Benzyl­triethyl­ammonium aqua­trichlorido­zincate

Jin, L.

doi:10.1107/S1600536811048823

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 12| December 2011| Page m1793

https://doi.org/10.1107/S1600536811048823

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Benzyltriethylammonium aquatrichloridozincate

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 5 November 2011; accepted 16 November 2011; online 19 November 2011)

In the crystal structure of the title molecular salt, (C₁₃H₂₂N)[ZnCl₃(H₂O)], the distorted tetrahedral anions are linked by O—H⋯Cl hydrogen bonds, generating [100] chains. Weak cation-to-anion C—H⋯Cl interactions generate a three-dimensional network.

Related literature

For background literature concerning molecular salts, see: Tan et al. (2010 ); Jin et al. (2011 ).

Experimental

Crystal data

(C₁₃H₂₂N)[ZnCl₃(H₂O)]
M_r = 382.05
Orthorhombic, P 2₁ 2₁ 2₁
a = 8.3236 (17) Å
b = 13.484 (3) Å
c = 15.808 (3) Å
V = 1774.2 (6) Å³
Z = 4
Mo Kα radiation
μ = 1.83 mm⁻¹
T = 291 K
0.28 × 0.24 × 0.22 mm

Data collection

Rigaku Mercury2 CCD diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.629, T_max = 0.689
18427 measured reflections
4054 independent reflections
3522 reflections with I > 2σ(I)
R_int = 0.045

Refinement

R[F² > 2σ(F²)] = 0.034
wR(F²) = 0.077
S = 1.09
4054 reflections
177 parameters
H-atom parameters constrained
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.37 e Å⁻³
Absolute structure: Flack (1983 ), 1735 Friedel pairs
Flack parameter: 0.022 (13)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1D⋯Cl2ⁱ	0.98	2.17	3.121 (2)	163
O1—H1E⋯Cl1ⁱⁱ	0.93	2.24	3.155 (2)	168
C1—H1B⋯Cl1ⁱⁱⁱ	0.96	2.82	3.599 (3)	139
Symmetry codes: (i) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, -z]$ ; (ii) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, -z]$ ; (iii) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, -z+1]$ .

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: https://doi.org/10.1107/S1600536811048823/hb6492sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536811048823/hb6492Isup2.hkl

checkCIF report

Related literature top

For background literature concerning molecular salts, see: Tan et al. (2010); Jin et al. (2011).

Experimental top

In room temperature benzyltriethylammoniumchlorine (10 mmol, 2.28 g) were dissolved in 30 ml water, then a solution with ZnCl₂(5 mmol, 0.68 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 two weeks in air with some colorless solid blocks appeared after days with yield about 75%.

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).

Structure description top

For background literature concerning molecular salts, see: Tan et al. (2010); Jin et al. (2011).

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 (I) showing 30% probability displacement ellipsoids.

Benzyltriethylammonium aquatrichloridozinc top

Crystal data top

(C₁₃H₂₂N)[ZnCl₃(H₂O)]	F(000) = 792
M_r = 382.05	D_x = 1.430 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	θ = 3.0–27.5°
a = 8.3236 (17) Å	µ = 1.83 mm⁻¹
b = 13.484 (3) Å	T = 291 K
c = 15.808 (3) Å	Block, colorless
V = 1774.2 (6) Å³	0.28 × 0.24 × 0.22 mm
Z = 4

Data collection top

Rigaku Mercury2 CCD diffractometer	4054 independent reflections
Radiation source: fine-focus sealed tube	3522 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.045
Detector resolution: 13.6612 pixels mm^-1	θ_max = 27.5°, θ_min = 3.0°
CCD_Profile_fitting scans	h = −10→10
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −17→17
T_min = 0.629, T_max = 0.689	l = −20→20
18427 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)] = 0.034	H-atom parameters constrained
wR(F²) = 0.077	w = 1/[σ²(F_o²) + (0.0349P)²] where P = (F_o² + 2F_c²)/3
S = 1.09	(Δ/σ)_max < 0.001
4054 reflections	Δρ_max = 0.27 e Å⁻³
177 parameters	Δρ_min = −0.37 e Å⁻³
0 restraints	Absolute structure: Flack (1983), 1735 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.022 (13)

Crystal data top

(C₁₃H₂₂N)[ZnCl₃(H₂O)]	V = 1774.2 (6) Å³
M_r = 382.05	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 8.3236 (17) Å	µ = 1.83 mm⁻¹
b = 13.484 (3) Å	T = 291 K
c = 15.808 (3) Å	0.28 × 0.24 × 0.22 mm

