(4-tert-Butyl-2-methyl­thio­semicarb­azido)(O-methyl­di­thio­phosphato)­palladium(II)

The title Pd complex, [Pd(C₆H₁₄N₃S)(CH₃O₂PS₂)], is formed from Pd(acetate)₂ and 5-tert-butyl­amino-4-methyl-2-sulfido-2-thio­xo-1,3,4,2λ⁵-thia­di­aza­phospho­lan-5-onium, (1), in meth­anol. The Pd atom is coordinated to two different ligands which are generated in situ as a result of methano­lysis of the starting compound (1). Thus, Pd is complexed by the O-methyl­di­thio­phosphate ligand and by 2-methyl-4-tert-butyl­thio­semicarbazide. Two mol­ecules of the Pd chelate are linked by two intermolecular N—H...O hydrogen bonds, the N...O distances of which are 3.361 and 2.827 Å.

Key indicators

• Powder X-ray study
• T = 120 K
• Mean [sigma](C-C) = 0.009 Å
• R factor = 0.060
• wR factor = 0.110
• Data-to-parameter ratio = 16.6

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


 Alert Level C:



WEIGH_01  Alert C Extra text has been found in the
          _refine_ls_weighting_scheme field. This should be in the
          _refine_ls_weighting_details field.
          Weighting scheme given as calc w = 1/[\s^2^(Fo^2^)+(0.0398P)^2^+3.35P
          Weighting scheme identified as calc


 0 Alert Level A = Potentially serious problem

 0 Alert Level B = Potential problem

 1 Alert Level C = Please check

---

Computing details

Data collection: KM-4 Software (Kuma, 1997); cell refinement: KM-4 Software; data reduction: KM-4 Software; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP in SHELXTL.

(4-tert-butyl-2-methylthiosemicarbazido)(O-methyldithiophosphato)palladium(II)

Crystal data

[Pd(C6H14N3OS2)(CH3OPS)]	F(000) = 820
Mr = 408.79	Dx = 1.809 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71069 Å
a = 12.889 (3) Å	Cell parameters from 50 reflections
b = 10.854 (2) Å	θ = 11.0–20.8°
c = 11.120 (2) Å	µ = 1.75 mm^−1
β = 105.23 (3)°	T = 120 K
V = 1501.0 (5) Å^3	Prism, orange
Z = 4	0.10 × 0.05 × 0.02 mm

Data collection

Kuma KM-4 CCD diffractometer with a CCD camera and an Oxford Cryosystems low-temperature device	2249 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.078
Graphite monochromator	θmax = 25.0°, θmin = 3.4°
ω scans	h = −15→13
9041 measured reflections	k = −12→12
2636 independent reflections	l = −11→13

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)] = 0.060	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.110	H atoms treated by a mixture of independent and constrained refinement
S = 1.16	Calculated w = 1/[σ^2(Fo^2) + (0.0398P)^2 + 3.35P] where P = (Fo^2 + 2Fc^2)/3
2636 reflections	(Δ/σ)max = 0.001
159 parameters	Δρmax = 1.18 e Å^−3
0 restraints	Δρmin = −1.04 e Å^−3

