Crystal structure of di­chlorido­bis­(4-ethyl­aniline-κN)zinc

Govindaraj, J.; Thirumurugan, S.; Reddy, D.S.; Anbalagan, K.; SubbiahPandi, A.

doi:10.1107/S2056989014027832

metal-organic compounds

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ISSN: 2056-9890

Volume 71| Part 2| February 2015| Pages m21-m22

doi:10.1107/S2056989014027832

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Crystal structure of dichloridobis(4-ethylaniline-κN)zinc

J. Govindaraj,^a S. Thirumurugan,^b D. Snehalatha Reddy,^b K. Anbalagan ^b and A. SubbiahPandi ^c ^*

^aDepartment of Physics, Pachaiyappa's College for Men, Kanchipuram 631 501, India, ^bDepartment of Chemistry, Pondicherry University, Pondicherry 605 014, India, and ^cDepartment of Physics, Presidency College (Autonomous), Chennai 600 005, India
^*Correspondence e-mail: aspandian59@gmail.com

Edited by K. Fejfarova, Institute of Macromolecular Chemistry, AS CR, v.v.i, Czech Republic (Received 17 November 2014; accepted 21 December 2014; online 14 January 2015)

The title compound, [ZnCl₂(C₈H₁₁N)₂], was synthesized by the reaction of zinc dichloride and 4-ethylaniline. The Zn²⁺ cation is coordinated by two Cl⁻ anions and the N atoms of two 4-ethylaniline ligands, forming a distorted Zn(N₂Cl₂) tetrahedron. The dihedral angle between the two benzene rings is 85.3 (2)° The Zn atom lies on a twofold rotation axis. The ethyl substituents are disordered over two sets of sites in a 0.74 (2):0.26 (2) ratio. In the crystal, N—H⋯Cl hydrogen bonds link the molecules into sheets perpendicular to the a axis. C—H⋯Cl interactions also occur.

Keywords: crystal structure; zinc complex; tetrahedral coordination; hydrogen bonding.

CCDC reference: 1040586

1. Related literature

For the biological activity and potential applications of mixed-ligand dichloridozinc complexes, see: Tang & Shay (2001 ); Lynch et al. (2001 ); Coulston & Dandona (1980 ); May & Contoreggi (1982 ). For a related structure, see; Ejaz et al. (2009 ).

2. Experimental

2.1. Crystal data

[ZnCl₂(C₈H₁₁N)₂]
M_r = 378.63
Monoclinic, C 2/c
a = 32.7291 (16) Å
b = 4.7499 (4) Å
c = 11.6479 (8) Å
β = 98.016 (7)°
V = 1793.1 (2) Å³
Z = 4
Mo Kα radiation
μ = 1.66 mm⁻¹
T = 293 K
0.35 × 0.30 × 0.25 mm

2.2. Data collection

Oxford diffraction Xcalibur diffractometer with an Eos detector
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis CCD, CrysAlis RED and CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$ ) T_min = 0.564, T_max = 0.660
4578 measured reflections
1578 independent reflections
1440 reflections with I > 2σ(I)
R_int = 0.029

2.3. Refinement

R[F² > 2σ(F²)] = 0.028
wR(F²) = 0.077
S = 1.10
1578 reflections
123 parameters
66 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.46 e Å⁻³
Δρ_min = −0.28 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2⋯Cl1ⁱ	0.93	2.94	3.630 (2)	132
N1—H1A⋯Cl1ⁱⁱ	0.88 (2)	2.65 (2)	3.424 (2)	149 (2)
N1—H1B⋯Cl1ⁱⁱⁱ	0.88 (2)	2.66 (2)	3.5083 (19)	161 (2)
Symmetry codes: (i) -x+1, -y+1, -z+2; (ii) $[-x+1, y-1, -z+{\script{3\over 2}}]$ ; (iii) -x+1, -y, -z+2.

Data collection: CrysAlis CCD (Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis CCD, CrysAlis RED and CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$ ); cell refinement: CrysAlis RED (Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis CCD, CrysAlis RED and CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$ ); data reduction: CrysAlis RED; 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, 2012 ) and DIAMOND (Brandenburg, 2006 ); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ).

Supporting information

CCDC reference: 1040586

Crystal structure: contains datablocks global, I. DOI: 10.1107/S2056989014027832/ff2133sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2056989014027832/ff2133Isup2.hkl

checkCIF report

Comment top

Zinc has many biological functions. It is considered to be an essential nutrient that is required for optimal growth and normal development of vertebrate organisms, as well as being important for maintaining the structure of many proteins. From previous research results, it has been known for many years that zinc mimics the actions of insulin on cells, including promotion of both lipogenesis and glucose transport. Zinc deficiency may indeed affect the optimal functioning of the insulin-signaling pathway (Tang & Shay, 2001; Lynch et al., 2001; Coulston & Dandona, 1980; May & Contoreggi, 1982).

