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

Lo, K.M.; Ng, S.W.

doi:10.1107/S1600536809028128

metal-organic compounds

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Volume 65| Part 8| August 2009| Page m972

doi:10.1107/S1600536809028128

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

Kong Mun Lo ^a and Seik Weng Ng ^a ^*

^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 ); Haddad & Al-Far (2008 ); Luque et al. (2001 ); Willet et al. (2000 , 2003 ).

Experimental

Crystal data

(C₇H₁₁N₂)₂[CuBr₄]
M_r = 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 ) T_min = 0.321, T_max = 0.746 (expected range = 0.180–0.418)
7224 measured reflections
4595 independent reflections
3168 reflections with I > 2σ(I)
R_int = 0.042

Refinement

R[F² > 2σ(F²)] = 0.043
wR(F²) = 0.123
S = 1.00
4595 reflections
213 parameters
H-atom parameters constrained
Δρ_max = 0.84 e Å⁻³
Δρ_min = −0.82 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	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 ); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT; 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 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809028128/tk2503sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809028128/tk2503Isup2.hkl

checkCIF report

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.

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

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
M_r = 629.54	F(000) = 606
Triclinic, P1	D_x = 2.010 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.1768 (2) Å	Cell parameters from 2442 reflections
b = 9.2406 (3) Å	θ = 2.3–27.5°
c = 14.3686 (4) Å	µ = 8.73 mm⁻¹
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 tube	3168 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.042
ω scans	θ_max = 27.5°, θ_min = 1.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −10→10
T_min = 0.321, T_max = 0.746	k = −10→12
7224 measured reflections	l = −18→18

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)] = 0.043	H-atom parameters constrained
wR(F²) = 0.123	w = 1/[σ²(F_o²) + (0.0566P)²] where P = (F_o² + 2F_c²)/3
S = 1.00	(Δ/σ)_max = 0.001
4595 reflections	Δρ_max = 0.84 e Å⁻³
213 parameters	Δρ_min = −0.82 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: 0.0078 (8)

