Ligands based on polycarboxylic acids are excellent building blocks for the construction of coordination polymers; they may bind to a variety of metal ions and form clusters, as well as extended chain or network structures. Among these building blocks, biphenyltetracarboxylic acids (H4bpta) with C2 symmetry have recently attracted attention because of their variable bridging and multidentate chelating modes. The new luminescent three-dimensional coordination polymer poly[(μ5-1,1′-biphenyl-2,2′,4,4′-tetracarboxylato)bis[μ2-1,4-bis(1H-imidazol-1-yl)benzene]dizinc(II)], [Zn2(C16H6O8)(C12H10N4)]n, was synthesized solvothermally and characterized by single-crystal X-ray diffraction, elemental analysis and IR spectroscopy. The crystal structure contains two crystallographically independent ZnII cations. Both metal cations are located on twofold axes and display distorted tetrahedral coordination geometries. Neighbouring ZnII centres are bridged by carboxylate groups in the syn–anti mode to form one-dimensional chains. Adjacent chains are linked through 1,1′-biphenyl-2,2′,4,4′-tetracarboxylate and 1,4-bis(1H-imidazol-1-yl)benzene ligands to form a three-dimensional network. In the solid state, the compound exhibits blue photoluminescence and represents a promising candidate for a thermally stable and solvent-resistant blue fluorescent material.
Supporting information
CCDC reference: 1525738
Data collection: APEX2 (Bruker, 2012); cell refinement: SAINT (Bruker, 2012); data reduction: SAINT (Bruker, 2012); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: SHELXTL (Sheldrick, 2015) and DIAMOND (Brandenburg, 2005); software used to prepare material for publication: PLATON (Spek, 2009) and publCIF (Westrip, 2010).
Poly[(µ
5-1,1'-biphenyl-2,2',4,4'-tetracarboxylato)bis[µ
2-1,4-bis(1
H-imidazol-1-yl)benzene]dizinc(II)]
top
Crystal data top
[Zn2(C16H6O8)(C12H10N4)] | F(000) = 1344 |
Mr = 667.18 | Dx = 1.767 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 9.4371 (11) Å | Cell parameters from 3692 reflections |
b = 18.909 (2) Å | θ = 2.5–25.5° |
c = 14.4981 (15) Å | µ = 1.98 mm−1 |
β = 104.162 (2)° | T = 296 K |
V = 2508.5 (5) Å3 | Block, colourless |
Z = 4 | 0.28 × 0.26 × 0.20 mm |
Data collection top
Bruker APEXII CCD area-detector diffractometer | 1877 reflections with I > 2σ(I) |
Radiation source: sealed tube | Rint = 0.033 |
φ and ω scans | θmax = 25.5°, θmin = 2.2° |
Absorption correction: multi-scan (SADABS; Bruker, 2012) | h = −11→11 |
Tmin = 0.608, Tmax = 0.693 | k = −22→22 |
7259 measured reflections | l = −17→15 |
2345 independent reflections | |
Refinement top
Refinement on F2 | 6 restraints |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.035 | H-atom parameters constrained |
wR(F2) = 0.095 | w = 1/[σ2(Fo2) + (0.0468P)2 + 4.1623P] where P = (Fo2 + 2Fc2)/3 |
S = 1.00 | (Δ/σ)max < 0.001 |
2345 reflections | Δρmax = 0.38 e Å−3 |
191 parameters | Δρmin = −0.64 e Å−3 |
Special details top
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell e.s.d.'s are taken
into account individually in the estimation of e.s.d.'s in distances, angles
and torsion angles; correlations between e.s.d.'s in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s.
