Tris(piperazine-1,4-diium) bis-[hexa-chloridoindate(III)] tetra-hydrate.

The asymmetric unit of the title compound, (C(4)H(12)N(2))(3)[InCl(6)](2)·4H(2)O, consists of one and half independent piperazinium cations, an hexa-chloridoindate anion and two mol-ecules of water. The In(III) ion is six-coordinated and forms a quasi-regular octa-hedral arrangement. In the crystal, alternating layers of cations and anions are arranged parallel to (10[Formula: see text]) and are linked with the water mol-ecules via intra- and inter-molecular N-H⋯O, O-H⋯Cl, C-H⋯O and N-H⋯Cl hydrogen bonds, forming a complex three-dimensional network. Additional stabilization within the layers is provided by weak inter-molecular C-H⋯Cl inter-actions.

Related literature

For related structures and protonated imines, see: Bouacida et al. (2005 ▶, 2007 ▶); Bouacida (2008 ▶); Murugavel et al. (2009 ▶); Polishchuk et al. (2009 ▶).

Experimental

Crystal data

(C4H12N2)3[InCl6]2·4H2O

M = 991.57

Triclinic,

a = 7.9267 (3) Å

b = 10.0940 (3) Å

c = 11.8265 (5) Å

α = 89.780 (1)°

β = 89.634 (1)°

γ = 73.087 (2)°

V = 905.31 (6) Å3

Z = 1

Mo Kα radiation

μ = 2.19 mm−1

T = 295 K

0.15 × 0.06 × 0.05 mm

Data collection

Nonius KappaCCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 2002 ▶) T min = 0.773, T max = 0.938

7414 measured reflections

4131 independent reflections

3293 reflections with I > 2σ(I)

R int = 0.024

Refinement

R[F 2 > 2σ(F 2)] = 0.030

wR(F 2) = 0.069

S = 1.09

4131 reflections

163 parameters

1 restraint

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.61 e Å−3

Δρmin = −0.75 e Å−3

Data collection: COLLECT (Hooft, 1998 ▶); cell refinement: DENZO (Otwinowski & Minor, 1997 ▶); data reduction: SCALEPACK (Otwinowski & Minor, 1997 ▶); program(s) used to solve structure: SIR2002 (Burla et al., 2003 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2009 ▶) and DIAMOND (Brandenburg et al., 2001 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811007355/pv2386sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811007355/pv2386Isup2.hkl

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

(C4H12N2)3[InCl6]2·4H2O	Z = 1
Mr = 991.57	F(000) = 492
Triclinic, P1	Dx = 1.819 Mg m−3
a = 7.9267 (3) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.0940 (3) Å	Cell parameters from 3980 reflections
c = 11.8265 (5) Å	θ = 2.9–27.5°
α = 89.780 (1)°	µ = 2.19 mm−1
β = 89.634 (1)°	T = 295 K
γ = 73.087 (2)°	Needle, colorless
V = 905.31 (6) Å3	0.15 × 0.06 × 0.05 mm

Nonius KappaCCD diffractometer	4131 independent reflections
Radiation source: Enraf Nonius FR590	3293 reflections with I > 2σ(I)
graphite	Rint = 0.024
Detector resolution: 9 pixels mm-1	θmax = 27.5°, θmin = 3.2°
CCD rotation images, thick slices scans	h = −8→10
Absorption correction: multi-scan (SADABS; Sheldrick, 2002)	k = −13→13
Tmin = 0.773, Tmax = 0.938	l = −15→15
7414 measured reflections

