The assembly of metal–organic frameworks (MOFs) with metal ions and organic ligands is currently attracting considerable attention in crystal engineering and materials science due to their intriguing architectures and potential applications. A new three-dimensional MOF, namely poly[[diaqua(μ8-para-terphenyl-3,3′,5,5′-tetracarboxylato)dizinc(II)] dimethylformamide disolvate monohydrate], {[Zn2(C22H10O8)(H2O)2]·2C3H7NO·H2O}n, was synthesized by the self-assembly of Zn(NO3)2·6H2O and para-terphenyl-3,3′,5,5′-tetracarboxylic acid (H4TPTC) under solvothermal conditions. The compound was structurally characterized by FT–IR spectroscopy, elemental analysis and single-crystal X-ray diffraction analysis. Each ZnII ion is located in a square-pyramidal geometry and is coordinated by four carboxylate O atoms from four different TPTC4− ligands. Pairs of adjacent equivalent ZnII ions are bridged by four carboxylate groups, forming [Zn2(O2CR)4] (R = terphenyl) paddle-wheel units. One aqua ligand binds to each ZnII centre along the paddle-wheel axis. Each [Zn2(O2CR)4] paddle wheel is further linked to four terphenyl connectors to give a three-dimensional framework with NBO-type topology. The thermal stability and solid-state photoluminescence properties of the title compound have also been investigated.
Supporting information
CCDC reference: 1894907
Data collection: APEX3 (Bruker, 2016); cell refinement: APEX3 (Bruker, 2016); data reduction: APEX3 (Bruker, 2016); program(s) used to solve structure: SHELXT2014 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015b); molecular graphics: DIAMOND (Brandenburg, 2010); software used to prepare material for publication: SHELXL2018 (Sheldrick, 2015b).
Poly[[diaqua(µ
8-
para-terphenyl-3,3',5,5'-tetracarboxylato)dizinc(II)]
dimethylformamide disolvate monohydrate]
top
Crystal data top
[Zn2(C22H10O8)(H2O)2]·2C3H7NO·H2O | Dx = 0.712 Mg m−3 |
Mr = 569.12 | Mo Kα radiation, λ = 0.71073 Å |
Trigonal, R3m:H | Cell parameters from 5433 reflections |
a = 19.170 (6) Å | θ = 2.5–23.5° |
c = 37.51 (2) Å | µ = 0.93 mm−1 |
V = 11936 (10) Å3 | T = 296 K |
Z = 9 | Block, colourless |
F(000) = 2574 | 0.19 × 0.17 × 0.14 mm |
Data collection top
Bruker APEXII CCD area detector diffractometer | 2195 reflections with I > 2σ(I) |
Radiation source: sealed tube | Rint = 0.042 |
phi and ω scans | θmax = 25.5°, θmin = 2.1° |
Absorption correction: multi-scan | h = −23→21 |
Tmin = 0.843, Tmax = 0.881 | k = −23→21 |
21157 measured reflections | l = −45→38 |
2715 independent reflections | |
Refinement top
