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

Abstract

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,

• a = 8.6803 (11) Å

• b = 23.0354 (8) Å

• c = 7.8543 (9) Å

• β = 109.419 (1)°

• V = 1481.2 (3) ų

• 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[F ² > 2σ(F ²)] = 0.045

• wR(F ²) = 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.

Supplementary Material

Supplementary material file. DOI: 10.1107/S1600536812021460/ru2034Isup2.cdx

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

supplementary crystallographic information

Comment

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)°.

Experimental

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.

Refinement

H atoms were placed in calculated positions with C—H = 0.93–0.97 Å, and refined in riding mode with U_iso(H) = 1.2U_eq(C).

Figures

Fig. 1.

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

Crystal data

[CuBr2(C14H11BrN4O)2]	F(000) = 862
Mr = 885.72	Dx = 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

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

Refinement

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(Fo2) + (0.0654P)2] where P = (Fo2 + 2Fc2)/3
2622 reflections	(Δ/σ)max < 0.001
196 parameters	Δρmax = 1.31 e Å−3
0 restraints	Δρmin = −0.90 e Å−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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)

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.