Redetermination of catena-poly[[chloridolead(II)]-μ2-chlorido-di-μ2-thio­urea-κ4S:S] at 100 K

Zouihri, H.; Yamni, K.; Messouss, Y.; Tijani, N.; Messaoudi, L.

doi:10.1107/S2414314616017454

metal-organic compounds

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ISSN: 2414-3146

Volume 1| Part 11| November 2016| x161745

https://doi.org/10.1107/S2414314616017454

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Redetermination of catena-poly[[chloridolead(II)]-μ₂-chlorido-di-μ₂-thiourea-κ⁴S:S] at 100 K

Hafid Zouihri,^a ^* Khalid Yamni,^a Youssef Messouss,^b Najib Tijani ^a and Lahcen Messaoudi ^a

^aLaboratoire de Chimie des Matériaux et Biotechnologie des Produits Naturels, E.Ma.Me.P.S., Université Moulay Ismail, Faculté des Sciences, Meknès, Morocco, and ^bCentre National de l'Energie, des Sciences et des Techniques Nucléaires, CNESTEN, BP 1382 R.P. Rabat, Morocco
^*Correspondence e-mail: hafid.zouihri@gmail.com

Edited by M. Weil, Vienna University of Technology, Austria (Received 12 October 2016; accepted 31 October 2016; online 8 November 2016)

Although the structure rerefinement (CCD data at 100 K) of the polymeric lead(II) thiourea complex, [PbCl₂·2tu]_n where (tu = SCN₂H₄), basically confirmed the previous study based on integrated Weissenberg data recorded at room temperature [Nardelli & Fava (1959 ). Acta Cryst. 12, 727–732]; all atomic positions could be determined with significantly higher precision and accuracy. In addition, all H atoms could be located from difference maps, revealing details of the hydrogen-bonding scheme.

Keywords: crystal structure; redetermination; polymeric lead thiourea salt.

CCDC reference: 1513661

Structure description

A survey in the Cambridge Structural Database (Groom et al., 2016 ) shows that the interaction of thiourea (tu) with lead(II) can result in a variety of different compounds and types of coordination. A sixfold coordination of lead by thiourea is found in triclinic Pb(ClO₄)₂·6tu (Goldberg & Herbstein, 1972 ), sevenfold coordination in PbCl₂·2tu (Nardelli & Fava, 1959) – which is redetermined in the present work – and eightfold coordination in PbH(COO)₂·4tu·H₂O (Goldberg & Herbstein, 1973 ) or Pb(CHOO)₂·2tu (Nardelli et al., 1960 ).

The crystal structure of the title compound comprises an infinite polymeric chain propagating along the b-axis direction (Fig. 1) in which the Pb^II ions are linked by six bridging atoms, namely four S atoms from two pairs of symmetry-related thiourea ligands and by two symmetry-related Cl⁻ anions. The distorted sevenfold coordination is completed by another terminal Cl⁻ anion. The resulting [PbS₄Cl₃] polyhedron can be derived from a distorted trigonal prism formed by four S and two Cl atoms that is capped on one of the lateral faces by another Cl atom. In comparison with the previous determination of the title compound (Nardelli & Fava, 1959) that was based on integrated Weissenberg data (room-temperature measurement), the current redetermination reveals not only a higher precision but also a significantly higher accuracy, in particular for the C=S, C—C and C—N bond lengths (Table 1). In contrast to the previous study, the H atoms could be determined in the current study. All of them are involved in hydrogen-bonding interactions. Intra-chain N—H⋯Cl hydrogen bonds as well as interchain N—H⋯Cl and N—H⋯S hydrogen bonds (Table 2) are observed in the crystal, leading to a three-dimensional network structure (Fig. 2).

Table 1
Comparison of bond lengths (Å) in the current and the previous (Nardelli & Fava, 1959) refinement of poly[μ₂-chlorido-chloridobis(μ₂-thiourea-κ²S:S)lead(II)]

For the previous refinement: a = 21.20 (4), b = 4.06 (1), c = 12.02 (2) Å; R = 0.114.

