1-Methyl­piperazine-1,4-diium tetra­chloridozincate hemihydrate

Walha, S.; Naïli, H.; Yahyaoui, S.; Mhiri, T.

doi:10.1107/S1600536811043236

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 11| November 2011| Page m1605

doi:10.1107/S1600536811043236

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1-Methylpiperazine-1,4-diium tetrachloridozincate hemihydrate

Sondra Walha,^a Houcine Naïli,^a ^* Samia Yahyaoui ^a and Tahar Mhiri ^a

^aLaboratoire de l'Etat Solide, Département de Chimie, Faculté des Sciences de Sfax, BP 1171, 3000 Sfax, Tunisia
^*Correspondence e-mail: houcine_naili@yahoo.com

(Received 9 September 2011; accepted 18 October 2011; online 29 October 2011)

The crystal structure of the title compound, (C₅H₁₄N₂)[ZnCl₄]·0.5H₂O, is built up from discrete 1-methylpiperazinediium cations with chair conformation, tetrahedral tetrachloridozincate anions and uncoordinated solvent water molecules linked together by three types of intermolecular 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_r = 318.36
Monoclinic, C 2/c
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[F² > 2σ(F²)] = 0.050
wR(F²) = 0.080
S = 1.24
4237 reflections
115 parameters
H-atom parameters constrained
Δρ_max = 0.49 e Å⁻³
Δρ_min = −0.68 e Å⁻³

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) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) $[x, -y+1, z+{\script{1\over 2}}]$ .

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 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811043236/zq2122sup1.cif

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

checkCIF report

Comment top

Preparation of organic-inorganic hybrid materials attracts great attention in chemistry and materials sciences because of their abilities to combine the properties of organic and inorganic compounds within one single molecular scale, such as second-order nonlinear optical (NLO) response, luminescence, magnetism and even multifonctional properties (Mitzi, 2001; Pecaut et al., 1993; Lacroix et al., 1994). In connection with ongoing studies (Walha et al., 2010; Walha et al., 2011), we report here the crystal structure of a new organic-inorganic hybrid with cations and tetrachloridozincate anions.

The asymmetric unit of the title compound (Fig. 1) contains one inorganic ZnCl₄^2- anion, one organic N-methylpiperazinediium cation and one half-molecule of water, which lies on a two-fold rotation axis. The isolated molecules form organic-inorganic layers parallels to the (b,c) plane and alternate along the a axis (Fig. 2). These layers are stabilized and interconnected by three types of hydrogen bonds: N—H···Cl, N—H···O and O—H···Cl. The anion exhibits a tetrahedral geometry with the Zn^II ion surrounded by four Cl atoms with a mean Zn—Cl bond length of 2.267 (2) Å and Cl—Zn—Cl bond angles ranging from 106.24 (3) to 112.42 (3)° (Deeth et al., 1984). The ZnCl₄ tetrahedra are linked to water molecules into zig-zag chains by O—H···Cl hydrogen bonds along the c axis, as illustrated in Fig. 3. The organic species adopts a typical chair conformation with average C—C and C—N of 1.501 (4) and 1.491 (3) Å, respectively (Fowkes & Harrison, 2004). The water molecules are located above and below the layers and they connect them via hydrogen bonds. Indeed, they participate in two types of hydrogen bonds O—H···Cl and N—H···O as donor or acceptor, respectively (Table 2), playing a subordinative role in the stabilization of the crystal structure.

Related literature top

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 top

ZnCl₂ (1 mmol) and methylpiperazine dihydrochloride (1 mmol) were dissolved in water. The solution was mixed with hydrochloric acid (1 mmol) and allowed to stand. Colourless plate-shaped crystals of the title compound were formed by slow evaporation of the solvent and separated from the solution after three days.

Computing details top

Data collection: COLLECT (Nonius, 1998); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997); 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).

Figures top

	Fig. 1. The asymmetric unit of the title compound, with the non-H atoms represented by 50% probability displacement ellipsoids. H atoms are shown as spheres of arbitrary radius.
	Fig. 2. Projection of the crystal structure of the title compound along the b axis, with hydrogen bonds indicated as dashed lines.
	Fig. 3. Zig-zag chains formed by the interactions of ZnCl₄ and H₂O molecules with O—H···Cl hydrogen bonds along the c axis.

