{N,N'-Bis[1-(2-pyrid-yl)ethyl-idene]ethane-1,2-diamine-κN,N',N'',N'''}(thio-cyanato-κN)zinc(II) perchlorate.

In the title compound, [Zn(NCS)(C(16)H(18)N(4))]ClO(4), the Zn(II) atom is five-coordinated by four N atoms of the Schiff base ligand N,N'-bis-[1-(2-pyrid-yl)ethyl-idene]ethane-1,2-diamine in the basal plane, and by the N atom of a thio-cyanate ligand at the apical position, forming a distorted square-pyramidal geometry. The r.m.s. deviation from a plane through the four N atoms of the Schiff base is 0.015 (3) Å, and the deviation of the Ni atom from that plane is 0.591 (2) Å. Bond lengths are comparable with those observed in similar zinc(II) complexes with Schiff bases. The two methyl-ene C atoms of the ethane-1,2-diamine bridge of the Schiff base ligand are disordered over two sites with occupancies of 0.587 (3) and 0.413 (3).

Related literature

For background to Schiff base compounds and their applications, see: Ruck & Jacobsen (2002 ▶); Mukhopadhyay et al. (2003 ▶); Polt et al. (2003 ▶); Mukherjee et al. (2001 ▶). For complexes derived from N,N′-bis­(1-(pyridin-2-yl)ethyl­idene)ethane-1,2-diamine, see: Gourbatsis et al. (1998 ▶); Louloudi et al. (1999 ▶); Karmakar et al. (2002 ▶); Banerjee et al. (2004 ▶). For bond lengths in similar zinc(II) complexes with Schiff bases, see: Ghosh et al. (2006 ▶); Chen et al. (2005 ▶). For the synthesis of the Schiff base ligand, see: Gourbatsis et al. (1990 ▶).

Experimental

Crystal data

[Zn(NCS)(C16H18N4)]ClO4

M = 489.24

Monoclinic,

a = 8.685 (2) Å

b = 13.963 (3) Å

c = 17.374 (2) Å

β = 99.690 (3)°

V = 2076.9 (7) Å3

Z = 4

Mo Kα radiation

μ = 1.45 mm−1

T = 298 K

0.32 × 0.30 × 0.30 mm

Data collection

Bruker SMART CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.655, T max = 0.671

16681 measured reflections

4529 independent reflections

2534 reflections with I > 2σ(I)

R int = 0.056

Refinement

R[F 2 > 2σ(F 2)] = 0.056

wR(F 2) = 0.170

S = 1.02

4529 reflections

282 parameters

48 restraints

H-atom parameters constrained

Δρmax = 0.50 e Å−3

Δρmin = −0.66 e Å−3

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.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810021628/sj5017sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810021628/sj5017Isup2.hkl

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

[Zn(NCS)(C16H18N4)]ClO4	F(000) = 1000
Mr = 489.24	Dx = 1.565 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2719 reflections
a = 8.685 (2) Å	θ = 2.4–25.0°
b = 13.963 (3) Å	µ = 1.45 mm−1
c = 17.374 (2) Å	T = 298 K
β = 99.690 (3)°	Block, colourless
V = 2076.9 (7) Å3	0.32 × 0.30 × 0.30 mm
Z = 4

Bruker SMART CCD area-detector diffractometer	4529 independent reflections
Radiation source: fine-focus sealed tube	2534 reflections with I > 2σ(I)
graphite	Rint = 0.056
ω scan	θmax = 27.0°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −11→10
Tmin = 0.655, Tmax = 0.671	k = −17→16
16681 measured reflections	l = −22→22

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)] = 0.056	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.170	H-atom parameters constrained
S = 1.02	w = 1/[σ2(Fo2) + (0.0792P)2 + 0.7526P] where P = (Fo2 + 2Fc2)/3
4529 reflections	(Δ/σ)max < 0.001
282 parameters	Δρmax = 0.50 e Å−3
48 restraints	Δρmin = −0.66 e Å−3