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
Pd	0.80705 (4)	0.15424 (4)	0.24173 (5)	0.01320 (17)
P	0.85527 (13)	0.42010 (16)	0.20465 (16)	0.0139 (4)
S1	0.72627 (13)	0.31608 (15)	0.11754 (17)	0.0181 (4)
S2	0.95287 (13)	0.28988 (16)	0.30541 (16)	0.0185 (4)
S3	0.67006 (13)	0.01907 (15)	0.16801 (16)	0.0168 (4)
O1	0.9000 (3)	0.4981 (4)	0.1202 (4)	0.0179 (11)
O2	0.8215 (3)	0.5155 (4)	0.2987 (4)	0.0188 (11)
N1	0.6813 (4)	−0.2218 (5)	0.2244 (5)	0.0152 (12)
H1	0.7159	−0.2819	0.2714	0.018*
N2	0.8267 (4)	−0.1055 (5)	0.3245 (5)	0.0142 (12)
N3	0.8767 (4)	0.0120 (4)	0.3576 (5)	0.0131 (12)
H3	0.9493	0.0057	0.3441	0.016*
C1	0.5775 (5)	−0.2572 (6)	0.1348 (6)	0.0180 (15)
C2	0.5877 (6)	−0.2492 (7)	0.0014 (6)	0.0266 (18)
H2A	0.6100	−0.1658	−0.0146	0.040*
H2B	0.5181	−0.2681	−0.0569	0.040*
H2C	0.6416	−0.3087	−0.0100	0.040*
C3	0.5581 (5)	−0.3918 (6)	0.1668 (7)	0.0233 (17)
H3A	0.6178	−0.4432	0.1569	0.035*
H3B	0.4907	−0.4213	0.1107	0.035*
H3C	0.5533	−0.3967	0.2532	0.035*
C4	0.4835 (5)	−0.1795 (6)	0.1515 (7)	0.0219 (16)
H4A	0.4901	−0.1677	0.2406	0.033*
H4B	0.4157	−0.2218	0.1130	0.033*
H4C	0.4843	−0.0991	0.1116	0.033*
C5	0.7290 (5)	−0.1111 (6)	0.2431 (6)	0.0124 (14)
C6	0.8784 (5)	−0.2080 (6)	0.4028 (6)	0.0172 (15)
H6A	0.8359	−0.2302	0.4608	0.026*
H6B	0.9508	−0.1834	0.4499	0.026*
H6C	0.8831	−0.2790	0.3501	0.026*
C7	0.7896 (6)	0.4709 (7)	0.4064 (7)	0.0264 (17)
H7A	0.7399	0.4015	0.3818	0.040*
H7B	0.7539	0.5372	0.4400	0.040*
H7C	0.8534	0.4437	0.4703	0.040*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Pd	0.0127 (3)	0.0128 (3)	0.0128 (3)	−0.0003 (2)	0.00110 (18)	0.0006 (2)
P	0.0132 (9)	0.0149 (9)	0.0127 (9)	−0.0018 (7)	0.0015 (7)	0.0006 (7)
S1	0.0160 (9)	0.0145 (9)	0.0194 (9)	−0.0008 (7)	−0.0032 (7)	0.0023 (7)
S2	0.0154 (9)	0.0174 (9)	0.0191 (10)	−0.0007 (7)	−0.0015 (7)	0.0051 (7)
S3	0.0152 (8)	0.0149 (9)	0.0173 (9)	−0.0003 (7)	−0.0010 (7)	0.0023 (7)
O1	0.019 (2)	0.020 (3)	0.014 (3)	−0.0049 (19)	0.0025 (19)	0.004 (2)
O2	0.022 (3)	0.015 (3)	0.021 (3)	−0.0012 (19)	0.009 (2)	0.000 (2)
N1	0.013 (3)	0.014 (3)	0.015 (3)	−0.002 (2)	−0.002 (2)	0.001 (2)
N2	0.014 (3)	0.006 (3)	0.020 (3)	0.000 (2)	0.000 (2)	0.000 (2)
N3	0.011 (3)	0.008 (3)	0.019 (3)	−0.002 (2)	0.001 (2)	−0.002 (2)
C1	0.014 (3)	0.020 (4)	0.017 (4)	−0.001 (3)	−0.001 (3)	−0.001 (3)
C2	0.026 (4)	0.040 (5)	0.014 (4)	−0.012 (3)	0.006 (3)	−0.009 (3)
C3	0.021 (4)	0.018 (4)	0.029 (4)	−0.003 (3)	0.003 (3)	−0.002 (3)
C4	0.016 (4)	0.024 (4)	0.023 (4)	0.000 (3)	0.000 (3)	−0.003 (3)
C5	0.016 (3)	0.014 (4)	0.010 (3)	0.002 (3)	0.007 (3)	0.002 (3)
C6	0.015 (3)	0.015 (4)	0.017 (4)	0.001 (3)	−0.004 (3)	0.003 (3)
C7	0.032 (4)	0.029 (4)	0.024 (4)	−0.003 (3)	0.017 (3)	0.001 (3)

