metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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ISSN: 2056-9890

Bis[4-(di­methyl­amino)pyridinium] tetra­bromidocuprate(II)

aDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
*Correspondence e-mail: seikweng@um.edu.my

(Received 16 July 2009; accepted 17 July 2009; online 22 July 2009)

The metal atom in the anion of the title salt, (C7H11N2)2[CuBr4], shows a distorted tetra­hedral coordination. The primary contacts between the ions are of the N—H⋯Br type.

Related literature

For other pyridinium tetra­bromidocuprates, see: Coffey et al. (1996[Coffey, T., Robinson, W. T. & Turnbull, M. M. (1996). Acta Cryst. C52, 248-250.]); Haddad & Al-Far (2008[Haddad, S. F. & Al-Far, R. H. (2008). J. Chem. Crystallogr. 38, 663-669.]); Luque et al. (2001[Luque, A., Sertucha, J., Castillo, O. & Roman, P. (2001). New J. Chem. 25, 1208-1214.]); Willet et al. (2000[Willett, R. D., Haddad, S. F. & Twamley, B. (2000). Acta Cryst. C56, e437.], 2003[Willet, R. D., Awwadi, F., Butcher, R., Haddad, S. & Twamley, B. (2003). Cryst. Growth Des. 3, 301-311.]).

[Scheme 1]

Experimental

Crystal data
  • (C7H11N2)2[CuBr4]

  • Mr = 629.54

  • Triclinic, [P \overline 1]

  • a = 8.1768 (2) Å

  • b = 9.2406 (3) Å

  • c = 14.3686 (4) Å

  • α = 93.689 (2)°

  • β = 94.814 (2)°

  • γ = 105.073 (2)°

  • V = 1040.42 (5) Å3

  • Z = 2

  • Mo Kα radiation

  • μ = 8.73 mm−1

  • T = 233 K

  • 0.35 × 0.30 × 0.10 mm

Data collection
  • Bruker SMART APEX diffractometer

  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996[Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.]) Tmin = 0.321, Tmax = 0.746 (expected range = 0.180–0.418)

  • 7224 measured reflections

  • 4595 independent reflections

  • 3168 reflections with I > 2σ(I)

  • Rint = 0.042

Refinement
  • R[F2 > 2σ(F2)] = 0.043

  • wR(F2) = 0.123

  • S = 1.00

  • 4595 reflections

  • 213 parameters

  • H-atom parameters constrained

  • Δρmax = 0.84 e Å−3

  • Δρmin = −0.82 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
N1—H1⋯Br1 0.88 2.54 3.380 (7) 162
N3—H3⋯Br2 0.88 2.65 3.449 (6) 152

Data collection: APEX2 (Bruker, 2008[Bruker (2008). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2008[Bruker (2008). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: X-SEED (Barbour, 2001[Barbour, L. J. (2001). J. Supramol. Chem. 1, 189-191.]); software used to prepare material for publication: publCIF (Westrip, 2009[Westrip, S. P. (2009). publCIF. In preparation.]).

Supporting information


Related literature top

For other pyridinium tetrabromidocuprates, see: Coffey et al. (1996); Haddad & Al-Far (2008); Luque et al. (2001); Willet et al. (2000, 2003).

Experimental top

Copper sulfate pentahydrate (2.1 g, 8.3 mmol) dissolved in water (5 ml) was mixed with 4-dimethylaminopyridine hydrobromide perbromide (3 g, 8.3 mmol) dissolved in ethanol (10 ml). The mixture was heated for 30 min. The filtered green solution when allowed to evaporate yielded black crystals.

Refinement top

Hydrogen atoms were placed at calculated positions (C–H 0.94–0.97 Å; N–H 0.88 Å) and were treated as riding on their parent atoms, with U(H) set to 1.2–1.5Ueq(C, N).

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2009).

