[2-(Piperidin-1-yl)ethyl­amine]dithio­cyanato­zinc(II)

Wang, C.-Y.; Ke, A.-F.; Wu, X.

doi:10.1107/S1600536810007300

metal-organic compounds

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ISSN: 2056-9890

Volume 66| Part 4| April 2010| Page m350

doi:10.1107/S1600536810007300

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[2-(Piperidin-1-yl)ethylamine]dithiocyanatozinc(II)

Chen-Yi Wang,^a ^* Ai-Fei Ke ^a and Xiang Wu ^a

^aDepartment of Chemistry, Huzhou University, Huzhou 313000, People's Republic of China
^*Correspondence e-mail: chenyi_wang@163.com

(Received 25 February 2010; accepted 25 February 2010; online 3 March 2010)

In the mononuclear title compound, [Zn(NCS)₂(C₇H₁₆N₂)], the Zn^II atom is four-coordinated by two N atoms of the chelating 2-(piperidin-1-yl)ethylamine ligand and two N atoms from two thiocyanate ligands in a distorted tetrahedral geometry. In the crystal structure, molecules are linked through intermolecular N—H⋯S hydrogen bonds, forming chains along the b axis.

Related literature

For related structures, see: Wang et al. (2009a ,b ); Wang (2009 ). For bond-length and angle data, see: Cameron et al. (1998 ); Hong (2007 ).

Experimental

Crystal data

[Zn(NCS)₂(C₇H₁₆N₂)]
M_r = 309.75
Monoclinic, P 2₁ /c
a = 9.561 (2) Å
b = 10.310 (2) Å
c = 14.398 (3) Å
β = 97.367 (3)°
V = 1407.6 (5) Å³
Z = 4
Mo Kα radiation
μ = 2.02 mm⁻¹
T = 298 K
0.20 × 0.20 × 0.18 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.688, T_max = 0.712
7615 measured reflections
3029 independent reflections
2196 reflections with I > 2σ(I)
R_int = 0.028

Refinement

R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.095
S = 1.04
3029 reflections
145 parameters
H-atom parameters constrained
Δρ_max = 0.32 e Å⁻³
Δρ_min = −0.39 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯S1ⁱ	0.90	2.65	3.523 (3)	165
N1—H1B⋯S2ⁱⁱ	0.90	2.71	3.509 (3)	148
Symmetry codes: (i) $[-x, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[-x, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 1998 ); cell refinement: SAINT (Bruker, 1998); 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.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810007300/ci5046sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810007300/ci5046Isup2.hkl

checkCIF report

Comment top

As part of our investigations into novel urease inhibitors (Wang et al., 2009a,b; Wang, 2009), we have synthesized the title compound, a new Zn^II complex, and its crystal structure is reported here.

The Zn^II atom in the complex is chelated by the two N atoms of 2-piperidin-1-ylethylamine ligand and two N atoms from two thiocyanate ligands, giving a distorted tetrahedral geometry (Fig. 1). The coordinate bond lengths and angles are typical and are comparable with those observed in other related zinc(II) complexes (Cameron et al., 1998; Hong, 2007).

In the crystal structure, molecules are linked through intermolecular N—H···S hydrogen bonds (Table 1), forming chains running along the b axis (Fig. 2).

Related literature top

For related structures, see: Wang et al. (2009a,b); Wang (2009). For bond-length and angle data, see: Cameron et al. (1998); Hong (2007).

Experimental top

2-Piperidin-1-ylethylamine (1.0 mmol, 128 mg), ammonium thiocyanate (1.0 mmol, 76 mg), and Zn(NO₃)₂.6H₂O (1.0 mmol, 290 mg) were dissolved in MeOH (30 ml). The mixture was stirred at room temperature for 10 min to give a clear colourless solution. After keeping the solution in air for a week, colourless block-shaped crystals were formed at the bottom of the vessel.

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998); 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

	Fig. 1. The molecular structure of the title compound, showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. The molecular packing of the title compound, viewed along the a axis. Intermolecular N—H···S hydrogen bonds are shown as dashed lines.

