metal-organic compounds
Dichloridobis(4-fluoroaniline-κN)zinc
aCrystal Growth and Thin Film Laboratory, School of Physics, Bharathidasan University, Tiruchirappalli, Tamil Nadu 620 024, India, and bInstitute of Physics, University of Neuchâtel, Rue Emile-Argand 11, CH-2000 Neuchâtel, Switzerland
*Correspondence e-mail: krmurthin@yahoo.co.in, helen.stoeckli-evans@unine.ch
In the title compound, [ZnCl2(C6H6FN)2], the ZnII atom has a slightly distorted tetrahedral geometry, being coordinated by the N atoms of two 4-fluoroaniline molecules and the two Cl− anions. The two benzene rings are almost perpendicular to one another, making a dihedral angle of 89.96 (13)°. In the crystal, molecules are linked via pairs of N—H⋯Cl hydrogen bonds, forming chains propagating along the b axis. These chains are in turn linked via a second pair of N—H⋯Cl hydrogen bonds, forming a two-dimensional network parallel to the ab plane. The title compound crystallizes in the Pca21 and exhibits weak second harmonic generation (SHG) properties.
Related literature
For the measurement of second harmonic generation (SHG) conversion efficiency, see: Kurtz & Perry (1968). For the of dichlorido-bis(p-chloroaniline)zinc, see: Subashini et al. (2012a) and for the of dichlorodo-bis(p-bromoaniline)zinc, see: Subashini et al. (2012b); Feng et al. (2003).
Experimental
Crystal data
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Data collection: X-AREA (Stoe & Cie, 2009); cell X-AREA; data reduction: X-RED32 (Stoe & Cie, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL97, PLATON and publCIF (Westrip, 2010).
Supporting information
10.1107/S1600536812033922/is5178sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536812033922/is5178Isup2.hkl
The title compound was prepared by the condensation reaction of p-fluoroaniline with ZnCl2 in a 1:1 molar ratio. The reaction mixture was dissolved in methanol and heated under reflux for 6 h. The resulting solution was filtered and allowed to evaporate. Colourless rod-like crystals of the title compound, suitable for X-ray
were obtained in a period of ca 7 days. The same method was used for the preparation of the p-chloroaniline and p-bromoaniline ZnCl2 complexes.All the H atoms could be located in a difference Fourier map. In the final cycles of
they were included in calculated positions and treated as riding atoms: N—H = 0.92 Å and C—H = 0.95 Å with Uiso(H) = 1.2Ueq(N or C).Data collection: X-AREA (Stoe & Cie, 2009); cell
X-AREA (Stoe & Cie, 2009); data reduction: X-RED32 (Stoe & Cie, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009) and publCIF (Westrip, 2010).[ZnCl2(C6H6FN)2] | F(000) = 720 |
Mr = 358.51 | Dx = 1.718 Mg m−3 |
Orthorhombic, Pca21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2c -2ac | Cell parameters from 10039 reflections |
a = 11.6817 (5) Å | θ = 1.6–26.1° |
b = 4.7080 (2) Å | µ = 2.17 mm−1 |
c = 25.2056 (15) Å | T = 173 K |
V = 1386.24 (12) Å3 | Rod, colourless |
Z = 4 | 0.45 × 0.22 × 0.10 mm |
Stoe IPDS 2 diffractometer | 2613 independent reflections |
