Piperazinediium tetra­chloridocadmate monohydrate

El Glaoui, M.; Ben Gharbia, I.; Ferretti, V.; Ben Nasr, C.

doi:10.1107/S1600536811005095

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 3| March 2011| Page m340

doi:10.1107/S1600536811005095

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Piperazinediium tetrachloridocadmate monohydrate

Meher El Glaoui,^a Imen Ben Gharbia,^a Valeria Ferretti ^b and Cherif Ben Nasr ^a ^*

^aLaboratoire de Chimie des Matériaux, Faculté des Sciences de Bizerte, 7021 Zarzouna, Tunisia, and ^bChemistry Department and Centro di Strutturistica Diffrattometrica, University of Ferrara, Via L. Borsari 46, I-44121 FerrarA, Italy
^*Correspondence e-mail: cherif_bennasr@yahoo.fr

(Received 1 February 2011; accepted 10 February 2011; online 16 February 2011)

In the title compound, (C₄H₁₂N₂)[CdCl₄]·H₂O, the [CdCl₄]²⁻ anions adopt a slightly distorted tetrahedral configuration. In the crystal, O—H⋯Cl hydrogen bonds link the anions and water molecules into corrugated inorganic chains along the b axis which are interconnected via piperazinediiumN—H⋯O and N—H⋯Cl interactions into a three-dimensional framework structure.

Related literature

For common applications of organic–inorganic hybrid materials, see: Kobel & Hanack (1986 ); Pierpont & Jung (1994 ). For a related structure and discussion of geometrical features, see: Sutherland & Harrison (2009 ). For the coordination around the Cd^II cation, see: El Glaoui et al. (2009 ).

Experimental

Crystal data

(C₄H₁₂N₂)[CdCl₄]·H₂O
M_r = 360.38
Monoclinic, P 2₁ /c
a = 6.6204 (2) Å
b = 12.8772 (3) Å
c = 14.0961 (4) Å
β = 92.1710 (12)°
V = 1200.86 (6) Å³
Z = 4
Mo Kα radiation
μ = 2.67 mm⁻¹
T = 295 K
0.52 × 0.48 × 0.30 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: multi-scan (SORTAV; Blessing, 1995 ) T_min = 0.374, T_max = 0.444
8531 measured reflections
3461 independent reflections
2903 reflections with I > 2σ(I)
R_int = 0.037

Refinement

R[F² > 2σ(F²)] = 0.033
wR(F²) = 0.081
S = 1.09
3461 reflections
126 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.78 e Å⁻³
Δρ_min = −1.75 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯Cl1ⁱ	0.93 (3)	2.35 (3)	3.254 (2)	164 (3)
N1—H2⋯Cl3	0.89 (3)	2.41 (4)	3.155 (2)	141 (3)
N2—H3⋯O1W	0.89 (3)	1.93 (3)	2.808 (3)	167 (3)
N2—H4⋯Cl4ⁱⁱ	0.81 (3)	2.46 (3)	3.190 (2)	151 (3)
O1W—H1W⋯Cl2ⁱⁱⁱ	0.84	2.44	3.267 (3)	168
O1W—H2W⋯Cl4^iv	0.85	2.54	3.304 (2)	150
Symmetry codes: (i) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[x+1, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (iii) -x, -y, -z+1; (iv) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: Kappa-CCD Server Software (Nonius, 1997 ); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997 ); data reduction: DENZO-SMN; program(s) used to solve structure: SIR97 (Altomare et al., 1999 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: ORTEPIII (Burnett & Johnson, 1996 ); software used to prepare material for publication: SHELXL97 and WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811005095/zs2095sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811005095/zs2095Isup2.hkl