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	Occ. (<1)
Zn1	0.40268 (7)	0.18336 (3)	0.23821 (3)	0.0532 (2)
Cl1	0.13446 (17)	0.32198 (10)	0.93392 (9)	0.0761 (4)
S1	0.80304 (19)	0.18105 (12)	0.08648 (10)	0.0888 (5)
O1	0.1863 (9)	0.2376 (4)	0.9693 (3)	0.170 (3)
O2	0.2281 (6)	0.3965 (4)	0.9651 (3)	0.145 (2)
O3	0.1346 (6)	0.3155 (3)	0.8524 (2)	0.0975 (14)
O4	−0.0172 (5)	0.3397 (4)	0.9480 (3)	0.1246 (19)
N1	0.2700 (4)	0.3093 (2)	0.2175 (2)	0.0516 (9)
N4	0.2661 (4)	0.0604 (3)	0.2040 (2)	0.0547 (10)
N5	0.5483 (6)	0.1840 (3)	0.1618 (3)	0.0725 (13)
C1	0.1666 (6)	0.3311 (4)	0.1535 (3)	0.0640 (13)
H1	0.1435	0.2853	0.1144	0.077*
C2	0.0928 (6)	0.4194 (4)	0.1434 (3)	0.0724 (15)
H2	0.0234	0.4328	0.0978	0.087*
C3	0.1231 (7)	0.4857 (4)	0.2009 (4)	0.0762 (16)
H3	0.0728	0.5447	0.1959	0.091*
C4	0.2296 (6)	0.4645 (3)	0.2672 (3)	0.0673 (14)
H4	0.2531	0.5097	0.3067	0.081*
C5	0.3015 (6)	0.3754 (3)	0.2744 (3)	0.0524 (11)
C6	0.4210 (6)	0.3474 (3)	0.3435 (3)	0.0608 (13)
C7	0.4484 (8)	0.4109 (4)	0.4138 (3)	0.0881 (19)
H7A	0.3514	0.4216	0.4320	0.132*
H7B	0.4902	0.4710	0.4003	0.132*
H7C	0.5212	0.3808	0.4543	0.132*
N2	0.4901 (5)	0.2687 (3)	0.3355 (3)	0.0713 (12)	0.59 (3)
N3	0.4830 (4)	0.0850 (3)	0.3273 (2)	0.0537 (10)	0.59 (3)
C8	0.573 (2)	0.2217 (8)	0.4079 (7)	0.076 (4)	0.59 (3)
H8A	0.5077	0.2231	0.4481	0.092*	0.59 (3)
H8B	0.6691	0.2557	0.4272	0.092*	0.59 (3)
C9	0.6085 (18)	0.1192 (11)	0.3889 (10)	0.073 (6)	0.59 (3)
H9A	0.7083	0.1159	0.3709	0.088*	0.59 (3)
H9B	0.6141	0.0795	0.4351	0.088*	0.59 (3)
N2'	0.4901 (5)	0.2687 (3)	0.3355 (3)	0.0713 (12)	0.41 (3)
N3'	0.4830 (4)	0.0850 (3)	0.3273 (2)	0.0537 (10)	0.41 (3)
C8'	0.6313 (16)	0.2226 (10)	0.3782 (13)	0.058 (5)	0.41 (3)
H8'A	0.6739	0.2587	0.4247	0.070*	0.41 (3)
H8'B	0.7109	0.2158	0.3456	0.070*	0.41 (3)
C9'	0.571 (3)	0.1262 (15)	0.3990 (8)	0.058 (6)	0.41 (3)
H9'A	0.6570	0.0846	0.4201	0.070*	0.41 (3)
H9'B	0.5035	0.1335	0.4379	0.070*	0.41 (3)
C10	0.4124 (6)	0.0058 (3)	0.3271 (3)	0.0531 (12)
C11	0.4348 (8)	−0.0665 (4)	0.3924 (3)	0.0878 (19)
H11A	0.5251	−0.0497	0.4299	0.132*
H11B	0.4493	−0.1290	0.3716	0.132*
H11C	0.3442	−0.0670	0.4174	0.132*
C12	0.2956 (5)	−0.0134 (3)	0.2555 (3)	0.0518 (11)
C13	0.2222 (6)	−0.1010 (4)	0.2399 (3)	0.0714 (15)
H13	0.2424	−0.1509	0.2756	0.086*
C14	0.1198 (7)	−0.1136 (4)	0.1718 (4)	0.089 (2)
H14	0.0677	−0.1716	0.1614	0.107*
C15	0.0947 (7)	−0.0406 (5)	0.1193 (4)	0.093 (2)
H15	0.0289	−0.0491	0.0717	0.112*
C16	0.1684 (6)	0.0465 (4)	0.1376 (3)	0.0775 (16)
H16	0.1487	0.0968	0.1022	0.093*
C17	0.6548 (7)	0.1821 (3)	0.1302 (3)	0.0544 (12)

