1,4-Diazo-niabicyclo-[2.2.2]octane tetra-bromidocuprate(II) monohydrate.

In the title monohydrated salt, (C(6)H(14)N(2))[CuBr(4)]·H(2)O, the copper(II) ion is coordinated by the four bromide ions in a flattened tetra-hedral geometry. In the crystal, the cations, anions and water mol-ecules inter-act via N-H⋯O, O-H⋯Br and N-H⋯Br hydrogen bonds, forming chains parallel to the b axis. The chains are further linked by O-H⋯Br hydrogen bonds into layers parallel to the bc plane.

Related literature

For related structures, see: Wei & Willett (1996 ▶, 2002 ▶); Brammer et al. (2002 ▶); Zhang et al. (2010 ▶).

Experimental

Crystal data

(C6H14N2)[CuBr4]·H2O

M = 515.39

Monoclinic,

a = 9.5171 (19) Å

b = 9.5341 (19) Å

c = 14.952 (3) Å

β = 93.93 (3)°

V = 1353.5 (5) Å3

Z = 4

Mo Kα radiation

μ = 13.40 mm−1

T = 298 K

0.20 × 0.20 × 0.20 mm

Data collection

Rigaku SCXmini diffractometer

Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ▶) T min = 0.055, T max = 0.086

13570 measured reflections

3111 independent reflections

2285 reflections with I > 2σ(I)

R int = 0.124

Refinement

R[F 2 > 2σ(F 2)] = 0.052

wR(F 2) = 0.116

S = 1.10

3111 reflections

128 parameters

H-atom parameters constrained

Δρmax = 1.22 e Å−3

Δρmin = −1.29 e Å−3

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 datablocks I, global. DOI: 10.1107/S1600536811005289/rz2552sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811005289/rz2552Isup2.hkl

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

(C6H14N2)[CuBr4]·H2O	F(000) = 972
Mr = 515.39	Dx = 2.529 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2622 reflections
a = 9.5171 (19) Å	θ = 3.0–27.5°
b = 9.5341 (19) Å	µ = 13.40 mm−1
c = 14.952 (3) Å	T = 298 K
β = 93.93 (3)°	Polyhedron, brown
V = 1353.5 (5) Å3	0.20 × 0.20 × 0.20 mm
Z = 4

Rigaku SCXmini diffractometer	3111 independent reflections
Radiation source: fine-focus sealed tube	2285 reflections with I > 2σ(I)
graphite	Rint = 0.124
Detector resolution: 13.6612 pixels mm-1	θmax = 27.5°, θmin = 3.0°
ω scans	h = −12→12
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −12→12
Tmin = 0.055, Tmax = 0.086	l = −19→19
13570 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)] = 0.052	H-atom parameters constrained
wR(F2) = 0.116	w = 1/[σ2(Fo2) + (0.0225P)2 + 2.0506P] where P = (Fo2 + 2Fc2)/3
S = 1.10	(Δ/σ)max < 0.001
3111 reflections	Δρmax = 1.22 e Å−3
128 parameters	Δρmin = −1.29 e Å−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0204 (7)

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.

