Poly[piperazine-1,4-diium [μ4-chlorido-μ3-chlorido-tri-μ2-chlorido-chloridodicadmate(II)] monohydrate]

Adib, M.; El Glaoui, M.; Pereira da Silva, P.S.; Ramos Silva, M.; Ben Nasr, C.

doi:10.1107/S1600536812001626

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 2| February 2012| Page m175

doi:10.1107/S1600536812001626

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Poly[piperazine-1,4-diium [μ₄-chlorido-μ₃-chlorido-tri-μ₂-chlorido-chloridodicadmate(II)] monohydrate]

Marwa Adib,^a Meher El Glaoui,^a Pedro Sidonio Pereira da Silva,^b Manuela Ramos Silva ^b and Cherif Ben Nasr ^a ^*

^aLaboratoire de Chimie des Matériaux, Faculté des Sciences de Bizerte, 7021 Zarzouna, Tunisia, and ^bCEMDRX, Physics Department, University of Coimbra, P-3004-516 Coimbra, Portugal
^*Correspondence e-mail: cherif_bennasr@yahoo.fr

(Received 29 December 2011; accepted 13 January 2012; online 21 January 2012)

In the title compound, {(C₅H₁₄N₂)[Cd₂Cl₆]·H₂O}_n, the asymmetric unit contains one piperazinediium cation, one [Cd₂Cl₆]²⁻ anion and a water molecule. The coordination geometries of the two Cd²⁺ cations are distorted octahedral. Adjacent Cd^II atoms are interconnected alternately by paired chloride bridges, generating polymeric chains parallel to [010]. Neighbouring chains are connected by O—H⋯Cl hydrogen bonds involving the water molecules, forming layers at z = n/2. The crystal packing is further stabilized by intermolecular N—H⋯Cl and N—H⋯O hydrogen bonds, one of which is bifurcated.

Related literature

For general background to polymeric chloridocadmate(II) materials, see: Corradi et al. (1997 ). For the geometry around the Cd^II ion, see: Corradi et al. (1997, 1998 ); Xia et al. (2005 ); Jian et al. (2006 ); Partin & O Keeffe (1991 ). For Cd—Cl bond lengths, see: El Glaoui et al. (2010 ). For geometrical features of the organic cation, see: Yin & Wu (2010 ).

Experimental

Crystal data

(C₅H₁₄N₂)[Cd₂Cl₆]·H₂O
M_r = 557.70
Monoclinic, P 2₁ /c
a = 12.1907 (3) Å
b = 6.8088 (2) Å
c = 21.4590 (5) Å
β = 120.521 (1)°
V = 1534.39 (7) Å³
Z = 4
Mo Kα radiation
μ = 3.80 mm⁻¹
T = 293 K
0.40 × 0.27 × 0.16 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2003 ) T_min = 0.411, T_max = 0.545
22206 measured reflections
3688 independent reflections
3449 reflections with I > 2σ(I)
R_int = 0.031

Refinement

R[F² > 2σ(F²)] = 0.018
wR(F²) = 0.045
S = 1.12
3688 reflections
154 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.48 e Å⁻³
Δρ_min = −0.73 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯Cl3ⁱ	0.90	2.32	3.0819 (17)	143
N1—H1B⋯Cl2	0.90	2.35	3.2451 (16)	171
N4—H4A⋯Cl6ⁱⁱ	0.90	2.44	3.1614 (17)	138
N4—H4A⋯O1Wⁱⁱⁱ	0.90	2.45	3.131 (2)	133
N4—H4B⋯O1W^iv	0.90	1.90	2.791 (2)	171
O1W—H1W⋯Cl6^v	0.83 (4)	2.40 (4)	3.2140 (19)	166 (3)
O1W—H2W⋯Cl1^vi	0.84 (4)	2.68 (4)	3.503 (2)	168 (3)
Symmetry codes: (i) x, y-1, z; (ii) $[x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (iii) $[x+1, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (iv) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (v) -x+1, -y+1, -z; (vi) x-1, y, z.

