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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.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S2056989014027832/ff2133sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2056989014027832/ff2133Isup2.hkl
Contains datablock I

CCDC reference: 1040586

Key indicators

  • Single-crystal X-ray study
  • T = 293 K
  • Mean [sigma](C-C) = 0.004 Å
  • Disorder in main residue
  • R factor = 0.028
  • wR factor = 0.077
  • Data-to-parameter ratio = 12.8

checkCIF/PLATON results

No syntax errors found



Alert level C PLAT220_ALERT_2_C Large Non-Solvent C Ueq(max)/Ueq(min) Range 3.4 Ratio PLAT334_ALERT_2_C Small Average Benzene C-C Dist. C1 -C6 1.37 Ang. PLAT480_ALERT_4_C Long H...A H-Bond Reported H2 .. CL1 .. 2.94 Ang. PLAT910_ALERT_3_C Missing # of FCF Reflection(s) Below Th(Min) ... 8 Report PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L= 0.595 6 Report PLAT913_ALERT_3_C Missing # of Very Strong Reflections in FCF .... 1 Note
Alert level G PLAT002_ALERT_2_G Number of Distance or Angle Restraints on AtSite 8 Note PLAT003_ALERT_2_G Number of Uiso or Uij Restrained non-H Atoms ... 4 Report PLAT005_ALERT_5_G No _iucr_refine_instructions_details in the CIF Please Do ! PLAT066_ALERT_1_G Predicted and Reported Tmin&Tmax Range Identical ? Check PLAT199_ALERT_1_G Reported _cell_measurement_temperature ..... (K) 293 Check PLAT200_ALERT_1_G Reported _diffrn_ambient_temperature ..... (K) 293 Check PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X) Zn1 -- Cl1 .. 5.8 su PLAT300_ALERT_4_G Atom Site Occupancy of >C7 is Constrained at 0.740 Check PLAT300_ALERT_4_G Atom Site Occupancy of >C8 is Constrained at 0.740 Check PLAT300_ALERT_4_G Atom Site Occupancy of <C7' is Constrained at 0.260 Check PLAT300_ALERT_4_G Atom Site Occupancy of <C8' is Constrained at 0.260 Check PLAT300_ALERT_4_G Atom Site Occupancy of >C7_a is Constrained at 0.740 Check PLAT300_ALERT_4_G Atom Site Occupancy of >C8_a is Constrained at 0.740 Check PLAT300_ALERT_4_G Atom Site Occupancy of <C7'_a is Constrained at 0.260 Check PLAT300_ALERT_4_G Atom Site Occupancy of <C8'_a is Constrained at 0.260 Check PLAT301_ALERT_3_G Main Residue Disorder ............ Percentage = 19 Note PLAT720_ALERT_4_G Number of Unusual/Non-Standard Labels .......... 5 Note PLAT779_ALERT_4_G Suspect or Irrelevant (Bond) Angle in CIF .... # 15 Check C7 -C4 -C7' 1.555 1.555 1.555 18.80 Deg. PLAT860_ALERT_3_G Number of Least-Squares Restraints ............. 66 Note PLAT899_ALERT_4_G SHELXL97 is Deprecated and Succeeded by SHELXL 2014 Note PLAT909_ALERT_3_G Percentage of Observed Data at Theta(Max) still 78 %
0 ALERT level A = Most likely a serious problem - resolve or explain 0 ALERT level B = A potentially serious problem, consider carefully 6 ALERT level C = Check. Ensure it is not caused by an omission or oversight 21 ALERT level G = General information/check it is not something unexpected 3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 5 ALERT type 2 Indicator that the structure model may be wrong or deficient 6 ALERT type 3 Indicator that the structure quality may be low 12 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check

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.

Refinement top

N and C-bound H atoms were positioned geometrically (C–H = 0.93–0.97 Å) and allowed to ride on their parent atoms, with Uiso(H) = 1.5Ueq(C) for methyl H atoms and 1.2Ueq(C) for all other H atoms.