	U11	U22	U33	U12	U13	U23
Zn1	0.0591 (4)	0.0415 (3)	0.0582 (4)	−0.0002 (3)	0.0079 (3)	0.0004 (2)
Cl1	0.0691 (9)	0.0799 (10)	0.0767 (9)	−0.0045 (8)	0.0053 (7)	−0.0098 (8)
S1	0.0678 (10)	0.1090 (13)	0.0936 (12)	0.0072 (9)	0.0252 (9)	0.0140 (9)
O1	0.247 (6)	0.129 (4)	0.128 (4)	0.090 (4)	0.019 (4)	0.038 (4)
O2	0.128 (4)	0.170 (5)	0.139 (4)	−0.084 (4)	0.031 (3)	−0.071 (4)
O3	0.117 (3)	0.115 (3)	0.063 (2)	−0.004 (3)	0.023 (2)	−0.015 (2)
O4	0.054 (3)	0.207 (6)	0.119 (4)	0.000 (3)	0.031 (3)	−0.013 (3)
N1	0.058 (2)	0.045 (2)	0.052 (2)	0.0013 (18)	0.0111 (18)	0.0031 (17)
N4	0.050 (2)	0.050 (2)	0.062 (2)	0.0005 (18)	0.0044 (19)	−0.0043 (19)
N5	0.088 (3)	0.055 (3)	0.080 (3)	0.003 (2)	0.032 (3)	0.009 (2)
C1	0.072 (3)	0.062 (3)	0.057 (3)	0.003 (3)	0.009 (3)	0.001 (2)
C2	0.077 (4)	0.062 (3)	0.077 (4)	0.018 (3)	0.008 (3)	0.017 (3)
C3	0.085 (4)	0.058 (3)	0.088 (4)	0.022 (3)	0.017 (3)	0.013 (3)
C4	0.076 (4)	0.043 (3)	0.086 (4)	0.001 (3)	0.024 (3)	−0.005 (3)
C5	0.057 (3)	0.045 (3)	0.058 (3)	−0.009 (2)	0.018 (2)	0.001 (2)
C6	0.068 (3)	0.043 (3)	0.069 (3)	−0.012 (2)	0.002 (3)	−0.001 (2)
C7	0.115 (5)	0.061 (3)	0.079 (4)	−0.008 (3)	−0.009 (3)	−0.017 (3)
N2	0.064 (3)	0.053 (3)	0.088 (3)	−0.001 (2)	−0.015 (2)	−0.004 (2)
N3	0.055 (2)	0.049 (2)	0.055 (2)	−0.0005 (19)	0.0049 (18)	−0.0021 (18)
C8	0.073 (8)	0.071 (6)	0.080 (7)	−0.002 (5)	−0.002 (6)	−0.008 (5)
C9	0.080 (9)	0.063 (8)	0.071 (8)	0.004 (6)	−0.003 (6)	−0.007 (5)
N2'	0.064 (3)	0.053 (3)	0.088 (3)	−0.001 (2)	−0.015 (2)	−0.004 (2)
N3'	0.055 (2)	0.049 (2)	0.055 (2)	−0.0005 (19)	0.0049 (18)	−0.0021 (18)
C8'	0.044 (7)	0.058 (7)	0.069 (8)	−0.001 (6)	0.001 (6)	−0.010 (6)
C9'	0.068 (9)	0.051 (9)	0.051 (8)	0.005 (7)	−0.003 (7)	0.004 (6)
C10	0.065 (3)	0.039 (2)	0.057 (3)	0.008 (2)	0.017 (2)	0.000 (2)
C11	0.129 (6)	0.055 (3)	0.076 (4)	−0.006 (3)	0.008 (4)	0.009 (3)
C12	0.048 (3)	0.043 (3)	0.068 (3)	0.004 (2)	0.020 (2)	−0.007 (2)
C13	0.065 (4)	0.050 (3)	0.098 (4)	−0.007 (3)	0.013 (3)	−0.006 (3)
C14	0.076 (4)	0.058 (4)	0.129 (6)	−0.015 (3)	0.001 (4)	−0.021 (4)
C15	0.077 (4)	0.085 (5)	0.104 (5)	−0.011 (4)	−0.023 (4)	−0.023 (4)
C16	0.071 (4)	0.069 (4)	0.084 (4)	0.001 (3)	−0.011 (3)	−0.004 (3)
C17	0.065 (3)	0.038 (2)	0.058 (3)	0.001 (2)	0.002 (3)	0.007 (2)