Data collection top

Rigaku Mercury2 CCD diffractometer	4054 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	3522 reflections with I > 2σ(I)
T_min = 0.629, T_max = 0.689	R_int = 0.045
18427 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	H-atom parameters constrained
wR(F²) = 0.077	Δρ_max = 0.27 e Å⁻³
S = 1.09	Δρ_min = −0.37 e Å⁻³
4054 reflections	Absolute structure: Flack (1983), 1735 Friedel pairs
177 parameters	Absolute structure parameter: 0.022 (13)
0 restraints

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
C1	1.0907 (4)	0.6986 (3)	0.6677 (2)	0.0704 (9)
H1A	1.1371	0.6335	0.6665	0.106*
H1B	1.1646	0.7440	0.6937	0.106*
H1C	1.0684	0.7200	0.6110	0.106*
C2	0.9359 (4)	0.6962 (2)	0.71813 (18)	0.0526 (7)
H2A	0.9607	0.6758	0.7755	0.063*
H2B	0.8929	0.7630	0.7208	0.063*
C3	0.9403 (5)	0.4758 (2)	0.7474 (2)	0.0691 (10)
H3A	1.0262	0.5159	0.7691	0.104*
H3B	0.9807	0.4112	0.7333	0.104*
H3C	0.8578	0.4696	0.7896	0.104*
C4	0.8714 (3)	0.52380 (19)	0.66941 (17)	0.0485 (7)
H4A	0.7847	0.4827	0.6482	0.058*
H4B	0.9541	0.5262	0.6262	0.058*
C5	0.5348 (4)	0.5569 (2)	0.7260 (2)	0.0631 (8)
H5A	0.5022	0.5662	0.6683	0.095*
H5B	0.4453	0.5694	0.7628	0.095*
H5C	0.5714	0.4900	0.7338	0.095*
C6	0.6706 (3)	0.6286 (2)	0.74693 (16)	0.0482 (6)
H6A	0.6267	0.6951	0.7503	0.058*
H6B	0.7131	0.6119	0.8023	0.058*
C7	0.7509 (3)	0.66402 (18)	0.59743 (15)	0.0425 (6)
H7A	0.8416	0.6621	0.5589	0.051*
H7B	0.6717	0.6173	0.5765	0.051*
C8	0.6785 (3)	0.76674 (19)	0.59399 (15)	0.0412 (6)
C9	0.7711 (4)	0.8488 (2)	0.57179 (18)	0.0594 (8)
H9	0.8812	0.8415	0.5639	0.071*
C10	0.7015 (5)	0.9410 (2)	0.5613 (2)	0.0720 (10)
H10	0.7649	0.9950	0.5462	0.086*
C11	0.5380 (5)	0.9536 (2)	0.57303 (18)	0.0646 (9)
H11	0.4911	1.0156	0.5657	0.078*
C12	0.4475 (4)	0.8747 (2)	0.59527 (18)	0.0566 (8)
H12	0.3378	0.8831	0.6040	0.068*
C13	0.5148 (4)	0.7814 (2)	0.60535 (16)	0.0481 (6)
H13	0.4496	0.7281	0.6199	0.058*
Cl1	0.82104 (9)	0.72961 (7)	0.14959 (5)	0.0678 (2)
Cl2	1.23689 (9)	0.63181 (6)	0.11597 (5)	0.0603 (2)
Cl3	0.89340 (10)	0.55114 (6)	−0.02493 (5)	0.0620 (2)
N1	0.8077 (2)	0.62856 (15)	0.68371 (12)	0.0372 (5)
O1	1.0364 (2)	0.78841 (15)	−0.01861 (15)	0.0646 (6)
H1D	0.9476	0.8264	−0.0434	0.136 (18)*
H1E	1.1189	0.7929	−0.0579	0.120 (16)*
Zn1	1.00040 (4)	0.66907 (2)	0.056683 (18)	0.04478 (10)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0440 (17)	0.089 (2)	0.078 (2)	−0.0088 (17)	−0.0040 (16)	−0.007 (2)
C2	0.0519 (16)	0.0584 (17)	0.0473 (15)	−0.0004 (14)	−0.0111 (13)	−0.0131 (14)
C3	0.083 (2)	0.061 (2)	0.0629 (19)	0.0251 (17)	0.0060 (17)	0.0056 (16)
C4	0.0562 (18)	0.0413 (15)	0.0479 (15)	0.0091 (13)	0.0042 (13)	−0.0071 (12)
C5	0.055 (2)	0.0617 (17)	0.0730 (19)	−0.0036 (15)	0.0157 (15)	0.0108 (16)
C6	0.0527 (16)	0.0529 (15)	0.0389 (14)	0.0097 (14)	0.0095 (12)	0.0028 (12)
C7	0.0488 (14)	0.0457 (13)	0.0331 (12)	−0.0015 (13)	−0.0011 (11)	−0.0044 (11)
C8	0.0447 (14)	0.0463 (14)	0.0326 (12)	−0.0064 (12)	−0.0026 (11)	0.0016 (11)
C9	0.0538 (18)	0.0612 (18)	0.0630 (19)	−0.0098 (15)	0.0029 (15)	0.0122 (15)
C10	0.082 (3)	0.0537 (18)	0.080 (2)	−0.0145 (18)	−0.002 (2)	0.0219 (18)
C11	0.091 (3)	0.0474 (16)	0.0556 (17)	0.0096 (17)	−0.0104 (17)	0.0049 (14)
C12	0.0546 (18)	0.0683 (19)	0.0469 (16)	0.0142 (15)	−0.0009 (13)	0.0061 (15)
C13	0.0450 (16)	0.0538 (15)	0.0456 (14)	−0.0046 (15)	−0.0037 (14)	0.0050 (11)
Cl1	0.0499 (4)	0.0890 (6)	0.0646 (5)	−0.0015 (4)	0.0090 (4)	−0.0227 (4)
Cl2	0.0412 (4)	0.0740 (5)	0.0658 (5)	−0.0034 (4)	−0.0119 (3)	0.0041 (4)
Cl3	0.0608 (5)	0.0689 (5)	0.0565 (4)	−0.0192 (4)	−0.0050 (4)	−0.0113 (4)
N1	0.0378 (11)	0.0402 (10)	0.0337 (10)	0.0039 (10)	0.0030 (9)	−0.0056 (9)
O1	0.0423 (12)	0.0623 (12)	0.0893 (15)	−0.0024 (10)	0.0078 (11)	0.0192 (12)
Zn1	0.03494 (16)	0.05128 (17)	0.04811 (17)	−0.00472 (16)	−0.00111 (15)	−0.00287 (12)