In the title compound (I), (Fig. 1), the Zn²⁺ cation lies on a crystallographic twofold rotation axis, with one half of the molecule connected to the other on by this symmetry operation. The bond distance Zn—Cl and Zn—N are 2.2409 (6) and 2.048 (2) Å, and the bond angles Cl—Zn—Cl and N—Zn—N are 109.41 (3) and 114.80 (11)°. All bond lengths and bond angles in (I) are in the range of expected values. The dihedral angle between the aromatic rings of the 4-ethylaniline ligands is 85.3 (2)°.

N—H···Cl hydrogen bonds serve to link the molecules into sheets perpendicular to the a axis.

Related literature top

For the biological activity and potential applications of mixed-ligand dichloridozinc complexes, see: Tang & Shay (2001); Lynch et al. (2001); Coulston & Dandona (1980); May & Contoreggi (1982). For related structure, see; Ejaz et al. (2009).

Experimental top

The title compound was synthesized using zinc chloride (0.5 g, 1 mmol) and 4-ethylaniline (0.91 ml, 2 mmol) in 20 ml of ethanol stirring for 2 h. Colorless crystals were obtained and recrystallized from ethanol. The resulting solution was subjected to crystallization by slow evaporation of the solvent resulting in single crystals suitable for X-ray crystallographic studies.

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2009); cell refinement: CrysAlis RED (Oxford Diffraction, 2009); data reduction: CrysAlis RED (Oxford Diffraction, 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, 2012) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of the title compound with displacement ellipsoids drawn at the 30% probability level.
	Fig. 2. The crystal packing of the title compound viewed down the a axis showing the hydrogen bonded sheet. Hydrogen bond are shown as dashed lines. The minor disorder component and hydrogen atoms not participating in N—H···Cl interactions are omitted for clarity.

Dichloridobis(4-ethylaniline-κN)zinc top

Crystal data top

[ZnCl₂(C₈H₁₁N)₂]	F(000) = 784
M_r = 378.63	D_x = 1.403 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 5623 reflections
a = 32.7291 (16) Å	θ = 2.6–24.9°
b = 4.7499 (4) Å	µ = 1.66 mm⁻¹
c = 11.6479 (8) Å	T = 293 K
β = 98.016 (7)°	Block, colourless
V = 1793.1 (2) Å³	0.35 × 0.30 × 0.25 mm
Z = 4

Data collection top

Oxford diffraction Xcalibur diffractometer with an Eos detector	1578 independent reflections
Radiation source: fine-focus sealed tube	1440 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.029
ω and ϕ scans	θ_max = 25.0°, θ_min = 4.6°
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	h = −36→38
T_min = 0.564, T_max = 0.660	k = −5→5
4578 measured reflections	l = −13→13

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)] = 0.028	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.077	H atoms treated by a mixture of independent and constrained refinement
S = 1.10	w = 1/[σ²(F_o²) + (0.0411P)²] where P = (F_o² + 2F_c²)/3
1578 reflections	(Δ/σ)_max = 0.001
123 parameters	Δρ_max = 0.46 e Å⁻³
66 restraints	Δρ_min = −0.28 e Å⁻³

Crystal data top

[ZnCl₂(C₈H₁₁N)₂]	V = 1793.1 (2) Å³
M_r = 378.63	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 32.7291 (16) Å	µ = 1.66 mm⁻¹
b = 4.7499 (4) Å	T = 293 K
c = 11.6479 (8) Å	0.35 × 0.30 × 0.25 mm
β = 98.016 (7)°

