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

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

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[Pietraszko, A., Bednarska-Bolek, B., Jakubas, R. & Zielinski, P. (2001). J. Phys. Condens. Matter, 13, 6471-6488.]); Feng et al. (2007[Feng, W.-J., Wang, H.-B., Ma, X.-J., Li, H.-Y. & Jin, Z.-M. (2007). Acta Cryst. E63, m1786-m1787.]); Bujak & Zaleski (1999[Bujak, M. & Zaleski, J. (1999). Acta Cryst. C55, 1775-1778.]); Knodler et al. (1988[Knodler, R., Ensinger, U., Schwarz, W. & Schmidt, A. (1988). Z. Anorg. Allg. Chem. 557, 208-218.]); Baker & Williams (1978[Baker, W. A. & Williams, D. E. (1978). Acta Cryst. B34, 1111-1116.]). For a related structure, see: Qu & Sun (2005[Qu, Y. & Sun, X.-M. (2005). Acta Cryst. E61, m2121-m2123.]).

[Scheme 1]

Experimental

Crystal data
  • (C6H14N2)2[Sb2Cl10]·2H2O

  • Mr = 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[North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351-359.]) Tmin = 0.334, Tmax = 0.431

  • 2797 measured reflections

  • 1700 independent reflections

  • 1488 reflections with I > 2σ(I)

  • Rint = 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

  • Δρmax = 0.59 e Å−3

  • Δρmin = −0.37 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA 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[Duisenberg, A. J. M. (1992). J. Appl. Cryst. 25, 92-96.]); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995[Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany.]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: DIAMOND (Brandenburg, 2006[Brandenburg, K. (2006). DIAMOND. Crystal Impact GbR, Bonn, Germany.]); software used to prepare material for publication: publCIF (Westrip, 2010[Westrip, S. P. (2010). J. Appl. Cryst. 43, 920-925.]).

Supporting information


Comment top

Halogenidoantimonates(III) and halogenidobismuthates(III) with organic cations defined by the general formula RaMbX3b+a (where R is an organic cation; M is SbIII or/and BiIII 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.

Refinement top

Hydrogen positions of the water molecule could not be located reliably and were eventually omitted from refinement. The C—H and N—H hydrogen atom positions were placed geometrically. They were included in the refinement using the riding-model approximation, with distance constraints of C—H = 0.97 Å, N—H = 0.91 and with Uiso(H) = 1.2Ueq(C,N).

