Bis(1-methyl-piperazine-1,4-diium) tetra-bromidocuprate(II).

The title compound, (C(5)H(14)N(2))[CuBr(4)], was synthesized by hydro-thermal reaction of CuBr(2) with 1-methyl-piperazine in an HBr/water solution. Both amine N atoms are protonated. The Cu-Br distances in the tetrahedral anion are in the range 2.3809 (11)-2.4131 (11) Å. In the crystal, moderately strong and weak inter-molecular N-H⋯Br hydrogen bonds link the anion and cation units into an infinite two-dimensional network parallel to the ab plane.

Related literature

For related amino coordination compounds, see: Fu et al. (2009 ▶); Aminabhavi et al. (1986 ▶); Dai & Fu (2008a ▶,b ▶). For halogen atoms as hydrogen-bond acceptors, see: Brammer et al. (2001 ▶). For the chlorine analogue of the title compound, see: Peng (2011 ▶).

Experimental

Crystal data

(C5H14N2)[CuBr4]

M = 485.36

Orthorhombic,

a = 9.1933 (18) Å

b = 10.341 (2) Å

c = 14.255 (3) Å

V = 1355.2 (5) Å3

Z = 4

Mo Kα radiation

μ = 13.37 mm−1

T = 298 K

0.20 × 0.05 × 0.05 mm

Data collection

Rigaku Mercury2 diffractometer

Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ▶) T min = 0.89, T max = 1.00

14009 measured reflections

3092 independent reflections

2545 reflections with I > 2σ(I)

R int = 0.079

Refinement

R[F 2 > 2σ(F 2)] = 0.044

wR(F 2) = 0.088

S = 1.08

3092 reflections

109 parameters

H-atom parameters constrained

Δρmax = 0.92 e Å−3

Δρmin = −0.71 e Å−3

Absolute structure: Flack (1983 ▶), 1312 Friedel pairs

Flack parameter: 0.05 (2)

Data collection: CrystalClear (Rigaku, 2005 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; 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.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811024184/vn2014sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811024184/vn2014Isup2.hkl

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

(C5H14N2)[CuBr4]	F(000) = 908
Mr = 485.36	Dx = 2.379 Mg m−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 3092 reflections
a = 9.1933 (18) Å	θ = 3.3–27.5°
b = 10.341 (2) Å	µ = 13.37 mm−1
c = 14.255 (3) Å	T = 298 K
V = 1355.2 (5) Å3	Block, blue
Z = 4	0.20 × 0.05 × 0.05 mm

Rigaku Mercury2 diffractometer	3092 independent reflections
Radiation source: fine-focus sealed tube	2545 reflections with I > 2σ(I)
graphite	Rint = 0.079
Detector resolution: 13.6612 pixels mm-1	θmax = 27.5°, θmin = 3.3°
profile data from φ scans	h = −11→11
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −13→13
Tmin = 0.89, Tmax = 1.00	l = −18→18
14009 measured reflections

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.044	H-atom parameters constrained
wR(F2) = 0.088	w = 1/[σ2(Fo2) + (0.0277P)2] where P = (Fo2 + 2Fc2)/3
S = 1.08	(Δ/σ)max < 0.001
3092 reflections	Δρmax = 0.92 e Å−3
109 parameters	Δρmin = −0.71 e Å−3
0 restraints	Absolute structure: Flack (1983), 1312 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.05 (2)

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.

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 > 2sigma(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.

	x	y	z	Uiso*/Ueq
Br1	0.99472 (8)	0.08523 (7)	0.59527 (5)	0.0496 (2)
Br2	0.89670 (8)	−0.22010 (7)	0.49622 (5)	0.0430 (2)
Br3	0.72439 (8)	−0.21019 (7)	0.72661 (5)	0.04138 (19)
Cu1	0.79551 (9)	−0.06642 (7)	0.60209 (5)	0.0365 (2)
Br4	0.60073 (8)	0.08567 (7)	0.61127 (6)	0.0501 (2)
N2	0.6726 (5)	0.5289 (5)	0.5927 (4)	0.0367 (14)
H2C	0.7150	0.5985	0.6190	0.044*
H2D	0.6225	0.5519	0.5411	0.044*
N1	0.7844 (6)	0.3272 (4)	0.7129 (3)	0.0298 (12)
H1	0.7703	0.2609	0.6731	0.036*
C4	0.8043 (7)	0.4533 (7)	0.5656 (5)	0.0384 (16)
H4A	0.8684	0.5069	0.5281	0.046*
H4B	0.7756	0.3793	0.5281	0.046*
C5	0.8841 (7)	0.4074 (6)	0.6529 (5)	0.0364 (16)
H5A	0.9680	0.3564	0.6348	0.044*
H5B	0.9181	0.4815	0.6884	0.044*
C2	0.6566 (7)	0.4061 (7)	0.7413 (4)	0.0413 (17)
H2A	0.6892	0.4790	0.7786	0.050*
H2B	0.5922	0.3541	0.7798	0.050*
C3	0.5744 (7)	0.4550 (7)	0.6565 (5)	0.0397 (17)
H3A	0.5329	0.3824	0.6228	0.048*
H3B	0.4953	0.5104	0.6769	0.048*
C1	0.8613 (8)	0.2694 (7)	0.7956 (5)	0.050 (2)
H1A	0.7941	0.2181	0.8312	0.075*
H1B	0.8992	0.3374	0.8344	0.075*
H1C	0.9398	0.2159	0.7741	0.075*

