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Acta Cryst. (2009). E65, m142    [ doi:10.1107/S1600536808044061 ]

[(2-Morpholinoethyl)(2-pyridylmethylene)amine]dithiocyanatozinc(II)

B.-H. Cai

Abstract top

The title compound, [Zn(NCS)2(C12H17N3O)], was prepared by the reaction of zinc acetate with pyridine-2-carbaldehyde, 2-morpholinoethylamine and ammonium thiocyanate in an ethanol solution. The ZnII atom is five coordinate with a distorted trigonal-bipyramidal geometry, coordinating with three N atoms of the Schiff base (2-morpholinoethyl)(2-pyridylmethylidene)amine and two N atoms from two thiocyanate ligands. The morpholine ring adopts a chair configuration.

Comment top

Schiff bases are extremely interesting ligands and many have been used to form a large number of metal complexes (Costes et al., 2002; Erxleben, 2001; Lacroix et al., 1996; Odoko et al., 2006; Ali et al., 2006). As a continuation of our work in this area, we report herein the crystal structure of a new zinc(II) complex of the Schiff base (2-morpholin-4-ylethyl)-(1-pyridin-2-ylmethylidene)amine and ammonium thiocyanate, (I).

The molecular structure of complex (I) is illustrated in Fig. 1. The ZnII atom is five-coordinate in a trigonal-bipyramidal geometry, coordinating with three N-atoms of the Schiff base ligand and two N-atoms from two thiocyanate ligands. All the coordinate bond lengths are typical and comparable with those in the similar zinc(II) complexes (Li et al., 2008; Eltayeb et al., 2007; Ali et al., 2008; Zhang & Wang, 2007). As expected, the morpholine ring adopts a chair configuration.

Related literature top

For background literature on Schiff base complexes, see: Costes et al. (2002); Erxleben (2001); Lacroix et al. (1996); Odoko et al. (2006); Ali et al. (2006). For literature on related zinc(II) complexes, see: Li et al. (2008); Eltayeb et al. (2007); Ali et al. (2008); Zhang & Wang (2007).

Experimental top

Pyridine-2-carbaldehyde (0.1 mmol, 10.7 mg), 2-morpholin-4-ylethylamine (0.1 mmol, 13.0 mg), ammonium thiocyanate (0.2 mmol, 15.2 mg), and zinc acetate dihydrate (0.1 mmol, 22.0 mg) were mixed in an ethanol solution (20 ml). The mixture was stirred for 2 h at room temperature, giving a colorless solution. Single-crystals were formed by gradual evaporation of the solution in air after several days.

Refinement top

H atoms were placed in calculated positions and treated as riding atoms: C–H = 0.93 - 0.97 Å, with Uiso(H) = 1.2Ueq(C).