Geometric parameters (Å, º) top

C1—C2	1.515 (4)	C7—C8	1.511 (4)
C1—H1A	0.9600	C7—N1	1.521 (3)
C1—H1B	0.9600	C7—H7A	0.9700
C1—H1C	0.9600	C7—H7B	0.9700
C2—N1	1.506 (3)	C8—C13	1.389 (4)
C2—H2A	0.9700	C8—C9	1.394 (4)
C2—H2B	0.9700	C9—C10	1.382 (4)
C3—C4	1.506 (4)	C9—H9	0.9300
C3—H3A	0.9600	C10—C11	1.384 (5)
C3—H3B	0.9600	C10—H10	0.9300
C3—H3C	0.9600	C11—C12	1.350 (5)
C4—N1	1.526 (3)	C11—H11	0.9300
C4—H4A	0.9700	C12—C13	1.386 (4)
C4—H4B	0.9700	C12—H12	0.9300
C5—C6	1.523 (4)	C13—H13	0.9300
C5—H5A	0.9600	Cl1—Zn1	2.2478 (8)
C5—H5B	0.9600	Cl2—Zn1	2.2373 (9)
C5—H5C	0.9600	Cl3—Zn1	2.2330 (8)
C6—N1	1.517 (3)	O1—Zn1	2.024 (2)
C6—H6A	0.9700	O1—H1D	0.9808
C6—H6B	0.9700	O1—H1E	0.9280

