trans-Diaqua­bis­(cyclo­hexane-1,2-diamine)­zinc(II) dichloride

Karimnejad, K.; Khaledi, H.; Mohd Ali, H.

doi:10.1107/S1600536811008166

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 4| April 2011| Page m421

doi:10.1107/S1600536811008166

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trans-Diaquabis(cyclohexane-1,2-diamine)zinc(II) dichloride

Kamelia Karimnejad,^a Hamid Khaledi ^a ^* and Hapipah Mohd Ali ^a

^aDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: khaledi@siswa.um.edu.my

(Received 28 February 2011; accepted 3 March 2011; online 12 March 2011)

In the title compound, [Zn(C₆H₁₄N₂)₂(H₂O)₂]Cl₂, the Zn(II) atom resides on a special position with site symmetry 2/m and is octahedrally coordinated by four N atoms from two trans 1,2-diaminocyclohexane ligands and two water O atoms. In the crystal, N—H⋯Cl and O—H⋯Cl hydrogen bonds link the molecules into a two-dimensional network parallel to the bc plane.

Related literature

For an isotypic nickel(II) complex, see: Capilla et al. (1980 ) and for an analogous copper(II) complex, see: Pariya et al. (1998 ).

Experimental

Crystal data

[Zn(C₆H₁₄N₂)₂(H₂O)₂]Cl₂
M_r = 400.69
Orthorhombic, C m c e
a = 24.6478 (4) Å
b = 9.5107 (2) Å
c = 7.6723 (2) Å
V = 1798.52 (7) Å³
Z = 4
Mo Kα radiation
μ = 1.67 mm⁻¹
T = 100 K
0.26 × 0.21 × 0.04 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.670, T_max = 0.936
4324 measured reflections
999 independent reflections
805 reflections with I > 2σ(I)
R_int = 0.019

Refinement

R[F² > 2σ(F²)] = 0.021
wR(F²) = 0.053
S = 1.04
999 reflections
61 parameters
3 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.36 e Å⁻³
Δρ_min = −0.24 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯Cl1ⁱ	0.87 (1)	2.80 (1)	3.6139 (13)	156 (1)
N1—H1B⋯Cl1	0.87 (1)	2.70 (1)	3.5206 (14)	157 (1)
O1—H1O⋯Cl1	0.83 (1)	2.26 (1)	3.0857 (12)	173 (2)
Symmetry code: (i) $[x, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001 ); software used to prepare material for publication: SHELXL97 and publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811008166/pv2395sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811008166/pv2395Isup2.hkl

checkCIF report

Comment top

The title Zn^II complex (Fig. 1) is isostructural with a previously reported Ni^II complex (Capilla et al., 1980). The metal center in the title complex is located on a special position with site symmetry 2/m, and is six-coordinated in a distorted octahedral geometry. The equatorial plane is defined by four N atoms from two trans-1,2-diaminocyclohexane, while the axial positions are occupied by two water molecule oxygen atoms. This arrangement is similar to what was observed in an analogous Cu^II complex (Pariya et al., 1998). In the crystal, an O—H···Cl interaction connects the cationic complexes and chloride anions into infinite chains along the c-axis. The chains are further linked by N—H···Cl hydrogen bonds into layers parallel to the bc plane.

Related literature top

For an isotypic nickel(II) complex, see: Capilla et al. (1980) and for an analogous copper(II) complex, see: Pariya et al. (1998).

Experimental top

The colorless crystals of the title compound were obtained upon slow evaporation of an ethanolic solution (20 ml) of trans-l,2-diaminocyclohexane (0.23 g, 2 mmol) and zinc(II) acetate dihydrate (0.22 g, 1 mmol) in the presence of a few drops of HCl (37%).

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and publCIF (Westrip, 2010).

