The combination of N-heterocyclic and multicarboxylate ligands is a good choice for the construction of metal-organic frameworks. In the title coordination polymer, poly[bis{
2-1-[(1
H-benzimidazol-2-yl)methyl]-1
H-tetrazole-
2N3:
N4}(
4-butanedioato-
4O1:
O1':
O4:
O4')(
2-butanedioato-
2O1:
O4)dicadmium], [Cd(C
4H
4O
4)(C
9H
8N
6)]
n, each Cd
II ion exhibits an irregular octahedral CdO
4N
2 coordination geometry and is coordinated by four O atoms from three carboxylate groups of three succinate (butanedioate) ligands and two N atoms from two 1-[(1
H-benzimidazol-2-yl)methyl]-1
H-tetrazole (bimt) ligands. Cd
II ions are connected by two kinds of crystallographically independent succinate ligands to generate a two-dimensional layered structure with bimt ligands located on each side of the layer. Adjacent layers are further connected by hydrogen bonding, leading to a three-dimensional supramolecular architecture in the solid state. Thermogravimetric analysis of the title polymer shows that it is stable up to 529 K and then loses weight from 529 to 918 K, corresponding to the decomposition of the bimt ligands and succinate groups. The polymer exhibits a strong fluorescence emission in the solid state at room temperature.
Supporting information
CCDC reference: 1400015
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{µ
2-1-[(1
H-benzimidazolyl)methyl]-1
H-tetrazole-
κ2N3:
N4}(µ
4-butanedioato-
κ4O1:
O1':
O4:
O4')(µ
2-butanedioato-
κ2O1:
O4)dicadmium]
top
Crystal data top
[Cd(C4H4O4)(C9H8N6)] | Z = 2 |
Mr = 428.69 | F(000) = 424 |
Triclinic, P1 | Dx = 1.935 Mg m−3 |
a = 7.9867 (16) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 8.3516 (17) Å | Cell parameters from 2613 reflections |
c = 11.604 (2) Å | θ = 1.8–27.8° |
α = 90.50 (3)° | µ = 1.52 mm−1 |
β = 103.76 (3)° | T = 293 K |
γ = 101.40 (3)° | Prism, colourless |
V = 735.7 (3) Å3 | 0.18 × 0.16 × 0.13 mm |
Data collection top
Rigaku Saturn diffractometer | 3480 independent reflections |
Radiation source: fine-focus sealed tube | 3336 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.020 |
Detector resolution: 28.5714 pixels mm-1 | θmax = 27.9°, θmin = 1.8° |
ω scans | h = −10→10 |
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2004) | k = −10→10 |
Tmin = 0.772, Tmax = 0.827 | l = −15→15 |
9080 measured reflections | |
Refinement top
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.023 | H-atom parameters constrained |
wR(F2) = 0.054 | w = 1/[σ2(Fo2) + (0.0214P)2 + 0.5546P] where P = (Fo2 + 2Fc2)/3 |
S = 1.09 | (Δ/σ)max = 0.001 |
3480 reflections | Δρmax = 0.78 e Å−3 |