Radiation source: fine-focus sealed tube | 2465 reflections with I > 2σ(I) |
Plane graphite monochromator | Rint = 0.031 |
ϕ and ω scans | θmax = 25.6°, θmin = 1.6° |
Absorption correction: multi-scan (MULscanABS in PLATON; Spek, 2009) | h = −14→12 |
Tmin = 0.742, Tmax = 0.805 | k = −5→5 |
7963 measured reflections | l = −30→30 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.020 | H-atom parameters constrained |
wR(F2) = 0.043 | w = 1/[σ2(Fo2) + (0.0253P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.02 | (Δ/σ)max = 0.001 |
2613 reflections | Δρmax = 0.21 e Å−3 |
172 parameters | Δρmin = −0.32 e Å−3 |
1 restraint | Absolute structure: Flack (1983), 1273 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.013 (10) |
[ZnCl2(C6H6FN)2] | V = 1386.24 (12) Å3 |
Mr = 358.51 | Z = 4 |
Orthorhombic, Pca21 | Mo Kα radiation |
a = 11.6817 (5) Å | µ = 2.17 mm−1 |
b = 4.7080 (2) Å | T = 173 K |
c = 25.2056 (15) Å | 0.45 × 0.22 × 0.10 mm |
Stoe IPDS 2 diffractometer | 2613 independent reflections |
Absorption correction: multi-scan (MULscanABS in PLATON; Spek, 2009) | 2465 reflections with I > 2σ(I) |
Tmin = 0.742, Tmax = 0.805 | Rint = 0.031 |
7963 measured reflections |
R[F2 > 2σ(F2)] = 0.020 | H-atom parameters constrained |
wR(F2) = 0.043 | Δρmax = 0.21 e Å−3 |
S = 1.02 | Δρmin = −0.32 e Å−3 |
2613 reflections | Absolute structure: Flack (1983), 1273 Friedel pairs |
172 parameters | Absolute structure parameter: 0.013 (10) |
1 restraint |
Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles |
x | y | z | Uiso*/Ueq | ||
Zn1 | 0.11820 (2) | 0.94853 (5) | 0.29991 (2) | 0.0175 (1) | |
Cl1 | 0.24924 (5) | 0.67311 (13) | 0.25893 (2) | 0.0231 (2) | |
Cl2 | −0.01369 (5) | 0.66951 (13) | 0.33956 (2) | 0.0224 (2) | |
F1 | 0.24874 (17) | 0.4882 (4) | 0.53656 (6) | 0.0375 (5) | |
F2 | 0.00539 (17) | 0.6379 (4) | 0.05020 (6) | 0.0386 (6) | |
N1 | 0.19821 (18) | 1.1742 (4) | 0.35892 (7) | 0.0190 (6) | |
N2 | 0.03682 (17) | 1.1921 (5) | 0.24427 (7) | 0.0193 (6) | |
C1 | 0.2140 (2) | 1.0033 (5) | 0.40640 (10) | 0.0173 (8) | |
C2 | 0.3039 (2) | 0.8160 (6) | 0.40935 (9) | 0.0206 (8) | |
C3 | 0.3164 (2) | 0.6390 (6) | 0.45336 (9) | 0.0236 (8) | |
C4 | 0.2366 (2) | 0.6601 (6) | 0.49308 (9) | 0.0267 (8) | |
C5 | 0.1466 (2) | 0.8448 (7) | 0.49146 (10) | 0.0279 (8) | |
C6 | 0.1343 (2) | 1.0192 (6) | 0.44767 (12) | 0.0247 (9) | |
C7 | 0.0273 (2) | 1.0505 (5) | 0.19283 (10) | 0.0181 (7) | |
C8 | 0.1041 (2) | 1.1133 (7) | 0.15318 (10) | 0.0242 (9) | |
C9 | 0.0976 (3) | 0.9741 (7) | 0.10479 (11) | 0.0305 (9) | |
C10 | 0.0127 (2) | 0.7762 (6) | 0.09785 (9) | 0.0263 (8) | |
C11 | −0.0645 (2) | 0.7084 (6) | 0.13658 (10) | 0.0258 (8) | |
C12 | −0.0570 (2) | 0.8484 (6) | 0.18522 (9) | 0.0236 (8) | |
H1A | 0.26840 | 1.23560 | 0.34700 | 0.0230* | |
H1B | 0.15510 | 1.33170 | 0.36710 | 0.0230* | |
H2 | 0.35790 | 0.80690 | 0.38120 | 0.0250* | |
H2A | −0.03540 | 1.23620 | 0.25630 | 0.0230* | |
H2B | 0.07640 | 1.35950 | 0.24000 | 0.0230* | |
H3 | 0.37820 | 0.50830 | 0.45570 | 0.0280* | |
H5 | 0.09330 | 0.85340 | 0.51990 | 0.0340* | |
