Bis[N-benzyl-N-(2-phenyl­eth­yl)dithio­carbamato-κ²S,S′]lead(II)

The mol­ecule of the title compound, [Pb(C₁₆H₁₆NS₂)₂], is located on a twofold rotation axis, which runs through the Pb^II atom. The two dithio­carbamate ligands coordinate the metal in a pyramidal configuration through the S atoms. The two phenyl rings of each dithocarbamate ligand are aligned at a dihedral angle of 78.4 (1)°. The mol­ecular conformation is stabilized by intra­molecular C—H...S inter­actions.

Key indicators

• Single-crystal X-ray study
• T = 292 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.028
• wR factor = 0.062
• Data-to-parameter ratio = 21.0

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for        C10
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600          8

Alert level G
PLAT005_ALERT_5_G No _iucr_refine_instructions_details in CIF ....          ?
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X)  Pb1    --  S1      ..        5.3 su
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600         24

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   2 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   3 ALERT level G = General information/check it is not something unexpected

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

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S1. Comment

The solid state structural chemistry of lead dithiocarbamates is rich and fascinating in that different structural motifs are found ranging from monomeric, dimeric, tetrameric to linear chain (Davidovich et al., 2010). Metal dithiocarbamate complexes have proven to be very successful as single source precursors for the preparation of metal sulfide nanoparticles (Picket & O'Brien, 2001; Srinivasan & Thirumaran, 2012). The title compound was also used as single source precursor for the synthesis of PbS nanoparticles (Sathiyaraj & Thirumaran, 2012). There is an indication that the molecular structure of the synthetic precursor may influence both the size and morphology of the nanoparticles (Green et al., 2004; Koh et al., 2003). In view of these importance we have undertaken the crystal structure determination of the title compound, and the results are presented here.

The X-ray study confirmed the molecular structure and atomic connectivity for (I), as illustrated in Fig. 1.

The structure consists of monomeric molecules composed of one Pb atom and two chelating dithiocarbamate ligands. The two dithiocarbamate ligands are coordinated through S atoms to the metal pyramidally and in each chelate ring one Pb-S bond is significantly shorter than other. The relative bond distances and angles for the title compound agree with the presence of an electron lone pair at an equatorial position of a distorted trigonal bipyramid PbS₄. Evidence for the presence of a stereochemically active electron lone pair of the lead atom has also been reported for other lead complexes (Davidovich et al., 2010).

The sum of the angles at N1 [359.8°] is in accordance with sp² hybridization. Two phenyl rings in dithiocarbmate ligand is make a dihedral angle of 78.4 (1) °.

In addition to the van der Waals interactions, the molecular structure is influenced only by intramolecular C—H···S hydrogen bonds involving atoms S1 and S2. (Fig. 2 and Table 1).

Related literature

For general background of the title compound, see: Davidovich et al. (2010); Picket & O'Brien (2001); Srinivasan & Thirumaran (2012); Sathiyaraj & Thirumaran (2012); Green et al. (2004); Koh et al. (2003). For the preparation, see: Sathiyaraj & Thirumaran (2012). For a related structure, see: Davidovich et al. (2010)

S2. Experimental

The title compound was prepared according to the literature procedure (Sathiyaraj & Thirumaran, 2012). Single crystals were obtained by slow evaporation of dichloromethane and acetone (1:1) solution of the title compound at room temperature.

S3. Refinement

H atoms were placed in idealized positions and allowed to ride on their parent atoms, with C—H distances of 0.93-0.97 Å, and Uiso(H) = 1.2U_eq(C) for H atoms.

Computing details

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures

	Fig. 1. The molecular structure of the title compound, showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. Molecular packing of the title compound, viewed along the b axis; H-bonds are shown as dashed lines. For the sake of clarity, H atoms, not involved in hydrogen bonds, have been omitted.

Bis[N-benzyl-N-(2-phenylethyl)dithiocarbamato- κ²S,S']lead(II)

Crystal data

[Pb(C16H16NS2)2]	F(000) = 1536
Mr = 780.03	Dx = 1.725 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 5527 reflections
a = 28.5467 (12) Å	θ = 1.5–28.3°
b = 5.5321 (2) Å	µ = 5.92 mm^−1
c = 19.4158 (8) Å	T = 292 K
β = 101.600 (2)°	Block, brown
V = 3003.6 (2) Å^3	0.20 × 0.20 × 0.20 mm
Z = 4

Data collection

Bruker SMART APEXII area-detector diffractometer	3711 independent reflections
Radiation source: fine-focus sealed tube	3006 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.038
ω and ϕ scans	θmax = 28.3°, θmin = 1.5°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −37→31
Tmin = 0.384, Tmax = 0.384	k = −7→7
13027 measured reflections	l = −25→25

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)] = 0.028	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.062	H-atom parameters constrained
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0254P)^2 + 1.657P] where P = (Fo^2 + 2Fc^2)/3
3711 reflections	(Δ/σ)max = 0.001
177 parameters	Δρmax = 0.43 e Å^−3
0 restraints	Δρmin = −1.25 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
Pb1	1.0000	1.14280 (3)	0.7500	0.05084 (8)
S1	0.99115 (3)	0.94809 (17)	0.61154 (4)	0.04494 (19)
S2	0.93213 (3)	0.80487 (16)	0.71424 (4)	0.0473 (2)
N1	0.92789 (9)	0.5899 (4)	0.59107 (12)	0.0373 (6)
C1	0.94871 (10)	0.7651 (6)	0.63419 (14)	0.0339 (6)
C2	0.94211 (11)	0.5417 (6)	0.52408 (15)	0.0440 (7)
H2A	0.9397	0.3691	0.5153	0.053*
H2B	0.9755	0.5862	0.5287	0.053*
C3	0.91358 (11)	0.6706 (5)	0.46061 (15)	0.0343 (6)
C4	0.88722 (12)	0.8758 (5)	0.46490 (17)	0.0427 (7)
H4	0.8853	0.9369	0.5089	0.051*
C5	0.86360 (12)	0.9926 (6)	0.40547 (17)	0.0498 (8)
H5	0.8460	1.1317	0.4095	0.060*
C6	0.86593 (13)	0.9041 (7)	0.34018 (18)	0.0571 (10)
H6	0.8501	0.9832	0.2999	0.069*
C7	0.89154 (14)	0.6993 (8)	0.33484 (17)	0.0569 (10)
H7	0.8931	0.6391	0.2906	0.068*
C8	0.91528 (12)	0.5799 (6)	0.39433 (16)	0.0453 (8)
H8	0.9323	0.4393	0.3900	0.054*
C9	0.89245 (11)	0.4222 (6)	0.61033 (17)	0.0419 (7)
H9A	0.8957	0.4225	0.6610	0.050*
H9B	0.8992	0.2598	0.5962	0.050*