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)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.069	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	w = 1/[σ2(Fo2) + 0.1261P] where P = (Fo2 + 2Fc2)/3
4131 reflections	(Δ/σ)max = 0.002
163 parameters	Δρmax = 0.61 e Å−3
1 restraint	Δρmin = −0.75 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
C1A	0.7212 (4)	0.9420 (3)	0.1784 (3)	0.0419 (7)
H11A	0.7106	0.9799	0.1024	0.05*
H12A	0.6401	0.8867	0.186	0.05*
C1B	0.5638 (4)	0.5134 (3)	0.1119 (3)	0.04
H11B	0.61	0.5657	0.166	0.048*
H12B	0.5554	0.4295	0.1488	0.048*
C2A	0.9056 (4)	0.8527 (3)	0.1970 (3)	0.0403 (7)
H21A	0.932	0.7756	0.1446	0.048*
H22A	0.9873	0.906	0.182	0.048*
C2B	0.3830 (4)	0.5984 (3)	0.0742 (3)	0.0400 (7)
H21B	0.3032	0.6173	0.1386	0.048*
H22B	0.3895	0.6862	0.0438	0.048*
C4A	0.8812 (4)	0.9141 (3)	0.3988 (3)	0.0415 (7)
H41A	0.9621	0.9697	0.3916	0.05*
H42A	0.8914	0.876	0.4747	0.05*
C5A	0.6963 (4)	1.0037 (3)	0.3801 (3)	0.0394 (7)
H51A	0.6144	0.9505	0.3946	0.047*
H52A	0.6696	1.0809	0.4324	0.047*
N3A	0.9296 (4)	0.7988 (3)	0.3150 (2)	0.0437 (6)
H31A	1.0429	0.7492	0.325	0.052*
H32A	0.862	0.7422	0.3266	0.052*
N3B	0.3148 (3)	0.5233 (3)	−0.0131 (2)	0.0367 (6)
H31B	0.2088	0.5765	−0.0365	0.044*
H32B	0.3001	0.4455	0.0172	0.044*
N6A	0.6748 (3)	1.0568 (3)	0.2620 (2)	0.0386 (6)
H61A	0.5623	1.1079	0.2514	0.046*
H62A	0.7444	1.1121	0.2506	0.046*
Cl1	0.01218 (9)	0.49590 (7)	0.16760 (6)	0.03375 (16)
Cl2	0.34370 (11)	0.31722 (8)	0.36015 (7)	0.0466 (2)
Cl3	0.36503 (9)	0.21152 (7)	0.07659 (6)	0.03619 (17)
Cl4	0.26386 (10)	0.00367 (7)	0.29365 (7)	0.04150 (18)
Cl5	−0.06834 (10)	0.17934 (7)	0.09051 (6)	0.03826 (17)
Cl6	−0.11484 (11)	0.28867 (8)	0.37179 (7)	0.0466 (2)
In1	0.13014 (2)	0.247144 (19)	0.228928 (17)	0.03017 (7)
O2W	0.7076 (5)	0.6333 (3)	0.3757 (2)	0.0694 (9)
H21W	0.756 (7)	0.554 (5)	0.360 (4)	0.104*
H22W	0.698 (7)	0.639 (6)	0.443 (5)	0.104*
O1W	0.2846 (4)	0.6490 (3)	0.3457 (3)	0.073
H11W	0.286 (6)	0.567 (5)	0.357 (4)	0.109*
H12W	0.361 (5)	0.666 (5)	0.385 (4)	0.109*

	U11	U22	U33	U12	U13	U23
C1A	0.0472 (19)	0.0439 (17)	0.0357 (17)	−0.0150 (15)	−0.0066 (14)	−0.0006 (14)
C1B	0.036	0.053	0.035	−0.019	−0.005	0.006
C2A	0.0504 (19)	0.0300 (15)	0.0373 (17)	−0.0067 (14)	0.0061 (14)	−0.0019 (13)
C2B	0.0317 (16)	0.0445 (17)	0.0440 (18)	−0.0113 (14)	0.0025 (13)	0.0001 (14)
C4A	0.0402 (18)	0.0475 (18)	0.0319 (16)	−0.0050 (14)	−0.0029 (13)	0.0027 (14)
C5A	0.0399 (17)	0.0427 (17)	0.0330 (16)	−0.0081 (14)	0.0011 (13)	−0.0022 (13)
N3A	0.0460 (16)	0.0325 (13)	0.0448 (16)	0.0007 (12)	0.0051 (12)	0.0063 (11)
N3B	0.0246 (12)	0.0435 (14)	0.0424 (15)	−0.0104 (11)	−0.0045 (10)	0.0130 (12)
N6A	0.0306 (13)	0.0370 (13)	0.0434 (15)	−0.0025 (11)	−0.0039 (11)	0.0032 (11)
Cl1	0.0330 (4)	0.0259 (3)	0.0408 (4)	−0.0062 (3)	−0.0018 (3)	0.0043 (3)
Cl2	0.0442 (4)	0.0442 (4)	0.0461 (5)	−0.0041 (4)	−0.0133 (4)	−0.0085 (4)
Cl3	0.0354 (4)	0.0350 (4)	0.0368 (4)	−0.0081 (3)	0.0054 (3)	0.0028 (3)
Cl4	0.0341 (4)	0.0337 (4)	0.0540 (5)	−0.0057 (3)	−0.0029 (3)	0.0137 (3)
Cl5	0.0391 (4)	0.0343 (4)	0.0426 (4)	−0.0125 (3)	−0.0104 (3)	0.0059 (3)
Cl6	0.0439 (4)	0.0448 (4)	0.0445 (5)	−0.0026 (4)	0.0131 (3)	0.0093 (3)
In1	0.02748 (12)	0.02921 (12)	0.03188 (12)	−0.00524 (8)	−0.00114 (8)	0.00527 (8)
O2W	0.107 (2)	0.0454 (14)	0.0504 (16)	−0.0145 (16)	0.0142 (17)	−0.0025 (14)
O1W	0.076	0.057	0.078	−0.007	−0.017	0.002

