Bis(μ-5-carb-oxy-benzene-1,3-dicarboxyl-ato)-κO,O:O;κO:O,O-bis-[(2-phenyl-1,3,7,8-tetra-aza-cyclo-penta-[l]phenanthrene-κN,N)lead(II)].

In the title compound, [Pb(2)(C(9)H(4)O(6))(2)(C(19)H(12)N(4))(2)], the Pb(II) atom is five-coordinated by two N atoms from a chelating 2-phenyl-1H-1,3,7,8-tetra-aza-cyclo-penta-[l]phenanthrene (L) ligand and three O atoms from two Hbtc ligands (H(3)btc is benzene-1,3,5-tricarb-oxy-lic acid), resulting in a distorted PbN(2)O(3) coordination. Two Pb(II) atoms are bridged by the Hbtc ligands, forming a discrete centrosymmetric dinuclear complex. Inter-molecular N-H⋯O and O-H⋯O hydrogen bonds and π-π inter-actions between the pyridine and imidazole rings, and between the pyridyl rings of the L ligands [centroid-centroid distances = 3.600 (6) and 3.732 (6) Å] lead to a three-dimensional supra-molecular structure.

Related literature

For general background to the structures and potential applications of supra­molecular architectures, see: Che et al. (2008 ▶). For a related structure, see: Liu et al. (2009 ▶). For the ligand synthesis, see: Steck & Day (1943 ▶).

Experimental

Crystal data

[Pb2(C9H4O6)2(C19H12N4)2]

M = 1423.28

Triclinic,

a = 9.2776 (3) Å

b = 11.4409 (5) Å

c = 12.2764 (6) Å

α = 73.820 (4)°

β = 72.754 (4)°

γ = 68.680 (4)°

V = 1137.74 (9) Å3

Z = 1

Mo Kα radiation

μ = 7.47 mm−1

T = 292 K

0.30 × 0.26 × 0.23 mm

Data collection

Oxford Diffraction Gemini R Ultra CCD diffractometer

Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2006 ▶) T min = 0.122, T max = 0.179

5399 measured reflections

3979 independent reflections

3547 reflections with I > 2σ(I)

R int = 0.021

Refinement

R[F 2 > 2σ(F 2)] = 0.024

wR(F 2) = 0.055

S = 1.00

3979 reflections

352 parameters

H-atom parameters constrained

Δρmax = 0.82 e Å−3

Δρmin = −1.28 e Å−3

Data collection: CrysAlis CCD (Oxford Diffraction, 2006 ▶); cell refinement: CrysAlis RED (Oxford Diffraction, 2006 ▶); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL and DIAMOND (Brandenburg, 1999 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810045812/hy2360sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810045812/hy2360Isup2.hkl

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

[Pb2(C9H4O6)2(C19H12N4)2]	Z = 1
Mr = 1423.28	F(000) = 684
Triclinic, P1	Dx = 2.077 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.2776 (3) Å	Cell parameters from 6223 reflections
b = 11.4409 (5) Å	θ = 4.3–29.1°
c = 12.2764 (6) Å	µ = 7.47 mm−1
α = 73.820 (4)°	T = 292 K
β = 72.754 (4)°	Block, yellow
γ = 68.680 (4)°	0.30 × 0.26 × 0.23 mm
V = 1137.74 (9) Å3

Oxford Diffraction Gemini R Ultra CCD diffractometer	3979 independent reflections
Radiation source: fine-focus sealed tube	3547 reflections with I > 2σ(I)
graphite	Rint = 0.021
ω scans	θmax = 25.0°, θmin = 4.3°
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2006)	h = −11→11
Tmin = 0.122, Tmax = 0.179	k = −12→13
5399 measured reflections	l = −14→14