H6 | 0.07220 | 1.14880 | 0.44570 | 0.0300* | |
H8 | 0.16170 | 1.25240 | 0.15890 | 0.0290* | |
H9 | 0.15060 | 1.01470 | 0.07720 | 0.0370* | |
H11 | −0.12190 | 0.56930 | 0.13050 | 0.0310* | |
H12 | −0.10940 | 0.80520 | 0.21290 | 0.0280* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Zn1 | 0.0174 (1) | 0.0186 (1) | 0.0167 (1) | −0.0009 (1) | −0.0010 (1) | −0.0002 (2) |
Cl1 | 0.0180 (3) | 0.0236 (3) | 0.0277 (3) | 0.0019 (3) | 0.0033 (2) | −0.0017 (2) |
Cl2 | 0.0187 (3) | 0.0224 (3) | 0.0261 (3) | −0.0031 (3) | 0.0034 (2) | −0.0004 (2) |
F1 | 0.0460 (9) | 0.0433 (11) | 0.0232 (8) | −0.0064 (9) | −0.0048 (9) | 0.0147 (6) |
F2 | 0.0423 (10) | 0.0516 (13) | 0.0218 (7) | 0.0015 (9) | −0.0016 (6) | −0.0145 (7) |
N1 | 0.0200 (10) | 0.0179 (11) | 0.0191 (9) | −0.0029 (9) | −0.0014 (8) | 0.0020 (8) |
N2 | 0.0215 (11) | 0.0185 (11) | 0.0180 (10) | 0.0010 (10) | −0.0011 (8) | −0.0016 (8) |
C1 | 0.0214 (13) | 0.0145 (15) | 0.0161 (13) | −0.0048 (10) | −0.0028 (10) | −0.0017 (8) |
C2 | 0.0168 (12) | 0.0252 (15) | 0.0199 (12) | −0.0052 (11) | −0.0001 (9) | −0.0016 (10) |
C3 | 0.0199 (13) | 0.0231 (14) | 0.0277 (13) | 0.0009 (11) | −0.0043 (10) | −0.0005 (10) |
C4 | 0.0335 (15) | 0.0261 (14) | 0.0204 (12) | −0.0074 (13) | −0.0050 (10) | 0.0044 (10) |
C5 | 0.0295 (14) | 0.0329 (17) | 0.0214 (12) | −0.0033 (14) | 0.0073 (11) | 0.0003 (12) |
C6 | 0.0221 (15) | 0.0241 (17) | 0.0279 (15) | 0.0057 (13) | 0.0006 (11) | −0.0025 (10) |
C7 | 0.0200 (12) | 0.0171 (12) | 0.0172 (12) | 0.0035 (11) | −0.0028 (10) | 0.0009 (10) |
C8 | 0.0232 (14) | 0.0240 (17) | 0.0254 (14) | −0.0010 (13) | 0.0010 (10) | −0.0001 (11) |
C9 | 0.0298 (15) | 0.040 (2) | 0.0216 (13) | −0.0025 (14) | 0.0068 (11) | 0.0018 (11) |
C10 | 0.0305 (14) | 0.0306 (15) | 0.0179 (12) | 0.0081 (13) | −0.0026 (10) | −0.0057 (11) |
C11 | 0.0213 (12) | 0.0277 (16) | 0.0284 (14) | −0.0025 (12) | −0.0050 (10) | −0.0069 (11) |
C12 | 0.0241 (13) | 0.0254 (14) | 0.0212 (13) | 0.0008 (12) | 0.0021 (10) | 0.0005 (10) |
Zn1—Cl1 | 2.2565 (7) | C4—C5 | 1.365 (4) |
Zn1—Cl2 | 2.2579 (7) | C5—C6 | 1.383 (4) |
Zn1—N1 | 2.0530 (19) | C7—C8 | 1.375 (3) |
Zn1—N2 | 2.046 (2) | C7—C12 | 1.383 (3) |
F1—C4 | 1.370 (3) | C8—C9 | 1.387 (4) |
F2—C10 | 1.369 (3) | C9—C10 | 1.372 (4) |
N1—C1 | 1.454 (3) | C10—C11 | 1.367 (3) |
N2—C7 | 1.462 (3) | C11—C12 | 1.395 (4) |
N1—H1B | 0.9200 | C2—H2 | 0.9500 |
N1—H1A | 0.9200 | C3—H3 | 0.9500 |
N2—H2A | 0.9200 | C5—H5 | 0.9500 |
N2—H2B | 0.9200 | C6—H6 | 0.9500 |
C1—C6 | 1.398 (4) | C8—H8 | 0.9500 |
C1—C2 | 1.373 (3) | C9—H9 | 0.9500 |
C2—C3 | 1.395 (4) | C11—H11 | 0.9500 |
C3—C4 | 1.372 (3) | C12—H12 | 0.9500 |
Cl1—Zn1—Cl2 | 109.34 (2) | C1—C6—C5 | 119.5 (2) |
Cl1—Zn1—N1 | 108.68 (6) | N2—C7—C12 | 119.4 (2) |
Cl1—Zn1—N2 | 108.88 (6) | N2—C7—C8 | 119.8 (2) |
Cl2—Zn1—N1 | 106.92 (6) | C8—C7—C12 | 120.8 (2) |
Cl2—Zn1—N2 | 108.21 (6) | C7—C8—C9 | 120.1 (3) |
N1—Zn1—N2 | 114.72 (8) | C8—C9—C10 | 118.2 (3) |
Zn1—N1—C1 | 111.58 (14) | F2—C10—C11 | 118.3 (2) |
Zn1—N2—C7 | 112.81 (16) | F2—C10—C9 | 118.7 (2) |
C1—N1—H1A | 109.00 | C9—C10—C11 | 123.0 (2) |
