(Piperazin-1-ium-κN4)tris­(thio­cyanato-κN)zinc(II)

He, X.; Liu, H.-J.; Li, M.-X.

doi:10.1107/S1600536807065087

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 1| January 2008| Page m122

https://doi.org/10.1107/S1600536807065087

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(Piperazin-1-ium-κN⁴)tris(thiocyanato-κN)zinc(II)

Xiang He,^a ^* Hong-Jiang Liu ^a and Ming-Xing Li ^a

^aDepartment of Chemistry, College of Science, Shanghai University, Shanghai 200444, People's Republic of China
^*Correspondence e-mail: hxiang@shu.edu.cn

(Received 16 November 2007; accepted 2 December 2007; online 6 December 2007)

Hydrothermal reaction of NaSCN, piperazine, Zn^II and 2,6-naphthalenedicarboxylic acid in aqueous solutions gave rise to the title complex, [Zn(NCS)₃(C₄H₁₁N₂)]. The Zn^II atom is four-coordinate with distorted tetrahedral geometry and lies in a mirror plane. N—H⋯S hydrogen bonds assemble the molecules to form a three-dimensional framework.

Related literature

For related literature, see: Bie et al. (2005 ); Dai et al. (2002 ); Gu et al. (2007 ); Liu et al. (2007 ); Ouyang et al. (2003 ); Tao et al. (2003 ).

Experimental

Crystal data

[Zn(NCS)₃(C₄H₁₁N₂)]
M_r = 326.72
Orthorhombic, P n m a
a = 16.8975 (8) Å
b = 11.0467 (4) Å
c = 7.3097 (3) Å
V = 1364.44 (10) Å³
Z = 4
Mo Kα radiation
μ = 2.24 mm⁻¹
T = 293 (2) K
0.40 × 0.20 × 0.15 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.830, T_max = 1.000 (expected range = 0.593–0.715)
3079 measured reflections
1237 independent reflections
901 reflections with I > 2σ(I)
R_int = 0.055

Refinement

R[F² > 2σ(F²)] = 0.064
wR(F²) = 0.154
S = 1.03
1237 reflections
82 parameters
H-atom parameters constrained
Δρ_max = 0.62 e Å⁻³
Δρ_min = −0.48 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H4C⋯S1ⁱ	0.90	2.72	3.470 (6)	141
N4—H4D⋯S2ⁱⁱ	0.90	2.38	3.281 (7)	175
Symmetry codes: (i) $[-x+{\script{1\over 2}}, -y+1, z+{\script{1\over 2}}]$ ; (ii) $[x+{\script{1\over 2}}, y, -z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2000 ); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2000); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536807065087/dn2286sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536807065087/dn2286Isup2.hkl

checkCIF report

Comment top

d¹⁰ metal complexes have been found to exhibit intriguing structural and photoluminescent properties (Liu et al., 2007; Dai et al., 2002; Ouyang et al., 2003; Gu et al., 2007; Tao et al., 2003). When trying to prepare the zinc complex containing 2,6-naphthalenedicarboxylic acid, piperazine and thiocyanate ligands by hydrothermal reaction, we did not obtain the expected compound but instead of the tri-isothiocyanato-(piperazinium-N')-zinc(II) compound (I). The new complex has been characterized by elemental analysis and single-crystal diffraction analysis.

The Zn atom adopts a distorted tetrahedral coordination geometry and is coordinated by three N atoms from the thiocyanate anions and one piperazine N atom (Fig. 1). The Zn atom, one thiocyanate ligands and N atoms of piperazine ligands are located on a mirror plane. The Zn—N3 (piperazine) bond length is 2.054 (6) Å and the Zn-NCS bond lengths are almost equal at 1.935 (5) Å for N1 and 1.933 (8) Å for N2, respectively. The N—Zn—N angles are in the range 107.7 (3) ° ~112.3 (3) °. All bond distances and angles are as observed for other zinc(II) complexes with piperazine and thiocyanate ligands (Bie et al., 2005). There are intermolecular N—H···S hydrogen bonds in the compound, which assemble the molecules to form a a three dimensionnal framework.(Table 1 and Fig. 2)

Related literature top

For related literature, see: Bie et al. (2005); Dai et al. (2002); Gu et al. (2007); Liu et al. (2007); Ouyang et al. (2003); Tao et al. (2003).

Experimental top

A mixture of ZnCl₂.6H₂O (0.49 g, 2 mmol), 2,6-naphthalenedicarboxylic acid (1 mmol, 0.26 g), piperazine (2 mmol, 0.17), NH₄SCN (10 mmol, 0.15) and H₂O (10 ml) was stirred for 0.5 h at room temperature. The reaction was carried out in a Teflon-lined steel autoclave, which was heated at 160oC for 2 d followed by slow cooling to room temperature. The resulting colorless prism-shaped crystals suitable for X-ray analysis were filtered off and washed with water. Analysis, calculated for C₇H₁₁N₅S₃Zn: C 25.96, H 3.13, N 21.79%; found: C 25.73, H 3.39, N 21.43%.

