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Acta Cryst. (2008). E64, m457    [ doi:10.1107/S1600536808003541 ]

Dichlorido[(S)-(1-phenylethyl)(2-pyridylmethyl)amine-[kappa]2N,N']zinc(II)

Q. T. Nguyen and J. H. Jeong

Abstract top

In the title compound, [ZnCl2(C14H16N2)], the ZnII atom is coordinated by two N atoms and two Cl atoms in an approximately tetrahedral arrangement. The dihedral angle between the N-Zn-N and Cl-Zn-Cl planes is 88.06 (8)°. The H atoms on the chiral C atom and the adjacent N atom have an anti conformation.

Comment top

The ligand, (S)-(1-Phenylethyl)(2-pyridylmethyl)amine, was obtained from reduction of (S)-2-pyridinal-1-phenylethylimine (Kang et al., 2006) with NaBH4 in methanol solution. The ligand was used as co-ligand with another chiral ligand in Ru or Rh complexes as the catalyst for hydrogenation of ketones (Moreau et al., 1999; Mizushima et al., 1999; Himeda et al., 2003). In the crystal structure, the geometry around the ZnII ion is approximately tetrahedral with bonds being formed by two chloride ions and the pyridyl and amine nitrogen atoms of the ligand (Fig. 1). The dihedral angle between the N—Zn—N and Cl—Zn—Cl planes is 88.06 (8)°. The H atoms on the chiral carbon atom and the adjacent nitrogen atom have an anti conformation.

Related literature top

For the synthesis of (S)-2-pyridinal-1-phenylethylimine, see: Kang et al. (2006). For related structures, see: Moreau et al. (1999); Mizushima et al. (1999); Himeda et al. (2003).

Experimental top

NaBH4 (0.33 g, 8.8 mmol) was added slowly to a solution of (S)-2- pyridinal-1-phenylethylimine (1.79 g, 8.5 mmol) in methanol (15 ml). The mixture was stirred overnight, and the solvent was removed by evaporation. The residue obtained was dissolved in 20 ml distilled water and the organic product was extracted with CH2Cl2 (3 x 20 ml) and dried over anhydrous MgSO4. The solvent was evaporated to give a pale yellow oil; 1.41 g (78% yield). 1H-NMR (400 MHz, CDCl3) δ 7.39 (t, 1H, ArH), 7.26 (m, 4H, ArH), 7.17 (m,1H, ArH), 6.90 (t, 2H, ArH), 3.74 (q, J=6.56 Hz, 1H, CH), 3.59 (s, 2H, CH2), 2.45 (s, 3H, PyCH3), 2.19 (br, s, 1H, NH), 1.30 (d, J=6.56 Hz, 3H, CH3). A solution of the ligand (0.96 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 a white solid product. Colorless crystals were obtained by slowly diffusing diethyl ether into a saturated solution in acetonitrile (1.36 g, 87%). Anal. Calcd. for C14H16Cl2N2Zn: C, 48.23; H, 4.63; N, 8.04. Found: C, 48.19; H, 4.70, N, 8.01%. 1H-NMR (400 MHz, CD3CN) δ 7.89 (m, 1H, ArH), 7.44 (m, 6H, ArH), 7,16 (d, J=7.79 Hz, 1H, ArH), 4.15 (m, 2H, NH & CH), 3.77 (m, 2H, CH2), 2.78 (s, 3H, PyCH3), 1.70 (d, J=3.24 Hz, CH3).

Refinement top

All H atoms were positioned geometrically and refined using a riding model, with C—H = 0.93 Å, Uiso(H) = 1.2Ueq(C) for C(sp2)H, C—H = 0.97 Å, Uiso(H) = 1.2Ueq(C) for CH2, C—H = 0.96 Å, Uiso(H) = 1.5Ueq(C) for CH3, and N—H = 0.91 Å, Uiso(H) = 1.2Ueq(N) for NH atoms.