C1—N1—H1B | 109.00 | C10—C11—C12 | 118.4 (2) |
H1A—N1—H1B | 108.00 | C7—C12—C11 | 119.5 (2) |
Zn1—N1—H1B | 109.00 | C1—C2—H2 | 120.00 |
Zn1—N1—H1A | 109.00 | C3—C2—H2 | 120.00 |
Zn1—N2—H2B | 109.00 | C2—C3—H3 | 121.00 |
Zn1—N2—H2A | 109.00 | C4—C3—H3 | 121.00 |
H2A—N2—H2B | 108.00 | C4—C5—H5 | 121.00 |
C7—N2—H2A | 109.00 | C6—C5—H5 | 121.00 |
C7—N2—H2B | 109.00 | C1—C6—H6 | 120.00 |
N1—C1—C6 | 119.9 (2) | C5—C6—H6 | 120.00 |
N1—C1—C2 | 119.8 (2) | C7—C8—H8 | 120.00 |
C2—C1—C6 | 120.2 (2) | C9—C8—H8 | 120.00 |
C1—C2—C3 | 120.4 (2) | C8—C9—H9 | 121.00 |
C2—C3—C4 | 117.8 (2) | C10—C9—H9 | 121.00 |
C3—C4—C5 | 123.2 (2) | C10—C11—H11 | 121.00 |
F1—C4—C3 | 118.1 (2) | C12—C11—H11 | 121.00 |
F1—C4—C5 | 118.7 (2) | C7—C12—H12 | 120.00 |
C4—C5—C6 | 118.8 (2) | C11—C12—H12 | 120.00 |
Cl1—Zn1—N1—C1 | −80.53 (15) | C2—C3—C4—F1 | −179.6 (2) |
Cl2—Zn1—N1—C1 | 37.40 (16) | C2—C3—C4—C5 | −0.1 (4) |
N2—Zn1—N1—C1 | 157.37 (14) | F1—C4—C5—C6 | 179.8 (2) |
Cl1—Zn1—N2—C7 | 31.74 (16) | C3—C4—C5—C6 | 0.3 (4) |
Cl2—Zn1—N2—C7 | −87.00 (15) | C4—C5—C6—C1 | −0.2 (4) |
N1—Zn1—N2—C7 | 153.74 (15) | N2—C7—C8—C9 | 178.2 (3) |
Zn1—N1—C1—C2 | 80.9 (2) | C12—C7—C8—C9 | 0.1 (4) |
Zn1—N1—C1—C6 | −95.7 (2) | N2—C7—C12—C11 | −178.5 (2) |
Zn1—N2—C7—C8 | −98.8 (2) | C8—C7—C12—C11 | −0.5 (4) |
Zn1—N2—C7—C12 | 79.2 (2) | C7—C8—C9—C10 | 0.5 (4) |
N1—C1—C2—C3 | −176.3 (2) | C8—C9—C10—F2 | 179.9 (2) |
C6—C1—C2—C3 | 0.3 (4) | C8—C9—C10—C11 | −0.8 (5) |
N1—C1—C6—C5 | 176.6 (2) | F2—C10—C11—C12 | 179.8 (2) |
C2—C1—C6—C5 | −0.1 (4) | C9—C10—C11—C12 | 0.5 (4) |
C1—C2—C3—C4 | −0.2 (4) | C10—C11—C12—C7 | 0.2 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1B···Cl2i | 0.92 | 2.63 | 3.436 (2) | 147 |
N2—H2B···Cl1i | 0.92 | 2.55 | 3.380 (2) | 151 |
N1—H1A···Cl2ii | 0.92 | 2.59 | 3.479 (2) | 162 |
N2—H2A···Cl1iii | 0.92 | 2.55 | 3.439 (2) | 162 |
Symmetry codes: (i) x, y+1, z; (ii) x+1/2, −y+2, z; (iii) x−1/2, −y+2, z. |
Experimental details
Crystal data | |
Chemical formula | [ZnCl2(C6H6FN)2] |
Mr | 358.51 |
Crystal system, space group | Orthorhombic, Pca21 |
Temperature (K) | 173 |
a, b, c (Å) | 11.6817 (5), 4.7080 (2), 25.2056 (15) |
V (Å3) | 1386.24 (12) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 2.17 |
Crystal size (mm) | 0.45 × 0.22 × 0.10 |
Data collection | |
Diffractometer | Stoe IPDS 2 diffractometer |
Absorption correction | Multi-scan (MULscanABS in PLATON; Spek, 2009) |
Tmin, Tmax | 0.742, 0.805 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7963, 2613, 2465 |
Rint | 0.031 |
(sin θ/λ)max (Å−1) | 0.608 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.020, 0.043, 1.02 |
No. of reflections | 2613 |
No. of parameters | 172 |
No. of restraints | 1 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.21, −0.32 |
Absolute structure | Flack (1983), 1273 Friedel pairs |
Absolute structure parameter | 0.013 (10) |
Computer programs: X-AREA (Stoe & Cie, 2009), X-RED32 (Stoe & Cie, 2009), SHELXS97 (Sheldrick, 2008), PLATON (Spek, 2009) and Mercury (Macrae et al., 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009) and publCIF (Westrip, 2010).
