Crystal structure of bis­[4-(4-chloro­benz­yl)pyridine-κN]bis­(thio­cyanato-κN)zinc

In the crystal structure of the title compound, [Zn(NCS)₂(C₁₂H₁₀ClN)₂], the Zn²⁺ cation is N-coordinated by two terminally bonded thio­cyante anions and by two 4-(4-chloro­benz­yl)pyridine ligands within a slightly distorted tetra­hedron. The asymmetric unit consists of half of the discrete complex, the central Zn²⁺ cation of which is located on a twofold rotation axis. The discrete complexes are linked into layers via a weak inter­molecular hydrogen-bonding inter­action, with a H...Cl distance of 2.85 Å and a C—H...Cl angle of 151°. These layers extend parallel to the ab plane and are held together by dispersion forces only.

Key indicators

• Single-crystal X-ray study
• T = 150 K
• Mean [sigma](C-C) = 0.008 Å
• R factor = 0.063
• wR factor = 0.148
• Data-to-parameter ratio = 16.2

checkCIF/PLATON results

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Alert level C
PLAT230_ALERT_2_C Hirshfeld Test Diff for    C20    --  C21     ..        5.5 su
PLAT242_ALERT_2_C Low       Ueq as Compared to Neighbors for .....        C20 Check
PLAT334_ALERT_2_C Small Average Benzene  C-C Dist. C17    -C22           1.37 Ang.
PLAT341_ALERT_3_C Low Bond Precision on  C-C Bonds ...............     0.0080 Ang.
PLAT906_ALERT_3_C Large K value in the Analysis of Variance ......     10.541 Check
PLAT906_ALERT_3_C Large K value in the Analysis of Variance ......      2.501 Check
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600          8 Report
PLAT913_ALERT_3_C Missing # of Very Strong Reflections in FCF ....          1 Note

Alert level G
PLAT005_ALERT_5_G No _iucr_refine_instructions_details  in the CIF     Please Do !
PLAT899_ALERT_4_G SHELXL97   is Deprecated and Succeeded by SHELXL       2014 Note

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   8 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   2 ALERT level G = General information/check it is not something unexpected

   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
   5 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

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S1. Synthesis and crystallization

ZnSO₄·H₂O was purchased from Merck and 4-(4-chloro­benzyl)­pyridine and Ba(NCS)₂·3H₂O were purchased from Alfa Aesar. Zn(NCS)₂ was synthesized by stirring 17.5 g (57.00 mmol) Ba(NCS)₂·3H₂O and 10.23 g (57.00 mmol) ZnSO₄·H₂O in 300 mL water at RT for three hours. The white residue of BaSO₄ was filtered off, and the solution was evaporated by heating. The homogeneity of the product was investigated by X-ray powder diffraction and elemental analysis. The title compound was prepared by the reaction of (0.6 mmol) 108.9 mg Zn(NCS)₂ and (0.15 mmol) 105.5 µL 4-(4-chloro­benzyl)­pyridine in 1.5 mL aceto­nitrile at RT. After few days, colorless needle-like crystals of the title compound were obtained.

S2. Refinement

Hydrogen atoms were positioned with idealized geometry and were refined with U_iso(H) = 1.2 U_eq(C) using a riding model with C—H = 0.95 Å for aromatic and C—H = 0.99 Å for methyl­ene H atoms.

Related literature

For related crystal structures with thiocyanate ligands and Zn²⁺ in a tetrahedral coordination sphere, see: Fettouhi et al. (2002); Kong et al. (2010); Zhu et al. (2008).

Computing details

Data collection: X-AREA (Stoe, 2008); cell refinement: X-AREA (Stoe, 2008); data reduction: X-AREA (Stoe, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 2011); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures

	Fig. 1. Molecular structure of the title compound with atom labelling and displacement ellipsoids drawn at the 50% probability level. [Symmetry code: i) -x, y, -z+1/2.]
	Fig. 2. Crystal structure of the title compound in a projection along the b axis.