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software (Enraf–Nonius, 1989); data reduction: XCAD (McArdle, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEXIII (McArdle, 1995); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure. Displacement ellipsoids are drawn at the 40% probability level.
Dichlorido[(S)-(1-phenylethyl)(2-pyridylmethyl)amine- κ2N,N']zinc(II) top
Crystal data top
[ZnCl2(C14H16N2)]F000 = 712
Mr = 348.56Dx = 1.487 Mg m−3
Orthorhombic, P212121Mo Kα radiation
λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 25 reflections
a = 9.2342 (6) Åθ = 9.9–13.0º
b = 12.5782 (10) ŵ = 1.91 mm−1
c = 13.4032 (8) ÅT = 293 (2) K
V = 1556.78 (18) Å3Block, colorless
Z = 40.40 × 0.40 × 0.30 mm
Data collection top
Enraf–Nonius CAD-4
diffractometer		Rint = 0.009
Radiation source: fine-focus sealed tubeθmax = 25.5º
Monochromator: graphiteθmin = 2.2º
T = 293(2) Kh = 0→11
ω/2θ scansk = −14→0
Absorption correction: ψ scan
(ABSCALC; McArdle & Daly, 1999)		l = 0→15
Tmin = 0.485, Tmax = 0.5643 standard reflections
1705 measured reflections every 60 min
1659 independent reflections intensity decay: 0.2%
1530 reflections with I > 2σ(I)
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.030  w = 1/[σ2(Fo2) + (0.0598P)2 + 0.2097P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.080(Δ/σ)max < 0.001
S = 1.07Δρmax = 0.56 e Å−3
1659 reflectionsΔρmin = −0.57 e Å−3
173 parametersExtinction correction: none
Primary atom site location: structure-invariant direct methodsAbsolute structure: Flack (1983), 2 Friedel pairs
Secondary atom site location: difference Fourier mapFlack parameter: 0.018 (19)
Crystal data top
[ZnCl2(C14H16N2)]V = 1556.78 (18) Å3
Mr = 348.56Z = 4
Orthorhombic, P212121Mo Kα
a = 9.2342 (6) ŵ = 1.91 mm−1
b = 12.5782 (10) ÅT = 293 (2) K
c = 13.4032 (8) Å0.40 × 0.40 × 0.30 mm
Data collection top
Enraf–Nonius CAD-4
diffractometer		1530 reflections with I > 2σ(I)
Absorption correction: ψ scan
(ABSCALC; McArdle & Daly, 1999)		Rint = 0.009
Tmin = 0.485, Tmax = 0.5643 standard reflections
1705 measured reflections every 60 min
1659 independent reflections intensity decay: 0.2%
Refinement top
R[F2 > 2σ(F2)] = 0.030H-atom parameters constrained
wR(F2) = 0.080Δρmax = 0.56 e Å−3
S = 1.07Δρmin = −0.57 e Å−3
1659 reflectionsAbsolute structure: Flack (1983), 2 Friedel pairs
173 parametersFlack parameter: 0.018 (19)
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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Zn0.04578 (5)0.93541 (3)0.73653 (3)0.04068 (15)
Cl1−0.15959 (12)0.94695 (8)0.65366 (7)0.0527 (3)
Cl20.14716 (13)1.08625 (8)0.78507 (9)0.0584 (3)
N10.1861 (4)0.8349 (3)0.6668 (2)0.0464 (8)
N20.0324 (3)0.8129 (2)0.8414 (2)0.0339 (6)
H2N−0.04960.77550.82790.041*
C10.2413 (6)0.8436 (4)0.5749 (3)0.0640 (13)
H10.22700.90680.54020.077*
