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In the development of coordination-driven crystalline materials, O- and N-atom donors from carboxylate and pyridyl-based ligands are widely used classes of multidentate bridging ligands composed of several terminal coordinating groups linked by either rigid or flexible spacers. The rigidity of the ligands can play a vital role in the determination of the structures formed. A new CdII supramolecular compound, namely poly[μ-adipato-κ2O1:O4-μ-adipato-κ4O1,O1′:O4,O4′-diaquabis[μ-1,4-bis(pyridin-4-yl)-1,3-butadiene-κ2N:N′]dicadmium(II)], [Cd2(C6H8O4)2(C14H12N2)2(H2O)2]n, (I), has been synthesized by the self-assembly of Cd(NO3)2·4H2O, adipic acid (hexane-1,6-dioic acid; H2adp) and the dipyridyl ligand 1,4-bis(pyridin-4-yl)buta-1,3-diene (1,4-bpbd) under hydrothermal conditions. Single-crystal X-ray diffraction analysis reveals that each CdII centre is located in a distorted octahedral coordination environment, coordinated by one water O atom, three carboxylate O atoms from two different adp2− ligands and two N atoms from two different 1,4-bpbd ligands. The Cd(H2O) units are interconnected by the μ2,κ2-adp2−, μ2,κ4-adp2− and 1,4-bpbd ligands, which lie across centres of inversion, to give a 66-dia network. Large cavities within a single diamondoid network permit the mutual threefold interpenetration of crystallographically equivalent frameworks. Hydrogen-bonding interactions between the coordinated water molecules and adp2− carboxylate O atoms anchor the interpenetrating networks into a unique three-dimensional supramolecular structure. Topologically, taking the coordinated water molecules and CdII centres as nodes, the whole architecture can be simplified as a binodal (3,7)-connected supramolecular framework. The identity of (I) was further characterized by IR spectroscopy, elemental analysis, thermogravimetric analysis and powder X-ray diffraction. The solid-state photoluminescence properties of (I) were also investigated.
Supporting information
CCDC reference: 1570244
Data collection: SMART (Bruker, 2001); cell refinement: SMART (Bruker, 2001); data reduction: SAINT-Plus (Bruker, 2009); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: DIAMOND (Brandenburg, 2010); software used to prepare material for publication: publCIF (Westrip, 2010).
Poly[µ-adipato-
κ2O1:
O4-µ-adipato-
κ4O1,
O1':
O4,
O4'-diaquabis[µ-1,4-bis(pyridin-4-yl)-1,3-butadiene-
κ2N:
N']dicadmium]
top
Crystal data top
[Cd2(C6H8O4)2(C14H12N2)2(H2O)2] | Z = 2 |
Mr = 482.81 | F(000) = 488 |
Triclinic, P1 | Dx = 1.656 Mg m−3 |
a = 8.7119 (17) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 10.318 (2) Å | Cell parameters from 17848 reflections |
c = 10.961 (2) Å | θ = 2.9–27.5° |
α = 83.47 (3)° | µ = 1.16 mm−1 |
β = 82.91 (3)° | T = 223 K |
γ = 84.71 (3)° | Block, light yellow |
V = 968.3 (3) Å3 | 0.27 × 0.25 × 0.22 mm |
Data collection top
Bruker D8 goniometer with an APEX CCD detector diffractometer | 4226 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.021 |
phi and ω scans | θmax = 27.5°, θmin = 2.9° |
Absorption correction: multi-scan (SADABS; Bruker, 2008) | h = −11→11 |
Tmin = 0.753, Tmax = 0.782 | k = −13→13 |
17848 measured reflections | l = −12→14 |
4429 independent reflections | |
Refinement top
Refinement on F2 | Hydrogen site location: mixed |
Least-squares matrix: full | H atoms treated by a mixture of independent and constrained refinement |
R[F2 > 2σ(F2)] = 0.028 | w = 1/[σ2(Fo2) + (0.0283P)2 + 1.5803P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.076 | (Δ/σ)max = 0.001 |
S = 1.16 | Δρmax = 1.59 e Å−3 |
4429 reflections | Δρmin = −0.53 e Å−3 |
262 parameters | Extinction correction: SHELXL2014 (Sheldrick, 2015b), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction coefficient: 0.061 (2) |
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Cd1 | 0.74987 (2) | 0.13373 (2) | 0.37448 (2) | 0.02405 (10) | |
N1 | 0.8738 (3) | −0.0343 (2) | 0.2647 (2) | 0.0289 (5) | |
N2 | 0.6341 (3) | 0.2425 (2) | 0.5447 (2) | 0.0286 (5) | |
O1 | 0.5161 (3) | 0.1143 (3) | 0.3132 (2) | 0.0418 (5) | |
O2 | 0.6578 (3) | 0.1785 (2) | 0.1403 (2) | 0.0427 (5) | |
O3 | 0.8479 (3) | 0.3472 (2) | 0.3058 (2) | 0.0436 (5) | |
O4 | 0.9929 (3) | 0.1970 (2) | 0.4055 (3) | 0.0440 (6) | |
O5 | 0.7440 (3) | −0.0435 (3) | 0.5344 (2) | 0.0447 (6) | |
H1W | 0.671 (5) | −0.060 (4) | 0.581 (4) | 0.050 (12)* | |
H2W | 0.814 (6) | −0.091 (5) | 0.555 (4) | 0.056 (13)* | |
C1 | 0.7978 (4) | −0.1420 (3) | 0.2698 (3) | 0.0390 (7) | |
H1 | 0.7094 | −0.1513 | 0.3277 | 0.047* | |
C2 | 0.8429 (4) | −0.2399 (3) | 0.1941 (3) | 0.0378 (7) | |
H2 | 0.7851 | −0.3134 | 0.2004 | 0.045* | |
C3 | 0.9740 (3) | −0.2296 (3) | 0.1084 (2) | 0.0259 (5) | |
C4 | 1.0532 (3) | −0.1179 (3) | 0.1040 (3) | 0.0296 (6) | |
H4 | 1.1425 | −0.1062 | 0.0477 | 0.036* | |
C5 | 0.9995 (3) | −0.0242 (3) | 0.1831 (3) | 0.0306 (6) | |
H5 | 1.0547 | 0.0505 | 0.1790 | 0.037* | |
C6 | 1.0256 (3) | −0.3310 (3) | 0.0256 (3) | 0.0308 (6) | |
H6 | 1.0998 | −0.3109 | −0.0422 | 0.037* | |
C7 | 0.9738 (4) | −0.4503 (3) | 0.0406 (3) | 0.0323 (6) | |
H7 | 0.8989 | −0.4705 | 0.1078 | 0.039* | |
C8 | 0.7131 (4) | 0.2372 (3) | 0.6429 (3) | 0.0356 (7) | |
H8 | 0.8032 | 0.1799 | 0.6460 | 0.043* | |
C9 | 0.6684 (4) | 0.3118 (3) | 0.7393 (3) | 0.0340 (6) | |
H9 | 0.7277 | 0.3048 | 0.8062 | 0.041* | |
C10 | 0.5353 (3) | 0.3978 (3) | 0.7382 (2) | 0.0256 (5) | |
C11 | 0.4542 (3) | 0.4028 (3) | 0.6360 (3) | 0.0282 (5) | |
H11 | 0.3639 | 0.4595 | 0.6302 | 0.034* | |
C12 | 0.5066 (3) | 0.3241 (3) | 0.5430 (3) | 0.0289 (6) | |
H12 | 0.4494 | 0.3285 | 0.4751 | 0.035* | |
C13 | 0.4815 (4) | 0.4793 (3) | 0.8385 (3) | 0.0317 (6) | |
H13 | 0.4091 | 0.5507 | 0.8224 | 0.038* | |
C14 | 0.5280 (4) | 0.4593 (3) | 0.9513 (3) | 0.0331 (6) | |
H14 | 0.6010 | 0.3886 | 0.9681 | 0.040* | |
C15 | 0.5377 (3) | 0.1377 (3) | 0.1951 (3) | 0.0307 (6) | |
C16 | 0.4053 (4) | 0.1118 (4) | 0.1254 (3) | 0.0463 (8) | |
H16A | 0.3369 | 0.1923 | 0.1157 | 0.056* | |
H16B | 0.3446 | 0.0452 | 0.1752 | 0.056* | |
C17 | 0.4561 (4) | 0.0663 (4) | −0.0015 (3) | 0.0451 (8) | |
H17A | 0.3639 | 0.0640 | −0.0440 | 0.054* | |
H17B | 0.5216 | 0.1304 | −0.0499 | 0.054* | |
C18 | 0.9685 (3) | 0.3119 (3) | 0.3545 (3) | 0.0319 (6) | |
C19 | 1.0891 (4) | 0.4085 (4) | 0.3573 (3) | 0.0446 (8) | |
H19A | 1.0752 | 0.4814 | 0.2931 | 0.053* | |
H19B | 1.1931 | 0.3651 | 0.3394 | 0.053* | |
C20 | 1.0757 (4) | 0.4612 (4) | 0.4827 (4) | 0.0477 (8) | |
H20A | 1.0887 | 0.3873 | 0.5462 | 0.057* | |
H20B | 1.1608 | 0.5169 | 0.4829 | 0.057* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cd1 | 0.02315 (12) | 0.02481 (12) | 0.02578 (13) | −0.00254 (7) | −0.00112 (7) | −0.01075 (7) |
N1 | 0.0311 (12) | 0.0271 (11) | 0.0292 (12) | −0.0027 (9) | 0.0003 (9) | −0.0095 (9) |
N2 | 0.0331 (12) | 0.0301 (12) | 0.0231 (11) | −0.0004 (9) | −0.0022 (9) | −0.0085 (9) |
O1 | 0.0303 (11) | 0.0687 (16) | 0.0285 (11) | −0.0076 (10) | −0.0038 (9) | −0.0107 (10) |
O2 | 0.0360 (12) | 0.0499 (14) | 0.0441 (13) | −0.0160 (10) | −0.0029 (10) | −0.0049 (11) |
O3 | 0.0430 (13) | 0.0470 (13) | 0.0445 (13) | −0.0149 (10) | −0.0157 (10) | 0.0006 (10) |
O4 | 0.0321 (11) | 0.0340 (12) | 0.0674 (16) | −0.0043 (9) | −0.0086 (11) | −0.0065 (11) |
O5 | 0.0370 (13) | 0.0448 (14) | 0.0426 (13) | 0.0085 (11) | 0.0101 (11) | 0.0110 (11) |
C1 | 0.0392 (16) | 0.0337 (15) | 0.0435 (17) | −0.0105 (13) | 0.0151 (13) | −0.0167 (13) |
C2 | 0.0377 (16) | 0.0311 (15) | 0.0454 (17) | −0.0116 (12) | 0.0101 (13) | −0.0168 (13) |
C3 | 0.0286 (13) | 0.0253 (12) | 0.0239 (12) | 0.0023 (10) | −0.0033 (10) | −0.0061 (10) |
C4 | 0.0269 (13) | 0.0293 (13) | 0.0308 (14) | −0.0009 (10) | 0.0038 (11) | −0.0041 (11) |
C5 | 0.0306 (14) | 0.0255 (13) | 0.0359 (15) | −0.0035 (11) | −0.0006 (11) | −0.0059 (11) |
C6 | 0.0336 (14) | 0.0298 (14) | 0.0278 (13) | 0.0024 (11) | 0.0024 (11) | −0.0089 (11) |
C7 | 0.0378 (15) | 0.0299 (14) | 0.0286 (14) | 0.0008 (12) | 0.0013 (12) | −0.0098 (12) |
C8 | 0.0349 (15) | 0.0411 (16) | 0.0308 (15) | 0.0117 (12) | −0.0070 (12) | −0.0124 (12) |
C9 | 0.0346 (15) | 0.0432 (16) | 0.0258 (13) | 0.0061 (12) | −0.0096 (11) | −0.0119 (12) |
C10 | 0.0300 (13) | 0.0259 (12) | 0.0207 (12) | −0.0018 (10) | 0.0010 (10) | −0.0058 (10) |
C11 | 0.0278 (13) | 0.0313 (13) | 0.0248 (13) | 0.0026 (10) | −0.0022 (10) | −0.0048 (10) |
C12 | 0.0313 (14) | 0.0333 (14) | 0.0232 (12) | −0.0020 (11) | −0.0056 (11) | −0.0062 (11) |
C13 | 0.0356 (15) | 0.0316 (14) | 0.0272 (14) | 0.0041 (11) | 0.0001 (11) | −0.0094 (11) |
C14 | 0.0388 (16) | 0.0335 (15) | 0.0270 (14) | 0.0040 (12) | −0.0017 (12) | −0.0112 (12) |
C15 | 0.0286 (14) | 0.0346 (14) | 0.0313 (14) | −0.0036 (11) | −0.0056 (11) | −0.0108 (11) |
C16 | 0.0342 (16) | 0.070 (2) | 0.0407 (18) | −0.0089 (16) | −0.0119 (14) | −0.0179 (17) |
C17 | 0.054 (2) | 0.055 (2) | 0.0317 (16) | −0.0115 (16) | −0.0181 (15) | −0.0083 (15) |
C18 | 0.0315 (14) | 0.0360 (15) | 0.0310 (14) | −0.0104 (12) | −0.0006 (11) | −0.0131 (12) |
C19 | 0.0424 (18) | 0.0475 (19) | 0.0488 (19) | −0.0230 (15) | −0.0060 (15) | −0.0098 (15) |
C20 | 0.052 (2) | 0.0438 (19) | 0.055 (2) | −0.0165 (16) | −0.0215 (17) | −0.0114 (16) |
Geometric parameters (Å, º) top
Cd1—O1 | 2.254 (2) | C7—C7i | 1.439 (5) |
Cd1—N1 | 2.330 (2) | C7—H7 | 0.9400 |
Cd1—O4 | 2.347 (2) | C8—C9 | 1.374 (4) |
Cd1—N2 | 2.358 (2) | C8—H8 | 0.9400 |
Cd1—O5 | 2.384 (3) | C9—C10 | 1.394 (4) |
Cd1—O3 | 2.441 (2) | C9—H9 | 0.9400 |
Cd1—C18 | 2.740 (3) | C10—C11 | 1.390 (4) |
Cd1—O2 | 2.760 (3) | C10—C13 | 1.466 (4) |
Cd1—C15 | 2.855 (3) | C11—C12 | 1.383 (4) |
N1—C5 | 1.329 (4) | C11—H11 | 0.9400 |
N1—C1 | 1.338 (4) | C12—H12 | 0.9400 |
N2—C12 | 1.331 (4) | C13—C14 | 1.336 (4) |
N2—C8 | 1.341 (4) | C13—H13 | 0.9400 |
O1—C15 | 1.284 (4) | C14—C14ii | 1.443 (5) |
O2—C15 | 1.226 (4) | C14—H14 | 0.9400 |
O3—C18 | 1.243 (4) | C15—C16 | 1.519 (4) |
O4—C18 | 1.263 (4) | C16—C17 | 1.519 (5) |
O5—H1W | 0.79 (5) | C16—H16A | 0.9800 |
O5—H2W | 0.79 (5) | C16—H16B | 0.9800 |
C1—C2 | 1.378 (4) | C17—C17iii | 1.504 (8) |
C1—H1 | 0.9400 | C17—H17A | 0.9800 |
C2—C3 | 1.391 (4) | C17—H17B | 0.9800 |
C2—H2 | 0.9400 | C18—C19 | 1.519 (4) |
C3—C4 | 1.390 (4) | C19—C20 | 1.522 (5) |
C3—C6 | 1.466 (4) | C19—H19A | 0.9800 |
C4—C5 | 1.384 (4) | C19—H19B | 0.9800 |
C4—H4 | 0.9400 | C20—C20iv | 1.509 (8) |
C5—H5 | 0.9400 | C20—H20A | 0.9800 |
C6—C7 | 1.336 (4) | C20—H20B | 0.9800 |
C6—H6 | 0.9400 | | |
| | | |
O1—Cd1—N1 | 94.00 (9) | C7—C6—C3 | 124.1 (3) |
O1—Cd1—O4 | 166.83 (9) | C7—C6—H6 | 118.0 |
N1—Cd1—O4 | 89.50 (9) | C3—C6—H6 | 118.0 |
O1—Cd1—N2 | 91.39 (9) | C6—C7—C7i | 123.6 (4) |
N1—Cd1—N2 | 159.02 (9) | C6—C7—H7 | 118.2 |
O4—Cd1—N2 | 89.82 (9) | C7i—C7—H7 | 118.2 |
O1—Cd1—O5 | 97.47 (10) | N2—C8—C9 | 123.0 (3) |
N1—Cd1—O5 | 79.87 (9) | N2—C8—H8 | 118.5 |
O4—Cd1—O5 | 95.64 (10) | C9—C8—H8 | 118.5 |
N2—Cd1—O5 | 79.34 (9) | C8—C9—C10 | 120.1 (3) |
O1—Cd1—O3 | 112.85 (9) | C8—C9—H9 | 119.9 |
N1—Cd1—O3 | 113.71 (9) | C10—C9—H9 | 119.9 |
O4—Cd1—O3 | 54.34 (8) | C11—C10—C9 | 116.5 (2) |
N2—Cd1—O3 | 82.51 (9) | C11—C10—C13 | 120.9 (3) |
O5—Cd1—O3 | 144.87 (9) | C9—C10—C13 | 122.6 (3) |
O1—Cd1—C18 | 139.81 (10) | C12—C11—C10 | 119.8 (3) |
N1—Cd1—C18 | 103.66 (9) | C12—C11—H11 | 120.1 |
O4—Cd1—C18 | 27.39 (9) | C10—C11—H11 | 120.1 |
N2—Cd1—C18 | 84.79 (9) | N2—C12—C11 | 123.3 (3) |
O5—Cd1—C18 | 120.83 (10) | N2—C12—H12 | 118.4 |
O3—Cd1—C18 | 26.97 (9) | C11—C12—H12 | 118.4 |
O1—Cd1—O2 | 50.86 (8) | C14—C13—C10 | 124.6 (3) |
N1—Cd1—O2 | 73.59 (9) | C14—C13—H13 | 117.7 |
O4—Cd1—O2 | 118.65 (9) | C10—C13—H13 | 117.7 |
N2—Cd1—O2 | 124.47 (8) | C13—C14—C14ii | 123.4 (4) |
O5—Cd1—O2 | 135.60 (9) | C13—C14—H14 | 118.3 |
O3—Cd1—O2 | 79.22 (8) | C14ii—C14—H14 | 118.3 |
C18—Cd1—O2 | 99.90 (8) | O2—C15—O1 | 122.5 (3) |
O1—Cd1—C15 | 25.84 (8) | O2—C15—C16 | 121.2 (3) |
N1—Cd1—C15 | 81.41 (9) | O1—C15—C16 | 116.3 (3) |
O4—Cd1—C15 | 143.64 (9) | O2—C15—Cd1 | 73.07 (17) |
N2—Cd1—C15 | 110.68 (9) | O1—C15—Cd1 | 49.93 (14) |
O5—Cd1—C15 | 116.96 (10) | C16—C15—Cd1 | 164.4 (2) |
O3—Cd1—C15 | 97.52 (9) | C15—C16—C17 | 114.5 (3) |
C18—Cd1—C15 | 122.00 (9) | C15—C16—H16A | 108.6 |
O2—Cd1—C15 | 25.14 (8) | C17—C16—H16A | 108.6 |
C5—N1—C1 | 117.3 (2) | C15—C16—H16B | 108.6 |
C5—N1—Cd1 | 125.39 (19) | C17—C16—H16B | 108.6 |
C1—N1—Cd1 | 116.40 (19) | H16A—C16—H16B | 107.6 |
C12—N2—C8 | 117.3 (2) | C17iii—C17—C16 | 114.1 (4) |
C12—N2—Cd1 | 124.09 (18) | C17iii—C17—H17A | 108.7 |
C8—N2—Cd1 | 117.91 (19) | C16—C17—H17A | 108.7 |
C15—O1—Cd1 | 104.22 (18) | C17iii—C17—H17B | 108.7 |
C15—O2—Cd1 | 81.79 (18) | C16—C17—H17B | 108.7 |
C18—O3—Cd1 | 90.03 (19) | H17A—C17—H17B | 107.6 |
C18—O4—Cd1 | 93.88 (18) | O3—C18—O4 | 121.6 (3) |
Cd1—O5—H1W | 125 (3) | O3—C18—C19 | 120.3 (3) |
Cd1—O5—H2W | 128 (3) | O4—C18—C19 | 118.1 (3) |
H1W—O5—H2W | 107 (5) | O3—C18—Cd1 | 63.00 (16) |
N1—C1—C2 | 123.1 (3) | O4—C18—Cd1 | 58.73 (15) |
N1—C1—H1 | 118.5 | C19—C18—Cd1 | 174.3 (2) |
C2—C1—H1 | 118.5 | C18—C19—C20 | 111.3 (3) |
C1—C2—C3 | 119.9 (3) | C18—C19—H19A | 109.4 |
C1—C2—H2 | 120.1 | C20—C19—H19A | 109.4 |
C3—C2—H2 | 120.1 | C18—C19—H19B | 109.4 |
C4—C3—C2 | 116.8 (2) | C20—C19—H19B | 109.4 |
C4—C3—C6 | 121.5 (3) | H19A—C19—H19B | 108.0 |
C2—C3—C6 | 121.7 (3) | C20iv—C20—C19 | 114.6 (4) |
C5—C4—C3 | 119.5 (3) | C20iv—C20—H20A | 108.6 |
C5—C4—H4 | 120.3 | C19—C20—H20A | 108.6 |
C3—C4—H4 | 120.3 | C20iv—C20—H20B | 108.6 |
N1—C5—C4 | 123.4 (3) | C19—C20—H20B | 108.6 |
N1—C5—H5 | 118.3 | H20A—C20—H20B | 107.6 |
C4—C5—H5 | 118.3 | | |
Symmetry codes: (i) −x+2, −y−1, −z; (ii) −x+1, −y+1, −z+2; (iii) −x+1, −y, −z; (iv) −x+2, −y+1, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O5—H1W···O1v | 0.79 (5) | 1.96 (5) | 2.748 (4) | 175 (5) |
O5—H2W···O4vi | 0.79 (5) | 1.98 (5) | 2.768 (4) | 173 (5) |
Symmetry codes: (v) −x+1, −y, −z+1; (vi) −x+2, −y, −z+1. |
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