Dibromidobis[1-(2-bromo­benz­yl)-3-(pyrimidin-2-yl)-1H-imidazol-2(3H)-one]copper(II)

Lu, C.-X.

doi:10.1107/S1600536812021460

metal-organic compounds

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Volume 68| Part 6| June 2012| Page m785

doi:10.1107/S1600536812021460

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Dibromidobis[1-(2-bromobenzyl)-3-(pyrimidin-2-yl)-1H-imidazol-2(3H)-one]copper(II)

Chun-Xin Lu ^a ^*

^aDepartment of Chemistry, Zhejiang University, Xixi Campus, Hangzhou 310028, People's Republic of China
^*Correspondence e-mail: chunxin0923@zju.edu.cn

(Received 30 April 2012; accepted 11 May 2012; online 19 May 2012)

In the title complex, [CuBr₂(C₁₄H₁₁BrN₄O)₂], the Cu^II ion is located on an inversion centre and is coordinated by two ketonic O atoms, two N atoms and two Br atoms, forming a distorted octahedral coordination environment. The two carbonyl groups are trans positioned with C=O bond lengths of 1.256 (5) Å, in agreement with a classical carbonyl bond. The Cu—O bond length is 2.011 (3) Å. The two bromobenzyl rings are approximately parallel to one another, forming a dihedral angle of 70.1 (4)° with the coordination plane.

Related literature

For general background, see: Moncol et al. (2008 ); Wu et al. (2003 ); Anbu & Kandaswamy (2012 ). For related structures, see: Citadelle et al. (2010 ); Liu et al. (2011 ); Marjani et al. (2005 ); Meghdadi et al. (2012 ).

Experimental

Crystal data

[CuBr₂(C₁₄H₁₁BrN₄O)₂]
M_r = 885.72
Monoclinic, P 2₁ /c
a = 8.6803 (11) Å
b = 23.0354 (8) Å
c = 7.8543 (9) Å
β = 109.419 (1)°
V = 1481.2 (3) Å³
Z = 2
Mo Kα radiation
μ = 6.18 mm⁻¹
T = 298 K
0.43 × 0.30 × 0.14 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.177, T_max = 0.479
7275 measured reflections
2622 independent reflections
2019 reflections with I > 2σ(I)
R_int = 0.066

Refinement

R[F² > 2σ(F²)] = 0.045
wR(F²) = 0.117
S = 1.01
2622 reflections
196 parameters
H-atom parameters constrained
Δρ_max = 1.31 e Å⁻³
Δρ_min = −0.90 e Å⁻³

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

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812021460/ru2034sup1.cif

Supporting information file. DOI: 10.1107/S1600536812021460/ru2034Isup2.cdx

Structure factors: contains datablock I. DOI: 10.1107/S1600536812021460/ru2034Isup2.hkl

checkCIF report

Comment top

Cu²⁺ cation has been widely studied since a host of low-molecular-weight copper complexes have been proven beneficial against several diseases such as turberculosis, rheumatoid, gastric ulcers, and cancers. And it is well known that copper(II) complexes with different ligands usually show flexible coordination environment. The 1-(2-bromobenzyl)-3-(pyrimidin-2-yl)imidazolium bromide was used as the ligand, reacting with excessive copper powder in air, giving a Cu^II compound. We here report the crystal structure of the title compound (I).

Bond lengths and angles in the title molecule (Fig. 1) are within normal ranges. The C=O bond distance is 1.256 (5) Å and Cu—O bond distance is 2.013 (3) Å. The two bromobenzyl rings are approximately parallel to each other. The dihedral angle between the bromobenzyl ring and the coordination plane is 70.1 (4)°.

Related literature top

For general background, see: Moncol et al. (2008); Wu et al. (2003); Anbu et al. (2012). For related structures, see: Citadelle et al. (2010); Liu et al. (2011);; Marjani et al. (2005); Meghdadi et al. (2012).

Experimental top

A solution of 1-(2-bromobenzyl)-3-(pyrimidin-2-yl)imidazolium bromide (396 mg, 1.0 mmol) in 10 ml of CH₃CN was treated with copper powder (38 mg, 0.6 mmol). The mixture was allowed to react at 80 °C for 2 days in air. The solution was filtered through silica to remove unreacted copper. The filtrate was concentrated to ca 2 ml. Addition of Et₂O (20 ml) to the filtrate afforded a yellow precipitate. The crystals of this complex suitable for X-ray diffraction were obtained by slow diffusion of diethyl ether into its acetonitrile solution.