Figures top

Fig. 1. Thermal ellipsoid plot of the title compound at the 50% probability level. Hydrogen atoms are drawn as spheres of arbitrary radius. Symmetry codes: ' = -x, -y, -z; " = x, -y, -z; "' = -x, y, z.

trans-Diaquabis(cyclohexane-1,2-diamine)zinc(II) dichloride top

Crystal data top

[Zn(C₆H₁₄N₂)₂(H₂O)₂]Cl₂	F(000) = 848
M_r = 400.69	D_x = 1.480 Mg m⁻³
Orthorhombic, Cmce	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2bc 2	Cell parameters from 2315 reflections
a = 24.6478 (4) Å	θ = 3.3–30.5°
b = 9.5107 (2) Å	µ = 1.67 mm⁻¹
c = 7.6723 (2) Å	T = 100 K
V = 1798.52 (7) Å³	Prism, colorless
Z = 4	0.26 × 0.21 × 0.04 mm

Data collection top

Bruker APEXII CCD diffractometer	999 independent reflections
Radiation source: fine-focus sealed tube	805 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.019
ϕ and ω scans	θ_max = 27.0°, θ_min = 3.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −31→31
T_min = 0.670, T_max = 0.936	k = −11→12
4324 measured reflections	l = −9→8

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)] = 0.021	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.053	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ²(F_o²) + (0.0239P)² + 1.6417P] where P = (F_o² + 2F_c²)/3
999 reflections	(Δ/σ)_max < 0.001
61 parameters	Δρ_max = 0.36 e Å⁻³
3 restraints	Δρ_min = −0.24 e Å⁻³

Crystal data top

[Zn(C₆H₁₄N₂)₂(H₂O)₂]Cl₂	V = 1798.52 (7) Å³
M_r = 400.69	Z = 4
Orthorhombic, Cmce	Mo Kα radiation
a = 24.6478 (4) Å	µ = 1.67 mm⁻¹
b = 9.5107 (2) Å	T = 100 K
c = 7.6723 (2) Å	0.26 × 0.21 × 0.04 mm

Data collection top

Bruker APEXII CCD diffractometer	999 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	805 reflections with I > 2σ(I)
T_min = 0.670, T_max = 0.936	R_int = 0.019
4324 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.021	3 restraints
wR(F²) = 0.053	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	Δρ_max = 0.36 e Å⁻³
999 reflections	Δρ_min = −0.24 e Å⁻³
61 parameters

Special details top

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
Zn1	0.0000	0.0000	0.0000	0.01354 (11)
O1	0.0000	−0.10232 (16)	0.2580 (2)	0.0194 (3)
H1O	0.0266 (6)	−0.0795 (18)	0.318 (2)	0.029*
N1	0.06632 (5)	0.13128 (13)	0.07888 (18)	0.0163 (3)
H1A	0.0617 (6)	0.2190 (15)	0.050 (2)	0.020*
H1B	0.0698 (7)	0.1249 (17)	0.1918 (18)	0.020*
C1	0.11721 (5)	0.08041 (15)	−0.0016 (2)	0.0168 (3)
H1	0.1174	0.1111	−0.1263	0.020*
C2	0.16808 (5)	0.13853 (17)	0.0850 (2)	0.0205 (3)
H2A	0.1678	0.1136	0.2102	0.025*
H2B	0.1681	0.2423	0.0757	0.025*
C3	0.21934 (6)	0.08004 (18)	0.0001 (2)	0.0255 (4)
H3A	0.2218	0.1146	−0.1213	0.031*
H3B	0.2516	0.1145	0.0643	0.031*
Cl1	0.091868 (19)	0.0000	0.5000	0.02019 (14)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.01056 (16)	0.01421 (18)	0.01585 (18)	0.000	0.000	−0.00039 (15)
O1	0.0165 (7)	0.0220 (8)	0.0197 (8)	0.000	0.000	0.0020 (7)
N1	0.0158 (6)	0.0144 (6)	0.0188 (6)	0.0013 (5)	0.0016 (5)	−0.0005 (6)
C1	0.0132 (6)	0.0175 (8)	0.0197 (7)	0.0003 (6)	0.0009 (7)	0.0003 (7)
C2	0.0159 (7)	0.0209 (8)	0.0247 (8)	−0.0033 (6)	−0.0007 (6)	−0.0013 (7)
C3	0.0148 (7)	0.0274 (9)	0.0342 (9)	−0.0031 (6)	−0.0007 (7)	0.0014 (9)
Cl1	0.0188 (3)	0.0243 (3)	0.0174 (3)	0.000	0.000	−0.0004 (2)

Geometric parameters (Å, º) top

Zn1—N1ⁱ	2.1440 (13)	C1—C2	1.5227 (19)
Zn1—N1ⁱⁱ	2.1440 (13)	C1—C1ⁱⁱⁱ	1.530 (3)
Zn1—N1ⁱⁱⁱ	2.1440 (13)	C1—H1	1.0000
Zn1—N1	2.1441 (13)	C2—C3	1.526 (2)
Zn1—O1	2.2057 (16)	C2—H2A	0.9900
Zn1—O1ⁱ	2.2057 (16)	C2—H2B	0.9900
O1—H1O	0.831 (13)	C3—C3ⁱⁱⁱ	1.522 (3)
N1—C1	1.4795 (18)	C3—H3A	0.9900
N1—H1A	0.871 (14)	C3—H3B	0.9900
N1—H1B	0.873 (13)