Zn1—N5	1.982 (5)	C7—H7C	0.9600
Zn1—N3	2.099 (4)	N2—C8	1.492 (8)
Zn1—N1	2.100 (4)	N3—C10	1.264 (5)
Zn1—N2	2.102 (4)	N3—C9	1.472 (8)
Zn1—N4	2.115 (4)	C8—C9	1.513 (10)
Cl1—O1	1.370 (5)	C8—H8A	0.9700
Cl1—O2	1.374 (4)	C8—H8B	0.9700
Cl1—O4	1.401 (4)	C9—H9A	0.9700
Cl1—O3	1.419 (4)	C9—H9B	0.9700
S1—C17	1.601 (6)	C8'—C9'	1.512 (10)
N1—C1	1.340 (6)	C8'—H8'A	0.9700
N1—C5	1.347 (5)	C8'—H8'B	0.9700
N4—C16	1.327 (6)	C9'—H9'A	0.9700
N4—C12	1.359 (6)	C9'—H9'B	0.9700
N5—C17	1.153 (7)	C10—C12	1.492 (6)
C1—C2	1.387 (7)	C10—C11	1.508 (7)
C1—H1	0.9300	C11—H11A	0.9600
C2—C3	1.355 (7)	C11—H11B	0.9600
C2—H2	0.9300	C11—H11C	0.9600
C3—C4	1.382 (7)	C12—C13	1.385 (6)
C3—H3	0.9300	C13—C14	1.368 (8)
C4—C5	1.388 (6)	C13—H13	0.9300
C4—H4	0.9300	C14—C15	1.360 (8)
C5—C6	1.501 (7)	C14—H14	0.9300
C6—N2	1.271 (6)	C15—C16	1.387 (7)
C6—C7	1.495 (7)	C15—H15	0.9300
C7—H7A	0.9600	C16—H16	0.9300
C7—H7B	0.9600
N5—Zn1—N3	109.08 (17)	C6—N2—Zn1	117.7 (3)
N5—Zn1—N1	105.95 (16)	C8—N2—Zn1	119.2 (5)
N3—Zn1—N1	141.17 (14)	C10—N3—C9	125.9 (9)
N5—Zn1—N2	110.56 (19)	C10—N3—Zn1	118.0 (3)
N3—Zn1—N2	75.37 (15)	C9—N3—Zn1	115.9 (8)
N1—Zn1—N2	77.12 (15)	N2—C8—C9	108.5 (11)
N5—Zn1—N4	101.91 (17)	N2—C8—H8A	110.0
N3—Zn1—N4	77.11 (14)	C9—C8—H8A	110.0
N1—Zn1—N4	111.48 (15)	N2—C8—H8B	110.0
N2—Zn1—N4	142.71 (17)	C9—C8—H8B	110.0
O1—Cl1—O2	110.3 (5)	H8A—C8—H8B	108.4
O1—Cl1—O4	108.8 (4)	N3—C9—C8	108.2 (9)
O2—Cl1—O4	108.0 (3)	N3—C9—H9A	110.1
O1—Cl1—O3	109.7 (3)	C8—C9—H9A	110.1
O2—Cl1—O3	110.0 (3)	N3—C9—H9B	110.1
O4—Cl1—O3	110.1 (3)	C8—C9—H9B	110.1
