catena-Poly[[bis­[aqua­(1,10-phenanthroline)lead(II)]-bis­(μ3-2-hy­droxy-5-sulfonato­benzoato)] acetic acid monosolvate]

Cheng, Y.-Z.; Shi, W.-W.; Wang, X.-D.; Deng, S.-E.; Zhang, L.-P.

doi:10.1107/S160053681202421X

metal-organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 68| Part 7| July 2012| Pages m878-m879

https://doi.org/10.1107/S160053681202421X

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catena-Poly[[bis[aqua(1,10-phenanthroline)lead(II)]-bis(μ₃-2-hydroxy-5-sulfonatobenzoato)] acetic acid monosolvate]

Yuan-Zheng Cheng,^a Wei-Wei Shi,^a Xue-Dong Wang,^a Shu-E Deng ^a and Li-Ping Zhang ^a ^*

^aDepartment of Chemistry, Weifang Medical University, Weifang 261053, People's Republic of China
^*Correspondence e-mail: zlpchyzh@163.com

(Received 18 May 2012; accepted 27 May 2012; online 13 June 2012)

In the title compound, [Pb₂(C₇H₄O₆S)₂(C₁₂H₈N₂)₂(H₂O)₂]·CH₃COOH, the seven-coordinate Pb^II atom is chelated by two N atoms of one 1,10-phenanthroline ligand, four O atoms from three 5-sulfosalicylate dianions and one water O atom. Each dianion serves as a bridging ligand, connecting adjacent Pb^II atoms into a centrosymmetric polymeric chain extending parallel to [001]. There are π–π interactions between the aromatic systems of neighbouring dianions, with plane-to-plane distances of 3.371 (2) Å, and between phenanthroline ligands, with a centroid-to-centroid distance of 3.484 (2) Å. O—H⋯O hydrogen bonding additionally stabilizes the crystal packing. The acetic acid molecules are incorporated in the voids of this arrangement. They exhibit half-occupancy due to disorder around a centre of inversion.

Related literature

For background to 5-sulfosalicylic acid and its metal complexes, see: Chen et al. (2003 ); Du et al. (2006 ); Fan & Zhu (2005a ,b , 2006 ); Li et al. (2004 ).

Experimental

Crystal data

[Pb₂(C₇H₄O₆S)₂(C₁₂H₈N₂)₂(H₂O)₂]·C₂H₄O₂
M_r = 1303.24
Triclinic, $[P \overline 1]$
a = 9.7372 (7) Å
b = 10.1619 (5) Å
c = 11.6637 (5) Å
α = 74.171 (4)°
β = 74.379 (5)°
γ = 79.748 (5)°
V = 1062.50 (11) Å³
Z = 1
Mo Kα radiation
μ = 8.09 mm⁻¹
T = 293 K
0.15 × 0.13 × 0.12 mm

Data collection

Oxford Xcalibur CCD diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2011 $[Oxford Diffraction (2011). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, Oxfordshire, England.]$ ) T_min = 0.309, T_max = 0.379
6374 measured reflections
3745 independent reflections
3438 reflections with I > 2σ(I)
R_int = 0.036

Refinement

R[F² > 2σ(F²)] = 0.027
wR(F²) = 0.064
S = 1.05
3745 reflections
310 parameters
28 restraints
H-atom parameters constrained
Δρ_max = 1.83 e Å⁻³
Δρ_min = −0.84 e Å⁻³

Table 1
Selected bond lengths (Å)

Pb1—O6	2.472 (3)
Pb1—N2	2.473 (3)
Pb1—N1	2.488 (3)
Pb1—O5	2.745 (3)
Pb1—O3ⁱ	2.757 (3)
Pb1—O7	2.835 (4)
Pb1—O1ⁱⁱ	2.792 (1)
Symmetry codes: (i) -x, -y+1, -z+1; (ii) x, y, z+1.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H4⋯O6	0.82	1.83	2.522 (4)	141
O7—H7A⋯O2ⁱⁱⁱ	0.85	2.11	2.959 (5)	172
Symmetry code: (iii) -x+1, -y+1, -z+1.

Data collection: CrysAlis PRO (Oxford Diffraction, 2011 $[Oxford Diffraction (2011). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, Oxfordshire, England.]$ ); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ) and DIAMOND (Brandenburg, 2006 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S160053681202421X/wm2635sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S160053681202421X/wm2635Isup2.hkl

checkCIF report

Comment top

5-Sulfosalicylic acid (H₃ssal) has three functional groups, viz -SO₃H, -COOH and -OH, and can form three kind of ions (H₂ssal^-, Hssal^2- and ssal^3-) (Fan & Zhu, 2006). Hssal^2- possesses the ability to bridge and chelate metal atoms using the carboxylate O atoms and the sulfonate O atoms (Chen et al., 2003). A few complexes containing Hssal^2- and phen ligands have been reported (Chen et al., 2003; Li et al., 2004; Fan & Zhu, 2005a,b, 2006; Du et al., 2006). Among the aforementioned complexes, there is a polymer (Fan & Zhu, 2006), which contains Pb^II atoms and N,N-dimethylformamide ligands. In this paper, we report a new polymeric Pb^II complex which contains water ligands instead of N,N-dimethylformamide ligands and acetic acid solvent molecules in the crystal lattice.

The Pb^II atom is seven-coordinated by two N atoms of one phenanthroline ligand, four O atoms from three Hssal^2- ligands, and one O atom from one H₂O molecule (Fig. 1). The Pb—O distances range from 2.472 (3) Å to 2.835 (4) Å, and the Pb—N distances from 2.473 (3) Å to 2.488 (3) Å (Table 1). The distances of Pb···Pb separated by the Hssal^2- ligand are 8.9162 (4) Å and 11.6637 (5) Å, while the Pb···Pb separation by sulfonate is 5.0722 (3) Å.

In the crystal, there is an intramolecular O4—H4···O6 hydrogen bond in the Hssal^2- ligand. In addition, there are intermolecular O—H···O hydrogen bonds linking water molecular and Hssal^2- ligands (Table 2 and Fig. 2). Aromatic π–π stacking occurs between neighbouring phenanthroline ligands (Fig. 3). The centroid–centroid distance between Cg3 (C1/C5–C8/C12) and Cg3 (C1/C5–C8/C12) [symmetry code: 1 - x, -y, 2 - z] is 3.484 (2) Å. π–π interactions between the aromatic systems of neighbouring dianions with plane-to-plane distances of 3.371 (2) Å also occur.

In the voids of this arrangement acetic acid molecules are incorporated. They exhibit half-occupancy due to disorder around a centre of inversion.

Related literature top

For background to 5-sulfosalicylic acid and its metal complexes, see: Chen et al. (2003); Du et al. (2006); Fan & Zhu (2005a,b, 2006); Li et al. (2004).

Experimental top

A mixture of Pb(CH₃COO)₂.3H₂O (0.5 mmol, 0.1897 g) and 1.10-phenanthroline (0.5 mmol, 0.0991 g) in a solution of dimethylacetylamide (DMAC; 20 ml) was stirred for 20 min. Then 5-sulfosalicylic acid dihydrate (0.5 mmol, 0.1271 g) and NaOH (0.5 mmol, 0.0200 g) were dissolved in water (20 ml), which was added dropwise into the previous solution under stirring. The mixed solution was stirred for 1 h and filtered. The resulting solution was set aside for evaporation at room temperature for 11 d, and colorless block-shaped single crystals were obtained.

Structure description top

In the voids of this arrangement acetic acid molecules are incorporated. They exhibit half-occupancy due to disorder around a centre of inversion.

For background to 5-sulfosalicylic acid and its metal complexes, see: Chen et al. (2003); Du et al. (2006); Fan & Zhu (2005a,b, 2006); Li et al. (2004).

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2011); cell refinement: CrysAlis PRO (Oxford Diffraction, 2011); data reduction: CrysAlis PRO (Oxford Diffraction, 2011); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. The molecular structure of the title compound with displacement ellipsoids drawn at the 30% probability level. [Symmetry codes: (A) -x, -y + 1, -z + 1; (B) x, y, z + 1]. Only one orientation of the disordered acetic acid molecule is shown.
	Fig. 2. Part of the crystal structure of the title compound, showing O—H···O hydrogen bonds as green dashed lines.
	Fig. 3. The π–π stacking of the 1,10-phenanthroline units in the title compound. Only one orientation of the disordered acetic acid molecule is shown.

catena-Poly[[bis[aqua(1,10-phenanthroline)lead(II)]-bis(µ₃-2-hydroxy- 5-sulfonatobenzoato)] acetic acid monosolvate] top

Crystal data top

[Pb₂(C₇H₄O₆S)₂(C₁₂H₈N₂)₂(H₂O)₂]·C₂H₄O₂	Z = 1
M_r = 1303.24	F(000) = 624
Triclinic, P1	D_x = 2.037 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.7372 (7) Å	Cell parameters from 4152 reflections
b = 10.1619 (5) Å	θ = 2.5–28.4°
c = 11.6637 (5) Å	µ = 8.09 mm⁻¹
α = 74.171 (4)°	T = 293 K
β = 74.379 (5)°	Block, colourless
γ = 79.748 (5)°	0.15 × 0.13 × 0.12 mm
V = 1062.50 (11) Å³

Data collection top

Oxford Xcalibur CCD diffractometer	3745 independent reflections
Radiation source: fine-focus sealed tube	3438 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.036
Detector resolution: 16.2563 pixels mm^-1	θ_max = 25.0°, θ_min = 3.1°
ω scans	h = −11→9
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2011)	k = −12→12
T_min = 0.309, T_max = 0.379	l = −13→13
6374 measured reflections

Refinement top

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)] = 0.027	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.064	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0245P)² + 1.8039P] where P = (F_o² + 2F_c²)/3
3745 reflections	(Δ/σ)_max = 0.002
310 parameters	Δρ_max = 1.83 e Å⁻³
28 restraints	Δρ_min = −0.84 e Å⁻³

Crystal data top

[Pb₂(C₇H₄O₆S)₂(C₁₂H₈N₂)₂(H₂O)₂]·C₂H₄O₂	γ = 79.748 (5)°
M_r = 1303.24	V = 1062.50 (11) Å³
Triclinic, P1	Z = 1
a = 9.7372 (7) Å	Mo Kα radiation
b = 10.1619 (5) Å	µ = 8.09 mm⁻¹
c = 11.6637 (5) Å	T = 293 K
α = 74.171 (4)°	0.15 × 0.13 × 0.12 mm
β = 74.379 (5)°

Data collection top

Oxford Xcalibur CCD diffractometer	3745 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2011)	3438 reflections with I > 2σ(I)
T_min = 0.309, T_max = 0.379	R_int = 0.036
6374 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.027	28 restraints
wR(F²) = 0.064	H-atom parameters constrained
S = 1.05	Δρ_max = 1.83 e Å⁻³
3745 reflections	Δρ_min = −0.84 e Å⁻³
310 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Pb1	0.189696 (15)	0.433942 (12)	0.821869 (11)	0.02627 (4)
S1	0.22096 (9)	0.49032 (9)	0.11157 (7)	0.0246 (2)
O1	0.2783 (3)	0.3880 (3)	0.0395 (2)	0.0432 (8)
O2	0.3283 (3)	0.5673 (3)	0.1171 (3)	0.0458 (8)
O3	0.0989 (3)	0.5773 (3)	0.0720 (3)	0.0491 (9)
O4	−0.0031 (3)	0.1689 (3)	0.6124 (2)	0.0383 (7)
H4	−0.0007	0.2086	0.6642	0.057*
O5	0.2292 (3)	0.4891 (3)	0.5720 (2)	0.0382 (7)
O6	0.1091 (3)	0.3183 (3)	0.6945 (2)	0.0364 (7)
O7	0.4185 (4)	0.5870 (4)	0.7930 (4)	0.0693 (11)
H7B	0.3910	0.6512	0.8307	0.104*
H7A	0.4854	0.5373	0.8243	0.104*
N1	0.1815 (3)	0.1900 (3)	0.9396 (2)	0.0254 (7)
N2	0.4095 (3)	0.2831 (3)	0.7557 (3)	0.0288 (8)
C1	0.2972 (4)	0.0991 (3)	0.9122 (3)	0.0269 (8)
C2	0.0744 (4)	0.1459 (4)	1.0323 (3)	0.0295 (9)
H2	−0.0063	0.2078	1.0504	0.035*
C3	0.0764 (4)	0.0128 (4)	1.1034 (3)	0.0347 (10)
H3	0.0005	−0.0124	1.1701	0.042*
C4	0.1901 (5)	−0.0810 (4)	1.0751 (3)	0.0380 (10)
H4A	0.1906	−0.1718	1.1205	0.046*
C5	0.3070 (4)	−0.0411 (4)	0.9775 (3)	0.0306 (9)
C6	0.4306 (5)	−0.1315 (4)	0.9431 (4)	0.0404 (11)
H6	0.4355	−0.2236	0.9850	0.048*
C7	0.5421 (5)	−0.0859 (4)	0.8498 (4)	0.0411 (11)
H7	0.6222	−0.1473	0.8287	0.049*
C8	0.5379 (4)	0.0553 (4)	0.7835 (3)	0.0313 (9)
C9	0.6530 (4)	0.1072 (4)	0.6884 (4)	0.0376 (10)
H9	0.7353	0.0491	0.6652	0.045*
C10	0.6423 (4)	0.2446 (4)	0.6304 (4)	0.0368 (10)
H10	0.7175	0.2806	0.5678	0.044*
C11	0.5202 (4)	0.3280 (4)	0.6656 (3)	0.0346 (10)
H11	0.5140	0.4205	0.6248	0.041*
C12	0.4181 (4)	0.1465 (3)	0.8141 (3)	0.0272 (9)
C13	0.1267 (4)	0.3569 (3)	0.4810 (3)	0.0231 (8)
C14	0.0492 (4)	0.2454 (4)	0.5000 (3)	0.0262 (9)
C15	0.0285 (4)	0.2095 (4)	0.3998 (3)	0.0342 (10)
H15	−0.0212	0.1349	0.4117	0.041*
C16	0.0813 (4)	0.2838 (4)	0.2825 (3)	0.0297 (9)
H16	0.0666	0.2594	0.2158	0.036*
C17	0.1568 (4)	0.3956 (3)	0.2634 (3)	0.0229 (8)
C18	0.1787 (3)	0.4310 (3)	0.3625 (3)	0.0217 (8)
H18	0.2289	0.5055	0.3499	0.026*
C19	0.1577 (4)	0.3934 (4)	0.5883 (3)	0.0275 (9)
O8	0.52594 (15)	1.0143 (5)	0.4767 (3)	0.0604 (17)	0.50
H8	0.4666	1.0824	0.4693	0.091*	0.50
O9	0.5369 (3)	0.8114 (4)	0.5772 (5)	0.0472 (15)	0.50
C20	0.3157 (9)	0.9480 (4)	0.6248 (6)	0.055 (2)	0.50
H20A	0.2969	0.8956	0.7083	0.082*	0.50
H20B	0.2530	0.9270	0.5829	0.082*	0.50
H20C	0.2993	1.0445	0.6231	0.082*	0.50
C21	0.4666 (8)	0.9126 (7)	0.5634 (7)	0.048 (2)	0.50

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Pb1	0.03519 (7)	0.02124 (7)	0.02146 (6)	−0.00169 (5)	−0.00812 (5)	−0.00301 (5)
S1	0.0322 (4)	0.0227 (4)	0.0179 (4)	−0.0038 (3)	−0.0059 (3)	−0.0025 (3)
O1	0.0686 (19)	0.0337 (14)	0.0251 (13)	−0.0031 (14)	−0.0067 (12)	−0.0094 (11)
O2	0.0594 (16)	0.0478 (16)	0.0329 (14)	−0.0329 (13)	−0.0095 (12)	0.0017 (12)
O3	0.0382 (15)	0.0552 (18)	0.0336 (15)	0.0070 (14)	−0.0060 (12)	0.0127 (13)
O4	0.0428 (15)	0.0428 (15)	0.0243 (13)	−0.0212 (12)	−0.0008 (11)	0.0039 (11)
O5	0.0516 (15)	0.0403 (14)	0.0297 (12)	−0.0105 (12)	−0.0177 (11)	−0.0082 (11)
O6	0.0495 (15)	0.0422 (15)	0.0185 (11)	−0.0128 (12)	−0.0095 (11)	−0.0027 (10)
O7	0.069 (2)	0.0504 (19)	0.087 (3)	−0.0183 (17)	−0.0103 (19)	−0.0140 (18)
N1	0.0366 (15)	0.0219 (14)	0.0202 (13)	−0.0090 (12)	−0.0092 (11)	−0.0028 (11)
N2	0.0364 (16)	0.0230 (14)	0.0267 (14)	−0.0075 (13)	−0.0093 (12)	−0.0008 (12)
C1	0.0422 (18)	0.0198 (16)	0.0242 (16)	−0.0086 (14)	−0.0155 (14)	−0.0035 (13)
C2	0.0375 (19)	0.0298 (18)	0.0226 (16)	−0.0102 (15)	−0.0076 (14)	−0.0039 (14)
C3	0.045 (2)	0.034 (2)	0.0244 (18)	−0.0142 (17)	−0.0074 (16)	−0.0001 (15)
C4	0.058 (2)	0.0277 (19)	0.0299 (19)	−0.0206 (17)	−0.0156 (17)	0.0060 (15)
C5	0.046 (2)	0.0229 (17)	0.0282 (17)	−0.0092 (15)	−0.0196 (15)	−0.0014 (14)
C6	0.057 (2)	0.0224 (18)	0.045 (2)	−0.0028 (17)	−0.0269 (18)	−0.0005 (16)
C7	0.051 (2)	0.0279 (19)	0.049 (2)	0.0030 (18)	−0.0229 (18)	−0.0090 (17)
C8	0.0362 (18)	0.0253 (17)	0.0379 (18)	−0.0001 (15)	−0.0169 (15)	−0.0103 (14)
C9	0.0322 (19)	0.041 (2)	0.042 (2)	−0.0001 (17)	−0.0122 (16)	−0.0127 (17)
C10	0.032 (2)	0.039 (2)	0.037 (2)	−0.0086 (17)	−0.0030 (16)	−0.0074 (17)
C11	0.037 (2)	0.0315 (19)	0.0325 (19)	−0.0107 (16)	−0.0061 (16)	−0.0017 (16)
C12	0.0346 (18)	0.0212 (16)	0.0294 (17)	−0.0062 (14)	−0.0141 (14)	−0.0033 (13)
C13	0.0235 (16)	0.0239 (16)	0.0228 (15)	0.0007 (13)	−0.0084 (13)	−0.0064 (13)
C14	0.0237 (16)	0.0279 (18)	0.0247 (17)	−0.0043 (14)	−0.0042 (13)	−0.0030 (14)
C15	0.040 (2)	0.0307 (18)	0.0345 (19)	−0.0175 (16)	−0.0059 (16)	−0.0061 (15)
C16	0.0372 (19)	0.0290 (18)	0.0267 (17)	−0.0106 (15)	−0.0085 (14)	−0.0076 (14)
C17	0.0252 (16)	0.0229 (16)	0.0203 (15)	−0.0038 (14)	−0.0043 (13)	−0.0050 (13)
C18	0.0234 (16)	0.0201 (16)	0.0216 (15)	−0.0041 (13)	−0.0061 (13)	−0.0033 (12)
C19	0.0295 (18)	0.0284 (18)	0.0264 (17)	0.0026 (15)	−0.0102 (14)	−0.0095 (14)
O8	0.055 (3)	0.059 (3)	0.063 (3)	0.004 (2)	−0.014 (2)	−0.014 (2)
O9	0.042 (2)	0.051 (3)	0.051 (2)	0.024 (2)	−0.022 (2)	−0.022 (2)
C20	0.048 (3)	0.073 (4)	0.054 (3)	0.008 (3)	−0.018 (3)	−0.036 (3)
C21	0.049 (3)	0.050 (3)	0.049 (3)	−0.006 (3)	−0.018 (3)	−0.010 (3)

Geometric parameters (Å, º) top

Pb1—O6	2.472 (3)	C5—C6	1.414 (5)
Pb1—N2	2.473 (3)	C6—C7	1.359 (6)
Pb1—N1	2.488 (3)	C6—H6	0.9300
Pb1—O5	2.745 (3)	C7—C8	1.432 (5)
Pb1—O3ⁱ	2.757 (3)	C7—H7	0.9300
Pb1—O7	2.835 (4)	C8—C12	1.385 (5)
Pb1—O1ⁱⁱ	2.792 (1)	C8—C9	1.410 (5)
S1—O2	1.436 (3)	C9—C10	1.375 (6)
S1—O3	1.451 (3)	C9—H9	0.9300
S1—O1	1.454 (3)	C10—C11	1.367 (5)
S1—C17	1.772 (3)	C10—H10	0.9300
O3—Pb1ⁱ	2.757 (3)	C11—H11	0.9300
O4—C14	1.345 (4)	C13—C18	1.387 (4)
O4—H4	0.8200	C13—C14	1.407 (5)
O5—C19	1.239 (5)	C13—C19	1.513 (5)
O6—C19	1.280 (4)	C14—C15	1.388 (6)
O7—H7B	0.8501	C15—C16	1.379 (5)
O7—H7A	0.8500	C15—H15	0.9300
N1—C2	1.324 (4)	C16—C17	1.397 (5)
N1—C1	1.349 (4)	C16—H16	0.9300
N2—C11	1.333 (5)	C17—C18	1.378 (5)
N2—C12	1.368 (4)	C18—H18	0.9300
C1—C5	1.421 (5)	O8—C21	1.324 (7)
C1—C12	1.450 (5)	O8—H8	0.8200
C2—C3	1.381 (5)	O9—C21	1.127 (8)
C2—H2	0.9300	C20—C21	1.479 (10)
C3—C4	1.357 (6)	C20—H20A	0.9600
C3—H3	0.9300	C20—H20B	0.9600
C4—C5	1.404 (5)	C20—H20C	0.9600
C4—H4A	0.9300

O6—Pb1—N2	78.58 (10)	C4—C5—C1	116.4 (3)
O6—Pb1—N1	74.87 (9)	C6—C5—C1	119.8 (3)
N2—Pb1—N1	67.00 (9)	C7—C6—C5	121.1 (3)
O6—Pb1—O5	49.83 (8)	C7—C6—H6	119.5
N2—Pb1—O5	75.83 (9)	C5—C6—H6	119.5
N1—Pb1—O5	118.07 (9)	C6—C7—C8	120.8 (4)
O6—Pb1—O3ⁱ	76.29 (10)	C6—C7—H7	119.6
N2—Pb1—O3ⁱ	140.58 (10)	C8—C7—H7	119.6
N1—Pb1—O3ⁱ	77.36 (9)	C12—C8—C9	117.9 (3)
O5—Pb1—O3ⁱ	108.70 (9)	C12—C8—C7	119.6 (3)
O6—Pb1—O7	136.69 (10)	C9—C8—C7	122.5 (3)
N2—Pb1—O7	75.24 (10)	C10—C9—C8	119.2 (4)
N1—Pb1—O7	123.15 (10)	C10—C9—H9	120.4
O5—Pb1—O7	90.23 (10)	C8—C9—H9	120.4
O3ⁱ—Pb1—O7	141.81 (11)	C11—C10—C9	119.4 (4)
O2—S1—O3	113.04 (19)	C11—C10—H10	120.3
O2—S1—O1	113.22 (19)	C9—C10—H10	120.3
O3—S1—O1	111.07 (19)	N2—C11—C10	123.1 (3)
O2—S1—C17	106.19 (17)	N2—C11—H11	118.4
O3—S1—C17	107.19 (16)	C10—C11—H11	118.4
O1—S1—C17	105.53 (16)	N2—C12—C8	122.1 (3)
S1—O3—Pb1ⁱ	128.98 (15)	N2—C12—C1	117.6 (3)
C14—O4—H4	109.5	C8—C12—C1	120.2 (3)
C19—O5—Pb1	87.7 (2)	C18—C13—C14	119.5 (3)
C19—O6—Pb1	99.6 (2)	C18—C13—C19	119.9 (3)
Pb1—O7—H7B	111.1	C14—C13—C19	120.5 (3)
Pb1—O7—H7A	111.5	O4—C14—C15	118.1 (3)
H7B—O7—H7A	105.1	O4—C14—C13	122.4 (3)
C2—N1—C1	118.1 (3)	C15—C14—C13	119.5 (3)
C2—N1—Pb1	123.9 (2)	C16—C15—C14	120.3 (4)
C1—N1—Pb1	117.9 (2)	C16—C15—H15	119.8
C11—N2—C12	118.2 (3)	C14—C15—H15	119.8
C11—N2—Pb1	123.3 (2)	C15—C16—C17	120.4 (4)
C12—N2—Pb1	118.5 (2)	C15—C16—H16	119.8
N1—C1—C5	122.7 (3)	C17—C16—H16	119.8
N1—C1—C12	119.0 (3)	C18—C17—C16	119.6 (3)
C5—C1—C12	118.3 (3)	C18—C17—S1	121.3 (3)
N1—C2—C3	123.4 (3)	C16—C17—S1	119.1 (3)
N1—C2—H2	118.3	C17—C18—C13	120.8 (3)
C3—C2—H2	118.3	C17—C18—H18	119.6
C4—C3—C2	119.3 (3)	C13—C18—H18	119.6
C4—C3—H3	120.3	O5—C19—O6	122.8 (3)
C2—C3—H3	120.3	O5—C19—C13	120.9 (3)
C3—C4—C5	120.1 (3)	O6—C19—C13	116.3 (3)
C3—C4—H4A	119.9	O9—C21—O8	115.5 (6)
C5—C4—H4A	119.9	O9—C21—C20	129.7 (5)
C4—C5—C6	123.8 (3)	O8—C21—C20	114.8 (5)