Data collection top

Oxford diffraction Xcalibur diffractometer with an Eos detector	1578 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	1440 reflections with I > 2σ(I)
T_min = 0.564, T_max = 0.660	R_int = 0.029
4578 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.028	66 restraints
wR(F²) = 0.077	H atoms treated by a mixture of independent and constrained refinement
S = 1.10	Δρ_max = 0.46 e Å⁻³
1578 reflections	Δρ_min = −0.28 e Å⁻³
123 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	Occ. (<1)
C1	0.41733 (7)	−0.0083 (5)	0.81147 (18)	0.0354 (5)
C2	0.41424 (8)	0.1721 (5)	0.90189 (19)	0.0434 (6)
H2	0.4358	0.1863	0.9628	0.052*
C3	0.37917 (9)	0.3321 (6)	0.9021 (2)	0.0583 (7)
H3	0.3775	0.4538	0.9638	0.070*
C4	0.34669 (9)	0.3176 (7)	0.8144 (3)	0.0638 (8)
C5	0.35114 (10)	0.1405 (8)	0.7234 (3)	0.0727 (9)
H5	0.3300	0.1306	0.6613	0.087*
C6	0.38593 (9)	−0.0229 (6)	0.7211 (2)	0.0557 (7)
H6	0.3880	−0.1417	0.6586	0.067*
C7	0.3096 (3)	0.505 (3)	0.8230 (13)	0.096 (4)	0.74 (2)
H7A	0.3191	0.6916	0.8480	0.115*	0.74 (2)
H7B	0.2935	0.5229	0.7469	0.115*	0.74 (2)
C8	0.2826 (2)	0.392 (3)	0.9062 (8)	0.108 (3)	0.74 (2)
H8A	0.2596	0.5159	0.9088	0.162*	0.74 (2)
H8B	0.2983	0.3773	0.9821	0.162*	0.74 (2)
H8C	0.2726	0.2085	0.8809	0.162*	0.74 (2)
C7'	0.3026 (5)	0.427 (8)	0.800 (3)	0.090 (7)	0.26 (2)
H7'1	0.2834	0.2723	0.7812	0.109*	0.26 (2)
H7'2	0.2984	0.5626	0.7372	0.109*	0.26 (2)
C8'	0.2950 (11)	0.565 (9)	0.913 (2)	0.119 (8)	0.26 (2)
H8'1	0.2672	0.6353	0.9054	0.178*	0.26 (2)
H8'2	0.3139	0.7185	0.9309	0.178*	0.26 (2)
H8'3	0.2990	0.4293	0.9748	0.178*	0.26 (2)
N1	0.45462 (6)	−0.1686 (4)	0.80964 (16)	0.0371 (4)
Cl1	0.530459 (19)	0.33620 (12)	0.89413 (4)	0.04150 (19)
Zn1	0.5000	0.06363 (7)	0.7500	0.03228 (16)
H1A	0.4494 (7)	−0.320 (4)	0.7676 (17)	0.048 (7)*
H1B	0.4647 (7)	−0.216 (5)	0.8810 (14)	0.058 (8)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0385 (13)	0.0332 (11)	0.0360 (12)	−0.0035 (11)	0.0103 (10)	0.0059 (9)
C2	0.0492 (15)	0.0410 (13)	0.0398 (12)	0.0043 (12)	0.0059 (10)	0.0019 (10)
C3	0.0674 (19)	0.0497 (16)	0.0624 (17)	0.0114 (16)	0.0253 (15)	0.0013 (13)
C4	0.0467 (16)	0.068 (2)	0.080 (2)	0.0142 (16)	0.0189 (15)	0.0256 (16)
C5	0.0452 (17)	0.104 (3)	0.0649 (19)	−0.0029 (18)	−0.0070 (14)	0.0154 (18)
C6	0.0479 (17)	0.0712 (18)	0.0472 (15)	−0.0081 (15)	0.0034 (13)	−0.0095 (13)
C7	0.061 (4)	0.103 (7)	0.129 (7)	0.030 (4)	0.036 (4)	0.032 (5)
C8	0.060 (4)	0.119 (7)	0.155 (6)	0.017 (4)	0.048 (4)	0.007 (5)
C7'	0.069 (10)	0.075 (11)	0.126 (11)	0.019 (8)	0.010 (9)	0.019 (9)
C8'	0.093 (14)	0.131 (16)	0.136 (13)	0.051 (12)	0.031 (11)	0.011 (13)
N1	0.0438 (12)	0.0288 (10)	0.0396 (11)	0.0005 (9)	0.0087 (9)	0.0011 (8)
Cl1	0.0565 (4)	0.0367 (3)	0.0300 (3)	0.0007 (3)	0.0015 (2)	−0.0050 (2)
Zn1	0.0388 (3)	0.0283 (2)	0.0307 (2)	0.000	0.00804 (16)	0.000

Geometric parameters (Å, º) top

C1—C6	1.367 (3)	C8—H8A	0.9600
C1—C2	1.372 (3)	C8—H8B	0.9600
C1—N1	1.441 (3)	C8—H8C	0.9600
C2—C3	1.377 (4)	C7'—C8'	1.527 (19)
C2—H2	0.9300	C7'—H7'1	0.9700
C3—C4	1.370 (4)	C7'—H7'2	0.9700
C3—H3	0.9300	C8'—H8'1	0.9600
C4—C5	1.377 (4)	C8'—H8'2	0.9600
C4—C7	1.521 (6)	C8'—H8'3	0.9600
C4—C7'	1.521 (10)	N1—Zn1	2.0478 (19)
C5—C6	1.381 (4)	N1—H1A	0.875 (16)
C5—H5	0.9300	N1—H1B	0.881 (16)
C6—H6	0.9300	Cl1—Zn1	2.2409 (5)
C7—C8	1.500 (11)	Zn1—N1ⁱ	2.0478 (19)
C7—H7A	0.9700	Zn1—Cl1ⁱ	2.2409 (6)
C7—H7B	0.9700

