Bis(trimethyl­phenyl­ammonium) tetra­bromidocuprate(II)

The crystal structure of the title compound, (C₉H₁₄N)₂[CuBr₄], consists of two quarternary ammonium cations and a tetra­hedral cuprate anions. Weak C—H...Br hydrogen bonding is present between the cation and anion in the crystal structure.

Key indicators

• Single-crystal X-ray study
• T = 295 K
• Mean [sigma](N-C) = 0.010 Å
• R factor = 0.048
• wR factor = 0.127
• Data-to-parameter ratio = 21.4

checkCIF/PLATON results

No syntax errors found



Alert level A
PLAT923_ALERT_1_A S    values in the CIF and FCF Differ by .......      -0.09

Author Response: It is a bug and I usually ignore it. It has something to do with the rounding up of numbers.

Alert level B
PLAT242_ALERT_2_B Check Low       Ueq as Compared to Neighbors for         N1

Alert level C
PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       3.15 Ratio
PLAT222_ALERT_3_C Large Non-Solvent    H     Ueq(max)/Ueq(min) ...       3.33 Ratio
PLAT230_ALERT_2_C Hirshfeld Test Diff for    N1     --  C1      ..       6.36 su
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for         C8
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         C4
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         N2
PLAT234_ALERT_4_C Large Hirshfeld Difference N1     --  C2      ..       0.17 Ang.

Alert level G
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......         27

   1 ALERT level A = In general: serious problem
   1 ALERT level B = Potentially serious problem
   7 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   6 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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Related literature

For bis(4-dimethylaminopyridinium) tetrabromidocuprate, see: Lo & Ng (2009).

S1. Experimental

Copper sulfate pentahydrate (0.52 g, 2 mmol) and trimethylphenylammonium tribromide (0.78 g, 2 mmol) were heated in ethanol (50 ml) for 2 h. After filtering of the reaction mixture, light blue crystals were obtained upon slow evaporation of the greenish-blue filtrate.

S2. Refinement

Carbon-bound H-atoms were placed in calculated positions (C–H 0.93–0.96 Å) and were included in the refinement in the riding model approximation, with U(H) set to 1.2–1.5U(C).

The phenyl rings were refined as rigid hexagons of 1.39 ° sides. One trimethylamino group shows somewhat large temperature factors. For investigate possible disorder, all carbon-nitrogen distances were restrained to within 0.01 Å of each other, as were the carbon–carbon distances. The six carbon atoms were restrained to lie within a circle. The temperature factors of the primed atoms were set to those of the unprimed ones. However, this disorder model had short H···H contacts, and the refinement was abandoned. The group was refined without disorder but subject to the same distance restraints. Also, the anisotropic temperature factors were restrained to be nearly isotropic.

The suggested weighting scheme included a large second parameter. This was arbitrarily set at 5.00; this gave a satisfactory Goodness-of-Fit.

Structure description

For bis(4-dimethylaminopyridinium) tetrabromidocuprate, see: Lo & Ng (2009).

Computing details

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, 2010).

Figures

Fig. 1. Thermal ellipsoid plot (Barbour, 2001) of bis(trimethylphenylammonium) tetrabromidocuprate at the 50% probability level; hydrogen atoms are drawn as spheres of arbitrary radius.

Bis(trimethylphenylammonium) tetrabromidocuprate(II)

Crystal data

(C9H14N)2[CuBr4]	F(000) = 2552
Mr = 655.60	Dx = 1.775 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 4958 reflections
a = 16.0146 (11) Å	θ = 2.4–22.3°
b = 9.8007 (7) Å	µ = 7.41 mm^−1
c = 31.363 (2) Å	T = 295 K
β = 94.459 (1)°	Prism, blue
V = 4907.7 (6) Å^3	0.30 × 0.20 × 0.10 mm
Z = 8

Data collection

Bruker SMART APEX diffractometer	4318 independent reflections
Radiation source: fine-focus sealed tube	2994 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.060
ω scans	θmax = 25.0°, θmin = 1.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −18→18
Tmin = 0.215, Tmax = 0.525	k = −11→11
25029 measured reflections	l = −37→37

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.127	H-atom parameters constrained
S = 1.28	w = 1/[σ^2(Fo^2) + (0.05P)^2 + 5.00] where P = (Fo^2 + 2Fc^2)/3
4318 reflections	(Δ/σ)max = 0.001
202 parameters	Δρmax = 0.61 e Å^−3
27 restraints	Δρmin = −0.80 e Å^−3