N1ⁱ—Zn1—N1ⁱⁱ	80.65 (7)	Zn1—N1—H1B	108.4 (11)
N1ⁱ—Zn1—N1ⁱⁱⁱ	99.35 (7)	H1A—N1—H1B	109.5 (16)
N1ⁱⁱ—Zn1—N1ⁱⁱⁱ	180.00 (8)	N1—C1—C2	113.42 (12)
N1ⁱ—Zn1—N1	180.0	N1—C1—C1ⁱⁱⁱ	108.68 (10)
N1ⁱⁱ—Zn1—N1	99.35 (7)	C2—C1—C1ⁱⁱⁱ	110.85 (10)
N1ⁱⁱⁱ—Zn1—N1	80.65 (7)	N1—C1—H1	107.9
N1ⁱ—Zn1—O1	89.79 (5)	C2—C1—H1	107.9
N1ⁱⁱ—Zn1—O1	90.21 (5)	C1ⁱⁱⁱ—C1—H1	107.9
N1ⁱⁱⁱ—Zn1—O1	89.79 (5)	C1—C2—C3	111.30 (13)
N1—Zn1—O1	90.21 (5)	C1—C2—H2A	109.4
N1ⁱ—Zn1—O1ⁱ	90.21 (5)	C3—C2—H2A	109.4
N1ⁱⁱ—Zn1—O1ⁱ	89.79 (5)	C1—C2—H2B	109.4
N1ⁱⁱⁱ—Zn1—O1ⁱ	90.21 (5)	C3—C2—H2B	109.4
N1—Zn1—O1ⁱ	89.79 (5)	H2A—C2—H2B	108.0
O1—Zn1—O1ⁱ	180.00 (7)	C3ⁱⁱⁱ—C3—C2	111.41 (11)
Zn1—O1—H1O	112.5 (13)	C3ⁱⁱⁱ—C3—H3A	109.3
C1—N1—Zn1	109.77 (9)	C2—C3—H3A	109.3
C1—N1—H1A	108.5 (11)	C3ⁱⁱⁱ—C3—H3B	109.3
Zn1—N1—H1A	112.7 (11)	C2—C3—H3B	109.3
C1—N1—H1B	107.9 (11)	H3A—C3—H3B	108.0

Symmetry codes: (i) −x, −y, −z; (ii) −x, y, z; (iii) x, −y, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Cl1^iv	0.87 (1)	2.80 (1)	3.6139 (13)	156 (1)
N1—H1B···Cl1	0.87 (1)	2.70 (1)	3.5206 (14)	157 (1)
O1—H1O···Cl1	0.83 (1)	2.26 (1)	3.0857 (12)	173 (2)

Symmetry code: (iv) x, y+1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	[Zn(C₆H₁₄N₂)₂(H₂O)₂]Cl₂
M_r	400.69
Crystal system, space group	Orthorhombic, Cmce
Temperature (K)	100
a, b, c (Å)	24.6478 (4), 9.5107 (2), 7.6723 (2)
V (Å³)	1798.52 (7)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.67
Crystal size (mm)	0.26 × 0.21 × 0.04

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.670, 0.936
No. of measured, independent and observed [I > 2σ(I)] reflections	4324, 999, 805
R_int	0.019
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.021, 0.053, 1.04
No. of reflections	999
No. of parameters	61
No. of restraints	3
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.36, −0.24

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), X-SEED (Barbour, 2001), SHELXL97 (Sheldrick, 2008) and publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Cl1ⁱ	0.871 (14)	2.800 (14)	3.6139 (13)	156.1 (14)
N1—H1B···Cl1	0.873 (13)	2.702 (14)	3.5206 (14)	156.8 (14)
O1—H1O···Cl1	0.831 (13)	2.260 (13)	3.0857 (12)	173.0 (17)

Symmetry code: (i) x, y+1/2, −z+1/2.

Acknowledgements

The authors thank University of Malaya for funding this study (FRGS grant No. FP004/2010B).

References

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