C6—C1—C2	119.7 (2)	H8A—C8—H8B	109.5
C6—C1—N1	120.6 (2)	C7—C8—H8C	109.5
C2—C1—N1	119.6 (2)	H8A—C8—H8C	109.5
C1—C2—C3	119.8 (2)	H8B—C8—H8C	109.5
C1—C2—H2	120.1	C4—C7'—C8'	108.5 (16)
C3—C2—H2	120.1	C4—C7'—H7'1	110.0
C4—C3—C2	122.1 (3)	C8'—C7'—H7'1	110.0
C4—C3—H3	119.0	C4—C7'—H7'2	110.0
C2—C3—H3	119.0	C8'—C7'—H7'2	110.0
C3—C4—C5	116.8 (3)	H7'1—C7'—H7'2	108.4
C3—C4—C7	117.7 (7)	C7'—C8'—H8'1	109.5
C5—C4—C7	125.4 (7)	C7'—C8'—H8'2	109.5
C3—C4—C7'	133.8 (10)	H8'1—C8'—H8'2	109.5
C5—C4—C7'	108.9 (10)	C7'—C8'—H8'3	109.5
C7—C4—C7'	18.8 (14)	H8'1—C8'—H8'3	109.5
C4—C5—C6	122.3 (3)	H8'2—C8'—H8'3	109.5
C4—C5—H5	118.9	C1—N1—Zn1	112.09 (13)
C6—C5—H5	118.9	C1—N1—H1A	110.0 (16)
C1—C6—C5	119.3 (3)	Zn1—N1—H1A	110.4 (16)
C1—C6—H6	120.3	C1—N1—H1B	109.2 (17)
C5—C6—H6	120.3	Zn1—N1—H1B	105.3 (17)
C8—C7—C4	112.3 (8)	H1A—N1—H1B	110 (2)
C8—C7—H7A	109.1	N1ⁱ—Zn1—N1	114.80 (11)
C4—C7—H7A	109.1	N1ⁱ—Zn1—Cl1ⁱ	108.97 (6)
C8—C7—H7B	109.1	N1—Zn1—Cl1ⁱ	107.31 (6)
C4—C7—H7B	109.1	N1ⁱ—Zn1—Cl1	107.31 (6)
H7A—C7—H7B	107.9	N1—Zn1—Cl1	108.97 (6)
C7—C8—H8A	109.5	Cl1ⁱ—Zn1—Cl1	109.41 (3)
C7—C8—H8B	109.5

C6—C1—C2—C3	1.5 (4)	C3—C4—C7—C8	−77.7 (15)
N1—C1—C2—C3	178.0 (2)	C5—C4—C7—C8	104.8 (14)
C1—C2—C3—C4	0.1 (4)	C7'—C4—C7—C8	74 (5)
C2—C3—C4—C5	−1.8 (4)	C3—C4—C7'—C8'	−4 (5)
C2—C3—C4—C7	−179.6 (5)	C5—C4—C7'—C8'	167 (3)
C2—C3—C4—C7'	168 (2)	C7—C4—C7'—C8'	−39 (4)
C3—C4—C5—C6	2.0 (5)	C6—C1—N1—Zn1	95.6 (2)
C7—C4—C5—C6	179.6 (6)	C2—C1—N1—Zn1	−80.9 (2)
C7'—C4—C5—C6	−170.4 (17)	C1—N1—Zn1—N1ⁱ	−159.46 (17)
C2—C1—C6—C5	−1.3 (4)	C1—N1—Zn1—Cl1ⁱ	−38.19 (16)
N1—C1—C6—C5	−177.8 (2)	C1—N1—Zn1—Cl1	80.18 (15)
C4—C5—C6—C1	−0.5 (5)

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
C2—H2···Cl1ⁱⁱ	0.93	2.94	3.630 (2)	132
N1—H1A···Cl1ⁱⁱⁱ	0.88 (2)	2.65 (2)	3.424 (2)	149 (2)
N1—H1B···Cl1^iv	0.88 (2)	2.66 (2)	3.5083 (19)	161 (2)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···Cl1ⁱ	0.93	2.94	3.630 (2)	132.4
N1—H1A···Cl1ⁱⁱ	0.875 (16)	2.645 (18)	3.424 (2)	149 (2)
N1—H1B···Cl1ⁱⁱⁱ	0.881 (16)	2.663 (18)	3.5083 (19)	161 (2)

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

Acknowledgements

KA is thankful to the CSIR, New Delhi [Lr: No. 01 (2570)/12/EMR-II/3.4.2012], for financial support through a major research project. The authors are thankful to the Department of Chemistry, Pondicherry University, for the single-crystal XRD instrumentation facility.

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