Bis[4-(4-chlorobenzyl)pyridine-κN]bis(thiocyanato-κN)zinc

Crystal data

[Zn(NCS)2(C12H10ClN)2]	Z = 4
Mr = 588.85	F(000) = 1200
Monoclinic, C2/c	Dx = 1.489 Mg m^−3
Hall symbol: -C 2yc	Mo Kα radiation, λ = 0.71073 Å
a = 29.094 (3) Å	θ = 1.4–26.0°
b = 4.9911 (3) Å	µ = 1.32 mm^−1
c = 18.312 (2) Å	T = 150 K
β = 98.867 (8)°	Needle, colourless
V = 2627.3 (4) Å^3	0.12 × 0.08 × 0.07 mm

Data collection

Stoe IPDS-2 diffractometer	2570 independent reflections
Radiation source: fine-focus sealed tube	1773 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.077
ω scans	θmax = 26.0°, θmin = 1.4°
Absorption correction: numerical (X-SHAPE and X-RED32; Stoe, 2008)	h = −35→35
Tmin = 0.879, Tmax = 0.906	k = −6→6
8309 measured reflections	l = −22→21

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)] = 0.063	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.148	H-atom parameters constrained
S = 1.08	w = 1/[σ^2(Fo^2) + (0.0577P)^2 + 3.849P] where P = (Fo^2 + 2Fc^2)/3
2570 reflections	(Δ/σ)max < 0.001
159 parameters	Δρmax = 0.68 e Å^−3
0 restraints	Δρmin = −0.46 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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	0.0000	−0.30960 (18)	0.2500	0.0536 (3)
N1	0.03121 (14)	−0.4936 (9)	0.3362 (3)	0.0632 (11)
C1	0.04787 (16)	−0.6043 (11)	0.3893 (3)	0.0564 (12)
S1	0.07036 (5)	−0.7701 (3)	0.46152 (9)	0.0767 (5)
N11	0.04855 (12)	−0.0763 (8)	0.2133 (2)	0.0482 (9)
C11	0.04345 (16)	0.0091 (10)	0.1431 (3)	0.0547 (12)
H11	0.0185	−0.0612	0.1088	0.066*
C12	0.07260 (16)	0.1938 (10)	0.1181 (3)	0.0552 (11)
H12	0.0671	0.2525	0.0682	0.066*
C13	0.11000 (16)	0.2929 (10)	0.1667 (3)	0.0551 (12)
C14	0.11577 (16)	0.2014 (12)	0.2384 (3)	0.0591 (13)
H14	0.1411	0.2640	0.2731	0.071*
C15	0.08515 (16)	0.0205 (10)	0.2597 (3)	0.0561 (12)
H15	0.0899	−0.0395	0.3096	0.067*
C16	0.14365 (18)	0.4920 (11)	0.1412 (3)	0.0654 (14)
H16A	0.1505	0.6354	0.1786	0.078*
H16B	0.1289	0.5759	0.0944	0.078*
C17	0.18905 (16)	0.3592 (11)	0.1292 (3)	0.0600 (14)
C18	0.18905 (17)	0.1565 (13)	0.0792 (3)	0.0688 (15)
H18	0.1603	0.0952	0.0529	0.083*
C19	0.22994 (19)	0.0380 (15)	0.0660 (4)	0.0815 (18)
H19	0.2292	−0.1021	0.0307	0.098*
C20	0.27132 (18)	0.1235 (16)	0.1039 (4)	0.0776 (18)
C21	0.2727 (2)	0.3210 (18)	0.1536 (4)	0.093 (2)
H21	0.3017	0.3783	0.1800	0.112*
C22	0.2313 (2)	0.4443 (15)	0.1669 (4)	0.0854 (19)
H22	0.2324	0.5859	0.2018	0.103*
Cl1	0.32321 (5)	−0.0187 (5)	0.08551 (11)	0.1091 (8)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.0483 (4)	0.0500 (5)	0.0615 (5)	0.000	0.0050 (3)	0.000
N1	0.058 (2)	0.057 (3)	0.074 (3)	0.006 (2)	0.008 (2)	0.004 (2)
C1	0.051 (2)	0.055 (3)	0.061 (3)	−0.003 (2)	0.003 (2)	−0.007 (3)
S1	0.0709 (8)	0.0855 (12)	0.0657 (9)	−0.0042 (7)	−0.0148 (7)	0.0094 (8)
N11	0.0429 (18)	0.050 (2)	0.050 (2)	0.0061 (17)	0.0016 (16)	−0.0037 (19)
C11	0.048 (2)	0.053 (3)	0.059 (3)	0.001 (2)	−0.004 (2)	−0.002 (2)
C12	0.053 (2)	0.051 (3)	0.058 (3)	−0.001 (2)	−0.004 (2)	0.004 (3)
C13	0.051 (2)	0.041 (3)	0.071 (3)	0.005 (2)	0.001 (2)	−0.006 (3)
C14	0.052 (2)	0.063 (3)	0.059 (3)	−0.002 (2)	−0.004 (2)	−0.007 (3)
C15	0.055 (3)	0.058 (3)	0.053 (3)	0.001 (2)	0.004 (2)	−0.005 (2)
C16	0.064 (3)	0.048 (3)	0.081 (4)	−0.007 (2)	0.003 (3)	−0.002 (3)
C17	0.050 (3)	0.061 (4)	0.066 (3)	−0.011 (2)	−0.003 (2)	0.014 (3)
C18	0.049 (3)	0.076 (4)	0.078 (4)	−0.008 (3)	−0.001 (2)	0.001 (3)
C19	0.061 (3)	0.103 (5)	0.080 (4)	0.009 (3)	0.008 (3)	0.000 (4)
C20	0.050 (3)	0.110 (5)	0.069 (4)	0.004 (3)	−0.001 (3)	0.027 (4)
C21	0.051 (3)	0.132 (6)	0.089 (5)	−0.024 (4)	−0.012 (3)	0.034 (5)
C22	0.066 (3)	0.091 (5)	0.093 (5)	−0.017 (3)	−0.006 (3)	−0.003 (4)
Cl1	0.0565 (8)	0.168 (2)	0.1023 (13)	0.0255 (10)	0.0118 (8)	0.0551 (14)

