1-Cyano­meth­yl-1,4-diazo­niabicyclo­[2.2.2]octane tetra­bromidocuprate(II)

Cai, Y.

doi:10.1107/S1600536810023469

metal-organic compounds

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Volume 66| Part 7| July 2010| Page m830

doi:10.1107/S1600536810023469

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1-Cyanomethyl-1,4-diazoniabicyclo[2.2.2]octane tetrabromidocuprate(II)

Ying Cai ^a ^*

^aOrdered Matter Science Research Center, Southeast University, Nanjing 211189, People's Republic of China
^*Correspondence e-mail: cyik@163.com

(Received 11 June 2010; accepted 17 June 2010; online 23 June 2010)

In the crystal structure of the title complex, (C₈H₁₅N₃)[CuBr₄], the Cu atom is coordinated by four bromido ligands within a strongly distorted tetrahedron. The anions and cations are connected by weak N—H⋯Br and C—H⋯Br hydrogen-bonding interactions.

Related literature

For the uses of DABCO (1,4-diazabicyclo[2.2.2]octane) and its derivatives, see: Basaviah et al. (2003 ); Chen et al. (2010 ).

Experimental

Crystal data

(C₈H₁₅N₃)[CuBr₄]
M_r = 536.41
Monoclinic, P 2₁ /c
a = 8.4793 (17) Å
b = 13.911 (3) Å
c = 12.506 (3) Å
β = 97.75 (3)°
V = 1461.7 (5) Å³
Z = 4
Mo Kα radiation
μ = 12.41 mm⁻¹
T = 293 K
0.3 × 0.3 × 0.2 mm

Data collection

Rigaku Mercury CCD diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.041, T_max = 0.092
14798 measured reflections
3347 independent reflections
2642 reflections with I > 2σ(I)
R_int = 0.069

Refinement

R[F² > 2σ(F²)] = 0.046
wR(F²) = 0.099
S = 1.10
3347 reflections
145 parameters
H-atom parameters constrained
Δρ_max = 1.48 e Å⁻³
Δρ_min = −0.93 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3C⋯Br3ⁱ	0.96	2.62	3.420 (5)	142
N3—H3C⋯Br2ⁱ	0.96	2.95	3.545 (5)	122
C4—H4A⋯Br3ⁱ	0.97	2.92	3.555 (6)	124
N3—H3C⋯Br4	0.96	2.86	3.406 (5)	117
C2—H2A⋯Br1ⁱⁱ	0.97	2.91	3.638 (6)	132
C2—H2B⋯Br4ⁱⁱⁱ	0.97	2.73	3.608 (6)	150
Symmetry codes: (i) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (ii) -x+1, -y, -z+1; (iii) x-1, y, z.

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: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810023469/nc2190sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810023469/nc2190Isup2.hkl

checkCIF report

Comment top

1,4-Diazabicyclo[2.2.2]octane (DABCO) is used as a good organocatalyst for a large number of reactions because of its nucleophilicity (Basaviah et al., 2003) and some of its derivatives are ferroelectrics (Chen et al., 2010). The structure determination of the title compound was performed within a project on the electric properties of 1,4-Diazabicyclo[2.2.2]octane derivatives. Within this project the crystals were obtained by accident.

The asymmetric unit of the title compound, (I), is shown in Fig. 1. The Cu atoms are coordinated by four Br atoms with very similar distances in the range of 2.36 (1) to 2.41 (4) Å. The Br—Cu—Br bond angles are between 97.32 (4) and 126.31 (4)° which shows that the coordination polyhedron can be described as a strongly disotorted tetrahedron. The (C₈H₁₄N₃)²⁺ cations are connected to the CuBr₄^2- anions via very weak intermolecular interactions (Fig. 2 and Table 1).

Related literature top

For the uses of DABCO (1,4-diazabicyclo[2.2.2]octane) and its derivatives, see: Basaviah et al. (2003); Chen et al. (2010).

Experimental top

1,4-Diaza-bicyclo[2.2.2]octane (dabco) (0.05 mol, 5.6 g) and bromoacetonitrile (0.1 mol, 12.00 g) were dissolved in CH₃CN (40 ml) with stirring for 1 h at room temperature. 1-(cyanomethyl)-4-aza-1-azonia-bicyclo[2.2.2]octane bromide quickly formed as a white solid was filtered, washed with acetonitrile and dried (yield: 80%).

