Bis(benzyl­trimethyl­ammonium) di-μ-bromido-bis­[dibromido­mercurate(II)]

Jin, L.

doi:10.1107/S1600536811055887

metal-organic compounds

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Volume 68| Part 2| February 2012| Page m123

doi:10.1107/S1600536811055887

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Bis(benzyltrimethylammonium) di-μ-bromido-bis[dibromidomercurate(II)]

Lei Jin ^a ^*

^aCollege of Chemistry and Chemical Engineering, Southeast University, Nanjing 210096, People's Republic of China
^*Correspondence e-mail: jinlei8812@163.com

(Received 29 November 2011; accepted 27 December 2011; online 7 January 2012)

In the crystal structure of the title compound, (C₁₀H₁₆N)₂[Hg₂Br₆], the condensed anion consists of two edge-sharing HgBr₄ tetrahedra and is situated on a centre of symmetry. The anions are linked to the cations through weak C—H⋯Br interactions.

Related literature

For related structures, see: Jin & Liu (2011 ); Nockemann & Meyer (2002 ).

Experimental

Crystal data

(C₁₀H₁₆N)₂[Hg₂Br₆]
M_r = 1181.06
Triclinic, $[P \overline 1]$
a = 9.0542 (11) Å
b = 9.7287 (9) Å
c = 9.894 (1) Å
α = 80.78 (1)°
β = 71.02 (1)°
γ = 62.39 (1)°
V = 730.24 (13) Å³
Z = 1
Mo Kα radiation
μ = 18.72 mm⁻¹
T = 298 K
0.26 × 0.22 × 0.20 mm

Data collection

Rigaku Mercury2 diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.011, T_max = 0.024
6877 measured reflections
2872 independent reflections
2166 reflections with I > 2σ(I)
R_int = 0.048

Refinement

R[F² > 2σ(F²)] = 0.052
wR(F²) = 0.131
S = 1.07
2862 reflections
139 parameters
H-atom parameters constrained
Δρ_max = 0.97 e Å⁻³
Δρ_min = −1.56 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3C⋯Br1	0.96	2.86	3.776 (7)	160
C2—H2B⋯Br2ⁱ	0.96	2.87	3.743 (7)	151
Symmetry code: (i) -x+1, -y+1, -z+1.

Data collection: CrystalClear (Rigaku, 2005); cell refinement: 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: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811055887/cv5212sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811055887/cv5212Isup2.hkl

checkCIF report

Comment top

Recently much attention has been devoted to simple molecular–ionic compounds containing organic ammonium cations and anions due to the tunability of their special structural features and their ferroelectric-dielectric properties (Nockemann & Meyer, 2002; Jin et al., 2011). Herewith we present the crystal structure of the title compound.

The title compound, (C₁₀H₁₆N⁺)₂^.Hg₂Br₆^2-, crystallizes in the triclinic P-1 space group (Fig. 1). The rigid [Hg₂Br₆]^2- anion situtaed on inversion center consists of two distorted tetrahedrons sharing one common edge. The terminal Hg—Br bond lengths are 2.4910 (10) and 2.4696 (8) Å, respectively, and the Br—Hg—Br bond angles are in the range 107.16 (3)° - 122.27 (3)°. The bridging Hg—Br bond lengths are 2.6039 (8) and 2.8320 (8) Å, respectively, and the bond angles of Br—Hg—Br are 102.21 (3)° - 106.41 (3)°.

In the crystal, weak intermolecular C—H···Br hydrogen bonds (Table 1) link anion and two cations into a neutral cluster (Fig. 1).

Related literature top

For related structures, see: Jin & Liu (2011); Nockemann & Meyer (2002).

Experimental top

In room temperature benzyltrimethylammoniumchlorine (10 mmol, 1.86 g) in 20 ml water, then a water solution with HgBr₂ (5 mmol, 1.36 g) was dropped slowly into the previous solution with properly sirring. Single crystals suitable for X-ray structure analysis were obtained by the slow evaporation of the above solution after one week in air with some colorless solid blocks appeared after days.

The dielectric constant of the compound as a function of temperature indicates that the permittivity is basically temperature-independent (ε = C/(T–T₀)), suggesting that this compound is not ferroelectric or there may be no distinct phase transition occurring within the measured temperature (below the melting point).

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: 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: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of the title compound showing the atomic numbering and 30% probability displacement ellipsoids [symmetry code: (A) 1-x, 1-y, 1-z]. Dashed lines denote C—H···Br interactions.