C20.3170 (7)0.7649 (4)0.5300 (4)0.0749 (15)
H20.35250.77360.46560.090*
C30.3405 (6)0.6719 (4)0.5811 (4)0.0653 (13)
H30.39120.61620.55170.078*
C40.2874 (5)0.6627 (3)0.6769 (3)0.0465 (9)
H40.30380.60130.71370.056*
C50.2098 (4)0.7455 (3)0.7174 (3)0.0359 (8)
C60.1564 (4)0.7408 (3)0.8239 (3)0.0378 (8)
H6A0.12760.66850.83940.045*
H6B0.23490.76010.86850.045*
C70.0213 (4)0.8512 (3)0.9465 (3)0.0371 (8)
H70.10600.89600.95940.045*
C8−0.1117 (5)0.9209 (4)0.9566 (3)0.0579 (11)
H8A−0.10470.97950.91100.087*
H8B−0.11800.94741.02360.087*
H8C−0.19670.87990.94150.087*
C90.0207 (4)0.7636 (3)1.0248 (3)0.0367 (8)
C10−0.0433 (4)0.6656 (3)1.0102 (3)0.0439 (8)
H10−0.08360.64940.94850.053*
C11−0.0482 (5)0.5911 (4)1.0863 (3)0.0546 (10)
H11−0.09180.52551.07530.065*
C120.0112 (5)0.6139 (4)1.1780 (3)0.0608 (13)
H120.00740.56411.22930.073*
C130.0767 (5)0.7114 (4)1.1932 (3)0.0581 (12)
H130.11830.72701.25470.070*
C140.0804 (5)0.7855 (4)1.1175 (3)0.0492 (10)
H140.12370.85111.12870.059*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Zn0.0526 (3)0.0350 (2)0.0345 (2)0.00634 (18)0.00028 (19)0.00188 (16)
Cl10.0638 (6)0.0493 (5)0.0448 (5)0.0054 (5)−0.0134 (5)−0.0018 (4)
Cl20.0673 (6)0.0459 (5)0.0621 (6)−0.0077 (5)−0.0033 (5)−0.0040 (5)
N10.056 (2)0.0442 (17)0.0388 (16)0.0054 (16)0.0066 (15)0.0006 (14)
N20.0335 (14)0.0380 (16)0.0300 (14)0.0003 (12)−0.0007 (12)−0.0015 (11)
C10.090 (3)0.062 (3)0.040 (2)0.018 (3)0.018 (2)0.015 (2)
C20.107 (4)0.076 (3)0.042 (2)0.022 (3)0.023 (3)0.008 (2)
C30.083 (3)0.061 (3)0.051 (3)0.018 (3)0.016 (3)−0.009 (2)
C40.062 (2)0.042 (2)0.0356 (19)0.0057 (19)0.0047 (18)−0.0014 (16)
C50.0412 (18)0.0338 (16)0.0327 (17)−0.0011 (14)0.0002 (15)−0.0014 (14)
C60.0420 (19)0.0367 (18)0.0347 (18)0.0029 (16)0.0051 (16)−0.0003 (15)
C70.0389 (18)0.0400 (18)0.0324 (17)0.0009 (15)0.0027 (15)−0.0043 (14)
C80.068 (3)0.058 (3)0.048 (2)0.025 (2)0.011 (2)0.006 (2)
C90.0335 (17)0.046 (2)0.0304 (17)0.0053 (15)0.0034 (15)0.0004 (15)
C100.0431 (19)0.047 (2)0.0415 (19)0.0011 (18)0.0057 (18)−0.0013 (16)
C110.060 (2)0.048 (2)0.056 (2)0.006 (2)0.011 (2)0.0083 (19)
C120.065 (3)0.071 (3)0.047 (2)0.027 (2)0.012 (2)0.017 (2)
C130.063 (3)0.079 (3)0.0326 (19)0.015 (3)−0.0036 (19)0.000 (2)
C140.046 (2)0.061 (2)0.040 (2)−0.0008 (19)−0.0015 (18)−0.0048 (19)
Geometric parameters (Å, °) top
Zn—N12.037 (3)C6—H6B0.970
Zn—N22.089 (3)C7—C81.516 (5)
Zn—Cl12.2025 (12)C7—C91.522 (5)
Zn—Cl22.2134 (11)C7—H70.980
N1—C51.332 (5)C8—H8A0.960
N1—C11.338 (5)C8—H8B0.960
N2—C61.479 (4)C8—H8C0.960
N2—C71.492 (4)C9—C101.380 (5)
N2—H2N0.910C9—C141.387 (5)
C1—C21.354 (7)C10—C111.386 (6)
C1—H10.930C10—H100.930
C2—C31.373 (7)C11—C121.377 (7)
C2—H20.930C11—H110.930
C3—C41.379 (6)C12—C131.382 (8)
C3—H30.930C12—H120.930
C4—C51.375 (5)C13—C141.378 (6)
C4—H40.930C13—H130.930
C5—C61.511 (5)C14—H140.930
C6—H6A0.970