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
[Figure 1] 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.
[Figure 2] 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]·2H2ODx = 1.980 Mg m3
Mr = 862.46Melting point: 571 K
Orthorhombic, PnnmMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2 2nCell parameters from 1700 reflections
a = 9.162 (1) Åθ = 2.4–27.0°
b = 20.869 (7) ŵ = 2.81 mm1
c = 7.566 (2) ÅT = 298 K
V = 1446.8 (7) Å3Prism, colourless
Z = 20.50 × 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 tubeRint = 0.029
Graphite monochromatorθmax = 27.0°, θmin = 2.4°
non–profiled ω/2θ scansh = 111
Absorption correction: ψ scan
(North et al., 1968)
k = 261
Tmin = 0.334, Tmax = 0.431l = 93
2797 measured reflections2 standard reflections every 120 min
1700 independent reflections intensity decay: 1%
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.023H-atom parameters constrained
wR(F2) = 0.061 w = 1/[σ2(Fo2) + (0.0268P)2 + 1.1425P]
where P = (Fo2 + 2Fc2)/3
S = 1.08(Δ/σ)max = 0.001
1700 reflectionsΔρmax = 0.59 e Å3
82 parametersΔρmin = 0.37 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0099 (5)
Crystal data top
(C6H14N2)2[Sb2Cl10]·2H2OV = 1446.8 (7) Å3
Mr = 862.46Z = 2
Orthorhombic, PnnmMo Kα radiation
a = 9.162 (1) ŵ = 2.81 mm1
b = 20.869 (7) ÅT = 298 K
c = 7.566 (2) Å0.50 × 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)
Rint = 0.029
Tmin = 0.334, Tmax = 0.4312 standard reflections every 120 min
2797 measured reflections intensity decay: 1%
1700 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0230 restraints
wR(F2) = 0.061H-atom parameters constrained
S = 1.08Δρmax = 0.59 e Å3
1700 reflectionsΔρmin = 0.37 e Å3
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
xyzUiso*/UeqOcc. (<1)
Sb0.40193 (3)0.407356 (11)0.50000.03327 (11)
Cl10.16885 (14)0.46510 (7)0.50000.0678 (4)
Cl20.62462 (11)0.31027 (6)0.50000.0471 (3)
Cl30.30372 (8)0.33776 (3)0.26053 (10)0.04669 (19)
Cl40.50000.50000.23812 (14)0.0534 (3)
N10.3554 (4)0.20234 (16)0.50000.0406 (8)
H10.38610.24380.50000.049*
N20.2710 (4)0.09024 (15)0.50000.0443 (8)
H20.23940.04890.50000.053*
C10.1931 (4)0.20125 (18)0.50000.0433 (9)
H1A0.15630.22310.39610.052*0.50
H1B0.15630.22310.60390.052*0.50
C20.1428 (5)0.1332 (2)0.50000.0537 (12)
H2A0.08360.12510.60390.064*0.50
H2B0.08360.12510.39610.064*0.50
C30.4100 (3)0.17034 (16)0.6617 (5)0.0535 (8)
H3A0.37300.19210.76570.064*
H3B0.51580.17200.66460.064*
C40.3595 (4)0.10141 (15)0.6615 (5)0.0541 (8)
H4A0.44320.07290.66260.065*
H4B0.30130.09290.76600.065*
O0.3071 (4)0.04203 (13)0.50000.0522 (8)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Sb0.03290 (16)0.02973 (15)0.03718 (16)0.00263 (10)0.0000.000
Cl10.0468 (6)0.0716 (8)0.0850 (9)0.0239 (6)0.0000.000
Cl20.0379 (5)0.0543 (6)0.0492 (6)0.0080 (4)0.0000.000
Cl30.0517 (4)0.0401 (4)0.0483 (4)0.0104 (3)0.0131 (3)0.0003 (3)
Cl40.0639 (7)0.0548 (6)0.0414 (5)0.0027 (5)0.0000.000
N10.0392 (17)0.0292 (15)0.053 (2)0.0064 (13)0.0000.000
N20.050 (2)0.0268 (15)0.056 (2)0.0011 (14)0.0000.000
C10.036 (2)0.0315 (18)0.062 (3)0.0061 (16)0.0000.000
C20.0314 (19)0.039 (2)0.091 (4)0.0053 (18)0.0000.000
C30.0447 (16)0.0601 (19)0.0557 (19)0.0037 (14)0.0143 (15)0.0024 (16)
C40.0640 (19)0.0475 (16)0.0508 (18)0.0084 (14)0.0059 (17)0.0100 (15)
O0.0487 (17)0.0359 (15)0.072 (2)0.0019 (13)0.0000.000
Geometric parameters (Å, º) top
Sb—Cl12.4520 (12)N2—H20.9100
Sb—Cl3i2.4904 (7)C1—C21.492 (6)
Sb—Cl32.4904 (7)C1—H1A0.9700
Sb—Cl22.8755 (11)C1—H1B0.9700
Sb—Cl42.9107 (8)C2—H2A0.9700
N1—C31.481 (4)C2—H2B0.9700
N1—C3i1.481 (4)C3—C41.511 (4)
N1—C11.487 (5)C3—H3A0.9700
N1—H10.9100C3—H3B0.9700
N2—C21.478 (5)C4—H4A0.9700
N2—C4i1.485 (4)C4—H4B0.9700
N2—C41.485 (4)
Cl1—Sb—Cl3i88.39 (3)N1—C1—H1A109.9
Cl1—Sb—Cl388.39 (3)C2—C1—H1A109.9
Cl3i—Sb—Cl393.37 (3)N1—C1—H1B109.9
Cl1—Sb—Cl2164.64 (4)C2—C1—H1B109.9
Cl3i—Sb—Cl281.11 (2)H1A—C1—H1B108.3
Cl3—Sb—Cl281.11 (2)N2—C2—C1109.4 (3)
Cl4—Sb—Cl390.19 (1)N2—C2—H2A109.8
Cl4—Sb—Cl3i173.84 (1)C1—C2—H2A109.8
Cl4—Sb—Cl186.69 (4)N2—C2—H2B109.8
Cl4—Sb—Cl2104.42 (1)C1—C2—H2B109.8
C3—N1—C3i111.4 (3)H2A—C2—H2B108.2
C3—N1—C1109.3 (2)N1—C3—C4109.0 (3)
C3i—N1—C1109.3 (2)N1—C3—H3A109.9
C3—N1—H1108.9C4—C3—H3A109.9
C3i—N1—H1108.9N1—C3—H3B109.9
C1—N1—H1108.9C4—C3—H3B109.9
C2—N2—C4i109.8 (2)H3A—C3—H3B108.3
C2—N2—C4109.8 (2)N2—C4—C3108.5 (3)
C4i—N2—C4110.8 (4)N2—C4—H4A110.0
C2—N2—H2108.8C3—C4—H4A110.0
C4i—N2—H2108.8N2—C4—H4B110.0
C4—N2—H2108.8C3—C4—H4B110.0
N1—C1—C2108.9 (3)H4A—C4—H4B108.4
Symmetry code: (i) x, y, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···Cl20.912.593.340 (4)140
N1—H1···Cl30.912.773.390 (3)126
N1—H1···Cl3i0.912.773.390 (3)126
N2—H2···O0.912.002.780 (4)143
Symmetry code: (i) x, y, z+1.