Computing details top

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

Figures top

Fig. 1. The molecular structure of the title compound, showing 50% probability displacement ellipsoids and the atomic numbering.

Dibromidobis[1-(2-bromobenzyl)-3-(pyrimidin-2-yl)-1H-imidazol- 2(3H)-one]copper(II) top

Crystal data top

[CuBr₂(C₁₄H₁₁BrN₄O)₂]	F(000) = 862
M_r = 885.72	D_x = 1.986 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 8.6803 (11) Å	Cell parameters from 7275 reflections
b = 23.0354 (8) Å	θ = 1.8–25.1°
c = 7.8543 (9) Å	µ = 6.18 mm⁻¹
β = 109.419 (1)°	T = 298 K
V = 1481.2 (3) Å³	Block, yellow
Z = 2	0.43 × 0.30 × 0.14 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	2622 independent reflections
Radiation source: fine-focus sealed tube	2019 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.066
phi and ω scans	θ_max = 25.1°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −10→8
T_min = 0.177, T_max = 0.479	k = −27→20
7275 measured reflections	l = −9→8

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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.117	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.0654P)²] where P = (F_o² + 2F_c²)/3
2622 reflections	(Δ/σ)_max < 0.001
196 parameters	Δρ_max = 1.31 e Å⁻³
0 restraints	Δρ_min = −0.90 e Å⁻³

Crystal data top

[CuBr₂(C₁₄H₁₁BrN₄O)₂]	V = 1481.2 (3) Å³
M_r = 885.72	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.6803 (11) Å	µ = 6.18 mm⁻¹
b = 23.0354 (8) Å	T = 298 K
c = 7.8543 (9) Å	0.43 × 0.30 × 0.14 mm
β = 109.419 (1)°

