1-Methyl-piperazine-1,4-diium tetra-chloridozincate hemihydrate.

The crystal structure of the title compound, (C(5)H(14)N(2))[ZnCl(4)]·0.5H(2)O, is built up from discrete 1-methyl-piperazine-diium cations with chair conformation, tetrahedral tetrachloridozincate anions and uncoordinated solvent water mol-ecules linked together by three types of inter-molecular hydrogen bonds, viz. N-H⋯Cl, N-H⋯O and O-H⋯Cl.

Related literature

For background on organic–inorganic hybrid materials, see: Lacroix et al. (1994 ▶); Mitzi (2001 ▶); Pecaut et al. (1993 ▶). For related structures, see: Deeth et al. (1984 ▶); Fowkes & Harrison (2004 ▶); Walha et al. (2010 ▶, 2011 ▶).

Experimental

Crystal data

(C5H14N2)[ZnCl4]·0.5H2O

M = 318.36

Monoclinic,

a = 14.3210 (5) Å

b = 12.7590 (5) Å

c = 13.7970 (3) Å

β = 102.821 (3)°

V = 2458.16 (14) Å3

Z = 8

Mo Kα radiation

μ = 2.83 mm−1

T = 293 K

0.47 × 0.11 × 0.03 mm

Data collection

Nonius KappaCCD diffractometer

Absorption correction: analytical (de Meulenaer & Tompa, 1965 ▶) T min = 0.393, T max = 0.661

27355 measured reflections

4237 independent reflections

2996 reflections with I > 2σ(I)

Refinement

R[F 2 > 2σ(F 2)] = 0.050

wR(F 2) = 0.080

S = 1.24

4237 reflections

115 parameters

H-atom parameters constrained

Δρmax = 0.49 e Å−3

Δρmin = −0.68 e Å−3

Data collection: COLLECT (Nonius, 1998 ▶); cell refinement: SCALEPACK (Otwinowski & Minor, 1997 ▶); data reduction: DENZO (Otwinowski & Minor, 1997 ▶) and SCALEPACK; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811043236/zq2122sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811043236/zq2122Isup2.hkl

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

(C5H14N2)[ZnCl4]·0.5H2O	Z = 8
Mr = 318.36	F(000) = 1288
Monoclinic, C2/c	Dx = 1.720 Mg m−3
Hall symbol: -C 2yc	Mo Kα radiation, λ = 0.71073 Å
a = 14.3210 (5) Å	θ = 3.5–32.0°
b = 12.7590 (5) Å	µ = 2.83 mm−1
c = 13.7970 (3) Å	T = 293 K
β = 102.821 (3)°	Plate-shaped, colourless
V = 2458.16 (14) Å3	0.47 × 0.11 × 0.03 mm

Nonius KappaCCD diffractometer	4237 independent reflections
Radiation source: fine-focus sealed tube	2996 reflections with I > 2σ(I)
graphite	Rint = 0.000
Detector resolution: 9 pixels mm-1	θmax = 32.0°, θmin = 3.5°
CCD rotation images, thick slices scans	h = −21→20
Absorption correction: analytical (de Meulenaer & Tompa, 1965)	k = 0→19
Tmin = 0.393, Tmax = 0.661	l = 0→20
4237 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)] = 0.050	H-atom parameters constrained
wR(F2) = 0.080	w = 1/[σ2(Fo2) + (0.0157P)2 + 3.8346P] where P = (Fo2 + 2Fc2)/3
S = 1.24	(Δ/σ)max < 0.001
4237 reflections	Δρmax = 0.49 e Å−3
115 parameters	Δρmin = −0.68 e Å−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008)
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0000

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
Zn	0.01435 (2)	0.25139 (2)	0.52565 (2)	0.02734 (8)
Cl1	−0.08951 (5)	0.20675 (6)	0.61886 (5)	0.04259 (18)
Cl3	0.14474 (5)	0.34080 (6)	0.61526 (5)	0.03835 (16)
Cl2	−0.05717 (5)	0.35910 (7)	0.40099 (6)	0.0468 (2)
Cl4	0.07327 (5)	0.11031 (6)	0.45991 (5)	0.04292 (19)
N2	0.14425 (16)	0.5183 (2)	0.90999 (19)	0.0396 (6)
H3	0.1119	0.5425	0.9598	0.048*
H2	0.0992	0.4842	0.8576	0.048*
N1	0.31874 (14)	0.49919 (18)	0.83935 (15)	0.0288 (5)
H1	0.3598	0.5316	0.8904	0.035*
C1	0.27548 (19)	0.4078 (2)	0.8808 (2)	0.0326 (6)
H1A	0.3258	0.3607	0.9112	0.039*
H1B	0.2325	0.3726	0.8274	0.039*
C2	0.2207 (2)	0.4431 (2)	0.9561 (2)	0.0360 (6)
H2A	0.1925	0.3832	0.9804	0.043*
H2B	0.2644	0.4764	1.0101	0.043*
C3	0.1851 (2)	0.6107 (2)	0.8677 (2)	0.0424 (7)
H3B	0.2258	0.6492	0.9203	0.051*
H3A	0.1339	0.6550	0.8341	0.051*
C4	0.2429 (2)	0.5757 (2)	0.7943 (2)	0.0344 (6)
H4A	0.2004	0.5427	0.7391	0.041*
H4B	0.2719	0.6359	0.7714	0.041*
C5	0.3743 (2)	0.4655 (3)	0.7650 (2)	0.0464 (8)
H5A	0.3369	0.4268	0.7103	0.056*
H5B	0.4265	0.4215	0.7970	0.056*
H5C	0.3991	0.5263	0.7382	0.056*
O	0.0000	0.4275 (2)	0.7500	0.0420 (7)
HW1	0.0338	0.3954	0.7050	0.050*