1-Methylpiperazine-1,4-diium tetrachloridozincate hemihydrate top

Crystal data top

(C₅H₁₄N₂)[ZnCl₄]·0.5H₂O	Z = 8
M_r = 318.36	F(000) = 1288
Monoclinic, C2/c	D_x = 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

Data collection top

Nonius KappaCCD diffractometer	4237 independent reflections
Radiation source: fine-focus sealed tube	2996 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.000
Detector resolution: 9 pixels mm^-1	θ_max = 32.0°, θ_min = 3.5°
CCD rotation images, thick slices scans	h = −21→20
Absorption correction: analytical (de Meulenaer & Tompa, 1965)	k = 0→19
T_min = 0.393, T_max = 0.661	l = 0→20
4237 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)] = 0.050	H-atom parameters constrained
wR(F²) = 0.080	w = 1/[σ²(F_o²) + (0.0157P)² + 3.8346P] where P = (F_o² + 2F_c²)/3
S = 1.24	(Δ/σ)_max < 0.001
4237 reflections	Δρ_max = 0.49 e Å⁻³
115 parameters	Δρ_min = −0.68 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008)
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0000

Crystal data top

(C₅H₁₄N₂)[ZnCl₄]·0.5H₂O	V = 2458.16 (14) Å³
M_r = 318.36	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 14.3210 (5) Å	µ = 2.83 mm⁻¹
b = 12.7590 (5) Å	T = 293 K
c = 13.7970 (3) Å	0.47 × 0.11 × 0.03 mm
β = 102.821 (3)°

Data collection top

Nonius KappaCCD diffractometer	4237 independent reflections
Absorption correction: analytical (de Meulenaer & Tompa, 1965)	2996 reflections with I > 2σ(I)
T_min = 0.393, T_max = 0.661	R_int = 0.000
4237 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.050	0 restraints
wR(F²) = 0.080	H-atom parameters constrained
S = 1.24	Δρ_max = 0.49 e Å⁻³
4237 reflections	Δρ_min = −0.68 e Å⁻³
115 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
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*

Atomic displacement parameters (Å²) top

	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

Geometric parameters (Å, º) top

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

Hydrogen-bond geometry (Å, º) top

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) −x+1/2, y+1/2, −z+3/2; (ii) x, −y+1, z+1/2.

Experimental details

Crystal data
Chemical formula	(C₅H₁₄N₂)[ZnCl₄]·0.5H₂O
M_r	318.36
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	293
a, b, c (Å)	14.3210 (5), 12.7590 (5), 13.7970 (3)
β (°)	102.821 (3)
V (Å³)	2458.16 (14)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	2.83
Crystal size (mm)	0.47 × 0.11 × 0.03

Data collection
Diffractometer	Nonius KappaCCD diffractometer
Absorption correction	Analytical (de Meulenaer & Tompa, 1965)
T_min, T_max	0.393, 0.661
No. of measured, independent and observed [I > 2σ(I)] reflections	4237, 4237, 2996
R_int	0.000
(sin θ/λ)_max (Å⁻¹)	0.746

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.050, 0.080, 1.24
No. of reflections	4237
No. of parameters	115
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.49, −0.68

Computer programs: COLLECT (Nonius, 1998), DENZO and SCALEPACK (Otwinowski & Minor, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 2006), WinGX (Farrugia, 1999).

Selected geometric parameters (Å, º) top

Zn—Cl1	2.2449 (8)	N1—C4	1.489 (3)
Zn—Cl2	2.2614 (7)	N1—C1	1.492 (3)
Zn—Cl4	2.2615 (8)	N1—C5	1.494 (3)
Zn—Cl3	2.3004 (7)	C1—C2	1.503 (4)
N2—C2	1.488 (4)	C3—C4	1.511 (4)
N2—C3	1.490 (4)

Cl1—Zn—Cl2	110.12 (3)	C4—N1—C1	110.2 (2)
Cl1—Zn—Cl4	112.42 (3)	C4—N1—C5	110.6 (2)
Cl2—Zn—Cl4	108.97 (3)	C1—N1—C5	111.6 (2)
Cl1—Zn—Cl3	112.33 (3)	N1—C1—C2	110.8 (2)
Cl2—Zn—Cl3	106.50 (3)	N2—C2—C1	110.2 (2)
Cl4—Zn—Cl3	106.24 (3)	N2—C3—C4	110.5 (2)
C2—N2—C3	111.2 (2)	N1—C4—C3	111.8 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···Cl4ⁱ	0.91	2.31	3.189 (2)	163.7
N2—H3···Cl3ⁱⁱ	0.96	2.57	3.353 (2)	139.1
N2—H3···Cl2ⁱⁱ	0.96	2.69	3.259 (2)	118.6
O—HW1···Cl3	0.96	2.33	3.2692 (12)	166.9
N2—H2···O	0.96	1.95	2.908 (3)	174.3

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

Acknowledgements

Grateful thanks are expressed to Dr J. Jaud (Service Rayons X, CEMES/CNRS Toulouse) for the X-ray data collection.

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