Crystal data top

(C₇H₁₁N₂)₂[CuBr₄]	γ = 105.073 (2)°
M_r = 629.54	V = 1040.42 (5) Å³
Triclinic, P1	Z = 2
a = 8.1768 (2) Å	Mo Kα radiation
b = 9.2406 (3) Å	µ = 8.73 mm⁻¹
c = 14.3686 (4) Å	T = 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)
T_min = 0.321, T_max = 0.746	R_int = 0.042
7224 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	0 restraints
wR(F²) = 0.123	H-atom parameters constrained
S = 1.00	Δρ_max = 0.84 e Å⁻³
4595 reflections	Δρ_min = −0.82 e Å⁻³
213 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Br1	0.46757 (8)	0.23274 (7)	0.31534 (5)	0.04383 (19)
Br2	0.44673 (8)	0.69937 (7)	0.29470 (5)	0.0458 (2)
Br3	0.11950 (8)	0.35808 (7)	0.20247 (4)	0.03895 (18)
Br4	0.65667 (8)	0.48740 (7)	0.15029 (4)	0.04107 (19)
Cu1	0.41731 (9)	0.44301 (7)	0.23676 (5)	0.0323 (2)
N1	0.8043 (9)	0.5220 (8)	0.4011 (5)	0.067 (2)
H1	0.7335	0.4434	0.3685	0.081*
N2	1.1304 (7)	0.8919 (6)	0.5502 (4)	0.0466 (13)
N3	0.6251 (7)	0.8455 (6)	0.1004 (4)	0.0478 (13)
H3	0.5794	0.7776	0.1376	0.057*
N4	0.8436 (7)	1.1604 (6)	−0.0731 (3)	0.0415 (12)
C1	0.9472 (12)	0.5930 (9)	0.3673 (5)	0.063 (2)
H1A	0.9709	0.5576	0.3085	0.075*
C2	1.0582 (9)	0.7127 (9)	0.4141 (5)	0.0521 (18)
H2	1.1589	0.7596	0.3887	0.062*
C3	1.0231 (7)	0.7695 (7)	0.5032 (4)	0.0343 (13)
C4	0.8711 (8)	0.6903 (8)	0.5360 (5)	0.0465 (16)
H4	0.8409	0.7213	0.5942	0.056*
C5	0.7692 (9)	0.5702 (9)	0.4836 (5)	0.064 (2)
H5	0.6683	0.5179	0.5067	0.077*
C6	1.2928 (10)	0.9673 (9)	0.5180 (6)	0.067 (2)
H6A	1.2723	1.0101	0.4597	0.100*
H6B	1.3585	0.8951	0.5080	0.100*
H6C	1.3556	1.0469	0.5650	0.100*
C7	1.0967 (10)	0.9465 (9)	0.6426 (5)	0.062 (2)
H7A	0.9814	0.9571	0.6393	0.093*
H7B	1.1767	1.0433	0.6623	0.093*
H7C	1.1095	0.8752	0.6875	0.093*
C8	0.6803 (9)	0.8036 (7)	0.0201 (5)	0.0472 (17)
H8	0.6688	0.7008	0.0045	0.057*
C9	0.7497 (8)	0.9012 (7)	−0.0374 (4)	0.0409 (15)
H9	0.7858	0.8671	−0.0931	0.049*
C10	0.7710 (7)	1.0591 (6)	−0.0161 (4)	0.0328 (13)
C11	0.7118 (7)	1.1009 (7)	0.0682 (4)	0.0374 (14)
H11	0.7217	1.2026	0.0863	0.045*
C12	0.6401 (8)	0.9918 (8)	0.1234 (4)	0.0462 (17)
H12	0.5999	1.0200	0.1793	0.055*
C13	0.9027 (9)	1.1174 (9)	−0.1615 (5)	0.0558 (18)
H13A	0.9415	1.0274	−0.1553	0.084*
H13B	0.9960	1.1986	−0.1764	0.084*
H13C	0.8099	1.0977	−0.2112	0.084*
C14	0.8708 (10)	1.3216 (6)	−0.0511 (5)	0.059 (2)
H14A	0.9513	1.3551	0.0044	0.088*
H14B	0.7635	1.3424	−0.0398	0.088*
H14C	0.9158	1.3747	−0.1035	0.088*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0494 (4)	0.0387 (4)	0.0482 (4)	0.0151 (3)	0.0101 (3)	0.0186 (3)
Br2	0.0496 (4)	0.0355 (3)	0.0513 (4)	0.0073 (3)	0.0199 (3)	−0.0051 (3)
Br3	0.0337 (3)	0.0415 (3)	0.0407 (3)	0.0089 (3)	0.0043 (2)	0.0009 (3)
Br4	0.0450 (4)	0.0397 (3)	0.0446 (4)	0.0155 (3)	0.0205 (3)	0.0109 (3)
Cu1	0.0331 (4)	0.0319 (4)	0.0336 (4)	0.0095 (3)	0.0084 (3)	0.0061 (3)
N1	0.062 (5)	0.074 (5)	0.060 (4)	0.022 (4)	−0.024 (4)	−0.017 (4)
N2	0.034 (3)	0.058 (3)	0.042 (3)	0.002 (3)	0.004 (2)	0.003 (3)
N3	0.053 (4)	0.045 (3)	0.040 (3)	0.002 (3)	0.003 (3)	0.009 (3)
N4	0.050 (3)	0.035 (3)	0.036 (3)	0.005 (2)	0.005 (2)	0.005 (2)
C1	0.078 (6)	0.075 (5)	0.050 (4)	0.052 (5)	0.000 (4)	−0.010 (4)
C2	0.041 (4)	0.077 (5)	0.048 (4)	0.031 (4)	0.014 (3)	0.001 (4)
C3	0.028 (3)	0.046 (3)	0.034 (3)	0.019 (3)	0.005 (2)	0.006 (3)
C4	0.040 (4)	0.060 (4)	0.036 (3)	0.005 (3)	0.010 (3)	0.007 (3)
C5	0.043 (5)	0.083 (6)	0.059 (5)	0.004 (4)	−0.005 (4)	0.014 (5)
C6	0.054 (5)	0.063 (5)	0.074 (5)	−0.005 (4)	0.001 (4)	0.029 (4)
C7	0.058 (5)	0.068 (5)	0.052 (4)	0.009 (4)	−0.003 (4)	−0.011 (4)
C8	0.060 (5)	0.030 (3)	0.048 (4)	0.008 (3)	−0.003 (3)	0.003 (3)
C9	0.050 (4)	0.041 (3)	0.031 (3)	0.014 (3)	0.000 (3)	−0.003 (3)
C10	0.028 (3)	0.036 (3)	0.030 (3)	0.004 (2)	−0.007 (2)	0.001 (3)
C11	0.037 (3)	0.037 (3)	0.034 (3)	0.005 (3)	0.000 (3)	−0.003 (3)
C12	0.038 (4)	0.069 (5)	0.031 (3)	0.015 (3)	0.002 (3)	0.000 (3)
C13	0.060 (5)	0.070 (5)	0.037 (4)	0.009 (4)	0.016 (3)	0.016 (4)
C14	0.091 (6)	0.022 (3)	0.061 (5)	0.007 (3)	0.000 (4)	0.017 (3)

Geometric parameters (Å, º) top

Br1—Cu1	2.4164 (9)	C4—H4	0.9400
Br2—Cu1	2.4039 (9)	C5—H5	0.9400
Br3—Cu1	2.3544 (9)	C6—H6A	0.9700
Br4—Cu1	2.3662 (9)	C6—H6B	0.9700
N1—C5	1.320 (10)	C6—H6C	0.9700
N1—C1	1.330 (11)	C7—H7A	0.9700
N1—H1	0.8800	C7—H7B	0.9700
N2—C3	1.339 (7)	C7—H7C	0.9700
N2—C6	1.458 (9)	C8—C9	1.314 (9)
N2—C7	1.463 (8)	C8—H8	0.9400
N3—C12	1.342 (8)	C9—C10	1.433 (8)
N3—C8	1.343 (9)	C9—H9	0.9400
N3—H3	0.8800	C10—C11	1.410 (8)
N4—C10	1.338 (7)	C11—C12	1.364 (9)
N4—C14	1.457 (7)	C11—H11	0.9400
N4—C13	1.464 (8)	C12—H12	0.9400
C1—C2	1.334 (10)	C13—H13A	0.9700
C1—H1A	0.9400	C13—H13B	0.9700
C2—C3	1.431 (8)	C13—H13C	0.9700
C2—H2	0.9400	C14—H14A	0.9700
C3—C4	1.404 (8)	C14—H14B	0.9700
C4—C5	1.341 (9)	C14—H14C	0.9700