O2—S1—O3—Pb1ⁱ	−130.0 (2)	C5—C6—C7—C8	0.1 (7)
O1—S1—O3—Pb1ⁱ	101.4 (2)	C6—C7—C8—C12	−0.5 (7)
C17—S1—O3—Pb1ⁱ	−13.4 (3)	C6—C7—C8—C9	178.2 (4)
O6—Pb1—O5—C19	1.53 (19)	C12—C8—C9—C10	0.0 (6)
N2—Pb1—O5—C19	88.4 (2)	C7—C8—C9—C10	−178.8 (4)
N1—Pb1—O5—C19	34.7 (2)	C8—C9—C10—C11	−0.3 (7)
O3ⁱ—Pb1—O5—C19	−50.7 (2)	C12—N2—C11—C10	−1.1 (6)
O7—Pb1—O5—C19	163.1 (2)	Pb1—N2—C11—C10	179.1 (3)
N2—Pb1—O6—C19	−82.5 (2)	C9—C10—C11—N2	0.9 (7)
N1—Pb1—O6—C19	−151.5 (2)	C11—N2—C12—C8	0.8 (6)
O5—Pb1—O6—C19	−1.50 (19)	Pb1—N2—C12—C8	−179.4 (3)
O3ⁱ—Pb1—O6—C19	128.1 (2)	C11—N2—C12—C1	179.8 (4)
O7—Pb1—O6—C19	−28.9 (3)	Pb1—N2—C12—C1	−0.4 (4)
O6—Pb1—N1—C2	−99.5 (3)	C9—C8—C12—N2	−0.3 (6)
N2—Pb1—N1—C2	176.7 (3)	C7—C8—C12—N2	178.6 (4)
O5—Pb1—N1—C2	−125.1 (3)	C9—C8—C12—C1	−179.2 (4)
O3ⁱ—Pb1—N1—C2	−20.5 (3)	C7—C8—C12—C1	−0.4 (6)
O7—Pb1—N1—C2	124.2 (3)	N1—C1—C12—N2	1.4 (5)
O6—Pb1—N1—C1	84.9 (3)	C5—C1—C12—N2	−177.2 (3)
N2—Pb1—N1—C1	1.1 (3)	N1—C1—C12—C8	−179.5 (4)
O5—Pb1—N1—C1	59.2 (3)	C5—C1—C12—C8	1.8 (6)
O3ⁱ—Pb1—N1—C1	163.9 (3)	C18—C13—C14—O4	179.5 (3)
O7—Pb1—N1—C1	−51.5 (3)	C19—C13—C14—O4	1.5 (5)
O6—Pb1—N2—C11	101.2 (3)	C18—C13—C14—C15	1.3 (5)
N1—Pb1—N2—C11	179.5 (3)	C19—C13—C14—C15	−176.7 (3)
O5—Pb1—N2—C11	50.1 (3)	O4—C14—C15—C16	−179.3 (3)
O3ⁱ—Pb1—N2—C11	152.4 (3)	C13—C14—C15—C16	−1.1 (5)
O7—Pb1—N2—C11	−43.9 (3)	C14—C15—C16—C17	0.3 (6)
O6—Pb1—N2—C12	−78.6 (3)	C15—C16—C17—C18	0.2 (5)
N1—Pb1—N2—C12	−0.3 (3)	C15—C16—C17—S1	−179.1 (3)
O5—Pb1—N2—C12	−129.7 (3)	O2—S1—C17—C18	18.1 (3)
O3ⁱ—Pb1—N2—C12	−27.4 (3)	O3—S1—C17—C18	−103.0 (3)
O7—Pb1—N2—C12	136.3 (3)	O1—S1—C17—C18	138.5 (3)
C2—N1—C1—C5	1.0 (5)	O2—S1—C17—C16	−162.6 (3)
Pb1—N1—C1—C5	176.9 (3)	O3—S1—C17—C16	76.3 (3)
C2—N1—C1—C12	−177.6 (3)	O1—S1—C17—C16	−42.1 (3)
Pb1—N1—C1—C12	−1.7 (4)	C16—C17—C18—C13	0.0 (5)
C1—N1—C2—C3	1.2 (6)	S1—C17—C18—C13	179.4 (2)
Pb1—N1—C2—C3	−174.4 (3)	C14—C13—C18—C17	−0.8 (5)
N1—C2—C3—C4	−3.1 (6)	C19—C13—C18—C17	177.2 (3)
C2—C3—C4—C5	2.6 (6)	Pb1—O5—C19—O6	−2.7 (3)
C3—C4—C5—C6	179.0 (4)	Pb1—O5—C19—C13	179.1 (3)
C3—C4—C5—C1	−0.5 (6)	Pb1—O6—C19—O5	3.0 (4)
N1—C1—C5—C4	−1.3 (6)	Pb1—O6—C19—C13	−178.7 (2)
C12—C1—C5—C4	177.3 (4)	C18—C13—C19—O5	0.0 (5)
N1—C1—C5—C6	179.1 (4)	C14—C13—C19—O5	178.0 (3)
C12—C1—C5—C6	−2.2 (6)	C18—C13—C19—O6	−178.3 (3)
C4—C5—C6—C7	−178.1 (4)	C14—C13—C19—O6	−0.4 (5)
C1—C5—C6—C7	1.3 (6)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4···O6	0.82	1.83	2.522 (4)	141
O7—H7A···O2ⁱⁱⁱ	0.85	2.11	2.959 (5)	172