CuBr₂(0.001 mol, 0.223 g) and 4 ml 60% HBr were dissolved in MeOH (20 ml) and 1-(cyanomethyl)-4-aza-1-azonia-bicyclo[2.2.2]octane bromide (0.002 mol, 0.464 g) dissolved in 10 ml of methanol was added. The mixture was stirred until a clear solution was obtained. After slow evaporation of the solvent, colourless plate crystals of the title compand suitable for X-ray analysis were obtained in about 68% yield.

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); 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: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. Crystal structure of the title compound with labelling and displacement ellipsoids drawn at the 30% probability level.
	Fig. 2. Crystal structure of the title compound with view along the a axis. Intermolecular interactions are shown as dashed lines.

1-Cyanomethyl-1,4-diazoniabicyclo[2.2.2]octane tetrabromidocuprate(II) top

Crystal data top

(C₈H₁₅N₃)[CuBr₄]	F(000) = 1012
M_r = 536.41	D_x = 2.438 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3450 reflections
a = 8.4793 (17) Å	θ = 6.2–55.3°
b = 13.911 (3) Å	µ = 12.41 mm⁻¹
c = 12.506 (3) Å	T = 293 K
β = 97.75 (3)°	Block, brown
V = 1461.7 (5) Å³	0.3 × 0.3 × 0.2 mm
Z = 4

Data collection top

Rigaku Mercury CCD diffractometer	3347 independent reflections
Radiation source: fine-focus sealed tube	2642 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.069
ω scans	θ_max = 27.5°, θ_min = 3.1°
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	h = −11→10
T_min = 0.041, T_max = 0.092	k = −18→17
14798 measured reflections	l = −16→16

Refinement top

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)] = 0.046	H-atom parameters constrained
wR(F²) = 0.099	w = 1/[σ²(F_o²) + (0.0321P)² + 5.2474P] where P = (F_o² + 2F_c²)/3
S = 1.10	(Δ/σ)_max < 0.001
3347 reflections	Δρ_max = 1.48 e Å⁻³
145 parameters	Δρ_min = −0.93 e Å⁻³
0 restraints	Extinction correction: SHELXS
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0476 (15)

Crystal data top

(C₈H₁₅N₃)[CuBr₄]	V = 1461.7 (5) Å³
M_r = 536.41	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.4793 (17) Å	µ = 12.41 mm⁻¹
b = 13.911 (3) Å	T = 293 K
c = 12.506 (3) Å	0.3 × 0.3 × 0.2 mm
β = 97.75 (3)°

