Crystal structure of [3-(1H-benzimidazol-2-yl)propano­ato-κN3][3-(1H-benzimid­azol-2-yl)propanoic acid-κN3]copper(I)

Liu, Z.; Zheng, S.; Feng, S.

doi:10.1107/S2056989014026656

metal-organic compounds

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Volume 71| Part 1| January 2015| Pages m5-m6

https://doi.org/10.1107/S2056989014026656

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Crystal structure of [3-(1H-benzimidazol-2-yl)propanoato-κN³][3-(1H-benzimidazol-2-yl)propanoic acid-κN³]copper(I)

Zhimin Liu,^a ^* Shengrun Zheng ^b and Sisi Feng ^c

^aSchool of Chemistry and Chemical Engineering, Shanxi University, Taiyuan 030006, People's Republic of China, ^bInstitute of Special Materials & School of Chemistry and Environment, South China Normal University, Guangzhou 510006, People's Republic of China, and ^cInstitute of Molecular Science, Key Laboratory of Chemical Biology and Molecular, Engineering of the Education Ministry, Shanxi University, Taiyuan, Shanxi 030006, People's Republic of China
^*Correspondence e-mail: luckzhmliu@sxu.edu.cn

Edited by W. Imhof, University Koblenz-Landau, Germany (Received 19 November 2014; accepted 4 December 2014; online 1 January 2015)

In the title compound, [Cu(C₁₀H₉N₂O₂)(C₁₀H₁₀N₂O₂)], the Cu^I ion is situated at a crystallographic centre of inversion and is coordinated in a linear environment by two benzimidazole N atoms from two symmetry-related 2-propanoic-1H-benzimidazole ligands. The ligands are disordered in a sense that statistically one of the carboxylic acid groups in each molecule is deprotonated. In the crystal, O—H⋯O hydrogen bonds link the molecules into chains along the a-axis direction. These chains are additionally linked into infinite two-dimensional networks in the ab plane by N—H⋯O hydrogen bonds.

Keywords: crystal structure; 3-(1H-benzimidazol-2-yl)propanoic acid; copper(I); hydrogen bonding.

CCDC reference: 1033367

1. Related literature

For background to benzimidazole complexes with copper(I), see: Lei et al. (2010 ). For the structures and properties of transition metal complexes with 3-(1H-benzimidazol-2-yl)propanoic acid ligands, see: Zheng et al. (2012 ); Zeng et al. (2007 ); Yao et al. (2008 ); Choi (2004 ).

2. Experimental

2.1. Crystal data

[Cu(C₁₀H₉N₂O₂)(C₁₀H₁₀N₂O₂)]
M_r = 442.93
Monoclinic, C 2/c
a = 21.137 (5) Å
b = 6.4979 (14) Å
c = 16.235 (4) Å
β = 121.949 (2)°
V = 1892.0 (7) Å³
Z = 4
Mo Kα radiation
μ = 1.19 mm⁻¹
T = 298 K
0.28 × 0.24 × 0.20 mm

2.2. Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.732, T_max = 0.797
4975 measured reflections
1855 independent reflections
1370 reflections with I > 2σ(I)
R_int = 0.031

2.3. Refinement

R[F² > 2σ(F²)] = 0.038
wR(F²) = 0.101
S = 1.01
1855 reflections
134 parameters
H-atom parameters constrained
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.26 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯O1ⁱ	0.86	1.97	2.725 (3)	146
O2—H2B⋯O2ⁱⁱ	0.82	1.69	2.491 (5)	166
Symmetry codes: (i) x, y+1, z; (ii) -x, -y, -z.

Data collection: APEX2 (Bruker, 2004 ); cell refinement: SAINT (Bruker, 2002 ); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

CCDC reference: 1033367

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: https://doi.org/10.1107/S2056989014026656/im2457sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989014026656/im2457Isup2.hkl

checkCIF report

Comment top

Benzimidazole and its derivatives have been extensively used in building pharmaceutical compounds. A number of metal-benzimidazole complexes have been studied due to their potential applications (Zheng et al., 2012). In this paper, we report a new structure, [Cu(C₁₀H₉N₂O₂)(C₁₀H₁₀N₂O₂)], which was synthesized by condensation of 3-(1H-benzimidazol-2-yl) propanoic acid in the presence of copper(I) chloride.