[2-(Piperidin-1-yl)ethylamine]dithiocyanatozinc(II) top

Crystal data top

[Zn(NCS)₂(C₇H₁₆N₂)]	F(000) = 640
M_r = 309.75	D_x = 1.462 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2403 reflections
a = 9.561 (2) Å	θ = 2.4–25.0°
b = 10.310 (2) Å	µ = 2.02 mm⁻¹
c = 14.398 (3) Å	T = 298 K
β = 97.367 (3)°	Block, colourless
V = 1407.6 (5) Å³	0.20 × 0.20 × 0.18 mm
Z = 4

Data collection top

Bruker SMART CCD area-detector diffractometer	3029 independent reflections
Radiation source: fine-focus sealed tube	2196 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.028
ω scan	θ_max = 27.0°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −12→11
T_min = 0.688, T_max = 0.712	k = −13→13
7615 measured reflections	l = −9→18

Refinement top

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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.095	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0475P)² + 0.1775P] where P = (F_o² + 2F_c²)/3
3029 reflections	(Δ/σ)_max = 0.001
145 parameters	Δρ_max = 0.32 e Å⁻³
0 restraints	Δρ_min = −0.39 e Å⁻³

Crystal data top

[Zn(NCS)₂(C₇H₁₆N₂)]	V = 1407.6 (5) Å³
M_r = 309.75	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 9.561 (2) Å	µ = 2.02 mm⁻¹
b = 10.310 (2) Å	T = 298 K
c = 14.398 (3) Å	0.20 × 0.20 × 0.18 mm
β = 97.367 (3)°

Data collection top

Bruker SMART CCD area-detector diffractometer	3029 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2196 reflections with I > 2σ(I)
T_min = 0.688, T_max = 0.712	R_int = 0.028
7615 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	0 restraints
wR(F²) = 0.095	H-atom parameters constrained
S = 1.04	Δρ_max = 0.32 e Å⁻³
3029 reflections	Δρ_min = −0.39 e Å⁻³
145 parameters

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 > σ(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