Data collection top

Bruker SMART CCD area-detector diffractometer	2622 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2019 reflections with I > 2σ(I)
T_min = 0.177, T_max = 0.479	R_int = 0.066
7275 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	0 restraints
wR(F²) = 0.117	H-atom parameters constrained
S = 1.01	Δρ_max = 1.31 e Å⁻³
2622 reflections	Δρ_min = −0.90 e Å⁻³
196 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
Cu1	0.5000	0.5000	0.5000	0.0270 (3)
N1	0.7847 (4)	0.41135 (18)	0.7064 (5)	0.0240 (9)
N2	0.6658 (4)	0.37501 (18)	0.8889 (5)	0.0245 (9)
N3	0.6973 (5)	0.46886 (18)	0.4448 (5)	0.0240 (9)
N4	0.9437 (5)	0.41415 (19)	0.5252 (6)	0.0307 (11)
Br1	0.68599 (7)	0.22945 (3)	1.05716 (9)	0.0525 (2)
Br2	0.70578 (6)	0.54952 (2)	0.82796 (7)	0.0343 (2)
O1	0.5017 (4)	0.42702 (15)	0.6410 (4)	0.0271 (8)
C1	0.6372 (5)	0.4069 (2)	0.7368 (6)	0.0249 (11)
C2	0.8315 (6)	0.3607 (2)	0.9542 (7)	0.0308 (13)
H2	0.8821	0.3393	1.0582	0.037*
C3	0.9052 (6)	0.3822 (2)	0.8467 (7)	0.0300 (12)
H3	1.0154	0.3788	0.8603	0.036*
C4	0.8100 (6)	0.4324 (2)	0.5504 (7)	0.0242 (11)
C5	0.9699 (6)	0.4335 (2)	0.3762 (8)	0.0372 (14)
H5	1.0654	0.4226	0.3557	0.045*
C6	0.8598 (6)	0.4692 (2)	0.2517 (7)	0.0342 (13)
H6	0.8773	0.4814	0.1467	0.041*
C7	0.7231 (6)	0.4854 (2)	0.2919 (7)	0.0286 (12)
H7	0.6457	0.5088	0.2104	0.034*
C8	0.5415 (6)	0.3582 (2)	0.9661 (7)	0.0295 (12)
H8A	0.4736	0.3916	0.9664	0.035*
H8B	0.5946	0.3464	1.0905	0.035*
C9	0.4349 (6)	0.3096 (2)	0.8659 (7)	0.0295 (12)
C10	0.4763 (6)	0.2516 (3)	0.8917 (7)	0.0344 (13)
C11	0.3759 (8)	0.2078 (3)	0.8035 (9)	0.0502 (17)
H11	0.4089	0.1693	0.8262	0.060*
C12	0.2274 (8)	0.2208 (3)	0.6820 (10)	0.058 (2)
H12	0.1585	0.1911	0.6207	0.070*
C13	0.1780 (7)	0.2780 (3)	0.6490 (9)	0.0559 (19)
H13	0.0767	0.2868	0.5648	0.067*
C14	0.2800 (6)	0.3221 (3)	0.7416 (8)	0.0414 (15)
H14	0.2455	0.3605	0.7213	0.050*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0258 (4)	0.0231 (5)	0.0378 (5)	0.0072 (4)	0.0181 (4)	0.0100 (4)
N1	0.023 (2)	0.023 (2)	0.028 (2)	0.0032 (18)	0.0107 (17)	0.0006 (19)
N2	0.027 (2)	0.022 (2)	0.026 (2)	−0.0005 (19)	0.0111 (17)	0.0003 (19)
N3	0.027 (2)	0.021 (2)	0.025 (2)	0.0001 (19)	0.0106 (18)	0.0016 (19)
N4	0.026 (2)	0.032 (3)	0.040 (3)	0.004 (2)	0.0180 (19)	0.002 (2)
Br1	0.0517 (4)	0.0387 (4)	0.0715 (5)	0.0133 (3)	0.0262 (3)	0.0235 (3)
Br2	0.0355 (3)	0.0329 (4)	0.0373 (4)	0.0010 (2)	0.0158 (2)	−0.0018 (2)
O1	0.0232 (17)	0.0231 (19)	0.037 (2)	0.0054 (15)	0.0129 (15)	0.0114 (16)
C1	0.027 (3)	0.025 (3)	0.025 (3)	−0.002 (2)	0.011 (2)	0.000 (2)
C2	0.029 (3)	0.034 (3)	0.027 (3)	0.004 (2)	0.006 (2)	0.006 (2)
C3	0.023 (2)	0.035 (3)	0.032 (3)	0.005 (2)	0.008 (2)	0.004 (3)
C4	0.027 (2)	0.018 (3)	0.031 (3)	−0.003 (2)	0.014 (2)	−0.004 (2)
C5	0.033 (3)	0.037 (4)	0.050 (4)	−0.001 (3)	0.025 (3)	−0.007 (3)
C6	0.042 (3)	0.034 (3)	0.035 (3)	−0.001 (3)	0.023 (3)	−0.005 (3)
C7	0.029 (3)	0.025 (3)	0.032 (3)	0.001 (2)	0.010 (2)	−0.002 (2)
C8	0.037 (3)	0.028 (3)	0.029 (3)	0.003 (3)	0.017 (2)	0.003 (2)
C9	0.035 (3)	0.027 (3)	0.034 (3)	−0.002 (2)	0.021 (2)	0.007 (2)
C10	0.034 (3)	0.034 (3)	0.042 (3)	0.000 (3)	0.021 (2)	0.003 (3)
C11	0.058 (4)	0.034 (4)	0.074 (5)	−0.012 (3)	0.042 (4)	−0.008 (3)
C12	0.055 (4)	0.055 (5)	0.073 (5)	−0.030 (4)	0.033 (4)	−0.027 (4)
C13	0.033 (3)	0.078 (6)	0.056 (4)	−0.013 (4)	0.014 (3)	−0.002 (4)
C14	0.037 (3)	0.047 (4)	0.046 (3)	0.002 (3)	0.022 (3)	0.006 (3)

Geometric parameters (Å, º) top

Cu1—O1ⁱ	2.011 (3)	C3—H3	0.9300
Cu1—O1	2.011 (3)	C5—C6	1.387 (8)
Cu1—N3ⁱ	2.032 (4)	C5—H5	0.9300
Cu1—N3	2.032 (4)	C6—C7	1.378 (7)
Cu1—Br2	2.8404 (6)	C6—H6	0.9300
Cu1—Br2ⁱ	2.8404 (6)	C7—H7	0.9300
N1—C1	1.383 (6)	C8—C9	1.498 (7)
N1—C4	1.400 (6)	C8—H8A	0.9700
N1—C3	1.412 (6)	C8—H8B	0.9700
N2—C1	1.353 (6)	C9—C10	1.381 (8)
N2—C2	1.396 (6)	C9—C14	1.404 (7)
N2—C8	1.455 (6)	C10—C11	1.362 (8)
N3—C4	1.346 (6)	C11—C12	1.358 (9)
N3—C7	1.348 (6)	C11—H11	0.9300
N4—C4	1.309 (6)	C12—C13	1.384 (9)
N4—C5	1.340 (7)	C12—H12	0.9300
Br1—C10	1.921 (5)	C13—C14	1.384 (9)
O1—C1	1.256 (5)	C13—H13	0.9300
C2—C3	1.314 (7)	C14—H14	0.9300
C2—H2	0.9300