checkCIF report

Comment top

Organic-inorganic hybrid materials continue to attract much attention due to their potential applications in various field (Kobel & Hanack, 1986; Pierpont & Jung, 1994). In this work, we report the crystal structure of one such compound, C₄H₁₂N₂ [CdCl₄] . H₂O (I), formed from the reaction of piperazine with cadmium chloride. In (I) the asymmetric unit comprises a piperazine-1,4-diium dication, a [CdCl₄]^2- anion and a water molecule of solvation (Fig. 1). The atomic arrangement of (I) can be described as built up of corrugated inorganic chains of [CdCl₄]^2- tetrahedra and water molecules held together by O—H···Cl hydrogen bonds and extending along the b direction of the unit cell. These chains are interconnected by a set of piperazinium N—H···Cl hydrogen bonds to form layers extending along the (1 1 O) planes (Fig. 2, Table 1). Fig 3 shows that two such layers cross the unit cell at z = 1/4 and z = 3/4 and the bodies of the organic groups are located between these layers and connect them by weak C—H···Cl hydrogen bonds [C···Cl, 3.535 (3) Å], giving a three-dimensional framework structure. In the organic entity, the piperazium ring adopts a typical chair conformation and all the geometrical features agree with those found in piperazindiium tetrachlorozincate(II) (Sutherland & Harrison, 2009). It is worth noting that in the anion of (I), the Cd—Cl bond lengths and Cl—Cd—Cl bond angles are not equal, but vary with the environment around the Cl atom. The Cd—Cl bond lengths vary between 2.4418 (6) and 2.4892 (7) Å and the Cl—Cd—Cl angles range from 103.07 (2) to 115.19 (2) °. These values are in good agreement with those reported previously, clearly indicating that the [CdCl₄]^2- anion has a slightly distorted tetrahedral stereochemistry (El Glaoui et al. (2009).

Related literature top

For common applications of organic–inorganic hybrid materials, see: Kobel & Hanack (1986); Pierpont & Jung (1994). For a related structure and discussion of geometrical features, see: Sutherland & Harrison (2009). For the coordination around the Cd^II cation, see: El Glaoui et al. (2009).

Experimental top

An aqueous solution of piperazine (4 mmol, 0.344 g), cadmium chloride (4 mmol, 0.732 g) and HCl (10 ml, 0.8 M) in a Petri dish was slowly evaporated at room temperature. Single crystals of the title compound, suitable for X-ray diffraction analysis, were obtained after several days (yield 68%).

Computing details top

Data collection: Kappa-CCD Server Software (Nonius, 1997); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and WinGX (Farrugia, 1999).

Figures top

	Fig. 1. A view of the title compound, showing 50% probability displacement ellipsoids and the atom numbering scheme. Dashed lines indicate N—H···O and N—H···Cl hydrogen bonds.
	Fig. 2. A projection along the c axis of the inorganic layer structure at z = 1/4.
	Fig. 3. The packing of the title compound viewed down the a axis. Hydrogen bonds are shown as dotted lines.

Piperazinediium tetrachloridocadmate monohydrate top

Crystal data top

(C₄H₁₂N₂)[CdCl₄]·H₂O	F(000) = 704
M_r = 360.38	D_x = 1.993 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 8531 reflections
a = 6.6204 (2) Å	θ = 2.0–30.0°
b = 12.8772 (3) Å	µ = 2.67 mm⁻¹
c = 14.0961 (4) Å	T = 295 K
β = 92.1710 (12)°	Prismatic, colourless
V = 1200.86 (6) Å³	0.52 × 0.48 × 0.30 mm
Z = 4

Data collection top

Nonius KappaCCD diffractometer	3461 independent reflections
Radiation source: fine-focus sealed tube	2903 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.037
ϕ scans and ω scans	θ_max = 30.0°, θ_min = 3.1°
Absorption correction: multi-scan (SORTAV; Blessing, 1995)	h = −9→9
T_min = 0.374, T_max = 0.444	k = −17→17
8531 measured reflections	l = −19→19

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F² > 2σ(F²)] = 0.033	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.081	w = 1/[σ²(F_o²) + (0.0389P)² + 0.4362P] where P = (F_o² + 2F_c²)/3
S = 1.09	(Δ/σ)_max < 0.001
3461 reflections	Δρ_max = 0.78 e Å⁻³
126 parameters	Δρ_min = −1.75 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: 0.0778 (19)

Crystal data top

(C₄H₁₂N₂)[CdCl₄]·H₂O	V = 1200.86 (6) Å³
M_r = 360.38	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 6.6204 (2) Å	µ = 2.67 mm⁻¹
b = 12.8772 (3) Å	T = 295 K
c = 14.0961 (4) Å	0.52 × 0.48 × 0.30 mm
β = 92.1710 (12)°