217 parameters | Δρmin = −0.42 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 | |
Cd1 | 0.10045 (2) | 0.15201 (2) | 0.15285 (2) | 0.02409 (6) | |
N1 | 0.0295 (3) | 0.3920 (2) | 0.24312 (19) | 0.0345 (4) | |
N2 | −0.0371 (3) | 0.3821 (3) | 0.3401 (2) | 0.0428 (5) | |
N3 | −0.0839 (3) | 0.5166 (3) | 0.36075 (19) | 0.0417 (5) | |
N4 | −0.0473 (2) | 0.6163 (2) | 0.27628 (16) | 0.0262 (4) | |
N5 | 0.1277 (2) | 0.8638 (2) | 0.47560 (16) | 0.0286 (4) | |
H5B | 0.0908 | 0.7779 | 0.5101 | 0.034* | |
N6 | 0.1457 (2) | 1.0389 (2) | 0.33447 (15) | 0.0245 (4) | |
O1 | 0.1546 (2) | −0.0858 (2) | 0.06800 (17) | 0.0385 (4) | |
O2 | 0.1912 (2) | −0.0712 (2) | −0.11436 (15) | 0.0388 (4) | |
O3 | 0.2140 (2) | 0.3375 (3) | 0.02322 (17) | 0.0542 (6) | |
O4 | 0.3894 (3) | 0.2954 (3) | 0.18917 (18) | 0.0528 (5) | |
C1 | 0.0214 (3) | 0.5382 (3) | 0.2052 (2) | 0.0315 (5) | |
H1A | 0.0578 | 0.5802 | 0.1392 | 0.038* | |
C2 | −0.0806 (3) | 0.7819 (3) | 0.2761 (2) | 0.0307 (5) | |
H2A | −0.1908 | 0.7804 | 0.2979 | 0.037* | |
H2B | −0.0918 | 0.8207 | 0.1966 | 0.037* | |
C3 | 0.0651 (3) | 0.8965 (2) | 0.36131 (18) | 0.0241 (4) | |
C4 | 0.2621 (3) | 0.9939 (3) | 0.52659 (19) | 0.0261 (4) | |
C5 | 0.3786 (3) | 1.0199 (3) | 0.6386 (2) | 0.0345 (5) | |
H5A | 0.3732 | 0.9440 | 0.6964 | 0.041* | |
C6 | 0.5016 (3) | 1.1636 (3) | 0.6588 (2) | 0.0367 (5) | |
H6A | 0.5820 | 1.1856 | 0.7323 | 0.044* | |
C7 | 0.5098 (3) | 1.2781 (3) | 0.5718 (2) | 0.0370 (5) | |
H7A | 0.5939 | 1.3750 | 0.5895 | 0.044* | |
C8 | 0.3962 (3) | 1.2506 (3) | 0.4605 (2) | 0.0336 (5) | |
H8A | 0.4025 | 1.3264 | 0.4027 | 0.040* | |
C9 | 0.2711 (3) | 1.1043 (3) | 0.43826 (18) | 0.0242 (4) | |
C10 | 0.2511 (3) | −0.0646 (3) | −0.0043 (2) | 0.0277 (4) | |
C11 | 0.4483 (3) | −0.0306 (3) | 0.04422 (19) | 0.0325 (5) | |
H11A | 0.4795 | 0.0499 | 0.1106 | 0.039* | |
H11B | 0.4822 | −0.1304 | 0.0744 | 0.039* | |
C12 | 0.3619 (3) | 0.3633 (3) | 0.0935 (2) | 0.0357 (5) | |
C13 | 0.5164 (4) | 0.4767 (4) | 0.0636 (2) | 0.0458 (7) | |
H13A | 0.5468 | 0.5756 | 0.1150 | 0.055* | |
H13C | 0.6170 | 0.4242 | 0.0805 | 0.055* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cd1 | 0.02097 (8) | 0.02589 (9) | 0.02485 (9) | 0.00194 (6) | 0.00675 (6) | 0.00505 (6) |
N1 | 0.0427 (11) | 0.0245 (10) | 0.0379 (11) | 0.0086 (8) | 0.0117 (9) | −0.0001 (8) |
N2 | 0.0663 (15) | 0.0258 (10) | 0.0427 (12) | 0.0131 (10) | 0.0224 (11) | 0.0116 (9) |
N3 | 0.0651 (15) | 0.0302 (11) | 0.0381 (12) | 0.0131 (10) | 0.0256 (11) | 0.0101 (9) |
N4 | 0.0304 (9) | 0.0196 (9) | 0.0277 (9) | 0.0040 (7) | 0.0061 (7) | 0.0046 (7) |
