1,4-Diazo-niabicyclo-[2.2.2]octane tetra-chloridozincate monohydrate.

In the title compound, (C(6)H(14)N(2))[ZnCl(4)]·H(2)O, the crystal packing is governed by an extensive three-dimensional network of N-H⋯Cl, N-H⋯O and O-H⋯Cl hydrogen bonds. The zinc(II) metal centre has a slightly distorted tetra-hedral coordination geometry.

Related literature

For the applications of ferroelectric materials, see: Fu et al. (2007 ▶); Dawber et al. (2005 ▶); Haertling (1999 ▶); Scott (2007 ▶). For the properties and structure of a related diaza­bicyclo­[2.2.2]octane (dabco) salt, see: Szafrański et al. (2002 ▶).

Experimental

Crystal data

(C6H14N2)[ZnCl4]·H2O

M = 339.40

Orthorhombic,

a = 8.4483 (17) Å

b = 11.705 (2) Å

c = 12.976 (3) Å

V = 1283.2 (5) Å3

Z = 4

Mo Kα radiation

μ = 2.72 mm−1

T = 291 K

0.30 × 0.28 × 0.26 mm

Data collection

Rigaku Mercury2 diffractometer

Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ▶) T min = 0.462, T max = 0.495

11890 measured reflections

2510 independent reflections

2166 reflections with I > 2σ(I)

R int = 0.053

Refinement

R[F 2 > 2σ(F 2)] = 0.046

wR(F 2) = 0.121

S = 1.03

2510 reflections

127 parameters

H-atom parameters constrained

Δρmax = 0.89 e Å−3

Δρmin = −0.48 e Å−3

Absolute structure: Flack (1983 ▶), 1050 Friedel pairs

Flack parameter: 0.07 (3)

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.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809014822/rz2310sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809014822/rz2310Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

(C6H14N2)[ZnCl4]·H2O	F(000) = 688
Mr = 339.40	Dx = 1.757 Mg m−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 11517 reflections
a = 8.4483 (17) Å	θ = 3.1–27.5°
b = 11.705 (2) Å	µ = 2.72 mm−1
c = 12.976 (3) Å	T = 291 K
V = 1283.2 (5) Å3	Block, colourless
Z = 4	0.30 × 0.28 × 0.26 mm

Rigaku Mercury2 diffractometer	2510 independent reflections
Radiation source: fine-focus sealed tube	2166 reflections with I > 2σ(I)
graphite	Rint = 0.053
Detector resolution: 13.6612 pixels mm-1	θmax = 26.0°, θmin = 3.1°
ω scans	h = −10→10
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −14→14
Tmin = 0.462, Tmax = 0.495	l = −16→16
11890 measured reflections

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)] = 0.046	H-atom parameters constrained
wR(F2) = 0.121	w = 1/[σ2(Fo2) + (0.0665P)2 + 1.4482P] where P = (Fo2 + 2Fc2)/3
S = 1.03	(Δ/σ)max = 0.001
2510 reflections	Δρmax = 0.89 e Å−3
127 parameters	Δρmin = −0.48 e Å−3
0 restraints	Absolute structure: Flack (1983), 1050 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.07 (3)

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.