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.036 | H-atom parameters constrained |
wR(F2) = 0.133 | w = 1/[σ2(Fo2) + (0.0958P)2 + 6.732P] where P = (Fo2 + 2Fc2)/3 |
S = 1.00 | (Δ/σ)max = 0.001 |
2715 reflections | Δρmax = 0.28 e Å−3 |
94 parameters | Δρmin = −0.37 e Å−3 |
Special details top
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. Refinement of F2 against ALL reflections. The weighted R-factor wR and
goodness of fit S are based on F2, conventional R-factors R are based
on F, with F set to zero for negative F2. The threshold expression of
F2 > 2sigma(F2) is used only for calculating R-factors(gt) etc. and is
not relevant to the choice of reflections for refinement. R-factors based
on F2 are statistically about twice as large as those based on F, and R-
factors based on ALL data will be even larger. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
Zn1 | 0.47587 (2) | 0.95175 (2) | 1.03318 (2) | 0.03741 (18) | |
O1 | 0.51609 (13) | 0.88673 (12) | 1.00689 (5) | 0.0637 (5) | |
O2 | 0.55427 (14) | 0.96206 (12) | 0.95778 (5) | 0.0676 (6) | |
O3 | 0.45154 (10) | 0.90309 (19) | 1.08089 (7) | 0.0829 (10) | |
H11A | 0.465669 | 0.931338 | 1.099456 | 0.124* | |
H11B | 0.425759 | 0.851518 | 1.082966 | 0.124* | |
C1 | 0.54271 (17) | 0.90229 (15) | 0.97558 (7) | 0.0514 (6) | |
C2 | 0.56237 (18) | 0.84360 (16) | 0.95816 (7) | 0.0536 (7) | |
C3 | 0.5922 (2) | 0.85795 (17) | 0.92329 (8) | 0.0613 (8) | |
H3A | 0.601985 | 0.904932 | 0.911740 | 0.074* | |
C4 | 0.6074 (3) | 0.80368 (15) | 0.90572 (12) | 0.0663 (12) | |
C5 | 0.5488 (2) | 0.77438 (12) | 0.97530 (10) | 0.0530 (9) | |
H5A | 0.530211 | 0.765104 | 0.998699 | 0.064* | |
C6 | 0.6382 (3) | 0.81908 (17) | 0.86841 (12) | 0.0707 (13) | |
C7 | 0.6884 (7) | 0.7938 (6) | 0.8561 (2) | 0.088 (3) | 0.5 |
H7A | 0.707250 | 0.768230 | 0.873280 | 0.106* | 0.5 |
C8 | 0.6135 (6) | 0.8565 (5) | 0.84427 (19) | 0.079 (2) | 0.5 |
H8A | 0.577630 | 0.875490 | 0.852500 | 0.095* | 0.5 |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Zn1 | 0.0463 (2) | 0.0304 (2) | 0.0302 (2) | 0.01521 (12) | 0.00199 (7) | 0.00399 (14) |
O1 | 0.0853 (14) | 0.0571 (12) | 0.0593 (12) | 0.0435 (11) | 0.0150 (11) | 0.0007 (9) |
O2 | 0.1007 (16) | 0.0565 (12) | 0.0642 (12) | 0.0532 (12) | 0.0125 (12) | 0.0020 (10) |
O3 | 0.120 (2) | 0.072 (2) | 0.0412 (15) | 0.0360 (10) | 0.0094 (7) | 0.0187 (14) |
C1 | 0.0594 (16) | 0.0402 (14) | 0.0553 (16) | 0.0253 (13) | 0.0023 (12) | −0.0032 (12) |
C2 | 0.0713 (18) | 0.0451 (14) | 0.0510 (15) | 0.0339 (14) | 0.0091 (13) | 0.0018 (11) |
