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A new three-dimensional interpenetrated Cd
II-organic framework based on 3,3'-azodibenzoic acid [3,3'-(diazenediyl)dibenzoic acid, H
2azdc] and the auxiliary flexible ligand 1,4-bis(1
H-imidazol-1-yl)butane (bimb), namely poly[[bis[
2-1,4-bis(1
H-imidazol-1-yl)butane-
2N3:
N3'][
2-3,3'-(diazenediyl)dibenzoato-
2O:
O']cadmium(II)] monohydrate], {[Cd(C
14H
8N
2O
4)(C
10H
14N
2)
2]·H
2O}
n, (1), was obtained by a typical solution reaction in mixed solvents (water and
N,
N'-dimethylformamide). Each Cd
II centre is six-coordinated by two O atoms of bis-monodentate bridging carboxylate groups from two azdc
2- ligands and by four N atoms from four bimb ligands, forming an octahedral coordination environment. The Cd
II ions are connected by the bimb ligands, resulting in two-dimensional (4,4) layers, which are further pillared by the azdc
2- ligands, affording a threefold interpenetrated three-dimensional
-Po topological framework with the Schläfli symbol 4
126
3. The thermal stability and solid-state fluorescence properties of (1) have been investigated.
Supporting information
CCDC reference: 1402259
Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT (Bruker, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: publCIF (Westrip, 2010).
Poly[[bis[µ
2-1,4-bis(1
H-imidazol-1-yl)butane-
κ2N3:
N3'][µ
2-3,3'-(diazenediyl)dibenzoato-
κ2O:
O']cadmium(II)] monohydrate]
top
Crystal data top
[Cd(C14H8N2O4)(C10H14N4)2]·H2O | F(000) = 1600 |
Mr = 779.14 | Dx = 1.490 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 10.3202 (13) Å | Cell parameters from 9906 reflections |
b = 14.3929 (13) Å | θ = 2.5–27.5° |
c = 23.679 (3) Å | µ = 0.69 mm−1 |
β = 99.157 (4)° | T = 296 K |
V = 3472.4 (7) Å3 | Block, yellow |
Z = 4 | 0.28 × 0.20 × 0.14 mm |
Data collection top
Bruker APEXII area-detector diffractometer | 3998 independent reflections |
Radiation source: fine-focus sealed tube | 3396 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.040 |
φ and ω scans | θmax = 27.5°, θmin = 2.5° |
Absorption correction: multi-scan (SADABS; Bruker, 2003) | h = −13→13 |
Tmin = 0.848, Tmax = 0.908 | k = −18→18 |
34516 measured reflections | l = −30→30 |
Refinement top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.064 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.156 | H-atom parameters constrained |
S = 1.29 | w = 1/[σ2(Fo2) + (0.0413P)2 + 26.4708P] where P = (Fo2 + 2Fc2)/3 |
3998 reflections | (Δ/σ)max < 0.001 |
228 parameters | Δρmax = 2.32 e Å−3 |
2 restraints | Δρmin = −0.72 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. |
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 >
σ(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) |
C1 | 0.1939 (5) | 1.0154 (3) | 0.3952 (2) | 0.0328 (11) | |
C2 | 0.3347 (5) | 1.0336 (3) | 0.3865 (2) | 0.0296 (10) | |
C3 | 0.3665 (5) | 1.0334 (4) | 0.3320 (2) | 0.0319 (10) | |
H3 | 0.3016 | 1.0256 | 0.3003 | 0.038* | |
C4 | 0.4974 (5) | 1.0450 (4) | 0.3252 (2) | 0.0403 (12) | |
C5 | 0.5952 (6) | 1.0565 (5) | 0.3718 (3) | 0.0559 (17) | |
H5 | 0.6824 | 1.0614 | 0.3667 | 0.067* | |
C6 | 0.5626 (6) | 1.0605 (6) | 0.4256 (3) | 0.0623 (19) | |
H6 | 0.6272 | 1.0713 | 0.4570 | 0.075* | |
C7 | 0.4331 (5) | 1.0484 (5) | 0.4331 (2) | 0.0449 (13) | |
H7 | 0.4117 | 1.0502 | 0.4698 | 0.054* | |
C8 | −0.1158 (6) | 0.8827 (4) | 0.3836 (2) | 0.0446 (13) | |
H8 | −0.0579 | 0.9129 | 0.3634 | 0.054* | |
C9 | −0.2662 (7) | 0.7895 (5) | 0.4035 (3) | 0.0587 (17) | |
H9 | −0.3306 | 0.7438 | 0.4011 | 0.070* | |
C10 | −0.2243 (6) | 0.8438 (5) | 0.4487 (3) | 0.0499 (14) | |
H10 | −0.2560 | 0.8419 | 0.4833 | 0.060* | |
C11 | −0.2070 (11) | 0.7727 (5) | 0.3035 (3) | 0.090 (3) | |
H11A | −0.1351 | 0.7294 | 0.3034 | 0.108* | |
H11B | −0.2882 | 0.7377 | 0.2954 | 0.108* | |
C12 | −0.2041 (11) | 0.8373 (7) | 0.2596 (3) | 0.095 (3) | |
H12A | −0.1205 | 0.8696 | 0.2659 | 0.114* | |
H12B | −0.2728 | 0.8830 | 0.2607 | 0.114* | |
C13 | 0.0838 (5) | 0.8493 (4) | 0.6034 (2) | 0.0364 (11) | |
H13 | 0.0661 | 0.8936 | 0.6298 | 0.044* | |
C14 | 0.1075 (8) | 0.7833 (5) | 0.5256 (3) | 0.069 (2) | |
H14 | 0.1096 | 0.7733 | 0.4870 | 0.083* | |
C15 | 0.1359 (10) | 0.7186 (5) | 0.5670 (3) | 0.078 (3) | |
H15 | 0.1604 | 0.6573 | 0.5624 | 0.093* | |
C16 | 0.1391 (8) | 0.7213 (5) | 0.6751 (3) | 0.0641 (19) | |
H16A | 0.0978 | 0.7612 | 0.7000 | 0.077* | |
H16B | 0.0957 | 0.6614 | 0.6734 | 0.077* | |
C17 | 0.2766 (9) | 0.7093 (8) | 0.6992 (3) | 0.093 (3) | |
H17A | 0.3193 | 0.7696 | 0.7023 | 0.112* | |
H17B | 0.3187 | 0.6714 | 0.6736 | 0.112* | |
Cd1 | 0.0000 | 1.0000 | 0.5000 | 0.02904 (16) | |
N1 | 0.5437 (5) | 1.0453 (4) | 0.2710 (2) | 0.0491 (12) | |
N2 | −0.1285 (4) | 0.9020 (3) | 0.43653 (17) | 0.0368 (10) | |
N3 | −0.1972 (6) | 0.8139 (4) | 0.3622 (2) | 0.0513 (13) | |
N4 | 0.0753 (4) | 0.8650 (3) | 0.54834 (18) | 0.0364 (9) | |
N5 | 0.1211 (6) | 0.7622 (3) | 0.6171 (2) | 0.0483 (12) | |
O1 | 0.1763 (4) | 1.0003 (3) | 0.44551 (16) | 0.0489 (10) | |
O2 | 0.1087 (4) | 1.0132 (3) | 0.35170 (17) | 0.0533 (11) | |
O1W | 0.0000 | 0.8945 (6) | 0.7500 | 0.106 (3) | |