	x	y	z	Uiso*/Ueq
C1	0.2122 (7)	0.3775 (6)	0.3733 (5)	0.0434 (17)
H1A	0.1610	0.3189	0.4143	0.052*
H1B	0.2347	0.4422	0.4177	0.052*
C2	0.3645 (8)	0.3316 (7)	0.3286 (5)	0.0489 (18)
H2A	0.3676	0.2490	0.3347	0.059*
H2B	0.4547	0.3632	0.3650	0.059*
C3	0.1700 (9)	0.5158 (6)	0.2364 (5)	0.0415 (16)
H3A	0.1655	0.5809	0.2826	0.050*
H3B	0.1064	0.5330	0.1761	0.050*
C4	0.3402 (8)	0.4934 (6)	0.2046 (6)	0.0474 (18)
H4A	0.3568	0.5167	0.1336	0.057*
H4B	0.4123	0.5361	0.2482	0.057*
C5	0.0884 (7)	0.3177 (5)	0.2132 (5)	0.0371 (15)
H5A	0.0055	0.3356	0.1641	0.045*
H5B	0.0602	0.2477	0.2487	0.045*
C6	0.2468 (8)	0.3030 (5)	0.1574 (4)	0.0405 (14)
H6A	0.2745	0.2227	0.1536	0.049*
H6B	0.2394	0.3328	0.0878	0.049*
Cl1	0.20057 (18)	−0.18534 (13)	1.07634 (13)	0.0420 (4)
Cl2	0.2573 (2)	−0.03346 (13)	0.81713 (10)	0.0444 (4)
Cl3	0.03672 (18)	0.09791 (13)	1.03379 (13)	0.0371 (4)
Cl4	0.47943 (19)	0.06684 (14)	1.03500 (14)	0.0414 (4)
N1	0.1070 (6)	0.4132 (4)	0.2888 (4)	0.0308 (11)
H1C	0.0103	0.4303	0.3156	0.037*
N2	0.3689 (6)	0.3664 (5)	0.2161 (5)	0.0444 (15)
H2C	0.4659	0.3493	0.1899	0.053*
O1	0.6587 (8)	0.2561 (5)	0.1794 (5)	0.086 (2)
H1D	0.6849	0.2659	0.1167	0.128*
H1E	0.7293	0.2845	0.2184	0.128*
Zn1	0.24738 (9)	−0.01799 (5)	0.99321 (4)	0.0333 (2)

	U11	U22	U33	U12	U13	U23
C1	0.043 (4)	0.054 (4)	0.033 (3)	0.007 (3)	−0.009 (3)	−0.004 (3)
C2	0.042 (4)	0.052 (4)	0.052 (4)	0.006 (3)	−0.020 (3)	−0.008 (4)
C3	0.044 (4)	0.031 (3)	0.050 (4)	0.005 (3)	0.005 (3)	0.003 (3)
C4	0.036 (4)	0.054 (4)	0.053 (4)	−0.011 (3)	0.012 (3)	−0.010 (4)
C5	0.038 (3)	0.037 (4)	0.037 (3)	−0.003 (3)	−0.004 (3)	0.003 (3)
C6	0.034 (3)	0.043 (3)	0.045 (3)	−0.007 (3)	−0.007 (3)	−0.018 (3)
Cl1	0.0443 (9)	0.0383 (8)	0.0435 (8)	0.0001 (7)	0.0069 (6)	0.0048 (7)
Cl2	0.0477 (9)	0.0536 (9)	0.0318 (7)	−0.0048 (9)	0.0041 (8)	−0.0058 (6)
Cl3	0.0322 (8)	0.0407 (8)	0.0384 (9)	0.0023 (6)	0.0004 (7)	−0.0041 (7)
Cl4	0.0368 (8)	0.0459 (8)	0.0414 (9)	−0.0079 (7)	−0.0055 (7)	0.0029 (8)
N1	0.022 (2)	0.042 (3)	0.029 (3)	0.004 (2)	0.0009 (19)	−0.002 (2)
N2	0.022 (3)	0.051 (3)	0.061 (4)	0.003 (2)	0.004 (2)	−0.018 (3)
O1	0.067 (4)	0.083 (5)	0.106 (5)	0.004 (4)	−0.014 (4)	−0.001 (4)
Zn1	0.0317 (3)	0.0375 (3)	0.0307 (3)	−0.0011 (3)	0.0009 (3)	0.0002 (3)