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
[Figure 1] Fig. 1. The molecular structure of the title compound with displacement ellipsoids drawn at the 30% probability level.
[Figure 2] 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
Mr = 378.63Dx = 1.403 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 5623 reflections
a = 32.7291 (16) Åθ = 2.6–24.9°
b = 4.7499 (4) ŵ = 1.66 mm1
c = 11.6479 (8) ÅT = 293 K
β = 98.016 (7)°Block, colourless
V = 1793.1 (2) Å30.35 × 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 tube1440 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.029
ω and ϕ scansθmax = 25.0°, θmin = 4.6°
Absorption correction: multi-scan
(CrysAlis PRO; Oxford Diffraction, 2009)
h = 3638
Tmin = 0.564, Tmax = 0.660k = 55
4578 measured reflectionsl = 1313
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)] = 0.028Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.077H atoms treated by a mixture of independent and constrained refinement
S = 1.10 w = 1/[σ2(Fo2) + (0.0411P)2]
where P = (Fo2 + 2Fc2)/3
1578 reflections(Δ/σ)max = 0.001
123 parametersΔρmax = 0.46 e Å3
66 restraintsΔρmin = 0.28 e Å3
Crystal data top
[ZnCl2(C8H11N)2]V = 1793.1 (2) Å3
Mr = 378.63Z = 4
Monoclinic, C2/cMo Kα radiation
a = 32.7291 (16) ŵ = 1.66 mm1
b = 4.7499 (4) ÅT = 293 K
c = 11.6479 (8) Å0.35 × 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)
Tmin = 0.564, Tmax = 0.660Rint = 0.029
4578 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.02866 restraints
wR(F2) = 0.077H atoms treated by a mixture of independent and constrained refinement
S = 1.10Δρmax = 0.46 e Å3
1578 reflectionsΔρmin = 0.28 e Å3
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
xyzUiso*/UeqOcc. (<1)
C10.41733 (7)0.0083 (5)0.81147 (18)0.0354 (5)
C20.41424 (8)0.1721 (5)0.90189 (19)0.0434 (6)
H20.43580.18630.96280.052*
C30.37917 (9)0.3321 (6)0.9021 (2)0.0583 (7)
H30.37750.45380.96380.070*
C40.34669 (9)0.3176 (7)0.8144 (3)0.0638 (8)
C50.35114 (10)0.1405 (8)0.7234 (3)0.0727 (9)
H50.33000.13060.66130.087*
C60.38593 (9)0.0229 (6)0.7211 (2)0.0557 (7)
H60.38800.14170.65860.067*
C70.3096 (3)0.505 (3)0.8230 (13)0.096 (4)0.74 (2)
H7A0.31910.69160.84800.115*0.74 (2)
H7B0.29350.52290.74690.115*0.74 (2)
C80.2826 (2)0.392 (3)0.9062 (8)0.108 (3)0.74 (2)
H8A0.25960.51590.90880.162*0.74 (2)
H8B0.29830.37730.98210.162*0.74 (2)
H8C0.27260.20850.88090.162*0.74 (2)
C7'0.3026 (5)0.427 (8)0.800 (3)0.090 (7)0.26 (2)
H7'10.28340.27230.78120.109*0.26 (2)
H7'20.29840.56260.73720.109*0.26 (2)
C8'0.2950 (11)0.565 (9)0.913 (2)0.119 (8)0.26 (2)
H8'10.26720.63530.90540.178*0.26 (2)
H8'20.31390.71850.93090.178*0.26 (2)
H8'30.29900.42930.97480.178*0.26 (2)
N10.45462 (6)0.1686 (4)0.80964 (16)0.0371 (4)
Cl10.530459 (19)0.33620 (12)0.89413 (4)0.04150 (19)
Zn10.50000.06363 (7)0.75000.03228 (16)
H1A0.4494 (7)0.320 (4)0.7676 (17)0.048 (7)*
H1B0.4647 (7)0.216 (5)0.8810 (14)0.058 (8)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0385 (13)0.0332 (11)0.0360 (12)0.0035 (11)0.0103 (10)0.0059 (9)
C20.0492 (15)0.0410 (13)0.0398 (12)0.0043 (12)0.0059 (10)0.0019 (10)