H1WA | 0.0363 | 0.9262 | 0.7785 | 0.127* | 0.50 |
H1WB | −0.0282 | 0.9307 | 0.7224 | 0.127* | 0.50 |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.031 (2) | 0.034 (3) | 0.037 (2) | 0.0030 (19) | 0.016 (2) | 0.006 (2) |
C2 | 0.028 (2) | 0.035 (2) | 0.029 (2) | 0.0035 (19) | 0.0135 (18) | 0.0032 (19) |
C3 | 0.030 (2) | 0.037 (2) | 0.031 (2) | 0.002 (2) | 0.0120 (19) | 0.004 (2) |
C4 | 0.037 (3) | 0.048 (3) | 0.041 (3) | 0.002 (2) | 0.024 (2) | 0.008 (2) |
C5 | 0.029 (3) | 0.085 (5) | 0.056 (4) | −0.007 (3) | 0.012 (3) | 0.011 (3) |
C6 | 0.039 (3) | 0.100 (6) | 0.046 (3) | −0.012 (3) | 0.001 (3) | 0.003 (4) |
C7 | 0.035 (3) | 0.068 (4) | 0.032 (3) | 0.001 (3) | 0.009 (2) | 0.004 (3) |
C8 | 0.056 (3) | 0.047 (3) | 0.031 (3) | −0.007 (3) | 0.007 (2) | 0.002 (2) |
C9 | 0.054 (4) | 0.062 (4) | 0.056 (4) | −0.025 (3) | −0.005 (3) | 0.001 (3) |
C10 | 0.053 (3) | 0.059 (4) | 0.039 (3) | −0.014 (3) | 0.011 (3) | 0.005 (3) |
C11 | 0.168 (10) | 0.046 (4) | 0.046 (4) | −0.018 (5) | −0.008 (5) | −0.008 (3) |
C12 | 0.143 (9) | 0.087 (6) | 0.047 (4) | −0.007 (6) | −0.008 (5) | −0.023 (4) |
C13 | 0.037 (3) | 0.033 (3) | 0.039 (3) | −0.001 (2) | 0.005 (2) | 0.001 (2) |
C14 | 0.103 (6) | 0.062 (4) | 0.041 (3) | 0.039 (4) | 0.008 (4) | −0.003 (3) |
C15 | 0.139 (8) | 0.047 (4) | 0.045 (4) | 0.043 (5) | 0.009 (4) | 0.000 (3) |
C16 | 0.096 (6) | 0.048 (4) | 0.051 (4) | 0.011 (4) | 0.019 (4) | 0.019 (3) |
C17 | 0.096 (7) | 0.139 (9) | 0.042 (4) | 0.012 (6) | 0.001 (4) | 0.032 (5) |
Cd1 | 0.0271 (2) | 0.0374 (3) | 0.0222 (2) | 0.0021 (2) | 0.00255 (16) | 0.0035 (2) |
N1 | 0.042 (3) | 0.068 (3) | 0.044 (3) | 0.007 (2) | 0.026 (2) | 0.006 (2) |
N2 | 0.037 (2) | 0.044 (2) | 0.028 (2) | −0.005 (2) | 0.0013 (17) | −0.0002 (18) |
N3 | 0.069 (3) | 0.047 (3) | 0.034 (2) | −0.011 (3) | −0.005 (2) | −0.005 (2) |
N4 | 0.035 (2) | 0.040 (2) | 0.033 (2) | 0.0051 (19) | 0.0008 (17) | 0.0038 (18) |
N5 | 0.068 (3) | 0.036 (2) | 0.040 (3) | 0.009 (2) | 0.007 (2) | 0.009 (2) |
O1 | 0.042 (2) | 0.073 (3) | 0.0368 (19) | 0.014 (2) | 0.0207 (16) | 0.013 (2) |
O2 | 0.0335 (19) | 0.086 (3) | 0.041 (2) | 0.000 (2) | 0.0082 (16) | 0.008 (2) |
O1W | 0.166 (10) | 0.080 (6) | 0.061 (5) | 0.000 | −0.010 (6) | 0.000 |
Geometric parameters (Å, º) top
C1—O2 | 1.244 (6) | C12—H12A | 0.9700 |
C1—O1 | 1.252 (6) | C12—H12B | 0.9700 |
C1—C2 | 1.523 (6) | C13—N4 | 1.312 (7) |
C2—C3 | 1.381 (6) | C13—N5 | 1.337 (7) |
C2—C7 | 1.391 (7) | C13—H13 | 0.9300 |
C3—C4 | 1.395 (7) | C14—C15 | 1.348 (9) |
C3—H3 | 0.9300 | C14—N4 | 1.357 (8) |
C4—C5 | 1.382 (8) | C14—H14 | 0.9300 |
