Dianilinedichloridozinc(II)

Khan, I.U.; Ejaz; Şahin, O.; Büyükgüngör, O.

doi:10.1107/S1600536810012274

metal-organic compounds

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ISSN: 2056-9890

Volume 66| Part 5| May 2010| Page m492

https://doi.org/10.1107/S1600536810012274

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Dianilinedichloridozinc(II)

Islam Ullah Khan,^a ^* Ejaz,^a Onur Şahin ^b and Orhan Büyükgüngör ^b

^aMaterials Chemistry Laboratory, Department of Chemistry, GC University, Lahore 54000, Pakistan, and ^bDepartment of Physics, Ondokuz Mayıs University, TR-55139 Samsun, Turkey
^*Correspondence e-mail: onurs@omu.edu.tr, iuklodhi@yahoo.com

(Received 30 March 2010; accepted 31 March 2010; online 10 April 2010)

In the title compound, [ZnCl₂(C₆H₇N)₂], the Zn^II ion (site symmetry 2) adopts a near-regular tetrahedral ZnN₂Cl₂ coordination geometry. In the crystal, molecules are linked by N—H⋯Cl hydrogen bonds, generating (100) sheets containing R₂²(8) loops.

Related literature

For the graph-set analysis of hydrogen-bond patterns, see: Bernstein et al. (1995 ). For applications of zinc complexes, see: Park et al. (2008 ) and for a related structure, see: Ejaz et al. (2009 ).

Experimental

Crystal data

[ZnCl₂(C₆H₇N)₂]
M_r = 322.52
Monoclinic, C 2/c
a = 26.0713 (7) Å
b = 4.7958 (1) Å
c = 11.5880 (3) Å
β = 108.823 (1)°
V = 1371.39 (6) Å³
Z = 4
Mo Kα radiation
μ = 2.16 mm⁻¹
T = 296 K
0.41 × 0.38 × 0.36 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
6369 measured reflections
1687 independent reflections
1523 reflections with I > 2σ(I)
R_int = 0.024

Refinement

R[F² > 2σ(F²)] = 0.025
wR(F²) = 0.102
S = 1.01
1687 reflections
86 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.42 e Å⁻³
Δρ_min = −0.60 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

Zn1—N1	2.0515 (16)
Zn1—Cl1	2.2454 (5)

N1—Zn1—Cl1	109.08 (5)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯Cl1ⁱ	0.85 (2)	2.60 (2)	3.4246 (17)	165 (2)
N1—H1B⋯Cl1ⁱⁱ	0.86 (2)	2.63 (2)	3.4253 (18)	155 (2)
Symmetry codes: (i) -x+1, -y, -z+1; (ii) $[-x+1, y-1, -z+{\script{3\over 2}}]$ .

Data collection: APEX2 (Bruker, 2009 ); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810012274/hb5384sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810012274/hb5384Isup2.hkl

checkCIF report

Comment top

The title compound is supramolecular complex of Zn^II having weak non-classical (N–H···Cl) hydrogen bonds, these non-classical hydrogen bonds act as structural motif for construction of hydrogen bonded polymeric compounds. The intermolecular N–H···Cl hydrogen bond interactions played important role to form a 2-dimensional framework. These hydrogen bonded zinc complexes have shown heterogeneous catalytic activities in some transesterification reaction (Park et al., 2008). The title compound is similar to our previously reported compound ''Dianilinedibromidozinc(II)'' Ejaz et al. (2009). Herein, we report the synthesis and crystal structure of the title compound, (I).

The molecular structure of (I) is presented in Fig.1. The compound crystallizes in the space group C2/c with Z'=1/2. The Zn^II ion is located on a 2-fold axis and is coordinated by two Cl atoms [Zn1—Cl1/Cl1ⁱ = 2.2454 (5) Å] and two amino N atoms from aniline ligands [Zn1—N1/N1ⁱ = 2.0515 (16) Å] [symmetry code: (i) 1-x, y, 3/2-z]. The geometry around the Zn^II ion is that of a tetrahedral. The benzene ring plane is approximately planar, with maximum deviation from the least-squares plane being 0.005 (2)Å for atom C1.

The amino nitrogen N1 in the molecule at (x, y, z) acts as a hydrogen-bond donor (Table 2) to atom Cl1ⁱ so forming a centrosymmetric R₂²(8) (Bernstein et al., 1995) ring centred at (1/2, 0, 1/2). Similarly, amino nitrogen N1 in the molecule at (x, y, z) acts as a hydrogen-bond donor to atom Cl1ⁱⁱ so forming a C(4)[R₂²(8)] chain of rings running parallel to the [0-10] direction. The combination of N—H···Cl hydrogen bonds generates R₄³(12) rings parallel to the bc plane (Fig. 2).

