Bis(1,4-diazo­niabi­cyclo­[2.2.2]octa­ne) di-μ-chlorido-bis­[tetra­chlorido­anti­monate(III)] dihydrate

Ben Rhaiem, T.; Boughzala, H.; Driss, A.

doi:10.1107/S160053681301307X

metal-organic compounds

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Volume 69| Part 6| June 2013| Page m330

doi:10.1107/S160053681301307X

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Bis(1,4-diazoniabicyclo[2.2.2]octane) di-μ-chlorido-bis[tetrachloridoantimonate(III)] dihydrate

Tarek Ben Rhaiem,^a Habib Boughzala ^a ^* and Ahmed Driss ^a

^aLaboratoire de Matériaux et Cristallochimie, Faculté des Sciences de Tunis, Université de Tunis El Manar, 2092 Manar II Tunis, Tunisia
^*Correspondence e-mail: habib.boughzala@ipein.rnu.tn

(Received 29 April 2013; accepted 13 May 2013; online 18 May 2013)

The title salt, (C₆H₁₄N₂)₂[Sb₂Cl₁₀]·2H₂O, was obtained by slow evaporation of an acidic solution of 1,4-diazabicyclo[2.2.2]octane and SbCl₃. The crystal structure consists of (C₆H₁₄N₂)²⁺ cations, [Sb₂Cl₁₀]⁴⁻ double octahedra and lattice water molecules. All molecular components are situated on special positions. The cation and the lattice water molecule exhibit mirror symmetry, whereas the anion has site symmetry 2/m. The cations, anions and water molecules are alternately arranged into columns along [010]. Individual columns are joined into layers extending along (001). Intralayer N—H⋯O and interlayer N—H⋯Cl hydrogen-bonding interactions lead to the formation of a three-dimensional network.

Related literature

For background to this class of compounds, see: Pietraszko et al. (2001 ); Feng et al. (2007 ); Bujak & Zaleski (1999 ); Knodler et al. (1988 ); Baker & Williams (1978 ). For a related structure, see: Qu & Sun (2005 ).

Experimental

Crystal data

(C₆H₁₄N₂)₂[Sb₂Cl₁₀]·2H₂O
M_r = 862.46
Orthorhombic, P n n m
a = 9.162 (1) Å
b = 20.869 (7) Å
c = 7.566 (2) Å
V = 1446.8 (7) Å³
Z = 2
Mo Kα radiation
μ = 2.81 mm⁻¹
T = 298 K
0.50 × 0.43 × 0.36 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.334, T_max = 0.431
2797 measured reflections
1700 independent reflections
1488 reflections with I > 2σ(I)
R_int = 0.029
2 standard reflections every 120 min intensity decay: 1%

Refinement

R[F² > 2σ(F²)] = 0.023
wR(F²) = 0.061
S = 1.08
1700 reflections
82 parameters
H-atom parameters constrained
Δρ_max = 0.59 e Å⁻³
Δρ_min = −0.37 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯Cl2	0.91	2.59	3.340 (4)	140
N1—H1⋯Cl3	0.91	2.77	3.390 (3)	126
N1—H1⋯Cl3ⁱ	0.91	2.77	3.390 (3)	126
N2—H2⋯O	0.91	2.00	2.780 (4)	143
Symmetry code: (i) x, y, -z+1.

Data collection: CAD-4 EXPRESS (Duisenberg, 1992 ); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995 ); 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: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053681301307X/wm2740sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681301307X/wm2740Isup2.hkl

checkCIF report

Comment top

Halogenidoantimonates(III) and halogenidobismuthates(III) with organic cations defined by the general formula R_aM_bX_3b+a (where R is an organic cation; M is Sb^III or/and Bi^III and X is Cl, Br or/and I) are an interesting group of compounds due to their ferroelectric properties (Pietraszko et al., 2001). Halogenidoantimonates(III) constitute a group of salts in which a number of compounds have a similar structural arrangement (Feng et al., 2007; Bujak & Zaleski, 1999; Knodler et al., 1988; Baker & Williams, 1978). Recently, the new chloridoantimonate(III), (C₆H₁₄N₂)₂[Sb₂Cl₁₀]^.2H₂O, has been synthesized in our laboratory. The synthesis and the structure determination are presented here.

The crystal structure of the title compound is formed by an alterning packing of layers along [001] (Fig. 1). Each layer spreads parallel to (001) and is located at x = 0 and x = 0.5 and consists of columns extending along [010] of alternating cations, anions and water molecules (Fig. 2).