Bis(benzyltrimethylammonium) di-µ-bromido-bis[dibromidomercurate(II)] top

Crystal data top

(C₁₀H₁₆N)₂[Hg₂Br₆]	Z = 1
M_r = 1181.06	F(000) = 536
Triclinic, P1	D_x = 2.686 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.0542 (11) Å	Cell parameters from 6235 reflections
b = 9.7287 (9) Å	θ = 6.4–26°
c = 9.894 (1) Å	µ = 18.72 mm⁻¹
α = 80.78 (1)°	T = 298 K
β = 71.02 (1)°	Block, colourless
γ = 62.39 (1)°	0.26 × 0.22 × 0.20 mm
V = 730.24 (13) Å³

Data collection top

Rigaku Mercury2 diffractometer	2872 independent reflections
Radiation source: fine-focus sealed tube	2166 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.048
Detector resolution: 13.6612 pixels mm^-1	θ_max = 26.0°, θ_min = 3.2°
CCD_Profile_fitting scans	h = −11→11
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −11→11
T_min = 0.011, T_max = 0.024	l = −12→12
6877 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.131	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.0524P)² + 4.9831P] where P = (F_o² + 2F_c²)/3
2862 reflections	(Δ/σ)_max < 0.001
139 parameters	Δρ_max = 0.97 e Å⁻³
0 restraints	Δρ_min = −1.56 e Å⁻³

Crystal data top

(C₁₀H₁₆N)₂[Hg₂Br₆]	γ = 62.39 (1)°
M_r = 1181.06	V = 730.24 (13) Å³
Triclinic, P1	Z = 1
a = 9.0542 (11) Å	Mo Kα radiation
b = 9.7287 (9) Å	µ = 18.72 mm⁻¹
c = 9.894 (1) Å	T = 298 K
α = 80.78 (1)°	0.26 × 0.22 × 0.20 mm
β = 71.02 (1)°

Data collection top

Rigaku Mercury2 diffractometer	2872 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	2166 reflections with I > 2σ(I)
T_min = 0.011, T_max = 0.024	R_int = 0.048
6877 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.052	0 restraints
wR(F²) = 0.131	H-atom parameters constrained
S = 1.07	Δρ_max = 0.97 e Å⁻³
2862 reflections	Δρ_min = −1.56 e Å⁻³
139 parameters

Special details top

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.

