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Acta Crystallogr Sect E Struct Rep Online. 2010 August 1; 66(Pt 8): m1027.
Published online 2010 July 31. doi:  10.1107/S1600536810029387
PMCID: PMC3007472

Dichlorido[(S)-N-(1-phenyl­ethyl­idene)-1-(pyridin-2-yl)ethanamine-κ2 N,N′]zinc(II) dichloro­methane solvate

Abstract

In the title compound, [ZnCl2(C15H16N2)]·CH2Cl2, the Zn(II) atom has a distorted tetra­hedral coordination by two Cl atoms and two N atoms from the organic ligand [the average Zn—N and Zn—Cl bond lengths are 2.060 (4) Å and Zn—Cl = 2.179 (16) Å, respectively]. The dihedral angle between the N—Zn—N and Cl—Zn—Cl planes is 89.9 (1)°. The phenyl ring forms a dihedral angle of 40.6 (5)° with the imine plane.

Related literature

For related structures see: Brunner & Fisch (1987 [triangle]); Nguyen & Jeong (2008 [triangle]).

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Object name is e-66-m1027-scheme1.jpg

Experimental

Crystal data

  • [ZnCl2(C15H16N2)]·CH2Cl2
  • M r = 445.51
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-m1027-efi1.jpg
  • a = 7.9381 (7) Å
  • b = 10.7187 (8) Å
  • c = 11.8426 (7) Å
  • α = 96.724 (6)°
  • β = 108.466 (6)°
  • γ = 97.968 (7)°
  • V = 932.53 (13) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 1.89 mm−1
  • T = 295 K
  • 0.45 × 0.40 × 0.35 mm

Data collection

  • Enraf–Nonius CAD-4 diffractometer
  • Absorption correction: ψ scan (ABSCALC; McArdle & Daly, 1999 [triangle]) T min = 0.489, T max = 0.569
  • 3871 measured reflections
  • 3463 independent reflections
  • 2873 reflections with I > 2σ(I)
  • R int = 0.009
  • 3 standard reflections every 60 min intensity decay: none

Refinement

  • R[F 2 > 2σ(F 2)] = 0.059
  • wR(F 2) = 0.197
  • S = 1.11
  • 3463 reflections
  • 210 parameters
  • H-atom parameters constrained
  • Δρmax = 0.85 e Å−3
  • Δρmin = −1.38 e Å−3

Data collection: CAD-4 Software (Enraf–Nonius, 1989 [triangle]); cell refinement: CAD-4 Software; data reduction: XCAD (McArdle, 1999 [triangle]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: ORTEPIII (Burnett & Johnson, 1996 [triangle]); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810029387/rk2219sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810029387/rk2219Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

This Research was supported by Kyungpook National University Research Fund, 2008.

supplementary crystallographic information

Comment

The ligand, (S)–N–(1–phenylethylidene)–1–(pyridin–2–yl)ethanamine, was obtained from reaction of (S)–1–(pyridin–2–yl)ethanamine with acetophenone in toluene solution. The similar ligand was used in Rh or Zn complex (Brunner & Fisch, 1987; Nguyen & Jeong, 2008). The geometry around the Zn atom is nearly tetrahedral with two chlorine atoms and the one pyridyl and one amine nitrogen atoms of the ligand (Fig. 1). The dihedral angle between N—Zn—N and Cl—Zn—Cl planes is 89.9 (1)°. The phenyl cycle forms dihedral angle 40.6 (5)° with imine plane. This value may be explained by steric hinderance between the Cl atoms and phenyl moiety of organic ligand.

