A new three-dimensional zinc(II) coordination polymer involving 2-[(1H-1,2,4-triazol-1-yl)meth­yl]-1H-benzimidazole and benzene-1,4-di­carboxyl­ate ligands

Metal–organic frameworks (MOFs) based on multidentate N-heterocyclic ligands involving imidazole, triazole, tetra­zole, benzimidazole, benzotriazole or pyridine present intriguing mol­ecular topologies and have potential appli­cations in ion exchange, magnetism, gas sorption and storage, catalysis, optics and biomedicine. The 2-[(1H-1,2,4-triazol-1-yl)meth­yl]-1H-benzimidazole (tmb) ligand has four potential N-atom donors and can act in monodentate, chelating, bridging and tridentate coordination modes in the construction of complexes, and can also act as both a hydrogen-bond donor and acceptor. In addition, the tmb ligand can adopt different coordination conformations, resulting in complexes with helical structures due to the presence of the flexible methyl­ene spacer. A new three-dimensional coordination polymer, poly[[bis(μ₂-benzene-1,4-di­carboxyl­ato)-κ⁴O¹,O^1′:O⁴,O^4′;κ²O¹:O⁴-bis{μ₂-2-[(1H-1,2,4-tri­azol-1-yl)methyl-κN⁴]-1H-benzimidazole-κN³}dizinc(II)] trihydrate], {[Zn(C₈H₄O₄)(C₁₀H₉N₅)]·1.5H₂O}_n, has been synthesized by the reaction of ZnCl₂ with tmb and benzene-1,4-di­carb­oxy­lic acid (H₂bdic) under solvothermal conditions. There are two crystallographically distinct bdic²⁻ ligands [bdic²⁻(A) and bdic²⁻(B)] in the structure which adopt different coordination modes. The Zn^II ions are bridged by tmb ligands, leading to one-dimensional helical chains with different handedness, and adjacent helices are linked by bdic²⁻(A) ligands, forming a two-dimensional network structure. The two-dimensional layers are further connected by bdic²⁻(B) ligands, resulting in a three-dimensional framework with the topological notation 6⁶. The IR spectra and thermogravimetric curves are consistent with the results of the X-ray crystal structure analysis and the title polymer exhibits good fluorescence in the solid state at room temperature.

Computing details

Data collection: CrystalClear (Rigaku/MSC, 2004); cell refinement: CrystalClear (Rigaku/MSC, 2004); data reduction: CrystalClear (Rigaku/MSC, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: publCIF (Westrip, 2010).

Poly[[bis(µ₂-benzene-1,4-dicarboxylato)-κ⁴O¹,O^1':O⁴,O^4';κ²O¹:O⁴-bis{µ₂-2-[(1H-1,2,4-triazol-1-yl)methyl-κN⁴]-1H-benzimidazole-κN³}dizinc(II)] triihydrate]

Crystal data

[Zn(C8H4O4)(C10H9N5)]·1.5H2O	F(000) = 1864
Mr = 455.75	Dx = 1.566 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 21.612 (4) Å	Cell parameters from 5920 reflections
b = 10.421 (2) Å	θ = 1.9–27.9°
c = 19.246 (4) Å	µ = 1.31 mm^−1
β = 116.85 (3)°	T = 293 K
V = 3867.3 (16) Å^3	Prism, colourless
Z = 8	0.21 × 0.19 × 0.15 mm

Data collection

Rigaku Saturn diffractometer	3542 independent reflections
Radiation source: fine-focus sealed tube	3208 reflections with I > 2σ(I)
Detector resolution: 28.5714 pixels mm^-1	Rint = 0.031
ω scans	θmax = 25.5°, θmin = 2.2°
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2004)	h = −23→26
Tmin = 0.922, Tmax = 1.000	k = −12→12
13193 measured reflections	l = −20→23

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.041	H-atom parameters constrained
wR(F^2) = 0.103	w = 1/[σ^2(Fo^2) + (0.0493P)^2 + 4.8983P] where P = (Fo^2 + 2Fc^2)/3
S = 1.10	(Δ/σ)max < 0.001
3542 reflections	Δρmax = 1.10 e Å^−3
286 parameters	Δρmin = −0.29 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.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Zn1	−0.16510 (2)	0.13195 (3)	−0.19250 (2)	0.03243 (13)
O1	−0.16060 (12)	0.3634 (2)	−0.15209 (14)	0.0512 (6)
O2	−0.07984 (11)	0.2133 (2)	−0.11443 (12)	0.0436 (5)
O3	−0.22270 (11)	0.1761 (2)	−0.30286 (12)	0.0406 (5)
O4	−0.11970 (13)	0.2021 (3)	−0.29719 (13)	0.0638 (7)
N1	−0.13283 (12)	−0.0524 (2)	−0.19594 (14)	0.0381 (6)
N3	−0.13389 (12)	−0.2559 (2)	−0.21848 (14)	0.0365 (6)
N4	−0.22956 (12)	0.1034 (2)	−0.14236 (14)	0.0323 (5)
N5	−0.32147 (14)	0.0903 (2)	−0.12042 (16)	0.0401 (6)
H5A	−0.3642	0.0856	−0.1297	0.048*
C1	−0.17087 (16)	−0.1565 (3)	−0.2180 (2)	0.0393 (7)
H1A	−0.2180	−0.1595	−0.2315	0.047*
C2	−0.0703 (7)	−0.1049 (14)	−0.167 (2)	0.056 (5)	0.50 (5)
H2A	−0.0305	−0.0562	−0.1393	0.067*	0.50 (5)
N2	−0.0667 (6)	−0.2247 (14)	−0.1779 (19)	0.062 (5)	0.50 (5)
C2'	−0.0724 (8)	−0.0878 (17)	−0.2013 (16)	0.051 (3)	0.50 (5)
H2'A	−0.0375	−0.0307	−0.1963	0.062*	0.50 (5)
N2'	−0.0712 (8)	−0.2115 (14)	−0.2145 (16)	0.051 (4)	0.50 (5)
C3	−0.15490 (16)	−0.3892 (3)	−0.24059 (18)	0.0389 (7)
H3A	−0.1785	−0.4211	−0.2116	0.047*
H3B	−0.1140	−0.4417	−0.2273	0.047*
C4	−0.29814 (15)	0.0998 (3)	−0.17429 (17)	0.0343 (7)
C5	−0.20765 (16)	0.0973 (3)	−0.06232 (17)	0.0364 (7)
C6	−0.14112 (18)	0.1015 (3)	0.00011 (19)	0.0483 (8)
H6A	−0.1018	0.1065	−0.0078	0.058*
C7	−0.1363 (2)	0.0978 (4)	0.0741 (2)	0.0588 (10)
H7A	−0.0928	0.1011	0.1169	0.071*
C8	−0.1947 (2)	0.0893 (3)	0.0861 (2)	0.0585 (10)
H8A	−0.1890	0.0862	0.1369	0.070*
C9	−0.2600 (2)	0.0855 (3)	0.0266 (2)	0.0506 (9)
H9A	−0.2989	0.0806	0.0354	0.061*
C10	−0.26559 (17)	0.0894 (3)	−0.04854 (18)	0.0383 (7)
C11	−0.10054 (17)	0.3269 (3)	−0.11109 (18)	0.0403 (7)
C12	0.02092 (17)	0.3805 (3)	−0.01181 (19)	0.0427 (8)
H12A	0.0351	0.2999	−0.0196	0.051*
C13	−0.04811 (16)	0.4162 (3)	−0.05295 (17)	0.0369 (7)
C14	−0.06845 (16)	0.5360 (3)	−0.04051 (18)	0.0426 (7)
H14A	−0.1147	0.5605	−0.0677	0.051*
C15	−0.18315 (17)	0.2029 (3)	−0.33402 (18)	0.0402 (7)
C16	−0.17914 (16)	0.2315 (3)	−0.46079 (17)	0.0406 (7)
H16A	−0.1314	0.2191	−0.4346	0.049*
C17	−0.21771 (15)	0.2306 (3)	−0.41962 (16)	0.0349 (7)
C18	−0.28920 (16)	0.2494 (3)	−0.45990 (18)	0.0412 (7)
H18A	−0.3157	0.2490	−0.4330	0.049*
O5	−0.04319 (14)	0.5750 (3)	−0.3473 (2)	0.0939 (11)
H1W	−0.0152	0.6351	−0.3229	0.113*
H2W	−0.0228	0.5051	−0.3269	0.113*
O6	0.0000	0.3555 (5)	−0.2500	0.170 (4)
H3W	−0.0338	0.3032	−0.2680	0.204*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.0335 (2)	0.0324 (2)	0.0292 (2)	−0.00429 (13)	0.01223 (15)	−0.00231 (13)
O1	0.0442 (14)	0.0455 (14)	0.0473 (14)	−0.0095 (10)	0.0060 (11)	−0.0032 (10)
O2	0.0466 (13)	0.0376 (12)	0.0430 (13)	−0.0122 (10)	0.0171 (10)	−0.0131 (10)
O3	0.0469 (13)	0.0480 (13)	0.0308 (11)	−0.0004 (10)	0.0210 (10)	0.0025 (9)
O4	0.0428 (14)	0.100 (2)	0.0394 (14)	−0.0096 (14)	0.0106 (11)	0.0083 (14)
N1	0.0353 (13)	0.0358 (14)	0.0391 (14)	−0.0022 (11)	0.0132 (11)	−0.0060 (11)
N3	0.0302 (13)	0.0347 (14)	0.0377 (14)	0.0019 (10)	0.0093 (11)	−0.0032 (11)
N4	0.0335 (13)	0.0326 (13)	0.0299 (13)	−0.0024 (10)	0.0136 (11)	0.0017 (10)
N5	0.0406 (14)	0.0366 (14)	0.0496 (16)	−0.0002 (11)	0.0261 (13)	0.0050 (12)
C1	0.0344 (16)	0.0340 (17)	0.0511 (19)	−0.0010 (13)	0.0207 (15)	−0.0020 (14)
C2	0.029 (4)	0.037 (5)	0.083 (13)	−0.003 (3)	0.009 (6)	−0.001 (7)
N2	0.029 (4)	0.051 (5)	0.087 (12)	0.003 (3)	0.010 (6)	−0.008 (7)
C2'	0.042 (5)	0.044 (6)	0.066 (10)	−0.009 (4)	0.022 (6)	−0.002 (6)
N2'	0.031 (4)	0.048 (5)	0.071 (10)	−0.003 (3)	0.020 (6)	−0.010 (6)
C3	0.0361 (16)	0.0316 (16)	0.0411 (18)	0.0049 (12)	0.0105 (14)	−0.0001 (13)
C4	0.0382 (16)	0.0242 (14)	0.0406 (17)	−0.0040 (12)	0.0179 (14)	0.0025 (12)
C5	0.0456 (18)	0.0313 (15)	0.0328 (16)	0.0001 (13)	0.0180 (14)	0.0031 (12)
C6	0.049 (2)	0.052 (2)	0.0394 (19)	0.0022 (16)	0.0160 (16)	0.0071 (15)
C7	0.070 (3)	0.056 (2)	0.036 (2)	0.0002 (19)	0.0123 (18)	0.0052 (16)
C8	0.099 (3)	0.043 (2)	0.038 (2)	0.007 (2)	0.036 (2)	0.0078 (16)
C9	0.079 (3)	0.0372 (18)	0.051 (2)	0.0036 (17)	0.043 (2)	0.0050 (15)
C10	0.0502 (18)	0.0273 (15)	0.0435 (18)	0.0029 (13)	0.0265 (16)	0.0042 (13)
C11	0.050 (2)	0.0362 (17)	0.0358 (17)	−0.0133 (14)	0.0210 (16)	−0.0046 (13)
C12	0.0465 (18)	0.0340 (17)	0.0445 (19)	−0.0050 (13)	0.0178 (15)	−0.0094 (13)
C13	0.0433 (17)	0.0361 (16)	0.0306 (16)	−0.0106 (13)	0.0160 (14)	−0.0046 (12)
C14	0.0366 (16)	0.0402 (18)	0.0441 (18)	−0.0043 (13)	0.0121 (14)	−0.0071 (14)
C15	0.0480 (19)	0.0361 (17)	0.0348 (17)	−0.0022 (14)	0.0172 (15)	0.0006 (13)
C16	0.0346 (16)	0.0492 (19)	0.0364 (17)	−0.0021 (14)	0.0147 (14)	0.0030 (14)
C17	0.0429 (17)	0.0321 (15)	0.0304 (15)	−0.0057 (12)	0.0172 (14)	0.0025 (12)
C18	0.0458 (18)	0.0455 (19)	0.0380 (18)	−0.0046 (14)	0.0240 (15)	0.0044 (14)
O5	0.0498 (17)	0.090 (2)	0.146 (3)	−0.0089 (16)	0.048 (2)	−0.017 (2)
O6	0.062 (3)	0.065 (4)	0.350 (12)	0.000	0.062 (5)	0.000

Geometric parameters (Å, º)

Zn1—O2	1.967 (2)	C3—H3B	0.9700
Zn1—O3	1.971 (2)	C4—C3^ii	1.492 (4)
Zn1—N4	2.043 (2)	C5—C10	1.395 (4)
Zn1—N1	2.055 (3)	C5—C6	1.397 (5)
Zn1—O1	2.522 (2)	C6—C7	1.380 (5)
Zn1—C11	2.560 (3)	C6—H6A	0.9300
O1—C11	1.236 (4)	C7—C8	1.384 (6)
O2—C11	1.277 (4)	C7—H7A	0.9300
O3—C15	1.277 (4)	C8—C9	1.359 (5)
O4—C15	1.227 (4)	C8—H8A	0.9300
N1—C1	1.311 (4)	C9—C10	1.396 (5)
N1—C2	1.325 (13)	C9—H9A	0.9300
N1—C2'	1.405 (16)	C11—C13	1.502 (4)
N3—C1	1.311 (4)	C12—C14^iii	1.376 (4)
N3—N2	1.341 (13)	C12—C13	1.387 (4)
N3—N2'	1.400 (13)	C12—H12A	0.9300
N3—C3	1.464 (4)	C13—C14	1.380 (4)
N4—C4	1.324 (4)	C14—C12^iii	1.376 (4)
N4—C5	1.394 (4)	C14—H14A	0.9300
N5—C4	1.346 (4)	C15—C17	1.498 (4)
N5—C10	1.365 (4)	C16—C18^iv	1.376 (4)
N5—H5A	0.8600	C16—C17	1.385 (4)
C1—H1A	0.9300	C16—H16A	0.9300
C2—N2	1.276 (19)	C17—C18	1.395 (4)
C2—H2A	0.9300	C18—C16^iv	1.376 (4)
C2'—N2'	1.32 (2)	C18—H18A	0.9300
C2'—H2'A	0.9300	O5—H1W	0.8500
C3—C4^i	1.492 (4)	O5—H2W	0.8500
C3—H3A	0.9700	O6—H3W	0.8497
O2—Zn1—O3	129.82 (9)	H3A—C3—H3B	108.0
O2—Zn1—N4	107.76 (9)	N4—C4—N5	112.0 (3)
O3—Zn1—N4	108.03 (9)	N4—C4—C3^ii	124.8 (3)
O2—Zn1—N1	102.30 (10)	N5—C4—C3^ii	123.1 (3)
O3—Zn1—N1	104.00 (10)	C10—C5—N4	109.1 (3)
N4—Zn1—N1	101.12 (10)	C10—C5—C6	120.1 (3)
O2—Zn1—O1	57.32 (8)	N4—C5—C6	130.8 (3)
O3—Zn1—O1	91.53 (9)	C7—C6—C5	117.1 (3)
N4—Zn1—O1	86.16 (9)	C7—C6—H6A	121.5
N1—Zn1—O1	159.61 (9)	C5—C6—H6A	121.5
O2—Zn1—C11	29.20 (10)	C8—C7—C6	121.6 (4)
O3—Zn1—C11	112.25 (10)	C8—C7—H7A	119.2
N4—Zn1—C11	97.23 (10)	C6—C7—H7A	119.2
N1—Zn1—C11	131.49 (11)	C9—C8—C7	122.7 (3)
O1—Zn1—C11	28.13 (9)	C9—C8—H8A	118.7
C11—O1—Zn1	77.65 (18)	C7—C8—H8A	118.7
C11—O2—Zn1	102.1 (2)	C8—C9—C10	116.3 (3)
C15—O3—Zn1	109.04 (19)	C8—C9—H9A	121.9
C1—N1—C2	99.6 (6)	C10—C9—H9A	121.9
C1—N1—C2'	103.1 (6)	N5—C10—C5	105.4 (3)
C1—N1—Zn1	127.7 (2)	N5—C10—C9	132.3 (3)
C2—N1—Zn1	131.9 (6)	C5—C10—C9	122.3 (3)
C2'—N1—Zn1	126.0 (8)	O1—C11—O2	122.9 (3)
C1—N3—N2	107.9 (7)	O1—C11—C13	120.5 (3)
C1—N3—N2'	108.5 (6)	O2—C11—C13	116.6 (3)
C1—N3—C3	129.9 (3)	O1—C11—Zn1	74.22 (18)
N2—N3—C3	120.7 (6)	O2—C11—Zn1	48.72 (14)
N2'—N3—C3	119.7 (6)	C13—C11—Zn1	165.2 (2)
C4—N4—C5	105.2 (2)	C14^iii—C12—C13	120.2 (3)
C4—N4—Zn1	130.1 (2)	C14^iii—C12—H12A	119.9
C5—N4—Zn1	124.4 (2)	C13—C12—H12A	119.9
C4—N5—C10	108.3 (2)	C14—C13—C12	119.2 (3)
C4—N5—H5A	125.9	C14—C13—C11	119.8 (3)
C10—N5—H5A	125.9	C12—C13—C11	121.0 (3)
N1—C1—N3	111.2 (3)	C12^iii—C14—C13	120.6 (3)
N1—C1—H1A	124.4	C12^iii—C14—H14A	119.7
N3—C1—H1A	124.4	C13—C14—H14A	119.7
N2—C2—N1	117.4 (11)	O4—C15—O3	122.5 (3)
N2—C2—H2A	121.3	O4—C15—C17	120.6 (3)
N1—C2—H2A	121.3	O3—C15—C17	116.8 (3)
C2—N2—N3	101.7 (11)	C18^iv—C16—C17	120.6 (3)
N2'—C2'—N1	111.8 (12)	C18^iv—C16—H16A	119.7
N2'—C2'—H2'A	124.1	C17—C16—H16A	119.7
N1—C2'—H2'A	124.1	C16—C17—C18	118.9 (3)
C2'—N2'—N3	103.4 (11)	C16—C17—C15	120.0 (3)
N3—C3—C4^i	111.1 (2)	C18—C17—C15	121.0 (3)
N3—C3—H3A	109.4	C16^iv—C18—C17	120.5 (3)
C4^i—C3—H3A	109.4	C16^iv—C18—H18A	119.7
N3—C3—H3B	109.4	C17—C18—H18A	119.7
C4^i—C3—H3B	109.4	H1W—O5—H2W	106.5
C2—N1—C1—N3	−14.1 (17)	C7—C8—C9—C10	0.6 (5)
C2'—N1—C1—N3	14.4 (13)	C4—N5—C10—C5	−0.7 (3)
Zn1—N1—C1—N3	175.0 (2)	C4—N5—C10—C9	177.6 (3)
N2—N3—C1—N1	15.3 (17)	N4—C5—C10—N5	0.2 (3)
N2'—N3—C1—N1	−14.8 (12)	C6—C5—C10—N5	178.6 (3)
C3—N3—C1—N1	−178.5 (3)	N4—C5—C10—C9	−178.2 (3)
C1—N1—C2—N2	8.8 (16)	C6—C5—C10—C9	0.1 (5)
Zn1—N1—C2—N2	179.1 (9)	C8—C9—C10—N5	−178.3 (3)
N1—C2—N2—N3	−0.3 (13)	C8—C9—C10—C5	−0.3 (5)
C1—N3—N2—C2	−8.8 (12)	Zn1—O1—C11—O2	1.3 (3)
C3—N3—N2—C2	−176.5 (9)	Zn1—O1—C11—C13	−177.6 (3)
C1—N1—C2'—N2'	−9.1 (12)	Zn1—O2—C11—O1	−1.7 (4)
Zn1—N1—C2'—N2'	−170.2 (7)	Zn1—O2—C11—C13	177.3 (2)
N1—C2'—N2'—N3	0.8 (11)	C14^iii—C12—C13—C14	−0.2 (5)
C1—N3—N2'—C2'	8.1 (10)	C14^iii—C12—C13—C11	179.2 (3)
C3—N3—N2'—C2'	173.8 (7)	O1—C11—C13—C14	5.5 (5)
C1—N3—C3—C4^i	67.2 (4)	O2—C11—C13—C14	−173.5 (3)
N2—N3—C3—C4^i	−128.1 (18)	Zn1—C11—C13—C14	−165.5 (7)
N2'—N3—C3—C4^i	−94.9 (13)	O1—C11—C13—C12	−173.9 (3)
C5—N4—C4—N5	−0.7 (3)	O2—C11—C13—C12	7.1 (4)
Zn1—N4—C4—N5	−174.31 (19)	Zn1—C11—C13—C12	15.1 (10)
C5—N4—C4—C3^ii	176.6 (3)	C12—C13—C14—C12^iii	0.2 (5)
Zn1—N4—C4—C3^ii	3.1 (4)	C11—C13—C14—C12^iii	−179.2 (3)
C10—N5—C4—N4	0.9 (3)	Zn1—O3—C15—O4	−1.4 (4)
C10—N5—C4—C3^ii	−176.5 (3)	Zn1—O3—C15—C17	176.1 (2)
C4—N4—C5—C10	0.3 (3)	C18^iv—C16—C17—C18	0.0 (5)
Zn1—N4—C5—C10	174.34 (19)	C18^iv—C16—C17—C15	176.8 (3)
C4—N4—C5—C6	−177.8 (3)	O4—C15—C17—C16	12.2 (5)
Zn1—N4—C5—C6	−3.8 (5)	O3—C15—C17—C16	−165.3 (3)
C10—C5—C6—C7	−0.2 (5)	O4—C15—C17—C18	−171.0 (3)
N4—C5—C6—C7	177.7 (3)	O3—C15—C17—C18	11.5 (4)
C5—C6—C7—C8	0.5 (5)	C16—C17—C18—C16^iv	0.0 (5)
C6—C7—C8—C9	−0.7 (6)	C15—C17—C18—C16^iv	−176.8 (3)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O5—H2W···O6	0.85	2.05	2.834 (6)	153
O6—H3W···O4	0.85	1.98	2.819 (4)	168
N5—H5A···O5^i	0.86	1.85	2.707 (4)	178
O5—H1W···N2^v	0.85	2.29	3.032 (14)	146
O5—H1W···N2′^v	0.85	2.31	3.134 (17)	163

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