C1—N1	1.472 (7)	C5—C6	1.531 (9)
C1—C2	1.510 (9)	C5—H5A	0.9700
C1—H1A	0.9700	C5—H5B	0.9700
C1—H1B	0.9700	C6—N2	1.482 (8)
C2—N2	1.515 (9)	C6—H6A	0.9700
C2—H2A	0.9700	C6—H6B	0.9700
C2—H2B	0.9700	Cl1—Zn1	2.2710 (17)
C3—N1	1.479 (8)	Cl2—Zn1	2.2936 (15)
C3—C4	1.519 (9)	Cl3—Zn1	2.2989 (17)
C3—H3A	0.9700	Cl4—Zn1	2.2635 (17)
C3—H3B	0.9700	N1—H1C	0.9100
C4—N2	1.514 (9)	N2—H2C	0.9100
C4—H4A	0.9700	O1—H1D	0.8499
C4—H4B	0.9700	O1—H1E	0.8500
C5—N1	1.496 (8)
N1—C1—C2	109.2 (5)	C6—C5—H5B	110.2
N1—C1—H1A	109.8	H5A—C5—H5B	108.5
C2—C1—H1A	109.8	N2—C6—C5	108.0 (5)
N1—C1—H1B	109.8	N2—C6—H6A	110.1
C2—C1—H1B	109.8	C5—C6—H6A	110.1
H1A—C1—H1B	108.3	N2—C6—H6B	110.1
C1—C2—N2	107.2 (5)	C5—C6—H6B	110.1
C1—C2—H2A	110.3	H6A—C6—H6B	108.4
N2—C2—H2A	110.3	C1—N1—C3	110.8 (5)
C1—C2—H2B	110.3	C1—N1—C5	109.9 (5)
N2—C2—H2B	110.3	C3—N1—C5	110.1 (5)
H2A—C2—H2B	108.5	C1—N1—H1C	108.7
N1—C3—C4	109.0 (5)	C3—N1—H1C	108.7
N1—C3—H3A	109.9	C5—N1—H1C	108.7
C4—C3—H3A	109.9	C6—N2—C4	109.2 (5)
N1—C3—H3B	109.9	C6—N2—C2	110.1 (5)
C4—C3—H3B	109.9	C4—N2—C2	110.8 (5)
H3A—C3—H3B	108.3	C6—N2—H2C	108.9
N2—C4—C3	107.1 (5)	C4—N2—H2C	108.9
N2—C4—H4A	110.3	C2—N2—H2C	108.9
C3—C4—H4A	110.3	H1D—O1—H1E	109.5
N2—C4—H4B	110.3	Cl4—Zn1—Cl1	114.55 (7)
C3—C4—H4B	110.3	Cl4—Zn1—Cl2	103.99 (7)
H4A—C4—H4B	108.5	Cl1—Zn1—Cl2	114.29 (6)
N1—C5—C6	107.6 (5)	Cl4—Zn1—Cl3	110.90 (6)
N1—C5—H5A	110.2	Cl1—Zn1—Cl3	105.40 (6)
C6—C5—H5A	110.2	Cl2—Zn1—Cl3	107.63 (7)
N1—C5—H5B	110.2

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2C···O1	0.91	1.96	2.809 (8)	154
N1—H1C···Cl1i	0.91	2.64	3.338 (5)	134
N1—H1C···Cl3i	0.91	2.80	3.383 (5)	123
O1—H1D···Cl3ii	0.85	2.82	3.410 (7)	129
O1—H1E···Cl1iii	0.85	2.75	3.454 (7)	141

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2C⋯O1	0.91	1.96	2.809 (8)	154
N1—H1C⋯Cl1i	0.91	2.64	3.338 (5)	134
N1—H1C⋯Cl3i	0.91	2.80	3.383 (5)	123
O1—H1D⋯Cl3ii	0.85	2.82	3.410 (7)	129
O1—H1E⋯Cl1iii	0.85	2.75	3.454 (7)	141

Symmetry codes: (i) ; (ii) ; (iii) .