	x	y	z	Uiso*/Ueq
Br1	0.13288 (8)	1.07551 (7)	−0.32168 (5)	0.0252 (2)
Br2	0.47455 (8)	1.29945 (9)	−0.17676 (5)	0.0294 (3)
Br3	0.24026 (10)	1.44329 (8)	−0.35401 (5)	0.0343 (3)
Br4	0.12020 (9)	1.24314 (8)	−0.10831 (5)	0.0291 (2)
C1	0.2071 (9)	0.7578 (7)	−0.1967 (5)	0.0250 (18)
H1A	0.1136	0.7276	−0.2186	0.030*
H1B	0.2588	0.7837	−0.2479	0.030*
C2	0.2812 (10)	0.6413 (8)	−0.1464 (5)	0.039 (2)
H2A	0.2182	0.5619	−0.1423	0.046*
H2B	0.3620	0.6113	−0.1776	0.046*
C3	0.1196 (8)	0.8404 (8)	−0.0560 (5)	0.0221 (17)
H3A	0.0265	0.8058	−0.0751	0.027*
H3B	0.1094	0.9204	−0.0170	0.027*
C4	0.2029 (9)	0.7281 (8)	−0.0075 (6)	0.032 (2)
H4A	0.2322	0.7602	0.0524	0.039*
H4B	0.1444	0.6456	−0.0023	0.039*
C5	0.3414 (8)	0.9335 (7)	−0.1063 (5)	0.0265 (19)
H5A	0.3357	1.0120	−0.0654	0.032*
H5B	0.3896	0.9644	−0.1579	0.032*
C6	0.4211 (9)	0.8136 (8)	−0.0601 (6)	0.040 (2)
H6A	0.5019	0.7893	−0.0932	0.048*
H6B	0.4551	0.8418	−0.0001	0.048*
Cu1	0.24156 (9)	1.27018 (9)	−0.24116 (6)	0.0190 (3)
N1	0.1962 (6)	0.8822 (6)	−0.1354 (4)	0.0164 (13)
H1C	0.1478	0.9520	−0.1654	0.020*
N2	0.3277 (6)	0.6913 (6)	−0.0552 (4)	0.0204 (14)
H2C	0.3753	0.6211	−0.0251	0.024*
O1W	0.6324 (6)	0.5717 (5)	−0.0241 (3)	0.0316 (14)
H1WA	0.6670	0.5956	0.0276	0.047*
H1WB	0.6832	0.6044	−0.0638	0.047*

	U11	U22	U33	U12	U13	U23
Br1	0.0381 (5)	0.0188 (4)	0.0181 (5)	−0.0005 (3)	−0.0012 (4)	−0.0011 (3)
Br2	0.0251 (4)	0.0452 (5)	0.0177 (5)	0.0018 (4)	0.0000 (3)	0.0023 (4)
Br3	0.0557 (6)	0.0281 (5)	0.0180 (5)	−0.0065 (4)	−0.0067 (4)	0.0144 (4)
Br4	0.0378 (5)	0.0327 (5)	0.0182 (5)	0.0007 (4)	0.0138 (4)	0.0031 (3)
C1	0.037 (5)	0.028 (4)	0.010 (4)	−0.003 (4)	0.002 (3)	−0.008 (3)
C2	0.077 (7)	0.025 (5)	0.015 (5)	0.015 (5)	0.009 (5)	−0.004 (4)
C3	0.027 (4)	0.029 (4)	0.010 (4)	0.003 (3)	0.003 (3)	−0.004 (3)
C4	0.046 (5)	0.029 (5)	0.024 (5)	0.009 (4)	0.012 (4)	0.010 (4)
C5	0.035 (4)	0.017 (4)	0.026 (5)	−0.007 (3)	−0.007 (4)	0.006 (3)
C6	0.029 (5)	0.035 (5)	0.054 (6)	−0.001 (4)	−0.011 (4)	0.029 (5)
Cu1	0.0288 (5)	0.0193 (5)	0.0087 (5)	−0.0016 (4)	0.0003 (4)	0.0041 (4)
N1	0.020 (3)	0.019 (3)	0.011 (3)	0.005 (3)	−0.002 (2)	0.007 (3)
N2	0.037 (4)	0.011 (3)	0.013 (3)	0.006 (3)	−0.002 (3)	0.008 (3)
O1W	0.045 (3)	0.027 (3)	0.023 (3)	0.000 (3)	0.008 (3)	0.010 (2)