C30.0674 (19)0.0497 (16)0.0624 (17)0.0114 (16)0.0253 (15)0.0013 (13)
C40.0467 (16)0.068 (2)0.080 (2)0.0142 (16)0.0189 (15)0.0256 (16)
C50.0452 (17)0.104 (3)0.0649 (19)0.0029 (18)0.0070 (14)0.0154 (18)
C60.0479 (17)0.0712 (18)0.0472 (15)0.0081 (15)0.0034 (13)0.0095 (13)
C70.061 (4)0.103 (7)0.129 (7)0.030 (4)0.036 (4)0.032 (5)
C80.060 (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)
N10.0438 (12)0.0288 (10)0.0396 (11)0.0005 (9)0.0087 (9)0.0011 (8)
Cl10.0565 (4)0.0367 (3)0.0300 (3)0.0007 (3)0.0015 (2)0.0050 (2)
Zn10.0388 (3)0.0283 (2)0.0307 (2)0.0000.00804 (16)0.000
Geometric parameters (Å, º) top
C1—C61.367 (3)C8—H8A0.9600
C1—C21.372 (3)C8—H8B0.9600
C1—N11.441 (3)C8—H8C0.9600
C2—C31.377 (4)C7'—C8'1.527 (19)
C2—H20.9300C7'—H7'10.9700
C3—C41.370 (4)C7'—H7'20.9700
C3—H30.9300C8'—H8'10.9600
C4—C51.377 (4)C8'—H8'20.9600
C4—C71.521 (6)C8'—H8'30.9600
C4—C7'1.521 (10)N1—Zn12.0478 (19)
C5—C61.381 (4)N1—H1A0.875 (16)
C5—H50.9300N1—H1B0.881 (16)
C6—H60.9300Cl1—Zn12.2409 (5)
C7—C81.500 (11)Zn1—N1i2.0478 (19)
C7—H7A0.9700Zn1—Cl1i2.2409 (6)
C7—H7B0.9700
C6—C1—C2119.7 (2)H8A—C8—H8B109.5
C6—C1—N1120.6 (2)C7—C8—H8C109.5
C2—C1—N1119.6 (2)H8A—C8—H8C109.5
C1—C2—C3119.8 (2)H8B—C8—H8C109.5
C1—C2—H2120.1C4—C7'—C8'108.5 (16)
C3—C2—H2120.1C4—C7'—H7'1110.0
C4—C3—C2122.1 (3)C8'—C7'—H7'1110.0
C4—C3—H3119.0C4—C7'—H7'2110.0
C2—C3—H3119.0C8'—C7'—H7'2110.0
C3—C4—C5116.8 (3)H7'1—C7'—H7'2108.4
C3—C4—C7117.7 (7)C7'—C8'—H8'1109.5
C5—C4—C7125.4 (7)C7'—C8'—H8'2109.5
C3—C4—C7'133.8 (10)H8'1—C8'—H8'2109.5
C5—C4—C7'108.9 (10)C7'—C8'—H8'3109.5
C7—C4—C7'18.8 (14)H8'1—C8'—H8'3109.5
C4—C5—C6122.3 (3)H8'2—C8'—H8'3109.5
C4—C5—H5118.9C1—N1—Zn1112.09 (13)
C6—C5—H5118.9C1—N1—H1A110.0 (16)
C1—C6—C5119.3 (3)Zn1—N1—H1A110.4 (16)
C1—C6—H6120.3C1—N1—H1B109.2 (17)
C5—C6—H6120.3Zn1—N1—H1B105.3 (17)
C8—C7—C4112.3 (8)H1A—N1—H1B110 (2)
C8—C7—H7A109.1N1i—Zn1—N1114.80 (11)
C4—C7—H7A109.1N1i—Zn1—Cl1i108.97 (6)
C8—C7—H7B109.1N1—Zn1—Cl1i107.31 (6)
C4—C7—H7B109.1N1i—Zn1—Cl1107.31 (6)
H7A—C7—H7B107.9N1—Zn1—Cl1108.97 (6)
C7—C8—H8A109.5Cl1i—Zn1—Cl1109.41 (3)
C7—C8—H8B109.5
C6—C1—C2—C31.5 (4)C3—C4—C7—C877.7 (15)
N1—C1—C2—C3178.0 (2)C5—C4—C7—C8104.8 (14)
C1—C2—C3—C40.1 (4)C7'—C4—C7—C874 (5)
C2—C3—C4—C51.8 (4)C3—C4—C7'—C8'4 (5)
C2—C3—C4—C7179.6 (5)C5—C4—C7'—C8'167 (3)
C2—C3—C4—C7'168 (2)C7—C4—C7'—C8'39 (4)
C3—C4—C5—C62.0 (5)C6—C1—N1—Zn195.6 (2)
C7—C4—C5—C6179.6 (6)C2—C1—N1—Zn180.9 (2)
C7'—C4—C5—C6170.4 (17)C1—N1—Zn1—N1i159.46 (17)
C2—C1—C6—C51.3 (4)C1—N1—Zn1—Cl1i38.19 (16)
N1—C1—C6—C5177.8 (2)C1—N1—Zn1—Cl180.18 (15)
C4—C5—C6—C10.5 (5)
Symmetry code: (i) x+1, y, z+3/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C2—H2···Cl1ii0.932.943.630 (2)132
N1—H1A···Cl1iii0.88 (2)2.65 (2)3.424 (2)149 (2)
N1—H1B···Cl1iv0.88 (2)2.66 (2)3.5083 (19)161 (2)
Symmetry codes: (ii) x+1, y+1, z+2; (iii) x+1, y1, z+3/2; (iv) x+1, y, z+2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C2—H2···Cl1i0.932.943.630 (2)132.4
N1—H1A···Cl1ii0.875 (16)2.645 (18)3.424 (2)149 (2)
N1—H1B···Cl1iii0.881 (16)2.663 (18)3.5083 (19)161 (2)
Symmetry codes: (i) x+1, y+1, z+2; (ii) x+1, y1, z+3/2; (iii) x+1, y, z+2.
 

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