The [Sb₂Cl₁₀]^4- anion has site symmetry 2/m and is composed of two distorted, edge-sharing SbCl₆ octahedra. The cis Sb–Cl–Sb angles vary from 81.11 (2) to 104.42 (1)°, whereas the trans angles are between 164.64 (4) and 173.84 (1)°. The longest Sb1–Cl4 bond length (2.9107 (8) Å) corresponds to the bridging chlorine atom while the shortest one, Sb1–Cl3 (2.4904 (7) Å) is terminal and located in opposite direction to the bridging one (Fig. 2). The anionic charge is balanced by organic (C₆H₁₄N₂)²⁺ (DABCO) cations that exhibit mirror symmetry. Bond lengths and angles in the (C₆H₁₄N₂)²⁺ cation are within normal ranges and are comparable with those observed in a related structure (Qu & Sun, 2005).

The cohesion of the layers is ensured by N—H···O and N—H···Cl hydrogen bonds between organic cations, inorganic anions and the water molecules (Fig. 2, Table 1).

Related literature top

For background to this class of compounds, see: Pietraszko et al. (2001); Feng et al. (2007); Bujak & Zaleski (1999); Knodler et al. (1988); Baker & Williams (1978). For a related structure, see: Qu & Sun (2005).

Experimental top

A mixture of SbCl₃ (0.23 g, 1 mmol) and DABCO (0.11 g, 1 mmol) was dissolved in an aqueous solution of hydrochloric and stirred for several minutes at room temperature. Colorless crystals suitable for X-ray diffraction analysis were obtained by slow evaporation at room temperature over 2 weeks.

Computing details top

Data collection: CAD-4 EXPRESS (Duisenberg, 1992); cell refinement: CAD-4 EXPRESS (Duisenberg, 1992); data reduction: XCAD4 (Harms & Wocadlo, 1995); 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: publCIF (Westrip, 2010).

Figures top

	Fig. 1. Three-dimensional view of (C₆H₁₄N₂)₂[Sb₂Cl₁₀]^.2H₂O showing the crystal packing. H atoms not involved in hydrogen bonding (dashed lines) have been omitted for clarity.
	Fig. 2. An ORTEP plot of the molecular entities of (C₆H₁₄N₂)₂[Sb₂Cl₁₀]^.2H₂O, showing the atom numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radius. [Symmetry code: (i) x, y, 1 - z; (ii) 1 - x, 1 - y, z; (iii) 1 - x, 1 - y, 1 - z.]

Bis(1,4-diazoniabicyclo[2.2.2]octane) di-µ-chlorido-bis[tetrachloridoantimonate(III)] dihydrate top

Crystal data top

(C₆H₁₄N₂)₂[Sb₂Cl₁₀]·2H₂O	D_x = 1.980 Mg m⁻³
M_r = 862.46	Melting point: 571 K
Orthorhombic, Pnnm	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2 2n	Cell parameters from 1700 reflections
a = 9.162 (1) Å	θ = 2.4–27.0°
b = 20.869 (7) Å	µ = 2.81 mm⁻¹
c = 7.566 (2) Å	T = 298 K
V = 1446.8 (7) Å³	Prism, colourless
Z = 2	0.50 × 0.43 × 0.36 mm
F(000) = 840

Data collection top

Enraf–Nonius CAD-4 diffractometer	1488 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.029
Graphite monochromator	θ_max = 27.0°, θ_min = 2.4°
non–profiled ω/2θ scans	h = −1→11
Absorption correction: ψ scan (North et al., 1968)	k = −26→1
T_min = 0.334, T_max = 0.431	l = −9→3
2797 measured reflections	2 standard reflections every 120 min
1700 independent reflections	intensity decay: 1%

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)] = 0.023	H-atom parameters constrained
wR(F²) = 0.061	w = 1/[σ²(F_o²) + (0.0268P)² + 1.1425P] where P = (F_o² + 2F_c²)/3
S = 1.08	(Δ/σ)_max = 0.001
1700 reflections	Δρ_max = 0.59 e Å⁻³
82 parameters	Δρ_min = −0.37 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: 0.0099 (5)

Crystal data top

(C₆H₁₄N₂)₂[Sb₂Cl₁₀]·2H₂O	V = 1446.8 (7) Å³
M_r = 862.46	Z = 2
Orthorhombic, Pnnm	Mo Kα radiation
a = 9.162 (1) Å	µ = 2.81 mm⁻¹
b = 20.869 (7) Å	T = 298 K
c = 7.566 (2) Å	0.50 × 0.43 × 0.36 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	1488 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.029
T_min = 0.334, T_max = 0.431	2 standard reflections every 120 min
2797 measured reflections	intensity decay: 1%
1700 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.023	0 restraints
wR(F²) = 0.061	H-atom parameters constrained
S = 1.08	Δρ_max = 0.59 e Å⁻³
1700 reflections	Δρ_min = −0.37 e Å⁻³
82 parameters

Special details top

Experimental. Number of psi-scan sets used was 5 Theta correction was applied. Averaged transmission function was used. No Fourier smoothing was applied.