Data collection top

Nonius KappaCCD diffractometer	3461 independent reflections
Absorption correction: multi-scan (SORTAV; Blessing, 1995)	2903 reflections with I > 2σ(I)
T_min = 0.374, T_max = 0.444	R_int = 0.037
8531 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.033	0 restraints
wR(F²) = 0.081	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	Δρ_max = 0.78 e Å⁻³
3461 reflections	Δρ_min = −1.75 e Å⁻³
126 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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
Cd1	0.02921 (3)	−0.001890 (11)	0.235463 (13)	0.03178 (9)
Cl1	0.07520 (10)	−0.19208 (5)	0.22725 (4)	0.03972 (16)
Cl2	−0.34472 (9)	0.01950 (5)	0.22883 (5)	0.03628 (15)
Cl3	0.17473 (9)	0.05843 (5)	0.38740 (5)	0.03822 (15)
Cl4	0.13421 (9)	0.09489 (5)	0.09660 (5)	0.03906 (16)
N1	0.5582 (3)	0.20385 (16)	0.38723 (15)	0.0312 (4)
N2	0.7142 (3)	0.28658 (16)	0.56419 (15)	0.0321 (4)
C1	0.4546 (4)	0.29108 (19)	0.43473 (18)	0.0358 (5)
H5	0.3509	0.2636	0.4746	0.043*
H6	0.3897	0.3355	0.3871	0.043*
C2	0.6036 (4)	0.35402 (17)	0.49466 (17)	0.0343 (5)
H7	0.6991	0.3875	0.4540	0.041*
H8	0.5322	0.4077	0.5281	0.041*
C3	0.8195 (4)	0.20021 (19)	0.51588 (18)	0.0345 (5)
H9	0.8879	0.1564	0.5629	0.041*
H10	0.9203	0.2285	0.4749	0.041*
C4	0.6703 (4)	0.13687 (17)	0.45821 (17)	0.0318 (5)
H11	0.5752	0.1046	0.4998	0.038*
H12	0.7406	0.0822	0.4255	0.038*
O1W	0.4133 (3)	0.2110 (2)	0.68116 (18)	0.0644 (7)
H1	0.646 (5)	0.232 (2)	0.344 (2)	0.038 (8)*
H2	0.461 (5)	0.168 (3)	0.357 (2)	0.053 (9)*
H3	0.632 (5)	0.255 (2)	0.604 (2)	0.040 (8)*
H4	0.803 (5)	0.319 (2)	0.592 (2)	0.041 (8)*
H1W	0.3888	0.1492	0.6962	0.080*
H2W	0.3114	0.2506	0.6752	0.080*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cd1	0.03183 (12)	0.03025 (13)	0.03330 (13)	0.00147 (6)	0.00181 (8)	0.00206 (6)
Cl1	0.0483 (4)	0.0303 (3)	0.0411 (3)	0.0064 (2)	0.0091 (3)	−0.0011 (2)
Cl2	0.0298 (3)	0.0379 (3)	0.0412 (3)	0.0020 (2)	0.0026 (2)	−0.0031 (2)
Cl3	0.0358 (3)	0.0386 (3)	0.0400 (3)	−0.0045 (2)	−0.0036 (2)	−0.0027 (2)
Cl4	0.0327 (3)	0.0419 (3)	0.0433 (3)	0.0050 (2)	0.0105 (2)	0.0109 (3)
N1	0.0336 (11)	0.0330 (10)	0.0270 (10)	−0.0009 (8)	0.0001 (8)	−0.0034 (8)
N2	0.0328 (11)	0.0316 (10)	0.0320 (10)	−0.0065 (8)	0.0030 (8)	−0.0065 (8)
C1	0.0362 (13)	0.0354 (12)	0.0361 (13)	0.0073 (10)	0.0022 (10)	0.0015 (10)
C2	0.0417 (14)	0.0238 (10)	0.0381 (13)	−0.0017 (9)	0.0097 (10)	−0.0025 (9)
C3	0.0304 (12)	0.0330 (11)	0.0397 (13)	0.0019 (9)	−0.0031 (10)	−0.0061 (10)
C4	0.0366 (12)	0.0252 (10)	0.0333 (12)	0.0016 (9)	−0.0009 (9)	−0.0026 (9)
O1W	0.0435 (13)	0.0692 (14)	0.0818 (18)	0.0050 (11)	0.0183 (12)	0.0334 (13)

Geometric parameters (Å, º) top

Cd1—Cl3	2.4418 (6)	C1—C2	1.510 (4)
Cd1—Cl4	2.4435 (6)	C1—H5	0.9700
Cd1—Cl1	2.4712 (6)	C1—H6	0.9700
Cd1—Cl2	2.4891 (7)	C2—H7	0.9700
N1—C1	1.488 (3)	C2—H8	0.9700
N1—C4	1.497 (3)	C3—C4	1.497 (3)
N1—H1	0.93 (3)	C3—H9	0.9700
N1—H2	0.89 (3)	C3—H10	0.9700
N2—C2	1.482 (3)	C4—H11	0.9700
N2—C3	1.491 (3)	C4—H12	0.9700
N2—H3	0.89 (3)	O1W—H1W	0.84
N2—H4	0.81 (3)	O1W—H2W	0.85