Data collection: APEX2 (Bruker, 2003 ); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT; 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: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812001626/lr2045sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812001626/lr2045Isup2.hkl

checkCIF report

Comment top

Polymeric chlorocadmates(II) represent a class of materials with chlorine atoms as ligands, connecting neighboring cadmium atoms, thus forming one or two- dimensional arrangements. One-dimensionality of metal chains allows easier modeling of physical properties and structure property correlations (Corradi et al., 1997). In these compounds, the cadmium(II) cations exhibits a variety of coordination geometries and coordination numbers. However, it is worth to note that octahedral coordination of Cd^II is essentially present only in polymeric chlorocadmates(II), although a variety of stoichiometries are possible. The CdCl₆ octahedra can form chains by face, edge, or vertex sharing [Corradi et al., 1997; Xia et al., 2005; Corradi et al., 1998; Jian et al., 2006). As a contribution to the investigation of the above materials, we report here the crystal structure of one such compound, Cd₂Cl₆C₅H₁₄N₂H₂O (I), formed from the reaction of piperazine, hydrochloride acid and cadmium chloride. The asymmetric unit of the title material contains one piperazinedium cation, one Cd₂Cl₆^2- anion and a water molecule (Fig. 1). Within Cd₂Cl₆ moiety, each Cd^II cations is coordinated by six chlorine atoms forming a distorted octahedron. Packing of Cd₂Cl₆C₅H₁₄N₂H₂O (Fig.2) shows that adjacent Cd ions are interconnected alternatively by paired chloride bridges to generate an infinite one-dimensional coordination chain crystallographic b axis. The closest Cd—Cd distance within the chain is 3.979 (1) A° is fairly close to the one determined in the one-dimensional chain of slightly distorted edge-charing octahedral(Partin & O Keeffe, 1991). These chains, situated at (1/2, 0, 0) and (1/2, 0, 1/2), are interconnected by the water molecules via O—H···Cl hydrogen bonds to form layers extending along the (a, c) plane at z = n/2 (Fig. 3). In the Cd₂Cl₆ entities, the Cd—Cl distances in the octahedra range between 2.4852 (5) and 2.9415 (5) A°. Cd—Cl distances of edge sharing chlorine atoms are 2.5449 (5) (Cd1—Cl4), 2.7148 (4) (Cd1—Cl5ⁱ), 2.6007 (5) (Cd2—Cl4) and 2.7293 (4) (Cd2—Cl5ⁱ) A° (symmetry codes in Table 1). The Cd—Cl—Cd bridges can thus be regarded as dissymmetric. These distances are longer than the terminal Cd—Cl ones 2.4852 (5) (Cd1—Cl3) and 2.51989 (5) (Cd2—Cl6) A°, which is typical of six coordinated Cd^II (El Glaoui et al., 2010).. The Cl—Cd—Cl bond angles average close to 90.0° and range between 81.82 (1)° (for Cl2—Cd1—Cl5) and Cl3—Cd1—Cl4 97.18 (2)°, again confirming the close to octahedral nature of the CdCl₆ building units. Overwise, owing to the obvious differences of Cd—Cl distances and Cl—Cd—Cl angles in Cd₂Cl₆C₅H₁₄N₂H₂O, the coordination geometry around the Cd atoms could be regarded as slightly distorted octahedron. The piperazinedium cations are anchored onto successive layers through N—H···Cl and N—H···O hydrogen bonds. The piperazinedium ring adopts a typical chair conformation and all the geometrical features agree with those found in the salt containing the same cation, 2-methylpiperazinediium tetrachlorozincate(II) (Yin & Wu, 2010). In this structure, the anionic and organic entities and the water molecules are connected through intricate O—H···Cl, N—H···Cl and N—H···O hydrogen bonding interactions, with one of these being three-center interactions, viz. N4—H4A···(Cl6^iv, O1W^v) (Fig. 3, details and symmetry codes in Table 1). It is worth noticing that the chlorine atoms Cl4 and Cl5 of the Cd₂Cl₆ are not involved in hydrogen bonding, while all hydrogen atoms that are attached to N1 and N4 nitrogen atoms are involved in hydrogen bondings.

