Coordination polymers of Cd^II and Pb^II derived from bi­pyridine–glycoluril: influence of metal-ion size and counter-ions

Two new one-dimensional (1D) coordination polymers (CPs), namely catena-poly[[[aqua­cadmium(II)]-bis­(μ-4b,5,7,7a-tetra­hydro-4b,7a-epimino­methano­imino-6H-imidazo[4,5-f][1,10]phenanthroline-6,13-dione)] bis­(perchlorate) dihydrate], {[Cd(C₁₄H₁₀N₆O₂)₂(H₂O)](ClO₄)₂·2H₂O}_n or {[Cd(BPG)₂(H₂O)](ClO₄)₂·2H₂O}_n, 1, and catena-poly[[lead(II)-bis­(μ-4b,5,7,7a-tetra­hydro-4b,7a-epimino­methano­imino-6H-imidazo[4,5-f][1,10]phenanthroline-6,13-dione)] bis­(perchlorate) di­hydrate], {[Pb(C₁₄H₁₀N₆O₂)₂](ClO₄)₂·2H₂O}_n or {[Pb(BPG)₂](ClO₄)₂·2H₂O}_n, 2, have been synthesized using bi­pyridine–glycoluril (BPG; systematic name: 4b,5,7,7a-tetra­hydro-4b,7a-epimino­methano­imino-6H-imidazo[4,5-f][1,10]phen­anthroline-6,13-dione), a urea-fused tecton, in a mixed-solvent system. The Cd^II ion in 1 is hepta­coordinated and the Pb^II ion in 2 is hexa­coordinated, with the Cd^II ion adopting a penta­gonal bipyramidal geometry and the Pb^II ion adopting a distorted octa­hedral geometry. Both CPs form infinite linear chain structures which are hydrogen bonded to each other leading to the formation of three-dimensional supra­molecular network structures. Topological analysis of CPs 1 and 2 reveals that the structures exhibit 1D chain-like arrangements in an AB–AB sequence and shows platonic uniform 2-connected uninodal topologies. Furthermore, a comparative analysis of a series of structures based on the BPG ligand indicates that the size of the metal ion and the types of counter-ions used have a great influence on the resulting frameworks and properties.

Computing details

Data collection: APEX2 (Bruker, 2013) for (1); CrysAlis PRO (Agilent, 2013) for (2). Cell refinement: SAINT (Bruker, 2013) for (1); CrysAlis PRO (Agilent, 2013) for (2). Data reduction: SAINT (Bruker, 2013) for (1); CrysAlis PRO (Agilent, 2013) for (2). For both structures, program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009), ORTEP-3 for Windows (Farrugia, 2012), Mercury (Macrae et al., 2008) and PLATON (Spek, 2009).

catena-Poly[[[aquacadmium(II)]-bis(µ-4b,5,7,7a-tetrahydro-4b,7a-epiminomethanoimino-6H-imidazo[4,5-f][1,10]phenanthroline-6,13-dione)] bis(perchlorate) dihydrate] (1)

Crystal data

[Cd(C14H10N6O2)2(H2O)](ClO4)2·2H2O	F(000) = 1920
Mr = 953.91	Dx = 1.960 Mg m^−3
Monoclinic, I2/a	Mo Kα radiation, λ = 0.71073 Å
a = 15.146 (3) Å	Cell parameters from 9068 reflections
b = 12.2411 (11) Å	θ = 3.0–25.1°
c = 17.6555 (16) Å	µ = 0.94 mm^−1
β = 99.104 (2)°	T = 293 K
V = 3232.2 (8) Å^3	Rectangle, pale yellow
Z = 4	0.4 × 0.4 × 0.2 mm

Data collection

Bruker APEXII CCD diffractometer	2683 reflections with I > 2σ(I)
φ and ω scans	Rint = 0.037
Absorption correction: multi-scan (SADABS; Bruker, 2013)	θmax = 25.1°, θmin = 3.0°
Tmin = 0.685, Tmax = 0.745	h = −18→18
52684 measured reflections	k = −14→14
2886 independent reflections	l = −21→21

Refinement

Refinement on F^2	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.026	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.064	w = 1/[σ^2(Fo^2) + (0.026P)^2 + 12.5975P] where P = (Fo^2 + 2Fc^2)/3
S = 1.11	(Δ/σ)max = 0.001
2886 reflections	Δρmax = 0.60 e Å^−3
316 parameters	Δρmin = −0.54 e Å^−3
0 restraints

