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

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890

1,4-Diazo­niabi­cyclo­[2.2.2]octane tetra­chlorido­cadmate(II) monohydrate

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 17 January 2014; accepted 3 April 2014; online 12 April 2014)

The asymmetric unit of the title compound (C6H14N2)[CdCl4]·H2O contained one 1,4-di­aza­bicyclo­[2.2.2]octane dication, a tetrahedral CdCl42− anion and a lattice water mol­ecule. In the crystal, the solvate water mol­ecule inter­acts with the cationic and anionic species via N—H⋯O and O—H⋯Cl [O⋯Cl = 3.289 (7) Å] hydrogen-bond inter­actions, respectively, leading to a layered supramolecular structure extending parallel to (011).

Related literature

For background to this class of compounds, see: Wei & Willett (2002[Wei, M. & Willett, R. D. (2002). J. Chem. Crystallogr. 32, 439-445.]); Billing & Lemmerer (2009[Billing, D. G. & Lemmerer, A. (2009). CrystEngComm, 11, 1549-1562.]); Samet et al. (2010[Samet, A., Boughzala, H., Khemekhem, H. & Abid, Y. (2010). J. Mol. Struct. 984, 23-29.]) Lemmerer & Billing (2012[Lemmerer, A. & Billing, D. G. (2012). CrystEngComm, 14, 1954-1966.]); Ben Rhaiem et al. (2013[Ben Rhaiem, T., Boughzala, H. & Driss, A. (2013). Acta Cryst. E69, m330.]). For related structures, see: Sun & Qu (2005[Sun, X.-M. & Qu, Y. (2005). Acta Cryst. E61, m1360-m1362.]); Zhang & Zhu (2012[Zhang, Y. & Zhu, B. H. (2012). Acta Cryst. E68, m687.]).

[Scheme 1]

Experimental

Crystal data
  • (C6H14N2)[CdCl4]·H2O

  • Mr = 386.40

  • Orthorhombic, P 21 21 21

  • a = 8.528 (5) Å

  • b = 11.653 (2) Å

  • c = 13.114 (6) Å

  • V = 1303.2 (10) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 2.47 mm−1

  • T = 298 K

  • 0.54 × 0.43 × 0.29 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 = 0.283, Tmax = 0.536

  • 5639 measured reflections

  • 2837 independent reflections

  • 2632 reflections with I > 2σ(I)

  • Rint = 0.075

  • 2 standard reflections every 120 min intensity decay: 1%

Refinement
  • R[F2 > 2σ(F2)] = 0.048

  • wR(F2) = 0.134

  • S = 1.19

  • 2837 reflections

  • 135 parameters

  • 10 restraints

  • H-atom parameters not refined

  • Δρmax = 1.58 e Å−3

  • Δρmin = −1.44 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
N2—H2⋯Oi 0.84 2.01 2.783 (1) 151
Symmetry code: (i) [-x, y+{\script{1\over 2}}, -z+{\script{1\over 2}}].

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; 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

In recent years, a significant number of organic–inorganic hybrid materials based on metal halide units have been prepared and studied (Lemmerer & Billing, 2012). It has been shown that their structures can vary considerably, ranging from systems based on isolated polyhydra to ones containing extended chains and up to two- or three-dimensional networks (Ben Rhaiem et al., 2013; Samet et al., 2010; Billing & Lemmerer, 2009). Generally, the organic cations contain ammonium groups linked to the anionic framework by hydrogen bonds via halogenous tetrahedral vertices (Sun & Qu, 2005) and (Zhang & Zhu, 2012). In pseudopolymorphic cases, the water molecules can be able to coordinate the charged components strengthening the crystal cohesion as it was observed in (dabcoH2)CuCl4 and (dabcoH2)CuCl4·H2O (Wei & Willett, 2002).

The new chloridocadmate(II) compound, (C6H14N2) [CdCl4]·H2O (I), is self-assembled into alternating organic and inorganic layered structure. the organic part is made up of 1,4-diazabicyclo[2.2.2]octane cations and water molecules. The inorganic component contains isolated [CdCl4]2- units. The layers are stacked along the c axis, as illustrated in Fig. 1.

The asymmetric unit of (I) comprises one 1,4-diazabicyclo[2.2.2]octane cation, one [CdCl4]2- anion and a lattice occluded water molecule (Fig. 2).

