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

Bang-Hong Cai

doi:10.1107/S1600536808044061

. 2009 Jan 8;65(Pt 2):m142. doi: 10.1107/S1600536808044061

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

Bang-Hong Cai ^a,^*

PMCID: PMC2968346 PMID: 21581757

Abstract

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 Zn^II 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.

Related literature

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

Crystal data

[Zn(NCS)₂(C₁₂H₁₇N₃O)]
M _r = 400.82
Triclinic,
a = 8.185 (2) Å
b = 8.654 (2) Å
c = 13.368 (4) Å
α = 98.439 (3)°
β = 102.587 (3)°
γ = 102.501 (3)°
V = 883.3 (4) Å³
Z = 2
Mo Kα radiation
μ = 1.64 mm⁻¹
T = 298 (2) K
0.23 × 0.23 × 0.20 mm

Data collection

Bruker SMART 1000 CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.705, T _max = 0.736
7386 measured reflections
3770 independent reflections
2989 reflections with I > 2σ(I)
R _int = 0.031

Refinement

R[F ² > 2σ(F ²)] = 0.045
wR(F ²) = 0.124
S = 1.04
3770 reflections
208 parameters
H-atom parameters constrained
Δρ_max = 0.57 e Å⁻³
Δρ_min = −0.47 e Å⁻³

Data collection: SMART (Bruker, 2002 ▶); cell refinement: SAINT (Bruker, 2002 ▶); data reduction: SAINT; 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.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808044061/su2087sup1.cif

e-65-0m142-sup1.cif^{(16.8KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808044061/su2087Isup2.hkl

e-65-0m142-Isup2.hkl^{(184.8KB, hkl)}

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

Acknowledgments

The author is grateful to Jiaying University for financial support.

supplementary crystallographic information

Comment

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 Zn^II 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.

Experimental

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.

Figures

Fig. 1. — The molecular structure of the compound (I), showing 30% probability displacement ellipsoids.

Crystal data

[Zn(NCS)₂(C₁₂H₁₇N₃O)]	Z = 2
M_r = 400.82	F(000) = 412
Triclinic, P1	D_x = 1.507 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.185 (2) Å	Cell parameters from 2675 reflections
b = 8.654 (2) Å	θ = 2.4–25.0°
c = 13.368 (4) Å	µ = 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

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Data collection

Bruker SMART 1000 CCD area-detector diffractometer	3770 independent reflections
Radiation source: fine-focus sealed tube	2989 reflections with I > 2σ(I)
graphite	R_int = 0.031
ω scans	θ_max = 27.0°, θ_min = 1.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −10→10
T_min = 0.705, T_max = 0.736	k = −11→10
7386 measured reflections	l = −17→16

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Refinement

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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.124	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.064P)² + 0.1459P] where P = (F_o² + 2F_c²)/3
3770 reflections	(Δ/σ)_max = 0.001
208 parameters	Δρ_max = 0.57 e Å⁻³
0 restraints	Δρ_min = −0.47 e Å⁻³

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Special details

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.

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

	x	y	z	U_iso*/U_eq
Zn1	0.87080 (4)	0.35121 (4)	0.23426 (3)	0.04844 (15)
S1	0.75132 (16)	0.05952 (14)	−0.10471 (7)	0.0759 (3)
S2	1.40376 (14)	0.73452 (15)	0.38080 (9)	0.0854 (4)
O1	1.1836 (4)	0.1269 (4)	0.4455 (2)	0.0791 (8)
N1	0.7747 (4)	0.5343 (3)	0.1472 (2)	0.0551 (7)
N2	0.6437 (3)	0.3649 (3)	0.2720 (2)	0.0552 (7)
N3	0.8546 (3)	0.1714 (3)	0.3427 (2)	0.0493 (6)
N4	0.8437 (4)	0.1978 (4)	0.1048 (2)	0.0662 (8)
N5	1.0969 (4)	0.5041 (4)	0.2956 (3)	0.0793 (10)
C1	0.6221 (4)	0.5515 (4)	0.1613 (3)	0.0531 (8)
C2	0.5377 (5)	0.6554 (4)	0.1166 (3)	0.0622 (9)
H2	0.4323	0.6652	0.1285	0.075*
C3	0.6133 (5)	0.7444 (4)	0.0539 (3)	0.0662 (10)
H3	0.5592	0.8155	0.0223	0.079*
C4	0.7674 (5)	0.7276 (4)	0.0385 (3)	0.0690 (10)
H4	0.8204	0.7867	−0.0038	0.083*
C5	0.8445 (5)	0.6212 (4)	0.0866 (3)	0.0648 (9)
H5	0.9503	0.6103	0.0759	0.078*
C6	0.5531 (4)	0.4478 (4)	0.2283 (3)	0.0603 (9)
H6	0.4434	0.4439	0.2382	0.072*
C7	0.5856 (5)	0.2577 (6)	0.3393 (3)	0.0776 (12)
H7A	0.4603	0.2194	0.3188	0.093*
H7B	0.6214	0.3151	0.4117	0.093*
C8	0.6656 (5)	0.1177 (5)	0.3275 (3)	0.0730 (11)
H8A	0.6415	0.0524	0.3782	0.088*
H8B	0.6134	0.0506	0.2581	0.088*
C9	0.9411 (5)	0.2391 (4)	0.4547 (3)	0.0612 (9)
H9A	0.8978	0.1647	0.4962	0.073*
H9B	0.9127	0.3402	0.4752	0.073*
C10	1.1332 (5)	0.2682 (5)	0.4768 (3)	0.0723 (11)
H10A	1.1776	0.3503	0.4404	0.087*
H10B	1.1840	0.3088	0.5513	0.087*
C11	1.1103 (5)	0.0677 (5)	0.3379 (3)	0.0757 (11)
H11A	1.1471	−0.0283	0.3162	0.091*
H11B	1.1522	0.1484	0.2998	0.091*
C12	0.9161 (5)	0.0269 (4)	0.3108 (3)	0.0639 (9)
H12A	0.8704	−0.0134	0.2360	0.077*
H12B	0.8735	−0.0576	0.3460	0.077*
C13	0.8047 (4)	0.1408 (4)	0.0181 (3)	0.0504 (7)
C14	1.2216 (5)	0.6003 (4)	0.3288 (3)	0.0560 (8)

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Atomic displacement parameters (Å²)

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.0390 (2)	0.0533 (2)	0.0485 (2)	0.00680 (15)	0.01199 (15)	0.00305 (16)
S1	0.0891 (7)	0.0910 (7)	0.0462 (5)	0.0300 (6)	0.0125 (5)	0.0066 (5)
S2	0.0656 (6)	0.0863 (7)	0.0827 (7)	−0.0173 (5)	0.0278 (6)	−0.0084 (6)
O1	0.0664 (17)	0.090 (2)	0.0778 (19)	0.0235 (15)	0.0049 (14)	0.0222 (16)
N1	0.0487 (15)	0.0542 (16)	0.0604 (17)	0.0143 (12)	0.0129 (13)	0.0061 (13)
N2	0.0465 (15)	0.0640 (16)	0.0577 (17)	0.0151 (13)	0.0190 (13)	0.0100 (14)
N3	0.0469 (14)	0.0472 (14)	0.0473 (14)	0.0036 (11)	0.0098 (11)	0.0060 (11)
N4	0.083 (2)	0.0677 (19)	0.0506 (17)	0.0277 (16)	0.0191 (15)	0.0057 (15)
N5	0.0497 (17)	0.077 (2)	0.090 (3)	−0.0094 (16)	−0.0065 (17)	0.0269 (19)
C1	0.0496 (18)	0.0513 (18)	0.0517 (19)	0.0153 (14)	0.0064 (14)	−0.0036 (14)
C2	0.056 (2)	0.059 (2)	0.067 (2)	0.0235 (16)	0.0071 (17)	−0.0023 (17)
C3	0.072 (2)	0.0517 (19)	0.068 (2)	0.0210 (17)	0.0016 (19)	0.0079 (17)
C4	0.070 (2)	0.058 (2)	0.077 (3)	0.0139 (18)	0.017 (2)	0.0159 (19)
C5	0.055 (2)	0.063 (2)	0.080 (3)	0.0176 (17)	0.0196 (18)	0.0153 (19)
C6	0.0466 (18)	0.070 (2)	0.063 (2)	0.0184 (16)	0.0179 (16)	0.0011 (18)
C7	0.053 (2)	0.107 (3)	0.086 (3)	0.018 (2)	0.034 (2)	0.038 (2)
C8	0.051 (2)	0.078 (3)	0.084 (3)	−0.0047 (18)	0.0138 (19)	0.031 (2)
C9	0.074 (2)	0.0553 (19)	0.0471 (19)	0.0103 (17)	0.0135 (17)	0.0017 (15)
C10	0.071 (2)	0.070 (2)	0.057 (2)	0.0043 (19)	−0.0076 (18)	0.0106 (18)
C11	0.075 (3)	0.085 (3)	0.081 (3)	0.035 (2)	0.031 (2)	0.022 (2)
C12	0.082 (3)	0.0477 (18)	0.055 (2)	0.0115 (17)	0.0100 (18)	0.0070 (16)
C13	0.0516 (18)	0.0499 (17)	0.057 (2)	0.0198 (14)	0.0182 (15)	0.0183 (16)
C14	0.061 (2)	0.064 (2)	0.0527 (19)	0.0207 (17)	0.0245 (17)	0.0200 (16)

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Geometric parameters (Å, °)

Zn1—N5	1.951 (3)	C3—C4	1.356 (6)
Zn1—N4	1.959 (3)	C3—H3	0.9300
Zn1—N2	2.051 (3)	C4—C5	1.381 (5)
Zn1—N1	2.273 (3)	C4—H4	0.9300
Zn1—N3	2.279 (3)	C5—H5	0.9300
S1—C13	1.611 (4)	C6—H6	0.9300
S2—C14	1.618 (4)	C7—C8	1.501 (6)
O1—C11	1.401 (5)	C7—H7A	0.9700
O1—C10	1.409 (5)	C7—H7B	0.9700
N1—C5	1.319 (5)	C8—H8A	0.9700
N1—C1	1.339 (4)	C8—H8B	0.9700
N2—C6	1.253 (4)	C9—C10	1.492 (5)
N2—C7	1.462 (5)	C9—H9A	0.9700
N3—C8	1.475 (4)	C9—H9B	0.9700
N3—C9	1.479 (4)	C10—H10A	0.9700
N3—C12	1.486 (4)	C10—H10B	0.9700
N4—C13	1.137 (4)	C11—C12	1.500 (6)
N5—C14	1.122 (4)	C11—H11A	0.9700
C1—C2	1.375 (5)	C11—H11B	0.9700
C1—C6	1.471 (5)	C12—H12A	0.9700
C2—C3	1.374 (6)	C12—H12B	0.9700
C2—H2	0.9300

N5—Zn1—N4	117.35 (16)	N2—C6—H6	120.4
N5—Zn1—N2	126.27 (15)	C1—C6—H6	120.4
N4—Zn1—N2	114.94 (12)	N2—C7—C8	107.8 (3)
N5—Zn1—N1	91.02 (12)	N2—C7—H7A	110.1
N4—Zn1—N1	93.10 (12)	C8—C7—H7A	110.1
N2—Zn1—N1	74.60 (11)	N2—C7—H7B	110.1
N5—Zn1—N3	104.43 (12)	C8—C7—H7B	110.1
N4—Zn1—N3	97.98 (11)	H7A—C7—H7B	108.5
N2—Zn1—N3	79.39 (11)	N3—C8—C7	112.0 (3)
N1—Zn1—N3	153.98 (10)	N3—C8—H8A	109.2
C11—O1—C10	109.3 (3)	C7—C8—H8A	109.2
C5—N1—C1	117.5 (3)	N3—C8—H8B	109.2
C5—N1—Zn1	130.3 (2)	C7—C8—H8B	109.2
C1—N1—Zn1	112.2 (2)	H8A—C8—H8B	107.9
C6—N2—C7	123.2 (3)	N3—C9—C10	112.0 (3)
C6—N2—Zn1	119.9 (2)	N3—C9—H9A	109.2
C7—N2—Zn1	116.5 (2)	C10—C9—H9A	109.2
C8—N3—C9	110.1 (3)	N3—C9—H9B	109.2
C8—N3—C12	107.7 (3)	C10—C9—H9B	109.2
C9—N3—C12	107.8 (3)	H9A—C9—H9B	107.9
C8—N3—Zn1	100.9 (2)	O1—C10—C9	112.2 (3)
C9—N3—Zn1	115.6 (2)	O1—C10—H10A	109.2
C12—N3—Zn1	114.3 (2)	C9—C10—H10A	109.2
C13—N4—Zn1	159.8 (3)	O1—C10—H10B	109.2
C14—N5—Zn1	175.1 (3)	C9—C10—H10B	109.2
N1—C1—C2	123.0 (3)	H10A—C10—H10B	107.9
N1—C1—C6	113.7 (3)	O1—C11—C12	111.9 (3)
C2—C1—C6	123.3 (3)	O1—C11—H11A	109.2
C3—C2—C1	118.2 (3)	C12—C11—H11A	109.2
C3—C2—H2	120.9	O1—C11—H11B	109.2
C1—C2—H2	120.9	C12—C11—H11B	109.2
C4—C3—C2	119.4 (3)	H11A—C11—H11B	107.9
C4—C3—H3	120.3	N3—C12—C11	110.8 (3)
C2—C3—H3	120.3	N3—C12—H12A	109.5
C3—C4—C5	118.9 (4)	C11—C12—H12A	109.5
C3—C4—H4	120.6	N3—C12—H12B	109.5
C5—C4—H4	120.6	C11—C12—H12B	109.5
N1—C5—C4	123.0 (4)	H12A—C12—H12B	108.1
N1—C5—H5	118.5	N4—C13—S1	179.4 (3)
C4—C5—H5	118.5	N5—C14—S2	177.4 (3)
N2—C6—C1	119.3 (3)