C2—C1—H1A	109.5	N1—C7—H7A	108.2
C2—C1—H1B	109.5	C8—C7—H7B	108.2
H1A—C1—H1B	109.5	N1—C7—H7B	108.2
C2—C1—H1C	109.5	H7A—C7—H7B	107.3
H1A—C1—H1C	109.5	C13—C8—C9	117.5 (3)
H1B—C1—H1C	109.5	C13—C8—C7	121.1 (2)
N1—C2—C1	115.2 (2)	C9—C8—C7	121.1 (2)
N1—C2—H2A	108.5	C10—C9—C8	120.9 (3)
C1—C2—H2A	108.5	C10—C9—H9	119.6
N1—C2—H2B	108.5	C8—C9—H9	119.6
C1—C2—H2B	108.5	C9—C10—C11	120.4 (3)
H2A—C2—H2B	107.5	C9—C10—H10	119.8
C4—C3—H3A	109.5	C11—C10—H10	119.8
C4—C3—H3B	109.5	C12—C11—C10	119.2 (3)
H3A—C3—H3B	109.5	C12—C11—H11	120.4
C4—C3—H3C	109.5	C10—C11—H11	120.4
H3A—C3—H3C	109.5	C11—C12—C13	121.3 (3)
H3B—C3—H3C	109.5	C11—C12—H12	119.4
C3—C4—N1	114.1 (2)	C13—C12—H12	119.4
C3—C4—H4A	108.7	C12—C13—C8	120.7 (3)
N1—C4—H4A	108.7	C12—C13—H13	119.6
C3—C4—H4B	108.7	C8—C13—H13	119.6
N1—C4—H4B	108.7	C2—N1—C6	107.17 (19)
H4A—C4—H4B	107.6	C2—N1—C7	110.7 (2)
C6—C5—H5A	109.5	C6—N1—C7	110.93 (19)
C6—C5—H5B	109.5	C2—N1—C4	111.6 (2)
H5A—C5—H5B	109.5	C6—N1—C4	111.1 (2)
C6—C5—H5C	109.5	C7—N1—C4	105.44 (18)
H5A—C5—H5C	109.5	Zn1—O1—H1D	122.6
H5B—C5—H5C	109.5	Zn1—O1—H1E	123.8
N1—C6—C5	114.5 (2)	H1D—O1—H1E	104.8
N1—C6—H6A	108.6	O1—Zn1—Cl3	106.59 (7)
C5—C6—H6A	108.6	O1—Zn1—Cl2	107.13 (6)
N1—C6—H6B	108.6	Cl3—Zn1—Cl2	115.66 (4)
C5—C6—H6B	108.6	O1—Zn1—Cl1	101.18 (7)
H6A—C6—H6B	107.6	Cl3—Zn1—Cl1	111.79 (3)
C8—C7—N1	116.38 (19)	Cl2—Zn1—Cl1	113.09 (3)
C8—C7—H7A	108.2

N1—C7—C8—C13	−90.3 (3)	C1—C2—N1—C7	−64.5 (3)
N1—C7—C8—C9	95.6 (3)	C1—C2—N1—C4	52.7 (3)
C13—C8—C9—C10	−0.3 (4)	C5—C6—N1—C2	−175.1 (2)
C7—C8—C9—C10	174.1 (3)	C5—C6—N1—C7	63.9 (3)
C8—C9—C10—C11	0.3 (5)	C5—C6—N1—C4	−53.0 (3)
C9—C10—C11—C12	0.3 (5)	C8—C7—N1—C2	−60.2 (3)
C10—C11—C12—C13	−0.9 (5)	C8—C7—N1—C6	58.7 (3)
C11—C12—C13—C8	0.9 (4)	C8—C7—N1—C4	179.0 (2)
C9—C8—C13—C12	−0.3 (4)	C3—C4—N1—C2	57.5 (3)
C7—C8—C13—C12	−174.7 (2)	C3—C4—N1—C6	−62.0 (3)
C1—C2—N1—C6	174.4 (2)	C3—C4—N1—C7	177.8 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1D···Cl2ⁱ	0.98	2.17	3.121 (2)	163
O1—H1E···Cl1ⁱⁱ	0.93	2.24	3.155 (2)	168
C1—H1B···Cl1ⁱⁱⁱ	0.96	2.82	3.599 (3)	139

Symmetry codes: (i) x−1/2, −y+3/2, −z; (ii) x+1/2, −y+3/2, −z; (iii) x+1/2, −y+3/2, −z+1.

Experimental details

Crystal data
Chemical formula	(C₁₃H₂₂N)[ZnCl₃(H₂O)]
M_r	382.05
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	291
a, b, c (Å)	8.3236 (17), 13.484 (3), 15.808 (3)
V (Å³)	1774.2 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.83
Crystal size (mm)	0.28 × 0.24 × 0.22

Data collection
Diffractometer	Rigaku Mercury2 CCD
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.629, 0.689
No. of measured, independent and observed [I > 2σ(I)] reflections	18427, 4054, 3522
R_int	0.045
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.077, 1.09
No. of reflections	4054
No. of parameters	177
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.27, −0.37
Absolute structure	Flack (1983), 1735 Friedel pairs
Absolute structure parameter	0.022 (13)

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
O1—H1D···Cl2ⁱ	0.98	2.17	3.121 (2)	163
O1—H1E···Cl1ⁱⁱ	0.93	2.24	3.155 (2)	168
C1—H1B···Cl1ⁱⁱⁱ	0.96	2.82	3.599 (3)	139

Symmetry codes: (i) x−1/2, −y+3/2, −z; (ii) x+1/2, −y+3/2, −z; (iii) x+1/2, −y+3/2, −z+1.

Acknowledgements

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

References

Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Jin, L., Liu, N., Li, Y.-J. & Wu, D.-H. (2011). Acta Cryst. E67, m1325. 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
Tan, K. W., Maah, M. J. & Ng, S. W. (2010). Acta Cryst. E66, m690. Web of Science CSD CrossRef IUCr Journals Google Scholar