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

Jin, L.

doi:10.1107/S1600536812017011

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 5| May 2012| Page m657

doi:10.1107/S1600536812017011

Open

access

Bis(butyltriethylammonium) 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 30 March 2012; accepted 18 April 2012; online 21 April 2012)

In the title molecular salt, (C₁₀H₂₄N)₂[Hg₂Br₆], the complete anion is generated by crystallographic inversion symmetry, forming a pair of edge-sharing HgBr₄ tetrahedra. In the crystal, the cations and anions are linked by weak C—H⋯Br interactions.

Related literature

For a related structure and background to molecular ferroelectrics, see: Jin (2012 ).

Experimental

Crystal data

(C₁₀H₂₄N)₂[Hg₂Br₆]
M_r = 1197.24
Triclinic, $[P \overline 1]$
a = 7.6372 (15) Å
b = 10.318 (2) Å
c = 11.185 (2) Å
α = 76.70 (3)°
β = 72.22 (3)°
γ = 85.57 (3)°
V = 816.8 (3) Å³
Z = 1
Mo Kα radiation
μ = 16.74 mm⁻¹
T = 293 K
0.28 × 0.24 × 0.20 mm

Data collection

Rigaku Mercury2 diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.013, T_max = 0.035
7659 measured reflections
3209 independent reflections
2596 reflections with I > 2σ(I)
R_int = 0.053

Refinement

R[F² > 2σ(F²)] = 0.056
wR(F²) = 0.151
S = 1.05
3209 reflections
141 parameters
H-atom parameters constrained
Δρ_max = 1.27 e Å⁻³
Δρ_min = −1.83 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

Hg1—Br2	2.4963 (18)
Hg1—Br3	2.5059 (17)
Hg1—Br1ⁱ	2.681 (2)
Hg1—Br1	2.7092 (19)

Hg1ⁱ—Br1—Hg1	88.53 (5)
Symmetry code: (i) -x+1, -y+2, -z.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3B⋯Br1ⁱⁱ	0.97	2.91	3.837 (15)	160
C6—H6A⋯Br2	0.96	3.00	3.833 (16)	147
C7—H7B⋯Br2	0.97	3.03	3.973 (13)	165
Symmetry code: (ii) -x, -y+2, -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/S1600536812017011/hb6722sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812017011/hb6722Isup2.hkl

checkCIF report

Comment top

Asa part of our studies (Jin, 2012) of molecular salts with possible ferroelectric properties, the title compound has been synthesized and its crystal structure is herein reported.

The title compound, (C₁₀H₁₆N⁺)₂^.Hg₂Br₆^2- crystallizes in the triclinic P-1 space group, and the structure of title compound contains isolated bitetrahedral [Hg₂Br₆]^2- units,which consisiting of two distorted tetrahedral sharing one common edge and two butyltriethylammonium cations (Fig 1). The terminal bond distance of Hg–Br being 2.4963 (18)Å and 2.5059 (17)Å, the bond angles of Br–Hg–Br being in the range from 107.16 (6)° to 122.48 (7)°; the bridging are in the range 2.681 (2)Å and 2.7092 (19)Å, and the bond angles of Br–Hg–Br varying from 107.16 (6)° to 113.07 (7)°, thus deviating from ideal tetrahedral angles of 109.5°. An inversion centre is located an the centre of the [Hg₂Br₆]^2- unit,and the bridge distance of Br–Br is 3.860Å.

In the crystal, there are weak C—H···Br hydrogen bonds (Table 1), which link the cations and anions into a three-dimensional network.

Related literature top

For a related structure and background to molecular ferroelectrics, see: Jin (2012).

Experimental top

In room temperature butyltriethylammonium (5 mmol,1.17 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. Colourless blocks 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)), indicating that this compound is not ferroelectric over the measured temperature range (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 mlecular structure of the title compound, showing 30% probability displacement ellipsoids. Unlabelled atoms are related to the labelled atoms by the (-x, -y + 2, -z + 1) symmetry transformation.