Computing details top

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of the compound (I), showing 30% probability displacement ellipsoids.
[(2-Morpholinoethyl)(2-pyridylmethylene)amine]dithiocyanatozinc(II) top
Crystal data top
[Zn(NCS)2(C12H17N3O)]Z = 2
Mr = 400.82F(000) = 412
Triclinic, P1Dx = 1.507 Mg m−3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 8.185 (2) ÅCell parameters from 2675 reflections
b = 8.654 (2) Åθ = 2.4–25.0°
c = 13.368 (4) ŵ = 1.64 mm−1
α = 98.439 (3)°T = 298 K
β = 102.587 (3)°Block, colorless
γ = 102.501 (3)°0.23 × 0.23 × 0.20 mm
V = 883.3 (4) Å3
Data collection top
Bruker SMART 1000 CCD area-detector
diffractometer		3770 independent reflections
Radiation source: fine-focus sealed tube2989 reflections with I > 2σ(I)
graphiteRint = 0.031
ω scansθmax = 27.0°, θmin = 1.6°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −10→10
Tmin = 0.705, Tmax = 0.736k = −11→10
7386 measured reflectionsl = −17→16
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)] = 0.045Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.124H-atom parameters constrained
S = 1.04 w = 1/[σ2(Fo2) + (0.064P)2 + 0.1459P]
where P = (Fo2 + 2Fc2)/3
3770 reflections(Δ/σ)max = 0.001
208 parametersΔρmax = 0.57 e Å−3
0 restraintsΔρmin = −0.47 e Å−3
Crystal data top
[Zn(NCS)2(C12H17N3O)]γ = 102.501 (3)°
Mr = 400.82V = 883.3 (4) Å3
Triclinic, P1Z = 2
a = 8.185 (2) ÅMo Kα radiation
b = 8.654 (2) ŵ = 1.64 mm−1
c = 13.368 (4) ÅT = 298 K
α = 98.439 (3)°0.23 × 0.23 × 0.20 mm
β = 102.587 (3)°
Data collection top
Bruker SMART 1000 CCD area-detector
diffractometer		3770 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		2989 reflections with I > 2σ(I)
Tmin = 0.705, Tmax = 0.736Rint = 0.031
7386 measured reflectionsθmax = 27.0°
Refinement top
R[F2 > 2σ(F2)] = 0.045H-atom parameters constrained
wR(F2) = 0.124Δρmax = 0.57 e Å−3
S = 1.04Δρmin = −0.47 e Å−3
3770 reflectionsAbsolute structure: ?
208 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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*/Ueq
Zn10.87080 (4)0.35121 (4)0.23426 (3)0.04844 (15)
S10.75132 (16)0.05952 (14)−0.10471 (7)0.0759 (3)
S21.40376 (14)0.73452 (15)0.38080 (9)0.0854 (4)
O11.1836 (4)0.1269 (4)0.4455 (2)0.0791 (8)
N10.7747 (4)0.5343 (3)0.1472 (2)0.0551 (7)
N20.6437 (3)0.3649 (3)0.2720 (2)0.0552 (7)
N30.8546 (3)0.1714 (3)0.3427 (2)0.0493 (6)
N40.8437 (4)0.1978 (4)0.1048 (2)0.0662 (8)
N51.0969 (4)0.5041 (4)0.2956 (3)0.0793 (10)
C10.6221 (4)0.5515 (4)0.1613 (3)0.0531 (8)
C20.5377 (5)0.6554 (4)0.1166 (3)0.0622 (9)
H20.43230.66520.12850.075*
C30.6133 (5)0.7444 (4)0.0539 (3)0.0662 (10)
H30.55920.81550.02230.079*
C40.7674 (5)0.7276 (4)0.0385 (3)0.0690 (10)
H40.82040.7867−0.00380.083*
C50.8445 (5)0.6212 (4)0.0866 (3)0.0648 (9)
H50.95030.61030.07590.078*
C60.5531 (4)0.4478 (4)0.2283 (3)0.0603 (9)
H60.44340.44390.23820.072*
C70.5856 (5)0.2577 (6)0.3393 (3)0.0776 (12)
H7A0.46030.21940.31880.093*
H7B0.62140.31510.41170.093*
C80.6656 (5)0.1177 (5)0.3275 (3)0.0730 (11)
H8A0.64150.05240.37820.088*
H8B0.61340.05060.25810.088*
C90.9411 (5)0.2391 (4)0.4547 (3)0.0612 (9)
H9A0.89780.16470.49620.073*
H9B0.91270.34020.47520.073*
C101.1332 (5)0.2682 (5)0.4768 (3)0.0723 (11)
H10A1.17760.35030.44040.087*
H10B1.18400.30880.55130.087*
C111.1103 (5)0.0677 (5)0.3379 (3)0.0757 (11)
H11A1.1471−0.02830.31620.091*
H11B1.15220.14840.29980.091*
C120.9161 (5)0.0269 (4)0.3108 (3)0.0639 (9)
H12A0.8704−0.01340.23600.077*
H12B0.8735−0.05760.34600.077*
C130.8047 (4)0.1408 (4)0.0181 (3)0.0504 (7)
