Bromidotetra­kis­(1H-2-ethyl-5-methyl­imidazole-κN3)copper(II) bromide

Godlewska, S.; Baranowska, K.; Socha, J.; Dołęga, A.

doi:10.1107/S1600536811051117

metal-organic compounds

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Volume 67| Part 12| December 2011| Page m1906

https://doi.org/10.1107/S1600536811051117

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Bromidotetrakis(1H-2-ethyl-5-methylimidazole-κN³)copper(II) bromide

Sylwia Godlewska,^a Katarzyna Baranowska,^a Joanna Socha ^a and Anna Dołęga ^a ^*

^aDepartment of Inorganic Chemistry, Faculty of Chemistry, Gdańsk University of Technology, 11/12 G. Narutowicz St., 80233 PL Gdańsk, Poland
^*Correspondence e-mail: anndoleg@pg.gda.pl

(Received 24 November 2011; accepted 28 November 2011; online 30 November 2011)

The Cu^II ion in the title compound, [CuBr(C₆H₁₀N₂)₄]Br, is coordinated in a square-based-pyramidal geometry by the N atoms of four imidazole ligands and a bromide anion in the apical site. Both the Cu^II and Br⁻ atoms lie on a crystallographic fourfold axis. In the crystal, the [CuBr(C₆H₁₀N₂)₄]⁺ complex cations are linked to the uncoordinated Br⁻ anions (site symmetry $[\overline{4}]$ ) by N—H⋯Br hydrogen bonds, generating a three-dimensional network. The ethyl group of the imidazole ligand was modelled as disordered over two orientations with occupancies of 0.620 (8) and 0.380 (8).

Related literature

For more copper(II) complexes with bromido and imidazole ligands, see: Godlewska et al. (2011 ); Hossaini Sadr et al. (2004 ); Li et al. (2007 ); Liu et al. (2007 ); Näther et al. (2002a ,b ). For the alignment of dipoles in crystalline materials, see: Anthony & Radhakrishnan (2001 ).

Experimental

Crystal data

[CuBr(C₆H₁₀N₂)₄]Br
M_r = 664
Tetragonal, P 4/n
a = 14.0961 (4) Å
c = 7.5236 (4) Å
V = 1494.94 (10) Å³
Z = 2
Mo Kα radiation
μ = 3.43 mm⁻¹
T = 294 K
0.54 × 0.45 × 0.33 mm

Data collection

Oxford Diffraction Xcalibur Sapphire2 diffractometer
Absorption correction: analytical [CrysAlis PRO (Oxford Diffraction, 2006 $[Oxford Diffraction (2006). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England.]$ ), based on expressions derived by Clark & Reid (1995 )] T_min = 0.248, T_max = 0.44
5099 measured reflections
1395 independent reflections
898 reflections with I > 2s(I)
R_int = 0.025

Refinement

R[F² > 2σ(F²)] = 0.027
wR(F²) = 0.076
S = 0.95
1395 reflections
103 parameters
H-atom parameters constrained
Δρ_max = 0.63 e Å⁻³
Δρ_min = −0.39 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

Cu1—Br1	2.7330 (8)
Cu1—N1ⁱ	2.029 (2)

N1ⁱ—Cu1—N1	89.708 (9)
N1—Cu1—N1ⁱⁱ	171.81 (12)
Symmetry codes: (i) $[-y+{\script{1\over 2}}, x, z]$ ; (ii) $[-x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z]$ .

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯Br2ⁱⁱⁱ	0.86	2.63	3.488 (2)	178
Symmetry code: (iii) -x+1, -y+1, -z+1.

Data collection: CrysAlis PRO (Oxford Diffraction, 2006 $[Oxford Diffraction (2006). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England.]$ ); cell refinement: CrysAlis PRO; data reduction: CrysAlis RED (Oxford Diffraction, 2006 $[Oxford Diffraction (2006). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England.]$ ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536811051117/hb6533sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536811051117/hb6533Isup2.hkl

checkCIF report

Comment top

The composition of (I) is very similar to the bromidotetrakis(1H2-isopropylimidazole-κN³)copper(II) bromide described previously (Godlewska et al., 2011). However these compounds display substantially different crystal packing. Four NH···Br hydrogen bonds surrounding Br2 in bromidotetrakis(1H2-isopropylimidazole-κN³)copper(II) bromide are almost planar whereas the corresponding hydrogen bonds in (I) form distorted tetrahedron around Br2 and therefore build a network extending in all three directions in crystal. Complex cations [Cu(C₆H₁₀N₂)₄Br]⁺ are dipoles aligned perfectly parallel to c axis in a head-to-tail manner (see Fig. 2). The disorder of alkyl substituents is typical of room temperature determinations (e.g. Näther et al. (2002a), Acta Cryst. E58, m63-m64).