planes. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Zn1 | 1.0000 | 0.95384 (3) | 0.7500 | 0.03573 (18) | |
Zn2 | 0.5000 | 0.99870 (3) | 0.7500 | 0.03422 (18) | |
N1 | 0.4976 (3) | 0.93735 (17) | 0.8612 (2) | 0.0429 (7) | |
N2 | 0.4196 (3) | 0.85803 (16) | 0.9481 (2) | 0.0406 (7) | |
O1 | 0.8157 (3) | 1.01066 (13) | 0.72820 (19) | 0.0453 (6) | |
O2 | 0.6601 (2) | 1.06660 (14) | 0.79288 (18) | 0.0456 (6) | |
O3 | 0.9643 (3) | 1.08620 (15) | 1.12784 (18) | 0.0502 (7) | |
O4 | 1.1585 (3) | 1.15690 (17) | 1.16171 (18) | 0.0613 (8) | |
C1 | 1.0050 (3) | 1.14035 (17) | 0.8022 (2) | 0.0325 (7) | |
C2 | 0.9060 (3) | 1.10220 (17) | 0.8403 (2) | 0.0299 (7) | |
C3 | 0.9213 (3) | 1.09980 (18) | 0.9383 (2) | 0.0338 (7) | |
H3 | 0.8551 | 1.0739 | 0.9628 | 0.041* | |
C4 | 1.0341 (4) | 1.13561 (18) | 0.9995 (2) | 0.0338 (8) | |
C5 | 1.1272 (4) | 1.1762 (2) | 0.9614 (2) | 0.0443 (9) | |
H5 | 1.2013 | 1.2018 | 1.0017 | 0.053* | |
C6 | 1.1124 (4) | 1.1795 (2) | 0.8642 (2) | 0.0432 (9) | |
H6 | 1.1748 | 1.2082 | 0.8400 | 0.052* | |
C7 | 0.7862 (3) | 1.05702 (18) | 0.7819 (2) | 0.0331 (7) | |
C8 | 1.0574 (4) | 1.1277 (2) | 1.1056 (2) | 0.0404 (8) | |
C9 | 0.5868 (5) | 0.9380 (3) | 0.9515 (3) | 0.0652 (13) | |
H9 | 0.6675 | 0.9672 | 0.9725 | 0.078* | |
C10 | 0.5395 (5) | 0.8898 (3) | 1.0048 (3) | 0.0677 (13) | |
H10 | 0.5807 | 0.8799 | 1.0686 | 0.081* | |
C11 | 0.3987 (4) | 0.88905 (19) | 0.8622 (3) | 0.0441 (9) | |
H11 | 0.3232 | 0.8775 | 0.8099 | 0.053* | |
C12 | 0.3326 (4) | 0.80272 (18) | 0.9739 (3) | 0.0390 (8) | |
C13 | 0.3485 (4) | 0.7870 (2) | 1.0691 (3) | 0.0465 (9) | |
H13 | 0.4152 | 0.8120 | 1.1155 | 0.056* | |
C14 | 0.2345 (4) | 0.7658 (2) | 0.9049 (3) | 0.0449 (9) | |
H14 | 0.2243 | 0.7764 | 0.8409 | 0.054* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Zn1 | 0.0346 (3) | 0.0404 (3) | 0.0334 (3) | 0.000 | 0.0106 (2) | 0.000 |
Zn2 | 0.0251 (3) | 0.0410 (3) | 0.0355 (3) | 0.000 | 0.0052 (2) | 0.000 |
N1 | 0.0380 (17) | 0.0485 (18) | 0.0402 (18) | 0.0035 (14) | 0.0058 (14) | 0.0074 (15) |
N2 | 0.0423 (17) | 0.0428 (17) | 0.0362 (16) | 0.0099 (14) | 0.0085 (13) | 0.0069 (14) |
O1 | 0.0322 (14) | 0.0498 (16) | 0.0526 (16) | −0.0010 (11) | 0.0079 (12) | −0.0197 (13) |
O2 | 0.0278 (13) | 0.0556 (16) | 0.0552 (16) | −0.0063 (11) | 0.0135 (11) | −0.0196 (13) |
O3 | 0.0540 (16) | 0.0601 (17) | 0.0368 (14) | −0.0092 (14) | 0.0120 (12) | 0.0075 (13) |
O4 | 0.0644 (19) | 0.085 (2) | 0.0287 (14) | −0.0238 (17) | 0.0002 (13) | 0.0009 (14) |
C1 | 0.0315 (18) | 0.0344 (17) | 0.0318 (18) | 0.0036 (14) | 0.0083 (14) | 0.0018 (14) |
C2 | 0.0279 (17) | 0.0309 (17) | 0.0302 (17) | 0.0022 (14) | 0.0060 (13) | −0.0024 (14) |
C3 | 0.0311 (17) | 0.0364 (18) | 0.0361 (19) | −0.0026 (15) | 0.0124 (14) | 0.0005 (15) |
C4 | 0.0355 (19) | 0.0366 (18) | 0.0293 (17) | −0.0029 (15) | 0.0077 (14) | 0.0009 (14) |
C5 | 0.048 (2) | 0.048 (2) | 0.034 (2) | −0.0193 (18) | 0.0045 (16) | −0.0034 (17) |
C6 | 0.048 (2) | 0.048 (2) | 0.035 (2) | −0.0157 (18) | 0.0123 (17) | 0.0023 (17) |
C7 | 0.0281 (17) | 0.0371 (18) | 0.0332 (18) | 0.0009 (14) | 0.0058 (14) | −0.0011 (15) |
C8 | 0.042 (2) | 0.047 (2) | 0.0315 (19) | 0.0037 (18) | 0.0084 (16) | 0.0046 (17) |
C9 | 0.050 (3) | 0.087 (3) | 0.050 (3) | −0.017 (2) | −0.003 (2) | 0.013 (2) |
C10 | 0.060 (3) | 0.091 (4) | 0.042 (2) | −0.013 (3) | −0.007 (2) | 0.018 (2) |
C11 | 0.046 (2) | 0.043 (2) | 0.038 (2) | 0.0059 (18) | 0.0007 (17) | 0.0069 (17) |
C12 | 0.044 (2) | 0.0346 (18) | 0.040 (2) | 0.0151 (16) | 0.0139 (17) | 0.0076 (17) |
C13 | 0.057 (2) | 0.043 (2) | 0.037 (2) | 0.0067 (18) | 0.0076 (18) | 0.0013 (17) |
C14 | 0.058 (2) | 0.047 (2) | 0.0308 (19) | 0.0077 (19) | 0.0117 (17) | 0.0047 (17) |
Geometric parameters (Å, º) top
Zn1—O3i | 1.879 (2) | C1—C1iii | 1.493 (6) |
Zn1—O3ii | 1.879 (2) | C2—C3 | 1.394 (4) |
Zn1—O1 | 2.002 (2) | C2—C7 | 1.502 (4) |
Zn1—O1iii | 2.002 (3) | C3—C4 | 1.385 (5) |
Zn2—O2iv | 1.964 (2) | C3—H3 | 0.9300 |
Zn2—O2 | 1.964 (2) | C4—C5 | 1.381 (5) |
Zn2—N1 | 1.990 (3) | C4—C8 | 1.506 (5) |
Zn2—N1iv | 1.990 (3) | C5—C6 | 1.383 (5) |
N1—C11 | 1.308 (5) | C5—H5 | 0.9300 |
N1—C9 | 1.374 (5) | C6—H6 | 0.9300 |
N2—C11 | 1.347 (4) | C9—C10 | 1.339 (6) |
N2—C10 | 1.365 (5) | C9—H9 | 0.9300 |
N2—C12 | 1.435 (5) | C10—H10 | 0.9300 |
O1—C7 | 1.248 (4) | C11—H11 | 0.9300 |
O2—C7 | 1.252 (4) | C12—C14 | 1.377 (5) |
O3—C8 | 1.277 (4) | C12—C13 | 1.383 (5) |
O3—Zn1ii | 1.879 (2) | C13—C14v | 1.376 (5) |
O4—C8 | 1.223 (4) | C13—H13 | 0.9300 |
C1—C6 | 1.392 (5) | C14—C13v | 1.376 (5) |
C1—C2 | 1.397 (4) | C14—H14 | 0.9300 |
| | | |
O3i—Zn1—O3ii | 132.49 (17) | C3—C4—C8 | 120.2 (3) |
O3i—Zn1—O1 | 96.84 (11) | C4—C5—C6 | 121.2 (3) |
O3ii—Zn1—O1 | 108.26 (12) | C4—C5—H5 | 119.4 |
O3i—Zn1—O1iii | 108.26 (12) | C6—C5—H5 | 119.4 |
O3ii—Zn1—O1iii | 96.84 (11) | C5—C6—C1 | 120.7 (3) |
O1—Zn1—O1iii | 115.10 (15) | C5—C6—H6 | 119.7 |
O2iv—Zn2—O2 | 98.36 (16) | C1—C6—H6 | 119.7 |
O2iv—Zn2—N1 | 118.49 (11) | O1—C7—O2 | 123.0 (3) |
O2—Zn2—N1 | 106.56 (12) | O1—C7—C2 | 119.9 (3) |
O2iv—Zn2—N1iv | 106.56 (12) | O2—C7—C2 | 117.0 (3) |
O2—Zn2—N1iv | 118.49 (11) | O4—C8—O3 | 125.6 (3) |
N1—Zn2—N1iv | 108.69 (19) | O4—C8—C4 | 122.0 (3) |
C11—N1—C9 | 105.5 (3) | O3—C8—C4 | 112.4 (3) |
C11—N1—Zn2 | 124.4 (3) | C10—C9—N1 | 109.4 (4) |
C9—N1—Zn2 | 129.9 (3) | C10—C9—H9 | 125.3 |
C11—N2—C10 | 106.1 (3) | N1—C9—H9 | 125.3 |
C11—N2—C12 | 126.5 (3) | C9—C10—N2 | 107.2 (4) |
C10—N2—C12 | 127.4 (3) | C9—C10—H10 | 126.4 |
C7—O1—Zn1 | 126.6 (2) | N2—C10—H10 | 126.4 |
C7—O2—Zn2 | 123.1 (2) | N1—C11—N2 | 111.8 (3) |
C8—O3—Zn1ii | 120.7 (2) | N1—C11—H11 | 124.1 |
C6—C1—C2 | 118.1 (3) | N2—C11—H11 | 124.1 |
C6—C1—C1iii | 120.7 (3) | C14—C12—C13 | 120.4 (4) |
C2—C1—C1iii | 121.2 (3) | C14—C12—N2 | 120.4 (3) |
C3—C2—C1 | 120.5 (3) | C13—C12—N2 | 119.2 (4) |
C3—C2—C7 | 115.6 (3) | C14v—C13—C12 | 120.0 (4) |
C1—C2—C7 | 123.7 (3) | C14v—C13—H13 | 120.0 |
C4—C3—C2 | 120.6 (3) | C12—C13—H13 | 120.0 |
C4—C3—H3 | 119.7 | C13v—C14—C12 | 119.7 (3) |
C2—C3—H3 | 119.7 | C13v—C14—H14 | 120.2 |
C5—C4—C3 | 118.7 (3) | C12—C14—H14 | 120.2 |
C5—C4—C8 | 121.0 (3) | | |
| | | |
C6—C1—C2—C3 | −4.3 (5) | Zn1ii—O3—C8—C4 | 161.8 (2) |
C1iii—C1—C2—C3 | 176.7 (3) | C5—C4—C8—O4 | 0.3 (6) |
C6—C1—C2—C7 | −179.1 (3) | C3—C4—C8—O4 | 177.8 (4) |
C1iii—C1—C2—C7 | 1.9 (5) | C5—C4—C8—O3 | −177.5 (3) |
C1—C2—C3—C4 | 0.5 (5) | C3—C4—C8—O3 | 0.0 (5) |
C7—C2—C3—C4 | 175.7 (3) | C11—N1—C9—C10 | 0.1 (5) |
C2—C3—C4—C5 | 2.8 (5) | Zn2—N1—C9—C10 | 176.2 (3) |
C2—C3—C4—C8 | −174.8 (3) | N1—C9—C10—N2 | 0.2 (6) |
C3—C4—C5—C6 | −2.3 (6) | C11—N2—C10—C9 | −0.5 (5) |
C8—C4—C5—C6 | 175.3 (4) | C12—N2—C10—C9 | 179.5 (4) |
C4—C5—C6—C1 | −1.6 (6) | C9—N1—C11—N2 | −0.4 (4) |
C2—C1—C6—C5 | 4.9 (5) | Zn2—N1—C11—N2 | −176.8 (2) |
C1iii—C1—C6—C5 | −176.1 (3) | C10—N2—C11—N1 | 0.5 (4) |
Zn1—O1—C7—O2 | −144.6 (3) | C12—N2—C11—N1 | −179.4 (3) |
Zn1—O1—C7—C2 | 32.6 (4) | C11—N2—C12—C14 | 13.7 (5) |
Zn2—O2—C7—O1 | 13.4 (5) | C10—N2—C12—C14 | −166.2 (4) |
Zn2—O2—C7—C2 | −163.8 (2) | C11—N2—C12—C13 | −166.3 (3) |
C3—C2—C7—O1 | −122.0 (4) | C10—N2—C12—C13 | 13.8 (6) |
C1—C2—C7—O1 | 53.1 (5) | C14—C12—C13—C14v | −0.2 (6) |
C3—C2—C7—O2 | 55.4 (4) | N2—C12—C13—C14v | 179.8 (3) |
C1—C2—C7—O2 | −129.6 (4) | C13—C12—C14—C13v | 0.2 (6) |
Zn1ii—O3—C8—O4 | −16.0 (5) | N2—C12—C14—C13v | −179.8 (3) |
Symmetry codes: (i) x, −y+2, z−1/2; (ii) −x+2, −y+2, −z+2; (iii) −x+2, y, −z+3/2; (iv) −x+1, y, −z+3/2; (v) −x+1/2, −y+3/2, −z+2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C11—H11···O4vi | 0.93 | 2.41 | 3.335 (5) | 171 |
Symmetry code: (vi) x−1, −y+2, z−1/2. |