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

Ben Rhaiem, T.; Boughzala, H.

doi:10.1107/S1600536814007533

metal-organic compounds

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Volume 70| Part 5| May 2014| Page m178

doi:10.1107/S1600536814007533

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

Tarek Ben Rhaiem ^a and Habib Boughzala ^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 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).

CCDC reference: 967916

Related literature

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

Crystal data

(C₆H₁₄N₂)[CdCl₄]·H₂O
M_r = 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 ) T_min = 0.283, T_max = 0.536
5639 measured reflections
2837 independent reflections
2632 reflections with I > 2σ(I)
R_int = 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
Δρ_max = 1.58 e Å⁻³
Δρ_min = −1.44 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	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 ); 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; molecular graphics: DIAMOND (Brandenburg, 2006 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 967916

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: 10.1107/S1600536814007533/ds2238sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814007533/ds2238Isup2.hkl

checkCIF report

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.

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. Packing diagram of (I), projected along the a axis.
	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.
	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]·H₂O	F(000) = 752
M_r = 386.40	D_x = 1.959 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 2837 reflections
a = 8.528 (5) Å	θ = 2.4–27°
b = 11.653 (2) Å	µ = 2.47 mm⁻¹
c = 13.114 (6) Å	T = 298 K
V = 1303.2 (10) Å³	Prism, colorless
Z = 4	0.54 × 0.43 × 0.29 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	2632 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.075
Graphite monochromator	θ_max = 27.0°, θ_min = 2.3°
non–profiled ω/2θ scans	h = −10→6
Absorption correction: ψ scan (North et al. (1968)	k = −14→1
T_min = 0.283, T_max = 0.536	l = −16→16
5639 measured reflections	2 standard reflections every 120 min
2837 independent reflections	intensity decay: 1%

Refinement top

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)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.134	H-atom parameters not refined
S = 1.19	w = 1/[σ²(F_o²) + (0.0587P)² + 1.6133P] where P = (F_o² + 2F_c²)/3
2837 reflections	(Δ/σ)_max = 0.001
135 parameters	Δρ_max = 1.58 e Å⁻³
10 restraints	Δρ_min = −1.44 e Å⁻³

Crystal data top

(C₆H₁₄N₂)[CdCl₄]·H₂O	V = 1303.2 (10) Å³
M_r = 386.40	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 8.528 (5) Å	µ = 2.47 mm⁻¹
b = 11.653 (2) Å	T = 298 K
c = 13.114 (6) Å	0.54 × 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)	R_int = 0.075
T_min = 0.283, T_max = 0.536	2 standard reflections every 120 min
5639 measured reflections	intensity decay: 1%
2837 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.048	10 restraints
wR(F²) = 0.134	H-atom parameters not refined
S = 1.19	Δρ_max = 1.58 e Å⁻³
2837 reflections	Δρ_min = −1.44 e Å⁻³
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

	x	y	z	U_iso*/U_eq
Cd	0.74636 (5)	0.52500 (4)	0.50315 (3)	0.04606 (17)
Cl1	0.52000 (18)	0.40196 (13)	0.46103 (13)	0.0465 (3)
Cl2	0.7583 (2)	0.53068 (14)	0.69230 (11)	0.0544 (4)
Cl3	0.9940 (2)	0.43346 (15)	0.46078 (15)	0.0557 (4)
Cl4	0.6884 (2)	0.71103 (15)	0.41831 (12)	0.0542 (4)
C1	0.4091 (7)	0.6836 (5)	0.2060 (5)	0.0457 (13)
H1A	0.498 (5)	0.6620 (12)	0.153 (3)	0.055*
H1B	0.4419 (18)	0.761 (4)	0.2435 (19)	0.055*
C2	0.2540 (8)	0.6998 (6)	0.1512 (5)	0.0514 (13)
H2A	0.2282 (17)	0.776 (5)	0.1496 (5)	0.062*
H2B	0.2617 (9)	0.6741 (16)	0.086 (4)	0.062*
C3	0.2824 (8)	0.6248 (7)	0.3636 (6)	0.0583 (18)
H3A	0.3266 (11)	0.6796 (11)	0.4005 (8)	0.070*
H3B	0.2613 (9)	0.5660 (12)	0.4042 (9)	0.070*
C4	0.1319 (9)	0.6690 (6)	0.3149 (6)	0.065 (2)
H4A	0.0481 (16)	0.6394 (8)	0.3470 (8)	0.078*
H4B	0.1274 (9)	0.7458 (14)	0.3198 (7)	0.078*
C5	0.3284 (9)	0.4857 (5)	0.2294 (6)	0.0519 (16)
H5A	0.3330 (9)	0.4244 (11)	0.2713 (9)	0.062*
H5B	0.3874 (13)	0.4708 (6)	0.1738 (11)	0.062*
C6	0.1623 (9)	0.5077 (6)	0.1985 (7)	0.0586 (18)
H6A	0.0970 (14)	0.4692 (9)	0.2392 (9)	0.070*
H6B	0.1468 (9)	0.4843 (7)	0.1344 (12)	0.070*
N1	0.3888 (6)	0.5887 (5)	0.2823 (4)	0.0431 (11)
H1	0.477 (2)	0.5730 (6)	0.3082 (7)	0.052*
N2	0.1318 (6)	0.6341 (5)	0.2067 (5)	0.0554 (15)
H2	0.043 (2)	0.6488 (6)	0.1811 (8)	0.067*
O	0.1563 (8)	0.2409 (6)	0.3238 (6)	0.0861 (19)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cd	0.0463 (3)	0.0409 (2)	0.0510 (3)	0.00213 (18)	−0.0028 (2)	0.00245 (17)
Cl1	0.0486 (8)	0.0402 (7)	0.0508 (8)	−0.0018 (6)	0.0024 (6)	−0.0039 (6)
Cl2	0.0613 (8)	0.0530 (8)	0.0490 (7)	0.0058 (9)	−0.0041 (8)	−0.0042 (6)
Cl3	0.0519 (8)	0.0515 (8)	0.0635 (9)	0.0105 (7)	0.0063 (7)	0.0105 (8)
Cl4	0.0684 (9)	0.0423 (7)	0.0520 (8)	0.0014 (7)	−0.0163 (7)	0.0047 (7)
C1	0.042 (3)	0.034 (3)	0.061 (3)	−0.005 (2)	0.004 (3)	0.007 (3)
C2	0.049 (3)	0.048 (3)	0.057 (3)	−0.006 (3)	−0.001 (3)	0.020 (3)
C3	0.063 (5)	0.057 (4)	0.056 (3)	−0.006 (3)	0.006 (3)	−0.005 (3)
C4	0.062 (4)	0.046 (4)	0.087 (5)	0.012 (3)	0.032 (4)	0.012 (4)
C5	0.055 (4)	0.026 (2)	0.075 (4)	0.001 (3)	−0.008 (3)	0.002 (3)
C6	0.061 (4)	0.041 (3)	0.075 (5)	−0.008 (3)	−0.016 (4)	0.006 (3)
N1	0.042 (2)	0.040 (2)	0.047 (3)	0.002 (2)	−0.005 (2)	0.004 (2)
N2	0.038 (3)	0.044 (3)	0.084 (4)	0.004 (2)	−0.004 (3)	0.027 (3)
O	0.085 (4)	0.070 (4)	0.103 (5)	−0.014 (3)	0.008 (4)	−0.009 (4)

