Di­chloro­bis(3,4,5,6-tetra­hydro­pyrimidinium-2-thiol­ato-S)­cobalt(II)

In the title compound, [CoCl₂(C₄H₈N₂S)₂], the coordination around the Co atom is slightly distorted tetrahedral, with an average angle of 109.46 (4)°. Intermolecular interactions between the N and Cl atoms result in interconnected two-dimensional molecular network ribbons throughout the structure.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.006 Å
• R factor = 0.051
• wR factor = 0.142
• Data-to-parameter ratio = 21.9

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry

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S1. Comment

Continuing our interest in the diverse complexing behaviour of cobalt complexes with monothione ligands, a crystal of the title compound, (I), has been studied. Earlier work has shown that 1-methylimidazolidine-2(3H)-thione (meimt) gives rise to complexes with the molecular formula Co(meimt)₄(NO₃)₂·H₂O in ethanol solvent and Co(meimt)₂(NO₃)₂ in ethyl acetate solvent (Raper & Nowell, 1980); a perchlorate has also been reported, viz. [Co(meimt)₄](ClO₄)₂ (Raper & Nowell, 1979).

The bond lengths and angles of the ligands in (I) are comparable with those reported for dichlorotetrakis(trimethylenethiourea)nickel(II) (Luth & Truter, 1968). The Co atom is tetrahedrally coordinated by two Cl atoms and two S atoms (Fig. 1). The angles around the Co atom are in the range 97.45 (3)–117.17 (4)°, with an average of 109.46 (4)°, implying that the tetrahedron is slightly distorted.

In the crystal, all the N atoms are involved in intramolecular and intermolecular interactions with the Cl atoms. Atoms N1 and N4 for intramolecular interactions, whereas atoms N3 and N2 form intermolecular interactions. The intermolecular interactions between N2 and Cl2(x, 1 + y, z) form molecular ribbons along the b axis, stacking along the a axis (Fig. 2). The other intermolecular interactions between N3 and Cl2(x, 1 - y, 1/2 + z) interconnect these ribbons into a two-dimensional molecular network throughout the structure.

S2. Experimental

2.4 g of propylenethiourea (20 mmol) was added to a solution of cobalt(II) chloride (1.3 g, 10 mmol) in acetonitrile (20 ml). The mixture was stirred at ambient temperature for 30 min. After stirring, the solution was poured into crystal dishes and covered with aluminium foil to allow the solvent to evaporate. After a few weeks, blue crystals were obtained, were washed with hexane and, after drying, a suitable single-crystal was selected for X-ray structure determination.

S3. Refinement

After checking their presence in a difference map, all the H atoms were geometrically fixed and allowed to ride on their attached atoms.

Computing details

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL, PARST (Nardelli, 1995) and PLATON (Spek, 1990).

Figures

	Fig. 1. The structure of the title compound showing 50% probability displacement ellipsoids and the atom-numbering scheme.
	Fig. 2. Packing diagram of the two-dimensional network, viewed down the a axis

Dichlorobis(3,4,5,6-tetrahydropyrimidinium-2-thiolato-S)cobalt(II)

Crystal data

[CoCl2(C4H8N2S)2]	F(000) = 1480
Mr = 362.20	Dx = 1.616 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 32.0245 (14) Å	Cell parameters from 7650 reflections
b = 7.1329 (3) Å	θ = 1.4–29.5°
c = 14.6141 (6) Å	µ = 1.78 mm^−1
β = 116.864 (1)°	T = 293 K
V = 2978.0 (2) Å^3	Slab, blue
Z = 8	0.46 × 0.24 × 0.16 mm

Data collection

Siemens SMART CCD area-detector diffractometer	3397 independent reflections
Radiation source: fine-focus sealed tube	2635 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.089
Detector resolution: 8.33 pixels mm^-1	θmax = 27.5°, θmin = 1.4°
ω scans	h = −36→41
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996)	k = −8→9
Tmin = 0.496, Tmax = 0.764	l = −18→18
9648 measured reflections

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)] = 0.051	H-atom parameters constrained
wR(F^2) = 0.142	w = 1/[σ^2(Fo^2) + (0.0748P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.98	(Δ/σ)max < 0.001
3397 reflections	Δρmax = 0.82 e Å^−3
155 parameters	Δρmin = −1.03 e Å^−3
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0033 (4)

Special details

Experimental. The data collection covered over a hemisphere of reciprocal space by a combination of three sets of exposures; each set had a different ϕ angle (0, 88 and 180°) for the crystal and each exposure of 30 s covered 0.3° in ω. The crystal-to-detector distance was 4 cm and the detector swing angle was -35°. Crystal decay was monitored by repeating thirty initial frames at the end of data collection and analysing the intensity of duplicate reflections, and was found to be negligible.