C10	0.84215 (12)	0.4865 (8)	0.5771 (2)	0.0612 (10)
H10A	0.8382	0.4756	0.5264	0.073*
H10B	0.8360	0.6523	0.5888	0.073*
C11	0.80629 (12)	0.3225 (6)	0.60110 (19)	0.0492 (8)
C12	0.78865 (14)	0.1181 (7)	0.5636 (2)	0.0564 (9)
H12	0.8000	0.0762	0.5236	0.068*
C13	0.75473 (12)	−0.0232 (7)	0.58444 (19)	0.0542 (9)
H13	0.7434	−0.1599	0.5585	0.065*
C14	0.73735 (13)	0.0338 (7)	0.6428 (2)	0.0579 (9)
H14	0.7137	−0.0608	0.6561	0.070*
C15	0.75511 (14)	0.2325 (8)	0.68166 (19)	0.0629 (10)
H15	0.7439	0.2719	0.7220	0.075*
C16	0.78937 (14)	0.3730 (6)	0.6612 (2)	0.0584 (10)
H16	0.8015	0.5057	0.6885	0.070*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Pb1	0.05114 (13)	0.03239 (11)	0.05977 (12)	0.000	−0.01087 (8)	0.000
S1	0.0350 (4)	0.0494 (5)	0.0505 (4)	−0.0041 (4)	0.0088 (3)	0.0104 (4)
S2	0.0515 (5)	0.0542 (5)	0.0374 (4)	−0.0131 (4)	0.0120 (4)	−0.0068 (4)
N1	0.0362 (14)	0.0397 (14)	0.0366 (12)	−0.0003 (11)	0.0088 (11)	−0.0024 (11)
C1	0.0303 (15)	0.0344 (15)	0.0355 (14)	0.0031 (13)	0.0033 (12)	0.0036 (13)
C2	0.0473 (19)	0.0463 (18)	0.0398 (15)	0.0094 (16)	0.0121 (14)	−0.0061 (15)
C3	0.0352 (16)	0.0323 (16)	0.0381 (14)	−0.0058 (12)	0.0142 (13)	−0.0051 (12)
C4	0.0476 (19)	0.0378 (18)	0.0431 (16)	−0.0015 (14)	0.0100 (14)	−0.0079 (14)
C5	0.054 (2)	0.0366 (19)	0.0565 (19)	0.0008 (15)	0.0067 (16)	0.0025 (16)
C6	0.055 (2)	0.068 (3)	0.0470 (19)	−0.0091 (19)	0.0068 (17)	0.0178 (18)
C7	0.062 (2)	0.075 (3)	0.0374 (17)	−0.008 (2)	0.0185 (17)	−0.0050 (17)
C8	0.0453 (19)	0.0483 (19)	0.0460 (17)	−0.0039 (15)	0.0182 (15)	−0.0098 (15)
C9	0.0423 (18)	0.0355 (16)	0.0459 (16)	0.0000 (14)	0.0045 (14)	−0.0028 (14)
C10	0.041 (2)	0.067 (3)	0.076 (2)	0.0087 (18)	0.0135 (18)	0.030 (2)
C11	0.0356 (18)	0.052 (2)	0.061 (2)	0.0064 (15)	0.0116 (16)	0.0140 (17)
C12	0.052 (2)	0.063 (3)	0.057 (2)	0.0107 (18)	0.0173 (18)	−0.0014 (19)
C13	0.049 (2)	0.043 (2)	0.066 (2)	−0.0022 (16)	0.0033 (17)	−0.0008 (18)
C14	0.047 (2)	0.057 (2)	0.071 (2)	−0.0051 (18)	0.0141 (19)	0.016 (2)
C15	0.069 (3)	0.069 (3)	0.058 (2)	−0.007 (2)	0.029 (2)	−0.001 (2)
C16	0.058 (2)	0.054 (2)	0.063 (2)	−0.0103 (17)	0.0127 (19)	−0.0096 (17)

Geometric parameters (Å, º)

Pb1—S2^i	2.6813 (8)	C7—C8	1.384 (5)
Pb1—S2	2.6813 (8)	C7—H7	0.9300
Pb1—S1^i	2.8597 (9)	C8—H8	0.9300
Pb1—S1	2.8597 (9)	C9—C10	1.494 (4)
S1—C1	1.703 (3)	C9—H9A	0.9700
S2—C1	1.727 (3)	C9—H9B	0.9700
N1—C1	1.339 (4)	C10—C11	1.510 (5)
N1—C2	1.463 (4)	C10—H10A	0.9700
N1—C9	1.475 (4)	C10—H10B	0.9700
C2—C3	1.512 (4)	C11—C16	1.378 (5)
C2—H2A	0.9700	C11—C12	1.384 (5)
C2—H2B	0.9700	C12—C13	1.368 (5)
C3—C4	1.373 (4)	C12—H12	0.9300
C3—C8	1.391 (4)	C13—C14	1.362 (5)
C4—C5	1.375 (4)	C13—H13	0.9300
C4—H4	0.9300	C14—C15	1.372 (6)
C5—C6	1.373 (5)	C14—H14	0.9300
C5—H5	0.9300	C15—C16	1.369 (5)
C6—C7	1.363 (5)	C15—H15	0.9300
C6—H6	0.9300	C16—H16	0.9300
S2^i—Pb1—S2	91.59 (4)	C8—C7—H7	119.6
S2^i—Pb1—S1^i	64.61 (2)	C7—C8—C3	119.8 (3)
S2—Pb1—S1^i	84.46 (2)	C7—C8—H8	120.1
S2^i—Pb1—S1	84.46 (2)	C3—C8—H8	120.1
S2—Pb1—S1	64.61 (2)	N1—C9—C10	112.9 (3)
S1^i—Pb1—S1	135.74 (4)	N1—C9—H9A	109.0
C1—S1—Pb1	85.08 (10)	C10—C9—H9A	109.0
C1—S2—Pb1	90.43 (11)	N1—C9—H9B	109.0
C1—N1—C2	121.3 (3)	C10—C9—H9B	109.0
C1—N1—C9	122.5 (2)	H9A—C9—H9B	107.8
C2—N1—C9	116.0 (2)	C9—C10—C11	112.1 (3)
N1—C1—S1	121.2 (2)	C9—C10—H10A	109.2
N1—C1—S2	119.2 (2)	C11—C10—H10A	109.2
S1—C1—S2	119.63 (17)	C9—C10—H10B	109.2
N1—C2—C3	116.0 (2)	C11—C10—H10B	109.2
N1—C2—H2A	108.3	H10A—C10—H10B	107.9
C3—C2—H2A	108.3	C16—C11—C12	117.3 (3)
N1—C2—H2B	108.3	C16—C11—C10	121.0 (3)
C3—C2—H2B	108.3	C12—C11—C10	121.7 (3)
H2A—C2—H2B	107.4	C13—C12—C11	121.1 (3)
C4—C3—C8	118.4 (3)	C13—C12—H12	119.5
C4—C3—C2	123.5 (3)	C11—C12—H12	119.5
C8—C3—C2	118.1 (3)	C14—C13—C12	120.8 (3)
C3—C4—C5	121.3 (3)	C14—C13—H13	119.6
C3—C4—H4	119.3	C12—C13—H13	119.6
C5—C4—H4	119.3	C13—C14—C15	119.2 (3)
C6—C5—C4	120.0 (3)	C13—C14—H14	120.4
C6—C5—H5	120.0	C15—C14—H14	120.4
C4—C5—H5	120.0	C16—C15—C14	120.1 (3)
C7—C6—C5	119.5 (3)	C16—C15—H15	119.9
C7—C6—H6	120.2	C14—C15—H15	119.9
C5—C6—H6	120.2	C15—C16—C11	121.5 (3)
C6—C7—C8	120.9 (3)	C15—C16—H16	119.2
C6—C7—H7	119.6	C11—C16—H16	119.2
S2^i—Pb1—S1—C1	91.43 (10)	C3—C4—C5—C6	0.3 (5)
S2—Pb1—S1—C1	−2.98 (10)	C4—C5—C6—C7	0.4 (5)
S1^i—Pb1—S1—C1	47.21 (10)	C5—C6—C7—C8	−0.1 (6)
S2^i—Pb1—S2—C1	−80.18 (10)	C6—C7—C8—C3	−0.8 (5)
S1^i—Pb1—S2—C1	−144.48 (10)	C4—C3—C8—C7	1.4 (5)
S1—Pb1—S2—C1	2.93 (10)	C2—C3—C8—C7	−176.9 (3)
C2—N1—C1—S1	2.6 (4)	C1—N1—C9—C10	101.6 (3)
C9—N1—C1—S1	177.5 (2)	C2—N1—C9—C10	−83.3 (3)
C2—N1—C1—S2	−177.3 (2)	N1—C9—C10—C11	−176.3 (3)
C9—N1—C1—S2	−2.4 (4)	C9—C10—C11—C16	87.0 (4)
Pb1—S1—C1—N1	−175.1 (2)	C9—C10—C11—C12	−93.8 (4)
Pb1—S1—C1—S2	4.81 (16)	C16—C11—C12—C13	1.9 (5)
Pb1—S2—C1—N1	174.8 (2)	C10—C11—C12—C13	−177.3 (3)
Pb1—S2—C1—S1	−5.11 (17)	C11—C12—C13—C14	0.1 (5)
C1—N1—C2—C3	−92.9 (3)	C12—C13—C14—C15	−1.5 (6)
C9—N1—C2—C3	91.9 (3)	C13—C14—C15—C16	1.0 (6)
N1—C2—C3—C4	20.9 (5)	C14—C15—C16—C11	1.1 (6)
N1—C2—C3—C8	−160.9 (3)	C12—C11—C16—C15	−2.5 (5)
C8—C3—C4—C5	−1.1 (5)	C10—C11—C16—C15	176.7 (4)
C2—C3—C4—C5	177.0 (3)

Symmetry code: (i) −x+2, y, −z+3/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9A···S2	0.97	2.49	2.986 (3)	112
C2—H2B···S1	0.97	2.55	2.990 (4)	107