Bond	Current refinement	Previous refinement
Pb—Cl1	2.7451 (8)	2.75 (4)
Pb—Cl2	3.1708 (7)	3.17 (3)
Pb—Cl1ⁱ	3.1635 (7)	3.28 (3)
Pb—S1	3.0057 (7)	3.02 (3)
Pb—S1ⁱⁱ	3.0494 (7)	3.04 (3)
Pb—S2ⁱ	2.9923 (7)	3.10 (3)
Pb—S2	2.9494 (7)	2.92 (3)
S1—C1	1.732 (3)	1.68 (9)
S2—C2	1.739 (3)	1.78 (17)
C1—N1	1.322 (4)	1.40 (12)
C1—N2	1.328 (4)	1.35 (14)
C2—N3	1.320 (4)	1.32 (20)
C2—N4	1.323 (4)	1.34 (17)
Symmetry codes: (i) x, y + 1, z; (ii) x, y − 1, z.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H1A⋯Cl1ⁱ	0.86	2.53	3.299 (3)	150
N4—H1B⋯Cl2ⁱⁱ	0.86	2.50	3.336 (3)	163
N3—H2A⋯Cl1ⁱ	0.86	2.78	3.494 (4)	142
N3—H2A⋯S1ⁱⁱⁱ	0.86	2.85	3.421 (3)	126
N3—H2B⋯Cl1^iv	0.86	2.44	3.285 (3)	168
N1—H3A⋯Cl2^v	0.86	2.72	3.480 (4)	149
N1—H3A⋯S2^v	0.86	2.75	3.414 (3)	135
N1—H3B⋯Cl2^vi	0.86	2.37	3.232 (4)	175
N2—H4A⋯Cl2^v	0.86	2.49	3.304 (3)	159
N2—H4B⋯Cl1^vii	0.86	2.44	3.275 (3)	164
Symmetry codes: (i) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (ii) $[-x, -y, z-{\script{1\over 2}}]$ ; (iii) $[-x+{\script{1\over 2}}, y-{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (iv) x, y-1, z; (v) $[-x, -y, z+{\script{1\over 2}}]$ ; (vi) x, y+1, z; (vii) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Figure 1
The polymeric chain in the crystal structure of the title compound. Displacement ellipsoids are drawn at the 30% probability level. H atoms are represented as small spheres of arbitrary radii. [Symmetry codes: (a) x, y + 1, z; (b) x, y − 1, z.]

Figure 2
The crystal packing of the title compound viewed along the b axis. The coordination sphere around the Pb^II atom is given in the polyhedral representation; N—H⋯Cl and N–H⋯S hydrogen bonds are shown as dashed lines (see Table 2

for details).

Synthesis and crystallization

To obtain the title compound, (diaminomethylidene)sulfonium chloride–thiourea (3/2) (Zouihri, 2012 ) (1 mmol) in ethanol (10 ml) was added dropwise to an aqueous solution (5 ml) of lead chlorate (2 mmol). The resulting solution was allowed to stand at room temperature. After two weeks, colourless crystals with good quality were obtained from the filtrate and dried in air.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. The same atom labelling as in the previous study (Nardelli & Fava, 1959) was used for better comparison (Table 1). All hydrogen atoms could be localized in difference Fourier syntheses. The structure was refined as an inversion twin (Table 3), using 5385 Friedel pairs. Reflections (200) and (201) were omitted from the refinement due to obstruction from the beam stop.

Table 3
Experimental details

Crystal data
Chemical formula	[PbCl₂(CH₄N₂S)₂]
M_r	430.33
Crystal system, space group	Orthorhombic, Pna2₁
Temperature (K)	100
a, b, c (Å)	21.1951 (6), 4.0280 (1), 11.9433 (3)
V (Å³)	1019.65 (5)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	17.43
Crystal size (mm)	0.46 × 0.17 × 0.14

Data collection
Diffractometer	Bruker APEXII CCD detector
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )
T_min, T_max	0.040, 0.087
No. of measured, independent and observed [I > 2σ(I)] reflections	23237, 6206, 5867
R_int	0.032
(sin θ/λ)_max (Å⁻¹)	0.904

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.018, 0.041, 1.04
No. of reflections	6206
No. of parameters	101
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.18, −2.38
Absolute structure	Refined as an inversion twin
Absolute structure parameter	0.315 (4)
Computer programs: APEX2 and SAINT (Bruker, 2009 ), SHELXT (Sheldrick, 2015a ), SHELXL2014 (Sheldrick, 2015b ), PLATON (Spek, 2009 ) and publCIF (Westrip, 2010 ).

Structural data

CCDC reference: 1513661

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314616017454/wm4030sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314616017454/wm4030Isup2.hkl

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: publCIF (Westrip, 2010).

catena-Poly[[chloridolead(II)]-µ₂-chlorido-di-µ₂-thiourea-κ²S:S] top

Crystal data top

[PbCl₂(CH₄N₂S)₂]	D_x = 2.803 Mg m⁻³
M_r = 430.33	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pna2₁	Cell parameters from 318 reflections
a = 21.1951 (6) Å	θ = 1.5–28.3°
b = 4.0280 (1) Å	µ = 17.43 mm⁻¹
c = 11.9433 (3) Å	T = 100 K
V = 1019.65 (5) Å³	Prism, colourless
Z = 4	0.46 × 0.17 × 0.14 mm
F(000) = 784

Data collection top

Bruker APEXII CCD detector diffractometer	6206 independent reflections
Radiation source: fine-focus sealed tube	5867 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.032
ω and φ scans	θ_max = 40.0°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	h = −38→36
T_min = 0.040, T_max = 0.087	k = −7→5
23237 measured reflections	l = −21→21

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.018	w = 1/[σ²(F_o²) + (0.0121P)²] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.041	(Δ/σ)_max = 0.001
S = 1.04	Δρ_max = 1.18 e Å⁻³
6206 reflections	Δρ_min = −2.38 e Å⁻³
101 parameters	Absolute structure: Refined as an inversion twin
1 restraint	Absolute structure parameter: 0.315 (4)

Special details top

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. Refined as a 2-component inversion twin

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Pb	0.10368 (2)	0.29058 (2)	0.09284 (2)	0.00922 (2)
Cl1	0.23177 (4)	0.24529 (17)	0.06240 (7)	0.01151 (10)
Cl2	−0.01146 (3)	−0.21081 (15)	0.10426 (7)	0.01147 (13)
S2	0.09634 (4)	−0.20155 (16)	−0.08955 (7)	0.00909 (11)
S1	0.15296 (4)	0.78245 (15)	0.26068 (7)	0.00912 (11)
C1	0.10345 (13)	0.6395 (9)	0.3655 (3)	0.0122 (4)
C2	0.15858 (15)	−0.1690 (6)	−0.1838 (2)	0.0102 (4)
N3	0.21531 (14)	−0.2855 (6)	−0.1607 (3)	0.0145 (4)
H2A	0.2453	−0.2656	−0.2088	0.017*
H2B	0.2223	−0.3812	−0.0975	0.017*
N1	0.04268 (13)	0.5872 (8)	0.3479 (3)	0.0187 (5)
H3A	0.0195	0.5066	0.4004	0.022*
H3B	0.0263	0.6338	0.2839	0.022*
N2	0.12793 (14)	0.5659 (8)	0.4648 (2)	0.0185 (5)
H4A	0.1043	0.4854	0.5166	0.022*
H4B	0.1674	0.5988	0.4772	0.022*
N4	0.14795 (14)	−0.0218 (8)	−0.2809 (2)	0.0196 (5)
H1A	0.1780	−0.0023	−0.3289	0.024*
H1B	0.1110	0.0543	−0.2961	0.024*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Pb	0.00719 (4)	0.01007 (3)	0.01040 (4)	0.00009 (2)	0.00000 (5)	−0.00047 (9)
Cl1	0.0079 (3)	0.0156 (2)	0.0110 (2)	0.00059 (18)	0.0001 (2)	−0.00040 (17)
Cl2	0.0080 (2)	0.0163 (2)	0.0101 (4)	−0.00025 (15)	0.0003 (2)	−0.0017 (2)
S2	0.0074 (3)	0.0108 (2)	0.0090 (3)	−0.00018 (17)	0.0008 (2)	−0.00054 (19)
S1	0.0080 (3)	0.0107 (2)	0.0086 (3)	−0.00211 (18)	0.0000 (2)	0.0005 (2)
C1	0.0103 (12)	0.0157 (10)	0.0107 (11)	−0.0031 (8)	0.0007 (8)	0.0012 (9)
C2	0.0097 (11)	0.0118 (9)	0.0091 (10)	0.0014 (7)	0.0004 (9)	−0.0004 (7)
N3	0.0087 (11)	0.0224 (11)	0.0125 (11)	0.0045 (8)	0.0014 (9)	0.0029 (8)
N1	0.0075 (10)	0.0341 (14)	0.0146 (11)	−0.0044 (9)	−0.0003 (9)	0.0046 (11)
N2	0.0114 (12)	0.0343 (15)	0.0099 (10)	−0.0059 (10)	−0.0019 (9)	0.0063 (9)
N4	0.0127 (12)	0.0342 (14)	0.0119 (11)	0.0076 (10)	0.0033 (9)	0.0081 (10)

Geometric parameters (Å, º) top

Pb—Cl1	2.7451 (8)	C1—N2	1.328 (4)
Pb—S2	2.9494 (7)	C2—N3	1.320 (4)
Pb—S2ⁱ	2.9923 (7)	C2—N4	1.323 (4)
Pb—S1	3.0057 (7)	N3—H2A	0.8600
Pb—S1ⁱⁱ	3.0494 (7)	N3—H2B	0.8600
Pb—Cl2	3.1708 (7)	N1—H3A	0.8600
S2—C2	1.739 (3)	N1—H3B	0.8600
S2—Pbⁱⁱ	2.9924 (7)	N2—H4A	0.8600
S1—C1	1.732 (3)	N2—H4B	0.8600
S1—Pbⁱ	3.0493 (7)	N4—H1A	0.8600
C1—N1	1.322 (4)	N4—H1B	0.8600

Cl1—Pb—S2	84.82 (2)	Pb—S1—Pbⁱ	83.40 (2)
Cl1—Pb—S2ⁱ	90.03 (2)	N1—C1—N2	119.1 (3)
S2—Pb—S2ⁱ	85.36 (2)	N1—C1—S1	121.9 (3)
Cl1—Pb—S1	77.79 (2)	N2—C1—S1	118.9 (2)
S2—Pb—S1	162.54 (2)	N3—C2—N4	119.9 (3)
S2ⁱ—Pb—S1	93.035 (19)	N3—C2—S2	122.0 (2)
Cl1—Pb—S1ⁱⁱ	72.76 (2)	N4—C2—S2	118.2 (2)
S2—Pb—S1ⁱⁱ	93.01 (2)	C2—N3—H2A	120.0
S2ⁱ—Pb—S1ⁱⁱ	162.79 (2)	C2—N3—H2B	120.0
S1—Pb—S1ⁱⁱ	83.40 (2)	H2A—N3—H2B	120.0
Cl1—Pb—Cl2	136.433 (18)	C1—N1—H3A	120.0
S2—Pb—Cl2	64.09 (2)	C1—N1—H3B	120.0
S2ⁱ—Pb—Cl2	115.26 (2)	H3A—N1—H3B	120.0
S1—Pb—Cl2	131.19 (2)	C1—N2—H4A	120.0
S1ⁱⁱ—Pb—Cl2	78.92 (2)	C1—N2—H4B	120.0
C2—S2—Pb	112.77 (10)	H4A—N2—H4B	120.0
C2—S2—Pbⁱⁱ	118.89 (10)	C2—N4—H1A	120.0
Pb—S2—Pbⁱⁱ	85.36 (2)	C2—N4—H1B	120.0
C1—S1—Pb	92.99 (11)	H1A—N4—H1B	120.0
C1—S1—Pbⁱ	119.38 (11)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H1A···Cl1ⁱⁱⁱ	0.86	2.53	3.299 (3)	150
N4—H1B···Cl2^iv	0.86	2.50	3.336 (3)	163
N3—H2A···Cl1ⁱⁱⁱ	0.86	2.78	3.494 (4)	142
N3—H2A···S1^v	0.86	2.85	3.421 (3)	126
N3—H2B···Cl1ⁱⁱ	0.86	2.44	3.285 (3)	168
N1—H3A···Cl2^vi	0.86	2.72	3.480 (4)	149
N1—H3A···S2^vi	0.86	2.75	3.414 (3)	135
N1—H3B···Cl2ⁱ	0.86	2.37	3.232 (4)	175
N2—H4A···Cl2^vi	0.86	2.49	3.304 (3)	159
N2—H4B···Cl1^vii	0.86	2.44	3.275 (3)	164

Symmetry codes: (i) x, y+1, z; (ii) x, y−1, z; (iii) −x+1/2, y−1/2, z−1/2; (iv) −x, −y, z−1/2; (v) −x+1/2, y−3/2, z−1/2; (vi) −x, −y, z+1/2; (vii) −x+1/2, y+1/2, z+1/2.

Comparison of bond lengths (Å) in the current and the previous (Nardelli & Fava, 1959) refinement of poly[µ₂-chlorido-chloridobis(µ₂-thiourea-κ²S:S)lead(II)] top

For the previous refinement: a = 21.20 (4), b = 4.06 (1), c = 12.02 (2) Å; R = 0.114.

Bond	Current refinement	Previous refinement
Pb—Cl1	2.7451 (8)	2.75 (4)
Pb—Cl2	3.1708 (7)	3.17 (3)
Pb—Cl1ⁱ	3.1635 (7)	3.28 (3)
Pb—S1	3.0057 (7)	3.02 (3)
Pb—S1ⁱⁱ	3.0494 (7)	3.04 (3)
Pb—S2ⁱ	2.9923 (7)	3.10 (3)
Pb—S2	2.9494 (7)	2.92 (3)
S1—C1	1.732 (3)	1.68 (9)
S2—C2	1.739 (3)	1.78 (17)
C1—N1	1.322 (4)	1.40 (12)
C1—N2	1.328 (4)	1.35 (14)
C2—N3	1.320 (4)	1.32 (20)
C2—N4	1.323 (4)	1.34 (17)

Symmetry codes: (i) x, y + 1, z; (ii) x, y - 1, z.

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