N5 | 0.0337 (10) | 0.0242 (9) | 0.0269 (9) | 0.0043 (8) | 0.0068 (8) | 0.0071 (7) |
N6 | 0.0284 (9) | 0.0210 (8) | 0.0223 (8) | 0.0049 (7) | 0.0028 (7) | 0.0026 (7) |
O1 | 0.0306 (8) | 0.0358 (9) | 0.0533 (11) | 0.0024 (7) | 0.0222 (8) | 0.0004 (8) |
O2 | 0.0225 (8) | 0.0550 (11) | 0.0335 (9) | 0.0047 (7) | −0.0009 (7) | −0.0030 (8) |
O3 | 0.0355 (10) | 0.0688 (14) | 0.0442 (11) | −0.0172 (9) | 0.0048 (8) | 0.0204 (10) |
O4 | 0.0396 (10) | 0.0684 (14) | 0.0452 (11) | −0.0047 (10) | 0.0125 (9) | 0.0236 (10) |
C1 | 0.0358 (12) | 0.0285 (12) | 0.0307 (11) | 0.0053 (9) | 0.0101 (10) | 0.0041 (9) |
C2 | 0.0314 (11) | 0.0203 (10) | 0.0372 (12) | 0.0063 (9) | 0.0012 (9) | 0.0024 (9) |
C3 | 0.0263 (10) | 0.0215 (10) | 0.0250 (10) | 0.0073 (8) | 0.0054 (8) | 0.0025 (8) |
C4 | 0.0295 (10) | 0.0266 (11) | 0.0238 (10) | 0.0084 (9) | 0.0073 (8) | 0.0039 (8) |
C5 | 0.0401 (13) | 0.0395 (13) | 0.0231 (11) | 0.0101 (11) | 0.0045 (9) | 0.0061 (10) |
C6 | 0.0367 (13) | 0.0445 (14) | 0.0256 (11) | 0.0103 (11) | −0.0002 (9) | −0.0044 (10) |
C7 | 0.0354 (12) | 0.0320 (12) | 0.0381 (13) | 0.0015 (10) | 0.0028 (10) | −0.0046 (10) |
C8 | 0.0370 (12) | 0.0259 (11) | 0.0334 (12) | 0.0023 (9) | 0.0034 (10) | 0.0032 (9) |
C9 | 0.0271 (10) | 0.0243 (10) | 0.0213 (9) | 0.0079 (8) | 0.0038 (8) | 0.0019 (8) |
C10 | 0.0211 (10) | 0.0259 (11) | 0.0351 (12) | 0.0049 (8) | 0.0052 (9) | −0.0013 (9) |
C11 | 0.0212 (10) | 0.0513 (15) | 0.0240 (11) | 0.0063 (10) | 0.0045 (9) | 0.0047 (10) |
C12 | 0.0366 (13) | 0.0325 (12) | 0.0350 (12) | −0.0070 (10) | 0.0146 (10) | 0.0007 (10) |
C13 | 0.0368 (13) | 0.0532 (16) | 0.0369 (14) | −0.0152 (12) | 0.0086 (11) | 0.0092 (12) |
Geometric parameters (Å, º) top
Cd1—O2i | 2.2271 (17) | C1—H1A | 0.9300 |
Cd1—N6ii | 2.2960 (18) | C2—C3 | 1.498 (3) |
Cd1—O4 | 2.318 (2) | C2—H2A | 0.9700 |
Cd1—O1 | 2.3681 (18) | C2—H2B | 0.9700 |
Cd1—O3 | 2.3703 (19) | C4—C9 | 1.390 (3) |
Cd1—N1 | 2.476 (2) | C4—C5 | 1.393 (3) |
N1—C1 | 1.309 (3) | C5—C6 | 1.371 (4) |
N1—N2 | 1.351 (3) | C5—H5A | 0.9300 |
N2—N3 | 1.290 (3) | C6—C7 | 1.401 (4) |
N3—N4 | 1.339 (3) | C6—H6A | 0.9300 |
N4—C1 | 1.324 (3) | C7—C8 | 1.377 (3) |
N4—C2 | 1.458 (3) | C7—H7A | 0.9300 |
N5—C3 | 1.352 (3) | C8—C9 | 1.396 (3) |
N5—C4 | 1.381 (3) | C8—H8A | 0.9300 |
N5—H5B | 0.8600 | C10—C11 | 1.509 (3) |
N6—C3 | 1.313 (3) | C11—C11iv | 1.498 (4) |
N6—C9 | 1.397 (3) | C11—H11A | 0.9700 |
N6—Cd1iii | 2.2961 (18) | C11—H11B | 0.9700 |
O1—C10 | 1.259 (3) | C12—C13 | 1.512 (3) |
O2—C10 | 1.249 (3) | C13—C13v | 1.505 (5) |
O2—Cd1i | 2.2271 (17) | C13—H13A | 0.9700 |
O3—C12 | 1.243 (3) | C13—H13C | 0.9700 |
O4—C12 | 1.244 (3) | | |