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1B···Cl2i | 0.92 | 2.63 | 3.436 (2) | 147 |
N2—H2B···Cl1i | 0.92 | 2.55 | 3.380 (2) | 151 |
N1—H1A···Cl2ii | 0.92 | 2.59 | 3.479 (2) | 162 |
N2—H2A···Cl1iii | 0.92 | 2.55 | 3.439 (2) | 162 |
Symmetry codes: (i) x, y+1, z; (ii) x+1/2, −y+2, z; (iii) x−1/2, −y+2, z. |
Acknowledgements
AS thanks the University Grants Commission, India, for the award of a Research Fellowship in Sciences for Meritorious Students [File No. 4–1/2008 (BSR)]. HSE thanks the XRD Application Laboratory, CSEM, Neuchâtel, for access to the X-ray diffraction equipment.
References
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This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
In our search for compounds exhibiting second harmonic generation (SHG) properties we have synthesized a series of ZnCl2 complexes of p-halogen substituted anilines. The title compound, the ZnCl2 complex of p-fluoroaniline crystallized in the noncentrosymmetric orthorhombic space group Pca21, while the p-chloroaniline (Subashini et al., 2012a) and p-bromoaniline (Subashini et al., 2012b; Feng et al., 2003) ZnCl2 complexes crystallized in the centrosymmetric monoclinic space group C2/c and both molecules have crystallographic 2-fold rotation symmetry.
In the title compound (Fig. 1), the zinc atom has a slightly distorted tetrahedral geometry, being coordinated by the atoms N1 and N2 of two p-fluoroaniline molecules and the two Cl- anions. The two benzene rings (C1—C6 and C7—C12) are perpendicular to one another with a dihedral angle of 89.96 (13)°. In the p-chloroaniline and p-bromoaniline ZnCl2 complexes mentioned above the same angles are 80.65 (16) and 80.0 (3)°, respectively.
In the crystal of the title compound, molecules are linked via a pair of N—H···Cl hydrogen bonds forming chains propagating along the b axis direction. These chains are in turn linked via a second pair of N—H···Cl hydrogen bonds to form a two-dimensional network lying parallel to the ab plane (Table 1 and Fig. 2). This contrasts with the packing in the crystals of the p-chloroaniline and p-bromoaniline ZnCl2 complexes. There molecules are linked by four N—H···halogen bonds to form chains propagating along [010], with no significant interactions between the chains.
As the title compound crystallized in a noncentrosymmetric space group it was decided to measure the second harmonic generation (SHG) properties of all three compounds; dichloro-bis(p-fluoroaniline)zinc, dichloro-bis(p-chloroaniline)zinc and dichloro-bis(p-bromoaniline)zinc. The SHG conversion efficiency was determined by the powder technique developed by (Kurtz & Perry, 1968). The crystals were powdered and the fine powdered samples were inserted in a micro-capillary tube and then subjected to a Q-switched Nd: YAG laser emitting 1064 nm radiation with 3.9 mJ/pulse. The frequency doubling was confirmed by the emission of green radiation of wavelength 532 nm collected by a monochromator after separating the 1064 nm pump beam with an IR-blocking filter. A detector connected to a power meter was used to detect the second harmonic intensity.
The output beam voltage produced by dichloro-bis(p-fluoroaniline)zinc, dichloro-bis(p-chloroaniline)zinc and dichloro-bis(p-bromoaniline)zinc derivatives were 15, 3 and 10 mV, respectively. The same quantity of crystalline KDP (potassium dihydrogen phosphate) powder, used as a reference material, produced 140 mV as output beam voltage. Hence the three samples exhibits SHG efficiency of only ca 0.11, 0.02 and 0.07 times that of the KDP.