Bis(μ-imino-diacetato)bis-[(2,2'-diamino-4,4'-bi-1,3-thia-zole)lead(II)] tetra-hydrate.

In the crystal structure of the title compound, [Pb(2)(C(4)H(5)NO(4))(2)(C(6)H(6)N(4)S(2))(2)]·4H(2)O, the dinuclear Pb(II) complex mol-ecule is centrosymmetric. The Pb atom is chelated by a tridentate imino-diacetate anion (IDA) and a diamino-bithia-zole (DABT) ligand, while a carboxyl-ate O atom from an adjacent IDA anion further bridges the Pb atom with a longer Pb-O bond [2.892 (3) Å]. The lone-pair electrons of the Pb atom occupy an axial site in the Ψ-penta-gonal-bipyramidal coordination polyhedron. The IDA anion displays a facial configuration: its chelating five-membered rings assume an envelope configuration. Within the DABT ligand, the two thia-zole rings are twisted relative to each other, making a dihedral angle of 9.51 (17)°. Extensive N-H⋯O, O-H⋯O and weak C-H⋯O hydrogen bonding helps to stabilize the crystal structure.

Related literature

For the potential applications of metal complexes of diamino­bithia­zole in the field of biology, see: Waring (1981 ▶); Fisher et al. (1985 ▶). For PbII complexes with a similar coordination geometry, see: Lacouture et al. (2001 ▶); Jones et al. (1988 ▶). For a complex with a longer Pb—O bond distance [2.968 (4) Å], see: Inoue et al. (1993 ▶). For the dihedral angles between thia­zole rings in diamino­bithia­zole complexes, see: Liu et al. (2006 ▶); Zhang et al. (2006 ▶).

Experimental

Crystal data

[Pb2(C4H5NO4)2(C6H6N4S2)2]·4H2O

M = 1145.16

Triclinic,

a = 9.2241 (8) Å

b = 9.8526 (9) Å

c = 10.6380 (11) Å

α = 77.0732 (12)°

β = 67.4141 (15)°

γ = 69.0690 (12)°

V = 829.54 (14) Å3

Z = 1

Mo Kα radiation

μ = 10.46 mm−1

T = 295 K

0.20 × 0.12 × 0.10 mm

Data collection

Rigaku R-AXIS RAPID diffractometer

Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ▶) T min = 0.132, T max = 0.350

5960 measured reflections

2878 independent reflections

2745 reflections with I > 2σ(I)

R int = 0.021

Refinement

R[F 2 > 2σ(F 2)] = 0.020

wR(F 2) = 0.048

S = 1.07

2878 reflections

244 parameters

9 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.54 e Å−3

Δρmin = −0.70 e Å−3

Data collection: PROCESS-AUTO (Rigaku, 1998 ▶); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002 ▶); program(s) used to solve structure: SIR92 (Altomare et al., 1993 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810006926/ng2733sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810006926/ng2733Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[Pb2(C4H5NO4)2(C6H6N4S2)2]·4H2O	Z = 1
Mr = 1145.16	F(000) = 544
Triclinic, P1	Dx = 2.292 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.2241 (8) Å	Cell parameters from 4336 reflections
b = 9.8526 (9) Å	θ = 2.1–24.6°
c = 10.6380 (11) Å	µ = 10.46 mm−1
α = 77.0732 (12)°	T = 295 K
β = 67.4141 (15)°	Block, yellow
γ = 69.0690 (12)°	0.20 × 0.12 × 0.10 mm
V = 829.54 (14) Å3

Rigaku R-AXIS RAPID diffractometer	2878 independent reflections
Radiation source: fine-focus sealed tube	2745 reflections with I > 2σ(I)
graphite	Rint = 0.021
Detector resolution: 10.00 pixels mm-1	θmax = 25.0°, θmin = 2.1°
ω scans	h = −10→10
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −11→11
Tmin = 0.132, Tmax = 0.350	l = −12→12
5960 measured reflections

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.020	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.048	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ2(Fo2) + (0.019P)2 + 0.7917P] where P = (Fo2 + 2Fc2)/3
2878 reflections	(Δ/σ)max = 0.001
244 parameters	Δρmax = 0.54 e Å−3
9 restraints	Δρmin = −0.70 e Å−3

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. 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.

	x	y	z	Uiso*/Ueq
Pb	0.545731 (18)	0.724630 (15)	0.424338 (14)	0.02919 (7)
S1	0.85653 (18)	1.10157 (14)	0.16319 (14)	0.0551 (3)
S2	0.70556 (17)	0.84111 (15)	0.78711 (13)	0.0513 (3)
O1	0.6288 (4)	0.4760 (3)	0.5554 (3)	0.0400 (7)
O2	0.8401 (5)	0.2774 (4)	0.5652 (4)	0.0696 (11)
O3	0.5809 (4)	0.7154 (3)	0.1777 (3)	0.0431 (7)
O4	0.6770 (6)	0.5550 (4)	0.0268 (4)	0.0714 (12)
O1W	0.7380 (5)	1.1758 (4)	−0.1588 (4)	0.0577 (9)
O2W	1.0741 (5)	0.6671 (5)	0.1186 (5)	0.0717 (11)
N1	0.7119 (4)	0.9098 (4)	0.3108 (4)	0.0359 (8)
N2	0.7160 (6)	0.9566 (5)	0.0832 (4)	0.0541 (11)
N3	0.6755 (4)	0.7770 (4)	0.5787 (3)	0.0357 (8)
N4	0.5919 (6)	0.6270 (5)	0.7807 (4)	0.0563 (11)
N5	0.8084 (4)	0.5688 (4)	0.2998 (4)	0.0355 (8)
C1	0.7507 (5)	0.9781 (5)	0.1862 (4)	0.0382 (10)
C2	0.8435 (6)	1.0598 (5)	0.3335 (5)	0.0494 (12)
H2	0.8841	1.1027	0.3770	0.059*
C3	0.7666 (5)	0.9569 (5)	0.3947 (4)	0.0372 (10)
C4	0.6525 (6)	0.7362 (5)	0.7099 (4)	0.0399 (10)
C5	0.7564 (6)	0.9461 (5)	0.6339 (5)	0.0461 (11)
H5	0.7934	1.0262	0.6206	0.055*
C6	0.7354 (5)	0.8967 (4)	0.5350 (5)	0.0368 (10)
C11	0.7810 (6)	0.4004 (5)	0.5131 (4)	0.0370 (10)
C12	0.8948 (6)	0.4667 (5)	0.3912 (5)	0.0418 (10)
H12A	0.9443	0.5183	0.4229	0.050*
H12B	0.9827	0.3892	0.3400	0.050*
C13	0.7855 (6)	0.4939 (5)	0.2072 (4)	0.0408 (10)
H13A	0.7393	0.4162	0.2599	0.049*
H13B	0.8919	0.4499	0.1420	0.049*
C14	0.6733 (6)	0.5959 (5)	0.1303 (4)	0.0427 (11)
H11	0.768 (8)	1.197 (7)	−0.2418 (10)	0.080*
H12	0.6393 (18)	1.220 (6)	−0.132 (6)	0.080*
H21	1.124 (7)	0.724 (5)	0.113 (7)	0.080*
H22	1.147 (6)	0.594 (4)	0.086 (7)	0.080*
H2A	0.662 (6)	0.895 (5)	0.101 (6)	0.080*
H2B	0.751 (8)	0.997 (6)	0.001 (2)	0.080*
H4A	0.582 (7)	0.570 (5)	0.736 (5)	0.080*
H4B	0.595 (7)	0.598 (6)	0.862 (2)	0.080*
H5N	0.865 (6)	0.626 (5)	0.247 (5)	0.080*