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

	x	y	z	U_iso*/U_eq
Br1	0.58630 (9)	0.70394 (8)	0.72319 (8)	0.0764 (2)
Br2	0.21880 (9)	0.50624 (8)	0.89596 (8)	0.0674 (2)
Br3	0.30736 (8)	0.68625 (8)	0.47194 (7)	0.0655 (2)
C1	0.9659 (8)	0.6586 (7)	0.3266 (8)	0.064 (2)
H1A	0.9220	0.6131	0.4143	0.095*
H1B	1.0736	0.6560	0.3256	0.095*
H1C	0.9853	0.6010	0.2473	0.095*
C2	0.6710 (7)	0.8258 (7)	0.3234 (7)	0.062 (2)
H2A	0.6334	0.7749	0.4096	0.094*
H2B	0.6846	0.7740	0.2423	0.094*
H2C	0.5859	0.9319	0.3234	0.094*
C3	0.8111 (8)	0.9073 (7)	0.4372 (7)	0.061 (2)
H3A	0.7292	1.0135	0.4305	0.092*
H3B	0.9198	0.9029	0.4358	0.092*
H3C	0.7667	0.8621	0.5248	0.092*
C4	0.8986 (6)	0.8952 (6)	0.1764 (6)	0.0449 (16)
H4A	0.9305	0.8282	0.0987	0.054*
H4B	0.8017	0.9924	0.1643	0.054*
C5	1.0480 (6)	0.9265 (6)	0.1642 (5)	0.0413 (16)
C6	1.2150 (8)	0.8236 (6)	0.1077 (6)	0.050 (2)
H6	1.2390	0.7280	0.0772	0.059*
C7	1.3495 (8)	0.8583 (8)	0.0949 (7)	0.060 (2)
H7	1.4641	0.7856	0.0583	0.072*
C8	1.3137 (7)	1.0004 (9)	0.1363 (6)	0.065 (2)
H8	1.4047	1.0236	0.1292	0.078*
C9	1.1445 (7)	1.1097 (7)	0.1885 (7)	0.058 (2)
H9	1.1201	1.2079	0.2134	0.069*
C10	1.0142 (7)	1.0708 (7)	0.2027 (7)	0.0511 (19)
H10	0.8994	1.1431	0.2392	0.061*
Hg1	0.45270 (3)	0.53868 (3)	0.69985 (3)	0.05152 (7)
N1	0.8382 (5)	0.8208 (5)	0.3156 (5)	0.0421 (13)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0961 (3)	0.0828 (3)	0.0710 (4)	−0.0584 (3)	−0.0195 (3)	−0.0032 (3)
Br2	0.0621 (3)	0.0625 (3)	0.0664 (4)	−0.0297 (2)	0.0040 (3)	−0.0121 (3)
Br3	0.0604 (3)	0.0597 (4)	0.0624 (3)	−0.0061 (3)	−0.0252 (3)	−0.0135 (3)
C1	0.064 (3)	0.052 (3)	0.074 (4)	−0.023 (3)	−0.029 (3)	0.011 (3)
C2	0.053 (2)	0.075 (3)	0.073 (4)	−0.037 (2)	−0.024 (3)	0.005 (3)
C3	0.068 (3)	0.073 (3)	0.049 (3)	−0.038 (2)	−0.005 (3)	−0.018 (3)
C4	0.058 (2)	0.042 (2)	0.048 (3)	−0.0279 (18)	−0.029 (2)	0.013 (2)
C5	0.041 (2)	0.049 (3)	0.031 (2)	−0.015 (2)	−0.0154 (19)	0.005 (2)
C6	0.065 (3)	0.034 (3)	0.031 (3)	−0.014 (2)	−0.004 (2)	0.001 (2)
C7	0.042 (3)	0.072 (4)	0.045 (3)	−0.013 (3)	−0.009 (3)	0.010 (3)
C8	0.046 (2)	0.119 (5)	0.041 (3)	−0.042 (3)	−0.020 (2)	0.011 (3)
C9	0.060 (3)	0.067 (3)	0.053 (3)	−0.037 (2)	−0.014 (3)	0.006 (3)
C10	0.038 (2)	0.053 (3)	0.056 (3)	−0.023 (2)	0.002 (2)	−0.008 (2)
Hg1	0.05128 (9)	0.05610 (11)	0.04991 (12)	−0.02925 (7)	−0.00626 (9)	−0.00723 (9)
N1	0.0451 (17)	0.041 (2)	0.048 (2)	−0.0216 (14)	−0.0197 (16)	−0.0010 (17)

Geometric parameters (Å, º) top

Br1—Hg1	2.4909 (10)	C4—N1	1.509 (7)
Br2—Hg1	2.4698 (8)	C4—H4A	0.9700
Br3—Hg1ⁱ	2.6039 (8)	C4—H4B	0.9700
Br3—Hg1	2.8318 (8)	C5—C6	1.351 (7)
C1—N1	1.475 (7)	C5—C10	1.381 (9)
C1—H1A	0.9600	C6—C7	1.371 (11)
C1—H1B	0.9600	C6—H6	0.9300
C1—H1C	0.9600	C7—C8	1.366 (11)
C2—N1	1.468 (8)	C7—H7	0.9300
C2—H2A	0.9600	C8—C9	1.377 (7)
C2—H2B	0.9600	C8—H8	0.9300
C2—H2C	0.9600	C9—C10	1.359 (10)
C3—N1	1.469 (8)	C9—H9	0.9300
C3—H3A	0.9600	C10—H10	0.9300
C3—H3B	0.9600	Hg1—Br1	2.4909 (10)
C3—H3C	0.9600	Hg1—Br3ⁱ	2.6039 (8)
C4—C5	1.484 (9)

