Poly[di-μ2-acetato-κ4O:O′-μ3-thio­urea-κ3S:S:S-lead(II)]: a redetermination

Zouihri, H.; Ait Mouha, M.; Ba Mohamed, B.; Yamni, K.; Tijani, N.

doi:10.1107/S2414314616018927

metal-organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 1| Part 12| December 2016| x161892

https://doi.org/10.1107/S2414314616018927

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Poly[di-μ₂-acetato-κ⁴O:O′-μ₃-thiourea-κ³S:S:S-lead(II)]: a redetermination

Hafid Zouihri,^a ^* Mbark Ait Mouha,^a Bouchra Ba Mohamed,^a Khalid Yamni ^a and Najib Tijani ^a

^aLaboratoire de Chimie des Matériaux et Biotechnologie des Produits Naturels, E.Ma.Me.P.S, Université Moulay Ismail, Faculté des Sciences, Meknès, Morocco
^*Correspondence e-mail: hafid.zouihri@gmail.com

Edited by J. Simpson, University of Otago, New Zealand (Received 19 November 2016; accepted 27 November 2016; online 2 December 2016)

The structure of the title polymeric lead(II) thiourea complex, [Pb(CH₃O)₂{SC(NH₂)₂}]_n, has been redetermined at significantly higher precision using diffractometer data at 100 K. The previous determination used data obtained from multiple-film integrated Weissenberg photographs [Nardelli et al. (1960 ). Acta Cryst. 13, 898–904]. The main difference between the two models is in the precision of the bond lengths, angles and cell parameters. In the crystal, the eight-coordinate Pb^II atom is chelated by two carboxylate groups and bridged by three S atoms from thiourea ligands. The coordination sphere is completed by an O atom from a third carboxylate group, the second O atom of which binds to a neighbouring Pb^II atom, forming a polymeric chain that runs the a axis. Two of these chains are related by centres of symmetry. Intermolecular hydrogen bonds connect neighbouring chains to one another, generating a three-dimensional network.

Keywords: crystal structure; low temperature; polymeric lead thiourea salt.

CCDC reference: 1519430

Structure description

In the polymeric complex, [Pb(CH₃O)₂{SC(NH₂)₂}]_n, (Fig. 1) an infinite one-dimensional polymeric chain propagates along the a axis (Fig. 2) with the Pb^II ions chelated by the O atoms of two carboxylate groups and bridged by three S atoms from thiourea ligands related to a neighbouring Pb atom by a centre of symmetry. The eightfold coordination is completed by an oxygen atom from a third carboxylate group (Fig. 2). The Pb—O bond lengths range from 2.483 (2) to 2.626 (2) Å, while the two unique Pb—S bonds are 3.0701 (9) and 3.1121 (9) Å, respectively. The Pb atom is displaced out of the least-squares planes of the carboxylate groups (A = O1/C1/O2) and (B = O3/C3/O4) by 0.0038 (2) and 0.0078 (3) Å, respectively. The dihedral angles between the mean planes of thiourea ligands (S1/C5/N1/N2) and the carboxylate groups A and B are 6.93 (18) and 64.37 (19)°, respectively.

Figure 1
The polymeric chain in the structure of the title compound, showing the atom-labeling scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms are represented as small spheres of arbitrary radii. Atom labels with the suffix a, b and c are related to those with no suffix by the symmetry operations (i), (ii) and (iii) in Table 1

Figure 2
View of a polymeric chain of in the structure of the title compound. For clarity, the [PbO₅S₃] units are shown as polyhedra, the atoms of the organic ligands are represented as spheres of uniform size selected for each atom type. N—H⋯O and C—H⋯O hydrogen bonds within the chain are shown as dashed lines.

