Poly[(2,2′-bi­pyridine-κ2N,N′)[μ4-2,2′-(1,3-phenyl­ene)bis­(imidazol-1-yl)-κ4N:N′:N′′:N′′′]dicopper(I)]

Zhou, R.; Meng, F.-Y.; Li, X.-H.

doi:10.1107/S2414314616010075

metal-organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 1| Part 6| June 2016| x161007

doi:10.1107/S2414314616010075

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Poly[(2,2′-bipyridine-κ²N,N′)[μ₄-2,2′-(1,3-phenylene)bis(imidazol-1-yl)-κ⁴N:N′:N′′:N′′′]dicopper(I)]

Rui Zhou,^a Fa-Yan Meng ^a and Xue-Hua Li ^a ^*

^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

Edited by M. Weil, Vienna University of Technology, Austria (Received 10 June 2016; accepted 21 June 2016; online 24 June 2016)

Two Cu^I atoms are present in the asymmetric unit 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.

Keywords: crystal structure; copper(I) complex; benzimidazole derivative; 2,2′-bipyridine.

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 asymmetric unit contains two Cu^I 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).

Figure 1
The coordination environments around the two different Cu^I atoms. Displacement ellipsoids are drawn at the 50% probability level. [Symmetry codes: (i) −x + 2, −y + 1, −z + 1; (ii) −x + $[{5\over 4}]$ , −y + $[{5\over 4}]$ , z; (iii) −x + 7/4, y, −z + $[{3\over 4}]$ .]

Figure 2
Part of the crystal packing in the title structure.

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 refinement details are summarized in Table 1.

Table 1
Experimental details

Crystal data
Chemical formula	[Cu₂(C₂₀H₁₂N₄)(C₁₀H₈N₂)]
M_r	591.60
Crystal system, space group	Orthorhombic, Fddd
Temperature (K)	298
a, b, c (Å)	10.857 (3), 26.523 (8), 33.064 (10)
V (Å³)	9521 (5)
Z	16
Radiation type	Mo Kα
μ (mm⁻¹)	1.82
Crystal size (mm)	0.3 × 0.2 × 0.1

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2013 )
T_min, T_max	0.752, 0.940
No. of measured, independent and observed [I > 2σ(I)] reflections	17682, 2438, 1969
R_int	0.042
(sin θ/λ)_max (Å⁻¹)	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.084, 1.09
No. of reflections	2438
No. of parameters	175
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.43, −0.24
Computer programs: APEX2 and SAINT (Bruker, 2013), SHELXT (Sheldrick, 2015a ), SHELXL2014 (Sheldrick, 2015b ) and OLEX2 (Dolomanov et al., 2009 ).

Structural data

CCDC reference: 1471071

Crystal structure: contains datablock I. DOI: 10.1107/S2414314616010075/wm5300sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2414314616010075/wm5300Isup2.hkl

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2013); cell refinement: 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).

Poly[(2,2'-bipyridine-κ²N,N')[µ₄-2,2'-(1,3-phenylene)bis(imidazol-1-yl)-κ⁴N:N':N'':N''']dicopper(I)] top

Crystal data top

[Cu₂(C₂₀H₁₂N₄)(C₁₀H₈N₂)]	D_x = 1.651 Mg m⁻³
M_r = 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

Data collection top

Bruker APEXII CCD diffractometer	1969 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.042
phi and ω scans	θ_max = 26.4°, θ_min = 2.7°
Absorption correction: multi-scan (SADABS; Bruker, 2013)	h = −13→13
T_min = 0.752, T_max = 0.940	k = −33→32
17682 measured reflections	l = −40→41
2438 independent reflections

Refinement top

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(F_o²) + (0.0421P)² + 18.4382P] where P = (F_o² + 2F_c²)/3
S = 1.09	(Δ/σ)_max < 0.001
2438 reflections	Δρ_max = 0.43 e Å⁻³
175 parameters	Δρ_min = −0.24 e Å⁻³
0 restraints

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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.

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