C1A—N6A	1.487 (4)	C5A—H51A	0.97
C1A—C2A	1.494 (4)	C5A—H52A	0.97
C1A—H11A	0.97	N3A—H31A	0.9
C1A—H12A	0.97	N3A—H32A	0.9
C1B—N3Bi	1.487 (4)	N3B—C1Bi	1.487 (4)
C1B—C2B	1.509 (4)	N3B—H31B	0.9
C1B—H11B	0.97	N3B—H32B	0.9
C1B—H12B	0.97	N6A—H61A	0.9
C2A—N3A	1.489 (4)	N6A—H62A	0.9
C2A—H21A	0.97	Cl1—In1	2.5167 (7)
C2A—H22A	0.97	Cl2—In1	2.5521 (8)
C2B—N3B	1.478 (4)	Cl3—In1	2.5327 (7)
C2B—H21B	0.97	Cl4—In1	2.4959 (7)
C2B—H22B	0.97	Cl5—In1	2.5083 (7)
C4A—N3A	1.492 (4)	Cl6—In1	2.5082 (8)
C4A—C5A	1.498 (4)	O2W—H21W	0.80 (5)
C4A—H41A	0.97	O2W—H22W	0.80 (5)
C4A—H42A	0.97	O1W—H11W	0.84 (5)
C5A—N6A	1.487 (4)	O1W—H12W	0.824 (19)
N6A—C1A—C2A	110.3 (2)	C2A—N3A—C4A	111.2 (2)
N6A—C1A—H11A	109.6	C2A—N3A—H31A	109.4
C2A—C1A—H11A	109.6	C4A—N3A—H31A	109.4
N6A—C1A—H12A	109.6	C2A—N3A—H32A	109.4
C2A—C1A—H12A	109.6	C4A—N3A—H32A	109.4
H11A—C1A—H12A	108.1	H31A—N3A—H32A	108
N3Bi—C1B—C2B	110.3 (2)	C2B—N3B—C1Bi	111.8 (2)
N3Bi—C1B—H11B	109.6	C2B—N3B—H31B	109.3
C2B—C1B—H11B	109.6	C1Bi—N3B—H31B	109.3
N3Bi—C1B—H12B	109.6	C2B—N3B—H32B	109.3
C2B—C1B—H12B	109.6	C1Bi—N3B—H32B	109.3
H11B—C1B—H12B	108.1	H31B—N3B—H32B	107.9
N3A—C2A—C1A	111.2 (2)	C1A—N6A—C5A	111.6 (2)
N3A—C2A—H21A	109.4	C1A—N6A—H61A	109.3
C1A—C2A—H21A	109.4	C5A—N6A—H61A	109.3
N3A—C2A—H22A	109.4	C1A—N6A—H62A	109.3
C1A—C2A—H22A	109.4	C5A—N6A—H62A	109.3
H21A—C2A—H22A	108	H61A—N6A—H62A	108
N3B—C2B—C1B	110.3 (2)	Cl4—In1—Cl6	92.66 (3)
N3B—C2B—H21B	109.6	Cl4—In1—Cl5	93.02 (3)
C1B—C2B—H21B	109.6	Cl6—In1—Cl5	88.24 (3)
N3B—C2B—H22B	109.6	Cl4—In1—Cl1	176.49 (2)
C1B—C2B—H22B	109.6	Cl6—In1—Cl1	88.87 (2)
H21B—C2B—H22B	108.1	Cl5—In1—Cl1	90.18 (2)
N3A—C4A—C5A	110.8 (3)	Cl4—In1—Cl3	89.56 (3)
N3A—C4A—H41A	109.5	Cl6—In1—Cl3	176.85 (3)
C5A—C4A—H41A	109.5	Cl5—In1—Cl3	89.41 (3)
N3A—C4A—H42A	109.5	Cl1—In1—Cl3	89.04 (2)
C5A—C4A—H42A	109.5	Cl4—In1—Cl2	87.68 (3)
H41A—C4A—H42A	108.1	Cl6—In1—Cl2	94.98 (3)
N6A—C5A—C4A	110.5 (2)	Cl5—In1—Cl2	176.67 (3)
N6A—C5A—H51A	109.6	Cl1—In1—Cl2	89.04 (2)
C4A—C5A—H51A	109.6	Cl3—In1—Cl2	87.34 (3)
N6A—C5A—H52A	109.6	H21W—O2W—H22W	108 (5)
C4A—C5A—H52A	109.6	H11W—O1W—H12W	109 (5)
H51A—C5A—H52A	108.1

