13) | 0.0308 (13) | 0.0032 (10) | −0.0018 (9) | −0.0034 (10) |
C8 | 0.0187 (11) | 0.0241 (12) | 0.0193 (12) | 0.0022 (9) | 0.0008 (9) | 0.0001 (10) |
C9 | 0.0180 (15) | 0.0186 (17) | 0.0239 (17) | 0.000 | 0.0011 (13) | 0.000 |
C1 | 0.0264 (13) | 0.0288 (14) | 0.0213 (12) | 0.0005 (11) | −0.0016 (10) | −0.0006 (10) |
C7 | 0.0190 (11) | 0.0227 (12) | 0.0192 (12) | 0.0012 (9) | 0.0004 (9) | 0.0016 (10) |
C10 | 0.0386 (15) | 0.0254 (13) | 0.0221 (13) | −0.0029 (11) | −0.0034 (11) | 0.0059 (11) |
C6 | 0.0251 (12) | 0.0283 (13) | 0.0217 (12) | 0.0014 (10) | 0.0000 (10) | −0.0024 (11) |
C11 | 0.054 (2) | 0.0175 (18) | 0.033 (2) | 0.000 | −0.0078 (19) | 0.000 |
C2 | 0.0425 (16) | 0.0435 (17) | 0.0232 (14) | 0.0038 (13) | −0.0090 (12) | −0.0015 (12) |
C5 | 0.0401 (16) | 0.0344 (16) | 0.0354 (16) | 0.0091 (13) | −0.0052 (12) | −0.0094 (13) |
C16 | 0.0248 (13) | 0.0427 (16) | 0.0283 (14) | 0.0151 (11) | −0.0018 (10) | −0.0096 (12) |
C3 | 0.0531 (19) | 0.055 (2) | 0.0283 (15) | 0.0016 (16) | −0.0095 (14) | −0.0177 (14) |
C4 | 0.0559 (19) | 0.0441 (19) | 0.0410 (18) | 0.0075 (15) | −0.0032 (15) | −0.0238 (15) |
C15 | 0.0415 (17) | 0.080 (3) | 0.0345 (17) | 0.0216 (18) | −0.0073 (14) | −0.0187 (18) |
C12 | 0.0423 (17) | 0.0397 (18) | 0.067 (2) | −0.0047 (14) | 0.0005 (16) | −0.0031 (17) |
C13 | 0.045 (2) | 0.049 (2) | 0.105 (4) | −0.0020 (17) | −0.008 (2) | −0.035 (2) |
C14 | 0.0407 (19) | 0.081 (3) | 0.082 (3) | 0.015 (2) | −0.0173 (19) | −0.056 (3) |
Cu1—N1 | 1.887 (2) | C10—C11 | 1.384 (3) |
Cu1—N1i | 1.887 (2) | C6—C5 | 1.391 (4) |
Cu2—N2ii | 2.024 (2) | C11—C10iii | 1.384 (3) |
Cu2—N2 | 2.024 (2) | C11—H11 | 0.9300 |
Cu2—N3ii | 2.075 (2) | C2—H2 | 0.9300 |
Cu2—N3 | 2.075 (2) | C2—C3 | 1.374 (4) |
N1—C1 | 1.391 (3) | C5—H5 | 0.9300 |
N1—C7 | 1.362 (3) | C5—C4 | 1.379 (4) |
N2—C7 | 1.343 (3) | C16—C16ii | 1.480 (6) |
N2—C6 | 1.381 (3) | C16—C15 | 1.393 (4) |
N3—C16 | 1.347 (3) | C3—H3 | 0.9300 |
N3—C12 | 1.332 (4) | C3—C4 | 1.397 (4) |
C8—C9 | 1.393 (3) | C4—H4 | 0.9300 |
C8—C7 | 1.477 (3) | C15—H15 | 0.9300 |
C8—C10 | 1.391 (3) | C15—C14 | 1.375 (5) |
C9—C8iii | 1.393 (3) | C12—H12 | 0.9300 |
C9—H9 | 0.9300 | C12—C13 | 1.372 (5) |
C1—C6 | 1.407 (3) | C13—H13 | 0.9300 |
C1—C2 | 1.401 (4) | C13—C14 | 1.363 (6) |
C10—H10 | 0.9300 | C14—H14 | 0.9300 |
N1—Cu1—N1i | 180.00 (8) | N2—C6—C5 | 130.1 (2) |
N2ii—Cu2—N2 | 110.13 (11) | C5—C6—C1 | 121.0 (2) |