C141.2216 (5)0.6003 (4)0.3288 (3)0.0560 (8)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Zn10.0390 (2)0.0533 (2)0.0485 (2)0.00680 (15)0.01199 (15)0.00305 (16)
S10.0891 (7)0.0910 (7)0.0462 (5)0.0300 (6)0.0125 (5)0.0066 (5)
S20.0656 (6)0.0863 (7)0.0827 (7)−0.0173 (5)0.0278 (6)−0.0084 (6)
O10.0664 (17)0.090 (2)0.0778 (19)0.0235 (15)0.0049 (14)0.0222 (16)
N10.0487 (15)0.0542 (16)0.0604 (17)0.0143 (12)0.0129 (13)0.0061 (13)
N20.0465 (15)0.0640 (16)0.0577 (17)0.0151 (13)0.0190 (13)0.0100 (14)
N30.0469 (14)0.0472 (14)0.0473 (14)0.0036 (11)0.0098 (11)0.0060 (11)
N40.083 (2)0.0677 (19)0.0506 (17)0.0277 (16)0.0191 (15)0.0057 (15)
N50.0497 (17)0.077 (2)0.090 (3)−0.0094 (16)−0.0065 (17)0.0269 (19)
C10.0496 (18)0.0513 (18)0.0517 (19)0.0153 (14)0.0064 (14)−0.0036 (14)
C20.056 (2)0.059 (2)0.067 (2)0.0235 (16)0.0071 (17)−0.0023 (17)
C30.072 (2)0.0517 (19)0.068 (2)0.0210 (17)0.0016 (19)0.0079 (17)
C40.070 (2)0.058 (2)0.077 (3)0.0139 (18)0.017 (2)0.0159 (19)
C50.055 (2)0.063 (2)0.080 (3)0.0176 (17)0.0196 (18)0.0153 (19)
C60.0466 (18)0.070 (2)0.063 (2)0.0184 (16)0.0179 (16)0.0011 (18)
C70.053 (2)0.107 (3)0.086 (3)0.018 (2)0.034 (2)0.038 (2)
C80.051 (2)0.078 (3)0.084 (3)−0.0047 (18)0.0138 (19)0.031 (2)
C90.074 (2)0.0553 (19)0.0471 (19)0.0103 (17)0.0135 (17)0.0017 (15)
C100.071 (2)0.070 (2)0.057 (2)0.0043 (19)−0.0076 (18)0.0106 (18)
C110.075 (3)0.085 (3)0.081 (3)0.035 (2)0.031 (2)0.022 (2)
C120.082 (3)0.0477 (18)0.055 (2)0.0115 (17)0.0100 (18)0.0070 (16)
C130.0516 (18)0.0499 (17)0.057 (2)0.0198 (14)0.0182 (15)0.0183 (16)
C140.061 (2)0.064 (2)0.0527 (19)0.0207 (17)0.0245 (17)0.0200 (16)
Geometric parameters (Å, °) top
Zn1—N51.951 (3)C3—C41.356 (6)
Zn1—N41.959 (3)C3—H30.9300
Zn1—N22.051 (3)C4—C51.381 (5)
Zn1—N12.273 (3)C4—H40.9300
Zn1—N32.279 (3)C5—H50.9300
S1—C131.611 (4)C6—H60.9300
S2—C141.618 (4)C7—C81.501 (6)
O1—C111.401 (5)C7—H7A0.9700
O1—C101.409 (5)C7—H7B0.9700
N1—C51.319 (5)C8—H8A0.9700
N1—C11.339 (4)C8—H8B0.9700
N2—C61.253 (4)C9—C101.492 (5)
N2—C71.462 (5)C9—H9A0.9700
N3—C81.475 (4)C9—H9B0.9700
N3—C91.479 (4)C10—H10A0.9700
N3—C121.486 (4)C10—H10B0.9700
N4—C131.137 (4)C11—C121.500 (6)
N5—C141.122 (4)C11—H11A0.9700
C1—C21.375 (5)C11—H11B0.9700
C1—C61.471 (5)C12—H12A0.9700
C2—C31.374 (6)C12—H12B0.9700
C2—H20.9300
N5—Zn1—N4117.35 (16)N2—C6—H6120.4
N5—Zn1—N2126.27 (15)C1—C6—H6120.4
N4—Zn1—N2114.94 (12)N2—C7—C8107.8 (3)
N5—Zn1—N191.02 (12)N2—C7—H7A110.1
N4—Zn1—N193.10 (12)C8—C7—H7A110.1
N2—Zn1—N174.60 (11)N2—C7—H7B110.1
N5—Zn1—N3104.43 (12)C8—C7—H7B110.1
N4—Zn1—N397.98 (11)H7A—C7—H7B108.5
N2—Zn1—N379.39 (11)N3—C8—C7112.0 (3)
N1—Zn1—N3153.98 (10)N3—C8—H8A109.2
C11—O1—C10109.3 (3)C7—C8—H8A109.2
C5—N1—C1117.5 (3)N3—C8—H8B109.2
C5—N1—Zn1130.3 (2)C7—C8—H8B109.2
C1—N1—Zn1112.2 (2)H8A—C8—H8B107.9
C6—N2—C7123.2 (3)N3—C9—C10112.0 (3)
C6—N2—Zn1119.9 (2)N3—C9—H9A109.2
C7—N2—Zn1116.5 (2)C10—C9—H9A109.2
C8—N3—C9110.1 (3)N3—C9—H9B109.2
C8—N3—C12107.7 (3)C10—C9—H9B109.2
C9—N3—C12107.8 (3)H9A—C9—H9B107.9
C8—N3—Zn1100.9 (2)O1—C10—C9112.2 (3)
C9—N3—Zn1115.6 (2)O1—C10—H10A109.2
C12—N3—Zn1114.3 (2)C9—C10—H10A109.2
C13—N4—Zn1159.8 (3)O1—C10—H10B109.2
C14—N5—Zn1175.1 (3)C9—C10—H10B109.2
N1—C1—C2123.0 (3)H10A—C10—H10B107.9
N1—C1—C6113.7 (3)O1—C11—C12111.9 (3)
C2—C1—C6123.3 (3)O1—C11—H11A109.2
C3—C2—C1118.2 (3)C12—C11—H11A109.2
C3—C2—H2120.9O1—C11—H11B109.2
C1—C2—H2120.9C12—C11—H11B109.2
C4—C3—C2119.4 (3)H11A—C11—H11B107.9
C4—C3—H3120.3N3—C12—C11110.8 (3)
C2—C3—H3120.3N3—C12—H12A109.5
C3—C4—C5118.9 (4)C11—C12—H12A109.5
C3—C4—H4120.6N3—C12—H12B109.5
C5—C4—H4120.6C11—C12—H12B109.5
N1—C5—C4123.0 (4)H12A—C12—H12B108.1
N1—C5—H5118.5N4—C13—S1179.4 (3)
C4—C5—H5118.5N5—C14—S2177.4 (3)
N2—C6—C1119.3 (3)
Acknowledgements top