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
Co1	0.118176 (15)	0.50686 (5)	0.48883 (3)	0.03424 (18)
S1	0.11364 (3)	0.82702 (11)	0.46066 (6)	0.0482 (3)
S2	0.14573 (3)	0.51676 (11)	0.66531 (6)	0.0401 (2)
Cl1	0.04857 (3)	0.37342 (13)	0.39704 (7)	0.0534 (3)
Cl2	0.17122 (3)	0.36072 (11)	0.44895 (6)	0.0411 (2)
N1	0.06068 (10)	0.7344 (4)	0.2634 (2)	0.0460 (7)
H1A	0.0586	0.6260	0.2868	0.055*
N2	0.08857 (13)	1.0329 (4)	0.2958 (2)	0.0528 (8)
H2A	0.1064	1.1140	0.3397	0.063*
N3	0.18877 (9)	0.2863 (4)	0.81879 (18)	0.0385 (6)
H3A	0.1813	0.3698	0.8513	0.046*
N4	0.18615 (9)	0.1867 (3)	0.66817 (19)	0.0361 (6)
H4A	0.1767	0.2060	0.6038	0.043*
C1	0.08513 (11)	0.8646 (4)	0.3293 (2)	0.0363 (7)
C2	0.03672 (13)	0.7635 (7)	0.1518 (3)	0.0562 (10)
H2B	0.0039	0.7909	0.1303	0.067*
H2C	0.0386	0.6499	0.1173	0.067*
C3	0.05843 (15)	0.9207 (7)	0.1223 (3)	0.0638 (11)
H3B	0.0391	0.9523	0.0508	0.077*
H3C	0.0889	0.8826	0.1300	0.077*
C4	0.06369 (15)	1.0892 (6)	0.1877 (3)	0.0588 (10)
H4B	0.0812	1.1860	0.1734	0.071*
H4C	0.0331	1.1391	0.1730	0.071*
C5	0.17546 (9)	0.3129 (4)	0.7205 (2)	0.0286 (6)
C6	0.21552 (13)	0.1233 (5)	0.8763 (3)	0.0492 (9)
H6A	0.2061	0.0903	0.9286	0.059*
H6B	0.2486	0.1539	0.9101	0.059*
C7	0.20736 (15)	−0.0415 (5)	0.8051 (3)	0.0542 (9)
H7A	0.2296	−0.1402	0.8411	0.065*
H7B	0.1761	−0.0905	0.7836	0.065*
C8	0.21288 (14)	0.0170 (5)	0.7130 (3)	0.0451 (8)
H8A	0.2457	0.0394	0.7326	0.054*
H8B	0.2021	−0.0829	0.6625	0.054*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.0378 (3)	0.0282 (3)	0.0330 (3)	0.00139 (15)	0.0127 (2)	0.00185 (15)
S1	0.0734 (6)	0.0274 (4)	0.0355 (4)	0.0007 (4)	0.0172 (4)	−0.0003 (3)
S2	0.0527 (5)	0.0310 (4)	0.0340 (4)	0.0134 (3)	0.0172 (4)	0.0014 (3)
Cl1	0.0408 (5)	0.0465 (5)	0.0616 (6)	−0.0082 (4)	0.0131 (4)	0.0005 (4)
Cl2	0.0530 (5)	0.0379 (4)	0.0404 (4)	0.0009 (3)	0.0281 (4)	0.0014 (3)
N1	0.0519 (17)	0.0388 (15)	0.0406 (14)	−0.0066 (13)	0.0150 (13)	0.0035 (12)
N2	0.075 (2)	0.0304 (14)	0.0449 (17)	0.0001 (14)	0.0195 (16)	0.0016 (12)
N3	0.0508 (16)	0.0353 (13)	0.0279 (12)	0.0085 (12)	0.0164 (12)	−0.0014 (10)
N4	0.0471 (15)	0.0329 (13)	0.0309 (12)	0.0104 (11)	0.0200 (11)	0.0021 (10)
C1	0.0439 (17)	0.0273 (14)	0.0401 (16)	0.0066 (12)	0.0211 (14)	0.0016 (12)
C2	0.047 (2)	0.073 (3)	0.0387 (18)	−0.0121 (19)	0.0107 (16)	0.0024 (18)
C3	0.059 (2)	0.077 (3)	0.049 (2)	0.009 (2)	0.0187 (19)	0.018 (2)
C4	0.070 (3)	0.048 (2)	0.055 (2)	0.0119 (19)	0.025 (2)	0.0232 (18)
C5	0.0268 (13)	0.0284 (14)	0.0297 (13)	−0.0014 (11)	0.0121 (11)	−0.0009 (11)
C6	0.064 (2)	0.0442 (18)	0.0353 (17)	0.0168 (17)	0.0184 (17)	0.0085 (15)
C7	0.069 (3)	0.0428 (18)	0.053 (2)	0.0139 (18)	0.030 (2)	0.0123 (17)
C8	0.055 (2)	0.0376 (18)	0.0438 (18)	0.0157 (14)	0.0230 (17)	0.0030 (14)

Geometric parameters (Å, º)