N2ii—Cu2—N3ii | 117.21 (8) | C10iii—C11—C10 | 120.7 (3) |
N2—Cu2—N3 | 117.21 (8) | C10—C11—H11 | 119.6 |
N2ii—Cu2—N3 | 115.24 (9) | C10iii—C11—H11 | 119.6 |
N2—Cu2—N3ii | 115.25 (9) | C1—C2—H2 | 121.3 |
N3ii—Cu2—N3 | 79.01 (13) | C3—C2—C1 | 117.3 (3) |
C1—N1—Cu1 | 124.19 (16) | C3—C2—H2 | 121.3 |
C7—N1—Cu1 | 131.87 (17) | C6—C5—H5 | 121.2 |
C7—N1—C1 | 103.9 (2) | C4—C5—C6 | 117.5 (3) |
C7—N2—Cu2 | 128.91 (16) | C4—C5—H5 | 121.2 |
C7—N2—C6 | 104.3 (2) | N3—C16—C16ii | 115.12 (16) |
C6—N2—Cu2 | 122.24 (16) | N3—C16—C15 | 121.5 (3) |
C16—N3—Cu2 | 114.70 (18) | C15—C16—C16ii | 123.4 (2) |
C12—N3—Cu2 | 127.0 (2) | C2—C3—H3 | 119.1 |
C12—N3—C16 | 117.8 (3) | C2—C3—C4 | 121.8 (3) |
C9—C8—C7 | 118.7 (2) | C4—C3—H3 | 119.1 |
C10—C8—C9 | 118.5 (2) | C5—C4—C3 | 121.5 (3) |
C10—C8—C7 | 122.7 (2) | C5—C4—H4 | 119.3 |
C8—C9—C8iii | 121.8 (3) | C3—C4—H4 | 119.3 |
C8iii—C9—H9 | 119.1 | C16—C15—H15 | 120.5 |
C8—C9—H9 | 119.1 | C14—C15—C16 | 119.0 (3) |
N1—C1—C6 | 107.9 (2) | C14—C15—H15 | 120.5 |
N1—C1—C2 | 131.2 (2) | N3—C12—H12 | 118.3 |
C2—C1—C6 | 120.8 (2) | N3—C12—C13 | 123.5 (4) |
N1—C7—C8 | 123.5 (2) | C13—C12—H12 | 118.3 |
N2—C7—N1 | 115.0 (2) | C12—C13—H13 | 120.6 |
N2—C7—C8 | 121.4 (2) | C14—C13—C12 | 118.8 (4) |
C8—C10—H10 | 119.9 | C14—C13—H13 | 120.6 |
C11—C10—C8 | 120.2 (2) | C15—C14—H14 | 120.3 |
C11—C10—H10 | 119.9 | C13—C14—C15 | 119.3 (3) |
N2—C6—C1 | 108.9 (2) | C13—C14—H14 | 120.3 |
Cu1—N1—C1—C6 | 179.22 (16) | C1—C2—C3—C4 | 0.1 (5) |
Cu1—N1—C1—C2 | 1.3 (4) | C7—N1—C1—C6 | 0.2 (3) |
Cu1—N1—C7—N2 | −179.99 (16) | C7—N1—C1—C2 | −177.7 (3) |
Cu1—N1—C7—C8 | −4.5 (4) | C7—N2—C6—C1 | −1.3 (3) |
Cu2—N2—C7—N1 | −154.51 (17) | C7—N2—C6—C5 | 177.2 (3) |
Cu2—N2—C7—C8 | 29.9 (3) | C7—C8—C9—C8iii | 179.7 (2) |
Cu2—N2—C6—C1 | 156.77 (17) | C7—C8—C10—C11 | −179.75 (19) |
Cu2—N2—C6—C5 | −24.8 (4) | C10—C8—C9—C8iii | 0.01 (16) |
Cu2—N3—C16—C16ii | 10.2 (3) | C10—C8—C7—N1 | 44.2 (3) |
Cu2—N3—C16—C15 | −169.4 (2) | C10—C8—C7—N2 | −140.5 (2) |
Cu2—N3—C12—C13 | 169.7 (2) | C6—N2—C7—N1 | 1.5 (3) |
N1—C1—C6—N2 | 0.7 (3) | C6—N2—C7—C8 | −174.1 (2) |
N1—C1—C6—C5 | −177.9 (2) | C6—C1—C2—C3 | −0.4 (4) |
N1—C1—C2—C3 | 177.3 (3) | C6—C5—C4—C3 | −0.7 (5) |
N2—C6—C5—C4 | −177.9 (3) | C2—C1—C6—N2 | 178.8 (2) |
N3—C16—C15—C14 | −1.5 (4) | C2—C1—C6—C5 | 0.2 (4) |
N3—C12—C13—C14 | −1.1 (5) | C2—C3—C4—C5 | 0.5 (5) |
