Novel Ba²⁺ and Pb²⁺ metal–organic frameworks based on a semi-rigid tetra­carb­oxy­lic acid: syntheses, structures, topologies and luminescence properties

Multidentate carboxyl­ate ligands have been widely used in the construction of metal–organic frameworks (MOFs) owing to the rich variety of their coordination modes, which can lead to crystalline products with inter­esting structures and properties. Two new main-group MOFs, namely, poly[[di-μ-aqua-di­aqua­(di­methyl­formamide)[μ₇-5,5′-methyl­enebis(2,4,6-tri­methyl­benzene-1,3-di­car­box­yl­ato)]dibarium(II)] trihydrate], {[Ba₂(C₂₃H₂₀O₈)(C₃H₇NO)(H₂O)₄]·3H₂O}_n or {[Ba₂(BTMIPA)(DMF)(H₂O)₄]·3H₂O}_n (1), and poly[[di­aqua­[μ₆-5,5′-methyl­enebis(2,4,6-tri­methyl­benzene-1,3-di­carboxyl­ato)]dilead(II)] 2.5-hydrate], {[Pb₂(C₂₃H₂₀O₈)(H₂O)₂]·2.5H₂O}_n or {[Pb₂(BTMIPA)(H₂O)₂]·2.5H₂O}_n (2), were pre­pared by the self-assembly of metal salts with the semi-rigid tetra­carb­oxy­lic acid ligand 5,5′-methyl­enebis(2,4,6-tri­methyl­iso­phthalic acid) (H₄BTMIPA). Both structures were characterized by elemental analysis (EA), single-crystal X-ray diffraction, powder X-ray diffraction (PXRD), IR spectroscopy and thermogravimetric analysis (TGA). Com­plex 1 reveals a three-dimensional (3D) flu network formed via bridging tetra­nuclear secondary building units (SBUs) and com­plex 2 displays a 3D framework with an sqp topology based on one-dimensional metal chains. The BTMIPA⁴⁻ ligands adopt a rare coordination mode in 2, although the ligands in both 1 and 2 are X-shaped. The luminescence properties of both com­plexes were investigated in the solid state.

Computing details

For both structures, data collection: APEX2 (Bruker, 2005); cell refinement: APEX2 (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

Poly[[di-µ-aqua-diaqua(dimethylformamide)[µ₇-5,5'-methylenebis(2,4,6-trimethylbenzene-1,3-dicarboxylato)]dibarium(II)] trihydrate] (1)

Crystal data

[Ba2(C23H20O8)(C3H7NO)(H2O)4]·3H2O	F(000) = 1768
Mr = 898.26	Dx = 1.803 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 15.826 (4) Å	Cell parameters from 9037 reflections
b = 13.033 (3) Å	θ = 2.4–27.5°
c = 16.030 (4) Å	µ = 2.44 mm^−1
β = 93.074 (4)°	T = 293 K
V = 3301.4 (15) Å^3	Block, colourless
Z = 4	0.2 × 0.2 × 0.15 mm

Data collection

Bruker APEXII CCD area detector diffractometer	5034 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.065
phi and ω scans	θmax = 25.0°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −18→18
Tmin = 0.641, Tmax = 0.711	k = −14→15
16023 measured reflections	l = −15→19
5819 independent reflections

Refinement

Refinement on F^2	619 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.032	H-atom parameters constrained
wR(F^2) = 0.082	w = 1/[σ^2(Fo^2) + (0.043P)^2 + 1.1405P] where P = (Fo^2 + 2Fc^2)/3
S = 1.06	(Δ/σ)max = 0.001
5819 reflections	Δρmax = 1.26 e Å^−3
426 parameters	Δρmin = −0.62 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.

Refinement. Diffraction data were collected with a Bruker APEXII CCD single-crystal X-ray diffractometer with a graphite monochromated Mo-Kα radiation (λ = 0.71073 Å) source at room temperature. All absorption corrections were applied using the multiscan program SADABS. In all cases, the highest possible space group was chosen. All structures were solved by direct methods using the SHELXS97 program of the SHELXTL package (Sheldrick, 1997) and refined by the full-matrix least-squares method with SHELXL2014 and OLEX2 (Sheldrick, 2015; Dolomanov, 2009) Atoms were located from iterative examination of difference F-maps following least squares refinements of the earlier models.

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

	x	y	z	Uiso*/Ueq
Ba1	0.49800 (2)	0.45100 (2)	0.18681 (2)	0.02189 (9)
Ba2	0.43906 (2)	0.16381 (2)	0.04545 (2)	0.02595 (9)
O5	−0.34968 (19)	0.5489 (3)	0.1114 (2)	0.0430 (8)
O1W	0.4619 (2)	0.3859 (2)	0.02373 (19)	0.0315 (7)
O8	−0.0410 (2)	0.7993 (2)	0.19857 (19)	0.0356 (7)
C15	0.0645 (2)	0.2262 (3)	0.3733 (2)	0.0224 (8)
O4	0.05600 (18)	0.1324 (2)	0.38489 (17)	0.0297 (6)
C3	0.0931 (2)	0.2654 (3)	0.2903 (2)	0.0211 (8)
O3	0.05071 (19)	0.2941 (2)	0.42678 (18)	0.0332 (7)
C13	−0.0341 (2)	0.5616 (3)	0.1687 (2)	0.0221 (8)
C2	0.1790 (2)	0.2687 (3)	0.2769 (2)	0.0242 (8)
C16	−0.3020 (2)	0.5063 (3)	0.1642 (3)	0.0284 (9)
C9	−0.1557 (2)	0.4590 (3)	0.1234 (2)	0.0215 (8)
C8	−0.0676 (2)	0.4733 (3)	0.1297 (2)	0.0210 (7)
C4	0.0326 (2)	0.3032 (3)	0.2318 (2)	0.0215 (7)
C5	0.0580 (2)	0.3485 (3)	0.1575 (2)	0.0224 (8)
C1	0.2040 (2)	0.3102 (3)	0.2020 (3)	0.0252 (8)
C12	−0.0877 (2)	0.6286 (3)	0.2099 (2)	0.0237 (8)
C7	−0.0076 (2)	0.3946 (3)	0.0948 (2)	0.0240 (8)
H7A	0.022185	0.426883	0.050383	0.029*
H7B	−0.041113	0.339076	0.069930	0.029*
O6	−0.3286 (2)	0.4462 (3)	0.2183 (3)	0.0607 (11)
C11	−0.1742 (2)	0.6077 (3)	0.2134 (2)	0.0238 (8)
C20	0.1781 (3)	0.3921 (4)	0.0620 (3)	0.0392 (11)
H20A	0.142686	0.369015	0.015317	0.059*
H20B	0.234971	0.368557	0.056076	0.059*
H20C	0.177592	0.465749	0.064013	0.059*
C23	−0.1967 (3)	0.3737 (3)	0.0717 (3)	0.0313 (9)
H23A	−0.173443	0.372385	0.017641	0.047*
H23B	−0.256616	0.385373	0.065483	0.047*
H23C	−0.186137	0.309203	0.099243	0.047*
C10	−0.2071 (2)	0.5260 (3)	0.1662 (2)	0.0229 (8)
C6	0.1454 (2)	0.3498 (3)	0.1418 (2)	0.0228 (8)
C22	−0.2298 (3)	0.6735 (4)	0.2654 (3)	0.0376 (11)
H22A	−0.227242	0.648711	0.321884	0.056*
H22B	−0.287159	0.670245	0.242760	0.056*
H22C	−0.210380	0.743211	0.264595	0.056*
O1	0.3361 (2)	0.3945 (3)	0.2082 (3)	0.0662 (12)
C17	−0.0520 (2)	0.7270 (3)	0.2483 (3)	0.0259 (8)
C18	0.2430 (3)	0.2311 (4)	0.3431 (3)	0.0440 (12)
H18A	0.226643	0.253227	0.397029	0.066*
H18B	0.297676	0.258606	0.332662	0.066*
H18C	0.245274	0.157509	0.341705	0.066*
C19	−0.0596 (2)	0.2932 (3)	0.2505 (3)	0.0303 (9)
H19A	−0.066126	0.238515	0.289815	0.045*
H19B	−0.092365	0.278275	0.199824	0.045*
H19C	−0.078875	0.356300	0.273773	0.045*
C21	0.0581 (2)	0.5886 (3)	0.1664 (3)	0.0304 (9)
H21A	0.091063	0.540315	0.199549	0.046*
H21B	0.067175	0.656430	0.188410	0.046*
H21C	0.074817	0.586262	0.109739	0.046*
O2	0.3294 (2)	0.2394 (4)	0.1532 (2)	0.0708 (13)
C14	0.2970 (3)	0.3146 (4)	0.1860 (3)	0.0372 (10)
O7	−0.03688 (19)	0.7326 (2)	0.32496 (18)	0.0341 (7)
N1	0.5269 (4)	0.6220 (4)	0.4573 (3)	0.0606 (13)
O9	0.5082 (4)	0.5566 (3)	0.3294 (3)	0.0872 (16)
C24	0.5541 (6)	0.5858 (5)	0.3896 (4)	0.087 (2)
H24	0.612314	0.581101	0.385432	0.104*
C25	0.4385 (6)	0.6358 (7)	0.4696 (6)	0.111 (3)
H25A	0.406182	0.618260	0.419280	0.167*
H25B	0.428086	0.706177	0.483597	0.167*
H25C	0.422090	0.592343	0.514326	0.167*
C26	0.5775 (7)	0.6482 (6)	0.5286 (5)	0.118 (3)
H26A	0.628675	0.608593	0.530059	0.177*
H26B	0.547276	0.634093	0.577662	0.177*
H26C	0.591134	0.719925	0.526831	0.177*
O3W	0.3249 (2)	0.2465 (3)	−0.0657 (2)	0.0506 (9)
H3WA	0.326639	0.307674	−0.084021	0.061*
H3WB	0.281939	0.216674	−0.088641	0.061*
O2W	0.5794 (2)	0.0158 (3)	0.0724 (2)	0.0567 (10)
O4W	0.4126 (3)	−0.0102 (3)	0.1332 (2)	0.0658 (12)
H4WA	0.420490	−0.070662	0.115231	0.079*
H4WB	0.360920	−0.004082	0.144181	0.079*
O5W	0.2724 (4)	0.0186 (7)	−0.0006 (5)	0.162 (3)
H5WA	0.235027	0.043686	−0.035199	0.194*
H5WB	0.243046	0.002587	0.040552	0.194*
O6W	0.1923 (3)	0.1264 (3)	−0.1269 (2)	0.0676 (11)
H6WA	0.196549	0.102619	−0.175873	0.081*
H6WB	0.142909	0.147869	−0.117973	0.081*
O7W	0.2391 (3)	0.0248 (4)	0.1741 (3)	0.0860 (14)
H7WA	0.239997	0.084981	0.194632	0.129*
H7WB	0.212761	−0.015072	0.205710	0.129*
H1WA	0.498 (3)	0.386 (3)	−0.006 (3)	0.027 (13)*
H1WB	0.414 (5)	0.415 (5)	0.003 (4)	0.09 (2)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ba1	0.01685 (13)	0.02292 (14)	0.02587 (15)	−0.00069 (9)	0.00089 (10)	0.00247 (9)
Ba2	0.02899 (15)	0.02361 (14)	0.02588 (15)	0.00047 (10)	0.00718 (11)	0.00129 (9)
O5	0.0212 (16)	0.053 (2)	0.053 (2)	0.0006 (14)	−0.0127 (15)	0.0130 (16)
O1W	0.0342 (18)	0.0355 (18)	0.0254 (16)	0.0047 (15)	0.0062 (15)	−0.0007 (13)
O8	0.0394 (18)	0.0286 (16)	0.0385 (18)	−0.0057 (14)	0.0002 (14)	−0.0026 (14)
C15	0.0153 (17)	0.029 (2)	0.0227 (19)	−0.0004 (15)	0.0020 (15)	0.0005 (16)
O4	0.0365 (16)	0.0219 (15)	0.0315 (16)	−0.0052 (12)	0.0072 (13)	0.0006 (12)
C3	0.0192 (17)	0.0229 (17)	0.0218 (17)	0.0010 (14)	0.0053 (14)	−0.0023 (14)
O3	0.0423 (17)	0.0297 (16)	0.0290 (16)	−0.0032 (13)	0.0143 (14)	−0.0039 (13)
C13	0.0152 (16)	0.0262 (18)	0.0249 (17)	0.0021 (14)	−0.0006 (14)	0.0036 (15)
C2	0.0178 (17)	0.0303 (19)	0.0248 (18)	0.0008 (15)	0.0035 (15)	0.0003 (15)
C16	0.0165 (18)	0.030 (2)	0.038 (2)	−0.0001 (16)	−0.0020 (17)	−0.0010 (18)
C9	0.0163 (16)	0.0250 (17)	0.0228 (17)	−0.0011 (14)	−0.0024 (14)	0.0024 (14)
C8	0.0165 (16)	0.0242 (17)	0.0222 (17)	0.0018 (14)	0.0009 (14)	0.0004 (14)
C4	0.0154 (16)	0.0256 (17)	0.0240 (17)	−0.0009 (14)	0.0052 (14)	−0.0018 (15)
C5	0.0181 (16)	0.0253 (17)	0.0242 (17)	0.0003 (14)	0.0039 (15)	−0.0007 (14)
C1	0.0169 (17)	0.0321 (19)	0.0272 (19)	0.0043 (15)	0.0064 (15)	0.0017 (16)
C12	0.0187 (17)	0.0246 (18)	0.0276 (18)	0.0011 (15)	−0.0021 (15)	−0.0018 (15)
C7	0.0186 (17)	0.0301 (19)	0.0233 (18)	0.0017 (15)	0.0024 (15)	−0.0020 (15)
O6	0.0209 (17)	0.082 (3)	0.079 (3)	−0.0121 (17)	0.0006 (18)	0.042 (2)
C11	0.0160 (17)	0.0284 (19)	0.0272 (18)	0.0019 (15)	0.0023 (15)	0.0024 (15)
C20	0.028 (2)	0.054 (3)	0.037 (2)	0.007 (2)	0.016 (2)	0.011 (2)
C23	0.022 (2)	0.031 (2)	0.040 (2)	−0.0006 (17)	−0.0048 (18)	−0.0059 (19)
C10	0.0136 (16)	0.0266 (18)	0.0285 (19)	−0.0003 (14)	0.0013 (15)	0.0034 (15)
C6	0.0168 (16)	0.0281 (18)	0.0237 (18)	0.0037 (14)	0.0047 (15)	0.0014 (15)
C22	0.022 (2)	0.044 (3)	0.047 (3)	0.0059 (19)	0.005 (2)	−0.009 (2)
O1	0.0238 (18)	0.091 (3)	0.084 (3)	−0.017 (2)	0.0043 (19)	0.027 (2)
C17	0.0129 (17)	0.031 (2)	0.033 (2)	0.0033 (15)	−0.0029 (16)	−0.0044 (18)
C18	0.025 (2)	0.072 (3)	0.035 (2)	0.012 (2)	0.0031 (19)	0.014 (2)
C19	0.0179 (19)	0.040 (2)	0.033 (2)	−0.0011 (17)	0.0031 (17)	0.0095 (18)
C21	0.0185 (19)	0.030 (2)	0.043 (2)	−0.0011 (16)	0.0042 (18)	−0.0036 (19)
O2	0.038 (2)	0.128 (4)	0.048 (2)	0.045 (2)	0.0142 (17)	−0.002 (2)
C14	0.020 (2)	0.060 (3)	0.031 (2)	0.005 (2)	0.0048 (18)	0.013 (2)
O7	0.0336 (17)	0.0384 (17)	0.0295 (17)	−0.0015 (14)	−0.0066 (13)	−0.0053 (13)
N1	0.087 (4)	0.051 (3)	0.044 (3)	−0.005 (3)	0.013 (3)	−0.004 (2)
O9	0.159 (5)	0.057 (3)	0.043 (2)	0.007 (3)	−0.014 (3)	−0.0116 (19)
C24	0.150 (6)	0.055 (4)	0.056 (4)	0.005 (4)	0.013 (4)	0.007 (3)
C25	0.124 (7)	0.088 (5)	0.127 (6)	0.003 (5)	0.048 (5)	0.031 (5)
C26	0.198 (8)	0.080 (5)	0.073 (5)	−0.022 (5)	−0.029 (5)	0.008 (4)
O3W	0.044 (2)	0.052 (2)	0.054 (2)	−0.0051 (17)	−0.0148 (17)	0.0039 (17)
O2W	0.050 (2)	0.060 (2)	0.060 (2)	0.0113 (19)	−0.0008 (19)	−0.0136 (19)
O4W	0.093 (3)	0.037 (2)	0.070 (3)	0.000 (2)	0.036 (2)	0.0077 (18)
O5W	0.084 (4)	0.280 (10)	0.124 (6)	0.069 (5)	0.025 (4)	0.084 (6)
O6W	0.056 (2)	0.087 (3)	0.058 (2)	−0.005 (2)	−0.012 (2)	0.002 (2)
O7W	0.077 (3)	0.070 (3)	0.111 (4)	0.000 (3)	0.012 (3)	−0.004 (3)

Geometric parameters (Å, º)

Ba1—Ba2	4.4483 (9)	C7—H7A	0.9700
Ba1—O5^i	3.035 (3)	C7—H7B	0.9700
Ba1—O1W	2.778 (3)	C11—C10	1.390 (6)
Ba1—O8^ii	2.760 (3)	C11—C22	1.511 (6)
Ba1—O4^iii	2.745 (3)	C20—H20A	0.9600
Ba1—C16^i	3.286 (4)	C20—H20B	0.9600
Ba1—O6^i	2.764 (3)	C20—H20C	0.9600
Ba1—O1	2.705 (3)	C20—C6	1.510 (5)
Ba1—C17^ii	3.201 (4)	C23—H23A	0.9600
Ba1—O7^ii	2.921 (3)	C23—H23B	0.9600
Ba1—O9	2.665 (4)	C23—H23C	0.9600
Ba2—O1W	2.940 (3)	C22—H22A	0.9600
Ba2—O3^iv	2.721 (3)	C22—H22B	0.9600
Ba2—O2	2.699 (3)	C22—H22C	0.9600
Ba2—O7^ii	2.678 (3)	O1—C14	1.253 (6)
Ba2—O3W	2.694 (3)	C17—O7	1.242 (5)
Ba2—O2W	2.955 (4)	C18—H18A	0.9600
Ba2—O2W^v	3.013 (4)	C18—H18B	0.9600
Ba2—O4W	2.713 (3)	C18—H18C	0.9600
Ba2—O5W	3.297 (9)	C19—H19A	0.9600
O5—C16	1.235 (5)	C19—H19B	0.9600
O1W—H1WA	0.77 (5)	C19—H19C	0.9600
O1W—H1WB	0.89 (8)	C21—H21A	0.9600
O8—C17	1.252 (5)	C21—H21B	0.9600
C15—O4	1.245 (5)	C21—H21C	0.9600
C15—C3	1.517 (5)	O2—C14	1.237 (6)
C15—O3	1.259 (5)	N1—C24	1.278 (8)
C3—C2	1.389 (5)	N1—C25	1.434 (10)
C3—C4	1.394 (5)	N1—C26	1.402 (9)
C13—C8	1.400 (5)	O9—C24	1.236 (9)
C13—C12	1.406 (5)	C24—H24	0.9300
C13—C21	1.503 (5)	C25—H25A	0.9600
C2—C1	1.394 (6)	C25—H25B	0.9600
C2—C18	1.508 (6)	C25—H25C	0.9600
C16—O6	1.257 (5)	C26—H26A	0.9600
C16—C10	1.522 (5)	C26—H26B	0.9600
C9—C8	1.404 (5)	C26—H26C	0.9600
C9—C23	1.512 (5)	O3W—H3WA	0.8500
C9—C10	1.398 (5)	O3W—H3WB	0.8499
C8—C7	1.525 (5)	O4W—H4WA	0.8500
C4—C5	1.407 (5)	O4W—H4WB	0.8500
C4—C19	1.510 (5)	O5W—H5WA	0.8537
C5—C7	1.529 (5)	O5W—H5WB	0.8537
C5—C6	1.419 (5)	O6W—H6WA	0.8499
C1—C6	1.400 (6)	O6W—H6WB	0.8499
C1—C14	1.508 (6)	O7W—H7WA	0.8502
C12—C11	1.400 (5)	O7W—H7WB	0.8501
C12—C17	1.517 (6)
O5^i—Ba1—Ba2	107.48 (7)	O5—C16—Ba1^vi	67.5 (2)
O5^i—Ba1—C16^i	22.08 (9)	O5—C16—O6	122.5 (4)
O5^i—Ba1—C17^ii	107.99 (9)	O5—C16—C10	120.3 (4)
O1W—Ba1—Ba2	40.26 (6)	O6—C16—Ba1^vi	55.0 (2)
O1W—Ba1—O5^i	83.19 (10)	O6—C16—C10	117.2 (4)
O1W—Ba1—C16^i	96.55 (11)	C10—C16—Ba1^vi	171.9 (3)
O1W—Ba1—C17^ii	93.73 (10)	C8—C9—C23	122.2 (4)
O1W—Ba1—O7^ii	71.04 (9)	C10—C9—C8	118.9 (3)
O8^ii—Ba1—Ba2	76.92 (7)	C10—C9—C23	119.0 (3)
O8^ii—Ba1—O5^i	113.16 (9)	C13—C8—C9	119.4 (3)
O8^ii—Ba1—O1W	116.01 (9)	C13—C8—C7	119.2 (3)
O8^ii—Ba1—C16^i	91.47 (10)	C9—C8—C7	121.3 (3)
O8^ii—Ba1—O6^i	69.83 (10)	C3—C4—C5	120.0 (3)
O8^ii—Ba1—C17^ii	22.75 (10)	C3—C4—C19	118.2 (3)
O8^ii—Ba1—O7^ii	45.51 (9)	C5—C4—C19	121.8 (3)
O4^iii—Ba1—Ba2	117.34 (6)	C4—C5—C7	120.5 (3)
O4^iii—Ba1—O5^i	72.98 (8)	C4—C5—C6	118.7 (3)
O4^iii—Ba1—O1W	79.94 (9)	C6—C5—C7	120.8 (3)
O4^iii—Ba1—O8^ii	162.96 (9)	C2—C1—C6	121.9 (3)
O4^iii—Ba1—C16^i	92.58 (10)	C2—C1—C14	119.0 (4)
O4^iii—Ba1—O6^i	112.31 (10)	C6—C1—C14	119.1 (3)
O4^iii—Ba1—C17^ii	173.49 (9)	C13—C12—C17	119.6 (3)
O4^iii—Ba1—O7^ii	150.96 (8)	C11—C12—C13	120.9 (4)
C16^i—Ba1—Ba2	107.79 (7)	C11—C12—C17	119.4 (3)
O6^i—Ba1—Ba2	104.65 (9)	C8—C7—C5	115.9 (3)
O6^i—Ba1—O5^i	43.95 (9)	C8—C7—H7A	108.3
O6^i—Ba1—O1W	108.46 (12)	C8—C7—H7B	108.3
O6^i—Ba1—C16^i	21.88 (10)	C5—C7—H7A	108.3
O6^i—Ba1—C17^ii	71.02 (10)	C5—C7—H7B	108.3
O6^i—Ba1—O7^ii	77.25 (10)	H7A—C7—H7B	107.4
O1—Ba1—Ba2	70.21 (10)	C16—O6—Ba1^vi	103.1 (3)
O1—Ba1—O5^i	160.52 (10)	C12—C11—C22	120.7 (4)
O1—Ba1—O1W	83.57 (12)	C10—C11—C12	117.8 (4)
O1—Ba1—O8^ii	85.54 (11)	C10—C11—C22	121.5 (3)
O1—Ba1—O4^iii	90.68 (11)	H20A—C20—H20B	109.5
O1—Ba1—C16^i	176.71 (12)	H20A—C20—H20C	109.5
O1—Ba1—O6^i	155.30 (11)	H20B—C20—H20C	109.5
O1—Ba1—C17^ii	87.07 (11)	C6—C20—H20A	109.5
O1—Ba1—O7^ii	86.97 (12)	C6—C20—H20B	109.5
C17^ii—Ba1—Ba2	56.15 (7)	C6—C20—H20C	109.5
C17^ii—Ba1—C16^i	89.64 (10)	C9—C23—H23A	109.5
O7^ii—Ba1—Ba2	35.53 (6)	C9—C23—H23B	109.5
O7^ii—Ba1—O5^i	102.09 (9)	C9—C23—H23C	109.5
O7^ii—Ba1—C16^i	89.96 (9)	H23A—C23—H23B	109.5
O7^ii—Ba1—C17^ii	22.82 (9)	H23A—C23—H23C	109.5
O9—Ba1—Ba2	150.78 (10)	H23B—C23—H23C	109.5
O9—Ba1—O5^i	96.38 (14)	C9—C10—C16	118.9 (3)
O9—Ba1—O1W	164.67 (12)	C11—C10—C16	118.7 (3)
O9—Ba1—O8^ii	78.33 (11)	C11—C10—C9	122.3 (3)
O9—Ba1—O4^iii	85.27 (11)	C5—C6—C20	122.4 (4)
O9—Ba1—C16^i	88.07 (15)	C1—C6—C5	119.3 (3)
O9—Ba1—O6^i	80.86 (16)	C1—C6—C20	118.2 (3)
O9—Ba1—O1	92.66 (16)	C11—C22—H22A	109.5
O9—Ba1—C17^ii	100.93 (12)	C11—C22—H22B	109.5
O9—Ba1—O7^ii	123.74 (11)	C11—C22—H22C	109.5
O1W—Ba2—Ba1	37.64 (6)	H22A—C22—H22B	109.5
O1W—Ba2—O2W^v	134.36 (10)	H22A—C22—H22C	109.5
O1W—Ba2—O2W	124.29 (11)	H22B—C22—H22C	109.5
O1W—Ba2—O5W	129.83 (14)	C14—O1—Ba1	130.3 (3)
O3^iv—Ba2—Ba1	93.46 (6)	O8—C17—Ba1^iii	58.4 (2)
O3^iv—Ba2—O1W	68.29 (9)	O8—C17—C12	116.1 (4)
O3^iv—Ba2—O2W	73.90 (10)	C12—C17—Ba1^iii	171.7 (3)
O3^iv—Ba2—O2W^v	76.28 (10)	O7—C17—Ba1^iii	65.8 (2)
O3^iv—Ba2—O5W	120.04 (14)	O7—C17—O8	124.0 (4)
O2—Ba2—Ba1	59.45 (11)	O7—C17—C12	119.9 (4)
O2—Ba2—O1W	78.70 (13)	C2—C18—H18A	109.5
O2—Ba2—O3^iv	146.90 (12)	C2—C18—H18B	109.5
O2—Ba2—O2W	130.43 (11)	C2—C18—H18C	109.5
O2—Ba2—O2W^v	129.85 (13)	H18A—C18—H18B	109.5
O2—Ba2—O4W	81.44 (13)	H18A—C18—H18C	109.5
O2—Ba2—O5W	79.55 (16)	H18B—C18—H18C	109.5
O7^ii—Ba2—Ba1	39.33 (6)	C4—C19—H19A	109.5
O7^ii—Ba2—O1W	72.11 (9)	C4—C19—H19B	109.5
O7^ii—Ba2—O3^iv	96.02 (10)	C4—C19—H19C	109.5
O7^ii—Ba2—O2	75.32 (11)	H19A—C19—H19B	109.5
O7^ii—Ba2—O3W	135.95 (10)	H19A—C19—H19C	109.5
O7^ii—Ba2—O2W^v	141.17 (10)	H19B—C19—H19C	109.5
O7^ii—Ba2—O2W	72.91 (10)	C13—C21—H21A	109.5
O7^ii—Ba2—O4W	88.65 (11)	C13—C21—H21B	109.5
O7^ii—Ba2—O5W	142.01 (13)	C13—C21—H21C	109.5
O3W—Ba2—Ba1	96.61 (8)	H21A—C21—H21B	109.5
O3W—Ba2—O1W	67.05 (10)	H21A—C21—H21C	109.5
O3W—Ba2—O3^iv	83.93 (10)	H21B—C21—H21C	109.5
O3W—Ba2—O2	81.13 (11)	C14—O2—Ba2	148.9 (4)
O3W—Ba2—O2W^v	81.79 (11)	O1—C14—C1	117.1 (4)
O3W—Ba2—O2W	146.09 (11)	O2—C14—C1	118.2 (5)
O3W—Ba2—O4W	124.12 (13)	O2—C14—O1	124.8 (5)
O3W—Ba2—O5W	65.26 (14)	Ba2^iii—O7—Ba1^iii	105.14 (9)
O2W—Ba2—Ba1	109.82 (7)	C17—O7—Ba1^iii	91.4 (2)
O2W^v—Ba2—Ba1	169.71 (8)	C17—O7—Ba2^iii	145.2 (3)
O2W—Ba2—O2W^v	68.37 (12)	C24—N1—C25	122.6 (7)
O2W—Ba2—O5W	104.12 (15)	C24—N1—C26	125.3 (8)
O2W^v—Ba2—O5W	50.52 (15)	C26—N1—C25	112.0 (7)
O4W—Ba2—Ba1	118.26 (9)	C24—O9—Ba1	146.6 (6)
O4W—Ba2—O1W	155.21 (10)	N1—C24—H24	117.8
O4W—Ba2—O3^iv	130.91 (11)	O9—C24—N1	124.5 (9)
O4W—Ba2—O2W^v	70.30 (12)	O9—C24—H24	117.8
O4W—Ba2—O2W	60.93 (12)	N1—C25—H25A	109.5
O4W—Ba2—O5W	59.51 (15)	N1—C25—H25B	109.5
O5W—Ba2—Ba1	137.76 (13)	N1—C25—H25C	109.5
C16—O5—Ba1^vi	90.4 (3)	H25A—C25—H25B	109.5
Ba1—O1W—Ba2	102.09 (10)	H25A—C25—H25C	109.5
Ba1—O1W—H1WA	118 (3)	H25B—C25—H25C	109.5
Ba1—O1W—H1WB	110 (4)	N1—C26—H26A	109.5
Ba2—O1W—H1WA	100 (3)	N1—C26—H26B	109.5
Ba2—O1W—H1WB	111 (4)	N1—C26—H26C	109.5
H1WA—O1W—H1WB	114 (5)	H26A—C26—H26B	109.5
C17—O8—Ba1^iii	98.8 (2)	H26A—C26—H26C	109.5
O4—C15—C3	120.1 (3)	H26B—C26—H26C	109.5
O4—C15—O3	124.4 (4)	Ba2—O3W—H3WA	124.8
O3—C15—C3	115.6 (3)	Ba2—O3W—H3WB	126.5
C15—O4—Ba1^ii	144.8 (3)	H3WA—O3W—H3WB	108.6
C2—C3—C15	119.2 (3)	Ba2—O2W—Ba2^v	111.63 (12)
C2—C3—C4	121.9 (3)	Ba2—O4W—H4WA	124.7
C4—C3—C15	118.8 (3)	Ba2—O4W—H4WB	101.9
C15—O3—Ba2^vii	139.5 (3)	H4WA—O4W—H4WB	108.5
C8—C13—C12	119.8 (3)	Ba2—O5W—H5WA	116.4
C8—C13—C21	121.7 (3)	Ba2—O5W—H5WB	115.4
C12—C13—C21	118.5 (4)	H5WA—O5W—H5WB	102.0
C3—C2—C1	118.1 (4)	H6WA—O6W—H6WB	113.2
C3—C2—C18	120.4 (4)	H7WA—O7W—H7WB	109.4
C1—C2—C18	121.5 (3)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C26—H26B···O8^viii	0.96	2.60	3.458 (11)	149
O3W—H3WA···O5^ix	0.85	1.96	2.798 (5)	169
O3W—H3WB···O6W	0.85	1.92	2.756 (5)	169
O4W—H4WA···O3^ii	0.85	1.95	2.797 (5)	175
O4W—H4WB···O7W	0.85	2.05	2.894 (7)	175
O5W—H5WA···O6W	0.85	1.92	2.720 (7)	156
O5W—H5WB···O7W	0.85	2.16	2.879 (9)	141
O6W—H6WA···O6^iv	0.85	1.84	2.660 (5)	163
O6W—H6WB···O8^ix	0.85	2.13	2.774 (5)	133
O1W—H1WA···O4^iv	0.77 (5)	2.03 (5)	2.754 (4)	158 (5)
O1W—H1WB···O5^ix	0.89 (8)	2.11 (7)	2.856 (4)	141 (6)

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

Poly[[diaqua[µ₆-5,5'-methylenebis(2,4,6-trimethylbenzene-1,3-dicarboxylato)]dilead(II)] 2.5-hydrate] (2)

Crystal data

[Pb2(C23H20O8)(H2O)2]·2.5H2O	F(000) = 1724
Mr = 919.84	Dx = 2.383 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 11.607 (5) Å	Cell parameters from 2381 reflections
b = 14.951 (6) Å	θ = 2.4–23.9°
c = 15.017 (6) Å	µ = 13.18 mm^−1
β = 100.287 (7)°	T = 293 K
V = 2564.2 (19) Å^3	Block, colourless
Z = 4	0.2 × 0.1 × 0.1 mm

Data collection

Bruker APEXII CCD area detector diffractometer	2181 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.082
phi and ω scans	θmax = 25.0°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −12→13
Tmin = 0.178, Tmax = 0.353	k = −17→12
12082 measured reflections	l = −17→17
4490 independent reflections

Refinement

Refinement on F^2	42 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.062	H-atom parameters constrained
wR(F^2) = 0.165	w = 1/[σ^2(Fo^2) + (0.0833P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.90	(Δ/σ)max = 0.001
4490 reflections	Δρmax = 1.75 e Å^−3
340 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.

Refinement. Diffraction data were collected with a Bruker APEX II CCD single-crystal X-ray diffractometer with a graphite monochromated Mo-Kα radiation (λ = 0.71073 Å) source at room temperature. All absorption corrections were applied using the multiscan program SADABS. In all cases, the highest possible space group was chosen. All structures were solved by direct methods using the SHELXS97 program of the SHELXTL package (Sheldrick, 1997) and refined by the full-matrix least-squares method with SHELXL2014 and OLEX2 (Sheldrick, 2015; Dolomanov, 2009) Atoms were located from iterative examination of difference F-maps following least squares refinements of the earlier models.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
C1	0.5587 (13)	0.8276 (14)	−0.3166 (10)	0.050 (4)
C2	0.6121 (12)	0.8055 (12)	−0.2186 (9)	0.050 (4)
C3	0.5499 (11)	0.7622 (10)	−0.1653 (8)	0.034 (4)
C4	0.6005 (12)	0.7499 (11)	−0.0710 (9)	0.040 (4)
C5	0.7112 (11)	0.7862 (10)	−0.0396 (8)	0.032 (4)
C6	0.7741 (11)	0.8272 (11)	−0.0989 (8)	0.036 (4)
C7	0.7276 (12)	0.8410 (10)	−0.1893 (9)	0.041 (4)
C8	0.7891 (12)	0.8914 (12)	−0.2514 (9)	0.054 (5)
H8A	0.758670	0.951175	−0.258313	0.081*
H8B	0.777113	0.862273	−0.309308	0.081*
H8C	0.871284	0.893364	−0.226952	0.081*
C9	0.4297 (11)	0.7278 (13)	−0.2031 (9)	0.056 (5)
H9A	0.422853	0.666997	−0.184249	0.084*
H9B	0.417054	0.730526	−0.267981	0.084*
H9C	0.372301	0.763965	−0.181256	0.084*
C10	0.7594 (13)	0.7859 (12)	0.0607 (8)	0.048 (4)
H10A	0.807217	0.733721	0.075732	0.073*
H10B	0.695918	0.785123	0.093750	0.073*
H10C	0.805925	0.838566	0.076261	0.073*
C11	0.8981 (17)	0.8506 (13)	−0.0672 (10)	0.053 (5)
C12	0.5316 (12)	0.7012 (10)	−0.0082 (9)	0.042 (4)
H12A	0.505384	0.744607	0.031867	0.051*
H12B	0.462607	0.674504	−0.044374	0.051*
C13	0.5985 (11)	0.6313 (12)	0.0466 (9)	0.040 (4)
C14	0.5981 (12)	0.6391 (13)	0.1427 (9)	0.053 (5)
C15	0.6592 (12)	0.5730 (12)	0.2025 (9)	0.045 (4)
C16	0.7280 (13)	0.5056 (14)	0.1687 (11)	0.063 (6)
C17	0.7251 (13)	0.5030 (13)	0.0788 (9)	0.051 (5)
C18	0.6595 (12)	0.5604 (11)	0.0195 (8)	0.036 (4)
C19	0.6454 (13)	0.5453 (13)	−0.0825 (8)	0.055 (5)
H19A	0.564881	0.553840	−0.110009	0.082*
H19B	0.668940	0.485478	−0.093958	0.082*
H19C	0.693414	0.587199	−0.107752	0.082*
C20	0.5394 (15)	0.7133 (13)	0.1807 (9)	0.064 (5)
H20A	0.587348	0.765982	0.183908	0.096*
H20B	0.527375	0.697669	0.240372	0.096*
H20C	0.465204	0.724836	0.142738	0.096*
C21	0.8009 (13)	0.4384 (15)	0.2320 (10)	0.073 (6)
H21A	0.882261	0.445932	0.229117	0.109*
H21B	0.776958	0.378675	0.213741	0.109*
H21C	0.789124	0.448316	0.292910	0.109*
C22	0.805 (2)	0.4427 (17)	0.0428 (12)	0.069 (6)
C23	0.6601 (18)	0.5734 (19)	0.3006 (12)	0.090 (4)
O1	0.5651 (10)	0.7680 (9)	−0.3737 (7)	0.072 (4)
O1W	0.4180 (14)	0.9234 (12)	−0.6763 (9)	0.114 (6)
O2	0.5144 (10)	0.9030 (8)	−0.3388 (7)	0.062 (3)
O2W	0.7612 (18)	0.717 (2)	0.5434 (14)	0.082 (5)	0.5
Pb2A	0.66222 (19)	0.6516 (3)	0.47983 (15)	0.0635 (10)	0.28
O2WA	0.585 (2)	0.5847 (17)	0.6611 (15)	0.072 (7)	0.5
O3	0.9155 (12)	0.9259 (11)	−0.0372 (9)	0.088 (4)
O4	0.9758 (11)	0.8020 (13)	−0.0733 (10)	0.102 (6)
O5	0.8863 (8)	0.4764 (9)	0.0085 (7)	0.058 (3)
O6	0.7955 (14)	0.3630 (13)	0.0476 (10)	0.105 (5)
O7	0.7144 (13)	0.6376 (12)	0.3462 (9)	0.112 (4)
O8	0.5973 (10)	0.5281 (10)	0.3372 (7)	0.083 (4)
Pb1	0.46165 (6)	0.86877 (5)	−0.50455 (4)	0.0621 (3)
Pb2	0.63141 (10)	0.57361 (11)	0.48633 (6)	0.0751 (5)	0.72

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.055 (8)	0.067 (10)	0.026 (7)	−0.007 (8)	−0.001 (6)	0.007 (7)
C2	0.041 (9)	0.063 (13)	0.041 (9)	−0.025 (9)	−0.005 (7)	−0.015 (9)
C3	0.035 (8)	0.042 (11)	0.025 (7)	−0.001 (7)	0.001 (6)	0.012 (7)
C4	0.041 (9)	0.048 (11)	0.032 (8)	−0.011 (8)	0.012 (6)	−0.006 (7)
C5	0.039 (8)	0.037 (10)	0.021 (7)	−0.018 (7)	0.008 (6)	0.006 (6)
C6	0.040 (8)	0.045 (11)	0.024 (7)	−0.016 (8)	0.006 (6)	0.003 (7)
C7	0.038 (8)	0.056 (13)	0.026 (7)	−0.008 (8)	0.002 (6)	0.009 (7)
C8	0.044 (9)	0.086 (16)	0.035 (8)	−0.008 (9)	0.013 (7)	0.021 (9)
C9	0.029 (8)	0.100 (17)	0.035 (8)	−0.016 (9)	−0.003 (6)	0.017 (9)
C10	0.060 (10)	0.061 (13)	0.023 (7)	−0.018 (9)	0.004 (7)	0.005 (8)
C11	0.068 (13)	0.060 (16)	0.033 (9)	−0.022 (11)	0.013 (8)	−0.012 (9)
C12	0.043 (9)	0.039 (10)	0.052 (9)	−0.022 (8)	0.026 (7)	0.000 (8)
C13	0.014 (7)	0.062 (12)	0.044 (9)	−0.014 (8)	0.003 (6)	0.014 (9)
C14	0.039 (9)	0.092 (15)	0.031 (8)	0.014 (10)	0.014 (7)	0.002 (9)
C15	0.033 (8)	0.078 (14)	0.029 (8)	−0.017 (9)	0.018 (7)	−0.002 (8)
C16	0.039 (9)	0.107 (18)	0.048 (10)	−0.022 (10)	0.018 (8)	0.008 (10)
C17	0.045 (9)	0.096 (16)	0.016 (7)	−0.029 (10)	0.016 (7)	−0.007 (9)
C18	0.039 (8)	0.060 (12)	0.011 (6)	−0.028 (8)	0.009 (6)	−0.001 (7)
C19	0.059 (10)	0.088 (15)	0.015 (7)	0.003 (10)	−0.001 (6)	0.012 (8)
C20	0.082 (12)	0.084 (16)	0.033 (8)	−0.005 (11)	0.032 (8)	−0.010 (9)
C21	0.049 (10)	0.115 (19)	0.047 (11)	−0.005 (11)	−0.008 (8)	0.023 (11)
C22	0.097 (16)	0.067 (16)	0.045 (11)	0.007 (14)	0.020 (10)	0.026 (11)
C23	0.083 (9)	0.152 (13)	0.045 (7)	−0.005 (8)	0.038 (6)	−0.008 (7)
O1	0.087 (9)	0.098 (11)	0.027 (6)	−0.016 (8)	0.003 (6)	−0.005 (7)
O1W	0.158 (14)	0.120 (15)	0.071 (9)	0.036 (11)	0.039 (9)	0.024 (9)
O2	0.082 (7)	0.064 (9)	0.032 (6)	0.002 (6)	−0.016 (5)	0.016 (5)
O2W	0.048 (8)	0.137 (10)	0.054 (8)	0.016 (9)	−0.013 (7)	−0.009 (9)
Pb2A	0.0314 (13)	0.132 (3)	0.0259 (12)	0.0276 (16)	0.0026 (9)	−0.0082 (15)
O2WA	0.091 (10)	0.069 (11)	0.066 (10)	0.019 (8)	0.043 (8)	0.000 (8)
O3	0.089 (6)	0.093 (6)	0.085 (6)	−0.026 (5)	0.023 (4)	−0.010 (4)
O4	0.042 (8)	0.147 (17)	0.116 (12)	−0.008 (9)	0.014 (7)	0.064 (11)
O5	0.043 (6)	0.093 (11)	0.039 (6)	−0.020 (7)	0.008 (5)	−0.008 (6)
O6	0.123 (13)	0.115 (15)	0.094 (11)	0.023 (12)	0.067 (9)	0.016 (11)
O7	0.107 (9)	0.177 (13)	0.061 (8)	−0.026 (9)	0.037 (7)	−0.037 (8)
O8	0.075 (7)	0.141 (12)	0.045 (6)	0.016 (7)	0.041 (5)	0.014 (7)
Pb1	0.0779 (5)	0.0674 (6)	0.0329 (4)	−0.0143 (4)	−0.0115 (3)	0.0087 (4)
Pb2	0.0669 (7)	0.1270 (13)	0.0349 (5)	0.0449 (8)	0.0187 (5)	0.0194 (7)

Geometric parameters (Å, º)

C1—C2	1.53 (2)	C16—C17	1.346 (19)
C1—O1	1.25 (2)	C16—C21	1.53 (2)
C1—O2	1.26 (2)	C17—C18	1.37 (2)
C2—C3	1.337 (19)	C17—C22	1.46 (3)
C2—C7	1.436 (18)	C18—C19	1.528 (16)
C3—C4	1.444 (17)	C19—H19A	0.9600
C3—C9	1.500 (18)	C19—H19B	0.9600
C4—C5	1.396 (18)	C19—H19C	0.9600
C4—C12	1.525 (17)	C20—H20A	0.9600
C5—C6	1.392 (17)	C20—H20B	0.9600
C5—C10	1.509 (16)	C20—H20C	0.9600
C6—C7	1.384 (17)	C21—H21A	0.9600
C6—C11	1.48 (2)	C21—H21B	0.9600
C7—C8	1.478 (18)	C21—H21C	0.9600
C8—H8A	0.9600	C22—O5	1.26 (2)
C8—H8B	0.9600	C22—O6	1.20 (2)
C8—H8C	0.9600	C23—O7	1.28 (3)
C9—H9A	0.9600	C23—O8	1.20 (2)
C9—H9B	0.9600	C23—Pb2	2.867 (17)
C9—H9C	0.9600	O1—Pb1	2.594 (12)
C10—H10A	0.9600	O1W—Pb1	2.666 (13)
C10—H10B	0.9600	O2—Pb1	2.508 (10)
C10—H10C	0.9600	O2W—Pb2A	1.67 (2)
C11—O3	1.22 (2)	O2W—Pb2	2.68 (3)
C11—O4	1.17 (2)	Pb2A—O4^i	2.277 (13)
C12—H12A	0.9700	Pb2A—O7	2.208 (12)
C12—H12B	0.9700	Pb2A—Pb2	1.229 (4)
C12—C13	1.46 (2)	O3—Pb2^ii	2.467 (13)
C13—C14	1.448 (19)	O3—Pb2^iii	2.431 (16)
C13—C18	1.38 (2)	O4—Pb2^ii	2.636 (16)
C14—C15	1.44 (2)	O5—Pb1^iv	2.397 (12)
C14—C20	1.47 (2)	O5—Pb1^v	2.495 (13)
C15—C16	1.43 (2)	O7—Pb2	2.645 (14)
C15—C23	1.47 (2)	O8—Pb2	2.307 (11)
O1—C1—C2	116.3 (17)	H20B—C20—H20C	109.5
O1—C1—O2	122.0 (14)	C16—C21—H21A	109.5
O2—C1—C2	121.6 (16)	C16—C21—H21B	109.5
C3—C2—C1	120.8 (12)	C16—C21—H21C	109.5
C3—C2—C7	124.7 (13)	H21A—C21—H21B	109.5
C7—C2—C1	114.3 (13)	H21A—C21—H21C	109.5
C2—C3—C4	118.7 (12)	H21B—C21—H21C	109.5
C2—C3—C9	120.3 (12)	O5—C22—C17	118 (2)
C4—C3—C9	121.0 (12)	O6—C22—C17	121 (2)
C3—C4—C12	120.0 (12)	O6—C22—O5	120 (2)
C5—C4—C3	118.0 (12)	C15—C23—Pb2	173.0 (13)
C5—C4—C12	121.9 (12)	O7—C23—C15	117 (2)
C4—C5—C10	119.4 (11)	O7—C23—Pb2	67.1 (10)
C6—C5—C4	120.8 (11)	O8—C23—C15	124 (2)
C6—C5—C10	119.7 (12)	O8—C23—O7	117.5 (17)
C5—C6—C11	119.5 (12)	O8—C23—Pb2	50.9 (9)
C7—C6—C5	122.4 (12)	C1—O1—Pb1	91.7 (11)
C7—C6—C11	117.9 (12)	C1—O2—Pb1	95.5 (10)
C2—C7—C8	121.6 (12)	Pb2A—O2W—Pb2	19.4 (5)
C6—C7—C2	115.2 (12)	O2W—Pb2A—O4^i	122.3 (10)
C6—C7—C8	123.2 (12)	O2W—Pb2A—O7	107.6 (9)
C7—C8—H8A	109.5	O7—Pb2A—O4^i	96.2 (6)
C7—C8—H8B	109.5	Pb2—Pb2A—O2W	133.7 (9)
C7—C8—H8C	109.5	Pb2—Pb2A—O4^i	92.6 (5)
H8A—C8—H8B	109.5	Pb2—Pb2A—O7	96.5 (5)
H8A—C8—H8C	109.5	C11—O3—Pb2^ii	98.8 (13)
H8B—C8—H8C	109.5	C11—O3—Pb2^iii	157.8 (14)
C3—C9—H9A	109.5	Pb2^iii—O3—Pb2^ii	103.4 (5)
C3—C9—H9B	109.5	C11—O4—Pb2A^ii	118.6 (16)
C3—C9—H9C	109.5	C11—O4—Pb2^ii	91.4 (14)
H9A—C9—H9B	109.5	Pb2A^ii—O4—Pb2^ii	27.8 (2)
H9A—C9—H9C	109.5	C22—O5—Pb1^iv	110.5 (13)
H9B—C9—H9C	109.5	C22—O5—Pb1^v	134.6 (14)
C5—C10—H10A	109.5	Pb1^iv—O5—Pb1^v	110.5 (4)
C5—C10—H10B	109.5	C23—O7—Pb2A	111.7 (12)
C5—C10—H10C	109.5	C23—O7—Pb2	86.5 (12)
H10A—C10—H10B	109.5	Pb2A—O7—Pb2	27.50 (19)
H10A—C10—H10C	109.5	C23—O8—Pb2	105.4 (14)
H10B—C10—H10C	109.5	O1—Pb1—O1W	153.2 (4)
O3—C11—C6	115.3 (19)	O2—Pb1—O1	50.8 (4)
O4—C11—C6	123.1 (18)	O2—Pb1—O1W	150.3 (5)
O4—C11—O3	121.6 (19)	O5^vi—Pb1—O1	99.5 (4)
C4—C12—H12A	108.8	O5^vii—Pb1—O1	126.9 (4)
C4—C12—H12B	108.8	O5^vii—Pb1—O1W	77.5 (4)
H12A—C12—H12B	107.7	O5^vi—Pb1—O1W	77.5 (5)
C13—C12—C4	113.8 (12)	O5^vi—Pb1—O2	80.7 (4)
C13—C12—H12A	108.8	O5^vii—Pb1—O2	76.1 (4)
C13—C12—H12B	108.8	O5^vi—Pb1—O5^vii	69.5 (4)
C14—C13—C12	114.0 (15)	O2W—Pb2—C23	99.0 (7)
C18—C13—C12	129.2 (13)	Pb2A—Pb2—C23	80.7 (6)
C18—C13—C14	116.8 (13)	Pb2A—Pb2—O2W	26.9 (5)
C13—C14—C20	122.2 (15)	Pb2A—Pb2—O3^i	106.7 (4)
C15—C14—C13	118.6 (14)	Pb2A—Pb2—O3^viii	166.5 (4)
C15—C14—C20	119.2 (13)	Pb2A—Pb2—O4^i	59.6 (4)
C14—C15—C23	122.5 (16)	Pb2A—Pb2—O7	56.0 (4)
C16—C15—C14	120.5 (13)	Pb2A—Pb2—O8	101.8 (4)
C16—C15—C23	116.9 (16)	O3^i—Pb2—C23	98.8 (5)
C15—C16—C21	121.5 (14)	O3^viii—Pb2—C23	112.1 (6)
C17—C16—C15	117.3 (16)	O3^i—Pb2—O2W	122.9 (6)
C17—C16—C21	121.1 (17)	O3^viii—Pb2—O2W	140.7 (6)
C16—C17—C18	123.2 (17)	O3^viii—Pb2—O3^i	76.6 (5)
C16—C17—C22	118.9 (16)	O3^i—Pb2—O4^i	48.1 (5)
C18—C17—C22	117.6 (13)	O3^viii—Pb2—O4^i	124.7 (5)
C13—C18—C19	116.2 (14)	O3^i—Pb2—O7	112.9 (5)
C17—C18—C13	123.2 (12)	O3^viii—Pb2—O7	135.4 (5)
C17—C18—C19	120.6 (15)	O4^i—Pb2—C23	82.0 (6)
C18—C19—H19A	109.5	O4^i—Pb2—O2W	81.6 (6)
C18—C19—H19B	109.5	O4^i—Pb2—O7	78.4 (5)
C18—C19—H19C	109.5	O7—Pb2—C23	26.4 (5)
H19A—C19—H19B	109.5	O7—Pb2—O2W	72.6 (6)
H19A—C19—H19C	109.5	O8—Pb2—C23	23.8 (6)
H19B—C19—H19C	109.5	O8—Pb2—O2W	122.5 (6)
C14—C20—H20A	109.5	O8—Pb2—O3^i	82.4 (4)
C14—C20—H20B	109.5	O8—Pb2—O3^viii	91.6 (5)
C14—C20—H20C	109.5	O8—Pb2—O4^i	83.7 (4)
H20A—C20—H20B	109.5	O8—Pb2—O7	50.0 (5)
H20A—C20—H20C	109.5

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