O1ⁱ—Cu1—O1	180.00 (11)	N4—C4—N1	115.2 (4)
O1ⁱ—Cu1—N3ⁱ	88.28 (15)	N3—C4—N1	117.5 (4)
O1—Cu1—N3ⁱ	91.72 (15)	N4—C5—C6	122.4 (5)
O1ⁱ—Cu1—N3	91.72 (15)	N4—C5—H5	118.8
O1—Cu1—N3	88.28 (15)	C6—C5—H5	118.8
N3ⁱ—Cu1—N3	180.000 (1)	C7—C6—C5	116.3 (5)
O1ⁱ—Cu1—Br2	92.92 (10)	C7—C6—H6	121.9
O1—Cu1—Br2	87.08 (10)	C5—C6—H6	121.9
N3ⁱ—Cu1—Br2	89.16 (11)	N3—C7—C6	122.6 (5)
N3—Cu1—Br2	90.84 (11)	N3—C7—H7	118.7
O1ⁱ—Cu1—Br2ⁱ	87.08 (10)	C6—C7—H7	118.7
O1—Cu1—Br2ⁱ	92.92 (10)	N2—C8—C9	113.2 (4)
N3ⁱ—Cu1—Br2ⁱ	90.84 (11)	N2—C8—H8A	108.9
N3—Cu1—Br2ⁱ	89.16 (11)	C9—C8—H8A	108.9
Br2—Cu1—Br2ⁱ	180.00 (2)	N2—C8—H8B	108.9
C1—N1—C4	126.9 (4)	C9—C8—H8B	108.9
C1—N1—C3	108.5 (4)	H8A—C8—H8B	107.8
C4—N1—C3	123.8 (4)	C10—C9—C14	116.3 (5)
C1—N2—C2	108.5 (4)	C10—C9—C8	124.1 (5)
C1—N2—C8	124.7 (4)	C14—C9—C8	119.5 (5)
C2—N2—C8	126.9 (4)	C11—C10—C9	123.4 (5)
C4—N3—C7	115.0 (4)	C11—C10—Br1	116.7 (5)
C4—N3—Cu1	125.5 (3)	C9—C10—Br1	119.9 (4)
C7—N3—Cu1	119.4 (3)	C12—C11—C10	119.4 (6)
C4—N4—C5	116.2 (4)	C12—C11—H11	120.3
C1—O1—Cu1	118.2 (3)	C10—C11—H11	120.3
O1—C1—N2	126.1 (4)	C11—C12—C13	120.3 (6)
O1—C1—N1	127.3 (4)	C11—C12—H12	119.9
N2—C1—N1	106.5 (4)	C13—C12—H12	119.9
C3—C2—N2	109.7 (4)	C12—C13—C14	119.8 (6)
C3—C2—H2	125.1	C12—C13—H13	120.1
N2—C2—H2	125.1	C14—C13—H13	120.1
C2—C3—N1	106.8 (4)	C13—C14—C9	120.8 (6)
C2—C3—H3	126.6	C13—C14—H14	119.6
N1—C3—H3	126.6	C9—C14—H14	119.6
N4—C4—N3	127.3 (5)

Symmetry code: (i) −x+1, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	[CuBr₂(C₁₄H₁₁BrN₄O)₂]
M_r	885.72
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	8.6803 (11), 23.0354 (8), 7.8543 (9)
β (°)	109.419 (1)
V (Å³)	1481.2 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	6.18
Crystal size (mm)	0.43 × 0.30 × 0.14

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.177, 0.479
No. of measured, independent and observed [I > 2σ(I)] reflections	7275, 2622, 2019
R_int	0.066
(sin θ/λ)_max (Å⁻¹)	0.596

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.117, 1.01
No. of reflections	2622
No. of parameters	196
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.31, −0.90

Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2002), SHELXTL (Sheldrick, 2008).

Acknowledgements

The author thanks the Natural Science Foundation of China (21072170).

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