Geometric parameters (Å, º) top

Cd—Cl3	2.430 (2)	C3—H3B	0.8860
Cd—Cl1	2.4673 (18)	C4—N2	1.476 (11)
Cd—Cl2	2.4835 (19)	C4—H4A	0.8977
Cd—Cl4	2.4864 (17)	C4—H4B	0.8977
C1—N1	1.502 (8)	C5—N1	1.479 (9)
C1—C2	1.517 (9)	C5—C6	1.496 (10)
C1—H1A	1.0614	C5—H5A	0.9026
C1—H1B	1.0614	C5—H5B	0.9026
C2—N2	1.485 (8)	C6—N2	1.499 (9)
C2—H2A	0.9127	C6—H6A	0.8931
C2—H2B	0.9127	C6—H6B	0.8931
C3—N1	1.461 (9)	N1—H1	0.8477
C3—C4	1.524 (10)	N2—H2	0.8420
C3—H3A	0.8860

Cl3—Cd—Cl1	111.93 (7)	N2—C4—H4B	110.1
Cl3—Cd—Cl2	101.80 (6)	C3—C4—H4B	110.1
Cl1—Cd—Cl2	105.73 (6)	H4A—C4—H4B	108.4
Cl3—Cd—Cl4	116.95 (6)	N1—C5—C6	108.5 (5)
Cl1—Cd—Cl4	104.53 (6)	N1—C5—H5A	110.0
Cl2—Cd—Cl4	115.58 (6)	C6—C5—H5A	110.0
N1—C1—C2	107.9 (5)	N1—C5—H5B	110.0
N1—C1—H1A	110.1	C6—C5—H5B	110.0
C2—C1—H1A	110.1	H5A—C5—H5B	108.4
N1—C1—H1B	110.1	C5—C6—N2	108.3 (5)
C2—C1—H1B	110.1	C5—C6—H6A	110.0
H1A—C1—H1B	108.4	N2—C6—H6A	110.0
N2—C2—C1	108.4 (5)	C5—C6—H6B	110.0
N2—C2—H2A	110.0	N2—C6—H6B	110.0
C1—C2—H2A	110.0	H6A—C6—H6B	108.4
N2—C2—H2B	110.0	C3—N1—C5	111.1 (6)
C1—C2—H2B	110.0	C3—N1—C1	110.2 (5)
H2A—C2—H2B	108.4	C5—N1—C1	109.0 (5)
N1—C3—C4	108.4 (6)	C3—N1—H1	108.8
N1—C3—H3A	110.0	C5—N1—H1	108.8
C4—C3—H3A	110.0	C1—N1—H1	108.8
N1—C3—H3B	110.0	C4—N2—C2	109.2 (6)
C4—C3—H3B	110.0	C4—N2—C6	109.9 (6)
H3A—C3—H3B	108.4	C2—N2—C6	110.5 (6)
N2—C4—C3	108.0 (5)	C4—N2—H2	109.1
N2—C4—H4A	110.1	C2—N2—H2	109.1
C3—C4—H4A	110.1	C6—N2—H2	109.1

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···Oⁱ	0.84	2.01	2.783 (1)	151

Symmetry code: (i) −x, y+1/2, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···Oⁱ	0.84	2.01	2.783 (1)	151

Symmetry code: (i) −x, y+1/2, −z+1/2.

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 70| Part 5| May 2014| Page m178

doi:10.1107/S1600536814007533

Open

access