Tetrakis(thiourea-κS)palladium(II) dithio-cyanate.

The title compound, [Pd(CH(4)N(2)S)(4)](SCN)(2), consists of complex [Pd(TU)(4)](2+) [TU = thio-urea, SC(NH(2))(2)] cations and thio-cyanate counter-anions. The Pd(II) cation is situated on an inversion centre and exhibits an almost square-planar coordination by the S atoms of the TU ligands. The complex cations are connected through the thio-cyanate ions via N-H⋯N [2.922 (3)-3.056 (3) Å] and N-H⋯S [3.369 (2)-3.645 (2) Å] hydrogen bonds.

Related literature

For the coordination chemistry of thio­nes and thio­nates, and for biomolecules possessing thio­amido binding sites, see: Akrivos (2001 ▶); Raper (1996 ▶); Cusumano et al. (2005 ▶). For other structures listed in the Cambridge Structural Database (Allen, 2002 ▶) that contain transition metals and thio­urea ligands, see: Bott et al. (1998 ▶); Dupa & Krebs (1973 ▶); Gale et al. (2006 ▶); Hunt et al. (1979 ▶); Taylor et al. (1974 ▶).

Experimental

Crystal data

[Pd(CH4N2S)4](SCN)2

M = 527.05

Monoclinic,

a = 8.136 (3) Å

b = 12.966 (5) Å

c = 8.810 (3) Å

β = 91.12 (5)°

V = 929.3 (6) Å3

Z = 2

Mo Kα radiation

μ = 1.69 mm−1

T = 123 (2) K

0.30 × 0.25 × 0.22 mm

Data collection

Rigaku/MSC Mercury CCD diffractometer

Absorption correction: integration (NUMABS; Higashi, 1999 ▶) T min = 0.632, T max = 0.708

7301 measured reflections

2117 independent reflections

2040 reflections with I > 2σ(I)

R int = 0.025

Refinement

R[F 2 > 2σ(F 2)] = 0.022

wR(F 2) = 0.043

S = 1.35

2117 reflections

106 parameters

H-atom parameters constrained

Δρmax = 0.66 e Å−3

Δρmin = −0.48 e Å−3

Data collection: CrystalClear (Molecular Structure Corporation & Rigaku, 2001 ▶); cell refinement: CrystalClear; data reduction: TEXSAN (Molecular Structure Corporation & Rigaku, 2004 ▶); program(s) used to solve structure: SIR97 (Altomare et al., 1999 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEPII (Johnson, 1976 ▶); software used to prepare material for publication: SHELXL97 and TEXSAN.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053680801088X/wm2176sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053680801088X/wm2176Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[Pd(CH4N2S)4](SCN)2	F000 = 528
Mr = 527.05	Dx = 1.884 Mg m−3
Monoclinic, P21/c	Mo Kα radiation λ = 0.71070 Å
Hall symbol: -P 2ybc	Cell parameters from 3103 reflections
a = 8.136 (3) Å	θ = 3.4–27.5º
b = 12.966 (5) Å	µ = 1.69 mm−1
c = 8.810 (3) Å	T = 123 (2) K
β = 91.12 (5)º	Prism, orange
V = 929.3 (6) Å3	0.30 × 0.25 × 0.22 mm
Z = 2

Rigaku/MSC Mercury CCD diffractometer	2117 independent reflections
Radiation source: fine-focus sealed tube	2040 reflections with I > 2σ(I)
Monochromator: graphite	Rint = 0.025
T = 123(2) K	θmax = 27.5º
ω scans	θmin = 3.9º
Absorption correction: integration(NUMABS; Higashi, 1999)	h = −8→10
Tmin = 0.632, Tmax = 0.708	k = −16→13
7301 measured reflections	l = −11→11

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.022	H-atom parameters constrained
wR(F2) = 0.043	w = 1/[σ2(Fo2) + 0.6382P] where P = (Fo2 + 2Fc2)/3
S = 1.35	(Δ/σ)max = 0.001
2117 reflections	Δρmax = 0.66 e Å−3
106 parameters	Δρmin = −0.48 e Å−3
Primary atom site location: structure-invariant direct methods	Extinction correction: none

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.

	x	y	z	Uiso*/Ueq
Pd1	0.0000	0.5000	0.5000	0.00900 (6)
S1	−0.19061 (6)	0.37251 (3)	0.56476 (5)	0.01265 (10)
C1	−0.1354 (2)	0.26304 (14)	0.4664 (2)	0.0140 (4)
N1	−0.0189 (2)	0.26297 (13)	0.36425 (19)	0.0197 (4)
H1A	0.0068	0.2054	0.3175	0.024*
H1B	0.0332	0.3205	0.3429	0.024*
N2	−0.2134 (2)	0.17612 (13)	0.49809 (19)	0.0199 (4)
H2A	−0.1874	0.1187	0.4511	0.024*
H2B	−0.2911	0.1759	0.5661	0.024*
S2	0.13159 (6)	0.47003 (4)	0.73312 (5)	0.01300 (10)
C2	0.3204 (2)	0.41505 (14)	0.7012 (2)	0.0141 (4)
N3	0.3774 (2)	0.39827 (14)	0.56415 (18)	0.0201 (4)
H3A	0.4743	0.3693	0.5534	0.024*
H3B	0.3184	0.4160	0.4835	0.024*
N4	0.4105 (2)	0.38793 (14)	0.82155 (19)	0.0219 (4)
H4A	0.5073	0.3591	0.8096	0.026*
H4B	0.3736	0.3988	0.9134	0.026*
S3	0.22933 (7)	0.42269 (4)	0.17265 (6)	0.02044 (12)
C3	0.4076 (3)	0.36611 (15)	0.2055 (2)	0.0186 (4)
N5	0.5334 (2)	0.32525 (15)	0.2287 (2)	0.0260 (4)

	U11	U22	U33	U12	U13	U23
Pd1	0.00878 (10)	0.00771 (9)	0.01049 (9)	0.00000 (7)	−0.00061 (7)	0.00047 (7)
S1	0.0121 (2)	0.0103 (2)	0.0156 (2)	−0.00127 (17)	0.00147 (17)	−0.00054 (16)
C1	0.0152 (10)	0.0128 (9)	0.0137 (9)	−0.0004 (7)	−0.0027 (7)	0.0001 (7)
N1	0.0228 (10)	0.0129 (8)	0.0238 (9)	−0.0030 (7)	0.0077 (7)	−0.0057 (6)
N2	0.0248 (10)	0.0115 (8)	0.0236 (9)	−0.0039 (7)	0.0073 (7)	−0.0027 (7)
S2	0.0111 (2)	0.0163 (2)	0.0115 (2)	0.00134 (17)	−0.00052 (16)	0.00123 (16)
C2	0.0126 (9)	0.0124 (9)	0.0172 (9)	−0.0010 (7)	−0.0007 (7)	0.0011 (7)
N3	0.0166 (9)	0.0275 (9)	0.0162 (8)	0.0096 (7)	0.0005 (7)	0.0019 (7)
N4	0.0170 (9)	0.0309 (10)	0.0176 (8)	0.0108 (8)	−0.0040 (7)	0.0005 (7)
S3	0.0193 (3)	0.0202 (2)	0.0220 (2)	0.0026 (2)	0.0054 (2)	0.00404 (19)
C3	0.0235 (12)	0.0183 (10)	0.0144 (9)	−0.0049 (8)	0.0061 (8)	−0.0029 (7)
N5	0.0232 (11)	0.0256 (9)	0.0292 (10)	0.0018 (8)	0.0031 (8)	−0.0007 (8)

Pd1—S2	2.3302 (11)	N2—H2B	0.8800
Pd1—S2i	2.3302 (11)	S2—C2	1.721 (2)
Pd1—S1	2.3448 (8)	C2—N3	1.320 (3)
Pd1—S1i	2.3448 (8)	C2—N4	1.325 (3)
S1—C1	1.727 (2)	N3—H3A	0.8800
C1—N1	1.320 (3)	N3—H3B	0.8800
C1—N2	1.326 (3)	N4—H4A	0.8800
N1—H1A	0.8800	N4—H4B	0.8800
N1—H1B	0.8800	S3—C3	1.646 (2)
N2—H2A	0.8800	C3—N5	1.167 (3)
S2—Pd1—S2i	180.0	C1—N2—H2B	120.0
S2—Pd1—S1	87.86 (3)	H2A—N2—H2B	120.0
S2i—Pd1—S1	92.14 (3)	C2—S2—Pd1	108.72 (7)
S2—Pd1—S1i	92.14 (3)	N3—C2—N4	119.29 (18)
S2i—Pd1—S1i	87.86 (3)	N3—C2—S2	123.27 (15)
S1—Pd1—S1i	180.0	N4—C2—S2	117.44 (15)
C1—S1—Pd1	106.11 (7)	C2—N3—H3A	120.0
N1—C1—N2	119.74 (17)	C2—N3—H3B	120.0
N1—C1—S1	122.68 (15)	H3A—N3—H3B	120.0
N2—C1—S1	117.57 (15)	C2—N4—H4A	120.0
C1—N1—H1A	120.0	C2—N4—H4B	120.0
C1—N1—H1B	120.0	H4A—N4—H4B	120.0
H1A—N1—H1B	120.0	N5—C3—S3	179.5 (2)
C1—N2—H2A	120.0
S2—Pd1—S1—C1	−101.78 (7)	S1—Pd1—S2—C2	112.12 (7)
S2i—Pd1—S1—C1	78.22 (7)	S1i—Pd1—S2—C2	−67.88 (7)
Pd1—S1—C1—N1	−6.95 (19)	Pd1—S2—C2—N3	2.44 (18)
Pd1—S1—C1—N2	172.15 (14)	Pd1—S2—C2—N4	−176.95 (14)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1B···S3	0.88	2.58	3.369 (2)	150
N1—H1A···S2ii	0.88	2.60	3.466 (2)	166
N2—H2A···S3iii	0.88	2.78	3.615 (2)	158
N2—H2B···N5iv	0.88	2.04	2.922 (3)	178
N3—H3B···S3	0.88	2.82	3.645 (2)	157
N3—H3A···S1v	0.88	2.73	3.531 (2)	153
N4—H4B···S3vi	0.88	2.61	3.482 (2)	173
N4—H4A···N5vii	0.88	2.50	3.056 (3)	121

Pd1—S2	2.3302 (11)
Pd1—S1	2.3448 (8)

S2—Pd1—S2i	180
S2—Pd1—S1	87.86 (3)
S2i—Pd1—S1	92.14 (3)

Symmetry code: (i) .

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1B⋯S3	0.88	2.58	3.369 (2)	150
N1—H1A⋯S2ii	0.88	2.60	3.466 (2)	166
N2—H2A⋯S3iii	0.88	2.78	3.615 (2)	158
N2—H2B⋯N5iv	0.88	2.04	2.922 (3)	178
N3—H3B⋯S3	0.88	2.82	3.645 (2)	157
N3—H3A⋯S1v	0.88	2.73	3.531 (2)	153
N4—H4B⋯S3vi	0.88	2.61	3.482 (2)	173
N4—H4A⋯N5vii	0.88	2.50	3.056 (3)	121

Symmetry codes: (ii) ; (iii) ; (iv) ; (v) ; (vi) ; (vii) .