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

Crystal data top

(C₁₀H₂₄N)₂[Hg₂Br₆]	V = 816.8 (3) Å³
M_r = 1197.24	Z = 1
Triclinic, P1	F(000) = 552
Hall symbol: -P 1	D_x = 2.434 Mg m⁻³
a = 7.6372 (15) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.318 (2) Å	θ = 3.1–26°
c = 11.185 (2) Å	µ = 16.74 mm⁻¹
α = 76.70 (3)°	T = 293 K
β = 72.22 (3)°	Block, colorless
γ = 85.57 (3)°	0.28 × 0.24 × 0.20 mm

Data collection top

Rigaku Mercury2 diffractometer	3209 independent reflections
Radiation source: fine-focus sealed tube	2596 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.053
Detector resolution: 13.6612 pixels mm^-1	θ_max = 26.0°, θ_min = 3.1°
CCD_Profile_fitting scans	h = −9→9
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −12→12
T_min = 0.013, T_max = 0.035	l = −13→13
7659 measured reflections

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)] = 0.056	H-atom parameters constrained
wR(F²) = 0.151	w = 1/[σ²(F_o²) + (0.0572P)² + 12.6923P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max < 0.001
3209 reflections	Δρ_max = 1.27 e Å⁻³
141 parameters	Δρ_min = −1.83 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: 0.0069 (8)

Crystal data top

(C₁₀H₂₄N)₂[Hg₂Br₆]	γ = 85.57 (3)°
M_r = 1197.24	V = 816.8 (3) Å³
Triclinic, P1	Z = 1
a = 7.6372 (15) Å	Mo Kα radiation
b = 10.318 (2) Å	µ = 16.74 mm⁻¹
c = 11.185 (2) Å	T = 293 K
α = 76.70 (3)°	0.28 × 0.24 × 0.20 mm
β = 72.22 (3)°

Data collection top

Rigaku Mercury2 diffractometer	3209 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	2596 reflections with I > 2σ(I)
T_min = 0.013, T_max = 0.035	R_int = 0.053
7659 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.056	0 restraints
wR(F²) = 0.151	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0572P)² + 12.6923P] where P = (F_o² + 2F_c²)/3
3209 reflections	Δρ_max = 1.27 e Å⁻³
141 parameters	Δρ_min = −1.83 e Å⁻³

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
Hg1	0.46437 (8)	0.89173 (5)	0.16554 (5)	0.0447 (3)
Br1	0.2377 (2)	1.01250 (17)	0.02768 (16)	0.0588 (4)
Br2	0.4361 (3)	1.01131 (17)	0.34093 (17)	0.0650 (5)
Br3	0.4370 (3)	0.64383 (15)	0.20690 (19)	0.0661 (5)
N1	0.0814 (15)	0.6872 (9)	0.7024 (10)	0.034 (2)
C7	0.0311 (17)	0.7828 (12)	0.5918 (12)	0.036 (3)
H7A	−0.0722	0.8369	0.6282	0.043*
H7B	0.1340	0.8421	0.5455	0.043*
C5	0.2418 (18)	0.5990 (12)	0.6507 (14)	0.042 (3)
H5A	0.2652	0.5351	0.7228	0.051*
H5B	0.2068	0.5495	0.5978	0.051*
C8	−0.018 (2)	0.7233 (13)	0.4966 (14)	0.047 (3)
H8A	−0.1218	0.6645	0.5409	0.056*
H8B	0.0852	0.6705	0.4573	0.056*
C9	−0.066 (2)	0.8301 (14)	0.3919 (14)	0.047 (3)
H9A	−0.1715	0.8804	0.4318	0.056*
H9B	0.0364	0.8911	0.3512	0.056*
C3	0.128 (2)	0.7737 (13)	0.7835 (13)	0.045 (3)
H3A	0.2291	0.8319	0.7292	0.054*
H3B	0.0227	0.8295	0.8124	0.054*
C2	−0.080 (2)	0.5964 (13)	0.7817 (13)	0.047 (3)
H2A	−0.1085	0.5471	0.7259	0.056*
H2B	−0.0419	0.5323	0.8474	0.056*
C10	−0.109 (2)	0.7763 (16)	0.2901 (15)	0.056 (4)
H10A	−0.0130	0.7158	0.2587	0.084*
H10B	−0.1167	0.8485	0.2204	0.084*
H10C	−0.2239	0.7302	0.3261	0.084*
C1	−0.249 (2)	0.6613 (15)	0.8449 (17)	0.062 (4)
H1A	−0.2266	0.7043	0.9062	0.094*
H1B	−0.3435	0.5958	0.8882	0.094*
H1C	−0.2884	0.7264	0.7816	0.094*
C6	0.417 (2)	0.6716 (16)	0.5727 (16)	0.059 (4)
H6A	0.3979	0.7321	0.4985	0.088*
H6B	0.5118	0.6085	0.5455	0.088*
H6C	0.4543	0.7206	0.6241	0.088*
C4	0.181 (3)	0.6951 (17)	0.9002 (17)	0.073 (5)
H4A	0.0940	0.6253	0.9458	0.109*
H4B	0.1817	0.7534	0.9558	0.109*
H4C	0.3017	0.6570	0.8726	0.109*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Hg1	0.0577 (4)	0.0362 (3)	0.0401 (3)	−0.0008 (2)	−0.0150 (2)	−0.0074 (2)
Br1	0.0477 (8)	0.0687 (10)	0.0574 (10)	0.0021 (7)	−0.0160 (7)	−0.0090 (8)
Br2	0.0730 (11)	0.0624 (10)	0.0602 (10)	−0.0025 (8)	−0.0153 (8)	−0.0200 (8)
Br3	0.0729 (11)	0.0390 (8)	0.0865 (12)	−0.0005 (7)	−0.0275 (9)	−0.0085 (8)
N1	0.050 (6)	0.019 (4)	0.034 (5)	−0.002 (4)	−0.012 (5)	−0.004 (4)
C7	0.040 (7)	0.034 (6)	0.035 (7)	−0.005 (5)	−0.011 (6)	−0.008 (5)
C5	0.040 (7)	0.031 (6)	0.054 (8)	0.009 (5)	−0.020 (6)	−0.002 (6)
C8	0.056 (8)	0.030 (6)	0.054 (9)	−0.004 (6)	−0.021 (7)	−0.003 (6)
C9	0.044 (7)	0.044 (7)	0.046 (8)	0.004 (6)	−0.017 (6)	0.005 (6)
C3	0.059 (8)	0.036 (7)	0.042 (8)	−0.015 (6)	−0.016 (7)	−0.009 (6)
C2	0.059 (9)	0.036 (7)	0.040 (8)	−0.014 (6)	−0.013 (7)	0.008 (6)
C10	0.060 (9)	0.057 (9)	0.059 (10)	−0.003 (7)	−0.035 (8)	−0.004 (7)
C1	0.056 (9)	0.047 (8)	0.068 (11)	−0.014 (7)	0.009 (8)	−0.013 (8)
C6	0.054 (9)	0.054 (9)	0.063 (10)	0.014 (7)	−0.016 (8)	−0.010 (8)
C4	0.110 (15)	0.059 (10)	0.058 (10)	−0.015 (10)	−0.048 (11)	0.005 (8)