The structure of (I) is shown in Fig. 1 and packing diagram of complex dipoles is presented in Fig.2.

Related literature top

For more copper(II) complexes with bromido and imidazole ligands, see: Godlewska et al. (2011); Hossaini Sadr et al. (2004); Li et al. (2007); Liu et al. (2007); Näther et al. (2002a,b). For the alignment of dipoles in crystalline materials, see: Anthony & Radhakrishnan (2001).

Experimental top

The title compound was prepared by adding the solution of 0.223 g (1 mmol) copper(II) bromide in 4 ml of methanol to the solution of 0.496 g (4.5 mmol) 2-ethyl-4(5)-methylimidazole in 2 ml of methanol. After a few days blue prisms were obtained by slow evaporation of solvent from the reaction mixture.

Structure description top

The structure of (I) is shown in Fig. 1 and packing diagram of complex dipoles is presented in Fig.2.

For more copper(II) complexes with bromido and imidazole ligands, see: Godlewska et al. (2011); Hossaini Sadr et al. (2004); Li et al. (2007); Liu et al. (2007); Näther et al. (2002a,b). For the alignment of dipoles in crystalline materials, see: Anthony & Radhakrishnan (2001).

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2006); cell refinement: CrysAlis PRO (Oxford Diffraction, 2006); data reduction: CrysAlis RED (Oxford Diffraction, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. A view of (I), showing displacement ellipsoids drawn at the 30% probability level. Labels are given only for the independent part.
	Fig. 2. The packing of dipoles in crystals of (I).

Bromidotetrakis(1H-2-ethyl-5-methylimidazole-κN³)copper(II) bromide top

Crystal data top

[CuBr(C₆H₁₀N₂)₄]Br	D_x = 1.475 Mg m⁻³
M_r = 664	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, P4/n	Cell parameters from 2155 reflections
Hall symbol: -P 4a	θ = 2.7–28.8°
a = 14.0961 (4) Å	µ = 3.43 mm⁻¹
c = 7.5236 (4) Å	T = 294 K
V = 1494.94 (10) Å³	Prism, blue
Z = 2	0.54 × 0.45 × 0.33 mm
F(000) = 678

Data collection top

Oxford Diffraction Xcalibur Sapphire2 diffractometer	1395 independent reflections
Graphite monochromator	898 reflections with I > 2s(I)
Detector resolution: 8.1883 pixels mm^-1	R_int = 0.025
ω scans	θ_max = 25.5°, θ_min = 2.7°
Absorption correction: analytical [CrysAlis PRO (Oxford Diffraction, 2006), based on expressions derived by Clark & Reid (1995)]	h = −17→10
T_min = 0.248, T_max = 0.44	k = −17→15
5099 measured reflections	l = −9→7

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)] = 0.027	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.076	H-atom parameters constrained
S = 0.95	w = 1/[σ²(F_o²) + (0.0447P)²] where P = (F_o² + 2F_c²)/3
1395 reflections	(Δ/σ)_max = 0.004
103 parameters	Δρ_max = 0.63 e Å⁻³
0 restraints	Δρ_min = −0.39 e Å⁻³

Crystal data top

[CuBr(C₆H₁₀N₂)₄]Br	Z = 2
M_r = 664	Mo Kα radiation
Tetragonal, P4/n	µ = 3.43 mm⁻¹
a = 14.0961 (4) Å	T = 294 K
c = 7.5236 (4) Å	0.54 × 0.45 × 0.33 mm
V = 1494.94 (10) Å³

Data collection top

Oxford Diffraction Xcalibur Sapphire2 diffractometer	1395 independent reflections
Absorption correction: analytical [CrysAlis PRO (Oxford Diffraction, 2006), based on expressions derived by Clark & Reid (1995)]	898 reflections with I > 2s(I)
T_min = 0.248, T_max = 0.44	R_int = 0.025
5099 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.027	0 restraints
wR(F²) = 0.076	H-atom parameters constrained
S = 0.95	Δρ_max = 0.63 e Å⁻³
1395 reflections	Δρ_min = −0.39 e Å⁻³
103 parameters

Special details top

Experimental. CrysAlisPro (Oxford Diffraction Ltd., 2006) Analytical numeric absorption correction using a multifaceted crystal model based on expressions derived by R.C. Clark & J.S. (Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)

