(Piperazin-1-ium-κN ⁴)tris­(thio­cyanato-κN)zinc(II)

Abstract

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,

• a = 16.8975 (8) Å

• b = 11.0467 (4) Å

• c = 7.3097 (3) Å

• V = 1364.44 (10) ų

• 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[F ² > 2σ(F ²)] = 0.064

• wR(F ²) = 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

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.

Supplementary Material

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

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) ; (ii) .

supplementary crystallographic information

Comment

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)

Experimental

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%.

Refinement

H atoms were placed in idealized positions, with C—H distances of 0.97 Å, N—H distances of 0.90 Å, and allowed to ride on their respective parent C atoms with the constraint U_iso(H) = 1.2U_eq(C).

Figures

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.

Crystal data

[Zn(NCS)3(C4H11N2)]	F000 = 664
Mr = 326.72	Dx = 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 = 3.0–25.0º
b = 11.0467 (4) Å	µ = 2.24 mm−1
c = 7.3097 (3) Å	T = 293 (2) K
V = 1364.44 (10) Å3	Prism, colorless
Z = 4	0.40 × 0.20 × 0.15 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer	1237 independent reflections
Radiation source: fine-focus sealed tube	901 reflections with I > 2σ(I)
Monochromator: graphite	Rint = 0.055
T = 293(2) K	θmax = 25.0º
ω scans	θmin = 3.0º
Absorption correction: empirical (using intensity measurements)(SADABS; Sheldrick, 1996)	h = −19→13
Tmin = 0.830, Tmax = 1.000	k = −13→8
3079 measured reflections	l = −8→7

Refinement

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.064	H-atom parameters constrained
wR(F2) = 0.154	w = 1/[σ2(Fo2) + (0.0605P)2] where P = (Fo2 + 2Fc2)/3
S = 1.03	(Δ/σ)max < 0.001
1237 reflections	Δρmax = 0.62 e Å−3
82 parameters	Δρmin = −0.48 e Å−3
Primary atom site location: structure-invariant direct methods	Extinction correction: none

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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, °)

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 codes: (i) x, −y+1/2, z.

Hydrogen-bond geometry (Å, °)

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.