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Br1	0.55154 (4)	0.30390 (9)	0.16560 (3)	0.0741 (3)
Br2	0.79401 (4)	0.33759 (8)	0.18242 (3)	0.0617 (2)
Br3	0.69988 (5)	0.09626 (8)	0.09258 (2)	0.0637 (2)
Br4	0.67593 (5)	0.49013 (7)	0.07793 (3)	0.0639 (2)
Cu1	0.67856 (5)	0.30817 (8)	0.12941 (3)	0.0521 (3)
N1	0.5591 (4)	0.7361 (6)	0.45281 (19)	0.0704 (18)
N2	0.7051 (3)	0.3098 (5)	0.31014 (15)	0.0434 (13)
C1	0.5386 (8)	0.7895 (12)	0.4099 (3)	0.167 (5)
H1A	0.5269	0.8853	0.4115	0.250*
H1B	0.4902	0.7429	0.3971	0.250*
H1C	0.5851	0.7753	0.3929	0.250*
C2	0.6406 (5)	0.7921 (9)	0.4693 (3)	0.114 (4)
H2A	0.6380	0.8900	0.4691	0.171*
H2B	0.6832	0.7621	0.4516	0.171*
H2C	0.6536	0.7608	0.4981	0.171*
C3	0.5684 (6)	0.5866 (9)	0.4500 (3)	0.123 (4)
H3A	0.5413	0.5548	0.4235	0.184*
H3B	0.5432	0.5443	0.4734	0.184*
H3C	0.6268	0.5636	0.4513	0.184*
C4	0.4924 (3)	0.7708 (5)	0.47999 (14)	0.0524 (17)
C5	0.4129 (3)	0.8104 (5)	0.46368 (13)	0.062 (2)
H5	0.4014	0.8206	0.4343	0.075*
C6	0.3506 (2)	0.8347 (5)	0.49123 (19)	0.080 (3)
H6	0.2974	0.8612	0.4803	0.096*
C7	0.3679 (3)	0.8195 (6)	0.53509 (18)	0.082 (3)
H7	0.3262	0.8357	0.5535	0.098*
C8	0.4474 (4)	0.7799 (7)	0.55141 (12)	0.106 (4)
H8	0.4589	0.7697	0.5808	0.127*
C9	0.5097 (3)	0.7556 (6)	0.52385 (15)	0.089 (3)
H9	0.5629	0.7291	0.5348	0.107*
C10	0.6678 (5)	0.4474 (7)	0.3025 (3)	0.087 (3)
H10A	0.6929	0.5104	0.3232	0.130*
H10B	0.6085	0.4431	0.3052	0.130*
H10C	0.6778	0.4776	0.2743	0.130*
C11	0.6610 (5)	0.2155 (8)	0.2782 (2)	0.072 (2)
H11A	0.6783	0.2351	0.2502	0.108*
H11B	0.6016	0.2282	0.2783	0.108*
H11C	0.6749	0.1227	0.2856	0.108*
C12	0.6895 (5)	0.2659 (9)	0.3546 (2)	0.075 (2)
H12A	0.7211	0.3226	0.3749	0.112*
H12B	0.7064	0.1726	0.3587	0.112*
H12C	0.6309	0.2744	0.3586	0.112*
C13	0.79634 (19)	0.3098 (4)	0.30638 (14)	0.0436 (15)
C14	0.8423 (3)	0.4295 (4)	0.30389 (15)	0.0606 (19)
H14	0.8154	0.5135	0.3043	0.073*
C15	0.9283 (3)	0.4235 (5)	0.30075 (16)	0.080 (3)
H15	0.9590	0.5035	0.2991	0.096*