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)
Br1	0.25	0.25	0.31140 (7)	0.0495 (2)
Br2	0.75	0.25	0	0.05286 (19)
Cu1	0.25	0.25	0.67466 (8)	0.0366 (2)
N1	0.22250 (14)	0.39093 (14)	0.6939 (3)	0.0397 (5)
N2	0.21196 (15)	0.54003 (15)	0.7653 (3)	0.0486 (6)
H2	0.2195	0.5922	0.823	0.058*
C1	0.16846 (19)	0.4385 (2)	0.5685 (4)	0.0481 (7)
H1	0.141	0.4104	0.4693	0.058*
C2	0.16140 (19)	0.5299 (2)	0.6100 (4)	0.0520 (8)
C3	0.24764 (19)	0.4552 (2)	0.8122 (4)	0.0446 (7)
C4	0.1150 (3)	0.6113 (2)	0.5178 (5)	0.0900 (14)
H4A	0.0826	0.5888	0.4138	0.135*
H4B	0.1623	0.6568	0.4836	0.135*
H4C	0.0702	0.6408	0.5966	0.135*
C5	0.2915 (9)	0.4385 (17)	0.980 (3)	0.059 (3)	0.620 (8)
H5A	0.2972	0.3709	1.001	0.071*	0.620 (8)
H5B	0.2533	0.4658	1.0744	0.071*	0.620 (8)
C6	0.3952 (5)	0.4870 (5)	0.9776 (9)	0.087 (3)	0.620 (8)
H6A	0.3886	0.5546	0.9672	0.131*	0.620 (8)
H6B	0.4307	0.4632	0.8783	0.131*	0.620 (8)
H6C	0.4279	0.4721	1.0859	0.131*	0.620 (8)
C5A	0.3233 (13)	0.438 (2)	0.966 (4)	0.043 (5)	0.380 (8)
H5A1	0.3232	0.3711	0.9977	0.052*	0.380 (8)
H5A2	0.386	0.4535	0.9218	0.052*	0.380 (8)
C6A	0.3036 (11)	0.4935 (7)	1.1209 (14)	0.123 (6)	0.380 (8)
H6A1	0.3115	0.5595	1.0934	0.184*	0.380 (8)
H6A2	0.3466	0.476	1.2143	0.184*	0.380 (8)
H6A3	0.2395	0.4822	1.1588	0.184*	0.380 (8)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0587 (3)	0.0587 (3)	0.0311 (3)	0	0	0
Br2	0.0394 (2)	0.0394 (2)	0.0798 (5)	0	0	0
Cu1	0.0350 (2)	0.0350 (2)	0.0397 (4)	0	0	0
N1	0.0396 (13)	0.0367 (12)	0.0428 (14)	0.0018 (10)	−0.0011 (10)	−0.0029 (10)
N2	0.0519 (15)	0.0364 (13)	0.0576 (17)	−0.0021 (11)	0.0071 (13)	−0.0080 (12)
C1	0.0411 (17)	0.0519 (19)	0.0514 (18)	0.0037 (14)	−0.0084 (14)	−0.0031 (15)
C2	0.0455 (18)	0.0466 (19)	0.064 (2)	0.0092 (14)	−0.0011 (16)	0.0027 (16)
C3	0.0485 (18)	0.0436 (17)	0.0418 (17)	−0.0049 (13)	0.0058 (14)	−0.0022 (14)
C4	0.086 (3)	0.058 (2)	0.127 (4)	0.0231 (19)	−0.030 (2)	0.007 (2)
C5	0.060 (9)	0.070 (5)	0.048 (6)	−0.003 (8)	−0.003 (7)	−0.007 (4)
C6	0.104 (6)	0.079 (4)	0.079 (6)	0.010 (4)	−0.047 (4)	−0.021 (3)
C5A	0.038 (11)	0.060 (8)	0.033 (8)	−0.024 (10)	−0.007 (8)	0.007 (6)
C6A	0.252 (18)	0.065 (7)	0.051 (7)	0.045 (8)	−0.051 (9)	−0.023 (6)

Geometric parameters (Å, º) top

Cu1—Br1	2.7330 (8)	C4—H4A	0.96
Cu1—N1ⁱ	2.029 (2)	C4—H4B	0.96
Cu1—N1	2.029 (2)	C4—H4C	0.96
Cu1—N1ⁱⁱ	2.029 (2)	C5—C6	1.613 (14)
Cu1—N1ⁱⁱⁱ	2.029 (2)	C5—H5A	0.97
N1—C3	1.319 (3)	C5—H5B	0.97
N1—C1	1.385 (3)	C6—H6A	0.96
N2—C3	1.344 (3)	C6—H6B	0.96
N2—C2	1.376 (4)	C6—H6C	0.96
N2—H2	0.86	C5A—C6A	1.43 (3)
C1—C2	1.330 (4)	C5A—H5A1	0.97
C1—H1	0.93	C5A—H5A2	0.97
C2—C4	1.492 (4)	C6A—H6A1	0.96
C3—C5	1.42 (2)	C6A—H6A2	0.96
C3—C5A	1.59 (3)	C6A—H6A3	0.96