Figures top
[Figure 1] Fig. 1. Thermal ellipsoid plot (Barbour, 2001) of 2[C7H11N2][CuBr4] at the 50% probability level. Hydrogen atoms are drawn as spheres of arbitrary radius.
Bis[4-(dimethylamino)pyridinium] tetrabromidocuprate(II) top
Crystal data top
(C7H11N2)2[CuBr4]Z = 2
Mr = 629.54F(000) = 606
Triclinic, P1Dx = 2.010 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 8.1768 (2) ÅCell parameters from 2442 reflections
b = 9.2406 (3) Åθ = 2.3–27.5°
c = 14.3686 (4) ŵ = 8.73 mm1
α = 93.689 (2)°T = 233 K
β = 94.814 (2)°Block, black
γ = 105.073 (2)°0.35 × 0.30 × 0.10 mm
V = 1040.42 (5) Å3
Data collection top
Bruker SMART APEX
diffractometer
4595 independent reflections
Radiation source: fine-focus sealed tube3168 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.042
ω scansθmax = 27.5°, θmin = 1.4°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 1010
Tmin = 0.321, Tmax = 0.746k = 1012
7224 measured reflectionsl = 1818
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.043H-atom parameters constrained
wR(F2) = 0.123 w = 1/[σ2(Fo2) + (0.0566P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.00(Δ/σ)max = 0.001
4595 reflectionsΔρmax = 0.84 e Å3
213 parametersΔρmin = 0.82 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0078 (8)
Crystal data top
(C7H11N2)2[CuBr4]γ = 105.073 (2)°
Mr = 629.54V = 1040.42 (5) Å3
Triclinic, P1Z = 2
a = 8.1768 (2) ÅMo Kα radiation
b = 9.2406 (3) ŵ = 8.73 mm1
c = 14.3686 (4) ÅT = 233 K
α = 93.689 (2)°0.35 × 0.30 × 0.10 mm
β = 94.814 (2)°
Data collection top
Bruker SMART APEX
diffractometer
4595 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
3168 reflections with I > 2σ(I)
Tmin = 0.321, Tmax = 0.746Rint = 0.042
7224 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0430 restraints
wR(F2) = 0.123H-atom parameters constrained
S = 1.00Δρmax = 0.84 e Å3
4595 reflectionsΔρmin = 0.82 e Å3
213 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Br10.46757 (8)0.23274 (7)0.31534 (5)0.04383 (19)
Br20.44673 (8)0.69937 (7)0.29470 (5)0.0458 (2)
Br30.11950 (8)0.35808 (7)0.20247 (4)0.03895 (18)
Br40.65667 (8)0.48740 (7)0.15029 (4)0.04107 (19)
Cu10.41731 (9)0.44301 (7)0.23676 (5)0.0323 (2)
N10.8043 (9)0.5220 (8)0.4011 (5)0.067 (2)
H10.73350.44340.36850.081*
N21.1304 (7)0.8919 (6)0.5502 (4)0.0466 (13)
N30.6251 (7)0.8455 (6)0.1004 (4)0.0478 (13)
H30.57940.77760.13760.057*
N40.8436 (7)1.1604 (6)0.0731 (3)0.0415 (12)
C10.9472 (12)0.5930 (9)0.3673 (5)0.063 (2)
H1A0.97090.55760.30850.075*
C21.0582 (9)0.7127 (9)0.4141 (5)0.0521 (18)
H21.15890.75960.38870.062*
C31.0231 (7)0.7695 (7)0.5032 (4)0.0343 (13)
C40.8711 (8)0.6903 (8)0.5360 (5)0.0465 (16)
H40.84090.72130.59420.056*
C50.7692 (9)0.5702 (9)0.4836 (5)0.064 (2)
H50.66830.51790.50670.077*
C61.2928 (10)0.9673 (9)0.5180 (6)0.067 (2)
H6A1.27231.01010.45970.100*
H6B1.35850.89510.50800.100*
H6C1.35561.04690.56500.100*
C71.0967 (10)0.9465 (9)0.6426 (5)0.062 (2)
H7A0.98140.95710.63930.093*
H7B1.17671.04330.66230.093*
H7C1.10950.87520.68750.093*
C80.6803 (9)0.8036 (7)0.0201 (5)0.0472 (17)
H80.66880.70080.00450.057*
C90.7497 (8)0.9012 (7)0.0374 (4)0.0409 (15)
H90.78580.86710.09310.049*
C100.7710 (7)1.0591 (6)0.0161 (4)0.0328 (13)
C110.7118 (7)1.1009 (7)0.0682 (4)0.0374 (14)
H110.72171.20260.08630.045*
C120.6401 (8)0.9918 (8)0.1234 (4)0.0462 (17)
H120.59991.02000.17930.055*
C130.9027 (9)1.1174 (9)0.1615 (5)0.0558 (18)
H13A0.94151.02740.15530.084*
H13B0.99601.19860.17640.084*
H13C0.80991.09770.21120.084*
C140.8708 (10)1.3216 (6)0.0511 (5)0.059 (2)
H14A0.95131.35510.00440.088*
H14B0.76351.34240.03980.088*
H14C0.91581.37470.10350.088*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br10.0494 (4)0.0387 (4)0.0482 (4)0.0151 (3)0.0101 (3)0.0186 (3)
Br20.0496 (4)0.0355 (3)0.0513 (4)0.0073 (3)0.0199 (3)0.0051 (3)
