A three-dimensional metal-organic polymer: poly[bis­([mu]₂-pyrimidine-2-thiol­ato-[kappa]⁴N¹,S:S,N³)lead(II)]

The title compound, [Pb(C₄H₃N₂S)₂]_n, was prepared by the reaction of [Pb(OAc)₂]·3H₂O (OAc is acetate) with pyrimidine-2-thione in the presence of tri­ethyl­amine in methanol. In the crystal structure, the Pb^II atom has an N₄S₄ coordination environment with four ligands coordinated by N- and S-donor atoms. This compound shows that the pyrimidine-2-thiol­ate anion can lead to a three-dimensional network when the coordination number of the metal ion can be higher than 6, as is the case with the Pb^II ion. This compound presents only covalent bonds, showing that despite the possibility of the hemidirected geometries of Pb^II, the eight-coordinated ion does not allow the formation of an isolated mol­ecular structure with pyrimidine-2-thiol­ate as the ligand.

Computing details

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2012); software used to prepare material for publication: WinGX (Farrugia, 2012) and PLATON (Spek, 2009).

Poly[bis(µ₂-pyrimidine-2-thiolato-κ⁴N¹,S:S,N³)lead(II)]

Crystal data

[Pb(C4H3N2S)2]	F(000) = 784
Mr = 429.48	Dx = 2.618 Mg m^−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 2815 reflections
a = 7.6296 (3) Å	θ = 2.9–29.4°
b = 7.8839 (3) Å	µ = 15.84 mm^−1
c = 18.1151 (8) Å	T = 296 K
V = 1089.64 (8) Å^3	Block, yellow
Z = 4	0.17 × 0.08 × 0.08 mm

Data collection

Bruker APEXII CCD diffractometer	2735 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.025
φ and ω scans	θmax = 29.7°, θmin = 2.3°
Absorption correction: gaussian (XPREP and SADABS; Bruker, 2008)	h = −10→10
Tmin = 0.882, Tmax = 1.000	k = −4→10
6643 measured reflections	l = −24→25
2998 independent reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.021	H-atom parameters constrained
wR(F^2) = 0.048	w = 1/[σ^2(Fo^2) + (0.0282P)^2 + 0.5627P] where P = (Fo^2 + 2Fc^2)/3
S = 0.69	(Δ/σ)max = 0.001
2998 reflections	Δρmax = 0.67 e Å^−3
136 parameters	Δρmin = −0.66 e Å^−3
0 restraints	Absolute structure: Flack (1983), with 1808 Friedel pairs
0 constraints	Absolute structure parameter: 0.000 (8)
Primary atom site location: structure-invariant direct methods

Special details

Experimental. Absorption correction: XPREP (Bruker, 2008) was used to perform the numeric absorption correction based onthe face-index crystal size. SADABS (Bruker, 2008) performed additional data scaling and corrections.

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s 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 > σ(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	0.45126 (2)	0.27672 (2)	0.873479 (9)	0.02505 (5)
S1	0.4556 (2)	0.58450 (16)	0.76287 (7)	0.0331 (3)
S2	0.6556 (2)	0.30154 (15)	1.01441 (7)	0.0369 (3)
N1	0.7368 (7)	0.4339 (6)	0.8168 (2)	0.0364 (10)
N2	0.7568 (7)	0.5361 (6)	0.6946 (3)	0.0399 (11)
N3	0.7376 (7)	−0.0152 (6)	1.0499 (2)	0.0392 (11)
N4	0.6244 (7)	0.0309 (5)	0.9300 (2)	0.0349 (10)
C1	0.6693 (7)	0.5123 (6)	0.7578 (3)	0.0286 (10)
C2	0.9030 (8)	0.3824 (9)	0.8128 (4)	0.0517 (17)
H2	0.9537	0.3307	0.8537	0.062*
C3	1.0002 (8)	0.4030 (10)	0.7509 (4)	0.0599 (19)
H3	1.1159	0.3663	0.7485	0.072*
C4	0.9207 (8)	0.4804 (9)	0.6919 (4)	0.0537 (17)
H4	0.9841	0.4944	0.6485	0.064*
C5	0.6754 (7)	0.0875 (6)	0.9967 (3)	0.0304 (11)
C6	0.7543 (9)	−0.1799 (7)	1.0328 (4)	0.0490 (16)
H6	0.7965	−0.2539	1.0686	0.059*
C7	0.7117 (9)	−0.2433 (7)	0.9647 (4)	0.0536 (17)
H7	0.727	−0.3575	0.9534	0.064*
C8	0.6458 (10)	−0.1319 (7)	0.9139 (3)	0.0451 (14)
H8	0.6153	−0.1711	0.8672	0.054*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Pb1	0.02997 (8)	0.02707 (7)	0.01812 (7)	0.00061 (7)	0.00028 (8)	0.00074 (6)
S1	0.0345 (6)	0.0378 (6)	0.0270 (6)	0.0044 (7)	0.0027 (7)	0.0065 (5)
S2	0.0526 (8)	0.0288 (6)	0.0293 (6)	0.0003 (6)	−0.0099 (6)	−0.0032 (5)
N1	0.037 (2)	0.047 (3)	0.026 (2)	−0.006 (2)	−0.011 (2)	0.0091 (19)
N2	0.038 (3)	0.049 (3)	0.033 (2)	0.006 (2)	0.007 (2)	0.013 (2)
N3	0.051 (3)	0.032 (2)	0.034 (2)	−0.001 (2)	−0.018 (2)	0.0072 (19)
N4	0.046 (3)	0.032 (2)	0.027 (2)	0.004 (2)	−0.005 (2)	−0.0033 (17)
C1	0.032 (2)	0.028 (2)	0.026 (2)	0.002 (2)	−0.003 (2)	0.0022 (19)
C2	0.044 (4)	0.057 (4)	0.054 (4)	0.003 (3)	−0.016 (3)	0.015 (3)
C3	0.029 (3)	0.078 (5)	0.073 (5)	0.007 (3)	0.003 (3)	0.026 (4)
C4	0.039 (4)	0.061 (4)	0.061 (4)	0.004 (3)	0.015 (3)	0.014 (3)
C5	0.030 (3)	0.031 (2)	0.031 (3)	−0.005 (2)	0.002 (2)	0.000 (2)
C6	0.045 (3)	0.033 (3)	0.070 (4)	0.001 (3)	−0.014 (3)	0.018 (3)
C7	0.062 (4)	0.026 (3)	0.073 (4)	−0.002 (3)	−0.006 (4)	−0.004 (3)
C8	0.061 (4)	0.037 (3)	0.037 (3)	0.002 (3)	−0.008 (3)	−0.006 (2)

Geometric parameters (Å, º)