Data collection top

Rigaku Mercury CCD diffractometer	3347 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	2642 reflections with I > 2σ(I)
T_min = 0.041, T_max = 0.092	R_int = 0.069
14798 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.046	0 restraints
wR(F²) = 0.099	H-atom parameters constrained
S = 1.10	Δρ_max = 1.48 e Å⁻³
3347 reflections	Δρ_min = −0.93 e Å⁻³
145 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
Br1	0.95523 (8)	0.14445 (5)	0.53910 (5)	0.03184 (18)
Br2	0.50194 (8)	0.14394 (5)	0.54689 (5)	0.02883 (17)
Br3	0.66511 (8)	0.39414 (4)	0.52626 (5)	0.02810 (17)
Br4	0.73530 (8)	0.25471 (5)	0.29836 (5)	0.02880 (17)
Cu1	0.71711 (9)	0.23115 (5)	0.48323 (6)	0.02398 (19)
N3	0.3831 (6)	0.1546 (3)	0.1900 (4)	0.0200 (11)
H3C	0.4761	0.1712	0.1585	0.024*
N2	0.1266 (5)	0.0841 (3)	0.2321 (4)	0.0142 (10)
C6	0.4153 (8)	0.0598 (4)	0.2422 (5)	0.0280 (14)
H6A	0.4988	0.0658	0.3030	0.034*
H6B	0.4505	0.0148	0.1912	0.034*
C4	0.2717 (7)	0.1424 (5)	0.0866 (5)	0.0244 (14)
H4A	0.3228	0.1055	0.0352	0.029*
H4B	0.2425	0.2047	0.0551	0.029*
C5	0.2642 (7)	0.0233 (5)	0.2805 (6)	0.0323 (16)
H5A	0.2461	−0.0432	0.2587	0.039*
H5B	0.2743	0.0264	0.3586	0.039*
C1	−0.0752 (7)	−0.0431 (4)	0.2002 (5)	0.0236 (14)
C2	−0.0285 (7)	0.0450 (4)	0.2597 (5)	0.0245 (14)
H2A	−0.0182	0.0319	0.3366	0.029*
H2B	−0.1112	0.0930	0.2431	0.029*
N1	−0.1173 (7)	−0.1086 (4)	0.1523 (5)	0.0367 (14)
C3	0.1243 (7)	0.0901 (5)	0.1130 (4)	0.0253 (14)
H3A	0.0296	0.1241	0.0811	0.030*
H3B	0.1212	0.0258	0.0826	0.030*
C7	0.3101 (7)	0.2214 (4)	0.2631 (5)	0.0234 (13)
H7A	0.3002	0.2852	0.2317	0.028*
H7B	0.3771	0.2255	0.3323	0.028*
C8	0.1493 (8)	0.1836 (4)	0.2783 (6)	0.0286 (15)
H8A	0.0675	0.2259	0.2427	0.034*
H8B	0.1390	0.1822	0.3546	0.034*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0348 (4)	0.0360 (4)	0.0249 (3)	0.0130 (3)	0.0046 (3)	0.0072 (3)
Br2	0.0327 (4)	0.0263 (3)	0.0280 (4)	−0.0016 (3)	0.0064 (3)	0.0013 (3)
Br3	0.0331 (4)	0.0195 (3)	0.0339 (4)	0.0001 (3)	0.0121 (3)	0.0011 (3)
Br4	0.0297 (3)	0.0368 (4)	0.0197 (3)	0.0029 (3)	0.0026 (3)	0.0015 (3)
Cu1	0.0270 (4)	0.0230 (4)	0.0223 (4)	0.0029 (3)	0.0050 (3)	0.0014 (3)
N3	0.019 (2)	0.025 (3)	0.017 (3)	−0.003 (2)	0.006 (2)	−0.004 (2)
N2	0.017 (2)	0.012 (2)	0.013 (2)	0.0007 (19)	0.0032 (19)	−0.0025 (18)
C6	0.026 (3)	0.029 (3)	0.028 (4)	0.007 (3)	−0.001 (3)	0.003 (3)
C4	0.020 (3)	0.036 (4)	0.016 (3)	−0.009 (3)	0.002 (2)	0.000 (3)
C5	0.023 (3)	0.024 (3)	0.048 (4)	0.002 (3)	−0.003 (3)	0.012 (3)
C1	0.026 (3)	0.018 (3)	0.025 (3)	−0.005 (3)	−0.003 (3)	0.008 (3)
C2	0.025 (3)	0.024 (3)	0.026 (3)	−0.007 (3)	0.010 (3)	−0.002 (3)
N1	0.042 (4)	0.028 (3)	0.036 (3)	−0.012 (3)	−0.008 (3)	0.009 (3)
C3	0.023 (3)	0.045 (4)	0.008 (3)	−0.007 (3)	0.001 (2)	−0.002 (3)
C7	0.023 (3)	0.019 (3)	0.029 (3)	−0.004 (3)	0.005 (3)	−0.006 (3)
C8	0.040 (4)	0.015 (3)	0.035 (4)	−0.010 (3)	0.022 (3)	−0.013 (3)

Geometric parameters (Å, º) top

Br1—Cu1	2.3747 (11)	C4—H4A	0.9700
Br2—Cu1	2.4137 (11)	C4—H4B	0.9700
Br3—Cu1	2.3852 (10)	C5—H5A	0.9700
Br4—Cu1	2.3606 (11)	C5—H5B	0.9700
N3—C6	1.480 (8)	C1—N1	1.122 (8)
N3—C7	1.494 (7)	C1—C2	1.460 (8)
N3—C4	1.505 (7)	C2—H2A	0.9700
N3—H3C	0.9568	C2—H2B	0.9700
N2—C3	1.490 (7)	C3—H3A	0.9700
N2—C5	1.501 (8)	C3—H3B	0.9700
N2—C8	1.502 (7)	C7—C8	1.497 (8)
N2—C2	1.506 (7)	C7—H7A	0.9700
C6—C5	1.515 (9)	C7—H7B	0.9700
C6—H6A	0.9700	C8—H8A	0.9700
C6—H6B	0.9700	C8—H8B	0.9700
C4—C3	1.520 (8)