N1—Zn—N283.58 (12)N2—C6—H6B109.2
N1—Zn—Cl1110.92 (11)C5—C6—H6B109.2
N2—Zn—Cl1109.70 (9)H6A—C6—H6B107.9
N1—Zn—Cl2113.45 (11)N2—C7—C8109.1 (3)
N2—Zn—Cl2117.35 (9)N2—C7—C9114.7 (3)
Cl1—Zn—Cl2117.13 (4)C8—C7—C9110.8 (3)
C5—N1—C1118.4 (4)N2—C7—H7107.3
C5—N1—Zn113.3 (2)C8—C7—H7107.3
C1—N1—Zn127.9 (3)C9—C7—H7107.3
C6—N2—C7113.6 (3)C7—C8—H8A109.5
C6—N2—Zn107.5 (2)C7—C8—H8B109.5
C7—N2—Zn113.7 (2)H8A—C8—H8B109.5
C6—N2—H2N107.3C7—C8—H8C109.5
C7—N2—H2N107.3H8A—C8—H8C109.5
Zn—N2—H2N107.3H8B—C8—H8C109.5
N1—C1—C2123.1 (4)C10—C9—C14118.3 (4)
N1—C1—H1118.4C10—C9—C7123.4 (3)
C2—C1—H1118.4C14—C9—C7118.2 (4)
C1—C2—C3118.9 (4)C9—C10—C11120.9 (4)
C1—C2—H2120.5C9—C10—H10119.5
C3—C2—H2120.5C11—C10—H10119.5
C2—C3—C4118.6 (4)C12—C11—C10120.2 (4)
C2—C3—H3120.7C12—C11—H11119.9
C4—C3—H3120.7C10—C11—H11119.9
C3—C4—C5119.4 (4)C11—C12—C13119.4 (4)
C3—C4—H4120.3C11—C12—H12120.3
C5—C4—H4120.3C13—C12—H12120.3
N1—C5—C4121.6 (3)C14—C13—C12120.2 (4)
N1—C5—C6117.4 (3)C14—C13—H13119.9
C4—C5—C6120.9 (3)C12—C13—H13119.9
N2—C6—C5112.2 (3)C13—C14—C9121.0 (4)
N2—C6—H6A109.2C13—C14—H14119.5
C5—C6—H6A109.2C9—C14—H14119.5
N2—Zn—N1—C5−2.7 (3)C3—C4—C5—C6−176.8 (4)
Cl1—Zn—N1—C5−111.4 (3)C7—N2—C6—C5−152.2 (3)
Cl2—Zn—N1—C5114.3 (3)Zn—N2—C6—C5−25.6 (3)
N2—Zn—N1—C1169.4 (5)N1—C5—C6—N226.0 (4)
Cl1—Zn—N1—C160.7 (5)C4—C5—C6—N2−157.8 (3)
Cl2—Zn—N1—C1−73.5 (5)C6—N2—C7—C8−178.0 (3)
N1—Zn—N2—C615.9 (2)Zn—N2—C7—C858.7 (4)
Cl1—Zn—N2—C6125.8 (2)C6—N2—C7—C9−53.2 (4)
Cl2—Zn—N2—C6−97.2 (2)Zn—N2—C7—C9−176.4 (2)
N1—Zn—N2—C7142.5 (3)N2—C7—C9—C10−34.9 (5)
Cl1—Zn—N2—C7−107.6 (2)C8—C7—C9—C1089.0 (4)
Cl2—Zn—N2—C729.3 (3)N2—C7—C9—C14148.8 (4)
C5—N1—C1—C21.7 (8)C8—C7—C9—C14−87.2 (4)
Zn—N1—C1—C2−170.0 (4)C14—C9—C10—C110.2 (6)
N1—C1—C2—C3−0.9 (10)C7—C9—C10—C11−176.1 (4)
C1—C2—C3—C4−0.8 (9)C9—C10—C11—C12−0.1 (6)
C2—C3—C4—C51.6 (8)C10—C11—C12—C13−0.5 (7)
C1—N1—C5—C4−0.8 (6)C11—C12—C13—C140.9 (7)
Zn—N1—C5—C4172.1 (3)C12—C13—C14—C9−0.8 (7)
C1—N1—C5—C6175.4 (4)C10—C9—C14—C130.2 (6)
Zn—N1—C5—C6−11.7 (4)C7—C9—C14—C13176.7 (4)
C3—C4—C5—N1−0.8 (6)
references
References top

Enraf–Nonius (1989). CAD-4 Software. Version 5.0. Enraf–Nonius, Delft, The Netherlands.

Flack, H. D. (1983). Acta Cryst. A39, 876–881.

Himeda, Y., Onozawa-Komatsuzaki, N., Sugihara, H., Arakawa, H. & Kasuga, K. (2003). J. Mol. Catal. A Chem. 195, 95–100.

Kang, B., Kim, M., Lee, J., Do, Y. & Chang, S. (2006). J. Org. Chem. 71, 6721–6727.

McArdle, P. (1995). J. Appl. Cryst. 28, 65–?.

McArdle, P. (1999). XCAD. National University of Ireland, Galway, Ireland.

McArdle, P. & Daly, P. (1999). ABSCALC. National University of Ireland, Galway, Ireland.

Mizushima, E., Ohi, H., Yamaguchi, M. & Yamagishi, T. J. (1999). J. Mol. Catal. A Chem. 149, 43–49.

Moreau, C., Frost, C. G. & Murrer, B. (1999). Tetrahedron Lett. 40, 5617–5620.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.