Related literature top

For general background to polymeric chlorocadmate(II) materials, see: Corradi et al. (1997). For the geometry around the Cd^II ion, see: Corradi et al. (1997, 1998); Xia et al. (2005); Jian et al. (2006); Partin & O Keeffe (1991). For Cd—Cl bond lengths, see: El Glaoui et al. (2010). For geometrical features of the organic cation, see: Yin & Wu (2010).

Experimental top

A mixture of an aqueous solution of 2-methylpiperazine (3 mmol, 0.300 g), cadmium chloride (1.5 mmol, 0.275 g) and HCl (10 ml, 0.3 M) in a Petri dish was slowly evaporated at room temperature. Colorless single crystals of the title compound were isolated after several days (yield 63%).

Computing details top

Data collection: APEX2 (Bruker, 2003); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT (Bruker, 2003); 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: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. A view of (I) showing 50% probability displacement ellipsoids.
	Fig. 2. A view of the crystal structure of (I) showing the layer organization between Cd₂Cl₆^2- anion and H₂O molecules. Dotted lines show intermolecular hydrogen bonding.
	Fig. 3. Packing diagram of the compound viewed down the b axis. Hydrogen bonds are shown as dashed lines.

Poly[piperazine-1,4-diium [µ₄-chlorido-µ₃-chlorido-tri-µ₂-chlorido-chloridodicadmate(II)] monohydrate] top

Crystal data top

(C₅H₁₄N₂)[Cd₂Cl₆]·H₂O	F(000) = 1064
M_r = 557.70	D_x = 2.414 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 8164 reflections
a = 12.1907 (3) Å	θ = 2.7–28.0°
b = 6.8088 (2) Å	µ = 3.80 mm⁻¹
c = 21.4590 (5) Å	T = 293 K
β = 120.521 (1)°	Block, colourless
V = 1534.39 (7) Å³	0.40 × 0.27 × 0.16 mm
Z = 4

Data collection top

Bruker APEXII CCD area-detector diffractometer	3688 independent reflections
Radiation source: fine-focus sealed tube	3449 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.031
ϕ and ω scans	θ_max = 28.0°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −16→15
T_min = 0.411, T_max = 0.545	k = −8→8
22206 measured reflections	l = −28→26

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.018	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.045	H atoms treated by a mixture of independent and constrained refinement
S = 1.12	w = 1/[σ²(F_o²) + (0.0198P)² + 0.7665P] where P = (F_o² + 2F_c²)/3
3688 reflections	(Δ/σ)_max = 0.001
154 parameters	Δρ_max = 0.48 e Å⁻³
0 restraints	Δρ_min = −0.73 e Å⁻³

Crystal data top

(C₅H₁₄N₂)[Cd₂Cl₆]·H₂O	V = 1534.39 (7) Å³
M_r = 557.70	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 12.1907 (3) Å	µ = 3.80 mm⁻¹
b = 6.8088 (2) Å	T = 293 K
c = 21.4590 (5) Å	0.40 × 0.27 × 0.16 mm
β = 120.521 (1)°