	x	y	z	U_iso*/U_eq
Zn1	0.10783 (3)	0.24465 (3)	0.24635 (2)	0.05057 (13)
S1	0.28910 (10)	0.60126 (8)	0.42530 (6)	0.0791 (3)
S2	−0.19929 (8)	0.06124 (9)	0.43790 (6)	0.0750 (3)
N1	0.0345 (3)	0.2689 (2)	0.10961 (16)	0.0620 (6)
H1A	−0.0556	0.2418	0.0979	0.074*
H1B	0.0382	0.3530	0.0936	0.074*
N2	0.2756 (2)	0.1410 (2)	0.20451 (14)	0.0495 (5)
N3	0.1803 (3)	0.4000 (2)	0.31175 (18)	0.0706 (7)
N4	−0.0197 (3)	0.1600 (3)	0.32020 (17)	0.0676 (6)
C1	0.1265 (4)	0.1900 (4)	0.0560 (2)	0.0756 (9)
H1C	0.1262	0.2262	−0.0062	0.091*
H1D	0.0907	0.1020	0.0495	0.091*
C2	0.2741 (3)	0.1887 (3)	0.1060 (2)	0.0671 (8)
H2A	0.3131	0.2756	0.1068	0.081*
H2B	0.3325	0.1328	0.0728	0.081*
C3	0.2624 (3)	−0.0025 (3)	0.2047 (2)	0.0678 (8)
H3A	0.3371	−0.0402	0.1738	0.081*
H3B	0.1729	−0.0272	0.1695	0.081*
C4	0.2706 (4)	−0.0557 (3)	0.3028 (2)	0.0791 (9)
H4A	0.2666	−0.1497	0.3001	0.095*
H4B	0.1900	−0.0255	0.3313	0.095*
C5	0.4045 (4)	−0.0145 (4)	0.3625 (2)	0.0883 (11)
H5A	0.4031	−0.0439	0.4264	0.106*
H5B	0.4853	−0.0533	0.3388	0.106*
C6	0.4168 (3)	0.1305 (4)	0.3608 (2)	0.0826 (10)
H6A	0.5048	0.1568	0.3970	0.099*
H6B	0.3400	0.1689	0.3892	0.099*
C7	0.4124 (3)	0.1786 (3)	0.2614 (2)	0.0691 (8)
H7A	0.4222	0.2723	0.2615	0.083*
H7B	0.4905	0.1418	0.2334	0.083*
C8	0.2262 (3)	0.4841 (3)	0.35825 (19)	0.0552 (7)
C9	−0.0958 (3)	0.1204 (3)	0.36869 (18)	0.0499 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.0569 (2)	0.0542 (2)	0.04129 (19)	0.00372 (13)	0.00884 (14)	−0.00022 (13)
S1	0.0986 (6)	0.0605 (5)	0.0736 (5)	−0.0117 (4)	−0.0061 (5)	−0.0036 (4)
S2	0.0604 (4)	0.0944 (6)	0.0750 (5)	−0.0167 (4)	0.0277 (4)	−0.0161 (4)
N1	0.0697 (15)	0.0669 (16)	0.0479 (13)	0.0098 (11)	0.0013 (12)	0.0075 (11)
N2	0.0570 (12)	0.0496 (12)	0.0432 (11)	0.0032 (10)	0.0111 (10)	0.0058 (9)
N3	0.101 (2)	0.0521 (15)	0.0585 (15)	−0.0003 (13)	0.0080 (13)	−0.0040 (12)
N4	0.0633 (14)	0.0833 (18)	0.0583 (14)	−0.0052 (13)	0.0162 (12)	0.0001 (13)
C1	0.107 (3)	0.080 (2)	0.0385 (15)	0.022 (2)	0.0079 (16)	0.0045 (15)
C2	0.080 (2)	0.075 (2)	0.0511 (17)	0.0150 (17)	0.0243 (15)	0.0135 (15)
C3	0.082 (2)	0.0526 (17)	0.0687 (19)	0.0049 (15)	0.0069 (16)	0.0014 (14)
C4	0.091 (2)	0.063 (2)	0.087 (2)	0.0138 (17)	0.0214 (19)	0.0278 (18)
C5	0.087 (2)	0.113 (3)	0.066 (2)	0.039 (2)	0.0130 (19)	0.028 (2)
C6	0.0624 (18)	0.118 (3)	0.063 (2)	0.0176 (19)	−0.0094 (15)	−0.003 (2)
C7	0.0511 (16)	0.073 (2)	0.084 (2)	−0.0015 (14)	0.0122 (16)	0.0011 (17)
C8	0.0658 (17)	0.0499 (16)	0.0513 (16)	0.0069 (13)	0.0126 (13)	0.0116 (13)
C9	0.0413 (13)	0.0584 (16)	0.0494 (15)	0.0024 (11)	0.0031 (11)	−0.0129 (12)

Geometric parameters (Å, º) top

Zn1—N4	1.927 (3)	C2—H2A	0.97
Zn1—N3	1.940 (3)	C2—H2B	0.97
Zn1—N1	2.019 (2)	C3—C4	1.508 (4)
Zn1—N2	2.080 (2)	C3—H3A	0.97
S1—C8	1.614 (3)	C3—H3B	0.97
S2—C9	1.611 (3)	C4—C5	1.509 (5)
N1—C1	1.485 (4)	C4—H4A	0.97
N1—H1A	0.90	C4—H4B	0.97
N1—H1B	0.90	C5—C6	1.500 (5)
N2—C3	1.485 (3)	C5—H5A	0.97
N2—C2	1.500 (3)	C5—H5B	0.97
N2—C7	1.503 (3)	C6—C7	1.510 (5)
N3—C8	1.148 (3)	C6—H6A	0.97
N4—C9	1.146 (3)	C6—H6B	0.97
C1—C2	1.500 (4)	C7—H7A	0.97
C1—H1C	0.97	C7—H7B	0.97
C1—H1D	0.97