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H11W···Cl2	0.84 (5)	2.43 (5)	3.248 (3)	167 (4)
O2W—H21W···Cl6ii	0.80 (5)	2.58 (5)	3.353 (3)	163 (5)
O2W—H22W···Cl2iii	0.80 (6)	2.37 (6)	3.170 (3)	174 (6)
N3A—H31A···O1Wii	0.90	1.91	2.805 (5)	178
N3A—H32A···O2W	0.90	1.95	2.843 (5)	171
N3B—H31B···Cl1iv	0.90	2.61	3.233 (3)	127
N3B—H31B···Cl5iv	0.90	2.47	3.202 (3)	138
N3B—H32B···Cl1	0.90	2.81	3.273 (3)	113
N3B—H32B···Cl3	0.90	2.37	3.231 (3)	160
N6A—H61A···Cl2v	0.90	2.64	3.334 (3)	134
N6A—H61A···Cl3v	0.90	2.62	3.330 (3)	136
N6A—H62A···Cl5vi	0.90	2.61	3.344 (3)	140
N6A—H62A···Cl6vi	0.90	2.77	3.502 (3)	139
C2B—H21B···O1W	0.97	2.47	3.306 (5)	144
C2A—H21A···Cl1ii	0.97	2.72	3.470 (3)	135
C2B—H22B···Cl3i	0.97	2.83	3.607 (3)	138
C4A—H41A···Cl4vi	0.97	2.76	3.620 (3)	148
C4A—H42A···Cl6iii	0.97	2.74	3.577 (3)	145

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H11W⋯Cl2	0.84 (5)	2.43 (5)	3.248 (3)	167 (4)
O2W—H21W⋯Cl6i	0.80 (5)	2.58 (5)	3.353 (3)	163 (5)
O2W—H22W⋯Cl2ii	0.80 (6)	2.37 (6)	3.170 (3)	174 (6)
N3A—H31A⋯O1Wi	0.90	1.91	2.805 (5)	178
N3A—H32A⋯O2W	0.90	1.95	2.843 (5)	171
N3B—H31B⋯Cl1iii	0.90	2.61	3.233 (3)	127
N3B—H31B⋯Cl5iii	0.90	2.47	3.202 (3)	138
N3B—H32B⋯Cl1	0.90	2.81	3.273 (3)	113
N3B—H32B⋯Cl3	0.90	2.37	3.231 (3)	160
N6A—H61A⋯Cl2iv	0.90	2.64	3.334 (3)	134
N6A—H61A⋯Cl3iv	0.90	2.62	3.330 (3)	136
N6A—H62A⋯Cl5v	0.90	2.61	3.344 (3)	140
N6A—H62A⋯Cl6v	0.90	2.77	3.502 (3)	139
C2B—H21B⋯O1W	0.97	2.47	3.306 (5)	144
C2A—H21A⋯Cl1i	0.97	2.72	3.470 (3)	135
C2B—H22B⋯Cl3vi	0.97	2.83	3.607 (3)	138
C4A—H41A⋯Cl4v	0.97	2.76	3.620 (3)	148
C4A—H42A⋯Cl6ii	0.97	2.74	3.577 (3)	145

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