Geometric parameters (Å, º) top

Hg1—Br2	2.4963 (18)	C9—H9B	0.9700
Hg1—Br3	2.5059 (17)	C3—C4	1.52 (2)
Hg1—Br1ⁱ	2.681 (2)	C3—H3A	0.9700
Hg1—Br1	2.7092 (19)	C3—H3B	0.9700
Br1—Hg1ⁱ	2.681 (2)	C2—C1	1.46 (2)
N1—C5	1.517 (16)	C2—H2A	0.9700
N1—C7	1.524 (15)	C2—H2B	0.9700
N1—C2	1.522 (16)	C10—H10A	0.9600
N1—C3	1.538 (15)	C10—H10B	0.9600
C7—C8	1.492 (18)	C10—H10C	0.9600
C7—H7A	0.9700	C1—H1A	0.9600
C7—H7B	0.9700	C1—H1B	0.9600
C5—C6	1.50 (2)	C1—H1C	0.9600
C5—H5A	0.9700	C6—H6A	0.9600
C5—H5B	0.9700	C6—H6B	0.9600
C8—C9	1.526 (18)	C6—H6C	0.9600
C8—H8A	0.9700	C4—H4A	0.9600
C8—H8B	0.9700	C4—H4B	0.9600
C9—C10	1.50 (2)	C4—H4C	0.9600
C9—H9A	0.9700