N4—Zn1—N3	108.54 (11)	N2—C3—C4	111.7 (3)
N4—Zn1—N1	115.39 (10)	N2—C3—H3A	109.3
N3—Zn1—N1	115.40 (10)	C4—C3—H3A	109.3
N4—Zn1—N2	119.57 (10)	N2—C3—H3B	109.3
N3—Zn1—N2	108.90 (10)	C4—C3—H3B	109.3
N1—Zn1—N2	88.02 (9)	H3A—C3—H3B	107.9
C1—N1—Zn1	106.51 (17)	C3—C4—C5	111.7 (3)
C1—N1—H1A	110.4	C3—C4—H4A	109.3
Zn1—N1—H1A	110.4	C5—C4—H4A	109.3
C1—N1—H1B	110.4	C3—C4—H4B	109.3
Zn1—N1—H1B	110.4	C5—C4—H4B	109.3
H1A—N1—H1B	108.6	H4A—C4—H4B	107.9
C3—N2—C2	109.8 (2)	C6—C5—C4	109.5 (3)
C3—N2—C7	108.9 (2)	C6—C5—H5A	109.8
C2—N2—C7	109.4 (2)	C4—C5—H5A	109.8
C3—N2—Zn1	116.27 (17)	C6—C5—H5B	109.8
C2—N2—Zn1	101.04 (16)	C4—C5—H5B	109.8
C7—N2—Zn1	111.06 (17)	H5A—C5—H5B	108.2
C8—N3—Zn1	173.1 (2)	C5—C6—C7	110.5 (3)
C9—N4—Zn1	173.6 (3)	C5—C6—H6A	109.5
N1—C1—C2	109.8 (3)	C7—C6—H6A	109.5
N1—C1—H1C	109.7	C5—C6—H6B	109.5
C2—C1—H1C	109.7	C7—C6—H6B	109.5
N1—C1—H1D	109.7	H6A—C6—H6B	108.1
C2—C1—H1D	109.7	N2—C7—C6	110.4 (2)
H1C—C1—H1D	108.2	N2—C7—H7A	109.6
C1—C2—N2	110.5 (2)	C6—C7—H7A	109.6
C1—C2—H2A	109.5	N2—C7—H7B	109.6
N2—C2—H2A	109.5	C6—C7—H7B	109.6
C1—C2—H2B	109.5	H7A—C7—H7B	108.1
N2—C2—H2B	109.5	N3—C8—S1	178.9 (3)
H2A—C2—H2B	108.1	N4—C9—S2	178.2 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···S1ⁱ	0.90	2.65	3.523 (3)	165
N1—H1B···S2ⁱⁱ	0.90	2.71	3.509 (3)	148

Symmetry codes: (i) −x, y−1/2, −z+1/2; (ii) −x, y+1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	[Zn(NCS)₂(C₇H₁₆N₂)]
M_r	309.75
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	9.561 (2), 10.310 (2), 14.398 (3)
β (°)	97.367 (3)
V (Å³)	1407.6 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	2.02
Crystal size (mm)	0.20 × 0.20 × 0.18

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.688, 0.712
No. of measured, independent and observed [I > 2σ(I)] reflections	7615, 3029, 2196
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.095, 1.04
No. of reflections	3029
No. of parameters	145
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.32, −0.39

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···S1ⁱ	0.90	2.65	3.523 (3)	165
N1—H1B···S2ⁱⁱ	0.90	2.71	3.509 (3)	148

Symmetry codes: (i) −x, y−1/2, −z+1/2; (ii) −x, y+1/2, −z+1/2.

Acknowledgements

This work was supported by the Natural Science Foundation of China (grant No. 30771696), the Natural Science Foundation of Zhejiang Province (grant No. Y407318) and the Science and Technology Plan of Huzhou (grant No. 2009 GG06).

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