C8—C10—C11—C10iii | 0.01 (17) | C16—N3—C12—C13 | −1.8 (4) |
C9—C8—C7—N1 | −135.5 (2) | C16ii—C16—C15—C14 | 178.9 (3) |
C9—C8—C7—N2 | 39.7 (3) | C16—C15—C14—C13 | −1.4 (5) |
C9—C8—C10—C11 | 0.0 (3) | C12—N3—C16—C16ii | −177.3 (3) |
C1—N1—C7—N2 | −1.1 (3) | C12—N3—C16—C15 | 3.1 (4) |
C1—N1—C7—C8 | 174.4 (2) | C12—C13—C14—C15 | 2.7 (5) |
C1—C6—C5—C4 | 0.3 (4) |
Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) −x+5/4, −y+5/4, z; (iii) −x+7/4, y, −z+3/4. |
Acknowledgements
The authors are grateful for the financial support from (i) the Youth Science Foundation of Guangxi Natural Science (No. 2014GXNSFBA118053), (ii) the Education Department of Guangxi (No. KY2015ZL020), (iii) the Natural Science Foundation of Guangxi (No. 2010GXNSF013159), (iv) the Program of Guangxi Provincial Department of Science and Technology (No. 12118005-1-2) and (v) the Innovation Project of Guangxi Postgraduate (No. YCSZ2015118) to this research.
References
Bruker (2013). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Coyle, B., McCann, M., Kavanagh, K., Devereux, M., McKee, V., Kayal, N., Egan, D., Deegan, C. & Finn, G. J. (2004). J. Inorg. Biochem. 98, 1361–1366. Web of Science CSD CrossRef PubMed CAS Google Scholar
Deng, Y. Y., Wu, H. Z., Jin, Y. L. & Liu, F. (2012). J. Chem. Crystallogr. 42, 739–745. CSD CrossRef CAS Google Scholar
Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339–341. Web of Science CrossRef CAS IUCr Journals Google Scholar
Gopalakrishnan, M., Senthilkumar, K., Rao, P. R., Siva, R. & Palanisami, N. (2014). Inorg. Chem. Commun. 46, 54–59. CSD CrossRef CAS Google Scholar
Lin, J. J., Meng, F. Y. & Li, X. H. (2015). Chin. J. Struc. Chem, 1, 41–48. Google Scholar
Rodríguez Solano, L. A., Aguiñiga, I., López Ortiz, M., Tiburcio, R., Luviano, A., Regla, I., Santiago-Osorio, E., Ugalde-Saldívar, V. M., Toscano, R. A. & Castillo, I. (2011). Eur. J. Inorg. Chem. pp. 3454–3460. Google Scholar
Rowan, R., Moran, C., McCann, M. & Kavanagh, K. (2009). Bio. Metals. 22, 461–467. CAS Google Scholar
Sączewski, F., Dziemidowicz-Borys, E., Bednarski, P. J., Grünert, R., Gdaniec, M. & Tabin, P. (2006). J. Inorg. Biochem. 100, 1389–1398. PubMed Google Scholar
Sheldrick, G. M. (2015a). Acta Cryst. A71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2015b). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
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