As shown in Fig1, the Cu(I) ion is situated at a crystallographic centre of symmetry and is coordinated by two N atoms from two -(2-propanoic) benzimidazole ligands in a linear environment. The ligands are disordered in a sense that statistically one of the carboxyl groups in each complex molecule is deprotonated. This means that there is one negatively charged ligand and the oxidation state of copper therefore is +1. Due to the low coordination number of Cu(I), the bond distances of Cu(I)–N (1.851 Å) is shorter than those reported recently (Lei et al., 2010). In the crystal structure, O—H···O hydrogen bonds link the molecules into one-dimensional chains along the a axis. These chains are additionally linked into infinte two-dimensional networks in the ab plane by N—H···O hydrogen bonds. (Table 1 and Fig. 2).

Related literature top

For background to benzimidazole complexes with copper(I), see: Lei et al. (2010). For the structures and properties of transition metal complexes with 3-(1H-benzimidazol-2-yl)propanoic acid ligands, see: Zheng et al. (2012); Zeng et al. (2007); Yao et al. (2008); Choi (2004).

Experimental top

The ligand 3-(1H-benzimidazol-2-yl) propanoic acid was prepared according to a procedure described by Yao et al. (2008). A mixture of copper(I) chloride (0.10 g, 1.0 mmol), 3-(1H-benzimidazol-2-yl) propanoic acid (0.38 g, 2.0 mmol) and methanol (15 ml) was sealed in 25ml Teflon-lined stainless steel reactor and heated to 423K for 72h. Yellow block crystals of the title compound suitable for X-ray analysis were obtainted (yield: 73% based on 3-(1H-benzimidazol-2-yl) propanoic acid).

Structure description top

For background to benzimidazole complexes with copper(I), see: Lei et al. (2010). For the structures and properties of transition metal complexes with 3-(1H-benzimidazol-2-yl)propanoic acid ligands, see: Zheng et al. (2012); Zeng et al. (2007); Yao et al. (2008); Choi (2004).

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The structure of the title compound, showing 30% probability displacement ellipsoids and the atom-numbering scheme.
	Fig. 2. Part of the crystal structure of the title compound, showing the formation of the two-dimensional network by hydrogen bonds (dashed lines). H atoms are omitted for clarity.

[3-(1H-Benzimidazol-2-yl)propanoato-κN³][3-(1H-benzimidazol-2-yl)propanoic acid-κN³]copper(I) top

Crystal data top

[Cu(C₁₀H₉N₂O₂)(C₁₀H₁₀N₂O₂)]	F(000) = 912
M_r = 442.93	D_x = 1.555 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 1118 reflections
a = 21.137 (5) Å	θ = 2.3–22.1°
b = 6.4979 (14) Å	µ = 1.19 mm⁻¹
c = 16.235 (4) Å	T = 298 K
β = 121.949 (2)°	Block, yellow
V = 1892.0 (7) Å³	0.28 × 0.24 × 0.20 mm
Z = 4

Data collection top

Bruker APEXII CCD diffractometer	1855 independent reflections
Radiation source: fine-focus sealed tube	1370 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.031
φ and ω scans	θ_max = 26.0°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −26→25
T_min = 0.732, T_max = 0.797	k = −8→7
4975 measured reflections	l = −17→20

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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.101	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.0474P)² + 1.3591P] where P = (F_o² + 2F_c²)/3
1855 reflections	(Δ/σ)_max < 0.001
134 parameters	Δρ_max = 0.29 e Å⁻³
0 restraints	Δρ_min = −0.26 e Å⁻³

Crystal data top

[Cu(C₁₀H₉N₂O₂)(C₁₀H₁₀N₂O₂)]	V = 1892.0 (7) Å³
M_r = 442.93	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 21.137 (5) Å	µ = 1.19 mm⁻¹
b = 6.4979 (14) Å	T = 298 K
c = 16.235 (4) Å	0.28 × 0.24 × 0.20 mm
β = 121.949 (2)°