Geometric parameters (Å, º)

Zn1—N1^i	1.928 (5)	C15—H15	0.9500
Zn1—N1	1.928 (5)	C16—C17	1.524 (7)
Zn1—N11	2.024 (4)	C16—H16A	0.9900
Zn1—N11^i	2.024 (4)	C16—H16B	0.9900
N1—C1	1.157 (6)	C17—C18	1.363 (8)
C1—S1	1.611 (6)	C17—C22	1.380 (7)
N11—C11	1.342 (6)	C18—C19	1.383 (8)
N11—C15	1.346 (6)	C18—H18	0.9500
C11—C12	1.377 (7)	C19—C20	1.363 (8)
C11—H11	0.9500	C19—H19	0.9500
C12—C13	1.386 (7)	C20—C21	1.338 (10)
C12—H12	0.9500	C20—Cl1	1.747 (6)
C13—C14	1.375 (7)	C21—C22	1.408 (10)
C13—C16	1.518 (7)	C21—H21	0.9500
C14—C15	1.367 (7)	C22—H22	0.9500
C14—H14	0.9500
N1^i—Zn1—N1	123.1 (3)	C14—C15—H15	118.6
N1^i—Zn1—N11	105.49 (17)	C13—C16—C17	112.0 (4)
N1—Zn1—N11	106.33 (16)	C13—C16—H16A	109.2
N1^i—Zn1—N11^i	106.32 (16)	C17—C16—H16A	109.2
N1—Zn1—N11^i	105.49 (17)	C13—C16—H16B	109.2
N11—Zn1—N11^i	109.7 (2)	C17—C16—H16B	109.2
C1—N1—Zn1	176.6 (4)	H16A—C16—H16B	107.9
N1—C1—S1	177.6 (5)	C18—C17—C22	118.2 (5)
C11—N11—C15	116.9 (4)	C18—C17—C16	120.6 (4)
C11—N11—Zn1	121.4 (3)	C22—C17—C16	121.2 (6)
C15—N11—Zn1	121.4 (3)	C17—C18—C19	121.6 (5)
N11—C11—C12	123.2 (4)	C17—C18—H18	119.2
N11—C11—H11	118.4	C19—C18—H18	119.2
C12—C11—H11	118.4	C20—C19—C18	119.5 (7)
C11—C12—C13	119.3 (5)	C20—C19—H19	120.2
C11—C12—H12	120.4	C18—C19—H19	120.2
C13—C12—H12	120.4	C21—C20—C19	120.6 (6)
C14—C13—C12	117.5 (5)	C21—C20—Cl1	119.6 (5)
C14—C13—C16	121.5 (5)	C19—C20—Cl1	119.7 (6)
C12—C13—C16	121.0 (5)	C20—C21—C22	120.2 (6)
C15—C14—C13	120.3 (5)	C20—C21—H21	119.9
C15—C14—H14	119.9	C22—C21—H21	119.9
C13—C14—H14	119.9	C17—C22—C21	119.9 (7)
N11—C15—C14	122.9 (5)	C17—C22—H22	120.1
N11—C15—H15	118.6	C21—C22—H22	120.1

Symmetry code: (i) −x, y, −z+1/2.