	U11	U22	U33	U12	U13	U23
Br1	0.0533 (5)	0.0344 (4)	0.0610 (5)	−0.0140 (4)	0.0190 (4)	−0.0117 (4)
Br2	0.0539 (4)	0.0333 (4)	0.0418 (4)	−0.0101 (4)	0.0066 (3)	−0.0080 (3)
Br3	0.0424 (4)	0.0365 (4)	0.0452 (4)	0.0005 (3)	0.0098 (3)	0.0034 (3)
Cu1	0.0389 (5)	0.0269 (4)	0.0436 (5)	−0.0011 (4)	0.0015 (4)	−0.0011 (4)
Br4	0.0374 (4)	0.0322 (4)	0.0805 (5)	0.0010 (3)	−0.0113 (4)	−0.0026 (4)
N2	0.033 (3)	0.035 (3)	0.041 (3)	0.002 (3)	−0.003 (3)	−0.001 (3)
N1	0.032 (3)	0.024 (3)	0.033 (3)	0.000 (2)	0.000 (2)	−0.002 (2)
C4	0.043 (4)	0.033 (4)	0.040 (4)	0.008 (3)	0.010 (3)	0.002 (3)
C5	0.026 (4)	0.027 (4)	0.057 (4)	0.006 (3)	0.003 (3)	−0.003 (3)
C2	0.038 (4)	0.046 (4)	0.040 (4)	0.009 (3)	0.011 (3)	0.003 (4)
C3	0.025 (4)	0.047 (4)	0.047 (4)	0.004 (3)	0.005 (3)	0.009 (4)
C1	0.053 (5)	0.048 (4)	0.049 (4)	0.015 (4)	−0.007 (3)	0.007 (4)

Br1—Cu1	2.4131 (11)	C4—H4A	0.9700
Br2—Cu1	2.3809 (11)	C4—H4B	0.9700
Br3—Cu1	2.4059 (10)	C5—H5A	0.9700
Cu1—Br4	2.3869 (11)	C5—H5B	0.9700
N2—C3	1.492 (8)	C2—C3	1.513 (9)
N2—C4	1.493 (7)	C2—H2A	0.9700
N2—H2C	0.9000	C2—H2B	0.9700
N2—H2D	0.9000	C3—H3A	0.9700
N1—C2	1.486 (8)	C3—H3B	0.9700
N1—C1	1.499 (8)	C1—H1A	0.9600
N1—C5	1.503 (8)	C1—H1B	0.9600
N1—H1	0.9000	C1—H1C	0.9600
C4—C5	1.520 (9)
Br2—Cu1—Br4	140.15 (4)	N1—C5—C4	110.1 (5)
Br2—Cu1—Br3	99.28 (4)	N1—C5—H5A	109.6
Br4—Cu1—Br3	99.38 (4)	C4—C5—H5A	109.6
Br2—Cu1—Br1	96.41 (4)	N1—C5—H5B	109.6
Br4—Cu1—Br1	98.24 (4)	C4—C5—H5B	109.6
Br3—Cu1—Br1	129.61 (4)	H5A—C5—H5B	108.2
C3—N2—C4	112.3 (5)	N1—C2—C3	111.1 (5)
C3—N2—H2C	114.7	N1—C2—H2A	109.4
C4—N2—H2C	100.1	C3—C2—H2A	109.4
C3—N2—H2D	109.0	N1—C2—H2B	109.4
C4—N2—H2D	109.9	C3—C2—H2B	109.4
H2C—N2—H2D	110.6	H2A—C2—H2B	108.0
C2—N1—C1	112.2 (5)	N2—C3—C2	110.9 (5)
C2—N1—C5	109.5 (5)	N2—C3—H3A	109.5
C1—N1—C5	112.3 (5)	C2—C3—H3A	109.5
C2—N1—H1	118.5	N2—C3—H3B	109.5
C1—N1—H1	105.1	C2—C3—H3B	109.5
C5—N1—H1	98.6	H3A—C3—H3B	108.1
N2—C4—C5	110.1 (5)	N1—C1—H1A	109.5
N2—C4—H4A	109.7	N1—C1—H1B	109.5
C5—C4—H4A	109.7	H1A—C1—H1B	109.5
N2—C4—H4B	109.7	N1—C1—H1C	109.5
C5—C4—H4B	109.7	H1A—C1—H1C	109.5
H4A—C4—H4B	108.2	H1B—C1—H1C	109.5

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2C···Br3i	0.90	2.50	3.339 (6)	154
N2—H2D···Br1ii	0.90	2.68	3.354 (5)	133
N2—H2D···Br2ii	0.90	2.76	3.457 (5)	135
N1—H1···Br4	0.90	2.55	3.345 (5)	148

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2C⋯Br3i	0.90	2.50	3.339 (6)	154
N2—H2D⋯Br1ii	0.90	2.68	3.354 (5)	133
N2—H2D⋯Br2ii	0.90	2.76	3.457 (5)	135
N1—H1⋯Br4	0.90	2.55	3.345 (5)	148

Symmetry codes: (i) ; (ii) .