Cl3—Cd1—Cl4	115.19 (2)	C2—C1—H6	109.5
Cl3—Cd1—Cl1	108.13 (2)	H5—C1—H6	108.1
Cl4—Cd1—Cl1	115.38 (2)	N2—C2—C1	110.57 (19)
Cl3—Cd1—Cl2	110.89 (2)	N2—C2—H7	109.5
Cl4—Cd1—Cl2	103.07 (2)	C1—C2—H7	109.5
Cl1—Cd1—Cl2	103.42 (2)	N2—C2—H8	109.5
C1—N1—C4	111.06 (18)	C1—C2—H8	109.5
C1—N1—H2	106 (2)	H7—C2—H8	108.1
C4—N1—H2	111 (2)	N2—C3—C4	110.14 (19)
C1—N1—H1	107.8 (18)	N2—C3—H9	109.6
C4—N1—H1	111.2 (19)	C4—C3—H9	109.6
H1—N1—H2	110 (3)	N2—C3—H10	109.6
C2—N2—C3	111.28 (19)	C4—C3—H10	109.6
C2—N2—H3	113 (2)	H9—C3—H10	108.1
C3—N2—H3	104.5 (18)	C3—C4—N1	110.45 (19)
C2—N2—H4	110 (2)	C3—C4—H11	109.6
C3—N2—H4	106 (2)	N1—C4—H11	109.6
H3—N2—H4	112 (3)	C3—C4—H12	109.6
N1—C1—C2	110.8 (2)	N1—C4—H12	109.6
N1—C1—H5	109.5	H11—C4—H12	108.1
C2—C1—H5	109.5	H1W—O1W—H2W	116
N1—C1—H6	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···Cl1ⁱ	0.93 (3)	2.35 (3)	3.254 (2)	164 (3)
N1—H2···Cl3	0.89 (3)	2.41 (4)	3.155 (2)	141 (3)
N2—H3···O1W	0.89 (3)	1.93 (3)	2.808 (3)	167 (3)
N2—H4···Cl4ⁱⁱ	0.81 (3)	2.46 (3)	3.190 (2)	151 (3)
O1W—H1W···Cl2ⁱⁱⁱ	0.84	2.44	3.267 (3)	168
O1W—H2W···Cl4^iv	0.85	2.54	3.304 (2)	150

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

Experimental details

Crystal data
Chemical formula	(C₄H₁₂N₂)[CdCl₄]·H₂O
M_r	360.38
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	295
a, b, c (Å)	6.6204 (2), 12.8772 (3), 14.0961 (4)
β (°)	92.1710 (12)
V (Å³)	1200.86 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	2.67
Crystal size (mm)	0.52 × 0.48 × 0.30

Data collection
Diffractometer	Nonius KappaCCD diffractometer
Absorption correction	Multi-scan (SORTAV; Blessing, 1995)
T_min, T_max	0.374, 0.444
No. of measured, independent and observed [I > 2σ(I)] reflections	8531, 3461, 2903
R_int	0.037
(sin θ/λ)_max (Å⁻¹)	0.703

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.033, 0.081, 1.09
No. of reflections	3461
No. of parameters	126
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.78, −1.75

Computer programs: Kappa-CCD Server Software (Nonius, 1997), DENZO-SMN (Otwinowski & Minor, 1997), SIR97 (Altomare et al., 1999), ORTEPIII (Burnett & Johnson, 1996), SHELXL97 (Sheldrick, 2008) and WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···Cl1ⁱ	0.93 (3)	2.35 (3)	3.254 (2)	164 (3)
N1—H2···Cl3	0.89 (3)	2.41 (4)	3.155 (2)	141 (3)
N2—H3···O1W	0.89 (3)	1.93 (3)	2.808 (3)	167 (3)
N2—H4···Cl4ⁱⁱ	0.81 (3)	2.46 (3)	3.190 (2)	151 (3)
O1W—H1W···Cl2ⁱⁱⁱ	0.84	2.44	3.267 (3)	168
O1W—H2W···Cl4^iv	0.85	2.54	3.304 (2)	150

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

Acknowledgements

We would like to acknowledge the support provided by the Secretary of State for Scientific Research and Technology of Tunisia.

References

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