Experimental

Acetophenone (2.04 g, 0.017 mol) was added to a solution of (S)–1–(pyridin–2–yl)ethanamine (2.07 g, 0.017 mol) in 40 ml of toluene. The reaction mixture was heated under reflux for 2 days in a Dean–Stark equipment. The solvent was removed by evaporation to yield pale brown oil, 3.43 g (90% yield). 1H NMR (400 MHz, CDCl3) δ 8.61 (t, 2H, ArH), 8.28 (d, 2H, ArH), 7.70 (m, 2H, ArH), 7.24 (m, 2H, ArH), 7.10 (m, 1H, ArH), 5.04 (q, J = 6.56 Hz, 1H, CH), 2.42 (s, 3H, CH3), 1.44 (d, J = 6.56 Hz, 3H, CH3). A solution of the ligand (1.01 g, 4.5 mmol) in ethanol (5 ml) was added dropwise to a solution of ZnCl2 (0.61 g, 4.5 mmol) in ethanol (10 ml). The mixture was stirred overnight at room temperature. The solvent was removed to yield white solid product. Colourless crystals were obtained by slow difussion of hexane to CH2Cl2 solution (1.43 g, 80%). Anal. Cacld. For [C15H16Cl2N2Zn].CH2Cl2: C, 43.14%; H, 4.07%; N, 6.29%. Found: C, 43.04%; H, 4.12%, N, 6.19%. 1H NMR (400 MHz, CDCl3) δ 8.63 (t, 2H, ArH), 8.44 (d, 2H, ArH), 7.81 (m, 2H, ArH), 7.24 (m, 2H, ArH), 7.11 (m, 1H, ArH), 5.23 (m, 1H, CH), 2.56 (s, 3H, CH3), 2.00 (d, J = 6.42 Hz, 3H, CH3).

Refinement

All H atoms were positioned geometrically and refined using a riding model with 0.96Å and Uiso(H) = 1.5Ueq(C) for CH3 groups; 0.93Å for aryl H atoms, 0.97Å for mehylene H atoms and 0.98Å for methine H atom with Uiso(H) = 1.2Ueq(C). The maximum remaining electron density was 0.85e/Å3 at 0.802Å from Zn.

Figures

Fig. 1.
The molecular structure of the title compound with the atom numbering scheme. Displacement ellipsoids are drawn at the 40% probability level. H atoms are presented as a small spheres of arbitrary radius.

Crystal data

[ZnCl2(C15H16N2)]·CH2Cl2Z = 2
Mr = 445.51F(000) = 452
Triclinic, P1Dx = 1.587 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 7.9381 (7) ÅCell parameters from 25 reflections
b = 10.7187 (8) Åθ = 10–12°
c = 11.8426 (7) ŵ = 1.89 mm1
α = 96.724 (6)°T = 295 K
β = 108.466 (6)°Block, colourless
γ = 97.968 (7)°0.45 × 0.40 × 0.35 mm
V = 932.53 (13) Å3

Data collection

Enraf–Nonius CAD-4 diffractometer2873 reflections with I > 2σ(I)
Radiation source: fine–focus sealed tubeRint = 0.009
graphiteθmax = 25.5°, θmin = 1.8°
ω/2θ–scansh = 0→9
Absorption correction: ψ scan (ABSCALC; McArdle & Daly, 1999)k = −12→12
Tmin = 0.489, Tmax = 0.569l = −14→13
3871 measured reflections3 standard reflections every 60 min
3463 independent reflections intensity decay: none

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.059Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.197H-atom parameters constrained
S = 1.11w = 1/[σ2(Fo2) + (0.124P)2 + 1.3285P] where P = (Fo2 + 2Fc2)/3
3463 reflections(Δ/σ)max = 0.001
210 parametersΔρmax = 0.85 e Å3
0 restraintsΔρmin = −1.38 e Å3