C3 | 0.092 (2) | 0.0467 (15) | 0.0566 (17) | 0.0434 (16) | 0.0174 (15) | 0.0094 (12) |
C4 | 0.100 (3) | 0.0604 (17) | 0.052 (2) | 0.0500 (17) | 0.022 (2) | 0.0111 (11) |
C5 | 0.069 (2) | 0.0512 (15) | 0.0452 (19) | 0.0343 (12) | 0.0068 (18) | 0.0034 (9) |
C6 | 0.115 (4) | 0.0589 (16) | 0.057 (3) | 0.058 (2) | 0.025 (2) | 0.0123 (12) |
C7 | 0.153 (8) | 0.098 (6) | 0.063 (4) | 0.100 (6) | 0.035 (5) | 0.031 (4) |
C8 | 0.123 (6) | 0.090 (5) | 0.065 (4) | 0.083 (5) | 0.032 (4) | 0.024 (4) |
Geometric parameters (Å, º) top
Zn1—O3 | 1.963 (3) | C2—C5 | 1.377 (3) |
Zn1—O1i | 2.020 (2) | C2—C3 | 1.398 (4) |
Zn1—O1 | 2.020 (2) | C3—C4 | 1.380 (3) |
Zn1—O2ii | 2.0330 (19) | C3—H3A | 0.9300 |
Zn1—O2iii | 2.033 (2) | C4—C6 | 1.490 (6) |
Zn1—Zn1ii | 2.9601 (15) | C5—H5A | 0.9300 |
O1—C1 | 1.255 (3) | C6—C7 | 1.357 (8) |
O2—C1 | 1.247 (3) | C6—C8 | 1.377 (8) |
O3—H11A | 0.8396 | C7—H7A | 0.9803 |
O3—H11B | 0.8596 | C8—H8A | 0.9758 |
C1—C2 | 1.503 (4) | | |
| | | |
O3—Zn1—O1i | 103.01 (10) | O2—C1—O1 | 125.7 (3) |
O3—Zn1—O1 | 103.01 (9) | O2—C1—C2 | 117.4 (2) |
O1i—Zn1—O1 | 87.27 (13) | O1—C1—C2 | 117.0 (2) |
O3—Zn1—O2ii | 97.91 (9) | C5—C2—C3 | 119.2 (3) |
O1i—Zn1—O2ii | 88.90 (10) | C5—C2—C1 | 121.4 (3) |
O1—Zn1—O2ii | 159.06 (9) | C3—C2—C1 | 119.4 (2) |
O3—Zn1—O2iii | 97.91 (9) | C4—C3—C2 | 121.2 (3) |
O1i—Zn1—O2iii | 159.06 (9) | C4—C3—H3A | 119.4 |
O1—Zn1—O2iii | 88.90 (10) | C2—C3—H3A | 119.4 |
O2ii—Zn1—O2iii | 87.35 (14) | C3—C4—C3iv | 118.5 (4) |
O3—Zn1—Zn1ii | 171.53 (10) | C3—C4—C6 | 120.75 (19) |
O1i—Zn1—Zn1ii | 83.03 (7) | C3iv—C4—C6 | 120.75 (19) |
O1—Zn1—Zn1ii | 83.03 (7) | C2—C5—C2iv | 120.7 (3) |
O2ii—Zn1—Zn1ii | 76.07 (6) | C2—C5—H5A | 119.7 |
O2iii—Zn1—Zn1ii | 76.07 (6) | C2iv—C5—H5A | 119.7 |
C1—O1—Zn1 | 123.05 (18) | C7—C6—C8 | 116.9 (5) |
C1—O2—Zn1ii | 131.74 (19) | C7—C6—C4 | 122.0 (4) |
Zn1—O3—H11A | 121.7 | C8—C6—C4 | 121.0 (4) |
Zn1—O3—H11B | 119.5 | C6—C7—H7A | 117.5 |
H11A—O3—H11B | 118.8 | C6—C8—H8A | 118.4 |
| | | |
Zn1ii—O2—C1—O1 | −9.1 (5) | C1—C2—C3—C4 | −176.9 (3) |
Zn1ii—O2—C1—C2 | 170.9 (2) | C2—C3—C4—C3iv | 0.2 (7) |
Zn1—O1—C1—O2 | 6.3 (4) | C2—C3—C4—C6 | 179.2 (4) |
Zn1—O1—C1—C2 | −173.79 (19) | C3—C2—C5—C2iv | −1.6 (6) |
O2—C1—C2—C5 | −177.6 (3) | C1—C2—C5—C2iv | 175.9 (2) |
O1—C1—C2—C5 | 2.5 (5) | C3—C4—C6—C7 | 147.6 (7) |
O2—C1—C2—C3 | −0.1 (4) | C3iv—C4—C6—C7 | −33.4 (9) |
O1—C1—C2—C3 | 180.0 (3) | C3—C4—C6—C8 | −35.6 (9) |
C5—C2—C3—C4 | 0.7 (6) | C3iv—C4—C6—C8 | 143.4 (6) |
Symmetry codes: (i) −x+y, y, z; (ii) −x+1, −y+2, −z+2; (iii) x−y+1, −y+2, −z+2; (iv) x, x−y+1, z. |