Geometric parameters (Å, º)

Pd—N3	2.060 (5)	C1—C4	1.527 (9)
Pd—S3	2.2762 (17)	C1—C3	1.540 (9)
Pd—S1	2.3069 (17)	C2—H2A	0.9800
Pd—S2	2.3457 (18)	C2—H2B	0.9800
P—O1	1.489 (5)	C2—H2C	0.9800
P—O2	1.610 (5)	C3—H3A	0.9800
P—S2	2.024 (2)	C3—H3B	0.9800
P—S1	2.033 (2)	C3—H3C	0.9800
S3—C5	1.714 (6)	C4—H4A	0.9800
O2—C7	1.449 (8)	C4—H4B	0.9800
N1—C5	1.341 (8)	C4—H4C	0.9800
N1—C1	1.493 (8)	C6—H6A	0.9800
N1—H1	0.8800	C6—H6B	0.9800
N2—C5	1.345 (8)	C6—H6C	0.9800
N2—N3	1.433 (7)	C7—H7A	0.9800
N2—C6	1.461 (8)	C7—H7B	0.9800
N3—H3	0.9878	C7—H7C	0.9800
C1—C2	1.526 (9)
N3—Pd—S3	84.92 (14)	C1—C2—H2B	109.5
N3—Pd—S1	177.91 (16)	H2A—C2—H2B	109.5
S3—Pd—S1	95.15 (6)	C1—C2—H2C	109.5
N3—Pd—S2	95.67 (14)	H2A—C2—H2C	109.5
S3—Pd—S2	175.90 (7)	H2B—C2—H2C	109.5
S1—Pd—S2	84.41 (6)	C1—C3—H3A	109.5
O1—P—O2	105.0 (3)	C1—C3—H3B	109.5
O1—P—S2	117.3 (2)	H3A—C3—H3B	109.5
O2—P—S2	108.92 (19)	C1—C3—H3C	109.5
O1—P—S1	114.8 (2)	H3A—C3—H3C	109.5
O2—P—S1	109.88 (18)	H3B—C3—H3C	109.5
S2—P—S1	100.81 (10)	C1—C4—H4A	109.5
P—S1—Pd	87.34 (8)	C1—C4—H4B	109.5
P—S2—Pd	86.50 (8)	H4A—C4—H4B	109.5
C5—S3—Pd	98.8 (2)	C1—C4—H4C	109.5
C7—O2—P	120.4 (4)	H4A—C4—H4C	109.5
C5—N1—C1	128.9 (5)	H4B—C4—H4C	109.5
C5—N1—H1	115.6	N1—C5—N2	117.0 (5)
C1—N1—H1	115.6	N1—C5—S3	122.5 (5)
C5—N2—N3	119.4 (5)	N2—C5—S3	120.5 (5)
C5—N2—C6	124.5 (5)	N2—C6—H6A	109.5
N3—N2—C6	114.9 (5)	N2—C6—H6B	109.5
N2—N3—Pd	114.4 (4)	H6A—C6—H6B	109.5
N2—N3—H3	106.3	N2—C6—H6C	109.5
Pd—N3—H3	103.4	H6A—C6—H6C	109.5
N1—C1—C2	110.1 (5)	H6B—C6—H6C	109.5
N1—C1—C4	112.2 (5)	O2—C7—H7A	109.5
C2—C1—C4	111.1 (6)	O2—C7—H7B	109.5
N1—C1—C3	105.1 (5)	H7A—C7—H7B	109.5
C2—C1—C3	109.8 (6)	O2—C7—H7C	109.5
C4—C1—C3	108.3 (5)	H7A—C7—H7C	109.5
C1—C2—H2A	109.5	H7B—C7—H7C	109.5

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3···O1^i	0.99	1.88	2.827 (6)	160
N1—H1···O2^ii	0.88	2.56	3.361 (7)	151

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