Related literature top

For the graph-set analysis of hydrogen-bond pattersn, see: Bernstein et al. (1995). For applications of zinc complexes, see: Park et al. (2008) and for a related structure, see: Ejaz et al. (2009).

Experimental top

The title compound was synthesized from zinc chloride (0.136 g, 1 mmol) and aniline (0.186 ml, 2 mmol) in methanol (20 ml). Colourless prisms of (I) were obtained from methanol.

Structure description top

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. A view of the molecule of (I), showing displacement ellipsoids drawn at the 30% probability level. [Symmetry code: (i) 1-x, y, 3/2-z.]
	Fig. 2. Part of the crystal structure of (I), showing the formation of R₂²(8) and R₄³(12) rings. H atoms not involved in these interactions have been omitted for clarity. (Symmetry codes as in Table 2).

Dianilinedichloridozinc(II) top

Crystal data top

[ZnCl₂(C₆H₇N)₂]	F(000) = 656
M_r = 322.52	D_x = 1.562 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 3956 reflections
a = 26.0713 (7) Å	θ = 2.9–28.3°
b = 4.7958 (1) Å	µ = 2.16 mm⁻¹
c = 11.5880 (3) Å	T = 296 K
β = 108.823 (1)°	Prism, colourless
V = 1371.39 (6) Å³	0.41 × 0.38 × 0.36 mm
Z = 4

Data collection top

Bruker Kappa APEXII CCD diffractometer	1523 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.024
Graphite monochromator	θ_max = 28.3°, θ_min = 1.7°
phi and ω scans	h = −33→34
6369 measured reflections	k = −6→6
1687 independent reflections	l = −15→15

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)] = 0.025	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.102	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	w = 1/[σ²(F_o²) + (0.084P)²] where P = (F_o² + 2F_c²)/3
1687 reflections	(Δ/σ)_max = 0.001
86 parameters	Δρ_max = 0.42 e Å⁻³
2 restraints	Δρ_min = −0.60 e Å⁻³

Crystal data top

[ZnCl₂(C₆H₇N)₂]	V = 1371.39 (6) Å³
M_r = 322.52	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 26.0713 (7) Å	µ = 2.16 mm⁻¹
b = 4.7958 (1) Å	T = 296 K
c = 11.5880 (3) Å	0.41 × 0.38 × 0.36 mm
β = 108.823 (1)°

Data collection top

Bruker Kappa APEXII CCD diffractometer	1523 reflections with I > 2σ(I)
6369 measured reflections	R_int = 0.024
1687 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.025	2 restraints
wR(F²) = 0.102	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	Δρ_max = 0.42 e Å⁻³
1687 reflections	Δρ_min = −0.60 e Å⁻³
86 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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
C1	0.60906 (8)	−0.0454 (4)	0.73942 (19)	0.0331 (4)
C2	0.61732 (9)	0.1536 (5)	0.6605 (2)	0.0439 (5)
H2	0.5901	0.1934	0.5877	0.053*
C3	0.66631 (11)	0.2925 (5)	0.6906 (3)	0.0576 (6)
H3	0.6721	0.4253	0.6376	0.069*
C4	0.70643 (10)	0.2359 (6)	0.7981 (3)	0.0607 (7)
H4	0.7394	0.3296	0.8179	0.073*
C5	0.69781 (12)	0.0404 (7)	0.8765 (3)	0.0627 (8)
H5	0.7250	0.0025	0.9495	0.075*
C6	0.64892 (10)	−0.1007 (5)	0.8474 (2)	0.0489 (5)
H6	0.6432	−0.2323	0.9009	0.059*
N1	0.55735 (7)	−0.1834 (3)	0.70997 (15)	0.0341 (3)
H1A	0.5471 (11)	−0.230 (6)	0.6350 (17)	0.054 (8)*
H1B	0.5617 (10)	−0.332 (4)	0.754 (2)	0.045 (6)*
Cl1	0.45849 (2)	0.32674 (10)	0.58908 (4)	0.04016 (17)
Zn1	0.5000	0.05523 (6)	0.7500	0.03138 (15)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0365 (9)	0.0326 (9)	0.0337 (10)	0.0014 (6)	0.0163 (8)	−0.0056 (7)
C2	0.0493 (11)	0.0451 (11)	0.0397 (11)	−0.0040 (9)	0.0179 (9)	0.0005 (9)
C3	0.0661 (15)	0.0534 (13)	0.0633 (16)	−0.0166 (11)	0.0350 (13)	−0.0052 (11)
C4	0.0435 (12)	0.0645 (15)	0.0768 (18)	−0.0120 (10)	0.0233 (12)	−0.0191 (14)
C5	0.0438 (13)	0.0722 (19)	0.0598 (18)	0.0019 (11)	−0.0002 (12)	−0.0077 (13)
C6	0.0484 (12)	0.0520 (12)	0.0429 (12)	0.0040 (9)	0.0098 (10)	0.0047 (10)
N1	0.0409 (8)	0.0301 (7)	0.0337 (8)	−0.0014 (6)	0.0154 (7)	−0.0032 (6)
Cl1	0.0538 (3)	0.0383 (3)	0.0275 (3)	0.00096 (19)	0.0120 (2)	0.00388 (17)
Zn1	0.0355 (2)	0.0309 (2)	0.0300 (2)	0.000	0.01373 (14)	0.000