Br4—Cu1—Br1	101.15 (4)	N2—C5—H5A	109.8
Br4—Cu1—Br3	97.32 (4)	C6—C5—H5A	109.8
Br1—Cu1—Br3	126.31 (4)	N2—C5—H5B	109.8
Br4—Cu1—Br2	123.02 (4)	C6—C5—H5B	109.8
Br1—Cu1—Br2	107.35 (4)	H5A—C5—H5B	108.3
Br3—Cu1—Br2	103.44 (4)	N1—C1—C2	176.7 (7)
C6—N3—C7	110.6 (5)	C1—C2—N2	111.8 (5)
C6—N3—C4	109.6 (5)	C1—C2—H2A	109.3
C7—N3—C4	109.4 (5)	N2—C2—H2A	109.3
C6—N3—H3C	106.5	C1—C2—H2B	109.3
C7—N3—H3C	122.3	N2—C2—H2B	109.3
C4—N3—H3C	97.4	H2A—C2—H2B	107.9
C3—N2—C5	109.8 (5)	N2—C3—C4	110.1 (5)
C3—N2—C8	108.5 (5)	N2—C3—H3A	109.6
C5—N2—C8	108.2 (5)	C4—C3—H3A	109.6
C3—N2—C2	110.8 (4)	N2—C3—H3B	109.6
C5—N2—C2	111.1 (4)	C4—C3—H3B	109.6
C8—N2—C2	108.4 (4)	H3A—C3—H3B	108.2
N3—C6—C5	108.9 (5)	N3—C7—C8	108.6 (5)
N3—C6—H6A	109.9	N3—C7—H7A	110.0
C5—C6—H6A	109.9	C8—C7—H7A	110.0
N3—C6—H6B	109.9	N3—C7—H7B	110.0
C5—C6—H6B	109.9	C8—C7—H7B	110.0
H6A—C6—H6B	108.3	H7A—C7—H7B	108.4
N3—C4—C3	107.8 (5)	C7—C8—N2	110.3 (5)
N3—C4—H4A	110.1	C7—C8—H8A	109.6
C3—C4—H4A	110.1	N2—C8—H8A	109.6
N3—C4—H4B	110.1	C7—C8—H8B	109.6
C3—C4—H4B	110.1	N2—C8—H8B	109.6
H4A—C4—H4B	108.5	H8A—C8—H8B	108.1
N2—C5—C6	109.2 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3C···Br3ⁱ	0.96	2.62	3.420 (5)	142
N3—H3C···Br2ⁱ	0.96	2.95	3.545 (5)	122
C4—H4A···Br3ⁱ	0.97	2.92	3.555 (6)	124
N3—H3C···Br4	0.96	2.86	3.406 (5)	117
C2—H2A···Br1ⁱⁱ	0.97	2.91	3.638 (6)	132
C2—H2B···Br4ⁱⁱⁱ	0.97	2.73	3.608 (6)	150

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

Experimental details

Crystal data
Chemical formula	(C₈H₁₅N₃)[CuBr₄]
M_r	536.41
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	8.4793 (17), 13.911 (3), 12.506 (3)
β (°)	97.75 (3)
V (Å³)	1461.7 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	12.41
Crystal size (mm)	0.3 × 0.3 × 0.2

Data collection
Diffractometer	Rigaku Mercury CCD diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.041, 0.092
No. of measured, independent and observed [I > 2σ(I)] reflections	14798, 3347, 2642
R_int	0.069
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.099, 1.10
No. of reflections	3347
No. of parameters	145
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.48, −0.93

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3C···Br3ⁱ	0.96	2.62	3.420 (5)	141.9
N3—H3C···Br2ⁱ	0.96	2.95	3.545 (5)	121.6
C4—H4A···Br3ⁱ	0.97	2.92	3.555 (6)	124.1
N3—H3C···Br4	0.96	2.86	3.406 (5)	117.0
C2—H2A···Br1ⁱⁱ	0.97	2.91	3.638 (6)	132.2
C2—H2B···Br4ⁱⁱⁱ	0.97	2.73	3.608 (6)	150.1

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

References

Basaviah, D., Rao, A. J. & Satyanarayana, T. (2003). Chem. Rev. 103, 811–891. Web of Science PubMed Google Scholar
Chen, L. Z., Huang, Y., Xiong, R. G. & Hu, H. W. (2010). J. Mol. Struct. 963, 16–21. Web of Science CSD CrossRef CAS Google Scholar
Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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doi:10.1107/S1600536810023469

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