Br2—Hg1—Br3	122.48 (7)	C4—C3—N1	114.4 (11)
Br2—Hg1—Br1ⁱ	107.16 (6)	C4—C3—H3A	108.7
Br3—Hg1—Br1ⁱ	113.07 (7)	N1—C3—H3A	108.7
Br2—Hg1—Br1	108.17 (6)	C4—C3—H3B	108.7
Br3—Hg1—Br1	110.02 (6)	N1—C3—H3B	108.7
Br1ⁱ—Hg1—Br1	91.47 (5)	H3A—C3—H3B	107.6
Hg1ⁱ—Br1—Hg1	88.53 (5)	C1—C2—N1	116.4 (11)
C5—N1—C7	110.3 (9)	C1—C2—H2A	108.2
C5—N1—C2	107.3 (9)	N1—C2—H2A	108.2
C7—N1—C2	109.7 (10)	C1—C2—H2B	108.2
C5—N1—C3	111.9 (10)	N1—C2—H2B	108.2
C7—N1—C3	106.6 (8)	H2A—C2—H2B	107.3
C2—N1—C3	111.1 (10)	C9—C10—H10A	109.5
C8—C7—N1	117.3 (10)	C9—C10—H10B	109.5
C8—C7—H7A	108.0	H10A—C10—H10B	109.5
N1—C7—H7A	108.0	C9—C10—H10C	109.5
C8—C7—H7B	108.0	H10A—C10—H10C	109.5
N1—C7—H7B	108.0	H10B—C10—H10C	109.5
H7A—C7—H7B	107.2	C2—C1—H1A	109.5
C6—C5—N1	114.9 (11)	C2—C1—H1B	109.5
C6—C5—H5A	108.5	H1A—C1—H1B	109.5
N1—C5—H5A	108.5	C2—C1—H1C	109.5
C6—C5—H5B	108.5	H1A—C1—H1C	109.5
N1—C5—H5B	108.5	H1B—C1—H1C	109.5
H5A—C5—H5B	107.5	C5—C6—H6A	109.5
C7—C8—C9	111.7 (11)	C5—C6—H6B	109.5
C7—C8—H8A	109.3	H6A—C6—H6B	109.5
C9—C8—H8A	109.3	C5—C6—H6C	109.5
C7—C8—H8B	109.3	H6A—C6—H6C	109.5
C9—C8—H8B	109.3	H6B—C6—H6C	109.5
H8A—C8—H8B	107.9	C3—C4—H4A	109.5
C10—C9—C8	114.1 (12)	C3—C4—H4B	109.5
C10—C9—H9A	108.7	H4A—C4—H4B	109.5
C8—C9—H9A	108.7	C3—C4—H4C	109.5
C10—C9—H9B	108.7	H4A—C4—H4C	109.5
C8—C9—H9B	108.7	H4B—C4—H4C	109.5
H9A—C9—H9B	107.6

Symmetry code: (i) −x+1, −y+2, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3B···Br1ⁱⁱ	0.97	2.91	3.837 (15)	160
C6—H6A···Br2	0.96	3.00	3.833 (16)	147
C7—H7B···Br2	0.97	3.03	3.973 (13)	165

Symmetry code: (ii) −x, −y+2, −z+1.

Experimental details

Crystal data
Chemical formula	(C₁₀H₂₄N)₂[Hg₂Br₆]
M_r	1197.24
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	7.6372 (15), 10.318 (2), 11.185 (2)
α, β, γ (°)	76.70 (3), 72.22 (3), 85.57 (3)
V (Å³)	816.8 (3)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	16.74
Crystal size (mm)	0.28 × 0.24 × 0.20

Data collection
Diffractometer	Rigaku Mercury2 diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.013, 0.035
No. of measured, independent and observed [I > 2σ(I)] reflections	7659, 3209, 2596
R_int	0.053
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.056, 0.151, 1.05
No. of reflections	3209
No. of parameters	141
H-atom treatment	H-atom parameters constrained
	w = 1/[σ²(F_o²) + (0.0572P)² + 12.6923P] where P = (F_o² + 2F_c²)/3
Δρ_max, Δρ_min (e Å⁻³)	1.27, −1.83

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

Selected geometric parameters (Å, º) top

Hg1—Br2	2.4963 (18)	Hg1—Br1ⁱ	2.681 (2)
Hg1—Br3	2.5059 (17)	Hg1—Br1	2.7092 (19)

Hg1ⁱ—Br1—Hg1	88.53 (5)

Symmetry code: (i) −x+1, −y+2, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3B···Br1ⁱⁱ	0.97	2.91	3.837 (15)	160
C6—H6A···Br2	0.96	3.00	3.833 (16)	147
C7—H7B···Br2	0.97	3.03	3.973 (13)	165

Symmetry code: (ii) −x, −y+2, −z+1.

Acknowledgements

The author thanks the Ordered Matter Science Research Centre, Southeast University.

References

Jin, L. (2012). Acta Cryst. E68, m123. 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