Construction of a Pb^II coordination polymer from a semi-rigid ditopic 2,2-bi­imidazole derivative: synthesis, crystal structure and characterization

<!?tlsb=-0.04pt>A new Pb^II coordination polymer, poly[0.75(aqua)[μ₃-4,4′-(1H,1′H-[2,2′-bi­imidazole]-1,1′-di­yl)dibenzoato-κ⁵O,O′;N;O′′,O′′′]]lead(II)] 1.25-hydrate], {[Pb(C₂₀H₁₂N₄O₄)(H₂O)_0.75]·1.25H₂O}_n or {[Pb(L)(H₂O)_0.75]·1.25H₂O}_n (1) [H₂L = 4,4′-(1H,1′H-[2,2′-bi­imidazole]-1,1′-di­yl)di­benzoic acid], was synthesized under solvothermal reaction conditions and characterized using microanalysis, IR spectroscopy and thermogravimetric analysis. Single-crystal structure analysis reveals that a two-dimensional corrugated layer structure is formed in 1 and that neighbouring layers are further extended into a three-dimensional structure by hydrogen-bonding inter­actions. In addition, a fluorescence sensing experiment towards Cu²⁺ based on the polymeric Pb^II com­plex was carried out.

Computing details

Data collection: SMART (Bruker, 2010); cell refinement: SMART (Bruker, 2010); data reduction: SAINT (Bruker, 2010); program(s) used to solve structure: SHELXS (Sheldrick, 2008); program(s) used to refine structure: SHELXL2019 (Sheldrick, 2015); molecular graphics: OLEX2 (Dolomanov et al., 2009) and DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

Poly[0.75(aqua)[µ₃-4,4'-(1H,1'H-[2,2'-biimidazole]-1,1'-diyl)dibenzoato-κ⁵O,O';N;O'',O''']]lead(II)] 1.25-hydrate]

Crystal data

[Pb(C20H12N4O4)(H2O)0.75]·1.25H2O	F(000) = 1176
Mr = 615.56	Dx = 1.763 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 7.769 (4) Å	Cell parameters from 3362 reflections
b = 22.149 (12) Å	θ = 2.4–25.3°
c = 13.656 (8) Å	µ = 7.32 mm^−1
β = 99.399 (9)°	T = 296 K
V = 2319 (2) Å^3	Block, colourless
Z = 4	0.28 × 0.22 × 0.2 mm

Data collection

Bruker CCD area detector diffractometer	3584 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.046
phi and ω scans	θmax = 27.5°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2010)	h = −10→9
Tmin = 0.234, Tmax = 0.322	k = −28→26
14385 measured reflections	l = −17→14
5305 independent reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.042	H-atom parameters constrained
wR(F^2) = 0.113	w = 1/[σ^2(Fo^2) + (0.0561P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.99	(Δ/σ)max = 0.001
5305 reflections	Δρmax = 1.17 e Å^−3
302 parameters	Δρmin = −1.22 e Å^−3
24 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.

Refinement. Single-crystal X-ray diffraction measurements was obtained using a Bruker SMART APEX II CCD diffractometer equipped with graphite-monochromated Mo Kα radiation (λ = 0.71073 Å) by using the φ/ω scan technique. The diffraction data were corrected for Lorentz and polarization effects as well as for empirical absorption based on multi-scan mode. The structures of 1 was solved by direct methods and refined anisotropically on F² by a full-matrix least-squares refinement with the OLEX2 program. Anisotropic thermal parameters were applied to non-H atoms.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Pb1	0.00548 (4)	0.03952 (2)	0.27835 (2)	0.04504 (11)
O1	0.2824 (8)	0.4740 (2)	0.1273 (4)	0.0615 (15)
O2	0.3061 (10)	0.4488 (3)	0.2830 (6)	0.090 (2)
O3	0.4300 (6)	0.3457 (2)	−0.1919 (4)	0.0481 (12)
O4	0.5730 (7)	0.4014 (2)	−0.0703 (4)	0.0540 (13)
N1	0.2586 (7)	0.0969 (2)	0.2441 (4)	0.0389 (13)
N2	0.3958 (6)	0.1673 (2)	0.1715 (4)	0.0380 (13)
N3	−0.0268 (7)	0.1029 (2)	0.0782 (5)	0.0454 (14)
N4	−0.0037 (6)	0.2029 (2)	0.0819 (4)	0.0347 (12)
C1	0.2561 (12)	0.4383 (3)	0.1943 (6)	0.058 (2)
C2	0.1750 (10)	0.3770 (3)	0.1649 (5)	0.0466 (17)
C3	0.1724 (10)	0.3339 (3)	0.2358 (6)	0.052 (2)
H3	0.211632	0.343035	0.302189	0.063*
C4	0.1109 (9)	0.2759 (3)	0.2090 (5)	0.0440 (17)
H4	0.109415	0.246320	0.257107	0.053*
C5	0.0530 (8)	0.2632 (3)	0.1110 (5)	0.0348 (15)
C6	0.0502 (9)	0.3073 (3)	0.0383 (6)	0.0464 (17)
H6	0.007283	0.298701	−0.027817	0.056*
C7	0.1131 (10)	0.3650 (3)	0.0666 (6)	0.0515 (19)
H7	0.113128	0.395154	0.019115	0.062*
C8	−0.1626 (8)	0.1892 (3)	0.0245 (6)	0.0479 (18)
H8	−0.244218	0.216400	−0.007404	0.058*
C9	−0.1753 (10)	0.1293 (3)	0.0241 (6)	0.057 (2)
H9	−0.270909	0.107830	−0.008164	0.069*
C10	0.0731 (8)	0.1492 (3)	0.1117 (5)	0.0321 (14)
C11	0.2400 (8)	0.1390 (3)	0.1747 (5)	0.0346 (14)
C12	0.4315 (10)	0.0982 (3)	0.2865 (6)	0.0487 (18)
H12	0.482237	0.072905	0.337517	0.058*
C13	0.5177 (9)	0.1413 (4)	0.2440 (6)	0.0498 (19)
H13	0.635045	0.151388	0.260309	0.060*
C14	0.4297 (8)	0.2129 (3)	0.1019 (5)	0.0356 (15)
C15	0.3736 (8)	0.2042 (3)	0.0024 (5)	0.0370 (15)
H15	0.319135	0.168325	−0.020258	0.044*
C16	0.3985 (8)	0.2491 (3)	−0.0638 (5)	0.0384 (15)
H16	0.359837	0.243561	−0.131271	0.046*
C17	0.4815 (8)	0.3030 (3)	−0.0299 (5)	0.0370 (15)
C18	0.5413 (9)	0.3098 (3)	0.0704 (6)	0.0470 (18)
H18	0.601002	0.344712	0.093380	0.056*
C19	0.5138 (9)	0.2653 (3)	0.1374 (5)	0.0461 (17)
H19	0.551208	0.270605	0.205096	0.055*
C20	0.4957 (9)	0.3526 (3)	−0.1028 (6)	0.0400 (16)
O5	−0.2064 (12)	−0.0007 (5)	0.4173 (6)	0.086 (3)	0.752 (12)
O6	0.947 (7)	0.4615 (18)	0.384 (5)	0.18 (2)	0.25
O6'	0.900 (6)	0.486 (2)	0.547 (4)	0.195 (19)	0.25
O7	0.656 (3)	0.3818 (9)	0.3134 (17)	0.164 (8)	0.5
O5A	−0.312 (4)	−0.0279 (14)	0.407 (2)	0.086 (3)	0.248 (12)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Pb1	0.0624 (2)	0.02865 (15)	0.04339 (18)	−0.00685 (12)	0.00662 (13)	0.00131 (13)
O1	0.100 (4)	0.031 (3)	0.053 (3)	−0.017 (3)	0.010 (3)	0.005 (2)
O2	0.131 (4)	0.066 (3)	0.072 (4)	−0.028 (3)	0.013 (3)	−0.007 (3)
O3	0.056 (3)	0.048 (3)	0.040 (3)	−0.004 (2)	0.006 (3)	0.004 (2)
O4	0.078 (3)	0.036 (3)	0.049 (3)	−0.010 (2)	0.013 (3)	0.001 (2)
N1	0.051 (3)	0.026 (3)	0.038 (3)	−0.002 (2)	0.003 (3)	0.009 (2)
N2	0.036 (3)	0.032 (3)	0.045 (3)	0.002 (2)	0.005 (3)	0.005 (3)
N3	0.048 (3)	0.031 (3)	0.053 (4)	−0.007 (3)	−0.004 (3)	−0.002 (3)
N4	0.039 (3)	0.026 (3)	0.038 (3)	−0.002 (2)	0.003 (2)	0.001 (2)
C1	0.099 (6)	0.033 (4)	0.043 (5)	−0.008 (4)	0.014 (5)	0.000 (4)
C2	0.079 (5)	0.024 (3)	0.038 (4)	0.001 (3)	0.016 (4)	−0.002 (3)
C3	0.082 (5)	0.033 (4)	0.045 (4)	−0.007 (4)	0.019 (4)	−0.009 (3)
C4	0.073 (5)	0.024 (3)	0.037 (4)	−0.008 (3)	0.015 (4)	0.002 (3)
C5	0.035 (3)	0.025 (3)	0.046 (4)	0.001 (3)	0.014 (3)	0.001 (3)
C6	0.066 (5)	0.030 (3)	0.042 (4)	0.000 (3)	0.003 (4)	0.002 (3)
C7	0.078 (5)	0.024 (3)	0.052 (5)	0.004 (3)	0.007 (4)	0.011 (3)
C8	0.034 (4)	0.045 (4)	0.060 (5)	0.002 (3)	−0.006 (3)	0.011 (4)
C9	0.049 (4)	0.050 (5)	0.066 (6)	−0.015 (4)	−0.010 (4)	0.000 (4)
C10	0.035 (3)	0.027 (3)	0.033 (4)	0.004 (3)	0.003 (3)	0.002 (3)
C11	0.039 (3)	0.027 (3)	0.039 (4)	0.002 (3)	0.008 (3)	−0.002 (3)
C12	0.054 (4)	0.043 (4)	0.047 (5)	0.007 (3)	−0.002 (4)	0.008 (3)
C13	0.039 (4)	0.058 (5)	0.048 (5)	−0.001 (3)	−0.007 (4)	0.004 (4)
C14	0.035 (3)	0.032 (3)	0.040 (4)	−0.001 (3)	0.007 (3)	0.004 (3)
C15	0.041 (4)	0.029 (3)	0.041 (4)	−0.007 (3)	0.006 (3)	0.002 (3)
C16	0.036 (3)	0.045 (4)	0.035 (4)	−0.001 (3)	0.009 (3)	0.002 (3)
C17	0.032 (3)	0.037 (4)	0.042 (4)	0.000 (3)	0.007 (3)	−0.001 (3)
C18	0.048 (4)	0.044 (4)	0.048 (5)	−0.009 (3)	0.002 (4)	−0.001 (4)
C19	0.053 (4)	0.053 (4)	0.032 (4)	−0.011 (3)	0.006 (3)	−0.005 (3)
C20	0.042 (4)	0.035 (4)	0.045 (5)	0.006 (3)	0.014 (3)	0.004 (3)
O5	0.080 (7)	0.133 (8)	0.046 (4)	−0.031 (5)	0.008 (5)	0.006 (5)
O6	0.18 (2)	0.18 (2)	0.18 (2)	0.002 (5)	0.029 (6)	0.003 (5)
O6'	0.198 (19)	0.192 (19)	0.195 (19)	0.003 (5)	0.032 (6)	0.003 (5)
O7	0.164 (8)	0.165 (8)	0.161 (9)	0.013 (5)	0.018 (5)	0.002 (5)
O5A	0.080 (7)	0.133 (8)	0.046 (4)	−0.031 (5)	0.008 (5)	0.006 (5)

Geometric parameters (Å, º)

Pb1—O1^i	2.406 (5)	C4—H4	0.9300
Pb1—O2^i	2.698 (7)	C4—C5	1.369 (9)
Pb1—O3^ii	2.654 (5)	C5—C6	1.392 (9)
Pb1—O4^ii	2.430 (5)	C6—H6	0.9300
Pb1—N1	2.450 (5)	C6—C7	1.400 (9)
Pb1—O5	2.850 (9)	C7—H7	0.9300
O1—C1	1.249 (9)	C8—H8	0.9300
O2—C1	1.232 (10)	C8—C9	1.330 (9)
O3—C20	1.249 (8)	C9—H9	0.9300
O4—C20	1.281 (8)	C10—C11	1.452 (8)
N1—C11	1.320 (8)	C12—H12	0.9300
N1—C12	1.374 (8)	C12—C13	1.350 (10)
N2—C11	1.370 (8)	C13—H13	0.9300
N2—C13	1.380 (8)	C14—C15	1.371 (9)
N2—C14	1.440 (8)	C14—C19	1.380 (9)
N3—C9	1.393 (9)	C15—H15	0.9300
N3—C10	1.321 (7)	C15—C16	1.378 (8)
N4—C5	1.442 (7)	C16—H16	0.9300
N4—C8	1.384 (8)	C16—C17	1.400 (8)
N4—C10	1.362 (7)	C17—C18	1.381 (10)
C1—C2	1.523 (9)	C17—C20	1.498 (9)
C2—C3	1.363 (9)	C18—H18	0.9300
C2—C7	1.376 (10)	C18—C19	1.385 (10)
C3—H3	0.9300	C19—H19	0.9300
C3—C4	1.398 (8)
O1^i—Pb1—O2^i	50.1 (2)	C5—C6—C7	118.8 (7)
O1^i—Pb1—O3^ii	130.16 (17)	C7—C6—H6	120.6
O1^i—Pb1—O4^ii	80.54 (17)	C2—C7—C6	119.7 (7)
O1^i—Pb1—N1	85.08 (19)	C2—C7—H7	120.1
O1^i—Pb1—O5	82.8 (2)	C6—C7—H7	120.1
O2^i—Pb1—O5	112.1 (3)	N4—C8—H8	126.9
O3^ii—Pb1—O2^i	154.8 (2)	C9—C8—N4	106.2 (6)
O3^ii—Pb1—O5	91.8 (2)	C9—C8—H8	126.9
O4^ii—Pb1—O2^i	127.7 (2)	N3—C9—H9	124.4
O4^ii—Pb1—O3^ii	51.46 (16)	C8—C9—N3	111.2 (6)
O4^ii—Pb1—N1	79.34 (18)	C8—C9—H9	124.4
O4^ii—Pb1—O5	70.7 (2)	N3—C10—N4	111.7 (5)
N1—Pb1—O2^i	80.4 (2)	N3—C10—C11	120.2 (5)
N1—Pb1—O3^ii	74.73 (16)	N4—C10—C11	128.1 (5)
N1—Pb1—O5	149.1 (2)	N1—C11—N2	110.6 (5)
C1—O1—Pb1^iii	99.7 (5)	N1—C11—C10	121.1 (5)
C1—O2—Pb1^iii	86.3 (5)	N2—C11—C10	128.2 (6)
C20—O3—Pb1^iv	88.1 (4)	N1—C12—H12	124.7
C20—O4—Pb1^iv	97.8 (4)	C13—C12—N1	110.6 (6)
C11—N1—Pb1	120.4 (4)	C13—C12—H12	124.7
C11—N1—C12	105.8 (5)	N2—C13—H13	127.1
C12—N1—Pb1	133.6 (4)	C12—C13—N2	105.9 (6)
C11—N2—C13	107.0 (6)	C12—C13—H13	127.1
C11—N2—C14	126.9 (5)	C15—C14—N2	119.5 (6)
C13—N2—C14	126.0 (5)	C15—C14—C19	121.4 (6)
C10—N3—C9	104.3 (5)	C19—C14—N2	119.0 (6)
C8—N4—C5	124.3 (5)	C14—C15—H15	120.2
C10—N4—C5	128.8 (5)	C14—C15—C16	119.5 (6)
C10—N4—C8	106.6 (5)	C16—C15—H15	120.2
O1—C1—C2	118.7 (7)	C15—C16—H16	119.8
O2—C1—O1	122.5 (7)	C15—C16—C17	120.4 (6)
O2—C1—C2	118.5 (7)	C17—C16—H16	119.8
C3—C2—C1	119.5 (7)	C16—C17—C20	119.0 (6)
C3—C2—C7	121.0 (6)	C18—C17—C16	118.8 (6)
C7—C2—C1	119.5 (6)	C18—C17—C20	122.1 (6)
C2—C3—H3	119.9	C17—C18—H18	119.5
C2—C3—C4	120.1 (7)	C17—C18—C19	121.0 (7)
C4—C3—H3	119.9	C19—C18—H18	119.5
C3—C4—H4	120.3	C14—C19—C18	118.8 (7)
C5—C4—C3	119.3 (6)	C14—C19—H19	120.6
C5—C4—H4	120.3	C18—C19—H19	120.6
C4—C5—N4	119.8 (6)	O3—C20—O4	122.3 (6)
C4—C5—C6	121.1 (6)	O3—C20—C17	119.8 (6)
C6—C5—N4	119.1 (6)	O4—C20—C17	117.9 (6)
C5—C6—H6	120.6
Pb1^iii—O1—C1—O2	13.3 (11)	C8—N4—C5—C4	127.8 (7)
Pb1^iii—O1—C1—C2	−160.7 (6)	C8—N4—C5—C6	−53.2 (9)
Pb1^iii—O2—C1—O1	−11.7 (9)	C8—N4—C10—N3	−0.7 (8)
Pb1^iii—O2—C1—C2	162.3 (7)	C8—N4—C10—C11	−178.9 (6)
Pb1^iv—O3—C20—O4	−5.7 (6)	C9—N3—C10—N4	0.0 (8)
Pb1^iv—O3—C20—C17	172.9 (5)	C9—N3—C10—C11	178.3 (6)
Pb1^iv—O4—C20—O3	6.3 (7)	C10—N3—C9—C8	0.8 (9)
Pb1^iv—O4—C20—C17	−172.3 (5)	C10—N4—C5—C4	−44.5 (9)
Pb1—N1—C11—N2	176.9 (4)	C10—N4—C5—C6	134.5 (7)
Pb1—N1—C11—C10	−5.0 (8)	C10—N4—C8—C9	1.2 (8)
Pb1—N1—C12—C13	−175.8 (5)	C11—N1—C12—C13	0.6 (8)
O1—C1—C2—C3	169.0 (8)	C11—N2—C13—C12	0.9 (8)
O1—C1—C2—C7	−7.9 (12)	C11—N2—C14—C15	−47.8 (9)
O2—C1—C2—C3	−5.2 (13)	C11—N2—C14—C19	130.3 (7)
O2—C1—C2—C7	177.9 (9)	C12—N1—C11—N2	0.0 (7)
N1—C12—C13—N2	−0.9 (9)	C12—N1—C11—C10	178.0 (6)
N2—C14—C15—C16	176.8 (5)	C13—N2—C11—N1	−0.5 (7)
N2—C14—C19—C18	−178.0 (6)	C13—N2—C11—C10	−178.4 (6)
N3—C10—C11—N1	−39.6 (9)	C13—N2—C14—C15	128.0 (7)
N3—C10—C11—N2	138.0 (7)	C13—N2—C14—C19	−54.0 (9)
N4—C5—C6—C7	−177.0 (6)	C14—N2—C11—N1	175.9 (6)
N4—C8—C9—N3	−1.2 (9)	C14—N2—C11—C10	−2.0 (10)
N4—C10—C11—N1	138.4 (7)	C14—N2—C13—C12	−175.6 (6)
N4—C10—C11—N2	−44.0 (10)	C14—C15—C16—C17	0.5 (9)
C1—C2—C3—C4	−175.0 (7)	C15—C14—C19—C18	0.0 (10)
C1—C2—C7—C6	175.3 (7)	C15—C16—C17—C18	1.4 (9)
C2—C3—C4—C5	−0.3 (11)	C15—C16—C17—C20	−175.9 (6)
C3—C2—C7—C6	−1.5 (12)	C16—C17—C18—C19	−2.7 (10)
C3—C4—C5—N4	177.3 (6)	C16—C17—C20—O3	1.7 (9)
C3—C4—C5—C6	−1.7 (10)	C16—C17—C20—O4	−179.7 (6)
C4—C5—C6—C7	2.0 (10)	C17—C18—C19—C14	2.0 (11)
C5—N4—C8—C9	−172.5 (7)	C18—C17—C20—O3	−175.5 (7)
C5—N4—C10—N3	172.6 (6)	C18—C17—C20—O4	3.1 (9)
C5—N4—C10—C11	−5.5 (11)	C19—C14—C15—C16	−1.2 (10)
C5—C6—C7—C2	−0.4 (11)	C20—C17—C18—C19	174.5 (6)
C7—C2—C3—C4	1.8 (12)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C13—H13···O3^v	0.93	2.28	3.190 (9)	168

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