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metal-organic compounds
1-Cyanomethyl-1,4-diazoniabicyclo[2.2.2]octane tetrabromidocuprate(II)
aOrdered Matter Science Research Center, Southeast University, Nanjing 211189, People's Republic of China
*Correspondence e-mail: cyik@163.com
In the 8H15N3)[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.
of the title complex, (CRelated 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
|
Refinement
|
|
Data collection: CrystalClear (Rigaku, 2005); cell 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
10.1107/S1600536810023469/nc2190sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536810023469/nc2190Isup2.hkl
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.
H atoms bound to carbon and nitrogen were placed in idealized positions [C—H = 0.97 Å and N—H = 0.96 Å] and allowed to ride on their parent atoms with Uiso fixed at 1.2 Ueq(C,N).
Data collection: CrystalClear (Rigaku, 2005); cell
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).(C8H15N3)[CuBr4] | F(000) = 1012 |
Mr = 536.41 | Dx = 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 |
Rigaku Mercury CCD diffractometer | 3347 independent reflections |
Radiation source: fine-focus sealed tube | 2642 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.069 |
ω scans | θmax = 27.5°, θmin = 3.1° |
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005) | h = −11→10 |
Tmin = 0.041, Tmax = 0.092 | k = −18→17 |
14798 measured reflections | l = −16→16 |
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(Fo2) + (0.0321P)2 + 5.2474P] where P = (Fo2 + 2Fc2)/3 |
S = 1.10 | (Δ/σ)max < 0.001 |
3347 reflections | Δρmax = 1.48 e Å−3 |
145 parameters | Δρmin = −0.93 e Å−3 |
0 restraints | Extinction correction: SHELXS |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0476 (15) |
(C8H15N3)[CuBr4] | V = 1461.7 (5) Å3 |
Mr = 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)° |
Rigaku Mercury CCD diffractometer | 3347 independent reflections |
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005) | 2642 reflections with I > 2σ(I) |
Tmin = 0.041, Tmax = 0.092 | Rint = 0.069 |
14798 measured reflections |
R[F2 > 2σ(F2)] = 0.046 | 0 restraints |
wR(F2) = 0.099 | H-atom parameters constrained |
S = 1.10 | Δρmax = 1.48 e Å−3 |
3347 reflections | Δρmin = −0.93 e Å−3 |
145 parameters |
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 | 0.95523 (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* |
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) |
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) |
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] |
Mr | 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) |
Tmin, Tmax | 0.041, 0.092 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 14798, 3347, 2642 |
Rint | 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 |
Δρmax, Δρmin (e Å−3) | 1.48, −0.93 |
Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
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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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 CuBr42- anions via very weak intermolecular interactions (Fig. 2 and Table 1).