The title compound, [ZnCl
2(C
8H
11N)
2], was synthesized by the reaction of zinc dichloride and 4-ethylaniline. The Zn
2+ cation is coordinated by two Cl
− anions and the N atoms of two 4-ethylaniline ligands, forming a distorted Zn(N
2Cl
2) 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
CCDC reference: 1040586
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean
(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
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.
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.
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).
Dichloridobis(4-ethylaniline-
κN)zinc
top
Crystal data top
[ZnCl2(C8H11N)2] | F(000) = 784 |
Mr = 378.63 | Dx = 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 | Rint = 0.029 |
ω and ϕ scans | θmax = 25.0°, θmin = 4.6° |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009) | h = −36→38 |
Tmin = 0.564, Tmax = 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(Fo2) + (0.0411P)2] where P = (Fo2 + 2Fc2)/3 |
1578 reflections | (Δ/σ)max = 0.001 |
123 parameters | Δρmax = 0.46 e Å−3 |
66 restraints | Δρmin = −0.28 e Å−3 |
Crystal data top
[ZnCl2(C8H11N)2] | V = 1793.1 (2) Å3 |
Mr = 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) |
Tmin = 0.564, Tmax = 0.660 | Rint = 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 | Δρmax = 0.46 e Å−3 |
1578 reflections | Δρmin = −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 | Uiso*/Ueq | 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···Cl1iv | 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. |
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.