Data collection top

Bruker APEXII CCD area-detector diffractometer	3688 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	3449 reflections with I > 2σ(I)
T_min = 0.411, T_max = 0.545	R_int = 0.031
22206 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.018	0 restraints
wR(F²) = 0.045	H atoms treated by a mixture of independent and constrained refinement
S = 1.12	Δρ_max = 0.48 e Å⁻³
3688 reflections	Δρ_min = −0.73 e Å⁻³
154 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
Cd1	0.676903 (13)	0.40204 (2)	0.082720 (7)	0.02594 (5)
Cd2	0.646100 (13)	0.89968 (2)	−0.019721 (7)	0.02546 (5)
Cl1	0.80264 (5)	0.07606 (7)	0.09737 (2)	0.02919 (10)
Cl2	0.54286 (4)	0.25219 (7)	0.13506 (2)	0.02547 (9)
Cl3	0.82700 (4)	0.53623 (8)	0.20479 (3)	0.03199 (10)
Cl4	0.77287 (5)	0.57158 (7)	0.01573 (3)	0.02863 (10)
Cl5	0.48547 (4)	0.24642 (7)	−0.04173 (2)	0.02682 (10)
Cl6	0.74505 (5)	1.02346 (7)	−0.09068 (3)	0.03096 (10)
N1	0.76370 (15)	−0.0550 (2)	0.23986 (8)	0.0255 (3)
H1A	0.7654	−0.1453	0.2097	0.031*
H1B	0.7095	0.0407	0.2127	0.031*
N4	0.85051 (16)	0.0786 (2)	0.38410 (8)	0.0302 (4)
H4A	0.8507	0.1670	0.4153	0.036*
H4B	0.9034	−0.0199	0.4100	0.036*
C2	0.71565 (17)	−0.1493 (3)	0.28474 (9)	0.0236 (4)
H2	0.7724	−0.2584	0.3119	0.028*
C3	0.71971 (18)	0.0001 (3)	0.33791 (10)	0.0282 (4)
H3A	0.6620	0.1072	0.3117	0.034*
H3B	0.6914	−0.0607	0.3682	0.034*
C5	0.8968 (2)	0.1733 (3)	0.33924 (11)	0.0343 (4)
H5A	0.9834	0.2194	0.3702	0.041*
H5B	0.8438	0.2859	0.3143	0.041*
C6	0.89316 (18)	0.0298 (3)	0.28479 (11)	0.0320 (4)
H6A	0.9178	0.0961	0.2538	0.038*
H6B	0.9537	−0.0750	0.3099	0.038*
C7	0.58312 (19)	−0.2299 (3)	0.23657 (11)	0.0341 (4)
H7A	0.5273	−0.1255	0.2079	0.051*
H7B	0.5525	−0.2864	0.2659	0.051*
H7C	0.5853	−0.3288	0.2053	0.051*
O1W	0.00855 (17)	0.2486 (3)	0.04060 (10)	0.0431 (4)
H1W	0.063 (4)	0.162 (6)	0.0509 (19)	0.090 (13)*
H2W	−0.046 (3)	0.197 (5)	0.0481 (18)	0.080 (11)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cd1	0.02794 (8)	0.02668 (8)	0.02527 (8)	−0.00503 (5)	0.01503 (6)	−0.00082 (5)
Cd2	0.02605 (8)	0.02669 (8)	0.02454 (8)	−0.00547 (5)	0.01350 (6)	−0.00232 (5)
Cl1	0.0319 (2)	0.0269 (2)	0.0251 (2)	0.00093 (18)	0.01181 (19)	−0.00354 (17)
Cl2	0.0243 (2)	0.0304 (2)	0.02289 (19)	−0.00335 (17)	0.01289 (17)	0.00013 (17)
Cl3	0.0277 (2)	0.0360 (3)	0.0297 (2)	0.00006 (19)	0.01262 (19)	−0.0073 (2)
Cl4	0.0334 (2)	0.0273 (2)	0.0313 (2)	0.00249 (18)	0.0209 (2)	0.00483 (18)
Cl5	0.0293 (2)	0.0287 (2)	0.0237 (2)	−0.00274 (18)	0.01440 (18)	−0.00028 (17)
Cl6	0.0367 (2)	0.0281 (2)	0.0349 (2)	−0.00504 (19)	0.0231 (2)	0.00181 (19)
N1	0.0279 (8)	0.0309 (8)	0.0210 (7)	0.0022 (6)	0.0148 (6)	0.0015 (6)
N4	0.0374 (9)	0.0261 (9)	0.0221 (7)	0.0039 (7)	0.0115 (7)	−0.0021 (6)
C2	0.0262 (9)	0.0252 (9)	0.0212 (8)	0.0008 (7)	0.0135 (7)	0.0034 (7)
C3	0.0312 (10)	0.0327 (11)	0.0248 (9)	0.0028 (8)	0.0172 (8)	−0.0002 (8)
C5	0.0325 (10)	0.0302 (11)	0.0348 (10)	−0.0052 (9)	0.0131 (9)	0.0006 (9)
C6	0.0248 (9)	0.0397 (12)	0.0337 (10)	−0.0003 (8)	0.0164 (8)	0.0035 (9)
C7	0.0307 (10)	0.0410 (12)	0.0302 (10)	−0.0071 (9)	0.0151 (8)	−0.0030 (9)
O1W	0.0328 (9)	0.0374 (10)	0.0524 (10)	−0.0048 (7)	0.0167 (8)	−0.0072 (8)