Br30.0337 (3)0.0415 (3)0.0407 (3)0.0089 (3)0.0043 (2)0.0009 (3)
Br40.0450 (4)0.0397 (3)0.0446 (4)0.0155 (3)0.0205 (3)0.0109 (3)
Cu10.0331 (4)0.0319 (4)0.0336 (4)0.0095 (3)0.0084 (3)0.0061 (3)
N10.062 (5)0.074 (5)0.060 (4)0.022 (4)0.024 (4)0.017 (4)
N20.034 (3)0.058 (3)0.042 (3)0.002 (3)0.004 (2)0.003 (3)
N30.053 (4)0.045 (3)0.040 (3)0.002 (3)0.003 (3)0.009 (3)
N40.050 (3)0.035 (3)0.036 (3)0.005 (2)0.005 (2)0.005 (2)
C10.078 (6)0.075 (5)0.050 (4)0.052 (5)0.000 (4)0.010 (4)
C20.041 (4)0.077 (5)0.048 (4)0.031 (4)0.014 (3)0.001 (4)
C30.028 (3)0.046 (3)0.034 (3)0.019 (3)0.005 (2)0.006 (3)
C40.040 (4)0.060 (4)0.036 (3)0.005 (3)0.010 (3)0.007 (3)
C50.043 (5)0.083 (6)0.059 (5)0.004 (4)0.005 (4)0.014 (5)
C60.054 (5)0.063 (5)0.074 (5)0.005 (4)0.001 (4)0.029 (4)
C70.058 (5)0.068 (5)0.052 (4)0.009 (4)0.003 (4)0.011 (4)
C80.060 (5)0.030 (3)0.048 (4)0.008 (3)0.003 (3)0.003 (3)
C90.050 (4)0.041 (3)0.031 (3)0.014 (3)0.000 (3)0.003 (3)
C100.028 (3)0.036 (3)0.030 (3)0.004 (2)0.007 (2)0.001 (3)
C110.037 (3)0.037 (3)0.034 (3)0.005 (3)0.000 (3)0.003 (3)
C120.038 (4)0.069 (5)0.031 (3)0.015 (3)0.002 (3)0.000 (3)
C130.060 (5)0.070 (5)0.037 (4)0.009 (4)0.016 (3)0.016 (4)
C140.091 (6)0.022 (3)0.061 (5)0.007 (3)0.000 (4)0.017 (3)
Geometric parameters (Å, º) top
Br1—Cu12.4164 (9)C4—H40.9400
Br2—Cu12.4039 (9)C5—H50.9400
Br3—Cu12.3544 (9)C6—H6A0.9700
Br4—Cu12.3662 (9)C6—H6B0.9700
N1—C51.320 (10)C6—H6C0.9700
N1—C11.330 (11)C7—H7A0.9700
N1—H10.8800C7—H7B0.9700
N2—C31.339 (7)C7—H7C0.9700
N2—C61.458 (9)C8—C91.314 (9)
N2—C71.463 (8)C8—H80.9400
N3—C121.342 (8)C9—C101.433 (8)
N3—C81.343 (9)C9—H90.9400
N3—H30.8800C10—C111.410 (8)
N4—C101.338 (7)C11—C121.364 (9)
N4—C141.457 (7)C11—H110.9400
N4—C131.464 (8)C12—H120.9400
C1—C21.334 (10)C13—H13A0.9700
C1—H1A0.9400C13—H13B0.9700
C2—C31.431 (8)C13—H13C0.9700
C2—H20.9400C14—H14A0.9700
C3—C41.404 (8)C14—H14B0.9700
C4—C51.341 (9)C14—H14C0.9700
Br1—Cu1—Br2131.05 (4)N2—C6—H6C109.5
Br1—Cu1—Br399.47 (3)H6A—C6—H6C109.5
Br1—Cu1—Br497.82 (3)H6B—C6—H6C109.5
Br2—Cu1—Br3100.27 (3)N2—C7—H7A109.5
Br2—Cu1—Br497.76 (3)N2—C7—H7B109.5
Br3—Cu1—Br4136.48 (4)H7A—C7—H7B109.5
C5—N1—C1119.7 (7)N2—C7—H7C109.5
C5—N1—H1120.2H7A—C7—H7C109.5
C1—N1—H1120.2H7B—C7—H7C109.5
C3—N2—C6122.6 (6)C9—C8—N3122.3 (6)
C3—N2—C7120.4 (6)C9—C8—H8118.9
C6—N2—C7116.7 (6)N3—C8—H8118.9
C12—N3—C8119.5 (6)C8—C9—C10120.8 (6)
C12—N3—H3120.2C8—C9—H9119.6
C8—N3—H3120.2C10—C9—H9119.6
C10—N4—C14122.4 (5)N4—C10—C11122.2 (5)
C10—N4—C13122.4 (5)N4—C10—C9121.7 (5)
C14—N4—C13115.2 (6)C11—C10—C9116.1 (6)
C2—C1—N1122.3 (7)C12—C11—C10119.2 (5)
C2—C1—H1A118.9C12—C11—H11120.4
N1—C1—H1A118.9C10—C11—H11120.4
C1—C2—C3119.6 (7)N3—C12—C11122.1 (6)
C1—C2—H2120.2N3—C12—H12118.9
C3—C2—H2120.2C11—C12—H12118.9
N2—C3—C4123.4 (5)N4—C13—H13A109.5
N2—C3—C2120.7 (6)N4—C13—H13B109.5
C4—C3—C2116.0 (6)H13A—C13—H13B109.5
C5—C4—C3119.5 (6)N4—C13—H13C109.5
C5—C4—H4120.2H13A—C13—H13C109.5
C3—C4—H4120.2H13B—C13—H13C109.5
N1—C5—C4122.9 (8)N4—C14—H14A109.5
N1—C5—H5118.5N4—C14—H14B109.5
C4—C5—H5118.5H14A—C14—H14B109.5
N2—C6—H6A109.5N4—C14—H14C109.5
N2—C6—H6B109.5H14A—C14—H14C109.5
H6A—C6—H6B109.5H14B—C14—H14C109.5
C5—N1—C1—C20.1 (12)C12—N3—C8—C90.2 (10)
N1—C1—C2—C30.9 (11)N3—C8—C9—C100.5 (10)
C6—N2—C3—C4176.1 (7)C14—N4—C10—C111.6 (9)
C7—N2—C3—C42.7 (9)C13—N4—C10—C11179.0 (5)
C6—N2—C3—C24.6 (9)C14—N4—C10—C9178.1 (6)
C7—N2—C3—C2178.0 (6)C13—N4—C10—C91.3 (8)
C1—C2—C3—N2178.2 (6)C8—C9—C10—N4179.0 (6)
C1—C2—C3—C41.2 (9)C8—C9—C10—C110.7 (8)
N2—C3—C4—C5178.9 (6)N4—C10—C11—C12179.6 (5)
C2—C3—C4—C50.5 (9)C9—C10—C11—C120.2 (8)
C1—N1—C5—C40.8 (12)C8—N3—C12—C110.8 (9)
C3—C4—C5—N10.4 (11)C10—C11—C12—N30.6 (9)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···Br10.882.543.380 (7)162
N3—H3···Br20.882.653.449 (6)152