Data collection top

Bruker APEXII CCD diffractometer	1855 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1370 reflections with I > 2σ(I)
T_min = 0.732, T_max = 0.797	R_int = 0.031
4975 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	0 restraints
wR(F²) = 0.101	H-atom parameters constrained
S = 1.01	Δρ_max = 0.29 e Å⁻³
1855 reflections	Δρ_min = −0.26 e Å⁻³
134 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	U_iso*/U_eq	Occ. (<1)
Cu1	0.2500	0.2500	0.0000	0.0438 (2)
N1	0.22545 (12)	0.4838 (3)	0.04227 (16)	0.0377 (5)
N2	0.16621 (13)	0.7649 (3)	0.03970 (17)	0.0406 (6)
H2A	0.1312	0.8548	0.0199	0.049*
C1	0.27220 (15)	0.5977 (4)	0.12627 (19)	0.0359 (6)
C7	0.16303 (15)	0.5906 (4)	−0.00686 (19)	0.0369 (6)
C6	0.23477 (16)	0.7750 (4)	0.1243 (2)	0.0386 (6)
C2	0.34360 (16)	0.5579 (5)	0.2038 (2)	0.0480 (7)
H2	0.3692	0.4396	0.2059	0.058*
C9	0.03220 (15)	0.4427 (4)	−0.0953 (2)	0.0441 (7)
H9A	0.0238	0.5342	−0.0548	0.053*
H9B	−0.0124	0.4456	−0.1598	0.053*
C10	0.04164 (16)	0.2279 (4)	−0.0559 (2)	0.0418 (7)
C5	0.26760 (17)	0.9213 (5)	0.1980 (2)	0.0496 (8)
H5	0.2430	1.0421	0.1954	0.059*
C8	0.09664 (15)	0.5287 (5)	−0.1016 (2)	0.0439 (7)
H8A	0.1118	0.4256	−0.1310	0.053*
H8B	0.0789	0.6475	−0.1443	0.053*
C3	0.37526 (18)	0.7010 (5)	0.2779 (2)	0.0520 (8)
H3	0.4228	0.6775	0.3314	0.062*
C4	0.33771 (18)	0.8787 (5)	0.2743 (2)	0.0532 (8)
H4	0.3609	0.9718	0.3254	0.064*
O2	−0.00441 (13)	0.1776 (3)	−0.03148 (19)	0.0594 (6)
H2B	0.0009	0.0554	−0.0166	0.089*	0.50
O1	0.08916 (14)	0.1136 (4)	−0.05134 (19)	0.0717 (7)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0501 (3)	0.0312 (3)	0.0496 (3)	0.0076 (2)	0.0261 (3)	−0.0045 (2)
N1	0.0411 (12)	0.0305 (13)	0.0430 (13)	0.0056 (10)	0.0234 (11)	0.0001 (10)
N2	0.0450 (13)	0.0300 (13)	0.0523 (15)	0.0121 (11)	0.0295 (12)	0.0029 (11)
C1	0.0414 (15)	0.0297 (15)	0.0442 (16)	0.0002 (12)	0.0278 (13)	−0.0006 (12)
C7	0.0421 (15)	0.0327 (15)	0.0406 (15)	0.0062 (13)	0.0250 (13)	0.0068 (12)
C6	0.0456 (16)	0.0323 (16)	0.0483 (16)	0.0016 (13)	0.0319 (14)	0.0006 (13)
C2	0.0433 (16)	0.0448 (19)	0.0552 (19)	0.0062 (14)	0.0256 (15)	0.0004 (15)
C9	0.0420 (16)	0.0406 (18)	0.0459 (17)	0.0105 (13)	0.0207 (14)	0.0035 (13)
C10	0.0392 (15)	0.0414 (18)	0.0429 (16)	0.0052 (14)	0.0203 (13)	−0.0018 (13)
C5	0.061 (2)	0.0399 (18)	0.061 (2)	−0.0009 (15)	0.0415 (18)	−0.0099 (15)
C8	0.0484 (16)	0.0423 (18)	0.0426 (16)	0.0092 (14)	0.0252 (14)	0.0075 (13)
C3	0.0431 (17)	0.062 (2)	0.0504 (18)	−0.0074 (15)	0.0242 (15)	−0.0065 (16)
C4	0.058 (2)	0.055 (2)	0.0547 (19)	−0.0152 (17)	0.0351 (17)	−0.0184 (16)
O2	0.0629 (14)	0.0438 (13)	0.0855 (17)	−0.0025 (12)	0.0489 (14)	−0.0009 (13)
O1	0.0807 (16)	0.0472 (15)	0.111 (2)	0.0285 (13)	0.0671 (16)	0.0266 (14)