Pb1—N1	2.709 (5)	N2—Pb1^iii	2.764 (5)
Pb1—N2^i	2.764 (5)	N3—C6	1.340 (7)
Pb1—N4	2.559 (5)	N3—C5	1.345 (6)
Pb1—N3^ii	2.849 (5)	N4—C8	1.327 (7)
Pb1—S1	3.1471 (12)	N4—C5	1.345 (6)
Pb1—S2	2.9976 (13)	C2—C3	1.353 (10)
Pb1—S1^i	2.9836 (12)	C2—H2	0.93
Pb1—S2^ii	3.0976 (14)	C3—C4	1.372 (9)
S1—C1	1.730 (5)	C3—H3	0.93
S1—Pb1^iii	2.9837 (12)	C4—H4	0.93
S2—C5	1.724 (5)	C6—C7	1.371 (9)
S2—Pb1^iv	3.0975 (14)	C6—H6	0.93
N1—C2	1.334 (8)	C7—C8	1.367 (8)
N1—C1	1.338 (6)	C7—H7	0.93
N2—C4	1.327 (8)	C8—H8	0.93
N2—C1	1.337 (6)
N4—Pb1—N1	94.75 (15)	C4—N2—Pb1^iii	138.7 (4)
N4—Pb1—N2^i	87.44 (16)	C1—N2—Pb1^iii	101.1 (3)
N1—Pb1—N2^i	127.35 (14)	C6—N3—C5	116.9 (5)
N4—Pb1—S1^i	79.84 (10)	C8—N4—C5	118.9 (5)
N1—Pb1—S1^i	74.17 (10)	C8—N4—Pb1	135.1 (4)
N2^i—Pb1—S1^i	54.45 (10)	C5—N4—Pb1	104.9 (3)
N4—Pb1—S2	55.96 (10)	N1—C2—C3	122.0 (6)
N1—Pb1—S2	82.79 (9)	N1—C2—H2	119
N2^i—Pb1—S2	136.35 (11)	C3—C2—H2	119
S1^i—Pb1—S2	127.90 (4)	C2—C3—C4	117.2 (6)
N4—Pb1—S2^ii	87.87 (12)	C2—C3—H3	121.4
N1—Pb1—S2^ii	157.73 (10)	C4—C3—H3	121.4
N2^i—Pb1—S2^ii	74.80 (10)	N2—C4—C3	122.3 (6)
S1^i—Pb1—S2^ii	127.96 (4)	N2—C4—H4	118.9
S2—Pb1—S2^ii	80.406 (12)	C3—C4—H4	118.9
N4—Pb1—S1	146.43 (12)	N2—C1—N1	123.8 (5)
N1—Pb1—S1	52.95 (10)	N2—C1—S1	118.0 (4)
N2^i—Pb1—S1	104.54 (11)	N1—C1—S1	118.2 (4)
S1^i—Pb1—S1	82.071 (12)	N3—C5—N4	123.0 (5)
S2—Pb1—S1	119.11 (4)	N3—C5—S2	119.2 (4)
S2^ii—Pb1—S1	125.36 (4)	N4—C5—S2	117.8 (4)
C1—S1—Pb1^iii	84.17 (17)	N3—C6—C7	122.6 (5)
C1—S1—Pb1	77.88 (17)	N3—C6—H6	118.7
Pb1^iii—S1—Pb1	157.10 (5)	C7—C6—H6	118.7
C5—S2—Pb1	79.82 (17)	C8—C7—C6	117.3 (5)
C5—S2—Pb1^iv	82.13 (18)	C8—C7—H7	121.4
Pb1—S2—Pb1^iv	157.53 (5)	C6—C7—H7	121.4
C2—N1—C1	117.6 (5)	N4—C8—C7	121.3 (5)
C2—N1—Pb1	130.3 (4)	N4—C8—H8	119.4
C1—N1—Pb1	101.8 (3)	C7—C8—H8	119.4
C4—N2—C1	117.1 (5)
N4—Pb1—S1—C1	−3.4 (3)	S1—Pb1—N4—C8	−92.2 (6)
N1—Pb1—S1—C1	14.8 (2)	N1—Pb1—N4—C5	86.1 (3)
N2^i—Pb1—S1—C1	−111.3 (2)	N2^i—Pb1—N4—C5	−146.6 (4)
S1^i—Pb1—S1—C1	−61.31 (17)	S1^i—Pb1—N4—C5	159.1 (4)
S2—Pb1—S1—C1	67.92 (17)	S2—Pb1—N4—C5	8.1 (3)
S2^ii—Pb1—S1—C1	167.20 (17)	S2^ii—Pb1—N4—C5	−71.7 (3)
N4—Pb1—S1—Pb1^iii	35.7 (2)	S1—Pb1—N4—C5	100.6 (3)
N1—Pb1—S1—Pb1^iii	53.97 (18)	C1—N1—C2—C3	−1.9 (10)
N2^i—Pb1—S1—Pb1^iii	−72.16 (18)	Pb1—N1—C2—C3	136.2 (6)
S1^i—Pb1—S1—Pb1^iii	−22.14 (11)	N1—C2—C3—C4	0.2 (12)
S2—Pb1—S1—Pb1^iii	107.09 (14)	C1—N2—C4—C3	−0.7 (10)
S2^ii—Pb1—S1—Pb1^iii	−153.64 (13)	Pb1^iii—N2—C4—C3	154.9 (6)
N4—Pb1—S2—C5	−6.2 (2)	C2—C3—C4—N2	1.1 (12)
N1—Pb1—S2—C5	−106.9 (2)	C4—N2—C1—N1	−1.2 (9)
N2^i—Pb1—S2—C5	32.0 (2)	Pb1^iii—N2—C1—N1	−165.0 (4)
S1^i—Pb1—S2—C5	−43.48 (19)	C4—N2—C1—S1	179.7 (5)
S2^ii—Pb1—S2—C5	87.74 (18)	Pb1^iii—N2—C1—S1	15.9 (4)
S1—Pb1—S2—C5	−146.98 (17)	C2—N1—C1—N2	2.4 (8)
N4—Pb1—S2—Pb1^iv	30.85 (18)	Pb1—N1—C1—N2	−146.2 (5)
N1—Pb1—S2—Pb1^iv	−69.88 (17)	C2—N1—C1—S1	−178.5 (5)
N2^i—Pb1—S2—Pb1^iv	69.0 (2)	Pb1—N1—C1—S1	32.9 (4)
S1^i—Pb1—S2—Pb1^iv	−6.43 (16)	Pb1^iii—S1—C1—N2	−14.5 (4)
S2^ii—Pb1—S2—Pb1^iv	124.79 (16)	Pb1—S1—C1—N2	151.2 (4)
S1—Pb1—S2—Pb1^iv	−109.93 (13)	Pb1^iii—S1—C1—N1	166.4 (4)
N4—Pb1—N1—C2	8.0 (6)	Pb1—S1—C1—N1	−27.9 (4)
N2^i—Pb1—N1—C2	−82.4 (6)	C6—N3—C5—N4	2.7 (9)
S1^i—Pb1—N1—C2	−70.0 (6)	C6—N3—C5—S2	−178.5 (5)
S2—Pb1—N1—C2	62.8 (6)	C8—N4—C5—N3	−4.1 (9)
S2^ii—Pb1—N1—C2	104.0 (6)	Pb1—N4—C5—N3	165.6 (5)
S1—Pb1—N1—C2	−162.0 (6)	C8—N4—C5—S2	177.0 (5)
N4—Pb1—N1—C1	150.7 (3)	Pb1—N4—C5—S2	−13.3 (5)
N2^i—Pb1—N1—C1	60.3 (4)	Pb1—S2—C5—N3	−167.8 (5)
S1^i—Pb1—N1—C1	72.7 (3)	Pb1^iv—S2—C5—N3	25.7 (4)
S2—Pb1—N1—C1	−154.5 (3)	Pb1—S2—C5—N4	11.1 (4)
S2^ii—Pb1—N1—C1	−113.3 (3)	Pb1^iv—S2—C5—N4	−155.5 (4)
S1—Pb1—N1—C1	−19.3 (3)	C5—N3—C6—C7	0.3 (10)
N1—Pb1—N4—C8	−106.7 (6)	N3—C6—C7—C8	−1.7 (11)
N2^i—Pb1—N4—C8	20.6 (6)	C5—N4—C8—C7	2.6 (10)
S1^i—Pb1—N4—C8	−33.8 (6)	Pb1—N4—C8—C7	−163.2 (5)
S2—Pb1—N4—C8	175.3 (7)	C6—C7—C8—N4	0.2 (11)
S2^ii—Pb1—N4—C8	95.4 (6)

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