Br1—Cu1	2.4070 (12)	C4—N2	1.469 (10)
Br2—Cu1	2.3726 (13)	C4—H4A	0.9700
Br3—Cu1	2.3598 (12)	C4—H4B	0.9700
Br4—Cu1	2.3792 (13)	C5—N1	1.502 (9)
C1—C2	1.492 (10)	C5—C6	1.512 (10)
C1—N1	1.507 (9)	C5—H5A	0.9700
C1—H1A	0.9700	C5—H5B	0.9700
C1—H1B	0.9700	C6—N2	1.471 (9)
C2—N2	1.483 (9)	C6—H6A	0.9700
C2—H2A	0.9700	C6—H6B	0.9700
C2—H2B	0.9700	N1—H1C	0.9100
C3—N1	1.489 (9)	N2—H2C	0.9100
C3—C4	1.490 (10)	O1W—H1WA	0.8501
C3—H3A	0.9700	O1W—H1WB	0.8500
C3—H3B	0.9700
C2—C1—N1	109.2 (6)	C6—C5—H5B	110.1
C2—C1—H1A	109.8	H5A—C5—H5B	108.4
N1—C1—H1A	109.8	N2—C6—C5	109.6 (6)
C2—C1—H1B	109.8	N2—C6—H6A	109.7
N1—C1—H1B	109.8	C5—C6—H6A	109.7
H1A—C1—H1B	108.3	N2—C6—H6B	109.7
N2—C2—C1	109.0 (6)	C5—C6—H6B	109.7
N2—C2—H2A	109.9	H6A—C6—H6B	108.2
C1—C2—H2A	109.9	Br3—Cu1—Br2	99.61 (5)
N2—C2—H2B	109.9	Br3—Cu1—Br4	133.92 (5)
C1—C2—H2B	109.9	Br2—Cu1—Br4	99.64 (5)
H2A—C2—H2B	108.3	Br3—Cu1—Br1	101.57 (4)
N1—C3—C4	107.9 (6)	Br2—Cu1—Br1	130.64 (5)
N1—C3—H3A	110.1	Br4—Cu1—Br1	96.75 (4)
C4—C3—H3A	110.1	C3—N1—C5	110.3 (5)
N1—C3—H3B	110.1	C3—N1—C1	109.4 (5)
C4—C3—H3B	110.1	C5—N1—C1	109.4 (6)
H3A—C3—H3B	108.4	C3—N1—H1C	109.2
N2—C4—C3	110.9 (6)	C5—N1—H1C	109.2
N2—C4—H4A	109.5	C1—N1—H1C	109.2
C3—C4—H4A	109.5	C4—N2—C6	110.2 (6)
N2—C4—H4B	109.5	C4—N2—C2	108.8 (6)
C3—C4—H4B	109.5	C6—N2—C2	110.7 (6)
H4A—C4—H4B	108.1	C4—N2—H2C	109.0
N1—C5—C6	108.0 (6)	C6—N2—H2C	109.0
N1—C5—H5A	110.1	C2—N2—H2C	109.0
C6—C5—H5A	110.1	H1WA—O1W—H1WB	109.5
N1—C5—H5B	110.1

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2C···O1W	0.91	2.49	3.121 (8)	127
N2—H2C···O1Wi	0.91	1.98	2.788 (7)	147
O1W—H1WA···Br4ii	0.85	2.75	3.456 (5)	141
O1W—H1WA···Br2ii	0.85	2.86	3.461 (5)	129
O1W—H1WB···Br1iii	0.85	2.55	3.319 (5)	152
N1—H1C···Br1	0.91	2.61	3.360 (5)	140
N1—H1C···Br4	0.91	2.92	3.546 (6)	127

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2C⋯O1W	0.91	2.49	3.121 (8)	127
N2—H2C⋯O1Wi	0.91	1.98	2.788 (7)	147
O1W—H1WA⋯Br4ii	0.85	2.75	3.456 (5)	141
O1W—H1WA⋯Br2ii	0.85	2.86	3.461 (5)	129
O1W—H1WB⋯Br1iii	0.85	2.55	3.319 (5)	152
N1—H1C⋯Br1	0.91	2.61	3.360 (5)	140
N1—H1C⋯Br4	0.91	2.92	3.546 (6)	127

Symmetry codes: (i) ; (ii) ; (iii) .