In the crystal, H atoms are involved in inter-chain N—H⋯O and intra-chain N—H⋯O and C—H⋯O hydrogen bonds. These link the polymeric chains and stabilize the crystal structure, forming a three-dimensional network (Fig. 3, Table 1).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2NB⋯O4ⁱ	0.86	1.99	2.836 (4)	169
N2—H2NA⋯O1ⁱⁱ	0.86	2.04	2.883 (4)	168
N1—H1NA⋯O2ⁱⁱⁱ	0.86	2.26	3.021 (4)	148
N1—H1NB⋯O3^iv	0.86	2.48	3.311 (4)	163
C4—H4A⋯O4	0.96	2.51	3.225 (5)	131
Symmetry codes: (i) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (ii) x+1, y, z; (iii) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (iv) -x+2, -y, -z.

Figure 3
The crystal packing of the title compound viewed along the a axis. N—H⋯O hydrogen bonds are shown as dashed lines (see Table 1

for details).

Synthesis and crystallization

The title compound was obtained from a mixture of (diaminomethylidene)sulfonium chloride/thiourea (3/2) (Zouihri, 2012 ) and lead acetate in a molar ratio of 1:1 in ethanol. The mixture was then left for slow evaporation and colourless crystals formed after four days.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. One reflection (011) with F_o <<< F_c, likely to have been affected by the beamstop, was omitted from the final refinement.

Table 2
Experimental details

Crystal data
Chemical formula	[Pb(C₂H₃O₂)₂(CH₄N₂S)]
M_r	401.40
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	100
a, b, c (Å)	4.4865 (2), 15.7001 (5), 13.6313 (5)
β (°)	91.481 (2)
V (Å³)	959.85 (6)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	17.78
Crystal size (mm)	0.32 × 0.27 × 0.13

Data collection
Diffractometer	Bruker APEXII CCD detector
Absorption correction	Multi-scan (SADABS; Bruker, 2009 )
T_min, T_max	0.005, 0.099
No. of measured, independent and observed [I > 2σ(I)] reflections	13626, 1893, 1824
R_int	0.036
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.015, 0.037, 1.08
No. of reflections	1893
No. of parameters	120
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.88, −1.22
Computer programs: APEX2 and SAINT (Bruker, 2009), SHELXT (Sheldrick, 2015a ), SHELXL2014 (Sheldrick, 2015b ), PLATON (Spek, 2009 ) and publCIF (Westrip, 2010 ).

Structural data

CCDC reference: 1519430

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314616018927/sj4071sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314616018927/sj4071Isup2.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).

Poly[di-µ₂-acetato-κ⁴O:O'-µ₃-thiourea-κ³S:S:S-lead(II)] top

Crystal data top

[Pb(C₂H₃O₂)₂(CH₄N₂S)]	F(000) = 736
M_r = 401.40	D_x = 2.778 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 4.4865 (2) Å	Cell parameters from 214 reflections
b = 15.7001 (5) Å	θ = 3.1–26.4°
c = 13.6313 (5) Å	µ = 17.78 mm⁻¹
β = 91.481 (2)°	T = 100 K
V = 959.85 (6) Å³	Prism, colourless
Z = 4	0.32 × 0.27 × 0.13 mm

Data collection top

Bruker APEXII CCD detector diffractometer	1893 independent reflections
Radiation source: fine-focus sealed tube	1824 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.036
ω and φ scans	θ_max = 26.0°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −5→5
T_min = 0.005, T_max = 0.099	k = −19→19
13626 measured reflections	l = −16→16

Refinement top

Refinement on F²	1 restraint
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.015	H-atom parameters constrained
wR(F²) = 0.037	w = 1/[σ²(F_o²) + (0.0115P)² + 1.9359P] where P = (F_o² + 2F_c²)/3
S = 1.08	(Δ/σ)_max = 0.001
1893 reflections	Δρ_max = 0.88 e Å⁻³
120 parameters	Δρ_min = −1.22 e Å⁻³

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.

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

	x	y	z	U_iso*/U_eq
Pb1	0.74423 (2)	0.09596 (2)	0.12971 (2)	0.01076 (6)
O2	1.0207 (5)	0.22282 (15)	0.19960 (18)	0.0179 (5)
O1	0.6719 (5)	0.24845 (16)	0.08699 (19)	0.0185 (5)
C1	0.8763 (7)	0.2736 (2)	0.1450 (2)	0.0148 (7)
C2	0.9506 (9)	0.3666 (2)	0.1503 (3)	0.0272 (8)
H2A	0.8392	0.3967	0.1002	0.041*
H2B	1.1601	0.3743	0.1406	0.041*
H2C	0.9001	0.3884	0.2135	0.041*
S1	1.22553 (19)	0.09283 (5)	−0.02631 (6)	0.01392 (17)
C3	1.3066 (7)	0.0675 (2)	0.2991 (3)	0.0156 (7)
O3	1.2009 (5)	0.02818 (15)	0.22544 (17)	0.0166 (5)
O4	0.5375 (6)	0.11365 (17)	0.29615 (19)	0.0204 (5)
C5	1.1245 (7)	0.1822 (2)	−0.0929 (2)	0.0127 (6)
N2	1.2377 (6)	0.25730 (18)	−0.0723 (2)	0.0154 (6)
H2NB	1.1832	0.3011	−0.1061	0.019*
H2NA	1.3665	0.2628	−0.0248	0.019*
N1	0.9253 (6)	0.1734 (2)	−0.1662 (2)	0.0194 (6)
H1NA	0.8702	0.2170	−0.2002	0.023*
H1NB	0.8516	0.1240	−0.1795	0.023*
C4	1.1663 (9)	0.0596 (3)	0.3979 (3)	0.0280 (8)
H4A	0.9607	0.0437	0.3892	0.042*
H4B	1.1793	0.1132	0.4316	0.042*
H4C	1.2695	0.0168	0.4359	0.042*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Pb1	0.01374 (8)	0.00827 (8)	0.01006 (8)	−0.00053 (4)	−0.00361 (5)	−0.00080 (4)
O2	0.0227 (12)	0.0117 (12)	0.0188 (13)	−0.0023 (9)	−0.0098 (10)	0.0009 (10)
O1	0.0213 (12)	0.0146 (12)	0.0191 (13)	−0.0020 (9)	−0.0092 (10)	−0.0023 (10)
C1	0.0189 (16)	0.0118 (16)	0.0136 (16)	−0.0018 (13)	−0.0015 (12)	−0.0016 (13)
C2	0.039 (2)	0.0124 (18)	0.029 (2)	−0.0067 (15)	−0.0150 (17)	0.0051 (15)
S1	0.0199 (4)	0.0078 (4)	0.0137 (4)	−0.0009 (3)	−0.0069 (3)	0.0015 (3)
C3	0.0180 (16)	0.0138 (16)	0.0146 (17)	0.0055 (13)	−0.0061 (13)	0.0008 (13)
O3	0.0219 (12)	0.0127 (12)	0.0147 (12)	0.0018 (9)	−0.0084 (9)	−0.0010 (9)
O4	0.0223 (13)	0.0199 (12)	0.0188 (13)	−0.0024 (10)	−0.0045 (10)	−0.0074 (10)
C5	0.0152 (14)	0.0142 (16)	0.0087 (15)	0.0019 (12)	−0.0009 (11)	0.0032 (12)
N2	0.0213 (14)	0.0115 (14)	0.0130 (14)	−0.0018 (11)	−0.0078 (11)	0.0046 (11)
N1	0.0225 (14)	0.0173 (15)	0.0180 (15)	−0.0014 (12)	−0.0086 (11)	0.0063 (12)
C4	0.0267 (19)	0.033 (2)	0.024 (2)	0.0037 (16)	−0.0017 (16)	0.0015 (17)