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	Occ. (<1)
Sb	0.40193 (3)	0.407356 (11)	0.5000	0.03327 (11)
Cl1	0.16885 (14)	0.46510 (7)	0.5000	0.0678 (4)
Cl2	0.62462 (11)	0.31027 (6)	0.5000	0.0471 (3)
Cl3	0.30372 (8)	0.33776 (3)	0.26053 (10)	0.04669 (19)
Cl4	0.5000	0.5000	0.23812 (14)	0.0534 (3)
N1	0.3554 (4)	0.20234 (16)	0.5000	0.0406 (8)
H1	0.3861	0.2438	0.5000	0.049*
N2	0.2710 (4)	0.09024 (15)	0.5000	0.0443 (8)
H2	0.2394	0.0489	0.5000	0.053*
C1	0.1931 (4)	0.20125 (18)	0.5000	0.0433 (9)
H1A	0.1563	0.2231	0.3961	0.052*	0.50
H1B	0.1563	0.2231	0.6039	0.052*	0.50
C2	0.1428 (5)	0.1332 (2)	0.5000	0.0537 (12)
H2A	0.0836	0.1251	0.6039	0.064*	0.50
H2B	0.0836	0.1251	0.3961	0.064*	0.50
C3	0.4100 (3)	0.17034 (16)	0.6617 (5)	0.0535 (8)
H3A	0.3730	0.1921	0.7657	0.064*
H3B	0.5158	0.1720	0.6646	0.064*
C4	0.3595 (4)	0.10141 (15)	0.6615 (5)	0.0541 (8)
H4A	0.4432	0.0729	0.6626	0.065*
H4B	0.3013	0.0929	0.7660	0.065*
O	0.3071 (4)	−0.04203 (13)	0.5000	0.0522 (8)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Sb	0.03290 (16)	0.02973 (15)	0.03718 (16)	−0.00263 (10)	0.000	0.000
Cl1	0.0468 (6)	0.0716 (8)	0.0850 (9)	0.0239 (6)	0.000	0.000
Cl2	0.0379 (5)	0.0543 (6)	0.0492 (6)	0.0080 (4)	0.000	0.000
Cl3	0.0517 (4)	0.0401 (4)	0.0483 (4)	−0.0104 (3)	−0.0131 (3)	0.0003 (3)
Cl4	0.0639 (7)	0.0548 (6)	0.0414 (5)	0.0027 (5)	0.000	0.000
N1	0.0392 (17)	0.0292 (15)	0.053 (2)	−0.0064 (13)	0.000	0.000
N2	0.050 (2)	0.0268 (15)	0.056 (2)	0.0011 (14)	0.000	0.000
C1	0.036 (2)	0.0315 (18)	0.062 (3)	0.0061 (16)	0.000	0.000
C2	0.0314 (19)	0.039 (2)	0.091 (4)	−0.0053 (18)	0.000	0.000
C3	0.0447 (16)	0.0601 (19)	0.0557 (19)	−0.0037 (14)	−0.0143 (15)	−0.0024 (16)
C4	0.0640 (19)	0.0475 (16)	0.0508 (18)	0.0084 (14)	−0.0059 (17)	0.0100 (15)
O	0.0487 (17)	0.0359 (15)	0.072 (2)	−0.0019 (13)	0.000	0.000

Geometric parameters (Å, º) top

Sb—Cl1	2.4520 (12)	N2—H2	0.9100
Sb—Cl3ⁱ	2.4904 (7)	C1—C2	1.492 (6)
Sb—Cl3	2.4904 (7)	C1—H1A	0.9700
Sb—Cl2	2.8755 (11)	C1—H1B	0.9700
Sb—Cl4	2.9107 (8)	C2—H2A	0.9700
N1—C3	1.481 (4)	C2—H2B	0.9700
N1—C3ⁱ	1.481 (4)	C3—C4	1.511 (4)
N1—C1	1.487 (5)	C3—H3A	0.9700
N1—H1	0.9100	C3—H3B	0.9700
N2—C2	1.478 (5)	C4—H4A	0.9700
N2—C4ⁱ	1.485 (4)	C4—H4B	0.9700
N2—C4	1.485 (4)