N1ⁱ—Cu1—N1	89.708 (9)	N2—C3—C5A	125.4 (12)
N1ⁱ—Cu1—N1ⁱⁱ	89.707 (9)	C2—C4—H4A	109.5
N1—Cu1—N1ⁱⁱ	171.81 (12)	C2—C4—H4B	109.5
N1ⁱ—Cu1—N1ⁱⁱⁱ	171.81 (12)	H4A—C4—H4B	109.5
N1—Cu1—N1ⁱⁱⁱ	89.707 (9)	C2—C4—H4C	109.5
N1ⁱⁱ—Cu1—N1ⁱⁱⁱ	89.708 (9)	H4A—C4—H4C	109.5
N1ⁱ—Cu1—Br1	94.10 (6)	H4B—C4—H4C	109.5
N1—Cu1—Br1	94.10 (6)	C3—C5—C6	108.3 (12)
N1ⁱⁱ—Cu1—Br1	94.10 (6)	C3—C5—H5A	110
N1ⁱⁱⁱ—Cu1—Br1	94.10 (6)	C6—C5—H5A	110
C3—N1—C1	106.0 (2)	C3—C5—H5B	110
C3—N1—Cu1	132.03 (19)	C6—C5—H5B	110
C1—N1—Cu1	122.00 (18)	H5A—C5—H5B	108.4
C3—N2—C2	108.9 (2)	C6A—C5A—C3	112.1 (18)
C3—N2—H2	125.5	C6A—C5A—H5A1	109.2
C2—N2—H2	125.5	C3—C5A—H5A1	109.2
C2—C1—N1	110.5 (3)	C6A—C5A—H5A2	109.2
C2—C1—H1	124.7	C3—C5A—H5A2	109.2
N1—C1—H1	124.7	H5A1—C5A—H5A2	107.9
C1—C2—N2	105.1 (2)	C5A—C6A—H6A1	109.5
C1—C2—C4	132.0 (3)	C5A—C6A—H6A2	109.5
N2—C2—C4	122.8 (3)	H6A1—C6A—H6A2	109.5
N1—C3—N2	109.5 (2)	C5A—C6A—H6A3	109.5
N1—C3—C5	127.0 (10)	H6A1—C6A—H6A3	109.5
N2—C3—C5	122.8 (10)	H6A2—C6A—H6A3	109.5
N1—C3—C5A	124.3 (12)

Symmetry codes: (i) −y+1/2, x, z; (ii) −x+1/2, −y+1/2, z; (iii) y, −x+1/2, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···Br2^iv	0.86	2.63	3.488 (2)	178

Symmetry code: (iv) −x+1, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	[CuBr(C₆H₁₀N₂)₄]Br
M_r	664
Crystal system, space group	Tetragonal, P4/n
Temperature (K)	294
a, c (Å)	14.0961 (4), 7.5236 (4)
V (Å³)	1494.94 (10)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	3.43
Crystal size (mm)	0.54 × 0.45 × 0.33

Data collection
Diffractometer	Oxford Diffraction Xcalibur Sapphire2
Absorption correction	Analytical [CrysAlis PRO (Oxford Diffraction, 2006), based on expressions derived by Clark & Reid (1995)]
T_min, T_max	0.248, 0.44
No. of measured, independent and observed [I > 2s(I)] reflections	5099, 1395, 898
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.027, 0.076, 0.95
No. of reflections	1395
No. of parameters	103
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.63, −0.39

Computer programs: CrysAlis PRO (Oxford Diffraction, 2006), CrysAlis RED (Oxford Diffraction, 2006), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), WinGX (Farrugia, 1999).

Selected geometric parameters (Å, º) top

Cu1—Br1	2.7330 (8)	Cu1—N1ⁱ	2.029 (2)

N1ⁱ—Cu1—N1	89.708 (9)	N1—Cu1—N1ⁱⁱ	171.81 (12)

Symmetry codes: (i) −y+1/2, x, z; (ii) −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—H2···Br2ⁱⁱⁱ	0.86	2.63	3.488 (2)	178

Symmetry code: (iii) −x+1, −y+1, −z+1.

References

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