Experimental details

Crystal data
Chemical formula(C7H11N2)2[CuBr4]
Mr629.54
Crystal system, space groupTriclinic, P1
Temperature (K)233
a, b, c (Å)8.1768 (2), 9.2406 (3), 14.3686 (4)
α, β, γ (°)93.689 (2), 94.814 (2), 105.073 (2)
V3)1040.42 (5)
Z2
Radiation typeMo Kα
µ (mm1)8.73
Crystal size (mm)0.35 × 0.30 × 0.10
Data collection
DiffractometerBruker SMART APEX
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.321, 0.746
No. of measured, independent and
observed [I > 2σ(I)] reflections
7224, 4595, 3168
Rint0.042
(sin θ/λ)max1)0.650
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.043, 0.123, 1.00
No. of reflections4595
No. of parameters213
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.84, 0.82

Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2009).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···Br10.882.543.380 (7)162
N3—H3···Br20.882.653.449 (6)152
 

Acknowledgements

We thank the University of Malaya (RG020/09AFR) for supporting this study.

References

First citationBarbour, L. J. (2001). J. Supramol. Chem. 1, 189–191.  CrossRef CAS Google Scholar
First citationBruker (2008). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationCoffey, T., Robinson, W. T. & Turnbull, M. M. (1996). Acta Cryst. C52, 248–250.  CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
First citationHaddad, S. F. & Al-Far, R. H. (2008). J. Chem. Crystallogr. 38, 663–669.  Web of Science CSD CrossRef CAS Google Scholar
First citationLuque, A., Sertucha, J., Castillo, O. & Roman, P. (2001). New J. Chem. 25, 1208–1214.  Web of Science CSD CrossRef CAS Google Scholar
First citationSheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.  Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationWestrip, S. P. (2009). publCIF. In preparation.  Google Scholar
First citationWillet, R. D., Awwadi, F., Butcher, R., Haddad, S. & Twamley, B. (2003). Cryst. Growth Des. 3, 301–311.  Web of Science CSD CrossRef Google Scholar
First citationWillett, R. D., Haddad, S. F. & Twamley, B. (2000). Acta Cryst. C56, e437.  Web of Science CSD CrossRef IUCr Journals Google Scholar

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