Geometric parameters (Å, º) top

Cd1—Cl3	2.4852 (5)	N1—H1B	0.9000
Cd1—Cl4	2.5449 (5)	N4—C5	1.488 (3)
Cd1—Cl2	2.6147 (4)	N4—C3	1.485 (2)
Cd1—Cl1	2.6239 (5)	N4—H4A	0.9000
Cd1—Cl5	2.7148 (4)	N4—H4B	0.9000
Cd1—Cl5ⁱ	2.9415 (5)	C2—C7	1.511 (3)
Cd2—Cl6	2.5198 (5)	C2—C3	1.510 (3)
Cd2—Cl1ⁱⁱ	2.5548 (5)	C2—H2	0.9800
Cd2—Cl2ⁱ	2.5905 (4)	C3—H3A	0.9700
Cd2—Cl4	2.6007 (5)	C3—H3B	0.9700
Cd2—Cl5ⁱ	2.7293 (4)	C5—C6	1.506 (3)
Cd2—Cl5ⁱⁱ	2.9483 (5)	C5—H5A	0.9700
Cl1—Cd2ⁱⁱⁱ	2.5549 (5)	C5—H5B	0.9700
Cl2—Cd2ⁱ	2.5904 (4)	C6—H6A	0.9700
Cl5—Cd2ⁱ	2.7293 (4)	C6—H6B	0.9700
Cl5—Cd1ⁱ	2.9415 (5)	C7—H7A	0.9600
Cl5—Cd2ⁱⁱⁱ	2.9482 (5)	C7—H7B	0.9600
N1—C6	1.486 (2)	C7—H7C	0.9600
N1—C2	1.502 (2)	O1W—H1W	0.83 (4)
N1—H1A	0.9000	O1W—H2W	0.84 (4)