Geometric parameters (Å, º) top

Cu1—N1ⁱ	1.851 (2)	C9—C8	1.526 (4)
Cu1—N1	1.851 (2)	C9—H9A	0.9700
N1—C7	1.321 (3)	C9—H9B	0.9700
N1—C1	1.399 (3)	C10—O1	1.220 (3)
N2—C7	1.343 (3)	C10—O2	1.273 (3)
N2—C6	1.373 (4)	C5—C4	1.366 (4)
N2—H2A	0.8600	C5—H5	0.9300
C1—C2	1.385 (4)	C8—H8A	0.9700
C1—C6	1.388 (4)	C8—H8B	0.9700
C7—C8	1.488 (4)	C3—C4	1.384 (4)
C6—C5	1.392 (4)	C3—H3	0.9300
C2—C3	1.381 (4)	C4—H4	0.9300
C2—H2	0.9300	O2—H2B	0.8200
C9—C10	1.504 (4)

N1ⁱ—Cu1—N1	180.00 (13)	C10—C9—H9B	108.2
C7—N1—C1	106.0 (2)	C8—C9—H9B	108.2
C7—N1—Cu1	126.43 (19)	H9A—C9—H9B	107.3
C1—N1—Cu1	127.13 (17)	O1—C10—O2	124.5 (3)
C7—N2—C6	108.4 (2)	O1—C10—C9	120.7 (3)
C7—N2—H2A	125.8	O2—C10—C9	114.8 (2)
C6—N2—H2A	125.8	C4—C5—C6	116.7 (3)
C2—C1—C6	120.6 (3)	C4—C5—H5	121.7
C2—C1—N1	130.9 (3)	C6—C5—H5	121.7
C6—C1—N1	108.5 (2)	C7—C8—C9	114.6 (2)
N1—C7—N2	111.5 (2)	C7—C8—H8A	108.6
N1—C7—C8	125.2 (2)	C9—C8—H8A	108.6
N2—C7—C8	123.3 (2)	C7—C8—H8B	108.6
N2—C6—C1	105.7 (2)	C9—C8—H8B	108.6
N2—C6—C5	132.5 (3)	H8A—C8—H8B	107.6
C1—C6—C5	121.9 (3)	C2—C3—C4	121.4 (3)
C3—C2—C1	117.3 (3)	C2—C3—H3	119.3
C3—C2—H2	121.3	C4—C3—H3	119.3
C1—C2—H2	121.3	C5—C4—C3	122.0 (3)
C10—C9—C8	116.5 (2)	C5—C4—H4	119.0
C10—C9—H9A	108.2	C3—C4—H4	119.0
C8—C9—H9A	108.2	C10—O2—H2B	109.5

C7—N1—C1—C2	179.1 (3)	C2—C1—C6—C5	1.7 (4)
Cu1—N1—C1—C2	−8.4 (4)	N1—C1—C6—C5	−179.1 (2)
C7—N1—C1—C6	0.0 (3)	C6—C1—C2—C3	0.0 (4)
Cu1—N1—C1—C6	172.48 (18)	N1—C1—C2—C3	−179.0 (3)
C1—N1—C7—N2	−0.2 (3)	C8—C9—C10—O1	−16.7 (4)
Cu1—N1—C7—N2	−172.78 (17)	C8—C9—C10—O2	165.2 (3)
C1—N1—C7—C8	−179.9 (2)	N2—C6—C5—C4	178.6 (3)
Cu1—N1—C7—C8	7.5 (4)	C1—C6—C5—C4	−2.2 (4)
C6—N2—C7—N1	0.4 (3)	N1—C7—C8—C9	103.1 (3)
C6—N2—C7—C8	−180.0 (2)	N2—C7—C8—C9	−76.5 (3)
C7—N2—C6—C1	−0.4 (3)	C10—C9—C8—C7	−74.7 (3)
C7—N2—C6—C5	178.9 (3)	C1—C2—C3—C4	−1.0 (4)
C2—C1—C6—N2	−179.0 (2)	C6—C5—C4—C3	1.2 (4)
N1—C1—C6—N2	0.2 (3)	C2—C3—C4—C5	0.4 (5)

Symmetry code: (i) −x+1/2, −y+1/2, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O1ⁱⁱ	0.86	1.97	2.725 (3)	146
O2—H2B···O2ⁱⁱⁱ	0.82	1.69	2.491 (5)	166

Symmetry codes: (ii) x, y+1, z; (iii) −x, −y, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O1ⁱ	0.86	1.97	2.725 (3)	146.4
O2—H2B···O2ⁱⁱ	0.82	1.69	2.491 (5)	166.2

Symmetry codes: (i) x, y+1, z; (ii) −x, −y, −z.

Acknowledgements

This work was supported by the National Natural Science Foundation of China (No. 21201113).

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