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	Occ. (<1)
Cd1	0.750000	0.30737 (2)	0.500000	0.01258 (9)
O1	0.37182 (11)	0.76446 (14)	0.60525 (10)	0.0173 (4)
O2	0.76411 (11)	0.84787 (14)	0.66612 (10)	0.0158 (4)
O2W	0.7336 (3)	0.1334 (3)	0.5187 (2)	0.0257 (10)	0.5
H2WA	0.714757	0.122456	0.561996	0.039*	0.5
H2WB	0.784769	0.100096	0.524708	0.039*	0.5
N1	0.66664 (13)	0.37167 (16)	0.59002 (11)	0.0123 (4)
N2	0.65803 (13)	0.46488 (16)	0.44986 (11)	0.0130 (4)
N3	0.50303 (14)	0.67836 (17)	0.65646 (13)	0.0143 (4)
H3	0.490 (2)	0.666 (3)	0.6973 (19)	0.021 (8)*
N4	0.65267 (14)	0.79246 (17)	0.56882 (12)	0.0142 (4)
H4	0.658 (2)	0.842 (3)	0.5350 (18)	0.021 (8)*
N5	0.66208 (14)	0.71383 (17)	0.68209 (12)	0.0143 (4)
H5	0.687 (2)	0.691 (3)	0.726 (2)	0.032 (9)*
N6	0.49283 (14)	0.74908 (18)	0.54115 (12)	0.0142 (4)
H6	0.475 (2)	0.790 (2)	0.5084 (18)	0.015 (8)*
C1	0.63275 (15)	0.52730 (19)	0.50528 (13)	0.0107 (5)
C2	0.66847 (16)	0.3219 (2)	0.65770 (15)	0.0157 (5)
H2	0.6919 (18)	0.248 (2)	0.6607 (15)	0.013 (7)*
C3	0.64942 (16)	0.5047 (2)	0.37848 (14)	0.0146 (5)
H3A	0.6715 (18)	0.458 (2)	0.3422 (16)	0.012 (7)*
C4	0.63718 (15)	0.47609 (19)	0.58194 (13)	0.0111 (5)
C5	0.44929 (16)	0.73508 (19)	0.60191 (14)	0.0131 (5)
C6	0.58955 (16)	0.6540 (2)	0.63680 (13)	0.0117 (5)
C7	0.60242 (15)	0.63367 (19)	0.49133 (13)	0.0124 (5)
C8	0.61586 (17)	0.6078 (2)	0.35898 (14)	0.0166 (5)
H8	0.6053 (19)	0.633 (2)	0.3017 (17)	0.018 (7)*
C9	0.64030 (16)	0.3720 (2)	0.71990 (14)	0.0159 (5)
H9	0.6434 (18)	0.332 (2)	0.7748 (16)	0.014 (7)*
C10	0.69842 (16)	0.79081 (19)	0.64124 (14)	0.0134 (5)
C11	0.61116 (15)	0.53276 (19)	0.64262 (13)	0.0118 (5)
C12	0.59320 (17)	0.6733 (2)	0.41651 (14)	0.0159 (5)
H12	0.573 (2)	0.744 (3)	0.4060 (17)	0.021 (7)*
C13	0.61223 (16)	0.4796 (2)	0.71210 (14)	0.0141 (5)
H13	0.5949 (18)	0.513 (2)	0.7524 (16)	0.012 (7)*
C14	0.58391 (16)	0.70852 (19)	0.55526 (14)	0.0125 (5)
Cl1	0.56731 (4)	1.05285 (5)	0.65385 (3)	0.01767 (14)
O3	0.51764 (13)	1.13666 (16)	0.68744 (10)	0.0237 (4)
O4	0.52714 (17)	0.94950 (19)	0.66243 (18)	0.0537 (8)
O5	0.5623 (2)	1.0768 (2)	0.57469 (13)	0.0745 (11)
O6	0.65599 (14)	1.05191 (19)	0.69196 (15)	0.0437 (6)
O1W	0.65439 (14)	0.95242 (16)	0.44434 (12)	0.0222 (4)
H1WA	0.605 (3)	0.978 (4)	0.426 (3)	0.064 (14)*
H1WB	0.677 (3)	0.930 (4)	0.407 (3)	0.064 (14)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cd1	0.01452 (14)	0.00776 (13)	0.01630 (14)	0.000	0.00499 (10)	0.000
O1	0.0151 (9)	0.0163 (9)	0.0192 (9)	0.0029 (7)	−0.0008 (7)	−0.0031 (7)
O2	0.0146 (8)	0.0157 (9)	0.0152 (9)	−0.0041 (7)	−0.0031 (7)	−0.0019 (7)
O2W	0.030 (3)	0.0144 (17)	0.028 (3)	−0.0005 (16)	−0.0090 (18)	0.0029 (15)
N1	0.0119 (10)	0.0087 (10)	0.0162 (10)	−0.0006 (8)	0.0024 (8)	0.0007 (8)
N2	0.0138 (10)	0.0123 (10)	0.0125 (10)	−0.0024 (8)	0.0008 (8)	−0.0017 (8)
N3	0.0136 (10)	0.0181 (11)	0.0115 (10)	0.0034 (8)	0.0030 (8)	0.0028 (9)
N4	0.0181 (11)	0.0121 (10)	0.0113 (10)	−0.0042 (8)	−0.0010 (8)	0.0012 (8)
N5	0.0166 (11)	0.0134 (10)	0.0109 (10)	−0.0032 (8)	−0.0047 (8)	0.0009 (8)
N6	0.0148 (10)	0.0137 (11)	0.0124 (10)	0.0044 (8)	−0.0032 (8)	0.0037 (9)
C1	0.0080 (11)	0.0126 (11)	0.0107 (11)	−0.0024 (9)	−0.0014 (9)	−0.0007 (9)
C2	0.0154 (12)	0.0112 (12)	0.0207 (13)	−0.0013 (10)	0.0036 (10)	0.0059 (10)
C3	0.0137 (12)	0.0193 (13)	0.0109 (12)	−0.0034 (10)	0.0017 (9)	−0.0033 (10)
C4	0.0090 (11)	0.0106 (11)	0.0130 (11)	−0.0015 (9)	0.0001 (9)	0.0013 (9)
C5	0.0148 (12)	0.0090 (11)	0.0145 (12)	−0.0003 (9)	−0.0013 (9)	−0.0036 (9)
C6	0.0125 (11)	0.0117 (12)	0.0100 (11)	0.0001 (9)	−0.0013 (9)	−0.0007 (9)
C7	0.0124 (11)	0.0129 (12)	0.0111 (11)	−0.0013 (9)	−0.0003 (9)	0.0000 (9)
C8	0.0181 (12)	0.0191 (13)	0.0116 (12)	−0.0042 (10)	−0.0010 (10)	0.0008 (10)
C9	0.0146 (12)	0.0163 (13)	0.0166 (12)	−0.0009 (10)	0.0024 (10)	0.0054 (10)
C10	0.0169 (12)	0.0097 (12)	0.0135 (12)	0.0043 (9)	0.0016 (10)	−0.0009 (9)
C11	0.0087 (11)	0.0129 (12)	0.0127 (12)	0.0001 (9)	−0.0016 (9)	0.0010 (9)
C12	0.0193 (13)	0.0128 (13)	0.0142 (12)	0.0001 (10)	−0.0016 (10)	0.0024 (10)
C13	0.0132 (12)	0.0164 (12)	0.0130 (12)	−0.0014 (10)	0.0026 (9)	−0.0020 (10)
C14	0.0127 (12)	0.0112 (12)	0.0127 (11)	0.0004 (9)	−0.0012 (9)	0.0020 (9)
Cl1	0.0200 (3)	0.0188 (3)	0.0134 (3)	0.0048 (2)	0.0001 (2)	−0.0002 (2)
O3	0.0316 (11)	0.0204 (10)	0.0198 (10)	0.0068 (8)	0.0065 (8)	−0.0031 (8)
O4	0.0507 (15)	0.0245 (12)	0.094 (2)	−0.0173 (11)	0.0379 (15)	−0.0302 (13)
O5	0.141 (3)	0.072 (2)	0.0133 (11)	0.076 (2)	0.0223 (14)	0.0138 (12)
O6	0.0219 (11)	0.0406 (14)	0.0635 (16)	0.0056 (10)	−0.0095 (10)	−0.0041 (12)
O1W	0.0199 (10)	0.0218 (10)	0.0241 (11)	0.0022 (8)	0.0009 (9)	−0.0043 (8)