Structure description top

For related literature, see: Bie et al. (2005); Dai et al. (2002); Gu et al. (2007); Liu et al. (2007); Ouyang et al. (2003); Tao et al. (2003).

Computing details top

Data collection: APEX2 (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2000); software used to prepare material for publication: SHELXTL (Bruker, 2000).

Figures top

	Fig. 1. View of (I) with the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. [symmetry codes: (i) x,-y + 1/2,z].
	Fig. 2. Crystal packing diagram of compound (I), Hydrogen bonding is indicated by dashed lines.

(Piperazin-1-ium-κN⁴)tris(thiocyanato-κN)zinc(II) top

Crystal data top

[Zn(NCS)₃(C₄H₁₁N₂)]	F(000) = 664
M_r = 326.72	D_x = 1.590 Mg m⁻³
Orthorhombic, Pnma	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2n	Cell parameters from 75 reflections
a = 16.8975 (8) Å	θ = 3.0–25.0°
b = 11.0467 (4) Å	µ = 2.24 mm⁻¹
c = 7.3097 (3) Å	T = 293 K
V = 1364.44 (10) Å³	Prism, colorless
Z = 4	0.40 × 0.20 × 0.15 mm

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	1237 independent reflections
Radiation source: fine-focus sealed tube	901 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.055
ω scans	θ_max = 25.0°, θ_min = 3.0°
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996)	h = −19→13
T_min = 0.830, T_max = 1.000	k = −13→8
3079 measured reflections	l = −8→7

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)] = 0.064	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.154	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0605P)²] where P = (F_o² + 2F_c²)/3
1237 reflections	(Δ/σ)_max < 0.001
82 parameters	Δρ_max = 0.62 e Å⁻³
0 restraints	Δρ_min = −0.48 e Å⁻³

Crystal data top

[Zn(NCS)₃(C₄H₁₁N₂)]	V = 1364.44 (10) Å³
M_r = 326.72	Z = 4
Orthorhombic, Pnma	Mo Kα radiation
a = 16.8975 (8) Å	µ = 2.24 mm⁻¹
b = 11.0467 (4) Å	T = 293 K
c = 7.3097 (3) Å	0.40 × 0.20 × 0.15 mm

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	1237 independent reflections
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996)	901 reflections with I > 2σ(I)
T_min = 0.830, T_max = 1.000	R_int = 0.055
3079 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.064	0 restraints
wR(F²) = 0.154	H-atom parameters constrained
S = 1.03	Δρ_max = 0.62 e Å⁻³
1237 reflections	Δρ_min = −0.48 e Å⁻³
82 parameters

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.

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	0.02672 (5)	0.2500	−0.08930 (13)	0.0469 (4)
S1	0.10918 (11)	0.59639 (14)	−0.4058 (3)	0.0696 (6)
S2	−0.24789 (14)	0.2500	−0.1884 (4)	0.0884 (10)
N1	0.0695 (3)	0.3956 (5)	−0.1985 (8)	0.0658 (16)
N2	−0.0875 (4)	0.2500	−0.1112 (11)	0.073 (2)
N3	0.0549 (3)	0.2500	0.1831 (8)	0.0402 (15)
H3C	0.0077	0.2500	0.2430	0.048*
N4	0.2239 (4)	0.2500	0.2443 (9)	0.060 (2)
H4C	0.2729	0.2500	0.1964	0.072*
H4D	0.2285	0.2500	0.3670	0.072*
C1	0.0871 (3)	0.4790 (5)	−0.2800 (8)	0.0456 (14)
C2	−0.1538 (5)	0.2500	−0.1416 (11)	0.050 (2)
C3	0.0968 (3)	0.1421 (6)	0.2496 (9)	0.0622 (17)
H3A	0.0697	0.0702	0.2063	0.075*
H3B	0.0956	0.1412	0.3822	0.075*
C4	0.1817 (3)	0.1387 (5)	0.1857 (9)	0.0579 (17)
H4A	0.2079	0.0682	0.2366	0.069*
H4B	0.1833	0.1323	0.0534	0.069*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.0334 (6)	0.0679 (7)	0.0394 (7)	0.000	−0.0036 (5)	0.000
S1	0.0691 (12)	0.0427 (9)	0.0970 (15)	−0.0117 (8)	−0.0099 (11)	0.0037 (8)
S2	0.0325 (14)	0.185 (3)	0.0474 (17)	0.000	−0.0027 (12)	0.000
N1	0.057 (4)	0.072 (4)	0.068 (4)	0.000 (3)	−0.001 (3)	0.028 (3)
N2	0.033 (4)	0.129 (7)	0.056 (5)	0.000	−0.007 (4)	0.000
N3	0.027 (3)	0.057 (4)	0.037 (4)	0.000	0.000 (3)	0.000
N4	0.033 (4)	0.104 (6)	0.044 (5)	0.000	−0.003 (4)	0.000
C1	0.036 (3)	0.055 (4)	0.046 (4)	0.009 (3)	−0.009 (3)	−0.014 (3)
C2	0.044 (6)	0.078 (6)	0.028 (5)	0.000	0.004 (4)	0.000
C3	0.054 (4)	0.076 (4)	0.056 (4)	−0.005 (3)	−0.004 (4)	0.015 (3)
C4	0.050 (4)	0.066 (4)	0.057 (4)	0.014 (3)	−0.007 (3)	0.006 (3)