Br1—Cu1—Br2	131.05 (4)	N2—C6—H6C	109.5
Br1—Cu1—Br3	99.47 (3)	H6A—C6—H6C	109.5
Br1—Cu1—Br4	97.82 (3)	H6B—C6—H6C	109.5
Br2—Cu1—Br3	100.27 (3)	N2—C7—H7A	109.5
Br2—Cu1—Br4	97.76 (3)	N2—C7—H7B	109.5
Br3—Cu1—Br4	136.48 (4)	H7A—C7—H7B	109.5
C5—N1—C1	119.7 (7)	N2—C7—H7C	109.5
C5—N1—H1	120.2	H7A—C7—H7C	109.5
C1—N1—H1	120.2	H7B—C7—H7C	109.5
C3—N2—C6	122.6 (6)	C9—C8—N3	122.3 (6)
C3—N2—C7	120.4 (6)	C9—C8—H8	118.9
C6—N2—C7	116.7 (6)	N3—C8—H8	118.9
C12—N3—C8	119.5 (6)	C8—C9—C10	120.8 (6)
C12—N3—H3	120.2	C8—C9—H9	119.6
C8—N3—H3	120.2	C10—C9—H9	119.6
C10—N4—C14	122.4 (5)	N4—C10—C11	122.2 (5)
C10—N4—C13	122.4 (5)	N4—C10—C9	121.7 (5)
C14—N4—C13	115.2 (6)	C11—C10—C9	116.1 (6)
C2—C1—N1	122.3 (7)	C12—C11—C10	119.2 (5)
C2—C1—H1A	118.9	C12—C11—H11	120.4
N1—C1—H1A	118.9	C10—C11—H11	120.4
C1—C2—C3	119.6 (7)	N3—C12—C11	122.1 (6)
C1—C2—H2	120.2	N3—C12—H12	118.9
C3—C2—H2	120.2	C11—C12—H12	118.9
N2—C3—C4	123.4 (5)	N4—C13—H13A	109.5
N2—C3—C2	120.7 (6)	N4—C13—H13B	109.5
C4—C3—C2	116.0 (6)	H13A—C13—H13B	109.5
C5—C4—C3	119.5 (6)	N4—C13—H13C	109.5
C5—C4—H4	120.2	H13A—C13—H13C	109.5
C3—C4—H4	120.2	H13B—C13—H13C	109.5
N1—C5—C4	122.9 (8)	N4—C14—H14A	109.5
N1—C5—H5	118.5	N4—C14—H14B	109.5
C4—C5—H5	118.5	H14A—C14—H14B	109.5
N2—C6—H6A	109.5	N4—C14—H14C	109.5
N2—C6—H6B	109.5	H14A—C14—H14C	109.5
H6A—C6—H6B	109.5	H14B—C14—H14C	109.5

C5—N1—C1—C2	−0.1 (12)	C12—N3—C8—C9	0.2 (10)
N1—C1—C2—C3	−0.9 (11)	N3—C8—C9—C10	0.5 (10)
C6—N2—C3—C4	176.1 (7)	C14—N4—C10—C11	1.6 (9)
C7—N2—C3—C4	2.7 (9)	C13—N4—C10—C11	−179.0 (5)
C6—N2—C3—C2	−4.6 (9)	C14—N4—C10—C9	−178.1 (6)
C7—N2—C3—C2	−178.0 (6)	C13—N4—C10—C9	1.3 (8)
C1—C2—C3—N2	−178.2 (6)	C8—C9—C10—N4	179.0 (6)
C1—C2—C3—C4	1.2 (9)	C8—C9—C10—C11	−0.7 (8)
N2—C3—C4—C5	178.9 (6)	N4—C10—C11—C12	−179.6 (5)
C2—C3—C4—C5	−0.5 (9)	C9—C10—C11—C12	0.2 (8)
C1—N1—C5—C4	0.8 (12)	C8—N3—C12—C11	−0.8 (9)
C3—C4—C5—N1	−0.4 (11)	C10—C11—C12—N3	0.6 (9)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	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

Experimental details

Crystal data
Chemical formula	(C₇H₁₁N₂)₂[CuBr₄]
M_r	629.54
Crystal system, space group	Triclinic, 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)
V (Å³)	1040.42 (5)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	8.73
Crystal size (mm)	0.35 × 0.30 × 0.10

Data collection
Diffractometer	Bruker SMART APEX diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.321, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	7224, 4595, 3168
R_int	0.042
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.123, 1.00
No. of reflections	4595
No. of parameters	213
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	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···A	D—H	H···A	D···A	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

Acknowledgements

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

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