Cl3—Cd1—Cl4	97.183 (17)	C2—N1—H1A	109.1
Cl3—Cd1—Cl2	88.677 (16)	C6—N1—H1B	109.1
Cl4—Cd1—Cl2	170.588 (16)	C2—N1—H1B	109.1
Cl3—Cd1—Cl1	96.435 (16)	H1A—N1—H1B	107.8
Cl4—Cd1—Cl1	92.478 (16)	C5—N4—C3	110.85 (14)
Cl2—Cd1—Cl1	94.181 (16)	C5—N4—H4A	109.5
Cl3—Cd1—Cl5	170.147 (15)	C3—N4—H4A	109.5
Cl4—Cd1—Cl5	91.920 (15)	C5—N4—H4B	109.5
Cl2—Cd1—Cl5	81.819 (14)	C3—N4—H4B	109.5
Cl1—Cd1—Cl5	86.892 (14)	H4A—N4—H4B	108.1
Cl3—Cd1—Cl5ⁱ	92.263 (15)	N1—C2—C7	110.25 (14)
Cl4—Cd1—Cl5ⁱ	83.946 (14)	N1—C2—C3	108.81 (15)
Cl2—Cd1—Cl5ⁱ	88.486 (14)	C7—C2—C3	112.00 (16)
Cl1—Cd1—Cl5ⁱ	170.954 (14)	N1—C2—H2	108.6
Cl5—Cd1—Cl5ⁱ	84.932 (14)	C7—C2—H2	108.6
Cl6—Cd2—Cl1ⁱⁱ	95.130 (16)	C3—C2—H2	108.6
Cl6—Cd2—Cl2ⁱ	91.288 (15)	N4—C3—C2	111.02 (15)
Cl1ⁱⁱ—Cd2—Cl2ⁱ	170.043 (16)	N4—C3—H3A	109.4
Cl6—Cd2—Cl4	93.917 (16)	C2—C3—H3A	109.4
Cl1ⁱⁱ—Cd2—Cl4	94.589 (16)	N4—C3—H3B	109.4
Cl2ⁱ—Cd2—Cl4	92.555 (16)	C2—C3—H3B	109.4
Cl6—Cd2—Cl5ⁱ	173.207 (15)	H3A—C3—H3B	108.0
Cl1ⁱⁱ—Cd2—Cl5ⁱ	91.424 (15)	N4—C5—C6	110.43 (17)
Cl2ⁱ—Cd2—Cl5ⁱ	81.980 (14)	N4—C5—H5A	109.6
Cl4—Cd2—Cl5ⁱ	87.324 (14)	C6—C5—H5A	109.6
Cl6—Cd2—Cl5ⁱⁱ	96.792 (15)	N4—C5—H5B	109.6
Cl1ⁱⁱ—Cd2—Cl5ⁱⁱ	83.379 (14)	C6—C5—H5B	109.6
Cl2ⁱ—Cd2—Cl5ⁱⁱ	88.316 (14)	H5A—C5—H5B	108.1
Cl4—Cd2—Cl5ⁱⁱ	169.235 (14)	N1—C6—C5	111.02 (16)
Cl5ⁱ—Cd2—Cl5ⁱⁱ	82.170 (14)	N1—C6—H6A	109.4
Cd2ⁱⁱⁱ—Cl1—Cd1	100.407 (17)	C5—C6—H6A	109.4
Cd2ⁱ—Cl2—Cd1	101.062 (15)	N1—C6—H6B	109.4
Cd1—Cl4—Cd2	100.341 (16)	C5—C6—H6B	109.4
Cd1—Cl5—Cd2ⁱ	95.136 (14)	H6A—C6—H6B	108.0
Cd1—Cl5—Cd1ⁱ	95.067 (14)	C2—C7—H7A	109.5
Cd2ⁱ—Cl5—Cd1ⁱ	88.267 (13)	C2—C7—H7B	109.5
Cd1—Cl5—Cd2ⁱⁱⁱ	89.184 (13)	H7A—C7—H7B	109.5
Cd2ⁱ—Cl5—Cd2ⁱⁱⁱ	97.829 (14)	C2—C7—H7C	109.5
Cd1ⁱ—Cl5—Cd2ⁱⁱⁱ	172.243 (17)	H7A—C7—H7C	109.5
C6—N1—C2	112.43 (14)	H7B—C7—H7C	109.5
C6—N1—H1A	109.1	H1W—O1W—H2W	105 (3)

Cl3—Cd1—Cl1—Cd2ⁱⁱⁱ	173.772 (17)	Cl1—Cd1—Cl5—Cd2ⁱ	95.163 (16)
Cl4—Cd1—Cl1—Cd2ⁱⁱⁱ	−88.710 (18)	Cl5ⁱ—Cd1—Cl5—Cd2ⁱ	−88.711 (14)
Cl2—Cd1—Cl1—Cd2ⁱⁱⁱ	84.634 (17)	Cl4—Cd1—Cl5—Cd1ⁱ	−83.748 (15)
Cl5—Cd1—Cl1—Cd2ⁱⁱⁱ	3.079 (16)	Cl2—Cd1—Cl5—Cd1ⁱ	89.194 (14)
Cl3—Cd1—Cl2—Cd2ⁱ	176.878 (18)	Cl1—Cd1—Cl5—Cd1ⁱ	−176.127 (16)
Cl1—Cd1—Cl2—Cd2ⁱ	−86.765 (17)	Cl5ⁱ—Cd1—Cl5—Cd1ⁱ	0.0
Cl5—Cd1—Cl2—Cd2ⁱ	−0.517 (14)	Cl4—Cd1—Cl5—Cd2ⁱⁱⁱ	89.754 (14)
Cl5ⁱ—Cd1—Cl2—Cd2ⁱ	84.579 (16)	Cl2—Cd1—Cl5—Cd2ⁱⁱⁱ	−97.304 (14)
Cl3—Cd1—Cl4—Cd2	−88.832 (18)	Cl1—Cd1—Cl5—Cd2ⁱⁱⁱ	−2.625 (14)
Cl1—Cd1—Cl4—Cd2	174.361 (16)	Cl5ⁱ—Cd1—Cl5—Cd2ⁱⁱⁱ	173.501 (18)
Cl5—Cd1—Cl4—Cd2	87.391 (17)	C6—N1—C2—C7	179.04 (17)
Cl5ⁱ—Cd1—Cl4—Cd2	2.695 (15)	C6—N1—C2—C3	55.8 (2)
Cl6—Cd2—Cl4—Cd1	−176.201 (16)	C5—N4—C3—C2	59.2 (2)
Cl1ⁱⁱ—Cd2—Cl4—Cd1	88.323 (18)	N1—C2—C3—N4	−57.26 (19)
Cl2ⁱ—Cd2—Cl4—Cd1	−84.734 (17)	C7—C2—C3—N4	−179.41 (16)
Cl5ⁱ—Cd2—Cl4—Cd1	−2.891 (16)	C3—N4—C5—C6	−57.2 (2)
Cl5ⁱⁱ—Cd2—Cl4—Cd1	9.69 (9)	C2—N1—C6—C5	−55.5 (2)
Cl4—Cd1—Cl5—Cd2ⁱ	−172.459 (15)	N4—C5—C6—N1	55.1 (2)
Cl2—Cd1—Cl5—Cd2ⁱ	0.484 (13)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Cl3ⁱⁱⁱ	0.90	2.32	3.0819 (17)	143
N1—H1B···Cl2	0.90	2.35	3.2451 (16)	171
N4—H4A···Cl6^iv	0.90	2.44	3.1614 (17)	138
N4—H4A···O1W^v	0.90	2.45	3.131 (2)	133
N4—H4B···O1W^vi	0.90	1.90	2.791 (2)	171
O1W—H1W···Cl6ⁱ	0.83 (4)	2.40 (4)	3.2140 (19)	166 (3)
O1W—H2W···Cl1^vii	0.84 (4)	2.68 (4)	3.503 (2)	168 (3)

Symmetry codes: (i) −x+1, −y+1, −z; (iii) x, y−1, z; (iv) x, −y+3/2, z+1/2; (v) x+1, −y+1/2, z+1/2; (vi) −x+1, y−1/2, −z+1/2; (vii) x−1, y, z.

Experimental details

Crystal data
Chemical formula	(C₅H₁₄N₂)[Cd₂Cl₆]·H₂O
M_r	557.70
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	12.1907 (3), 6.8088 (2), 21.4590 (5)
β (°)	120.521 (1)
V (Å³)	1534.39 (7)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	3.80
Crystal size (mm)	0.40 × 0.27 × 0.16

Data collection
Diffractometer	Bruker APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2003)
T_min, T_max	0.411, 0.545
No. of measured, independent and observed [I > 2σ(I)] reflections	22206, 3688, 3449
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.661

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.018, 0.045, 1.12
No. of reflections	3688
No. of parameters	154
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.48, −0.73

Computer programs: APEX2 (Bruker, 2003), SAINT (Bruker, 2003), 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
N1—H1A···Cl3ⁱ	0.90	2.32	3.0819 (17)	143.0
N1—H1B···Cl2	0.90	2.35	3.2451 (16)	170.9
N4—H4A···Cl6ⁱⁱ	0.90	2.44	3.1614 (17)	137.5
N4—H4A···O1Wⁱⁱⁱ	0.90	2.45	3.131 (2)	132.6
N4—H4B···O1W^iv	0.90	1.90	2.791 (2)	171.0
O1W—H1W···Cl6^v	0.83 (4)	2.40 (4)	3.2140 (19)	166 (3)
O1W—H2W···Cl1^vi	0.84 (4)	2.68 (4)	3.503 (2)	168 (3)

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

Acknowledgements

This work was supported by the Fundação para a Ciência e a Tecnologia (FCT), under scholarship SFRH/BD/38387/2008.

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