Geometric parameters (Å, º) top

Zn1—N2	1.937 (8)	N3—H3C	0.9100
Zn1—N1ⁱ	1.936 (5)	N4—C4	1.484 (7)
Zn1—N1	1.936 (5)	N4—C4ⁱ	1.484 (7)
Zn1—N3	2.048 (6)	N4—H4C	0.9000
S1—C1	1.633 (7)	N4—H4D	0.9000
S2—C2	1.626 (9)	C3—C4	1.509 (7)
N1—C1	1.136 (7)	C3—H3A	0.9700
N2—C2	1.143 (10)	C3—H3B	0.9700
N3—C3ⁱ	1.469 (6)	C4—H4A	0.9700
N3—C3	1.469 (6)	C4—H4B	0.9700

N2—Zn1—N1ⁱ	109.77 (18)	C4—N4—H4D	109.2
N2—Zn1—N1	109.77 (18)	C4ⁱ—N4—H4D	109.2
N1ⁱ—Zn1—N1	112.4 (3)	H4C—N4—H4D	107.9
N2—Zn1—N3	108.2 (3)	N1—C1—S1	176.9 (6)
N1ⁱ—Zn1—N3	108.30 (19)	N2—C2—S2	179.0 (8)
N1—Zn1—N3	108.30 (19)	N3—C3—C4	112.1 (5)
C1—N1—Zn1	170.9 (5)	N3—C3—H3A	109.2
C2—N2—Zn1	173.5 (8)	C4—C3—H3A	109.2
C3ⁱ—N3—C3	108.5 (6)	N3—C3—H3B	109.2
C3ⁱ—N3—Zn1	115.7 (4)	C4—C3—H3B	109.2
C3—N3—Zn1	115.7 (4)	H3A—C3—H3B	107.9
C3ⁱ—N3—H3C	105.3	N4—C4—C3	110.3 (5)
C3—N3—H3C	105.3	N4—C4—H4A	109.6
Zn1—N3—H3C	105.3	C3—C4—H4A	109.6
C4—N4—C4ⁱ	111.9 (6)	N4—C4—H4B	109.6
C4—N4—H4C	109.2	C3—C4—H4B	109.6
C4ⁱ—N4—H4C	109.2	H4A—C4—H4B	108.1

Symmetry code: (i) x, −y+1/2, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4C···S1ⁱⁱ	0.90	2.72	3.470 (6)	141
N4—H4D···S2ⁱⁱⁱ	0.90	2.38	3.281 (7)	175

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

Experimental details

Crystal data
Chemical formula	[Zn(NCS)₃(C₄H₁₁N₂)]
M_r	326.72
Crystal system, space group	Orthorhombic, Pnma
Temperature (K)	293
a, b, c (Å)	16.8975 (8), 11.0467 (4), 7.3097 (3)
V (Å³)	1364.44 (10)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	2.24
Crystal size (mm)	0.40 × 0.20 × 0.15

Data collection
Diffractometer	Bruker SMART APEXII CCD area-detector
Absorption correction	Empirical (using intensity measurements) (SADABS; Sheldrick, 1996)
T_min, T_max	0.830, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	3079, 1237, 901
R_int	0.055
(sin θ/λ)_max (Å⁻¹)	0.594

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.064, 0.154, 1.03
No. of reflections	1237
No. of parameters	82
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.62, −0.48

Computer programs: APEX2 (Bruker, 2000), SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2000).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4C···S1ⁱ	0.90	2.72	3.470 (6)	141.4
N4—H4D···S2ⁱⁱ	0.90	2.38	3.281 (7)	175.4

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

Acknowledgements

The project was supported by the Development Foundation of Shanghai Municipal Education Commission, China, and the Science Foundation for Excellent Young Scholars of Higher Education of Shanghai.

References

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