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Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: SU2087).

References

Ali, H. M., Mohamed Mustafa, M. I., Rizal, M. R. & Ng, S. W. (2008). Acta Cryst. E64, m421. [DOI] [PMC free article] [PubMed]
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. [DOI] [PubMed]
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. [DOI] [PubMed]
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. [DOI] [PMC free article] [PubMed]
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. [DOI] [PubMed]
Zhang, Q.-W. & Wang, G.-X. (2007). Acta Cryst. E63, m652–m653.

Associated Data

This section collects any data citations, data availability statements, or supplementary materials included in this article.

Supplementary Materials

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808044061/su2087sup1.cif

e-65-0m142-sup1.cif^{(16.8KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808044061/su2087Isup2.hkl

e-65-0m142-Isup2.hkl^{(184.8KB, hkl)}

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

[bb1] Ali, H. M., Mohamed Mustafa, M. I., Rizal, M. R. & Ng, S. W. (2008). Acta Cryst. E64, m421. [DOI] [PMC free article] [PubMed]

[bb2] Ali, H. M., Puvaneswary, S. & Ng, S. W. (2006). Acta Cryst. E62, m2737–m2738.

[bb3] Bruker (2002). SMART and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.

[bb4] Costes, J.-P., Clemente-Juan, J. M., Dahan, F., Dumestre, F. & Tuchagues, J.-P. (2002). Inorg. Chem.41, 2886–2891. [DOI] [PubMed]

[bb5] Eltayeb, N. E., Teoh, S. G., Chantrapromma, S., Fun, H.-K. & Ibrahim, K. (2007). Acta Cryst. E63, m2024–m2025.

[bb6] Erxleben, A. (2001). Inorg. Chem.40, 208–213. [DOI] [PubMed]

[bb7] Lacroix, P. G., Di Bella, S. & Ledoux, I. (1996). Chem. Mater.8, 541–545.

[bb8] Li, H.-Q., Xian, H.-D., Liu, J.-F. & Zhao, G.-L. (2008). Acta Cryst. E64, m1495. [DOI] [PMC free article] [PubMed]

[bb9] Odoko, M., Tsuchida, N. & Okabe, N. (2006). Acta Cryst. E62, m710–m711.

[bb10] Sheldrick, G. M. (1996). SADABS University of Göttingen, Germany.

[bb11] Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [DOI] [PubMed]

[bb12] Zhang, Q.-W. & Wang, G.-X. (2007). Acta Cryst. E63, m652–m653.

PERMALINK

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

Bang-Hong Cai

Abstract

Related literature

Experimental

Crystal data

Data collection

Refinement

Supplementary Material

Acknowledgments

supplementary crystallographic information

Comment

Experimental

Refinement

Figures

Fig. 1.

Crystal data

Data collection

Refinement

Special details

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

Atomic displacement parameters (Å²)

Geometric parameters (Å, °)

Footnotes

References

Associated Data

Supplementary Materials

ACTIONS

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Cite

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PERMALINK

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

Bang-Hong Cai

Abstract

Related literature

Experimental

Crystal data

Data collection

Refinement

Supplementary Material

Acknowledgments

supplementary crystallographic information

Comment

Experimental

Refinement

Figures

Fig. 1.

Crystal data

Data collection

Refinement

Special details

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

Atomic displacement parameters (Å2)

Geometric parameters (Å, °)

Footnotes

References

Associated Data

Supplementary Materials

ACTIONS

PERMALINK

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