	U11	U22	U33	U12	U13	U23
Zn	0.02624 (14)	0.02913 (16)	0.02555 (15)	0.00289 (13)	0.00340 (10)	0.00195 (13)
Cl1	0.0478 (4)	0.0476 (4)	0.0363 (4)	−0.0085 (3)	0.0176 (3)	0.0033 (3)
Cl3	0.0348 (3)	0.0437 (4)	0.0338 (4)	−0.0077 (3)	0.0017 (3)	−0.0049 (3)
Cl2	0.0306 (3)	0.0632 (5)	0.0451 (4)	0.0098 (3)	0.0053 (3)	0.0291 (4)
Cl4	0.0473 (4)	0.0451 (4)	0.0321 (4)	0.0176 (3)	−0.0002 (3)	−0.0089 (3)
N2	0.0286 (12)	0.0513 (16)	0.0420 (14)	−0.0053 (11)	0.0141 (10)	−0.0153 (12)
N1	0.0209 (10)	0.0452 (14)	0.0197 (10)	−0.0038 (9)	0.0030 (8)	0.0009 (9)
C1	0.0307 (13)	0.0359 (15)	0.0315 (14)	0.0033 (11)	0.0074 (11)	0.0070 (11)
C2	0.0350 (14)	0.0465 (18)	0.0285 (14)	−0.0083 (13)	0.0117 (11)	0.0023 (12)
C3	0.0401 (16)	0.0379 (17)	0.0486 (18)	0.0067 (13)	0.0088 (13)	−0.0043 (14)
C4	0.0363 (14)	0.0353 (16)	0.0305 (14)	0.0031 (12)	0.0054 (11)	0.0054 (12)
C5	0.0294 (14)	0.081 (2)	0.0313 (15)	0.0083 (15)	0.0129 (12)	0.0041 (15)
O	0.0452 (17)	0.0406 (17)	0.0374 (16)	0.000	0.0033 (13)	0.000

Zn—Cl1	2.2449 (8)	C1—H1A	0.9600
Zn—Cl2	2.2614 (7)	C1—H1B	0.9599
Zn—Cl4	2.2615 (8)	C2—H2A	0.9599
Zn—Cl3	2.3004 (7)	C2—H2B	0.9601
N2—C2	1.488 (4)	C3—C4	1.511 (4)
N2—C3	1.490 (4)	C3—H3B	0.9599
N2—H3	0.9600	C3—H3A	0.9599
N2—H2	0.9599	C4—H4A	0.9601
N1—C4	1.489 (3)	C4—H4B	0.9600
N1—C1	1.492 (3)	C5—H5A	0.9601
N1—C5	1.494 (3)	C5—H5B	0.9599
N1—H1	0.9100	C5—H5C	0.9601
C1—C2	1.503 (4)	O—HW1	0.9600
Cl1—Zn—Cl2	110.12 (3)	N2—C2—C1	110.2 (2)
Cl1—Zn—Cl4	112.42 (3)	N2—C2—H2A	109.6
Cl2—Zn—Cl4	108.97 (3)	C1—C2—H2A	109.2
Cl1—Zn—Cl3	112.33 (3)	N2—C2—H2B	109.7
Cl2—Zn—Cl3	106.50 (3)	C1—C2—H2B	108.6
Cl4—Zn—Cl3	106.24 (3)	H2A—C2—H2B	109.5
C2—N2—C3	111.2 (2)	N2—C3—C4	110.5 (2)
C2—N2—H3	109.1	N2—C3—H3B	109.6
C3—N2—H3	108.6	C4—C3—H3B	109.1
C2—N2—H2	109.7	N2—C3—H3A	109.4
C3—N2—H2	108.7	C4—C3—H3A	108.9
H3—N2—H2	109.5	H3B—C3—H3A	109.5
C4—N1—C1	110.2 (2)	N1—C4—C3	111.8 (2)
C4—N1—C5	110.6 (2)	N1—C4—H4A	108.6
C1—N1—C5	111.6 (2)	C3—C4—H4A	108.4
C4—N1—H1	108.1	N1—C4—H4B	109.5
C1—N1—H1	108.1	C3—C4—H4B	109.1
C5—N1—H1	108.1	H4A—C4—H4B	109.5
N1—C1—C2	110.8 (2)	N1—C5—H5A	113.4
N1—C1—H1A	108.8	N1—C5—H5B	109.4
C2—C1—H1A	110.0	H5A—C5—H5B	107.6
N1—C1—H1B	108.7	N1—C5—H5C	109.3
C2—C1—H1B	109.0	H5A—C5—H5C	107.6
H1A—C1—H1B	109.5	H5B—C5—H5C	109.5

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···Cl4i	0.91	2.31	3.189 (2)	164.
N2—H3···Cl3ii	0.96	2.57	3.353 (2)	139.
N2—H3···Cl2ii	0.96	2.69	3.259 (2)	119.
O—HW1···Cl3	0.96	2.33	3.2692 (12)	167.
N2—H2···O	0.96	1.95	2.908 (3)	174.

Table 1

Selected bond lengths (Å)

Zn—Cl1	2.2449 (8)
Zn—Cl2	2.2614 (7)
Zn—Cl4	2.2615 (8)
Zn—Cl3	2.3004 (7)

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯Cl4i	0.91	2.31	3.189 (2)	164
N2—H3⋯Cl3ii	0.96	2.57	3.353 (2)	139
N2—H3⋯Cl2ii	0.96	2.69	3.259 (2)	119
O—HW1⋯Cl3	0.96	2.33	3.2692 (12)	167
N2—H2⋯O	0.96	1.95	2.908 (3)	174

Symmetry codes: (i) ; (ii) .