C4—N1 | 1.440 (6) | C15—N5 | 1.373 (8) |
C5—C6 | 1.368 (9) | C15—H15 | 0.9300 |
C5—H5 | 0.9300 | C16—C17 | 1.453 (11) |
C6—C7 | 1.388 (8) | C16—N5 | 1.477 (7) |
C6—H6 | 0.9300 | C16—H16A | 0.9700 |
C7—H7 | 0.9300 | C16—H16B | 0.9700 |
C8—N2 | 1.311 (7) | C17—C12ii | 1.563 (10) |
C8—N3 | 1.345 (7) | C17—H17A | 0.9700 |
C8—H8 | 0.9300 | C17—H17B | 0.9700 |
C9—C10 | 1.340 (9) | Cd1—N2 | 2.318 (4) |
C9—N3 | 1.346 (9) | Cd1—N2iii | 2.318 (4) |
C9—H9 | 0.9300 | Cd1—N4iii | 2.325 (4) |
C10—N2 | 1.361 (7) | Cd1—N4 | 2.325 (4) |
C10—H10 | 0.9300 | Cd1—O1iii | 2.392 (3) |
C11—C12 | 1.399 (11) | Cd1—O1 | 2.392 (3) |
C11—N3 | 1.498 (8) | N1—N1iv | 1.231 (10) |
C11—H11A | 0.9700 | O1W—H1WA | 0.8500 |
C11—H11B | 0.9700 | O1W—H1WB | 0.8500 |
C12—C17i | 1.563 (10) | | |
| | | |
O2—C1—O1 | 126.4 (5) | N4—C14—H14 | 124.8 |
O2—C1—C2 | 117.1 (4) | C14—C15—N5 | 105.8 (6) |
O1—C1—C2 | 116.4 (5) | C14—C15—H15 | 127.1 |
C3—C2—C7 | 119.3 (4) | N5—C15—H15 | 127.1 |
C3—C2—C1 | 120.0 (4) | C17—C16—N5 | 112.6 (6) |
C7—C2—C1 | 120.7 (4) | C17—C16—H16A | 109.1 |
C2—C3—C4 | 119.1 (5) | N5—C16—H16A | 109.1 |
C2—C3—H3 | 120.5 | C17—C16—H16B | 109.1 |
C4—C3—H3 | 120.5 | N5—C16—H16B | 109.1 |
C5—C4—C3 | 121.3 (5) | H16A—C16—H16B | 107.8 |
C5—C4—N1 | 114.1 (5) | C16—C17—C12ii | 112.7 (8) |
C3—C4—N1 | 124.7 (5) | C16—C17—H17A | 109.1 |
C6—C5—C4 | 119.4 (5) | C12ii—C17—H17A | 109.1 |
C6—C5—H5 | 120.3 | C16—C17—H17B | 109.1 |
C4—C5—H5 | 120.3 | C12ii—C17—H17B | 109.1 |
C5—C6—C7 | 119.9 (6) | H17A—C17—H17B | 107.8 |
C5—C6—H6 | 120.0 | N2—Cd1—N2iii | 180.00 (18) |
C7—C6—H6 | 120.0 | N2—Cd1—N4iii | 94.45 (16) |
C6—C7—C2 | 120.9 (5) | N2iii—Cd1—N4iii | 85.55 (16) |
C6—C7—H7 | 119.5 | N2—Cd1—N4 | 85.55 (16) |
C2—C7—H7 | 119.5 | N2iii—Cd1—N4 | 94.45 (16) |
N2—C8—N3 | 111.4 (5) | N4iii—Cd1—N4 | 180.00 (19) |
N2—C8—H8 | 124.3 | N2—Cd1—O1iii | 86.73 (16) |
N3—C8—H8 | 124.3 | N2iii—Cd1—O1iii | 93.27 (15) |
C10—C9—N3 | 106.7 (5) | N4iii—Cd1—O1iii | 92.50 (15) |
C10—C9—H9 | 126.6 | N4—Cd1—O1iii | 87.50 (15) |
N3—C9—H9 | 126.6 | N2—Cd1—O1 | 93.27 (15) |
C9—C10—N2 | 110.0 (5) | N2iii—Cd1—O1 | 86.73 (16) |
C9—C10—H10 | 125.0 | N4iii—Cd1—O1 | 87.50 (15) |
N2—C10—H10 | 125.0 | N4—Cd1—O1 | 92.50 (15) |
C12—C11—N3 | 114.8 (6) | O1iii—Cd1—O1 | 180.000 (1) |
C12—C11—H11A | 108.6 | N1iv—N1—C4 | 114.5 (6) |
N3—C11—H11A | 108.6 | C8—N2—C10 | 105.0 (5) |
C12—C11—H11B | 108.6 | C8—N2—Cd1 | 127.9 (4) |
N3—C11—H11B | 108.6 | C10—N2—Cd1 | 126.7 (4) |
H11A—C11—H11B | 107.5 | C8—N3—C9 | 106.8 (5) |
C11—C12—C17i | 112.3 (8) | C8—N3—C11 | 125.9 (6) |