The [CdCl4]2- unit possesses a configuration of distorted tetrahedron, so that the central cadmium (II) ion is surrounded by four chlorine atoms. The Cd–Cl bond lengths vary from 2.430 (2) Å to 2.4864 (17) Å and the Cl–Cd–Cl angles fall in the range 101.80 (6)°–116.95 (6)°.

The protonated N2 atom of the organic cation interacts via a simple hydrogen bond with oxygen atom of the water molecule (Fig. 3 and Tab. 1).

Related literature top

For background to this class of compounds, see: Wei & Willett (2002); Billing & Lemmerer (2009); Samet et al. (2010) Lemmerer & Billing (2012); Ben Rhaiem et al. (2013). For related structures, see: Sun & Qu (2005); Zhang & Zhu (2012).

Experimental top

The title compound (C6H14N2) [CdCl4]·H2O, (I), was obtained by the reaction of cadmium iodide CdI2 (0.19 g, 0.5 mmol) with DABCO (1,4-diazabicyclo[2.2.2]octane) (0.112 g, 1 mmol) in aqueous hydrochloric acid solution with pH ranging between 3 and 4. The mixture was stirred for several minutes. Colorless crystals suitable for X-ray diffraction analysis were obtained by slow evaporation at room temperature over 2 weeks.

Refinement top

Hydrogen water molecules are omited. The C—H and N—H hydrogen atoms positions are generated geometrically by HFIX SHELXL command.

