metal-organic compounds
Redetermination of catena-poly[[chloridolead(II)]-μ2-chlorido-di-μ2-thiourea-κ4S:S] at 100 K
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
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.
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 b-axis direction (Fig. 1) in which the PbII 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).
of the title compound comprises an infinite polymeric chain propagating along the
|
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 . 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 (Table 3), using 5385 Friedel pairs. Reflections (200) and (201) were omitted from the due to obstruction from the beam stop.
details are summarized in Table 3
|
Structural data
CCDC reference: 1513661
https://doi.org/10.1107/S2414314616017454/wm4030sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314616017454/wm4030Isup2.hkl
Data collection: APEX2 (Bruker, 2009); cell
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).[PbCl2(CH4N2S)2] | Dx = 2.803 Mg m−3 |
Mr = 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 |
Bruker APEXII CCD detector diffractometer | 6206 independent reflections |
Radiation source: fine-focus sealed tube | 5867 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.032 |
ω and φ scans | θmax = 40.0°, θmin = 2.6° |
Absorption correction: multi-scan (SADABS; Krause et al., 2015) | h = −38→36 |
Tmin = 0.040, Tmax = 0.087 | k = −7→5 |
23237 measured reflections | l = −21→21 |
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(Fo2) + (0.0121P)2] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.041 | (Δ/σ)max = 0.001 |
S = 1.04 | Δρmax = 1.18 e Å−3 |
6206 reflections | Δρmin = −2.38 e Å−3 |
101 parameters | Absolute structure: Refined as an inversion twin |
1 restraint | Absolute structure parameter: 0.315 (4) |
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 |
x | y | z | Uiso*/Ueq | ||
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* |
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) |
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. |
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···Cl2iv | 0.86 | 2.50 | 3.336 (3) | 163 |
N3—H2A···Cl1iii | 0.86 | 2.78 | 3.494 (4) | 142 |
N3—H2A···S1v | 0.86 | 2.85 | 3.421 (3) | 126 |
N3—H2B···Cl1ii | 0.86 | 2.44 | 3.285 (3) | 168 |
N1—H3A···Cl2vi | 0.86 | 2.72 | 3.480 (4) | 149 |
N1—H3A···S2vi | 0.86 | 2.75 | 3.414 (3) | 135 |
N1—H3B···Cl2i | 0.86 | 2.37 | 3.232 (4) | 175 |
N2—H4A···Cl2vi | 0.86 | 2.49 | 3.304 (3) | 159 |
N2—H4B···Cl1vii | 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. |
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. |
References
Bruker (2009). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Goldberg, I. & Herbstein, F. H. (1972). Acta Cryst. B28, 410–415. CSD CrossRef IUCr Journals Web of Science Google Scholar
Goldberg, I. & Herbstein, F. H. (1973). Acta Cryst. B29, 246–250. CSD CrossRef IUCr Journals Web of Science Google Scholar
Groom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. (2016). Acta Cryst. B72, 171–179. Web of Science CSD CrossRef IUCr Journals Google Scholar
Krause, L., Herbst-Irmer, R., Sheldrick, G. M. & Stalke, D. (2015). J. Appl. Cryst. 48, 3–10. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Nardelli, M. & Fava, G. (1959). Acta Cryst. 12, 727–732. CSD CrossRef IUCr Journals Web of Science Google Scholar
Nardelli, M., Fava, G. & Branchi, G. (1960). Acta Cryst. 13, 898–904. CSD CrossRef IUCr Journals Web of Science Google Scholar
Sheldrick, G. M. (2015a). Acta Cryst. A71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2015b). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar
Zouihri, H. (2012). Acta Cryst. E68, o257. Web of Science CSD CrossRef IUCr Journals Google Scholar
This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.