Experimental details

Crystal data
Chemical formula(C6H14N2)2[Sb2Cl10]·2H2O
Mr862.46
Crystal system, space groupOrthorhombic, Pnnm
Temperature (K)298
a, b, c (Å)9.162 (1), 20.869 (7), 7.566 (2)
V3)1446.8 (7)
Z2
Radiation typeMo Kα
µ (mm1)2.81
Crystal size (mm)0.50 × 0.43 × 0.36
Data collection
DiffractometerEnraf–Nonius CAD-4
diffractometer
Absorption correctionψ scan
(North et al., 1968)
Tmin, Tmax0.334, 0.431
No. of measured, independent and
observed [I > 2σ(I)] reflections
2797, 1700, 1488
Rint0.029
(sin θ/λ)max1)0.638
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.023, 0.061, 1.08
No. of reflections1700
No. of parameters82
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)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···AD—HH···AD···AD—H···A
N1—H1···Cl20.912.593.340 (4)140
N1—H1···Cl30.912.773.390 (3)126
N1—H1···Cl3i0.912.773.390 (3)126
N2—H2···O0.912.002.780 (4)143
Symmetry code: (i) x, y, z+1.
 

References

First citationBaker, W. A. & Williams, D. E. (1978). Acta Cryst. B34, 1111–1116.  CSD CrossRef CAS IUCr Journals Web of Science
First citationBrandenburg, K. (2006). DIAMOND. Crystal Impact GbR, Bonn, Germany.
First citationBujak, M. & Zaleski, J. (1999). Acta Cryst. C55, 1775–1778.  Web of Science CSD CrossRef CAS IUCr Journals
First citationDuisenberg, A. J. M. (1992). J. Appl. Cryst. 25, 92–96.  CrossRef CAS Web of Science IUCr Journals
First citationFeng, W.-J., Wang, H.-B., Ma, X.-J., Li, H.-Y. & Jin, Z.-M. (2007). Acta Cryst. E63, m1786–m1787.  Web of Science CSD CrossRef CAS IUCr Journals
First citationHarms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany.
First citationKnodler, R., Ensinger, U., Schwarz, W. & Schmidt, A. (1988). Z. Anorg. Allg. Chem. 557, 208–218.  CSD CrossRef Web of Science
First citationNorth, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359.  CrossRef IUCr Journals Web of Science
First citationPietraszko, A., Bednarska-Bolek, B., Jakubas, R. & Zielinski, P. (2001). J. Phys. Condens. Matter, 13, 6471–6488.  Web of Science CrossRef CAS
First citationQu, Y. & Sun, X.-M. (2005). Acta Cryst. E61, m2121–m2123.  Web of Science CSD CrossRef CAS IUCr Journals
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals
First citationWestrip, S. P. (2010). J. Appl. Cryst. 43, 920–925.  Web of Science CrossRef CAS IUCr Journals

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