The author is grateful to Jiaying University for financial support.

references
References top

Ali, H. M., Mohamed Mustafa, M. I., Rizal, M. R. & Ng, S. W. (2008). Acta Cryst. E64, m421.

Ali, H. M., Puvaneswary, S. & Ng, S. W. (2006). Acta Cryst. E62, m2737–m2738.

Bruker (2002). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.

Costes, J.-P., Clemente-Juan, J. M., Dahan, F., Dumestre, F. & Tuchagues, J.-P. (2002). Inorg. Chem. 41, 2886–2891.

Eltayeb, N. E., Teoh, S. G., Chantrapromma, S., Fun, H.-K. & Ibrahim, K. (2007). Acta Cryst. E63, m2024–m2025.

Erxleben, A. (2001). Inorg. Chem. 40, 208–213.

Lacroix, P. G., Di Bella, S. & Ledoux, I. (1996). Chem. Mater. 8, 541–545.

Li, H.-Q., Xian, H.-D., Liu, J.-F. & Zhao, G.-L. (2008). Acta Cryst. E64, m1495.

Odoko, M., Tsuchida, N. & Okabe, N. (2006). Acta Cryst. E62, m710–m711.

Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.

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

Zhang, Q.-W. & Wang, G.-X. (2007). Acta Cryst. E63, m652–m653.