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. Packing diagram of (I), projected along the a axis.
[Figure 2] Fig. 2. The asymmetric unit of (I), showing the atom numbering scheme. Displacement ellipsoids are drawn at 50% probability level and H atoms are shown as small spheres of arbitrary radii.
[Figure 3] Fig. 3. The arrangement of ions of (I), projected along the b axis. [Symmetry code: (i) -x, y+1/2, -z + 1/2.]
1,4-Diazoniabicyclo[2.2.2]octane tetrachloridocadmate(II) monohydrate top
Crystal data top
(C6H14N2)[CdCl4]·H2OF(000) = 752
Mr = 386.40Dx = 1.959 Mg m3
Orthorhombic, P212121Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 2837 reflections
a = 8.528 (5) Åθ = 2.4–27°
b = 11.653 (2) ŵ = 2.47 mm1
c = 13.114 (6) ÅT = 298 K
V = 1303.2 (10) Å3Prism, colorless
Z = 40.54 × 0.43 × 0.29 mm
Data collection top
Enraf–Nonius CAD-4
diffractometer
2632 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.075
Graphite monochromatorθmax = 27.0°, θmin = 2.3°
non–profiled ω/2θ scansh = 106
Absorption correction: ψ scan
(North et al. (1968)
k = 141
Tmin = 0.283, Tmax = 0.536l = 1616
5639 measured reflections2 standard reflections every 120 min
2837 independent reflections intensity decay: 1%
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.048Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.134H-atom parameters not refined
S = 1.19 w = 1/[σ2(Fo2) + (0.0587P)2 + 1.6133P]
where P = (Fo2 + 2Fc2)/3
2837 reflections(Δ/σ)max = 0.001
135 parametersΔρmax = 1.58 e Å3
10 restraintsΔρmin = 1.44 e Å3
Crystal data top
(C6H14N2)[CdCl4]·H2OV = 1303.2 (10) Å3
Mr = 386.40Z = 4
Orthorhombic, P212121Mo Kα radiation
a = 8.528 (5) ŵ = 2.47 mm1
b = 11.653 (2) ÅT = 298 K
c = 13.114 (6) Å0.54 × 0.43 × 0.29 mm
Data collection top
Enraf–Nonius CAD-4
diffractometer
2632 reflections with I > 2σ(I)
Absorption correction: ψ scan
(North et al. (1968)
Rint = 0.075
Tmin = 0.283, Tmax = 0.5362 standard reflections every 120 min
5639 measured reflections intensity decay: 1%
2837 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.04810 restraints
wR(F2) = 0.134H-atom parameters not refined
S = 1.19Δρmax = 1.58 e Å3
2837 reflectionsΔρmin = 1.44 e Å3
135 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*/Ueq
Cd0.74636 (5)0.52500 (4)0.50315 (3)0.04606 (17)
Cl10.52000 (18)0.40196 (13)0.46103 (13)0.0465 (3)
Cl20.7583 (2)0.53068 (14)0.69230 (11)0.0544 (4)
Cl30.9940 (2)0.43346 (15)0.46078 (15)0.0557 (4)
Cl40.6884 (2)0.71103 (15)0.41831 (12)0.0542 (4)
C10.4091 (7)0.6836 (5)0.2060 (5)0.0457 (13)
H1A0.498 (5)0.6620 (12)0.153 (3)0.055*
H1B0.4419 (18)0.761 (4)0.2435 (19)0.055*
C20.2540 (8)0.6998 (6)0.1512 (5)0.0514 (13)
H2A0.2282 (17)0.776 (5)0.1496 (5)0.062*
H2B0.2617 (9)0.6741 (16)0.086 (4)0.062*
C30.2824 (8)0.6248 (7)0.3636 (6)0.0583 (18)
H3A0.3266 (11)0.6796 (11)0.4005 (8)0.070*
H3B0.2613 (9)0.5660 (12)0.4042 (9)0.070*
C40.1319 (9)0.6690 (6)0.3149 (6)0.065 (2)
H4A0.0481 (16)0.6394 (8)0.3470 (8)0.078*
H4B0.1274 (9)0.7458 (14)0.3198 (7)0.078*
C50.3284 (9)0.4857 (5)0.2294 (6)0.0519 (16)
H5A0.3330 (9)0.4244 (11)0.2713 (9)0.062*
H5B0.3874 (13)0.4708 (6)0.1738 (11)0.062*
C60.1623 (9)0.5077 (6)0.1985 (7)0.0586 (18)
H6A0.0970 (14)0.4692 (9)0.2392 (9)0.070*
H6B0.1468 (9)0.4843 (7)0.1344 (12)0.070*
N10.3888 (6)0.5887 (5)0.2823 (4)0.0431 (11)
H10.477 (2)0.5730 (6)0.3082 (7)0.052*
N20.1318 (6)0.6341 (5)0.2067 (5)0.0554 (15)
H20.043 (2)0.6488 (6)0.1811 (8)0.067*
O0.1563 (8)0.2409 (6)0.3238 (6)0.0861 (19)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cd0.0463 (3)0.0409 (2)0.0510 (3)0.00213 (18)0.0028 (2)0.00245 (17)
Cl10.0486 (8)0.0402 (7)0.0508 (8)0.0018 (6)0.0024 (6)0.0039 (6)
Cl20.0613 (8)0.0530 (8)0.0490 (7)0.0058 (9)0.0041 (8)0.0042 (6)
Cl30.0519 (8)0.0515 (8)0.0635 (9)0.0105 (7)0.0063 (7)0.0105 (8)
Cl40.0684 (9)0.0423 (7)0.0520 (8)0.0014 (7)0.0163 (7)0.0047 (7)
C10.042 (3)0.034 (3)0.061 (3)0.005 (2)0.004 (3)0.007 (3)
C20.049 (3)0.048 (3)0.057 (3)0.006 (3)0.001 (3)0.020 (3)
C30.063 (5)0.057 (4)0.056 (3)0.006 (3)0.006 (3)0.005 (3)
C40.062 (4)0.046 (4)0.087 (5)0.012 (3)0.032 (4)0.012 (4)
C50.055 (4)0.026 (2)0.075 (4)0.001 (3)0.008 (3)0.002 (3)
C60.061 (4)0.041 (3)0.075 (5)0.008 (3)0.016 (4)0.006 (3)
N10.042 (2)0.040 (2)0.047 (3)0.002 (2)0.005 (2)0.004 (2)
N20.038 (3)0.044 (3)0.084 (4)0.004 (2)0.004 (3)0.027 (3)
O0.085 (4)0.070 (4)0.103 (5)0.014 (3)0.008 (4)0.009 (4)
Geometric parameters (Å, º) top
Cd—Cl32.430 (2)C3—H3B0.8860
Cd—Cl12.4673 (18)C4—N21.476 (11)
Cd—Cl22.4835 (19)C4—H4A0.8977
Cd—Cl42.4864 (17)C4—H4B0.8977
C1—N11.502 (8)C5—N11.479 (9)
C1—C21.517 (9)C5—C61.496 (10)
C1—H1A1.0614C5—H5A0.9026
C1—H1B1.0614C5—H5B0.9026
C2—N21.485 (8)C6—N21.499 (9)
C2—H2A0.9127C6—H6A0.8931
C2—H2B0.9127C6—H6B0.8931
C3—N11.461 (9)N1—H10.8477
C3—C41.524 (10)N2—H20.8420
C3—H3A0.8860
Cl3—Cd—Cl1111.93 (7)N2—C4—H4B110.1
Cl3—Cd—Cl2101.80 (6)C3—C4—H4B110.1
Cl1—Cd—Cl2105.73 (6)H4A—C4—H4B108.4
Cl3—Cd—Cl4116.95 (6)N1—C5—C6108.5 (5)
Cl1—Cd—Cl4104.53 (6)N1—C5—H5A110.0
Cl2—Cd—Cl4115.58 (6)C6—C5—H5A110.0
N1—C1—C2107.9 (5)N1—C5—H5B110.0
N1—C1—H1A110.1C6—C5—H5B110.0
C2—C1—H1A110.1H5A—C5—H5B108.4
N1—C1—H1B110.1C5—C6—N2108.3 (5)
C2—C1—H1B110.1C5—C6—H6A110.0
H1A—C1—H1B108.4N2—C6—H6A110.0
N2—C2—C1108.4 (5)C5—C6—H6B110.0
N2—C2—H2A110.0N2—C6—H6B110.0
C1—C2—H2A110.0H6A—C6—H6B108.4
N2—C2—H2B110.0C3—N1—C5111.1 (6)
C1—C2—H2B110.0C3—N1—C1110.2 (5)
H2A—C2—H2B108.4C5—N1—C1109.0 (5)
N1—C3—C4108.4 (6)C3—N1—H1108.8
N1—C3—H3A110.0C5—N1—H1108.8
C4—C3—H3A110.0C1—N1—H1108.8
N1—C3—H3B110.0C4—N2—C2109.2 (6)
C4—C3—H3B110.0C4—N2—C6109.9 (6)
H3A—C3—H3B108.4C2—N2—C6110.5 (6)
N2—C4—C3108.0 (5)C4—N2—H2109.1
N2—C4—H4A110.1C2—N2—H2109.1
C3—C4—H4A110.1C6—N2—H2109.1
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2···Oi0.842.012.783 (1)151
Symmetry code: (i) x, y+1/2, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2···Oi0.842.012.783 (1)151
Symmetry code: (i) x, y+1/2, z+1/2.
 