Geometric parameters (Å, º) top

Pb1—O1	2.483 (2)	S1—Pb1ⁱⁱ	3.1121 (9)
Pb1—O4	2.489 (3)	C3—O3	1.261 (4)
Pb1—O2	2.520 (2)	C3—O4ⁱⁱ	1.265 (4)
Pb1—O3	2.626 (2)	C3—C4	1.507 (5)
Pb1—C1	2.858 (3)	O4—C3ⁱ	1.265 (4)
Pb1—S1	3.0701 (9)	C5—N2	1.311 (4)
Pb1—S1ⁱ	3.1121 (9)	C5—N1	1.330 (4)
O2—C1	1.259 (4)	N2—H2NB	0.8600
O1—C1	1.259 (4)	N2—H2NA	0.8600
C1—C2	1.499 (5)	N1—H1NA	0.8600
C2—H2A	0.9600	N1—H1NB	0.8600
C2—H2B	0.9600	C4—H4A	0.9600
C2—H2C	0.9600	C4—H4B	0.9600
S1—C5	1.726 (3)	C4—H4C	0.9600

O1—Pb1—O4	93.25 (8)	C1—C2—H2C	109.5
O1—Pb1—O2	52.18 (8)	H2A—C2—H2C	109.5
O4—Pb1—O2	76.03 (8)	H2B—C2—H2C	109.5
O1—Pb1—O3	127.07 (8)	C5—S1—Pb1	99.88 (10)
O4—Pb1—O3	84.07 (8)	C5—S1—Pb1ⁱⁱ	121.89 (12)
O2—Pb1—O3	76.25 (7)	Pb1—S1—Pb1ⁱⁱ	93.05 (2)
O1—Pb1—S1	86.73 (6)	O3—C3—O4ⁱⁱ	123.1 (3)
O4—Pb1—S1	156.73 (6)	O3—C3—C4	120.9 (3)
O2—Pb1—S1	85.78 (6)	O4ⁱⁱ—C3—C4	115.9 (3)
O3—Pb1—S1	77.53 (5)	C3—O3—Pb1	118.0 (2)
C1—Pb1—S1	85.29 (7)	C3ⁱ—O4—Pb1	106.9 (2)
O1—Pb1—S1ⁱ	76.36 (6)	N2—C5—N1	120.3 (3)
O4—Pb1—S1ⁱ	109.57 (6)	N2—C5—S1	121.5 (3)
O2—Pb1—S1ⁱ	128.52 (6)	N1—C5—S1	118.2 (3)
O3—Pb1—S1ⁱ	153.29 (5)	C5—N2—H2NB	120.0
S1—Pb1—S1ⁱ	93.05 (2)	C5—N2—H2NA	120.0
C1—O2—Pb1	92.08 (19)	H2NB—N2—H2NA	120.0
C1—O1—Pb1	93.8 (2)	C5—N1—H1NA	120.0
O2—C1—O1	121.9 (3)	C5—N1—H1NB	120.0
O2—C1—C2	118.6 (3)	H1NA—N1—H1NB	120.0
O1—C1—C2	119.6 (3)	C3—C4—H4A	109.5
O2—C1—Pb1	61.80 (17)	C3—C4—H4B	109.5
O1—C1—Pb1	60.11 (17)	H4A—C4—H4B	109.5
C2—C1—Pb1	178.3 (3)	C3—C4—H4C	109.5
C1—C2—H2A	109.5	H4A—C4—H4C	109.5
C1—C2—H2B	109.5	H4B—C4—H4C	109.5
H2A—C2—H2B	109.5

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2NB···O4ⁱⁱⁱ	0.86	1.99	2.836 (4)	169
N2—H2NA···O1ⁱⁱ	0.86	2.04	2.883 (4)	168
N1—H1NA···O2^iv	0.86	2.26	3.021 (4)	148
N1—H1NB···O3^v	0.86	2.48	3.311 (4)	163
C4—H4A···O4	0.96	2.51	3.225 (5)	131

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

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