(Piperazin-1-ium-κN)tris-(thio-cyanato-κN)zinc(II).

Hydro-thermal reaction of NaSCN, piperazine, Zn(II) and 2,6-naphthalenedicarboxylic acid in aqueous solutions gave rise to the title complex, [Zn(NCS)(3)(C(4)H(11)N(2))]. The Zn(II) atom is four-coordinate with distorted tetra-hedral geometry and lies in a mirror plane. N-H⋯S hydrogen bonds assemble the mol-ecules 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 = 326.72

Orthorhombic,

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[F 2 > 2σ(F 2)] = 0.064

wR(F 2) = 0.154

S = 1.03

1237 reflections

82 parameters

H-atom parameters constrained

Δρmax = 0.62 e Å−3

Δρmin = −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.

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

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807065087/dn2286Isup2.hkl

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

[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

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 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

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.

	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*

	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)

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

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

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) .