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)] = 0.024	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.055	H-atom parameters constrained
S = 1.00	w = 1/[σ2(Fo2) + (0.0349P)2] where P = (Fo2 + 2Fc2)/3
3979 reflections	(Δ/σ)max = 0.006
352 parameters	Δρmax = 0.82 e Å−3
0 restraints	Δρmin = −1.28 e Å−3

	x	y	z	Uiso*/Ueq
C1	0.7189 (5)	0.2900 (4)	0.0863 (4)	0.0311 (11)
H1	0.6208	0.3528	0.0892	0.037*
C2	0.8282 (6)	0.2868 (5)	−0.0199 (4)	0.0340 (11)
H2	0.8024	0.3455	−0.0862	0.041*
C3	0.9727 (5)	0.1970 (4)	−0.0252 (4)	0.0284 (10)
H3	1.0473	0.1940	−0.0952	0.034*
C4	1.0091 (5)	0.1086 (4)	0.0756 (4)	0.0230 (9)
C5	1.1546 (5)	0.0094 (4)	0.0827 (4)	0.0235 (9)
C6	1.1849 (5)	−0.0717 (4)	0.1856 (4)	0.0219 (9)
C7	1.0700 (4)	−0.0637 (4)	0.2914 (3)	0.0183 (8)
C8	1.0944 (5)	−0.1447 (4)	0.3980 (4)	0.0236 (9)
H8	1.1921	−0.2058	0.4036	0.028*
C9	0.9727 (5)	−0.1323 (4)	0.4929 (4)	0.0257 (10)
H9	0.9871	−0.1848	0.5643	0.031*
C10	0.8272 (5)	−0.0415 (4)	0.4835 (4)	0.0239 (9)
H10	0.7448	−0.0361	0.5491	0.029*
C11	0.9200 (5)	0.0296 (4)	0.2884 (3)	0.0188 (8)
C12	0.8917 (5)	0.1180 (4)	0.1795 (3)	0.0207 (9)
C13	1.3926 (5)	−0.1295 (4)	0.0540 (4)	0.0251 (9)
C14	1.5482 (5)	−0.2019 (4)	−0.0049 (4)	0.0248 (9)
C19	1.6161 (5)	−0.1588 (5)	−0.1198 (4)	0.0335 (11)
H19	1.5631	−0.0815	−0.1614	0.040*
C18	1.7622 (6)	−0.2314 (5)	−0.1714 (4)	0.0407 (13)
H18	1.8074	−0.2031	−0.2483	0.049*
C17	1.8423 (6)	−0.3458 (6)	−0.1105 (5)	0.0493 (15)
H17	1.9410	−0.3941	−0.1462	0.059*
C26	0.2977 (4)	0.2718 (4)	0.6601 (3)	0.0183 (8)
C24	0.1360 (5)	0.3197 (4)	0.6642 (3)	0.0219 (9)
H24	0.0784	0.2638	0.6764	0.026*
C23	0.0600 (5)	0.4498 (4)	0.6502 (4)	0.0206 (9)
C22	0.1453 (5)	0.5317 (4)	0.6363 (4)	0.0223 (9)
H22	0.0948	0.6194	0.6255	0.027*
C21	0.3059 (4)	0.4849 (4)	0.6381 (4)	0.0203 (9)
C25	0.3821 (4)	0.3546 (4)	0.6483 (3)	0.0191 (9)
H25	0.4901	0.3226	0.6472	0.023*
C27	0.3789 (5)	0.1300 (4)	0.6694 (4)	0.0204 (9)
C28	−0.1124 (5)	0.5072 (4)	0.6481 (4)	0.0230 (9)
C20	0.3893 (5)	0.5775 (4)	0.6332 (4)	0.0224 (9)
C16	1.7755 (6)	−0.3883 (6)	0.0038 (5)	0.0504 (15)
H16	1.8298	−0.4651	0.0452	0.060*
C15	1.6285 (6)	−0.3171 (5)	0.0564 (4)	0.0380 (12)
H15	1.5834	−0.3462	0.1330	0.046*
N1	0.7482 (4)	0.2074 (3)	0.1833 (3)	0.0232 (8)
N2	0.8010 (4)	0.0378 (3)	0.3847 (3)	0.0191 (7)
N4	1.2883 (4)	−0.0273 (3)	−0.0012 (3)	0.0244 (8)
H4	1.3037	0.0068	−0.0739	0.029*
N3	1.3343 (4)	−0.1584 (4)	0.1674 (3)	0.0259 (8)
O3	0.4905 (4)	0.0925 (3)	0.5863 (3)	0.0346 (8)
O2	0.3312 (4)	0.0561 (3)	0.7562 (3)	0.0312 (7)
O1	0.3317 (3)	0.6937 (3)	0.5876 (3)	0.0281 (7)
O6	0.5074 (3)	0.5389 (3)	0.6780 (3)	0.0380 (8)
O5	−0.1757 (3)	0.6197 (3)	0.6241 (3)	0.0371 (8)
O4	−0.1880 (3)	0.4204 (3)	0.6780 (3)	0.0395 (8)
H4A	−0.2815	0.4561	0.6755	0.059*
Pb	0.537207 (17)	0.188377 (15)	0.371460 (14)	0.02330 (7)

	U11	U22	U33	U12	U13	U23
C1	0.032 (2)	0.023 (2)	0.035 (3)	−0.0044 (19)	−0.012 (2)	0.000 (2)
C2	0.042 (3)	0.029 (3)	0.024 (2)	−0.007 (2)	−0.014 (2)	0.007 (2)
C3	0.036 (2)	0.028 (2)	0.017 (2)	−0.011 (2)	−0.0024 (19)	0.000 (2)
C4	0.026 (2)	0.023 (2)	0.020 (2)	−0.0090 (18)	−0.0063 (18)	−0.0022 (18)
C5	0.024 (2)	0.024 (2)	0.023 (2)	−0.0074 (18)	−0.0021 (18)	−0.0083 (19)
C6	0.022 (2)	0.024 (2)	0.021 (2)	−0.0061 (18)	−0.0059 (18)	−0.0061 (19)
C7	0.020 (2)	0.021 (2)	0.016 (2)	−0.0078 (16)	−0.0030 (17)	−0.0051 (17)
C8	0.026 (2)	0.018 (2)	0.022 (2)	−0.0015 (17)	−0.0045 (18)	−0.0030 (18)
C9	0.031 (2)	0.024 (2)	0.015 (2)	−0.0024 (19)	−0.0059 (19)	−0.0004 (18)
C10	0.027 (2)	0.024 (2)	0.016 (2)	−0.0069 (18)	−0.0001 (18)	−0.0027 (19)
C11	0.022 (2)	0.020 (2)	0.017 (2)	−0.0097 (17)	−0.0022 (17)	−0.0051 (17)
C12	0.028 (2)	0.019 (2)	0.016 (2)	−0.0071 (17)	−0.0076 (18)	−0.0024 (17)
C13	0.022 (2)	0.029 (2)	0.022 (2)	−0.0086 (18)	−0.0009 (18)	−0.007 (2)
C14	0.023 (2)	0.032 (3)	0.021 (2)	−0.0108 (19)	0.0004 (18)	−0.010 (2)
C19	0.030 (2)	0.039 (3)	0.027 (2)	−0.006 (2)	−0.002 (2)	−0.009 (2)
C18	0.031 (3)	0.059 (4)	0.026 (3)	−0.010 (2)	0.003 (2)	−0.013 (3)
C17	0.033 (3)	0.056 (4)	0.050 (4)	0.003 (3)	−0.003 (3)	−0.027 (3)
C26	0.020 (2)	0.020 (2)	0.013 (2)	−0.0057 (16)	−0.0014 (16)	−0.0024 (17)
C24	0.023 (2)	0.023 (2)	0.022 (2)	−0.0109 (18)	−0.0027 (18)	−0.0046 (18)
C23	0.019 (2)	0.022 (2)	0.022 (2)	−0.0048 (17)	−0.0064 (17)	−0.0042 (18)
C22	0.022 (2)	0.017 (2)	0.024 (2)	−0.0020 (17)	−0.0048 (18)	−0.0033 (18)
C21	0.018 (2)	0.018 (2)	0.023 (2)	−0.0045 (16)	−0.0051 (17)	−0.0022 (18)
C25	0.0150 (19)	0.018 (2)	0.020 (2)	−0.0027 (16)	−0.0007 (16)	−0.0034 (17)
C27	0.020 (2)	0.019 (2)	0.025 (2)	−0.0054 (17)	−0.0094 (19)	−0.0044 (19)
C28	0.017 (2)	0.026 (2)	0.024 (2)	−0.0057 (18)	−0.0034 (18)	−0.0049 (19)
C20	0.017 (2)	0.024 (2)	0.025 (2)	−0.0067 (17)	0.0019 (18)	−0.0089 (19)
C16	0.044 (3)	0.046 (3)	0.047 (3)	0.006 (3)	−0.010 (3)	−0.014 (3)
C15	0.039 (3)	0.036 (3)	0.027 (3)	0.003 (2)	−0.007 (2)	−0.008 (2)
N1	0.0248 (18)	0.0207 (19)	0.0231 (19)	−0.0057 (15)	−0.0088 (15)	−0.0008 (16)
N2	0.0187 (16)	0.0216 (18)	0.0160 (18)	−0.0080 (14)	−0.0015 (14)	−0.0024 (15)
N4	0.0246 (18)	0.027 (2)	0.0182 (19)	−0.0072 (15)	0.0006 (15)	−0.0051 (16)
N3	0.0224 (18)	0.030 (2)	0.021 (2)	−0.0047 (16)	−0.0026 (15)	−0.0052 (17)
O3	0.0308 (17)	0.0241 (17)	0.0301 (18)	0.0034 (14)	0.0087 (14)	−0.0088 (15)
O2	0.0413 (18)	0.0236 (17)	0.0254 (17)	−0.0120 (14)	−0.0078 (14)	0.0033 (14)
O1	0.0315 (16)	0.0210 (16)	0.0350 (18)	−0.0103 (13)	−0.0128 (14)	−0.0013 (14)
O6	0.0233 (16)	0.0293 (18)	0.067 (2)	−0.0096 (14)	−0.0204 (17)	−0.0045 (17)
O5	0.0235 (16)	0.0238 (18)	0.060 (2)	−0.0008 (13)	−0.0140 (16)	−0.0062 (16)
O4	0.0156 (14)	0.0305 (18)	0.071 (2)	−0.0068 (13)	−0.0128 (16)	−0.0040 (17)
Pb	0.01918 (9)	0.02098 (10)	0.02834 (11)	−0.00717 (6)	−0.00471 (7)	−0.00173 (7)

C1—N1	1.328 (6)	C18—H18	0.9300
C1—C2	1.394 (7)	C17—C16	1.383 (8)
C1—H1	0.9300	C17—H17	0.9300
C2—C3	1.357 (6)	C26—C25	1.388 (6)
C2—H2	0.9300	C26—C24	1.388 (5)
C3—C4	1.403 (6)	C26—C27	1.508 (5)
C3—H3	0.9300	C24—C23	1.382 (6)
C4—C12	1.412 (6)	C24—H24	0.9300
C4—C5	1.421 (6)	C23—C22	1.379 (6)
C5—N4	1.371 (5)	C23—C28	1.497 (5)
C5—C6	1.380 (6)	C22—C21	1.393 (5)
C6—N3	1.377 (5)	C22—H22	0.9300
C6—C7	1.416 (6)	C21—C25	1.386 (5)
C7—C8	1.404 (6)	C21—C20	1.502 (6)
C7—C11	1.416 (5)	C25—H25	0.9300
C8—C9	1.359 (6)	C27—O2	1.239 (5)
C8—H8	0.9300	C27—O3	1.262 (5)
C9—C10	1.386 (6)	C28—O5	1.196 (5)
C9—H9	0.9300	C28—O4	1.327 (5)
C10—N2	1.324 (5)	C20—O6	1.253 (5)
C10—H10	0.9300	C20—O1	1.269 (5)
C11—N2	1.356 (5)	C16—C15	1.380 (7)
C11—C12	1.463 (6)	C16—H16	0.9300
C12—N1	1.350 (5)	C15—H15	0.9300
C13—N3	1.330 (6)	Pb—N1	2.561 (4)
C13—N4	1.374 (5)	Pb—N2	2.449 (3)
C13—C14	1.462 (6)	Pb—O1i	2.342 (3)
C14—C15	1.387 (6)	Pb—O3	2.530 (3)
C14—C19	1.394 (6)	Pb—O6i	2.903 (3)
C19—C18	1.376 (6)	O4—H4A	0.8200
C19—H19	0.9300	N4—H4	0.8600
C18—C17	1.379 (8)
N1—C1—C2	123.1 (4)	C23—C24—C26	120.5 (4)
N1—C1—H1	118.5	C23—C24—H24	119.8
C2—C1—H1	118.5	C26—C24—H24	119.8
C3—C2—C1	119.1 (4)	C22—C23—C24	119.3 (4)
C3—C2—H2	120.4	C22—C23—C28	117.9 (4)
C1—C2—H2	120.4	C24—C23—C28	122.8 (4)
C2—C3—C4	119.6 (4)	C23—C22—C21	121.0 (4)
C2—C3—H3	120.2	C23—C22—H22	119.5
C4—C3—H3	120.2	C21—C22—H22	119.5
C3—C4—C12	117.7 (4)	C25—C21—C22	119.2 (4)
C3—C4—C5	125.7 (4)	C25—C21—C20	122.2 (3)
C12—C4—C5	116.5 (4)	C22—C21—C20	118.6 (4)
N4—C5—C6	106.2 (3)	C21—C25—C26	120.1 (3)
N4—C5—C4	131.0 (4)	C21—C25—H25	119.9
C6—C5—C4	122.8 (4)	C26—C25—H25	119.9
N3—C6—C5	110.6 (4)	O2—C27—O3	123.3 (4)
N3—C6—C7	127.5 (4)	O2—C27—C26	118.9 (4)
C5—C6—C7	121.8 (4)	O3—C27—C26	117.7 (4)
C8—C7—C11	118.2 (4)	O5—C28—O4	123.7 (4)
C8—C7—C6	124.0 (4)	O5—C28—C23	123.3 (4)
C11—C7—C6	117.8 (3)	O4—C28—C23	113.0 (4)
C9—C8—C7	118.9 (4)	O6—C20—O1	122.8 (4)
C9—C8—H8	120.6	O6—C20—C21	119.3 (4)
C7—C8—H8	120.6	O1—C20—C21	117.8 (3)
C8—C9—C10	120.1 (4)	C17—C16—C15	120.1 (5)
C8—C9—H9	119.9	C17—C16—H16	120.0
C10—C9—H9	119.9	C15—C16—H16	120.0
N2—C10—C9	122.6 (4)	C16—C15—C14	120.0 (5)
N2—C10—H10	118.7	C16—C15—H15	120.0
C9—C10—H10	118.7	C14—C15—H15	120.0
N2—C11—C7	121.1 (3)	C1—N1—C12	118.4 (4)
N2—C11—C12	119.2 (3)	C1—N1—Pb	123.8 (3)
C7—C11—C12	119.7 (4)	C12—N1—Pb	117.3 (3)
N1—C12—C4	122.0 (4)	C10—N2—C11	119.1 (3)
N1—C12—C11	116.8 (4)	C10—N2—Pb	120.9 (3)
C4—C12—C11	121.2 (3)	C11—N2—Pb	119.9 (2)
N3—C13—N4	112.4 (4)	C5—N4—C13	106.3 (3)
N3—C13—C14	123.3 (4)	C5—N4—H4	126.9
N4—C13—C14	124.3 (4)	C13—N4—H4	126.9
C15—C14—C19	119.8 (4)	C13—N3—C6	104.5 (3)
C15—C14—C13	118.3 (4)	C27—O3—Pb	130.6 (3)
C19—C14—C13	121.9 (4)	C20—O1—Pbi	107.3 (2)
C18—C19—C14	119.5 (5)	C28—O4—H4A	109.5
C18—C19—H19	120.3	O1i—Pb—N2	75.71 (10)
C14—C19—H19	120.3	O1i—Pb—O3	86.66 (11)
C19—C18—C17	120.8 (5)	N2—Pb—O3	79.48 (10)
C19—C18—H18	119.6	O1i—Pb—N1	78.54 (11)
C17—C18—H18	119.6	N2—Pb—N1	66.07 (10)
C18—C17—C16	119.8 (5)	O3—Pb—N1	144.85 (10)
C18—C17—H17	120.1	O6i—Pb—N1	79.58 (10)
C16—C17—H17	120.1	O6i—Pb—N2	119.29 (10)
C25—C26—C24	119.8 (4)	O6i—Pb—O1i	48.50 (10)
C25—C26—C27	121.0 (3)	O6i—Pb—O3	113.57 (10)
C24—C26—C27	119.3 (4)

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4···O2ii	0.86	1.97	2.815 (5)	169
O4—H4A···O6iii	0.82	1.83	2.653 (4)	177

Table 1

Selected bond lengths (Å)

Pb—N1	2.561 (4)
Pb—N2	2.449 (3)
Pb—O1i	2.342 (3)
Pb—O3	2.530 (3)
Pb—O6i	2.903 (3)

Symmetry code: (i) .

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H4⋯O2ii	0.86	1.97	2.815 (5)	169
O4—H4A⋯O6iii	0.82	1.83	2.653 (4)	177

Symmetry codes: (ii) ; (iii) .