Cl1—Sb—Cl3ⁱ	88.39 (3)	N1—C1—H1A	109.9
Cl1—Sb—Cl3	88.39 (3)	C2—C1—H1A	109.9
Cl3ⁱ—Sb—Cl3	93.37 (3)	N1—C1—H1B	109.9
Cl1—Sb—Cl2	164.64 (4)	C2—C1—H1B	109.9
Cl3ⁱ—Sb—Cl2	81.11 (2)	H1A—C1—H1B	108.3
Cl3—Sb—Cl2	81.11 (2)	N2—C2—C1	109.4 (3)
Cl4—Sb—Cl3	90.19 (1)	N2—C2—H2A	109.8
Cl4—Sb—Cl3ⁱ	173.84 (1)	C1—C2—H2A	109.8
Cl4—Sb—Cl1	86.69 (4)	N2—C2—H2B	109.8
Cl4—Sb—Cl2	104.42 (1)	C1—C2—H2B	109.8
C3—N1—C3ⁱ	111.4 (3)	H2A—C2—H2B	108.2
C3—N1—C1	109.3 (2)	N1—C3—C4	109.0 (3)
C3ⁱ—N1—C1	109.3 (2)	N1—C3—H3A	109.9
C3—N1—H1	108.9	C4—C3—H3A	109.9
C3ⁱ—N1—H1	108.9	N1—C3—H3B	109.9
C1—N1—H1	108.9	C4—C3—H3B	109.9
C2—N2—C4ⁱ	109.8 (2)	H3A—C3—H3B	108.3
C2—N2—C4	109.8 (2)	N2—C4—C3	108.5 (3)
C4ⁱ—N2—C4	110.8 (4)	N2—C4—H4A	110.0
C2—N2—H2	108.8	C3—C4—H4A	110.0
C4ⁱ—N2—H2	108.8	N2—C4—H4B	110.0
C4—N2—H2	108.8	C3—C4—H4B	110.0
N1—C1—C2	108.9 (3)	H4A—C4—H4B	108.4

Symmetry code: (i) x, y, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···Cl2	0.91	2.59	3.340 (4)	140
N1—H1···Cl3	0.91	2.77	3.390 (3)	126
N1—H1···Cl3ⁱ	0.91	2.77	3.390 (3)	126
N2—H2···O	0.91	2.00	2.780 (4)	143

Symmetry code: (i) x, y, −z+1.

Experimental details

Crystal data
Chemical formula	(C₆H₁₄N₂)₂[Sb₂Cl₁₀]·2H₂O
M_r	862.46
Crystal system, space group	Orthorhombic, Pnnm
Temperature (K)	298
a, b, c (Å)	9.162 (1), 20.869 (7), 7.566 (2)
V (Å³)	1446.8 (7)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	2.81
Crystal size (mm)	0.50 × 0.43 × 0.36

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.334, 0.431
No. of measured, independent and observed [I > 2σ(I)] reflections	2797, 1700, 1488
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.638

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.023, 0.061, 1.08
No. of reflections	1700
No. of parameters	82
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.59, −0.37

Computer programs: CAD-4 EXPRESS (Duisenberg, 1992), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 2006), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···Cl2	0.91	2.59	3.340 (4)	140
N1—H1···Cl3	0.91	2.77	3.390 (3)	126
N1—H1···Cl3ⁱ	0.91	2.77	3.390 (3)	126
N2—H2···O	0.91	2.00	2.780 (4)	143

Symmetry code: (i) x, y, −z+1.

References

Baker, W. A. & Williams, D. E. (1978). Acta Cryst. B34, 1111–1116. CSD CrossRef CAS IUCr Journals Web of Science Google Scholar
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Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany. Google Scholar
Knodler, R., Ensinger, U., Schwarz, W. & Schmidt, A. (1988). Z. Anorg. Allg. Chem. 557, 208–218. CSD CrossRef Web of Science Google Scholar
North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359. CrossRef IUCr Journals Web of Science Google Scholar
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doi:10.1107/S160053681301307X

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metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Bis(1,4-diazo­niabi­cyclo­[2.2.2]octa­ne) di-μ-chlorido-bis­­[tetra­chlorido­anti­monate(III)] dihydrate

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

References

metal-organic compounds

Bis(1,4-diazoniabicyclo[2.2.2]octane) di-μ-chlorido-bis[tetrachloridoantimonate(III)] dihydrate