Geometric parameters (Å, º)

Cd1—O1^i	2.5585 (17)	N6—C5	1.356 (3)
Cd1—O1^ii	2.5585 (17)	N6—C14	1.450 (3)
Cd1—O2W	2.176 (3)	C1—C4	1.483 (3)
Cd1—O2W^iii	2.176 (3)	C1—C7	1.390 (3)
Cd1—N1^iii	2.318 (2)	C2—H2	0.97 (3)
Cd1—N1	2.318 (2)	C2—C9	1.383 (4)
Cd1—N2^iii	2.460 (2)	C3—H3A	0.96 (3)
Cd1—N2	2.460 (2)	C3—C8	1.384 (4)
O1—C5	1.238 (3)	C4—C11	1.385 (3)
O2—C10	1.238 (3)	C6—C11	1.520 (3)
O2W—H2WA	0.8668	C6—C14	1.577 (3)
O2W—H2WB	0.8675	C7—C12	1.393 (3)
O2W—H2WB^iii	0.874 (9)	C7—C14	1.514 (3)
N1—C2	1.338 (3)	C8—H8	1.05 (3)
N1—C4	1.354 (3)	C8—C12	1.380 (4)
N2—C1	1.344 (3)	C9—H9	1.08 (3)
N2—C3	1.338 (3)	C9—C13	1.384 (4)
N3—H3	0.79 (3)	C11—C13	1.387 (3)
N3—C5	1.351 (3)	C12—H12	0.92 (3)
N3—C6	1.439 (3)	C13—H13	0.90 (3)
N4—H4	0.86 (3)	Cl1—O3	1.4529 (19)
N4—C10	1.355 (3)	Cl1—O4	1.422 (2)
N4—C14	1.456 (3)	Cl1—O5	1.418 (2)
N5—H5	0.86 (4)	Cl1—O6	1.404 (2)
N5—C6	1.451 (3)	O1W—H1WA	0.83 (5)
N5—C10	1.355 (3)	O1W—H1WB	0.84 (5)
N6—H6	0.78 (3)
O1^ii—Cd1—O1^i	139.80 (8)	N2—C1—C7	121.9 (2)
O2W^iii—Cd1—O1^i	71.77 (12)	C7—C1—C4	121.6 (2)
O2W—Cd1—O1^i	68.89 (12)	N1—C2—H2	115.4 (16)
O2W—Cd1—O1^ii	71.77 (12)	N1—C2—C9	122.8 (2)
O2W^iii—Cd1—O1^ii	68.89 (12)	C9—C2—H2	121.8 (16)
O2W^iii—Cd1—O2W	23.6 (2)	N2—C3—H3A	114.8 (16)
O2W^iii—Cd1—N1^iii	98.07 (12)	N2—C3—C8	123.0 (2)
O2W^iii—Cd1—N1	121.62 (12)	C8—C3—H3A	122.2 (16)
O2W—Cd1—N1	98.07 (12)	N1—C4—C1	117.5 (2)
O2W—Cd1—N1^iii	121.63 (12)	N1—C4—C11	121.4 (2)
O2W—Cd1—N2	138.60 (13)	C11—C4—C1	121.1 (2)
O2W—Cd1—N2^iii	141.68 (13)	O1—C5—N3	125.8 (2)
O2W^iii—Cd1—N2	141.68 (13)	O1—C5—N6	125.8 (2)
O2W^iii—Cd1—N2^iii	138.60 (13)	N3—C5—N6	108.4 (2)
N1—Cd1—O1^i	91.56 (6)	N3—C6—N5	113.7 (2)
N1^iii—Cd1—O1^i	101.90 (6)	N3—C6—C11	112.4 (2)
N1^iii—Cd1—O1^ii	91.56 (6)	N3—C6—C14	102.28 (18)
N1—Cd1—O1^ii	101.90 (6)	N5—C6—C11	108.63 (19)
N1^iii—Cd1—N1	140.31 (10)	N5—C6—C14	102.51 (19)
N1—Cd1—N2	69.01 (7)	C11—C6—C14	117.06 (19)
N1—Cd1—N2^iii	79.98 (7)	C1—C7—C12	118.4 (2)
N1^iii—Cd1—N2	79.98 (7)	C1—C7—C14	122.0 (2)
N1^iii—Cd1—N2^iii	69.01 (7)	C12—C7—C14	119.6 (2)
N2—Cd1—O1^ii	72.89 (6)	C3—C8—H8	120.5 (16)
N2^iii—Cd1—O1^ii	146.41 (6)	C12—C8—C3	118.1 (2)
N2^iii—Cd1—O1^i	72.89 (6)	C12—C8—H8	121.3 (16)
N2—Cd1—O1^i	146.41 (6)	C2—C9—H9	122.2 (15)
N2^iii—Cd1—N2	76.78 (9)	C2—C9—C13	118.2 (2)
C5—O1—Cd1^ii	116.47 (15)	C13—C9—H9	119.5 (15)
Cd1—O2W—H2WA	110.2	O2—C10—N4	126.1 (2)
Cd1—O2W—H2WB	110.9	O2—C10—N5	125.1 (2)
Cd1—O2W—H2WB^iii	110.5 (12)	N4—C10—N5	108.8 (2)
H2WA—O2W—H2WB^iii	126.8	C4—C11—C6	121.4 (2)
H2WA—O2W—H2WB	103.4	C4—C11—C13	119.0 (2)
H2WB—O2W—H2WB^iii	92.4	C13—C11—C6	119.4 (2)
C2—N1—Cd1	121.40 (16)	C7—C12—H12	119.7 (18)
C2—N1—C4	119.0 (2)	C8—C12—C7	119.7 (2)
C4—N1—Cd1	117.03 (15)	C8—C12—H12	120.6 (18)
C1—N2—Cd1	113.20 (15)	C9—C13—C11	119.7 (2)
C3—N2—Cd1	126.14 (16)	C9—C13—H13	118.7 (18)
C3—N2—C1	118.8 (2)	C11—C13—H13	121.6 (18)
C5—N3—H3	123 (2)	N4—C14—C6	102.39 (18)
C5—N3—C6	113.8 (2)	N4—C14—C7	109.7 (2)
C6—N3—H3	123 (2)	N6—C14—N4	115.0 (2)
C10—N4—H4	125 (2)	N6—C14—C6	102.38 (19)
C10—N4—C14	113.0 (2)	N6—C14—C7	111.26 (19)
C14—N4—H4	122 (2)	C7—C14—C6	115.77 (19)
C6—N5—H5	122 (2)	O4—Cl1—O3	109.07 (13)
C10—N5—H5	123 (2)	O5—Cl1—O3	107.81 (13)
C10—N5—C6	113.2 (2)	O5—Cl1—O4	109.4 (2)
C5—N6—H6	121 (2)	O6—Cl1—O3	109.15 (13)
C5—N6—C14	112.9 (2)	O6—Cl1—O4	109.55 (16)
C14—N6—H6	124 (2)	O6—Cl1—O5	111.8 (2)
N2—C1—C4	116.6 (2)	H1WA—O1W—H1WB	106 (4)
Cd1^ii—O1—C5—N3	−120.1 (2)	C3—C8—C12—C7	−1.6 (4)
Cd1^ii—O1—C5—N6	56.0 (3)	C4—N1—C2—C9	0.9 (4)
Cd1—N1—C2—C9	162.07 (19)	C4—C1—C7—C12	−174.8 (2)
Cd1—N1—C4—C1	20.3 (3)	C4—C1—C7—C14	8.3 (3)
Cd1—N1—C4—C11	−160.37 (17)	C4—C11—C13—C9	0.9 (3)
Cd1—N2—C1—C4	−19.1 (2)	C5—N3—C6—N5	110.2 (2)
Cd1—N2—C1—C7	162.06 (17)	C5—N3—C6—C11	−125.9 (2)
Cd1—N2—C3—C8	−163.14 (18)	C5—N3—C6—C14	0.5 (3)
N1—C2—C9—C13	−2.4 (4)	C5—N6—C14—N4	−105.2 (2)
N1—C4—C11—C6	172.0 (2)	C5—N6—C14—C6	4.9 (3)
N1—C4—C11—C13	−2.5 (3)	C5—N6—C14—C7	129.2 (2)
N2—C1—C4—N1	0.4 (3)	C6—N3—C5—O1	179.2 (2)
N2—C1—C4—C11	−178.9 (2)	C6—N3—C5—N6	2.5 (3)
N2—C1—C7—C12	3.9 (3)	C6—N5—C10—O2	−175.8 (2)
N2—C1—C7—C14	−172.9 (2)	C6—N5—C10—N4	2.6 (3)
N2—C3—C8—C12	2.2 (4)	C6—C11—C13—C9	−173.7 (2)
N3—C6—C11—C4	126.9 (2)	C7—C1—C4—N1	179.3 (2)
N3—C6—C11—C13	−58.7 (3)	C7—C1—C4—C11	0.0 (3)
N3—C6—C14—N4	116.4 (2)	C10—N4—C14—N6	113.5 (2)
N3—C6—C14—N6	−3.1 (2)	C10—N4—C14—C6	3.3 (3)
N3—C6—C14—C7	−124.3 (2)	C10—N4—C14—C7	−120.1 (2)
N5—C6—C11—C4	−106.5 (2)	C10—N5—C6—N3	−110.0 (2)
N5—C6—C11—C13	68.0 (3)	C10—N5—C6—C11	124.1 (2)
N5—C6—C14—N4	−1.6 (2)	C10—N5—C6—C14	−0.4 (3)
N5—C6—C14—N6	−121.08 (19)	C11—C6—C14—N4	−120.4 (2)
N5—C6—C14—C7	117.7 (2)	C11—C6—C14—N6	120.2 (2)
C1—N2—C3—C8	0.3 (3)	C11—C6—C14—C7	−1.0 (3)
C1—C4—C11—C6	−8.7 (3)	C12—C7—C14—N4	−68.9 (3)
C1—C4—C11—C13	176.8 (2)	C12—C7—C14—N6	59.5 (3)
C1—C7—C12—C8	−1.3 (4)	C12—C7—C14—C6	175.9 (2)
C1—C7—C14—N4	107.9 (2)	C14—N4—C10—O2	174.5 (2)
C1—C7—C14—N6	−123.6 (2)	C14—N4—C10—N5	−3.8 (3)
C1—C7—C14—C6	−7.3 (3)	C14—N6—C5—O1	178.5 (2)
C2—N1—C4—C1	−177.7 (2)	C14—N6—C5—N3	−4.9 (3)
C2—N1—C4—C11	1.6 (3)	C14—C6—C11—C4	8.9 (3)
C2—C9—C13—C11	1.4 (4)	C14—C6—C11—C13	−176.6 (2)
C3—N2—C1—C4	175.4 (2)	C14—C7—C12—C8	175.6 (2)
C3—N2—C1—C7	−3.4 (3)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2W—H2WB···O1W^iv	0.87	2.06	2.804 (4)	143
N3—H3···O3^v	0.79 (3)	2.09 (3)	2.868 (3)	169 (3)
N5—H5···O2^vi	0.86 (4)	1.98 (4)	2.838 (3)	172 (3)
O1W—H1WB···O2^iii	0.84 (5)	1.95 (5)	2.780 (3)	167 (4)

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

catena-Poly[[lead(II)-bis(µ-4b,5,7,7a-tetrahydro-4b,7a-epiminomethanoimino-6H-imidazo[4,5-f][1,10]phenanthroline-6,13-dione)] bis(perchlorate) dihydrate] (2)

Crystal data

[Pb(C14H10N6O2)2](ClO4)2·2H2O	F(000) = 2016
Mr = 1030.68	Dx = 2.038 Mg m^−3
Monoclinic, I2/a	Mo Kα radiation, λ = 0.71073 Å
a = 15.2909 (3) Å	Cell parameters from 3673 reflections
b = 14.2702 (3) Å	θ = 3.3–27.1°
c = 15.4064 (4) Å	µ = 5.27 mm^−1
β = 92.174 (2)°	T = 293 K
V = 3359.32 (13) Å^3	Block, colorless
Z = 4	0.2 × 0.15 × 0.15 mm

Data collection

Goniometer KM4/Xcalibur, detector: Sapphire3 diffractometer	3692 reflections with I > 2σ(I)
Detector resolution: 16.1048 pixels mm^-1	Rint = 0.019
φ and ω scans	θmax = 29.2°, θmin = 3.3°
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2013)	h = −19→20
Tmin = 0.419, Tmax = 0.505	k = −13→19
13500 measured reflections	l = −17→20
4008 independent reflections

Refinement

Refinement on F^2	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.026	H-atom parameters constrained
wR(F^2) = 0.071	w = 1/[σ^2(Fo^2) + (0.0427P)^2 + 7.4648P] where P = (Fo^2 + 2Fc^2)/3
S = 1.06	(Δ/σ)max = 0.002
4008 reflections	Δρmax = 1.23 e Å^−3
261 parameters	Δρmin = −0.68 e Å^−3
0 restraints

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	0.250000	1.17680 (2)	0.500000	0.02815 (7)
O1	0.64130 (15)	0.77739 (18)	0.36773 (18)	0.0372 (6)
O2	0.26959 (19)	0.66658 (18)	0.33525 (19)	0.0404 (6)
N1	0.33977 (17)	1.02768 (19)	0.54831 (17)	0.0277 (5)
N2	0.34276 (18)	1.09595 (19)	0.38429 (19)	0.0307 (6)
N3	0.5092 (2)	0.8301 (2)	0.3118 (2)	0.0347 (7)
H3	0.524609	0.838666	0.259275	0.042*
N4	0.51911 (19)	0.7901 (2)	0.4497 (2)	0.0348 (6)
H4	0.542975	0.774416	0.499006	0.042*
N5	0.3547 (2)	0.7922 (2)	0.30041 (19)	0.0335 (6)
H5	0.334880	0.799381	0.247860	0.040*
N6	0.3708 (2)	0.7319 (2)	0.4313 (2)	0.0359 (7)
H6	0.365616	0.692282	0.472893	0.043*
C1	0.3433 (2)	0.9985 (2)	0.6304 (2)	0.0312 (7)
H1	0.323791	1.038775	0.673020	0.037*
C2	0.3744 (3)	0.9116 (3)	0.6554 (2)	0.0392 (8)
H2	0.377395	0.894472	0.713684	0.047*
C3	0.4008 (3)	0.8511 (3)	0.5927 (2)	0.0391 (8)
H3A	0.419915	0.791192	0.607692	0.047*
C4	0.3988 (2)	0.8798 (2)	0.5061 (2)	0.0264 (6)
C5	0.36904 (19)	0.9698 (2)	0.48686 (19)	0.0239 (6)
C6	0.4275 (2)	0.8128 (2)	0.4369 (2)	0.0255 (6)
C7	0.4220 (2)	0.8507 (2)	0.3411 (2)	0.0248 (6)
C8	0.37027 (19)	1.0061 (2)	0.3969 (2)	0.0238 (6)
C9	0.3990 (2)	0.9525 (2)	0.3293 (2)	0.0261 (6)
C10	0.4021 (2)	0.9922 (3)	0.2469 (2)	0.0362 (8)
H10	0.423001	0.957859	0.200775	0.043*
C11	0.3738 (3)	1.0830 (3)	0.2348 (2)	0.0407 (8)
H11	0.374725	1.110825	0.180262	0.049*
C12	0.3443 (3)	1.1318 (2)	0.3045 (2)	0.0364 (8)
H12	0.324491	1.192765	0.295703	0.044*
C13	0.5634 (2)	0.7964 (2)	0.3752 (2)	0.0302 (7)
C14	0.3269 (2)	0.7251 (2)	0.3545 (2)	0.0296 (7)
Cl1	0.38295 (7)	0.39334 (7)	0.39974 (7)	0.0464 (2)
O3	0.3955 (6)	0.4128 (6)	0.4862 (4)	0.172 (4)
O4	0.4482 (4)	0.3231 (3)	0.3789 (4)	0.1053 (19)
O5	0.3011 (5)	0.3618 (8)	0.3815 (9)	0.239 (6)
O6	0.3992 (6)	0.4650 (5)	0.3503 (6)	0.189 (4)
O1W	0.3527 (3)	0.5970 (3)	0.5563 (2)	0.0685 (10)
H1WA	0.305881	0.580653	0.528893	0.103*
H1WB	0.364616	0.551137	0.590015	0.103*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Pb1	0.02771 (9)	0.02163 (9)	0.03463 (11)	0.000	−0.00537 (6)	0.000
O1	0.0263 (11)	0.0365 (14)	0.0483 (15)	0.0066 (10)	−0.0055 (10)	−0.0135 (11)
O2	0.0422 (14)	0.0376 (14)	0.0404 (15)	−0.0128 (11)	−0.0105 (12)	0.0041 (11)
N1	0.0308 (13)	0.0266 (13)	0.0253 (13)	0.0024 (11)	−0.0024 (10)	0.0009 (11)
N2	0.0339 (14)	0.0248 (13)	0.0330 (15)	0.0020 (11)	−0.0032 (11)	0.0065 (11)
N3	0.0292 (14)	0.0449 (18)	0.0301 (15)	0.0090 (12)	0.0009 (12)	0.0019 (12)
N4	0.0314 (14)	0.0424 (16)	0.0300 (15)	0.0096 (13)	−0.0082 (11)	0.0023 (13)
N5	0.0383 (15)	0.0345 (15)	0.0267 (14)	−0.0085 (13)	−0.0129 (12)	0.0042 (12)
N6	0.0498 (17)	0.0285 (14)	0.0287 (15)	−0.0082 (13)	−0.0087 (12)	0.0049 (12)
C1	0.0369 (16)	0.0312 (16)	0.0254 (16)	0.0019 (14)	−0.0004 (13)	−0.0013 (13)
C2	0.056 (2)	0.0384 (19)	0.0228 (16)	0.0062 (17)	0.0002 (15)	0.0053 (14)
C3	0.058 (2)	0.0311 (17)	0.0285 (18)	0.0098 (17)	−0.0008 (16)	0.0079 (14)
C4	0.0288 (14)	0.0270 (15)	0.0231 (15)	0.0026 (12)	−0.0037 (12)	0.0029 (12)
C5	0.0237 (13)	0.0245 (14)	0.0230 (14)	0.0004 (12)	−0.0047 (11)	0.0012 (11)
C6	0.0287 (15)	0.0231 (14)	0.0242 (15)	0.0024 (12)	−0.0051 (12)	0.0022 (11)
C7	0.0260 (14)	0.0263 (14)	0.0217 (14)	0.0004 (12)	−0.0033 (11)	0.0014 (11)
C8	0.0243 (13)	0.0231 (14)	0.0239 (15)	−0.0021 (11)	−0.0016 (11)	0.0038 (11)
C9	0.0254 (14)	0.0266 (15)	0.0258 (15)	−0.0007 (12)	−0.0044 (11)	0.0048 (12)
C10	0.0440 (19)	0.0387 (19)	0.0257 (17)	0.0021 (15)	0.0015 (14)	0.0037 (14)
C11	0.058 (2)	0.0376 (19)	0.0262 (17)	−0.0049 (17)	−0.0031 (16)	0.0116 (14)
C12	0.0446 (19)	0.0270 (17)	0.0372 (19)	0.0011 (15)	−0.0039 (15)	0.0113 (14)
C13	0.0305 (15)	0.0244 (14)	0.0351 (18)	0.0028 (13)	−0.0069 (13)	−0.0082 (13)
C14	0.0294 (15)	0.0268 (16)	0.0322 (17)	0.0002 (13)	−0.0026 (13)	−0.0001 (13)
Cl1	0.0514 (5)	0.0424 (5)	0.0454 (5)	0.0022 (4)	−0.0004 (4)	0.0062 (4)
O3	0.262 (9)	0.190 (7)	0.065 (3)	0.125 (7)	0.010 (4)	−0.013 (4)
O4	0.124 (4)	0.100 (4)	0.090 (4)	0.058 (3)	−0.019 (3)	−0.022 (3)
O5	0.070 (4)	0.236 (10)	0.407 (18)	−0.022 (6)	−0.059 (7)	−0.014 (12)
O6	0.211 (8)	0.141 (6)	0.220 (8)	0.040 (6)	0.083 (7)	0.126 (6)
O1W	0.097 (3)	0.059 (2)	0.050 (2)	0.020 (2)	0.0141 (19)	0.0186 (17)

Geometric parameters (Å, º)

Pb1—O1^i	2.662 (2)	C1—H1	0.9300
Pb1—O1^ii	2.662 (2)	C1—C2	1.378 (5)
Pb1—N1	2.625 (3)	C2—H2	0.9300
Pb1—N1^iii	2.625 (3)	C2—C3	1.368 (5)
Pb1—N2^iii	2.591 (3)	C3—H3A	0.9300
Pb1—N2	2.591 (3)	C3—C4	1.395 (5)
O1—C13	1.231 (4)	C4—C5	1.390 (4)
O2—C14	1.238 (4)	C4—C6	1.510 (4)
N1—C1	1.331 (4)	C5—C8	1.480 (4)
N1—C5	1.346 (4)	C6—C7	1.572 (4)
N2—C8	1.361 (4)	C7—C9	1.503 (4)
N2—C12	1.332 (4)	C8—C9	1.378 (5)
N3—H3	0.8600	C9—C10	1.392 (5)
N3—C7	1.454 (4)	C10—H10	0.9300
N3—C13	1.345 (5)	C10—C11	1.377 (5)
N4—H4	0.8600	C11—H11	0.9300
N4—C6	1.443 (4)	C11—C12	1.370 (6)
N4—C13	1.358 (5)	C12—H12	0.9300
N5—H5	0.8600	Cl1—O3	1.368 (6)
N5—C7	1.449 (4)	Cl1—O4	1.458 (5)
N5—C14	1.349 (4)	Cl1—O5	1.350 (7)
N6—H6	0.8600	Cl1—O6	1.305 (6)
N6—C6	1.445 (4)	O1W—H1WA	0.8498
N6—C14	1.342 (4)	O1W—H1WB	0.8505
O1^i—Pb1—O1^ii	151.57 (12)	C5—C4—C6	122.4 (3)
N1—Pb1—O1^ii	136.12 (9)	N1—C5—C4	122.1 (3)
N1^iii—Pb1—O1^i	136.12 (9)	N1—C5—C8	117.4 (3)
N1^iii—Pb1—O1^ii	71.18 (8)	C4—C5—C8	120.5 (3)
N1—Pb1—O1^i	71.17 (8)	N4—C6—N6	114.0 (3)
N1^iii—Pb1—N1	71.66 (12)	N4—C6—C4	110.7 (3)
N2—Pb1—O1^ii	85.69 (9)	N4—C6—C7	102.8 (3)
N2—Pb1—O1^i	107.09 (8)	N6—C6—C4	111.0 (3)
N2^iii—Pb1—O1^ii	107.09 (8)	N6—C6—C7	102.0 (2)
N2^iii—Pb1—O1^i	85.69 (9)	C4—C6—C7	116.0 (3)
N2^iii—Pb1—N1^iii	62.61 (8)	N3—C7—C6	101.8 (2)
N2—Pb1—N1	62.61 (8)	N3—C7—C9	111.8 (3)
N2—Pb1—N1^iii	74.80 (9)	N5—C7—N3	113.2 (3)
N2^iii—Pb1—N1	74.80 (9)	N5—C7—C6	102.7 (3)
N2^iii—Pb1—N2	127.11 (12)	N5—C7—C9	110.2 (3)
C13—O1—Pb1^i	116.9 (2)	C9—C7—C6	116.7 (3)
C1—N1—Pb1	121.7 (2)	N2—C8—C5	116.7 (3)
C1—N1—C5	118.3 (3)	N2—C8—C9	121.4 (3)
C5—N1—Pb1	118.8 (2)	C9—C8—C5	121.9 (3)
C8—N2—Pb1	119.7 (2)	C8—C9—C7	121.7 (3)
C12—N2—Pb1	119.6 (2)	C8—C9—C10	119.1 (3)
C12—N2—C8	118.5 (3)	C10—C9—C7	119.2 (3)
C7—N3—H3	123.4	C9—C10—H10	120.5
C13—N3—H3	123.4	C11—C10—C9	119.0 (3)
C13—N3—C7	113.2 (3)	C11—C10—H10	120.5
C6—N4—H4	123.8	C10—C11—H11	120.6
C13—N4—H4	123.8	C12—C11—C10	118.9 (3)
C13—N4—C6	112.5 (3)	C12—C11—H11	120.6
C7—N5—H5	123.9	N2—C12—C11	123.1 (3)
C14—N5—H5	123.9	N2—C12—H12	118.4
C14—N5—C7	112.2 (3)	C11—C12—H12	118.4
C6—N6—H6	123.5	O1—C13—N3	125.6 (4)
C14—N6—H6	123.5	O1—C13—N4	125.4 (3)
C14—N6—C6	112.9 (3)	N3—C13—N4	108.9 (3)
N1—C1—H1	118.4	O2—C14—N5	124.6 (3)
N1—C1—C2	123.3 (3)	O2—C14—N6	125.8 (3)
C2—C1—H1	118.4	N6—C14—N5	109.5 (3)
C1—C2—H2	120.7	O3—Cl1—O4	106.4 (4)
C3—C2—C1	118.6 (3)	O5—Cl1—O3	111.5 (7)
C3—C2—H2	120.7	O5—Cl1—O4	111.2 (6)
C2—C3—H3A	120.2	O6—Cl1—O3	112.8 (6)
C2—C3—C4	119.6 (3)	O6—Cl1—O4	105.3 (5)
C4—C3—H3A	120.2	O6—Cl1—O5	109.5 (7)
C3—C4—C6	119.5 (3)	H1WA—O1W—H1WB	104.5
C5—C4—C3	118.1 (3)
Pb1^i—O1—C13—N3	139.8 (3)	C5—N1—C1—C2	−0.8 (5)
Pb1^i—O1—C13—N4	−37.5 (4)	C5—C4—C6—N4	116.7 (3)
Pb1—N1—C1—C2	166.6 (3)	C5—C4—C6—N6	−115.7 (3)
Pb1—N1—C5—C4	−164.8 (2)	C5—C4—C6—C7	0.0 (4)
Pb1—N1—C5—C8	16.4 (4)	C5—C8—C9—C7	6.5 (5)
Pb1—N2—C8—C5	−18.2 (4)	C5—C8—C9—C10	−177.2 (3)
Pb1—N2—C8—C9	162.7 (2)	C6—N4—C13—O1	−177.1 (3)
Pb1—N2—C12—C11	−164.2 (3)	C6—N4—C13—N3	5.2 (4)
N1—C1—C2—C3	−1.9 (6)	C6—N6—C14—O2	−174.4 (3)
N1—C5—C8—N2	1.0 (4)	C6—N6—C14—N5	5.7 (4)
N1—C5—C8—C9	180.0 (3)	C6—C4—C5—N1	176.9 (3)
N2—C8—C9—C7	−174.5 (3)	C6—C4—C5—C8	−4.3 (5)
N2—C8—C9—C10	1.8 (5)	C6—C7—C9—C8	−10.3 (4)
N3—C7—C9—C8	−126.9 (3)	C6—C7—C9—C10	173.4 (3)
N3—C7—C9—C10	56.8 (4)	C7—N3—C13—O1	−176.8 (3)
N4—C6—C7—N3	8.0 (3)	C7—N3—C13—N4	0.8 (4)
N4—C6—C7—N5	125.3 (3)	C7—N5—C14—O2	179.7 (3)
N4—C6—C7—C9	−114.0 (3)	C7—N5—C14—N6	−0.4 (4)
N5—C7—C9—C8	106.3 (3)	C7—C9—C10—C11	174.4 (3)
N5—C7—C9—C10	−70.0 (4)	C8—N2—C12—C11	−1.2 (5)
N6—C6—C7—N3	−110.4 (3)	C8—C9—C10—C11	−2.0 (5)
N6—C6—C7—N5	7.0 (3)	C9—C10—C11—C12	0.7 (6)
N6—C6—C7—C9	127.7 (3)	C10—C11—C12—N2	1.0 (6)
C1—N1—C5—C4	3.0 (5)	C12—N2—C8—C5	178.8 (3)
C1—N1—C5—C8	−175.8 (3)	C12—N2—C8—C9	−0.2 (5)
C1—C2—C3—C4	2.5 (6)	C13—N3—C7—N5	−115.2 (3)
C2—C3—C4—C5	−0.5 (6)	C13—N3—C7—C6	−5.7 (4)
C2—C3—C4—C6	−179.7 (4)	C13—N3—C7—C9	119.6 (3)
C3—C4—C5—N1	−2.3 (5)	C13—N4—C6—N6	101.2 (3)
C3—C4—C5—C8	176.4 (3)	C13—N4—C6—C4	−132.9 (3)
C3—C4—C6—N4	−64.1 (4)	C13—N4—C6—C7	−8.4 (4)
C3—C4—C6—N6	63.5 (4)	C14—N5—C7—N3	104.6 (3)
C3—C4—C6—C7	179.3 (3)	C14—N5—C7—C6	−4.4 (4)
C4—C5—C8—N2	−177.9 (3)	C14—N5—C7—C9	−129.4 (3)
C4—C5—C8—C9	1.2 (5)	C14—N6—C6—N4	−118.0 (3)
C4—C6—C7—N3	128.9 (3)	C14—N6—C6—C4	116.2 (3)
C4—C6—C7—N5	−113.7 (3)	C14—N6—C6—C7	−7.9 (4)
C4—C6—C7—C9	7.0 (4)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N5—H5···O2^iv	0.86	2.07	2.833 (4)	148
N6—H6···O1W	0.86	1.89	2.744 (5)	175

Symmetry code: (iv) −x+1/2, −y+3/2, −z+1/2.