Dichlorido(di-2-pyridyl sulfide-κ²N,N′)zinc(II)

The crystal structure of the title compound, [ZnCl₂(C₁₀H₈N₂S)], consists of a six-membered chelate ring in which the Zn atom is approximately tetra­hedrally coordinated by two chloride ions and by the two pyridyl N atoms of a single di-2-pyridyl sulfide ligand. As usual for this type of complex, the sulfide group does not participate in zinc coordination. The dihedral angle between the two pyridine rings is 50.4 (1)°.

Key indicators

• Single-crystal X-ray study
• T = 170 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.036
• wR factor = 0.096
• Data-to-parameter ratio = 20.1

checkCIF/PLATON results

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Alert level C
CELLV02_ALERT_1_C  The supplied cell volume s.u. differs from that
            calculated from the cell parameter s.u.'s by > 2
            Calculated cell volume su =      21.41
            Cell volume su given      =      19.00
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low .......       0.96
PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given .......          ?

   0 ALERT level A = In general: serious problem
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S1. Comment

Recently, we are interested in the synthesis, structures and thermal properties of coordination polymers based on zinc(II) halides and N-donor ligands (Bhosekar et al., 2007). We have found for example that most of the ligand rich compounds can be transformed into ligand deficient compounds on heating. Starting from these findings we have initiated systematic investigations on this topic. In these investigations we have reacted zinc(II) chloride with 2,2'-bipyridyldisulfide. In this reaction, simultaneously a cleavage of the S—S bond takes place leading to the formation of di-2-pyridyl sulfide (dps). In further reaction with zinc(II) chloride the title compound (I) is formed. To identify this product in further reaction by X-ray powder diffraction, a structure determination was performed.

In general dps is a versatile ambidentate ligand that, due to its conformational flexibility, can act in N,N'-bidentate (Tresoldi et al., 1992; Kondo et al., 1995 and Nicolò et al., 1996) or bridging (Tresoldi et al., 1991 and Teles et al., 1999) coordination modes toward many metals, resulting in complexes with different stereochemistry. When dps is bonded to the metal as a chelate ligand, a six-membered ring in boat conformation is formed, differently from its rigid analogues 2,2'-bipyridine that generates a pentacyclic chelate in a planar arragement. In addition, in some cases dps can act as tridentate ligand in a N,N,S-coordination mode involving metal-sulfur interactions (Anderson & Steel, 1998).

In the crystal structure the coordination geometry about the Zn(II) ion is approximately tetrahedral with bonds being formed to two chloride ions and the two pyridyl nitrogen atoms of a single dps ligand (Fig. 1). These latter interactions result in the formation of a six-membered chelate ring, which is in a boat conformation. The angles at Zn(II) range from 93.85 to 115.66°, the largest being N—Zn—Cl. The Zn—Cl and Zn—N distances are in the range of 2.057 (2)–2.061 (2) and 2.2192 (8)–2.2261 (8) Å. The structural parameters in the dps molecule are quite regular. In particular the C—S bonds, 1.782 (3) and 1.780 (3) Å, are in good agreement with those expected for C(sp²)-S bonds (1.77 Å).

Related literature

For related literature, see: Anderson & Steel (1998); Bhosekar et al. (2007); Kondo et al. (1995); Nicolò et al. (1996); Teles et al. (1999); Tresoldi et al. (1991, 1992).

S2. Experimental

ZnCl₂ and 2,2'-bipyridyldisulfide was obtained from Alfa Aesar and methanol was obtained from Fluka. 0.0313 mmol (4.3 mg) zinc(II) chloride, 0.125 mmol (27.5 mg) 2,2'-bipyridyldisulfide and 3 ml of methanol were transfered in test-tube, which were closed and heated to 110 °C for three days. On cooling colourless block-shaped single crystals of (I) are obtained.

S3. Refinement

All H atoms were located in difference map but were positioned with idealized geometry and were refined isotropic with U_eq(H) = 1.2U_eq(C) of the parent atom using a riding model with C—H = 0.97 Å.

Computing details

Data collection: IPDS Program Package (Stoe & Cie, 1998); cell refinement: IPDS Program Package (Stoe & Cie, 1998); data reduction: IPDS Program Package (Stoe & Cie, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997; program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP in SHELXTL (Bruker, 1998); software used to prepare material for publication: CIFTAB in SHELXTL (Bruker, 1998).

Figures

Fig. 1. : Crystal structure of compound I with labelling and displacement ellipsoids drawn at the 50% probability level.

Dichlorido(di-2-pyridyl sulfide-κ²N,N')zinc(II)

Crystal data

[ZnCl2(C10H8N2S)]	F(000) = 648
Mr = 324.51	Dx = 1.732 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 12.1944 (12) Å	Cell parameters from 7174 reflections
b = 7.6404 (4) Å	θ = 3–28.1°
c = 14.2572 (15) Å	µ = 2.54 mm^−1
β = 110.426 (12)°	T = 170 K
V = 1244.82 (19) Å^3	Block, colourless
Z = 4	0.14 × 0.10 × 0.07 mm

Data collection

Stoe IPDSI diffractometer	2939 independent reflections
Radiation source: fine-focus sealed tube	2297 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.036
Phi scans	θmax = 28.1°, θmin = 3.0°
Absorption correction: numerical (X-SHAPE; Stoe & Cie, 1998)	h = −16→15
Tmin = 0.751, Tmax = 0.852	k = −8→10
7272 measured reflections	l = −15→18

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.036	H-atom parameters constrained
wR(F^2) = 0.096	w = 1/[σ^2(Fo^2) + (0.0636P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.00	(Δ/σ)max < 0.001
2939 reflections	Δρmax = 0.47 e Å^−3
146 parameters	Δρmin = −0.60 e Å^−3
0 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0121 (14)

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	0.75122 (3)	0.38978 (4)	0.21941 (2)	0.02084 (13)
Cl1	0.85027 (6)	0.14097 (10)	0.23692 (6)	0.02808 (18)
Cl2	0.71512 (7)	0.54386 (11)	0.07932 (6)	0.03121 (19)
N11	0.59754 (19)	0.3765 (3)	0.24881 (19)	0.0218 (5)
C11	0.5996 (2)	0.3642 (4)	0.3433 (2)	0.0225 (6)
C12	0.4973 (3)	0.3575 (4)	0.3656 (3)	0.0304 (7)
H12	0.5007	0.3458	0.4329	0.036*
C13	0.3906 (3)	0.3682 (4)	0.2884 (3)	0.0346 (8)
H13	0.3198	0.3626	0.3021	0.042*
C14	0.3878 (3)	0.3870 (4)	0.1910 (3)	0.0329 (7)
H14	0.3154	0.3970	0.1371	0.039*
C15	0.4925 (2)	0.3910 (4)	0.1739 (2)	0.0272 (6)
H15	0.4909	0.4044	0.1072	0.033*
N1	0.83245 (18)	0.5499 (3)	0.33969 (18)	0.0202 (5)
C1	0.8192 (2)	0.5231 (4)	0.4286 (2)	0.0214 (5)
C2	0.8775 (2)	0.6216 (4)	0.5128 (2)	0.0250 (6)
H2	0.8654	0.6015	0.5742	0.030*
C3	0.9546 (2)	0.7517 (4)	0.5049 (2)	0.0289 (7)
H3	0.9974	0.8194	0.5618	0.035*
C4	0.9679 (2)	0.7808 (4)	0.4139 (3)	0.0292 (6)
H4	1.0199	0.8684	0.4071	0.035*
C5	0.9039 (2)	0.6795 (4)	0.3328 (2)	0.0229 (6)
H5	0.9107	0.7025	0.2696	0.027*
S1	0.73529 (6)	0.34212 (11)	0.44428 (6)	0.02965 (19)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.02206 (18)	0.0255 (2)	0.01652 (18)	−0.00095 (12)	0.00868 (12)	−0.00111 (13)
Cl1	0.0294 (3)	0.0284 (4)	0.0268 (4)	0.0042 (3)	0.0101 (3)	−0.0009 (3)
Cl2	0.0438 (4)	0.0333 (4)	0.0195 (4)	0.0018 (3)	0.0148 (3)	0.0042 (3)
N11	0.0207 (10)	0.0244 (12)	0.0216 (12)	−0.0007 (9)	0.0090 (9)	0.0001 (10)
C11	0.0245 (12)	0.0212 (14)	0.0248 (14)	−0.0028 (10)	0.0123 (11)	0.0008 (11)
C12	0.0327 (15)	0.0324 (17)	0.0335 (17)	−0.0010 (12)	0.0210 (13)	0.0041 (14)
C13	0.0250 (14)	0.0336 (18)	0.050 (2)	−0.0013 (12)	0.0196 (14)	0.0035 (15)
C14	0.0227 (13)	0.0330 (17)	0.0390 (19)	−0.0019 (12)	0.0056 (13)	0.0073 (15)
C15	0.0246 (13)	0.0304 (16)	0.0240 (15)	−0.0021 (11)	0.0053 (11)	0.0035 (13)
N1	0.0213 (10)	0.0208 (12)	0.0186 (11)	0.0014 (9)	0.0072 (9)	0.0003 (9)
C1	0.0229 (12)	0.0239 (14)	0.0176 (13)	0.0042 (10)	0.0075 (10)	0.0009 (11)
C2	0.0286 (13)	0.0290 (16)	0.0161 (13)	0.0099 (11)	0.0060 (11)	−0.0001 (12)
C3	0.0328 (15)	0.0212 (15)	0.0255 (15)	0.0056 (11)	0.0011 (12)	−0.0086 (12)
C4	0.0284 (14)	0.0204 (14)	0.0350 (17)	−0.0009 (11)	0.0064 (12)	−0.0025 (13)
C5	0.0237 (13)	0.0219 (14)	0.0230 (14)	0.0012 (10)	0.0081 (11)	0.0033 (12)
S1	0.0296 (4)	0.0375 (4)	0.0206 (4)	−0.0047 (3)	0.0073 (3)	0.0094 (3)

Geometric parameters (Å, º)

Zn1—N1	2.057 (2)	C14—H14	0.9500
Zn1—N11	2.061 (2)	C15—H15	0.9500
Zn1—Cl1	2.2192 (8)	N1—C5	1.345 (4)
Zn1—Cl2	2.2261 (8)	N1—C1	1.349 (4)
N11—C11	1.342 (4)	C1—C2	1.384 (4)
N11—C15	1.355 (4)	C1—S1	1.780 (3)
C11—C12	1.392 (4)	C2—C3	1.399 (4)
C11—S1	1.782 (3)	C2—H2	0.9500
C12—C13	1.382 (5)	C3—C4	1.381 (5)
C12—H12	0.9500	C3—H3	0.9500
C13—C14	1.384 (5)	C4—C5	1.384 (4)
C13—H13	0.9500	C4—H4	0.9500
C14—C15	1.382 (4)	C5—H5	0.9500
N1—Zn1—N11	93.85 (9)	N11—C15—H15	118.8
N1—Zn1—Cl1	109.32 (7)	C14—C15—H15	118.8
N11—Zn1—Cl1	115.66 (7)	C5—N1—C1	118.3 (3)
N1—Zn1—Cl2	108.68 (7)	C5—N1—Zn1	120.83 (19)
N11—Zn1—Cl2	107.42 (7)	C1—N1—Zn1	120.83 (19)
Cl1—Zn1—Cl2	118.90 (3)	N1—C1—C2	122.6 (3)
C11—N11—C15	118.5 (2)	N1—C1—S1	119.9 (2)
C11—N11—Zn1	120.53 (18)	C2—C1—S1	117.2 (2)
C15—N11—Zn1	120.8 (2)	C1—C2—C3	118.2 (3)
N11—C11—C12	121.8 (3)	C1—C2—H2	120.9
N11—C11—S1	120.3 (2)	C3—C2—H2	120.9
C12—C11—S1	117.7 (2)	C4—C3—C2	119.5 (3)
C13—C12—C11	119.1 (3)	C4—C3—H3	120.2
C13—C12—H12	120.5	C2—C3—H3	120.2
C11—C12—H12	120.5	C3—C4—C5	118.5 (3)
C12—C13—C14	119.5 (3)	C3—C4—H4	120.7
C12—C13—H13	120.3	C5—C4—H4	120.7
C14—C13—H13	120.3	N1—C5—C4	122.8 (3)
C15—C14—C13	118.5 (3)	N1—C5—H5	118.6
C15—C14—H14	120.7	C4—C5—H5	118.6
C13—C14—H14	120.7	C1—S1—C11	103.75 (13)
N11—C15—C14	122.5 (3)