C16	0.9684 (2)	0.2978 (7)	0.30009 (17)	0.083 (3)
H16	1.0259	0.2938	0.2980	0.099*
C17	0.9225 (3)	0.1781 (5)	0.30258 (18)	0.079 (3)
H17	0.9493	0.0940	0.3021	0.095*
C18	0.8364 (3)	0.1841 (4)	0.30573 (16)	0.062 (2)
H18	0.8057	0.1040	0.3074	0.074*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Br1	0.0404 (4)	0.1076 (7)	0.0762 (6)	−0.0036 (4)	0.0179 (4)	−0.0069 (5)
Br2	0.0425 (4)	0.0797 (5)	0.0608 (5)	0.0046 (4)	−0.0100 (3)	−0.0093 (4)
Br3	0.0839 (6)	0.0540 (5)	0.0539 (5)	0.0020 (4)	0.0094 (4)	−0.0078 (4)
Br4	0.0684 (5)	0.0573 (5)	0.0654 (5)	−0.0038 (4)	0.0005 (4)	0.0146 (4)
Cu1	0.0433 (5)	0.0610 (5)	0.0518 (5)	0.0006 (4)	0.0032 (4)	0.0000 (4)
N1	0.062 (4)	0.095 (5)	0.057 (4)	−0.014 (4)	0.021 (3)	−0.011 (4)
N2	0.044 (3)	0.047 (3)	0.040 (3)	0.000 (2)	0.008 (2)	0.003 (3)
C1	0.167 (9)	0.222 (10)	0.120 (8)	0.019 (8)	0.064 (7)	0.013 (8)
C2	0.089 (6)	0.127 (7)	0.133 (7)	−0.029 (5)	0.049 (6)	−0.037 (6)
C3	0.118 (7)	0.108 (7)	0.148 (8)	−0.010 (6)	0.050 (6)	−0.058 (6)
C4	0.054 (4)	0.054 (4)	0.050 (5)	−0.001 (3)	0.006 (4)	−0.003 (3)
C5	0.062 (5)	0.073 (5)	0.050 (5)	−0.006 (4)	−0.008 (4)	0.007 (4)
C6	0.049 (5)	0.083 (6)	0.109 (8)	0.014 (4)	0.005 (5)	0.010 (5)
C7	0.070 (6)	0.092 (6)	0.088 (7)	0.022 (5)	0.032 (5)	0.009 (5)
C8	0.112 (8)	0.160 (10)	0.047 (5)	0.059 (7)	0.019 (5)	0.017 (6)
C9	0.069 (5)	0.149 (8)	0.049 (5)	0.043 (6)	0.000 (4)	0.002 (5)
C10	0.070 (5)	0.070 (6)	0.120 (8)	0.008 (4)	0.002 (5)	0.021 (5)
C11	0.055 (5)	0.095 (6)	0.065 (5)	−0.013 (4)	−0.004 (4)	−0.014 (5)
C12	0.058 (5)	0.119 (7)	0.050 (5)	−0.003 (5)	0.022 (4)	0.010 (5)
C13	0.044 (4)	0.054 (4)	0.034 (4)	−0.007 (3)	0.004 (3)	0.002 (3)
C14	0.070 (5)	0.056 (5)	0.056 (5)	−0.016 (4)	0.012 (4)	−0.003 (4)
C15	0.066 (6)	0.115 (8)	0.061 (5)	−0.045 (5)	0.016 (4)	0.000 (5)
C16	0.048 (5)	0.144 (9)	0.057 (5)	−0.011 (6)	0.011 (4)	0.004 (6)
C17	0.052 (5)	0.108 (7)	0.079 (6)	0.016 (5)	0.012 (4)	0.004 (5)
C18	0.047 (4)	0.066 (5)	0.073 (5)	−0.006 (4)	0.009 (4)	0.007 (4)