References

First citationBen Rhaiem, T., Boughzala, H. & Driss, A. (2013). Acta Cryst. E69, m330.  CSD CrossRef IUCr Journals
First citationBilling, D. G. & Lemmerer, A. (2009). CrystEngComm, 11, 1549–1562.  Web of Science CSD CrossRef CAS
First citationBrandenburg, K. (2006). DIAMOND. Crystal Impact GbR, Bonn, Germany.
First citationDuisenberg, A. J. M. (1992). J. Appl. Cryst. 25, 92–96.  CrossRef CAS Web of Science IUCr Journals
First citationHarms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany.
First citationLemmerer, A. & Billing, D. G. (2012). CrystEngComm, 14, 1954–1966.  Web of Science CSD CrossRef CAS
First citationNorth, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359.  CrossRef IUCr Journals Web of Science
First citationSamet, A., Boughzala, H., Khemekhem, H. & Abid, Y. (2010). J. Mol. Struct. 984, 23–29.  Web of Science CSD CrossRef CAS
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals
First citationSun, X.-M. & Qu, Y. (2005). Acta Cryst. E61, m1360–m1362.  Web of Science CSD CrossRef CAS IUCr Journals
First citationWei, M. & Willett, R. D. (2002). J. Chem. Crystallogr. 32, 439–445.  Web of Science CSD CrossRef CAS
First citationWestrip, S. P. (2010). J. Appl. Cryst. 43, 920–925.  Web of Science CrossRef CAS IUCr Journals
First citationZhang, Y. & Zhu, B. H. (2012). Acta Cryst. E68, m687.  CSD CrossRef IUCr Journals

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Follow Acta Cryst. E
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds