Poly[piperazine-1,4-diium [μ(4)-chlorido-μ(3)-chlorido-tri-μ(2)-chlorido-chloridodicadmate(II)] monohydrate].

In the title compound, {(C(5)H(14)N(2))[Cd(2)Cl(6)]·H(2)O}(n), the asymmetric unit contains one piperazinediium cation, one [Cd(2)Cl(6)](2-) anion and a water mol-ecule. The coordination geometries of the two Cd(2+) cations are distorted octa-hedral. Adjacent Cd(II) atoms are inter-connected alternately by paired chloride bridges, generating polymeric chains parallel to [010]. Neighbouring chains are connected by O-H⋯Cl hydrogen bonds involving the water mol-ecules, forming layers at z = n/2. The crystal packing is further stabilized by inter-molecular 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 CdII 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 = 557.70

Monoclinic,

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[F 2 > 2σ(F 2)] = 0.018

wR(F 2) = 0.045

S = 1.12

3688 reflections

154 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.48 e Å−3

Δρmin = −0.73 e Å−3

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.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812001626/lr2045sup1.cif

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

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

(C5H14N2)[Cd2Cl6]·H2O	F(000) = 1064
Mr = 557.70	Dx = 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

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

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(Fo2) + (0.0198P)2 + 0.7665P] where P = (Fo2 + 2Fc2)/3
3688 reflections	(Δ/σ)max = 0.001
154 parameters	Δρmax = 0.48 e Å−3
0 restraints	Δρmin = −0.73 e Å−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
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)*

	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)

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)

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···Cl6iv	0.90	2.44	3.1614 (17)	138
N4—H4A···O1Wv	0.90	2.45	3.131 (2)	133
N4—H4B···O1Wvi	0.90	1.90	2.791 (2)	171
O1W—H1W···Cl6i	0.83 (4)	2.40 (4)	3.2140 (19)	166 (3)
O1W—H2W···Cl1vii	0.84 (4)	2.68 (4)	3.503 (2)	168 (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⋯O1Wiv	0.90	1.90	2.791 (2)	171
O1W—H1W⋯Cl6v	0.83 (4)	2.40 (4)	3.2140 (19)	166 (3)
O1W—H2W⋯Cl1vi	0.84 (4)	2.68 (4)	3.503 (2)	168 (3)

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) ; (vi) .