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

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.

Key indicators

• Single-crystal X-ray study
• T = 100 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.015
• wR factor = 0.037
• Data-to-parameter ratio = 15.8

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT232_ALERT_2_B Hirshfeld Test Diff (M-X)  Pb1    --  S1      ..       21.3 s.u.

Alert level C
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ....        2.3 Note
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600          3 Report
PLAT977_ALERT_2_C Check the Negative Difference Density on    H2NB      -0.32 eA-3

Alert level G
PLAT003_ALERT_2_G Number of Uiso or Uij Restrained non-H Atoms ...          2 Report
PLAT004_ALERT_5_G Polymeric Structure Found with Maximum Dimension          1 Info
PLAT007_ALERT_5_G Number of Unrefined Donor-H Atoms ..............          4 Report
PLAT066_ALERT_1_G Predicted and Reported Tmin&Tmax Range Identical          ? Check
PLAT177_ALERT_4_G The CIF-Embedded .res File Contains DELU Records          1 Report
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X)  Pb1    --  O1      ..        6.0 s.u.
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X)  Pb1    --  O4      ..        6.5 s.u.
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X)  Pb1    --  O3_a    ..       10.2 s.u.
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X)  Pb1    --  S1_c    ..        5.8 s.u.
PLAT720_ALERT_4_G Number of Unusual/Non-Standard Labels ..........          4 Note
PLAT860_ALERT_3_G Number of Least-Squares Restraints .............          1 Note
PLAT910_ALERT_3_G Missing # of FCF Reflection(s) Below Theta(Min)           1 Note
PLAT933_ALERT_2_G Number of OMIT records in Embedded RES .........          4 Note
PLAT961_ALERT_5_G Dataset Contains no Negative Intensities .......     Please Check
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density           1 Note

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

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

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Computing details

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)]

Crystal data

[Pb(C2H3O2)2(CH4N2S)]	F(000) = 736
Mr = 401.40	Dx = 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) Å^3	Prism, colourless
Z = 4	0.32 × 0.27 × 0.13 mm

Data collection

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

Refinement

Refinement on F^2	1 restraint
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.015	H-atom parameters constrained
wR(F^2) = 0.037	w = 1/[σ^2(Fo^2) + (0.0115P)^2 + 1.9359P] where P = (Fo^2 + 2Fc^2)/3
S = 1.08	(Δ/σ)max = 0.001
1893 reflections	Δρmax = 0.88 e Å^−3
120 parameters	Δρmin = −1.22 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Pb1—O1	2.483 (2)	S1—Pb1^ii	3.1121 (9)
Pb1—O4	2.489 (3)	C3—O3	1.261 (4)
Pb1—O2	2.520 (2)	C3—O4^ii	1.265 (4)
Pb1—O3	2.626 (2)	C3—C4	1.507 (5)
Pb1—C1	2.858 (3)	O4—C3^i	1.265 (4)
Pb1—S1	3.0701 (9)	C5—N2	1.311 (4)
Pb1—S1^i	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—Pb1^ii	121.89 (12)
O2—Pb1—O3	76.25 (7)	Pb1—S1—Pb1^ii	93.05 (2)
O1—Pb1—S1	86.73 (6)	O3—C3—O4^ii	123.1 (3)
O4—Pb1—S1	156.73 (6)	O3—C3—C4	120.9 (3)
O2—Pb1—S1	85.78 (6)	O4^ii—C3—C4	115.9 (3)
O3—Pb1—S1	77.53 (5)	C3—O3—Pb1	118.0 (2)
C1—Pb1—S1	85.29 (7)	C3^i—O4—Pb1	106.9 (2)
O1—Pb1—S1^i	76.36 (6)	N2—C5—N1	120.3 (3)
O4—Pb1—S1^i	109.57 (6)	N2—C5—S1	121.5 (3)
O2—Pb1—S1^i	128.52 (6)	N1—C5—S1	118.2 (3)
O3—Pb1—S1^i	153.29 (5)	C5—N2—H2NB	120.0
S1—Pb1—S1^i	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)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2NB···O4^iii	0.86	1.99	2.836 (4)	169
N2—H2NA···O1^ii	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.