Crystal structure of bis-[S-hexyl 3-(4-methyl-benzyl-idene)di-thio-carbazato-κ(2) N (3),S]palladium(II).

The whole mol-ecule of the title complex, [Pd(C15H21N2S2)2], is generated by twofold rotational symmetry. The palladium(II) atom exhibits a square-planar coordination geometry, and is located on the crystallographic twofold axis that induces a cis configuration of the N,S chelating ligands. In the crystal, mol-ecules stack along the c-axis direction and there are no significant inter-molecular inter-actions present. The structure was refined as an inversion twin with a final BASF parameter of 0.34 (2).

Related literature

For the crystal structures of the free Schiff base ligand and of its NiII complex, see: Howlader et al. (2015a ▸,b ▸). For similar bis­(di­thio­carbazato)Pd complexes with a cis configuration of the azomethine N and thiol­ate S atoms, see: Ali et al. (2002 ▸); Liu et al. (2011 ▸); Duan et al. (1998 ▸); Tampouris et al. (2007 ▸). For complexes with a trans configuration, see: Khaledi & Mohd Ali (2011 ▸); Tampouris et al. (2007 ▸); Tarafder et al. (2010 ▸).

Experimental

Crystal data

[Pd(C15H21N2S2)2]

M = 693.32

Monoclinic,

a = 18.3559 (11) Å

b = 9.6747 (5) Å

c = 10.3368 (6) Å

β = 116.810 (2)°

V = 1638.37 (16) Å3

Z = 2

Cu Kα radiation

μ = 7.14 mm−1

T = 173 K

0.25 × 0.16 × 0.11 mm

Data collection

Rigaku R-AXIS RAPID diffractometer

Absorption correction: multi-scan (ABSCOR; Rigaku, 1995 ▸) T min = 0.268, T max = 0.507

9318 measured reflections

2710 independent reflections

2121 reflections with I > 2σ(I)

R int = 0.120

Refinement

R[F 2 > 2σ(F 2)] = 0.091

wR(F 2) = 0.225

S = 1.03

2710 reflections

180 parameters

1 restraint

H-atom parameters constrained

Δρmax = 2.07 e Å−3

Δρmin = −1.32 e Å−3

Absolute structure: Flack (1983 ▸), 1218 Friedel pairs

Absolute structure parameter: 0.34 (2)

Data collection: RAPID-AUTO (Rigaku, 2010 ▸); cell refinement: RAPID-AUTO; data reduction: RAPID-AUTO; program(s) used to solve structure: SIR92 (Altomare et al., 1994 ▸); program(s) used to refine structure: SHELXL97 (Sheldrick, 2015 ▸); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▸); software used to prepare material for publication: PLATON (Spek, 2009 ▸) and publCIF (Westrip, 2010 ▸).

Crystal structure: contains datablock(s) Global, I. DOI: 10.1107/S2056989015002236/su5071sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015002236/su5071Isup2.hkl

Click here for additional data file.

x y z . DOI: 10.1107/S2056989015002236/su5071fig1.tif

A view of the mol­ecular structure of the title complex, with atom labelling (symmetry code: (i) −x + 1, y, −z). Displacement ellipsoids are drawn at the 50% probability level.

Click here for additional data file.

b . DOI: 10.1107/S2056989015002236/su5071fig2.tif

Crystal packing of the title complex viewed along the b axis.

CCDC reference: 1046981

Additional supporting information: crystallographic information; 3D view; checkCIF report

[Pd(C15H21N2S2)2]	Z = 2
Mr = 693.32	F(000) = 720
Monoclinic, C2	Dx = 1.405 Mg m−3
Hall symbol: C 2y	Cu Kα radiation, λ = 1.54187 Å
a = 18.3559 (11) Å	θ = 4.8–67.0°
b = 9.6747 (5) Å	µ = 7.14 mm−1
c = 10.3368 (6) Å	T = 173 K
β = 116.810 (2)°	Prism, orange
V = 1638.37 (16) Å3	0.25 × 0.16 × 0.11 mm

Rigaku R-AXIS RAPID diffractometer	2710 independent reflections
Radiation source: fine-focus sealed tube	2121 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.120
Detector resolution: 10.000 pixels mm-1	θmax = 65.1°, θmin = 4.8°
ω scans	h = −21→21
Absorption correction: multi-scan (ABSCOR; Rigaku, 1995)	k = −11→11
Tmin = 0.268, Tmax = 0.507	l = −12→12
9318 measured reflections

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)] = 0.091	H-atom parameters constrained
wR(F2) = 0.225	w = 1/[σ2(Fo2) + (0.1251P)2] where P = (Fo2 + 2Fc2)/3
S = 1.03	(Δ/σ)max < 0.001
2710 reflections	Δρmax = 2.07 e Å−3
180 parameters	Δρmin = −1.31 e Å−3
1 restraint	Absolute structure: Flack (1983), 1218 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.34 (2)

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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	0.5000	0.5495	0.0000	0.0607 (4)
S1	0.4807 (3)	0.3802 (4)	0.1325 (5)	0.0725 (11)
S2	0.4003 (2)	0.3956 (4)	0.3156 (4)	0.0726 (9)
N1	0.4949 (7)	0.6818 (12)	0.1634 (13)	0.060 (3)
N2	0.4526 (9)	0.6244 (17)	0.2347 (16)	0.071 (4)
C1	0.7185 (10)	1.1510 (17)	0.0408 (17)	0.087 (4)
H1A	0.7670	1.1034	0.0465	0.130*
H1B	0.7353	1.2327	0.1036	0.130*
H1C	0.6839	1.1796	−0.0594	0.130*
C2	0.6712 (6)	1.0545 (19)	0.0900 (11)	0.063 (3)
C3	0.6745 (8)	0.9122 (16)	0.0758 (15)	0.072 (4)
H3	0.7083	0.8746	0.0369	0.086*
C4	0.6290 (7)	0.8236 (13)	0.1178 (14)	0.062 (3)
H4	0.6339	0.7262	0.1124	0.075*
C5	0.5759 (7)	0.8797 (13)	0.1679 (13)	0.061 (3)
C6	0.5741 (8)	1.0255 (14)	0.1841 (14)	0.070 (4)
H6	0.5412	1.0656	0.2234	0.084*
C7	0.6196 (8)	1.1052 (14)	0.1431 (14)	0.071 (3)
H7	0.6161	1.2025	0.1509	0.085*
C8	0.5215 (8)	0.7962 (12)	0.2045 (14)	0.062 (3)
H8	0.5048	0.8378	0.2700	0.074*
C9	0.4449 (11)	0.4926 (16)	0.2274 (18)	0.059 (4)
C10	0.3742 (9)	0.529 (2)	0.4125 (15)	0.080 (5)
H10A	0.4242	0.5722	0.4885	0.096*
H10B	0.3406	0.6025	0.3449	0.096*
C11	0.3247 (9)	0.4534 (18)	0.4821 (16)	0.081 (4)
H11A	0.2809	0.3981	0.4062	0.097*
H11B	0.3617	0.3886	0.5571	0.097*
C12	0.2885 (8)	0.545 (2)	0.5472 (14)	0.081 (3)
H12A	0.2580	0.6183	0.4765	0.097*
H12B	0.3327	0.5904	0.6324	0.097*
C13	0.2311 (9)	0.4735 (19)	0.5952 (19)	0.091 (5)
H13A	0.1951	0.4112	0.5161	0.109*
H13B	0.2642	0.4148	0.6800	0.109*
C14	0.1813 (12)	0.559 (3)	0.632 (2)	0.133 (7)
H14A	0.1500	0.6224	0.5504	0.160*
H14B	0.2165	0.6168	0.7170	0.160*
C15	0.1205 (10)	0.475 (2)	0.670 (2)	0.110 (6)
H15A	0.0888	0.5391	0.6982	0.165*
H15B	0.1512	0.4118	0.7499	0.165*
H15C	0.0835	0.4224	0.5845	0.165*

	U11	U22	U33	U12	U13	U23
Pd1	0.0664 (7)	0.0506 (7)	0.0761 (7)	0.000	0.0419 (5)	0.000
S1	0.093 (3)	0.051 (2)	0.095 (3)	0.001 (2)	0.062 (2)	0.004 (2)
S2	0.084 (2)	0.059 (2)	0.092 (2)	−0.0072 (17)	0.0542 (19)	0.0009 (17)
N1	0.055 (6)	0.057 (7)	0.076 (7)	−0.011 (5)	0.037 (6)	0.006 (5)
N2	0.067 (8)	0.072 (9)	0.091 (9)	−0.027 (7)	0.050 (7)	−0.017 (7)
C1	0.081 (9)	0.094 (12)	0.096 (11)	−0.013 (8)	0.048 (9)	0.004 (8)
C2	0.063 (6)	0.054 (7)	0.073 (6)	0.014 (9)	0.032 (5)	−0.003 (9)
C3	0.063 (8)	0.084 (11)	0.086 (9)	0.003 (7)	0.048 (7)	−0.002 (7)
C4	0.058 (6)	0.048 (7)	0.082 (8)	0.003 (5)	0.034 (6)	0.003 (6)
C5	0.060 (7)	0.052 (7)	0.076 (8)	0.000 (6)	0.036 (6)	0.001 (5)
C6	0.076 (7)	0.053 (10)	0.093 (8)	0.001 (7)	0.048 (7)	−0.005 (6)
C7	0.074 (8)	0.055 (8)	0.080 (9)	−0.004 (6)	0.032 (7)	0.011 (6)
C8	0.079 (8)	0.030 (6)	0.096 (9)	0.006 (6)	0.057 (7)	0.005 (6)
C9	0.068 (9)	0.052 (9)	0.063 (9)	−0.004 (7)	0.034 (7)	0.000 (6)
C10	0.085 (8)	0.090 (14)	0.081 (8)	−0.017 (10)	0.053 (7)	0.007 (9)
C11	0.084 (9)	0.083 (11)	0.086 (10)	−0.009 (8)	0.048 (8)	0.002 (8)
C12	0.084 (7)	0.088 (9)	0.081 (7)	−0.019 (12)	0.047 (6)	−0.019 (12)
C13	0.082 (10)	0.104 (12)	0.109 (12)	0.010 (9)	0.063 (9)	0.002 (9)
C14	0.162 (16)	0.118 (16)	0.150 (15)	0.043 (19)	0.098 (14)	−0.003 (17)
C15	0.106 (12)	0.112 (14)	0.160 (17)	−0.024 (10)	0.102 (13)	−0.010 (11)

Pd1—N1	2.154 (12)	C6—C7	1.337 (16)
Pd1—N1i	2.154 (12)	C6—H6	0.9500
Pd1—S1	2.264 (4)	C7—H7	0.9500
Pd1—S1i	2.264 (4)	C8—H8	0.9500
S1—C9	1.777 (17)	C10—C11	1.573 (19)
S2—C9	1.747 (16)	C10—H10A	0.9900
S2—C10	1.829 (18)	C10—H10B	0.9900
N1—C8	1.208 (16)	C11—C12	1.44 (2)
N1—N2	1.404 (17)	C11—H11A	0.9900
N2—C9	1.282 (15)	C11—H11B	0.9900
C1—C2	1.511 (19)	C12—C13	1.52 (2)
C1—H1A	0.9800	C12—H12A	0.9900
C1—H1B	0.9800	C12—H12B	0.9900
C1—H1C	0.9800	C13—C14	1.41 (2)
C2—C7	1.381 (16)	C13—H13A	0.9900
C2—C3	1.39 (2)	C13—H13B	0.9900
C3—C4	1.397 (18)	C14—C15	1.56 (3)
C3—H3	0.9500	C14—H14A	0.9900
C4—C5	1.403 (16)	C14—H14B	0.9900
C4—H4	0.9500	C15—H15A	0.9800
C5—C6	1.423 (17)	C15—H15B	0.9800
C5—C8	1.460 (16)	C15—H15C	0.9800
N1—Pd1—N1i	107.1 (6)	N2—C9—S2	124.7 (15)
N1—Pd1—S1	83.2 (3)	N2—C9—S1	125.6 (15)
N1i—Pd1—S1	168.1 (3)	S2—C9—S1	109.6 (9)
N1—Pd1—S1i	168.1 (3)	C11—C10—S2	105.5 (13)
N1i—Pd1—S1i	83.2 (3)	C11—C10—H10A	110.6
S1—Pd1—S1i	87.3 (2)	S2—C10—H10A	110.6
C9—S1—Pd1	95.1 (5)	C11—C10—H10B	110.6
C9—S2—C10	101.8 (7)	S2—C10—H10B	110.6
C8—N1—N2	114.2 (12)	H10A—C10—H10B	108.8
C8—N1—Pd1	131.8 (10)	C12—C11—C10	114.0 (15)
N2—N1—Pd1	114.0 (9)	C12—C11—H11A	108.7
C9—N2—N1	115.8 (16)	C10—C11—H11A	108.7
C2—C1—H1A	109.5	C12—C11—H11B	108.7
C2—C1—H1B	109.5	C10—C11—H11B	108.7
H1A—C1—H1B	109.5	H11A—C11—H11B	107.6
C2—C1—H1C	109.5	C11—C12—C13	113.9 (18)
H1A—C1—H1C	109.5	C11—C12—H12A	108.8
H1B—C1—H1C	109.5	C13—C12—H12A	108.8
C7—C2—C3	117.7 (14)	C11—C12—H12B	108.8
C7—C2—C1	121.0 (16)	C13—C12—H12B	108.8
C3—C2—C1	121.2 (12)	H12A—C12—H12B	107.7
C2—C3—C4	120.9 (12)	C14—C13—C12	116.7 (19)
C2—C3—H3	119.5	C14—C13—H13A	108.1
C4—C3—H3	119.5	C12—C13—H13A	108.1
C3—C4—C5	119.4 (12)	C14—C13—H13B	108.1
C3—C4—H4	120.3	C12—C13—H13B	108.1
C5—C4—H4	120.3	H13A—C13—H13B	107.3
C4—C5—C6	118.9 (11)	C13—C14—C15	112 (2)
C4—C5—C8	123.5 (11)	C13—C14—H14A	109.1
C6—C5—C8	117.6 (11)	C15—C14—H14A	109.1
C7—C6—C5	118.9 (12)	C13—C14—H14B	109.1
C7—C6—H6	120.5	C15—C14—H14B	109.1
C5—C6—H6	120.5	H14A—C14—H14B	107.8
C6—C7—C2	124.0 (14)	C14—C15—H15A	109.5
C6—C7—H7	118.0	C14—C15—H15B	109.5
C2—C7—H7	118.0	H15A—C15—H15B	109.5
N1—C8—C5	129.2 (12)	C14—C15—H15C	109.5
N1—C8—H8	115.4	H15A—C15—H15C	109.5
C5—C8—H8	115.4	H15B—C15—H15C	109.5