Geometric parameters (Å, º) top

C1—C6	1.370 (3)	C5—C6	1.385 (4)
C1—C2	1.386 (3)	C5—H5	0.9300
C1—N1	1.441 (3)	C6—H6	0.9300
C2—C3	1.382 (3)	Zn1—N1	2.0515 (16)
C2—H2	0.9300	N1—H1A	0.852 (17)
C3—C4	1.371 (4)	N1—H1B	0.860 (17)
C3—H3	0.9300	Zn1—Cl1	2.2454 (5)
C4—C5	1.373 (5)	Zn1—N1ⁱ	2.0515 (16)
C4—H4	0.9300	Zn1—Cl1ⁱ	2.2454 (5)

C6—C1—C2	120.2 (2)	C1—C6—C5	119.6 (3)
C6—C1—N1	120.2 (2)	C1—C6—H6	120.2
C2—C1—N1	119.52 (19)	C5—C6—H6	120.2
C3—C2—C1	119.5 (2)	C1—N1—Zn1	112.63 (11)
C3—C2—H2	120.2	C1—N1—H1A	108.9 (19)
C1—C2—H2	120.2	Zn1—N1—H1A	111.4 (19)
C4—C3—C2	120.4 (3)	C1—N1—H1B	107.8 (16)
C4—C3—H3	119.8	Zn1—N1—H1B	107.1 (17)
C2—C3—H3	119.8	H1A—N1—H1B	109 (3)
C3—C4—C5	119.8 (2)	N1—Zn1—N1ⁱ	112.17 (9)
C3—C4—H4	120.1	N1—Zn1—Cl1ⁱ	108.68 (5)
C5—C4—H4	120.1	N1ⁱ—Zn1—Cl1ⁱ	109.08 (5)
C4—C5—C6	120.5 (3)	N1—Zn1—Cl1	109.08 (5)
C4—C5—H5	119.8	N1ⁱ—Zn1—Cl1	108.68 (5)
C6—C5—H5	119.8	Cl1ⁱ—Zn1—Cl1	109.11 (3)

C6—C1—C2—C3	1.0 (3)	C4—C5—C6—C1	0.3 (4)
N1—C1—C2—C3	177.9 (2)	C6—C1—N1—Zn1	97.29 (19)
C1—C2—C3—C4	−0.5 (4)	C2—C1—N1—Zn1	−79.6 (2)
C2—C3—C4—C5	−0.2 (4)	C1—N1—Zn1—N1ⁱ	−151.65 (16)
C3—C4—C5—C6	0.2 (5)	C1—N1—Zn1—Cl1ⁱ	−30.96 (15)
C2—C1—C6—C5	−0.9 (4)	C1—N1—Zn1—Cl1	87.90 (14)
N1—C1—C6—C5	−177.8 (2)

Symmetry code: (i) −x+1, y, −z+3/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Cl1ⁱⁱ	0.85 (2)	2.60 (2)	3.4246 (17)	165 (2)
N1—H1B···Cl1ⁱⁱⁱ	0.86 (2)	2.63 (2)	3.4253 (18)	155 (2)

Symmetry codes: (ii) −x+1, −y, −z+1; (iii) −x+1, y−1, −z+3/2.

Experimental details

Crystal data
Chemical formula	[ZnCl₂(C₆H₇N)₂]
M_r	322.52
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	296
a, b, c (Å)	26.0713 (7), 4.7958 (1), 11.5880 (3)
β (°)	108.823 (1)
V (Å³)	1371.39 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	2.16
Crystal size (mm)	0.41 × 0.38 × 0.36

Data collection
Diffractometer	Bruker Kappa APEXII CCD
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	6369, 1687, 1523
R_int	0.024
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.025, 0.102, 1.01
No. of reflections	1687
No. of parameters	86
No. of restraints	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.42, −0.60

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Selected geometric parameters (Å, º) top

Zn1—N1	2.0515 (16)	Zn1—Cl1	2.2454 (5)

N1—Zn1—Cl1	109.08 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Cl1ⁱ	0.852 (17)	2.595 (18)	3.4246 (17)	165 (2)
N1—H1B···Cl1ⁱⁱ	0.860 (17)	2.625 (19)	3.4253 (18)	155 (2)

Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x+1, y−1, −z+3/2.

Acknowledgements

IUK thanks the Higher Education Commission of Pakistan for its financial support under the project `Strengthening of the Materials Chemistry Laboratory' at GCUL.

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