Hg1ⁱ—Br3—Hg1	91.14 (2)	C5—C6—H6	119.5
N1—C1—H1A	109.5	C7—C6—H6	119.5
N1—C1—H1B	109.5	C8—C7—C6	119.4 (5)
H1A—C1—H1B	109.5	C8—C7—H7	120.3
N1—C1—H1C	109.5	C6—C7—H7	120.3
H1A—C1—H1C	109.5	C7—C8—C9	120.8 (7)
H1B—C1—H1C	109.5	C7—C8—H8	119.6
N1—C2—H2A	109.5	C9—C8—H8	119.6
N1—C2—H2B	109.5	C10—C9—C8	118.4 (7)
H2A—C2—H2B	109.5	C10—C9—H9	120.8
N1—C2—H2C	109.5	C8—C9—H9	120.8
H2A—C2—H2C	109.5	C9—C10—C5	121.6 (5)
H2B—C2—H2C	109.5	C9—C10—H10	119.2
N1—C3—H3A	109.5	C5—C10—H10	119.2
N1—C3—H3B	109.5	Br2—Hg1—Br1	122.26 (3)
H3A—C3—H3B	109.5	Br2—Hg1—Br1	122.26 (3)
N1—C3—H3C	109.5	Br2—Hg1—Br3ⁱ	122.24 (3)
H3A—C3—H3C	109.5	Br1—Hg1—Br3ⁱ	107.18 (3)
H3B—C3—H3C	109.5	Br1—Hg1—Br3ⁱ	107.18 (3)
C5—C4—N1	115.1 (5)	Br2—Hg1—Br3	106.40 (3)
C5—C4—H4A	108.5	Br1—Hg1—Br3	102.23 (3)
N1—C4—H4A	108.5	Br1—Hg1—Br3	102.23 (3)
C5—C4—H4B	108.5	Br3ⁱ—Hg1—Br3	88.86 (2)
N1—C4—H4B	108.5	C2—N1—C3	108.1 (4)
H4A—C4—H4B	107.5	C2—N1—C1	109.7 (5)
C6—C5—C10	118.8 (6)	C3—N1—C1	108.7 (5)
C6—C5—C4	122.6 (6)	C2—N1—C4	108.5 (5)
C10—C5—C4	118.4 (4)	C3—N1—C4	110.4 (5)
C5—C6—C7	121.0 (6)	C1—N1—C4	111.4 (4)

N1—C4—C5—C6	91.4 (6)	C6—C5—C10—C9	−1.7 (9)
N1—C4—C5—C10	−93.3 (6)	C4—C5—C10—C9	−177.2 (6)
C10—C5—C6—C7	3.1 (9)	Hg1ⁱ—Br3—Hg1—Br2	−123.39 (3)
C4—C5—C6—C7	178.3 (5)	Hg1ⁱ—Br3—Hg1—Br1	107.33 (3)
C5—C6—C7—C8	−1.8 (9)	Hg1ⁱ—Br3—Hg1—Br1	107.33 (3)
C6—C7—C8—C9	−1.1 (10)	C5—C4—N1—C2	168.8 (4)
C7—C8—C9—C10	2.4 (10)	C5—C4—N1—C3	50.6 (5)
C8—C9—C10—C5	−1.0 (10)	C5—C4—N1—C1	−70.3 (7)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3C···Br1	0.96	2.86	3.776 (7)	160
C2—H2B···Br2ⁱ	0.96	2.87	3.743 (7)	151

Symmetry code: (i) −x+1, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	(C₁₀H₁₆N)₂[Hg₂Br₆]
M_r	1181.06
Crystal system, space group	Triclinic, P1
Temperature (K)	298
a, b, c (Å)	9.0542 (11), 9.7287 (9), 9.894 (1)
α, β, γ (°)	80.78 (1), 71.02 (1), 62.39 (1)
V (Å³)	730.24 (13)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	18.72
Crystal size (mm)	0.26 × 0.22 × 0.20

Data collection
Diffractometer	Rigaku Mercury2 diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.011, 0.024
No. of measured, independent and observed [I > 2σ(I)] reflections	6877, 2872, 2166
R_int	0.048
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.052, 0.131, 1.07
No. of reflections	2862
No. of parameters	139
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.97, −1.56

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3C···Br1	0.96	2.86	3.776 (7)	160
C2—H2B···Br2ⁱ	0.96	2.87	3.743 (7)	151

Symmetry code: (i) −x+1, −y+1, −z+1.

Acknowledgements

The author thanks Ordered Matter Science Research Centre, Southeast University, for support of this study.

References

Jin, L. & Liu, N. (2011). Acta Cryst. E67, m1586. Web of Science CSD CrossRef IUCr Journals Google Scholar
Nockemann, P. & Meyer, G. (2002). Acta Cryst. E58, m529–m530. Web of Science CSD CrossRef IUCr Journals 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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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 2| February 2012| Page m123

doi:10.1107/S1600536811055887

Open

access