Special details

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'s involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/Ueq
Zn0.75251 (7)0.65883 (5)0.79296 (5)0.0462 (2)
Cl10.57114 (18)0.80013 (15)0.78335 (15)0.0610 (4)
Cl20.6555 (2)0.45749 (14)0.80264 (16)0.0704 (5)
N10.8371 (6)0.6589 (4)0.6459 (4)0.0460 (9)
N21.0239 (5)0.7302 (4)0.8835 (3)0.0385 (8)
C10.7332 (8)0.6417 (6)0.5294 (5)0.0572 (13)
H10.60830.62360.51000.069*
C20.8008 (9)0.6494 (6)0.4393 (5)0.0631 (15)
H20.72440.63590.35940.076*
C30.9837 (10)0.6773 (7)0.4673 (6)0.0697 (17)
H31.03360.68390.40650.084*
C41.0944 (8)0.6959 (6)0.5869 (5)0.0578 (14)
H41.21950.71510.60770.069*
C51.0162 (7)0.6852 (5)0.6742 (4)0.0428 (10)
C61.1306 (6)0.6999 (5)0.8060 (4)0.0415 (10)
H61.23450.76950.82460.050*
C71.1975 (8)0.5778 (6)0.8317 (5)0.0587 (14)
H7A1.26450.58670.91630.088*
H7B1.27440.56050.78570.088*
H7C1.09630.50850.80940.088*
C81.1009 (6)0.7966 (5)0.9897 (4)0.0410 (10)
C91.2985 (7)0.8533 (6)1.0420 (5)0.0597 (14)
H9A1.35770.82620.98680.090*
H9B1.35030.82521.11740.090*
H9C1.31410.94491.05540.090*
C100.9907 (6)0.8173 (5)1.0667 (4)0.0406 (10)
C110.8521 (7)0.7222 (5)1.0654 (5)0.0516 (12)
H110.83150.64251.01780.062*
C120.7449 (8)0.7450 (7)1.1340 (6)0.0623 (15)
H120.65190.68051.13170.075*
C130.7731 (9)0.8608 (7)1.2053 (6)0.0654 (16)
H130.69870.87531.25040.078*
C140.9100 (10)0.9546 (6)1.2103 (6)0.0665 (16)
H140.92941.03311.25950.080*
C151.0214 (8)0.9348 (6)1.1429 (5)0.0557 (13)
H151.11630.99931.14810.067*
Cl1S0.4042 (8)0.8397 (6)0.3886 (5)0.204 (2)
Cl2S0.2730 (12)1.0098 (6)0.5042 (6)0.243 (3)
C1S0.368 (2)0.9595 (16)0.4503 (14)0.168 (7)
H1S10.48770.99260.50930.201*
H1S20.35961.01190.38800.201*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Zn0.0334 (3)0.0516 (4)0.0525 (4)0.0000 (2)0.0164 (3)0.0086 (3)
Cl10.0397 (7)0.0689 (9)0.0770 (9)0.0123 (6)0.0210 (6)0.0166 (7)
Cl20.0694 (10)0.0540 (8)0.0794 (10)−0.0110 (7)0.0235 (8)0.0106 (7)
N10.040 (2)0.053 (2)0.043 (2)0.0033 (17)0.0138 (17)0.0084 (18)
N20.0327 (19)0.044 (2)0.0399 (19)0.0044 (15)0.0150 (16)0.0062 (16)
C10.050 (3)0.065 (3)0.048 (3)0.005 (2)0.008 (2)0.005 (2)
C20.070 (4)0.072 (4)0.040 (3)0.007 (3)0.011 (3)0.006 (3)
C30.083 (4)0.085 (4)0.048 (3)0.011 (3)0.033 (3)0.013 (3)
C40.054 (3)0.073 (4)0.050 (3)0.008 (3)0.026 (3)0.007 (3)
C50.042 (2)0.042 (2)0.044 (2)0.0045 (19)0.015 (2)0.0058 (19)
C60.033 (2)0.051 (3)0.043 (2)0.0041 (19)0.0182 (19)0.006 (2)
C70.060 (3)0.069 (4)0.054 (3)0.028 (3)0.022 (3)0.011 (3)
C80.040 (2)0.042 (2)0.041 (2)0.0069 (19)0.0132 (19)0.0090 (19)
C90.041 (3)0.074 (4)0.055 (3)0.002 (3)0.013 (2)−0.004 (3)
C100.040 (2)0.046 (2)0.038 (2)0.0100 (19)0.0141 (19)0.0112 (19)
C110.051 (3)0.055 (3)0.051 (3)0.004 (2)0.020 (2)0.014 (2)
C120.055 (3)0.079 (4)0.062 (3)0.009 (3)0.029 (3)0.025 (3)
C130.074 (4)0.084 (4)0.060 (3)0.034 (3)0.040 (3)0.025 (3)
C140.087 (5)0.064 (4)0.057 (3)0.024 (3)0.033 (3)0.004 (3)
C150.062 (3)0.053 (3)0.051 (3)0.008 (3)0.022 (3)0.004 (2)
Cl1S0.228 (5)0.247 (6)0.205 (5)0.112 (5)0.120 (4)0.085 (4)
Cl2S0.366 (10)0.203 (5)0.186 (5)0.083 (6)0.120 (6)0.022 (4)
C1S0.155 (12)0.176 (14)0.126 (10)0.047 (11)0.004 (9)−0.051 (10)