Co1—Cl1	2.230 (1)	N4—H4A	0.8600
Co1—Cl2	2.282 (1)	C2—C3	1.483 (6)
Co1—S1	2.313 (1)	C2—H2B	0.9700
Co1—S2	2.319 (1)	C2—H2C	0.9700
S1—C1	1.734 (3)	C3—C4	1.498 (6)
S2—C5	1.726 (3)	C3—H3B	0.9700
N1—C1	1.312 (4)	C3—H3C	0.9700
N1—C2	1.470 (4)	C4—H4B	0.9700
N1—H1A	0.8600	C4—H4C	0.9700
N2—C1	1.320 (4)	C6—C7	1.512 (5)
N2—C4	1.468 (5)	C6—H6A	0.9700
N2—H2A	0.8600	C6—H6B	0.9700
N3—C5	1.315 (4)	C7—C8	1.494 (5)
N3—C6	1.463 (4)	C7—H7A	0.9700
N3—H3A	0.8600	C7—H7B	0.9700
N4—C5	1.322 (3)	C8—H8A	0.9700
N4—C8	1.456 (4)	C8—H8B	0.9700
Cl1—Co1—Cl2	107.97 (4)	C4—C3—H3B	109.5
Cl1—Co1—S1	110.43 (4)	C2—C3—H3C	109.5
Cl2—Co1—S1	113.55 (4)	C4—C3—H3C	109.5
Cl1—Co1—S2	117.17 (4)	H3B—C3—H3C	108.1
Cl2—Co1—S2	110.17 (3)	N2—C4—C3	108.5 (3)
S1—Co1—S2	97.45 (3)	N2—C4—H4B	110.0
C1—S1—Co1	108.00 (10)	C3—C4—H4B	110.0
C5—S2—Co1	110.25 (10)	N2—C4—H4C	110.0
C1—N1—C2	123.6 (3)	C3—C4—H4C	110.0
C1—N1—H1A	118.2	H4B—C4—H4C	108.4
C2—N1—H1A	118.2	N3—C5—N4	119.5 (3)
C1—N2—C4	123.5 (3)	N3—C5—S2	118.0 (2)
C1—N2—H2A	118.2	N4—C5—S2	122.4 (2)
C4—N2—H2A	118.2	N3—C6—C7	110.4 (3)
C5—N3—C6	124.0 (3)	N3—C6—H6A	109.6
C5—N3—H3A	118.0	C7—C6—H6A	109.6
C6—N3—H3A	118.0	N3—C6—H6B	109.6
C5—N4—C8	124.0 (3)	C7—C6—H6B	109.6
C5—N4—H4A	118.0	H6A—C6—H6B	108.1
C8—N4—H4A	118.0	C8—C7—C6	110.4 (3)
N1—C1—N2	119.6 (3)	C8—C7—H7A	109.6
N1—C1—S1	122.9 (2)	C6—C7—H7A	109.6
N2—C1—S1	117.4 (2)	C8—C7—H7B	109.6
N1—C2—C3	110.6 (3)	C6—C7—H7B	109.6
N1—C2—H2B	109.5	H7A—C7—H7B	108.1
C3—C2—H2B	109.5	N4—C8—C7	110.6 (3)
N1—C2—H2C	109.5	N4—C8—H8A	109.5
C3—C2—H2C	109.5	C7—C8—H8A	109.5
H2B—C2—H2C	108.1	N4—C8—H8B	109.5
C2—C3—C4	110.7 (4)	C7—C8—H8B	109.5
C2—C3—H3B	109.5	H8A—C8—H8B	108.1
Cl1—Co1—S1—C1	−48.47 (13)	N1—C2—C3—C4	−49.3 (5)
Cl2—Co1—S1—C1	72.97 (12)	C1—N2—C4—C3	−31.7 (5)
S2—Co1—S1—C1	−171.16 (12)	C2—C3—C4—N2	53.0 (4)
Cl1—Co1—S2—C5	86.82 (11)	C6—N3—C5—N4	0.4 (5)
Cl2—Co1—S2—C5	−37.11 (11)	C6—N3—C5—S2	−177.9 (3)
S1—Co1—S2—C5	−155.62 (11)	C8—N4—C5—N3	−0.9 (5)
C2—N1—C1—N2	0.8 (5)	C8—N4—C5—S2	177.3 (3)
C2—N1—C1—S1	−179.4 (3)	Co1—S2—C5—N3	−172.4 (2)
C4—N2—C1—N1	4.4 (6)	Co1—S2—C5—N4	9.4 (3)
C4—N2—C1—S1	−175.5 (3)	C5—N3—C6—C7	−25.1 (5)
Co1—S1—C1—N1	15.9 (3)	N3—C6—C7—C8	48.4 (4)
Co1—S1—C1—N2	−164.3 (3)	C5—N4—C8—C7	26.4 (5)
C1—N1—C2—C3	22.8 (5)	C6—C7—C8—N4	−49.0 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4A···Cl2	0.86	2.45	3.263 (3)	158
N1—H1A···Cl1	0.86	2.53	3.358 (3)	161
N2—H2A···Cl2^i	0.86	2.64	3.483 (3)	167
N3—H3A···Cl2^ii	0.86	2.50	3.353 (3)	171

Symmetry codes: (i) x, y+1, z; (ii) x, −y+1, z+1/2.