{N,N′-Bis[1-(2-pyrid­yl)ethyl­idene]ethane-1,2-diamine-κ⁴N,N′,N′′,N′′′}(thio­cyanato-κN)zinc(II) perchlorate

In the title compound, [Zn(NCS)(C₁₆H₁₈N₄)]ClO₄, the Zn^II atom is five-coordinated by four N atoms of the Schiff base ligand N,N′-bis­[1-(2-pyrid­yl)ethyl­idene]ethane-1,2-diamine in the basal plane, and by the N atom of a thio­cyanate 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 methyl­ene 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).

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.008 Å
• Disorder in main residue
• R factor = 0.056
• wR factor = 0.170
• Data-to-parameter ratio = 16.1

checkCIF/PLATON results

No syntax errors found



Alert level C
SHFSU01_ALERT_2_C  Test not performed. _refine_ls_shift/su_max and
            _refine_ls_shift/esd_max not present.
            Absolute value of the parameter shift to su ratio given   0.001
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for         N5
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C17
PLAT341_ALERT_3_C Low Bond Precision on  C-C Bonds (x 1000) Ang ..          8
PLAT910_ALERT_3_C Missing # of FCF Reflections Below Th(Min) .....          1

Alert level G
PLAT301_ALERT_3_G Note: Main Residue  Disorder ...................      14.00 Perc.
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......         48
PLAT720_ALERT_4_G Number of Unusual/Non-Standard Labels ..........          4

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   5 ALERT level C = Check and explain
   3 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   3 ALERT type 2 Indicator that the structure model may be wrong or deficient
   4 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

---

S1. Comment

Metal complexes with Schiff bases have been known since 1840. The Schiff bases and their complexes have played an important role in the development of coordination chemistry, biological and material sciences (Ruck & Jacobsen, 2002; Mukhopadhyay et al., 2003; Polt et al., 2003; Mukherjee et al., 2001). Several complexes derived from N,N'-bis(1-(pyridin-2-yl)ethylidene)ethane-1,2-diamine have been reported (Gourbatsis et al., 1998; Louloudi et al., 1999; Karmakar et al., 2002; Banerjee et al., 2004). In this paper, the title new zinc(II) complex is reported.

The title compound consists of a mononuclear zinc(II) complex cation and a perchlorate anion, Fig. 1. The Zn^II atom is five-coordinated by four N atoms of the Schiff base ligand N,N'-bis(1-(pyridin-2-yl)ethylidene)ethane-1,2-diamine, and by one N atom of a thiocyanate ligand, forming a square pyramidal geometry. The coordinate bond lengths (Table 1) are comparable to those observed in other similar zinc(II) complexes with Schiff bases (Ghosh et al., 2006; Chen et al., 2005).

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).

S2. Experimental

The Schiff base ligand N,N'-bis(1-(pyridin-2-yl)ethylidene)ethane-1,2-diamine was synthesized according to the literature method (Gourbatsis et al., 1990). To a stirred methanol solution of the Schiff base ligand (1.0 mmol, 0.266 g) was added a methanol solution of zinc(II) perchlorate (1.0 mmol, 0.390 g) and ammonium thiocyanate (1.0 mmol, 0.076 g). The mixture was boiled under reflux for 2 h, then cooled to room temperature. Colourless block-like single crystals, suitable for X-ray diffraction, were formed after slow evaporation of the solution in air for a few days.

S3. Refinement

Hydrogen atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms, with C–H distances of 0.93–0.97 Å, and with U_iso(H) set at 1.2U_eq(C) and 1.5U_eq(C_methyl). The C8 and C9 atoms are disordered over two sites with occupancies of 0.587 (3) and 0.413 (3).

Computing details

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

Fig. 1. The asymmetric unit of the title compound, showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. Only the major component of the disordered group is shown.

{N,N'-Bis[1-(2-pyridyl)ethylidene]ethane-1,2-diamine- κ⁴N,N',N'',N'''}(thiocyanato- κN)zinc(II) perchlorate

Crystal data

[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) Å^3	0.32 × 0.30 × 0.30 mm
Z = 4

Data collection

Bruker SMART CCD area-detector diffractometer	4529 independent reflections
Radiation source: fine-focus sealed tube	2534 reflections with I > 2σ(I)
Graphite monochromator	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

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.056	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.170	H-atom parameters constrained
S = 1.02	w = 1/[σ^2(Fo^2) + (0.0792P)^2 + 0.7526P] where P = (Fo^2 + 2Fc^2)/3
4529 reflections	(Δ/σ)max < 0.001
282 parameters	Δρmax = 0.50 e Å^−3
48 restraints	Δρmin = −0.66 e Å^−3

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	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)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Geometric parameters (Å, º)

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)