Symmetry code: (iii) −x+1, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	[Pb₂(C₇H₄O₆S)₂(C₁₂H₈N₂)₂(H₂O)₂]·C₂H₄O₂
M_r	1303.24
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	9.7372 (7), 10.1619 (5), 11.6637 (5)
α, β, γ (°)	74.171 (4), 74.379 (5), 79.748 (5)
V (Å³)	1062.50 (11)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	8.09
Crystal size (mm)	0.15 × 0.13 × 0.12

Data collection
Diffractometer	Oxford Xcalibur CCD
Absorption correction	Multi-scan (CrysAlis PRO; Oxford Diffraction, 2011)
T_min, T_max	0.309, 0.379
No. of measured, independent and observed [I > 2σ(I)] reflections	6374, 3745, 3438
R_int	0.036
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.027, 0.064, 1.05
No. of reflections	3745
No. of parameters	310
No. of restraints	28
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.83, −0.84

Computer programs: CrysAlis PRO (Oxford Diffraction, 2011), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997) and DIAMOND (Brandenburg, 2006), publCIF (Westrip, 2010).

Selected bond lengths (Å) top

Pb1—O6	2.472 (3)	Pb1—O3ⁱ	2.757 (3)
Pb1—N2	2.473 (3)	Pb1—O7	2.835 (4)
Pb1—N1	2.488 (3)	Pb1—O1ⁱⁱ	2.792 (1)
Pb1—O5	2.745 (3)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4···O6	0.82	1.83	2.522 (4)	141
O7—H7A···O2ⁱⁱⁱ	0.85	2.11	2.959 (5)	172

Symmetry code: (iii) −x+1, −y+1, −z+1.

Acknowledgements

The authors gratefully acknowledge financial support from Shandong Provincial Education Department (grant No. J09LB57)

References

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