	U11	U22	U33	U12	U13	U23
Pb	0.03072 (10)	0.03010 (10)	0.02682 (10)	−0.00792 (7)	−0.01080 (7)	−0.00292 (6)
S1	0.0619 (9)	0.0475 (7)	0.0531 (7)	−0.0305 (6)	−0.0092 (6)	0.0054 (6)
S2	0.0594 (8)	0.0592 (8)	0.0430 (7)	−0.0105 (6)	−0.0248 (6)	−0.0183 (6)
O1	0.0430 (19)	0.0399 (17)	0.0384 (17)	−0.0150 (15)	−0.0159 (14)	0.0016 (13)
O2	0.070 (3)	0.051 (2)	0.064 (2)	−0.0008 (19)	−0.025 (2)	0.0136 (19)
O3	0.051 (2)	0.0448 (18)	0.0352 (16)	−0.0102 (15)	−0.0218 (15)	−0.0005 (14)
O4	0.110 (3)	0.068 (2)	0.049 (2)	−0.016 (2)	−0.046 (2)	−0.0134 (19)
O1W	0.063 (2)	0.059 (2)	0.054 (2)	−0.0169 (19)	−0.030 (2)	0.0050 (19)
O2W	0.062 (3)	0.076 (3)	0.074 (3)	−0.035 (2)	−0.002 (2)	−0.013 (2)
N1	0.040 (2)	0.0315 (18)	0.0362 (19)	−0.0136 (16)	−0.0107 (16)	−0.0017 (15)
N2	0.068 (3)	0.058 (3)	0.039 (2)	−0.030 (2)	−0.019 (2)	0.010 (2)
N3	0.038 (2)	0.041 (2)	0.0309 (18)	−0.0143 (16)	−0.0126 (16)	−0.0041 (15)
N4	0.081 (3)	0.066 (3)	0.032 (2)	−0.033 (3)	−0.026 (2)	0.007 (2)
N5	0.034 (2)	0.039 (2)	0.035 (2)	−0.0125 (16)	−0.0138 (16)	−0.0001 (16)
C1	0.038 (2)	0.033 (2)	0.037 (2)	−0.0107 (19)	−0.0072 (19)	−0.0009 (18)
C2	0.050 (3)	0.046 (3)	0.058 (3)	−0.024 (2)	−0.013 (2)	−0.010 (2)
C3	0.034 (2)	0.035 (2)	0.040 (2)	−0.0065 (19)	−0.0086 (19)	−0.0115 (19)
C4	0.043 (3)	0.047 (3)	0.032 (2)	−0.008 (2)	−0.015 (2)	−0.010 (2)
C5	0.052 (3)	0.044 (3)	0.051 (3)	−0.012 (2)	−0.024 (2)	−0.014 (2)
C6	0.033 (2)	0.034 (2)	0.045 (2)	−0.0053 (18)	−0.015 (2)	−0.0113 (19)
C11	0.043 (3)	0.038 (2)	0.034 (2)	−0.008 (2)	−0.021 (2)	−0.0024 (19)
C12	0.038 (3)	0.048 (3)	0.042 (2)	−0.012 (2)	−0.021 (2)	0.001 (2)
C13	0.049 (3)	0.040 (2)	0.036 (2)	−0.009 (2)	−0.019 (2)	−0.0080 (19)
C14	0.054 (3)	0.045 (3)	0.032 (2)	−0.020 (2)	−0.014 (2)	0.000 (2)

Pb—O1	2.546 (3)	N2—H2A	0.86 (6)
Pb—O1i	2.892 (3)	N2—H2B	0.86 (3)
Pb—O3	2.536 (3)	N3—C4	1.318 (5)
Pb—N1	2.593 (3)	N3—C6	1.391 (5)
Pb—N3	2.594 (3)	N4—C4	1.335 (6)
Pb—N5	2.402 (4)	N4—H4A	0.86 (5)
S1—C2	1.732 (5)	N4—H4B	0.86 (3)
S1—C1	1.739 (4)	N5—C13	1.468 (5)
S2—C5	1.718 (5)	N5—C12	1.475 (5)
S2—C4	1.741 (4)	N5—H5N	0.86 (5)
O1—C11	1.283 (5)	C2—C3	1.348 (6)
O2—C11	1.237 (5)	C2—H2	0.9300
O3—C14	1.259 (5)	C3—C6	1.435 (6)
O4—C14	1.239 (5)	C5—C6	1.354 (6)
O1W—H11	0.819 (16)	C5—H5	0.9300
O1W—H12	0.82 (5)	C11—C12	1.509 (6)
O2W—H21	0.82 (7)	C12—H12A	0.9700
O2W—H22	0.82 (5)	C12—H12B	0.9700
N1—C1	1.321 (5)	C13—C14	1.513 (6)
N1—C3	1.403 (5)	C13—H13A	0.9700
N2—C1	1.331 (6)	C13—H13B	0.9700
N5—Pb—O3	66.12 (11)	N1—C1—S1	114.6 (3)
N5—Pb—O1	67.04 (11)	N2—C1—S1	120.7 (3)
O3—Pb—O1	114.56 (10)	C3—C2—S1	110.9 (4)
N5—Pb—N1	78.68 (11)	C3—C2—H2	124.5
O3—Pb—N1	81.95 (10)	S1—C2—H2	124.5
O1—Pb—N1	128.64 (10)	C2—C3—N1	115.0 (4)
N5—Pb—N3	90.68 (12)	C2—C3—C6	125.7 (4)
O3—Pb—N3	143.48 (11)	N1—C3—C6	119.3 (4)
O1—Pb—N3	77.56 (10)	N3—C4—N4	124.6 (4)
N1—Pb—N3	65.44 (11)	N3—C4—S2	113.7 (3)
C2—S1—C1	89.0 (2)	N4—C4—S2	121.7 (3)
C5—S2—C4	89.4 (2)	C6—C5—S2	111.0 (4)
C11—O1—Pb	116.9 (3)	C6—C5—H5	124.5
C14—O3—Pb	114.4 (3)	S2—C5—H5	124.5
H11—O1W—H12	105 (6)	C5—C6—N3	114.7 (4)
H21—O2W—H22	104 (6)	C5—C6—C3	126.4 (4)
C1—N1—C3	110.4 (4)	N3—C6—C3	119.0 (4)
C1—N1—Pb	132.4 (3)	O2—C11—O1	124.6 (4)
C3—N1—Pb	117.1 (3)	O2—C11—C12	118.1 (4)
C1—N2—H2A	116 (4)	O1—C11—C12	117.3 (4)
C1—N2—H2B	122 (4)	N5—C12—C11	112.3 (4)
H2A—N2—H2B	121 (6)	N5—C12—H12A	109.1
C4—N3—C6	111.2 (4)	C11—C12—H12A	109.1
C4—N3—Pb	128.8 (3)	N5—C12—H12B	109.1
C6—N3—Pb	116.8 (3)	C11—C12—H12B	109.1
C4—N4—H4A	118 (4)	H12A—C12—H12B	107.9
C4—N4—H4B	119 (4)	N5—C13—C14	112.6 (4)
H4A—N4—H4B	119 (6)	N5—C13—H13A	109.1
C13—N5—C12	112.7 (3)	C14—C13—H13A	109.1
C13—N5—Pb	109.0 (3)	N5—C13—H13B	109.1
C12—N5—Pb	112.3 (3)	C14—C13—H13B	109.1
C13—N5—H5N	105 (4)	H13A—C13—H13B	107.8
C12—N5—H5N	111 (4)	O4—C14—O3	124.8 (5)
Pb—N5—H5N	106 (4)	O4—C14—C13	117.8 (4)
N1—C1—N2	124.7 (4)	O3—C14—C13	117.4 (4)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O3	0.86 (6)	2.05 (5)	2.880 (6)	162 (5)
N2—H2B···O1W	0.86 (3)	2.16 (4)	2.959 (6)	153 (6)
N4—H4A···O1	0.86 (5)	2.15 (5)	2.946 (5)	155 (5)
N4—H4B···O4ii	0.86 (3)	2.07 (5)	2.885 (7)	159 (6)
N5—H5N···O2W	0.87 (5)	2.01 (6)	2.809 (7)	153 (4)
O1W—H11···O2iii	0.82 (2)	1.97 (2)	2.783 (6)	171 (5)
O1W—H12···O3iv	0.82 (5)	2.11 (4)	2.819 (6)	144 (5)
O2W—H21···O1Wv	0.82 (7)	2.10 (7)	2.892 (7)	161 (6)
O2W—H22···O4vi	0.82 (5)	1.95 (5)	2.766 (6)	168 (7)
C5—H5···O2vii	0.93	2.56	3.476 (6)	167

Table 1

Selected bond lengths (Å)

Pb—O1	2.546 (3)
Pb—O1i	2.892 (3)
Pb—O3	2.536 (3)
Pb—N1	2.593 (3)
Pb—N3	2.594 (3)
Pb—N5	2.402 (4)

Symmetry code: (i) .

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯O3	0.86 (6)	2.05 (5)	2.880 (6)	162 (5)
N2—H2B⋯O1W	0.86 (3)	2.16 (4)	2.959 (6)	153 (6)
N4—H4A⋯O1	0.86 (5)	2.15 (5)	2.946 (5)	155 (5)
N4—H4B⋯O4ii	0.86 (3)	2.07 (5)	2.885 (7)	159 (6)
N5—H5N⋯O2W	0.87 (5)	2.01 (6)	2.809 (7)	153 (4)
O1W—H11⋯O2iii	0.82 (2)	1.97 (2)	2.783 (6)	171 (5)
O1W—H12⋯O3iv	0.82 (5)	2.11 (4)	2.819 (6)	144 (5)
O2W—H21⋯O1Wv	0.82 (7)	2.10 (7)	2.892 (7)	161 (6)
O2W—H22⋯O4vi	0.82 (5)	1.95 (5)	2.766 (6)	168 (7)
C5—H5⋯O2vii	0.93	2.56	3.476 (6)	167

Symmetry codes: (ii) ; (iii) ; (iv) ; (v) ; (vi) ; (vii) .