Geometric parameters (Å, °)

Zn—N12.055 (4)C7—H7C0.9600
Zn—N22.065 (4)C8—C101.469 (7)
Zn—Cl22.2175 (16)C8—C91.499 (7)
Zn—Cl12.2182 (15)C9—H9A0.9600
N1—C51.333 (6)C9—H9B0.9600
N1—C11.340 (7)C9—H9C0.9600
N2—C81.282 (6)C10—C111.388 (7)
N2—C61.471 (6)C10—C151.403 (7)
C1—C21.343 (9)C11—C121.375 (8)
C1—H10.9300C11—H110.9300
C2—C31.363 (10)C12—C131.365 (9)
C2—H20.9300C12—H120.9300
C3—C41.384 (9)C13—C141.355 (10)
C3—H30.9300C13—H130.9300
C4—C51.372 (7)C14—C151.388 (8)
C4—H40.9300C14—H140.9300
C5—C61.513 (7)C15—H150.9300
C6—C71.507 (8)Cl1S—C1S1.509 (14)
C6—H60.9800Cl2S—C1S1.268 (15)
C7—H7A0.9600C1S—H1S10.9700
C7—H7B0.9600C1S—H1S20.9700
N1—Zn—N281.55 (16)C6—C7—H7C109.5
N1—Zn—Cl2107.97 (13)H7A—C7—H7C109.5
N2—Zn—Cl2116.13 (12)H7B—C7—H7C109.5
N1—Zn—Cl1107.49 (13)N2—C8—C10118.5 (4)
N2—Zn—Cl1115.59 (12)N2—C8—C9124.1 (4)
Cl2—Zn—Cl1120.09 (6)C10—C8—C9117.3 (4)
C5—N1—C1118.7 (5)C8—C9—H9A109.5
C5—N1—Zn114.0 (3)C8—C9—H9B109.5
C1—N1—Zn127.2 (4)H9A—C9—H9B109.5
C8—N2—C6120.5 (4)C8—C9—H9C109.5
C8—N2—Zn129.0 (3)H9A—C9—H9C109.5
C6—N2—Zn110.4 (3)H9B—C9—H9C109.5
N1—C1—C2123.1 (6)C11—C10—C15118.0 (5)
N1—C1—H1118.5C11—C10—C8121.2 (5)
C2—C1—H1118.5C15—C10—C8120.8 (5)
C1—C2—C3118.7 (5)C12—C11—C10120.5 (5)
C1—C2—H2120.6C12—C11—H11119.8
C3—C2—H2120.6C10—C11—H11119.8
C2—C3—C4119.5 (6)C13—C12—C11121.0 (6)
C2—C3—H3120.3C13—C12—H12119.5
C4—C3—H3120.3C11—C12—H12119.5
C5—C4—C3118.7 (6)C14—C13—C12119.8 (6)
C5—C4—H4120.6C14—C13—H13120.1
C3—C4—H4120.6C12—C13—H13120.1
N1—C5—C4121.3 (5)C13—C14—C15120.8 (6)
N1—C5—C6117.6 (4)C13—C14—H14119.6
C4—C5—C6121.1 (5)C15—C14—H14119.6
N2—C6—C7108.9 (4)C14—C15—C10119.9 (6)
N2—C6—C5110.2 (4)C14—C15—H15120.1
C7—C6—C5110.2 (4)C10—C15—H15120.1
N2—C6—H6109.2Cl2S—C1S—Cl1S147.9 (16)
C7—C6—H6109.2Cl2S—C1S—H1S199.8
C5—C6—H6109.2Cl1S—C1S—H1S199.8
