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Acta Cryst. (2009). E65, m560    [ doi:10.1107/S1600536809014366 ]

Bis[4-(dimethylamino)pyridinium] tetrabromidocadmate(II) monohydrate

K. M. Lo and S. W. Ng

Abstract top

The Cd atom in the hydrated title salt, (C7H11N2)2[CdBr4]·H2O, exists in an approximately tetrahedral coordination geometry, with Br-Cd-Br angles in the range 105.52 (3)-111.50 (3)°. The cation, anion and water molecule interact by O-H...Br, N-H...Br and N-H...O hydrogen bonds, forming a linear chain structure running along the a axis.

Related literature top

For other tetrahedral ammonium tetrabromidocadmates, see: Altermatt et al. (1979); Battaglia et al. (1991); Casals et al. (1987); Geselle & Fuess (1994); Ishihara et al. (1998); Krishnan et al. (1991); Sato et al. (1986); Waskowska (1994).

Experimental top

Cadmium chloride (0.5 g, 2 mmol) dissolved in water (10 ml) and 4-dimethylaminopyridine hydrobromide perbromide (0.8 g, 2 mmol) dissolved in ethanol (80 ml) were mixed and the mixture heated for 1 h. Slow evaporation of the filtrate gave colorless crystals.

Refinement top

Carbon- and nitrogen-bound H atoms were placed in calculated positions (C—H 0.95 to 0.98 Å, N—H 0.88 Å) and were included in the refinement in the riding model approximation, with U(H) fixed at 1.2–1.5U(C). The water H atoms were placed in chemically sensible positions on the basis of hydrogen-bonding interactions, but were not refined.

The final difference Fourier map had a large peak at 1.3 Å from H5 and a deep hole at 0.7 Å from Br1.

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: APEX2 (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: pubCIF (Westrip, 2009).

Figures top
[Figure 1] Fig. 1. Thermal ellipsoid plot (Barbour, 2001) of (C7H11N2)2(CdBr4).H2O at the 70% probability level. H atoms are drawn as spheres of arbitrary radius.
Bis[4-(dimethylamino)pyridinium] tetrabromidocadmate(II) monohydrate top
Crystal data top
(C7H11N2)2[CdBr4]·H2OZ = 2
Mr = 696.41F(000) = 664
Triclinic, P1Dx = 2.149 Mg m−3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 7.8918 (2) ÅCell parameters from 3763 reflections
b = 8.1197 (2) Åθ = 2.4–28.2°
c = 17.2719 (4) ŵ = 8.45 mm−1
α = 95.481 (1)°T = 100 K
β = 99.747 (1)°Irregular block, colourless
γ = 96.489 (1)°0.25 × 0.25 × 0.25 mm
V = 1076.35 (5) Å3
Data collection top
Bruker SMART APEX
diffractometer		3711 independent reflections
Radiation source: fine-focus sealed tube3255 reflections with I > 2σ(I)
graphiteRint = 0.022
ω scansθmax = 25.0°, θmin = 2.4°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −9→9
Tmin = 0.258, Tmax = 0.431k = −9→9
6014 measured reflectionsl = −20→20
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.037Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.131H-atom parameters constrained
S = 1.07 w = 1/[σ2(Fo2) + (0.0774P)2 + 6.748P]
where P = (Fo2 + 2Fc2)/3
3711 reflections(Δ/σ)max = 0.001
221 parametersΔρmax = 1.53 e Å−3
0 restraintsΔρmin = −1.65 e Å−3
Crystal data top
(C7H11N2)2[CdBr4]·H2Oγ = 96.489 (1)°
Mr = 696.41V = 1076.35 (5) Å3
Triclinic, P1Z = 2
a = 7.8918 (2) ÅMo Kα radiation
b = 8.1197 (2) ŵ = 8.45 mm−1
c = 17.2719 (4) ÅT = 100 K
α = 95.481 (1)°0.25 × 0.25 × 0.25 mm
β = 99.747 (1)°
Data collection top
Bruker SMART APEX
diffractometer		3711 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		3255 reflections with I > 2σ(I)
Tmin = 0.258, Tmax = 0.431Rint = 0.022
6014 measured reflectionsθmax = 25.0°
Refinement top
R[F2 > 2σ(F2)] = 0.037H-atom parameters constrained
wR(F2) = 0.131Δρmax = 1.53 e Å−3
S = 1.07Δρmin = −1.65 e Å−3
3711 reflectionsAbsolute structure: ?
221 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cd10.56389 (6)0.31451 (6)0.25658 (3)0.01616 (17)
Br10.43625 (10)0.44170 (10)0.37244 (5)0.0256 (2)
Br20.53082 (10)0.50457 (9)0.14316 (5)0.0237 (2)
Br30.89498 (9)0.31530 (10)0.30001 (4)0.0205 (2)
Br40.41821 (9)0.01732 (9)0.20678 (4)0.0209 (2)
O10.1769 (9)0.6316 (8)0.2453 (4)0.0438 (17)
H110.26660.58540.24310.066*
H120.10050.56270.25750.066*
N10.8619 (9)0.3422 (9)0.0770 (4)0.0280 (16)
H10.79740.38120.10950.034*
N21.1657 (8)0.1572 (8)−0.0724 (4)0.0187 (13)
N30.2927 (8)0.8098 (8)0.4100 (4)0.0233 (14)
H30.30980.72530.37770.028*
N40.1981 (8)1.1958 (7)0.5626 (3)0.0150 (12)
C10.3353 (10)0.8102 (9)0.4877 (5)0.0210 (16)
H1A0.38950.71970.50700.025*
C20.3061 (9)0.9320 (9)0.5412 (5)0.0199 (16)
H20.33520.92460.59630.024*
C30.2300 (9)1.0730 (9)0.5130 (4)0.0143 (14)
C40.1916 (9)1.0680 (9)0.4308 (5)0.0179 (15)
H40.14141.15790.40890.022*
C50.2228 (9)0.9411 (9)0.3813 (4)0.0197 (15)
H50.19550.94380.32580.024*
C60.2363 (11)1.1943 (10)0.6469 (5)0.0258 (18)
H6A0.18011.09010.66080.039*
H6B0.19281.28930.67290.039*
H6C0.36201.20250.66450.039*
C70.1264 (10)1.3411 (9)0.5317 (5)0.0195 (15)
H7A0.20571.39560.50120.029*
H7B0.11221.42030.57590.029*
H7C0.01341.30430.49750.029*
C81.0058 (10)0.2831 (10)0.1052 (5)0.0249 (17)
H81.03810.28450.16080.030*
C91.1099 (10)0.2201 (10)0.0575 (4)0.0199 (15)
H91.21240.17790.08000.024*
C101.0651 (9)0.2175 (8)−0.0254 (4)0.0163 (15)
C110.9084 (10)0.2811 (9)−0.0549 (5)0.0221 (17)
H11A0.87090.2804−0.11020.026*
C120.8130 (10)0.3430 (9)−0.0026 (5)0.0245 (17)
H12A0.71000.3877−0.02200.029*
C131.3311 (10)0.1038 (11)−0.0401 (5)0.0274 (18)
H13A1.39380.18700.00310.041*
H13B1.40060.0925−0.08180.041*
H13C1.3100−0.0040−0.01990.041*
C141.1133 (11)0.1373 (10)−0.1580 (4)0.0242 (17)
H14A1.19680.0788−0.18220.036*
H14B1.11000.2474−0.17660.036*
H14C0.99790.0723−0.17280.036*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cd10.0151 (3)0.0170 (3)0.0153 (3)0.0015 (2)0.0019 (2)−0.0014 (2)
Br10.0261 (4)0.0246 (4)0.0270 (5)0.0027 (3)0.0108 (3)−0.0031 (3)
Br20.0229 (4)0.0236 (4)0.0244 (4)0.0049 (3)0.0000 (3)0.0067 (3)
Br30.0158 (4)0.0304 (4)0.0148 (4)0.0038 (3)0.0021 (3)0.0002 (3)
Br40.0239 (4)0.0184 (4)0.0187 (4)−0.0008 (3)0.0038 (3)−0.0013 (3)
O10.049 (4)0.037 (4)0.044 (4)0.010 (3)0.004 (3)0.000 (3)
N10.025 (4)0.027 (4)0.034 (4)−0.001 (3)0.019 (3)−0.005 (3)
N20.020 (3)0.026 (3)0.011 (3)0.002 (3)0.004 (2)0.007 (3)
N30.024 (3)0.024 (3)0.023 (4)0.000 (3)0.010 (3)0.000 (3)
N40.019 (3)0.017 (3)0.009 (3)0.003 (2)0.001 (2)0.004 (2)
C10.022 (4)0.016 (4)0.028 (4)0.004 (3)0.007 (3)0.013 (3)
C20.016 (3)0.019 (4)0.024 (4)−0.002 (3)0.003 (3)0.003 (3)
C30.012 (3)0.017 (3)0.013 (4)−0.002 (3)−0.001 (3)0.012 (3)
C40.011 (3)0.020 (4)0.022 (4)−0.001 (3)0.002 (3)0.003 (3)
C50.021 (4)0.023 (4)0.015 (4)0.000 (3)0.007 (3)0.001 (3)
C60.031 (4)0.027 (4)0.017 (4)−0.008 (3)0.010 (3)−0.006 (3)
C70.023 (4)0.013 (3)0.023 (4)0.006 (3)0.003 (3)−0.001 (3)
C80.026 (4)0.026 (4)0.022 (4)−0.002 (3)0.009 (3)−0.007 (3)
C90.022 (4)0.025 (4)0.012 (4)0.000 (3)0.005 (3)−0.001 (3)
C100.019 (4)0.011 (3)0.016 (4)−0.006 (3)−0.004 (3)0.008 (3)
C110.020 (4)0.021 (4)0.020 (4)−0.010 (3)−0.005 (3)0.009 (3)
C120.020 (4)0.015 (4)0.037 (5)0.000 (3)0.003 (3)0.005 (3)
C130.022 (4)0.028 (4)0.031 (5)0.002 (3)0.003 (3)0.001 (4)
C140.031 (4)0.028 (4)0.012 (4)0.001 (3)0.003 (3)0.001 (3)
Geometric parameters (Å, °) top
Cd1—Br12.5706 (9)C4—C51.347 (11)
Cd1—Br22.6044 (9)C4—H40.9500
Cd1—Br32.5926 (8)C5—H50.9500
Cd1—Br42.5546 (8)C6—H6A0.9800
O1—H110.8418C6—H6B0.9800
O1—H120.8427C6—H6C0.9800
N1—C81.318 (11)C7—H7A0.9800
N1—C121.364 (11)C7—H7B0.9800
N1—H10.8800C7—H7C0.9800
N2—C101.326 (10)C8—C91.364 (11)
N2—C141.455 (10)C8—H80.9500
N2—C131.460 (10)C9—C101.414 (10)
N3—C11.327 (10)C9—H90.9500
N3—C51.352 (10)C10—C111.427 (11)
N3—H30.8800C11—C121.367 (12)
N4—C31.325 (10)C11—H11A0.9500
N4—C61.438 (10)C12—H12A0.9500
N4—C71.472 (9)C13—H13A0.9800
C1—C21.355 (11)C13—H13B0.9800
C1—H1A0.9500C13—H13C0.9800
C2—C31.439 (10)C14—H14A0.9800
C2—H20.9500C14—H14B0.9800
C3—C41.396 (10)C14—H14C0.9800
Br1—Cd1—Br2109.23 (3)N4—C6—H6C109.5
Br1—Cd1—Br3109.83 (3)H6A—C6—H6C109.5
Br4—Cd1—Br1111.50 (3)H6B—C6—H6C109.5
Br2—Cd1—Br3105.52 (3)N4—C7—H7A109.5
Br2—Cd1—Br4110.72 (3)N4—C7—H7B109.5
Br3—Cd1—Br4109.87 (3)H7A—C7—H7B109.5
H11—O1—H12108.9N4—C7—H7C109.5
C8—N1—C12120.1 (7)H7A—C7—H7C109.5
C8—N1—H1120.0H7B—C7—H7C109.5
C12—N1—H1120.0N1—C8—C9122.4 (8)
C10—N2—C14121.3 (6)N1—C8—H8118.8
C10—N2—C13121.3 (6)C9—C8—H8118.8
C14—N2—C13117.4 (6)C8—C9—C10119.8 (7)
C1—N3—C5119.1 (7)C8—C9—H9120.1
C1—N3—H3120.5C10—C9—H9120.1
C5—N3—H3120.5N2—C10—C9120.4 (7)
C3—N4—C6121.8 (6)N2—C10—C11122.7 (7)
C3—N4—C7120.0 (6)C9—C10—C11116.9 (7)
C6—N4—C7118.2 (6)C12—C11—C10119.1 (7)
N3—C1—C2123.8 (7)C12—C11—H11A120.4
N3—C1—H1A118.1C10—C11—H11A120.4
C2—C1—H1A118.1N1—C12—C11121.6 (7)
C1—C2—C3118.8 (7)N1—C12—H12A119.2
C1—C2—H2120.6C11—C12—H12A119.2
C3—C2—H2120.6N2—C13—H13A109.5
N4—C3—C4123.6 (6)N2—C13—H13B109.5
N4—C3—C2121.4 (6)H13A—C13—H13B109.5
C4—C3—C2114.9 (7)N2—C13—H13C109.5
C5—C4—C3122.9 (7)H13A—C13—H13C109.5
C5—C4—H4118.6H13B—C13—H13C109.5
C3—C4—H4118.6N2—C14—H14A109.5
C4—C5—N3120.5 (7)N2—C14—H14B109.5
C4—C5—H5119.8H14A—C14—H14B109.5
N3—C5—H5119.8N2—C14—H14C109.5
N4—C6—H6A109.5H14A—C14—H14C109.5
N4—C6—H6B109.5H14B—C14—H14C109.5
H6A—C6—H6B109.5
C5—N3—C1—C23.0 (11)C12—N1—C8—C9−0.5 (12)
N3—C1—C2—C3−2.3 (11)N1—C8—C9—C100.4 (12)
C6—N4—C3—C4178.6 (7)C14—N2—C10—C9173.5 (7)
C7—N4—C3—C4−3.1 (10)C13—N2—C10—C9−4.7 (10)
C6—N4—C3—C2−0.5 (10)C14—N2—C10—C11−6.1 (10)
C7—N4—C3—C2177.7 (6)C13—N2—C10—C11175.7 (7)
C1—C2—C3—N4179.9 (7)C8—C9—C10—N2179.7 (7)
C1—C2—C3—C40.6 (10)C8—C9—C10—C11−0.7 (10)
N4—C3—C4—C5−179.1 (7)N2—C10—C11—C12−179.2 (7)
C2—C3—C4—C50.1 (10)C9—C10—C11—C121.2 (10)
C3—C4—C5—N30.6 (11)C8—N1—C12—C111.1 (11)
C1—N3—C5—C4−2.1 (11)C10—C11—C12—N1−1.4 (11)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H11···Br10.842.833.351 (7)122
O1—H12···Br3i0.842.673.511 (7)172
N1—H1···Br20.882.563.373 (7)154
N3—H3···O10.882.363.011 (10)131
Symmetry codes: (i) x−1, y, z.
Table 1
Selected geometric parameters (°) top
Br1—Cd1—Br2109.23 (3)Br2—Cd1—Br3105.52 (3)
Br1—Cd1—Br3109.83 (3)Br2—Cd1—Br4110.72 (3)
Br4—Cd1—Br1111.50 (3)Br3—Cd1—Br4109.87 (3)
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H11···Br10.842.833.351 (7)122
O1—H12···Br3i0.842.673.511 (7)172
N1—H1···Br20.882.563.373 (7)154
N3—H3···O10.882.363.011 (10)131
Symmetry codes: (i) x−1, y, z.
Acknowledgements top

The authors thank the University of Malaya (grant No. FS339/2008 A) for supporting this study.

references
References top

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Westrip, S. P. (2009). publCIF. In preparation.