Geometric parameters (Å, º)

Br1—Cu1	2.4055 (11)	C6—H6	0.9300
Br2—Cu1	2.4057 (11)	C7—C8	1.3900
Br3—Cu1	2.4136 (11)	C7—H7	0.9300
Br4—Cu1	2.4039 (11)	C8—C9	1.3900
N1—C4	1.457 (7)	C8—H8	0.9300
N1—C1	1.457 (8)	C9—H9	0.9300
N1—C2	1.472 (8)	C10—H10A	0.9600
N1—C3	1.476 (8)	C10—H10B	0.9600
N2—C13	1.475 (6)	C10—H10C	0.9600
N2—C10	1.487 (6)	C11—H11A	0.9600
N2—C12	1.498 (6)	C11—H11B	0.9600
N2—C11	1.499 (6)	C11—H11C	0.9600
C1—H1A	0.9600	C12—H12A	0.9600
C1—H1B	0.9600	C12—H12B	0.9600
C1—H1C	0.9600	C12—H12C	0.9600
C2—H2A	0.9600	C13—C14	1.3900
C2—H2B	0.9600	C13—C18	1.3900
C2—H2C	0.9600	C14—C15	1.3900
C3—H3A	0.9600	C14—H14	0.9300
C3—H3B	0.9600	C15—C16	1.3900
C3—H3C	0.9600	C15—H15	0.9300
C4—C5	1.3900	C16—C17	1.3900
C4—C9	1.3900	C16—H16	0.9300
C5—C6	1.3900	C17—C18	1.3900
C5—H5	0.9300	C17—H17	0.9300
C6—C7	1.3900	C18—H18	0.9300
Br4—Cu1—Br2	110.35 (4)	C6—C7—C8	120.0
Br4—Cu1—Br1	111.01 (4)	C6—C7—H7	120.0
Br2—Cu1—Br1	107.98 (4)	C8—C7—H7	120.0
Br4—Cu1—Br3	108.21 (4)	C9—C8—C7	120.0
Br2—Cu1—Br3	107.71 (4)	C9—C8—H8	120.0
Br1—Cu1—Br3	111.54 (4)	C7—C8—H8	120.0
C4—N1—C1	109.5 (7)	C8—C9—C4	120.0
C4—N1—C2	112.2 (6)	C8—C9—H9	120.0
C1—N1—C2	108.7 (6)	C4—C9—H9	120.0
C4—N1—C3	110.4 (6)	N2—C10—H10A	109.5
C1—N1—C3	108.6 (6)	N2—C10—H10B	109.5
C2—N1—C3	107.4 (5)	H10A—C10—H10B	109.5
C13—N2—C10	112.1 (5)	N2—C10—H10C	109.5
C13—N2—C12	108.2 (5)	H10A—C10—H10C	109.5
C10—N2—C12	108.4 (6)	H10B—C10—H10C	109.5
C13—N2—C11	111.4 (4)	N2—C11—H11A	109.5
C10—N2—C11	106.8 (6)	N2—C11—H11B	109.5
C12—N2—C11	109.9 (5)	H11A—C11—H11B	109.5
N1—C1—H1A	109.5	N2—C11—H11C	109.5
N1—C1—H1B	109.5	H11A—C11—H11C	109.5
H1A—C1—H1B	109.5	H11B—C11—H11C	109.5
N1—C1—H1C	109.5	N2—C12—H12A	109.5
H1A—C1—H1C	109.5	N2—C12—H12B	109.5
H1B—C1—H1C	109.5	H12A—C12—H12B	109.5
N1—C2—H2A	109.5	N2—C12—H12C	109.5
N1—C2—H2B	109.5	H12A—C12—H12C	109.5
H2A—C2—H2B	109.5	H12B—C12—H12C	109.5
N1—C2—H2C	109.5	C14—C13—C18	120.0
H2A—C2—H2C	109.5	C14—C13—N2	122.4 (3)
H2B—C2—H2C	109.5	C18—C13—N2	117.6 (3)
N1—C3—H3A	109.5	C15—C14—C13	120.0
N1—C3—H3B	109.5	C15—C14—H14	120.0
H3A—C3—H3B	109.5	C13—C14—H14	120.0
N1—C3—H3C	109.5	C14—C15—C16	120.0
H3A—C3—H3C	109.5	C14—C15—H15	120.0
H3B—C3—H3C	109.5	C16—C15—H15	120.0
C5—C4—C9	120.0	C17—C16—C15	120.0
C5—C4—N1	122.8 (4)	C17—C16—H16	120.0
C9—C4—N1	117.1 (4)	C15—C16—H16	120.0
C6—C5—C4	120.0	C16—C17—C18	120.0
C6—C5—H5	120.0	C16—C17—H17	120.0
C4—C5—H5	120.0	C18—C17—H17	120.0
C5—C6—C7	120.0	C17—C18—C13	120.0
C5—C6—H6	120.0	C17—C18—H18	120.0
C7—C6—H6	120.0	C13—C18—H18	120.0
C1—N1—C4—C5	17.7 (7)	C10—N2—C13—C14	11.0 (7)
C2—N1—C4—C5	138.5 (5)	C12—N2—C13—C14	−108.5 (5)
C3—N1—C4—C5	−101.8 (6)	C11—N2—C13—C14	130.6 (5)
C1—N1—C4—C9	−165.8 (5)	C10—N2—C13—C18	−169.6 (5)
C2—N1—C4—C9	−45.1 (6)	C12—N2—C13—C18	71.0 (6)
C3—N1—C4—C9	74.7 (6)	C11—N2—C13—C18	−50.0 (6)
C9—C4—C5—C6	0.0	C18—C13—C14—C15	0.0
N1—C4—C5—C6	176.4 (5)	N2—C13—C14—C15	179.5 (4)
C4—C5—C6—C7	0.0	C13—C14—C15—C16	0.0
C5—C6—C7—C8	0.0	C14—C15—C16—C17	0.0
C6—C7—C8—C9	0.0	C15—C16—C17—C18	0.0
C7—C8—C9—C4	0.0	C16—C17—C18—C13	0.0
C5—C4—C9—C8	0.0	C14—C13—C18—C17	0.0
N1—C4—C9—C8	−176.6 (5)	N2—C13—C18—C17	−179.5 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2B···Br3^i	0.96	2.91	3.840 (9)	164

Symmetry code: (i) −x+3/2, y+1/2, −z+1/2.