C11—C12—H12A | 109.1 | C9—N3—C11 | 127.2 (6) |
C17i—C12—H12A | 109.1 | C13—N4—C14 | 105.2 (5) |
C11—C12—H12B | 109.1 | C13—N4—Cd1 | 126.7 (4) |
C17i—C12—H12B | 109.1 | C14—N4—Cd1 | 127.8 (4) |
H12A—C12—H12B | 107.9 | C13—N5—C15 | 106.6 (5) |
N4—C13—N5 | 112.0 (5) | C13—N5—C16 | 126.1 (5) |
N4—C13—H13 | 124.0 | C15—N5—C16 | 127.4 (5) |
N5—C13—H13 | 124.0 | C1—O1—Cd1 | 138.7 (3) |
C15—C14—N4 | 110.5 (6) | H1WA—O1W—H1WB | 109.5 |
C15—C14—H14 | 124.8 | | |
| | | |
O2—C1—C2—C3 | −9.4 (7) | O1—Cd1—N2—C10 | 154.3 (5) |
O1—C1—C2—C3 | 167.7 (5) | N2—C8—N3—C9 | 1.0 (8) |
O2—C1—C2—C7 | 172.1 (5) | N2—C8—N3—C11 | −178.6 (7) |
O1—C1—C2—C7 | −10.8 (8) | C10—C9—N3—C8 | −0.3 (8) |
C7—C2—C3—C4 | 2.1 (8) | C10—C9—N3—C11 | 179.2 (7) |
C1—C2—C3—C4 | −176.5 (5) | C12—C11—N3—C8 | −42.5 (13) |
C2—C3—C4—C5 | 0.2 (9) | C12—C11—N3—C9 | 138.0 (10) |
C2—C3—C4—N1 | 179.4 (5) | N5—C13—N4—C14 | 0.6 (7) |
C3—C4—C5—C6 | −2.9 (11) | N5—C13—N4—Cd1 | 175.0 (4) |
N1—C4—C5—C6 | 177.8 (7) | C15—C14—N4—C13 | −0.3 (9) |
C4—C5—C6—C7 | 3.2 (12) | C15—C14—N4—Cd1 | −174.5 (6) |
C5—C6—C7—C2 | −1.0 (12) | N2—Cd1—N4—C13 | −131.2 (5) |
C3—C2—C7—C6 | −1.7 (9) | N2iii—Cd1—N4—C13 | 48.8 (5) |
C1—C2—C7—C6 | 176.8 (6) | O1iii—Cd1—N4—C13 | −44.3 (4) |
N3—C9—C10—N2 | −0.4 (8) | O1—Cd1—N4—C13 | 135.7 (4) |
N3—C11—C12—C17i | −176.4 (8) | N2—Cd1—N4—C14 | 41.9 (6) |
N4—C14—C15—N5 | −0.2 (11) | N2iii—Cd1—N4—C14 | −138.1 (6) |
N5—C16—C17—C12ii | −177.9 (7) | O1iii—Cd1—N4—C14 | 128.8 (6) |
C5—C4—N1—N1iv | −172.5 (4) | O1—Cd1—N4—C14 | −51.2 (6) |
C3—C4—N1—N1iv | 8.2 (7) | N4—C13—N5—C15 | −0.8 (8) |
N3—C8—N2—C10 | −1.2 (7) | N4—C13—N5—C16 | −179.4 (6) |
N3—C8—N2—Cd1 | 172.0 (4) | C14—C15—N5—C13 | 0.6 (10) |
C9—C10—N2—C8 | 1.0 (7) | C14—C15—N5—C16 | 179.2 (8) |
C9—C10—N2—Cd1 | −172.3 (4) | C17—C16—N5—C13 | −106.0 (9) |
N4iii—Cd1—N2—C8 | 70.2 (5) | C17—C16—N5—C15 | 75.6 (11) |
N4—Cd1—N2—C8 | −109.8 (5) | O2—C1—O1—Cd1 | −20.9 (10) |
O1iii—Cd1—N2—C8 | 162.5 (5) | C2—C1—O1—Cd1 | 162.4 (4) |
O1—Cd1—N2—C8 | −17.5 (5) | N2—Cd1—O1—C1 | 52.8 (6) |
N4iii—Cd1—N2—C10 | −118.0 (5) | N2iii—Cd1—O1—C1 | −127.2 (6) |
N4—Cd1—N2—C10 | 62.0 (5) | N4iii—Cd1—O1—C1 | −41.5 (6) |
O1iii—Cd1—N2—C10 | −25.7 (5) | N4—Cd1—O1—C1 | 138.5 (6) |
Symmetry codes: (i) x−1/2, −y+3/2, z−1/2; (ii) x+1/2, −y+3/2, z+1/2; (iii) −x, −y+2, −z+1; (iv) −x+1, y, −z+1/2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1WA···O2v | 0.85 | 1.98 | 2.822 (6) | 172 |
O1W—H1WB···O2iii | 0.85 | 1.99 | 2.822 (6) | 166 |
Symmetry codes: (iii) −x, −y+2, −z+1; (v) x, −y+2, z+1/2. |
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