C1—N1—C5	118.6 (4)	H9A—C9—H9B	108.4
C1—N1—Zn1	127.1 (3)	C9'—C8'—H8'A	111.3
C5—N1—Zn1	114.2 (3)	C9'—C8'—H8'B	111.3
C16—N4—C12	118.9 (4)	H8'A—C8'—H8'B	109.2
C16—N4—Zn1	127.5 (4)	C8'—C9'—H9'A	110.2
C12—N4—Zn1	113.3 (3)	C8'—C9'—H9'B	110.2
C17—N5—Zn1	166.6 (5)	H9'A—C9'—H9'B	108.5
N1—C1—C2	122.5 (5)	N3—C10—C12	114.9 (4)
N1—C1—H1	118.7	N3—C10—C11	125.6 (5)
C2—C1—H1	118.7	C12—C10—C11	119.4 (4)
C3—C2—C1	119.1 (5)	C10—C11—H11A	109.5
C3—C2—H2	120.5	C10—C11—H11B	109.5
C1—C2—H2	120.5	H11A—C11—H11B	109.5
C2—C3—C4	119.2 (5)	C10—C11—H11C	109.5
C2—C3—H3	120.4	H11A—C11—H11C	109.5
C4—C3—H3	120.4	H11B—C11—H11C	109.5
C3—C4—C5	119.7 (5)	N4—C12—C13	120.8 (4)
C3—C4—H4	120.1	N4—C12—C10	116.0 (4)
C5—C4—H4	120.1	C13—C12—C10	123.2 (4)
N1—C5—C4	121.0 (5)	C14—C13—C12	119.6 (5)
N1—C5—C6	115.9 (4)	C14—C13—H13	120.2
C4—C5—C6	123.1 (5)	C12—C13—H13	120.2
N2—C6—C7	126.1 (5)	C15—C14—C13	119.4 (5)
N2—C6—C5	114.4 (4)	C15—C14—H14	120.3
C7—C6—C5	119.5 (5)	C13—C14—H14	120.3
C6—C7—H7A	109.5	C14—C15—C16	119.2 (5)
C6—C7—H7B	109.5	C14—C15—H15	120.4
H7A—C7—H7B	109.5	C16—C15—H15	120.4
C6—C7—H7C	109.5	N4—C16—C15	122.0 (5)
H7A—C7—H7C	109.5	N4—C16—H16	119.0
H7B—C7—H7C	109.5	C15—C16—H16	119.0
C6—N2—C8	117.1 (7)	N5—C17—S1	179.2 (5)

Zn1—N5	1.982 (5)
Zn1—N3	2.099 (4)
Zn1—N1	2.100 (4)
Zn1—N2	2.102 (4)
Zn1—N4	2.115 (4)

N5—Zn1—N3	109.08 (17)
N5—Zn1—N1	105.95 (16)
N3—Zn1—N1	141.17 (14)
N5—Zn1—N2	110.56 (19)
N3—Zn1—N2	75.37 (15)
N1—Zn1—N2	77.12 (15)
N5—Zn1—N4	101.91 (17)
N3—Zn1—N4	77.11 (14)
N1—Zn1—N4	111.48 (15)
N2—Zn1—N4	142.71 (17)