C6—C7—H7A109.5Cl2S—C1S—H1S299.8
C6—C7—H7B109.5Cl1S—C1S—H1S299.8
H7A—C7—H7B109.5H1S1—C1S—H1S2104.1
N2—Zn—N1—C58.3 (3)Zn—N2—C6—C7−94.2 (4)
Cl2—Zn—N1—C5−106.5 (3)C8—N2—C6—C5−150.7 (4)
Cl1—Zn—N1—C5122.6 (3)Zn—N2—C6—C526.8 (4)
N2—Zn—N1—C1−168.3 (5)N1—C5—C6—N2−21.5 (6)
Cl2—Zn—N1—C176.9 (5)C4—C5—C6—N2159.9 (5)
Cl1—Zn—N1—C1−54.0 (5)N1—C5—C6—C798.6 (5)
N1—Zn—N2—C8157.6 (4)C4—C5—C6—C7−79.9 (6)
Cl2—Zn—N2—C8−96.5 (4)C6—N2—C8—C10−176.1 (4)
Cl1—Zn—N2—C852.2 (4)Zn—N2—C8—C106.9 (7)
N1—Zn—N2—C6−19.7 (3)C6—N2—C8—C92.8 (7)
Cl2—Zn—N2—C686.2 (3)Zn—N2—C8—C9−174.2 (4)
Cl1—Zn—N2—C6−125.1 (3)N2—C8—C10—C1136.8 (7)
C5—N1—C1—C20.2 (9)C9—C8—C10—C11−142.2 (5)
Zn—N1—C1—C2176.7 (5)N2—C8—C10—C15−142.5 (5)
N1—C1—C2—C3−0.8 (10)C9—C8—C10—C1538.5 (7)
C1—C2—C3—C40.6 (11)C15—C10—C11—C122.2 (8)
C2—C3—C4—C50.1 (10)C8—C10—C11—C12−177.1 (5)
C1—N1—C5—C40.5 (8)C10—C11—C12—C13−0.5 (9)
Zn—N1—C5—C4−176.4 (4)C11—C12—C13—C14−0.9 (9)
C1—N1—C5—C6−178.0 (5)C12—C13—C14—C150.5 (10)
Zn—N1—C5—C65.0 (6)C13—C14—C15—C101.2 (9)
C3—C4—C5—N1−0.7 (9)C11—C10—C15—C14−2.5 (8)
C3—C4—C5—C6177.9 (5)C8—C10—C15—C14176.8 (5)
C8—N2—C6—C788.3 (5)

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: RK2219).

References

  • Brunner, H. & Fisch, H. (1987). J. Organomet. Chem.335, 1–14.
  • Burnett, M. N. & Johnson, C. K. (1996). ORTEPIII. Report ORNL-6895. Oak Ridge National Laboratory, Tennessee, USA.
  • Enraf–Nonius (1989). CAD-4 Software. Enraf–Nonius, Delft, The Netherlands.
  • McArdle, P. (1999). XCAD. National University of Ireland, Galway, Ireland.
  • McArdle, P. & Daly, P. (1999). ABSCALC. National University of Ireland, Galway, Ireland.
  • Nguyen, Q. T. & Jeong, J. H. (2008). Acta Cryst. E64, m457. [PMC free article] [PubMed]
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography