Di­chloro­bis(1,3-di­methyl­thio­urea-κS)­zinc(II)

Burrows, A.D.; Harrington, R.W.; Mahon, M.F.

doi:10.1107/S1600536804020550

metal-organic compounds

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ISSN: 2056-9890

Volume 60| Part 9| September 2004| Pages m1317-m1318

https://doi.org/10.1107/S1600536804020550

Dichlorobis(1,3-dimethylthiourea-κS)zinc(II)

Andrew D. Burrows,^a Ross W. Harrington ^a ^*‡ and Mary F. Mahon ^a

^aDepartment of Chemistry, University of Bath, Claverton Down, Bath BA1 7AY, England
^*Correspondence e-mail: r.w.harrington@ncl.ac.uk

(Received 15 July 2004; accepted 18 August 2004; online 28 August 2004)

Determination of the crystal structure of the title compound, [ZnCl₂(C₃H₆N₂S)₂], reveals a distorted tetrahedral geometry around the zinc centre which occupies a twofold axis. Both intra- and intermolecular hydrogen bonding is observed between the 1,3-dimethylthiourea NH groups and the coordinated Cl atoms.

Comment

The title compound, (I), was formed as part of our investigations into the formation of bis-thiourea zinc(II) dicarboxylate polymers (Burrows et al., 2000 , 2004 ; Burke et al., 2003 ).

The asymmetric unit of (I) (Fig. 1) consists of a zinc(II) centre occupying a twofold symmetry axis, to which is coordinated one 1,3-dimethylthiourea ligand, via the S atom, and one Cl⁻. The complete molecule is generated by transformation through a twofold rotation axis, inherent in the space group. The geometry around the Zn centre is distorted tetrahedral, with bond angles ranging from 104.35 (3) to 113.300 (19)°. This study confirms previous conclusions on the structure of (I) which emerged on the basis of IR studies (Marcotrigiano, 1975 ).

The NH groups of the 1,3-dimethylthiourea ligands are arranged such that they facilitate the formation of both intra- and intermolecular hydrogen bonds, involving Cl⁻ anions as acceptors in both cases; details are given in Table 1. As seen in a number of zinc(II) bis(thiourea) dicarboxylate polymers (Burrows et al., 2000), the intramolecular hydrogen bonds have graph-set notation S(6). The intermolecular hydrogen bonds link the molecules into infinite hydrogen-bonded chains (Fig. 2). These interactions occur pairwise and lead to hydrogen-bonded rings with graph-set notation R₂²(12). There is no inter-chain hydrogen bonding present.

Figure 1
A view of the molecule of (I

), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms represented by small spheres. [Symmetry code: (i) 1 − x, y, $[{1 \over 2}]$ − z.]

Figure 2
A view of the intermolecular hydrogen-bond interactions in (I

), leading to chains along the crystallographic [101] direction.

Experimental

Equimolar aqueous solutions of zinc(II) tetra(1,3-dimethylthiourea) dichloride (Ashcroft, 1970 ) and sodium salts of succinic, itaconic or mesaconic acids were allowed to evaporate slowly over a period of two weeks, in each case resulting in the formation of colourless crystals. Analysis by single-crystal X-ray diffraction revealed the identity of the products as (I) and confirmed that the dicarboxylate was not incorporated into the structure.

Crystal data

[ZnCl₂(C₃H₆N₂S)₂]
M_r = 344.62
Monoclinic, C2/c
a = 13.0230 (4) Å
b = 8.9470 (3) Å
c = 12.4350 (3) Å
β = 106.967 (2)°
V = 1385.82 (7) Å³
Z = 4
D_x = 1.652 Mg m⁻³
Mo Kα radiation
Cell parameters from 1063 reflections
θ = 0.2–26.3°
μ = 2.44 mm⁻¹
T = 150 (2) K
Block, colourless
0.18 × 0.15 × 0.15 mm

Data collection

Nonius KappaCCD area-detector diffractometer
φ and ω scans
Absorption correction: multi-scan (Blessing, 1995 ) T_min = 0.655, T_max = 0.697
8273 measured reflections
1580 independent reflections
1439 reflections with I > 2σ(I)
R_int = 0.034
θ_max = 27.5°
h = −16 → 16
k = −11 → 11
l = −16 → 16

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.028
wR(F²) = 0.067
S = 1.14
1580 reflections
85 parameters
H atoms treated by a mixture of independent and constrained refinement
w = 1/[σ²(F_o²) + (0.0178P)² + 2.1477P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max < 0.001
Δρ_max = 0.43 e Å⁻³
Δρ_min = −0.44 e Å⁻³

Table 1
Hydrogen-bonding geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯Cl1	0.884 (17)	2.337 (18)	3.2110 (19)	170 (3)
N1—H1⋯Cl1ⁱ	0.887 (17)	2.47 (2)	3.2737 (19)	152 (2)
Symmetry code: (i) $[{\script{1\over 2}}+x,{\script{3\over 2}}-y,{\script{1\over 2}}+z]$ .

H atoms were included at calculated positions on all carbon centres, being constrained to an ideal geometry with C—H distances of 0.98 Å and U_iso(H) = 1.5U_eq(C). Each group was allowed to rotate freely about its C—N bond. The position of the amino H atoms were located from the difference map and refined isotropically subject to a distance constraint of 0.89 Å.

Data collection: COLLECT (Hooft, 1998 ); cell refinement: HKL DENZO (Otwinowski & Minor, 1997 ); data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2001 ); software used to prepare material for publication: SHELXTL and local programs.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536804020550/bt6489sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536804020550/bt6489Isup2.hkl

Computing details top

Data collection: COLLECT (Hooft, 1998); cell refinement: HKL DENZO (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2001); software used to prepare material for publication: SHELXTL and local programs.

Dichlorobis(1,3-dimethylthiourea-κS)zinc(II) top

Crystal data top

[ZnCl₂(C₃H₆N₂S)₂]	F(000) = 704
M_r = 344.62	D_x = 1.652 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71070 Å
Hall symbol: -C2yc	Cell parameters from 25 reflections
a = 13.0230 (4) Å	θ = 0.2–26.3°
b = 8.9470 (3) Å	µ = 2.44 mm⁻¹
c = 12.4350 (3) Å	T = 150 K
β = 106.967 (2)°	Block, colourless
V = 1385.82 (7) Å³	0.18 × 0.15 × 0.15 mm
Z = 4

Data collection top

Nonius KappaCCD area-detector diffractometer	1580 independent reflections
Radiation source: sealed tube	1439 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.034
φ and ω scans	θ_max = 27.5°, θ_min = 4.0°
Absorption correction: multi-scan (Blessing, 1995)	h = −16→16
T_min = 0.655, T_max = 0.697	k = −11→11
8273 measured reflections	l = −16→16

Refinement top

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)] = 0.028	Hydrogen site location: difference Fourier map
wR(F²) = 0.067	H atoms treated by a mixture of independent and constrained refinement
S = 1.14	w = 1/[σ²(F_o²) + (0.0178P)² + 2.1477P] where P = (F_o² + 2F_c²)/3
1580 reflections	(Δ/σ)_max < 0.001
85 parameters	Δρ_max = 0.43 e Å⁻³
2 restraints	Δρ_min = −0.44 e Å⁻³

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
Zn1	0.5000	0.65085 (4)	0.2500	0.02036 (12)
Cl1	0.39368 (4)	0.80208 (7)	0.32074 (4)	0.03019 (15)
S1	0.60867 (4)	0.49039 (6)	0.38451 (4)	0.02451 (15)
N1	0.74153 (14)	0.5551 (2)	0.58578 (15)	0.0249 (4)
H1	0.760 (2)	0.611 (3)	0.6472 (19)	0.043 (8)*
N2	0.59505 (15)	0.7072 (2)	0.52832 (15)	0.0248 (4)
H2	0.5344 (16)	0.730 (3)	0.477 (2)	0.034 (7)*
C1	0.65113 (16)	0.5921 (2)	0.50836 (17)	0.0205 (4)
C2	0.8128 (2)	0.4339 (3)	0.5763 (2)	0.0334 (5)
H2A	0.8203	0.4326	0.5001	0.043 (8)*
H2C	0.7827	0.3385	0.5914	0.052 (9)*
H2B	0.8834	0.4490	0.6309	0.054 (9)*
C3	0.62235 (19)	0.7902 (3)	0.63317 (19)	0.0302 (5)
H3A	0.6953	0.8301	0.6488	0.022 (6)*
H3B	0.6185	0.7237	0.6945	0.043 (8)*
H3C	0.5716	0.8730	0.6270	0.042 (8)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.02062 (19)	0.02289 (19)	0.01535 (18)	0.000	0.00177 (13)	0.000
Cl1	0.0290 (3)	0.0365 (3)	0.0220 (3)	0.0119 (2)	0.0026 (2)	−0.0025 (2)
S1	0.0288 (3)	0.0223 (3)	0.0178 (3)	0.0039 (2)	−0.0006 (2)	−0.00186 (19)
N1	0.0237 (9)	0.0275 (9)	0.0198 (9)	0.0034 (7)	0.0005 (7)	−0.0016 (7)
N2	0.0226 (9)	0.0285 (10)	0.0196 (9)	0.0047 (7)	0.0002 (7)	−0.0026 (7)
C1	0.0200 (10)	0.0223 (10)	0.0187 (9)	−0.0023 (8)	0.0047 (8)	0.0015 (8)
C2	0.0321 (12)	0.0357 (13)	0.0277 (11)	0.0124 (10)	0.0016 (9)	0.0000 (10)
C3	0.0304 (12)	0.0328 (12)	0.0256 (12)	0.0019 (10)	0.0051 (9)	−0.0072 (9)

Geometric parameters (Å, º) top

Zn1—Cl1	2.2874 (6)	N2—C1	1.327 (3)
Zn1—Cl1ⁱ	2.2874 (6)	N2—C3	1.452 (3)
Zn1—S1	2.3410 (5)	C2—H2A	0.9800
Zn1—S1ⁱ	2.3410 (5)	C2—H2C	0.9800
S1—C1	1.734 (2)	C2—H2B	0.9800
N1—H1	0.887 (17)	C3—H3A	0.9800
N1—C1	1.327 (3)	C3—H3B	0.9800
N1—C2	1.454 (3)	C3—H3C	0.9800
N2—H2	0.884 (17)

Cl1—Zn1—Cl1ⁱ	107.47 (3)	S1—C1—N2	121.53 (15)
Cl1—Zn1—S1	113.300 (19)	N1—C1—N2	118.55 (19)
Cl1ⁱ—Zn1—S1ⁱ	113.300 (19)	N1—C2—H2A	109.5
Cl1—Zn1—S1ⁱ	109.27 (2)	N1—C2—H2C	109.5
Cl1ⁱ—Zn1—S1	109.27 (2)	N1—C2—H2B	109.5
S1—Zn1—S1ⁱ	104.35 (3)	H2A—C2—H2C	109.5
Zn1—S1—C1	106.40 (7)	H2A—C2—H2B	109.5
H1—N1—C1	116.6 (19)	H2C—C2—H2B	109.5
H1—N1—C2	118.0 (19)	N2—C3—H3A	109.5
C1—N1—C2	125.39 (19)	N2—C3—H3B	109.5
H2—N2—C1	117.8 (18)	N2—C3—H3C	109.5
H2—N2—C3	117.8 (18)	H3A—C3—H3B	109.5
C1—N2—C3	124.14 (18)	H3A—C3—H3C	109.5
S1—C1—N1	119.92 (16)	H3B—C3—H3C	109.5

Cl1—Zn1—S1—C1	−38.29 (8)	C3—N2—C1—S1	175.64 (17)
Cl1ⁱ—Zn1—S1—C1	81.50 (7)	C3—N2—C1—N1	−4.3 (3)
S1ⁱ—Zn1—S1—C1	−157.04 (8)	Zn1—S1—C1—N1	−155.05 (15)
C2—N1—C1—S1	1.1 (3)	Zn1—S1—C1—N2	25.05 (19)
C2—N1—C1—N2	−179.0 (2)

Symmetry code: (i) −x+1, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···Cl1	0.88 (2)	2.34 (2)	3.2110 (19)	170 (3)
N1—H1···Cl1ⁱⁱ	0.89 (2)	2.47 (2)	3.2737 (19)	152 (2)

Symmetry code: (ii) x+1/2, −y+3/2, z+1/2.

Footnotes

‡Current address: School of Natural Sciences, Bedson Building, University of Newcastle, Newcastle upon Tyne NE1 7RU, England.

Acknowledgements

The EPSRC is thanked for funding.

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