| | | |
O2i—Cd1—N6ii | 93.56 (7) | N6—C3—N5 | 112.49 (19) |
O2i—Cd1—O4 | 166.87 (8) | N6—C3—C2 | 124.39 (19) |
N6ii—Cd1—O4 | 92.97 (7) | N5—C3—C2 | 123.11 (19) |
O2i—Cd1—O1 | 96.50 (7) | N5—C4—C9 | 105.66 (18) |
N6ii—Cd1—O1 | 89.19 (7) | N5—C4—C5 | 131.7 (2) |
O4—Cd1—O1 | 94.98 (8) | C9—C4—C5 | 122.5 (2) |
O2i—Cd1—O3 | 116.94 (7) | C6—C5—C4 | 116.3 (2) |
N6ii—Cd1—O3 | 147.96 (7) | C6—C5—H5A | 121.8 |
O4—Cd1—O3 | 55.19 (7) | C4—C5—H5A | 121.8 |
O1—Cd1—O3 | 96.40 (8) | C5—C6—C7 | 121.9 (2) |
O2i—Cd1—N1 | 80.82 (7) | C5—C6—H6A | 119.0 |
N6ii—Cd1—N1 | 89.75 (7) | C7—C6—H6A | 119.0 |
O4—Cd1—N1 | 87.83 (8) | C8—C7—C6 | 121.5 (2) |
O1—Cd1—N1 | 177.05 (6) | C8—C7—H7A | 119.2 |
O3—Cd1—N1 | 85.95 (8) | C6—C7—H7A | 119.2 |
C1—N1—N2 | 105.9 (2) | C7—C8—C9 | 117.2 (2) |
C1—N1—Cd1 | 131.29 (17) | C7—C8—H8A | 121.4 |
N2—N1—Cd1 | 122.16 (15) | C9—C8—H8A | 121.4 |
N3—N2—N1 | 110.38 (19) | C4—C9—C8 | 120.4 (2) |
N2—N3—N4 | 106.56 (19) | C4—C9—N6 | 108.96 (19) |
C1—N4—N3 | 108.31 (18) | C8—C9—N6 | 130.6 (2) |
C1—N4—C2 | 131.2 (2) | O2—C10—O1 | 123.1 (2) |
N3—N4—C2 | 120.45 (19) | O2—C10—C11 | 118.5 (2) |
C3—N5—C4 | 107.28 (18) | O1—C10—C11 | 118.5 (2) |
C3—N5—H5B | 126.4 | C11iv—C11—C10 | 114.5 (2) |
C4—N5—H5B | 126.4 | C11iv—C11—H11A | 108.6 |
C3—N6—C9 | 105.59 (17) | C10—C11—H11A | 108.6 |
C3—N6—Cd1iii | 127.42 (14) | C11iv—C11—H11B | 108.6 |
C9—N6—Cd1iii | 126.92 (14) | C10—C11—H11B | 108.6 |
C10—O1—Cd1 | 116.91 (15) | H11A—C11—H11B | 107.6 |
C10—O2—Cd1i | 108.15 (15) | O3—C12—O4 | 121.7 (2) |
C12—O3—Cd1 | 90.33 (15) | O3—C12—C13 | 120.6 (2) |
C12—O4—Cd1 | 92.75 (16) | O4—C12—C13 | 117.6 (2) |
N1—C1—N4 | 108.9 (2) | O3—C12—Cd1 | 62.07 (13) |
N1—C1—H1A | 125.6 | O4—C12—Cd1 | 59.66 (13) |
N4—C1—H1A | 125.6 | C13—C12—Cd1 | 176.8 (2) |
N4—C2—C3 | 111.35 (18) | C13v—C13—C12 | 114.3 (3) |
N4—C2—H2A | 109.4 | C13v—C13—H13A | 108.7 |
C3—C2—H2A | 109.4 | C12—C13—H13A | 108.7 |
N4—C2—H2B | 109.4 | C13v—C13—H13C | 108.7 |
C3—C2—H2B | 109.4 | C12—C13—H13C | 108.7 |
H2A—C2—H2B | 108.0 | H13A—C13—H13C | 107.6 |
| | | |
C1—N1—N2—N3 | −0.1 (3) | C5—C6—C7—C8 | −1.2 (4) |
Cd1—N1—N2—N3 | −171.73 (17) | C6—C7—C8—C9 | 0.6 (4) |
N1—N2—N3—N4 | −0.1 (3) | N5—C4—C9—C8 | −179.4 (2) |
N2—N3—N4—C1 | 0.2 (3) | C5—C4—C9—C8 | −2.2 (3) |
N2—N3—N4—C2 | −178.4 (2) | N5—C4—C9—N6 | −1.3 (2) |
N2—N1—C1—N4 | 0.2 (3) | C5—C4—C9—N6 | 175.9 (2) |
Cd1—N1—C1—N4 | 170.77 (15) | C7—C8—C9—C4 | 1.0 (3) |
N3—N4—C1—N1 | −0.2 (3) | C7—C8—C9—N6 | −176.6 (2) |
C2—N4—C1—N1 | 178.1 (2) | C3—N6—C9—C4 | 0.6 (2) |
C1—N4—C2—C3 | −97.0 (3) | Cd1iii—N6—C9—C4 | −176.65 (14) |
N3—N4—C2—C3 | 81.2 (3) | C3—N6—C9—C8 | 178.4 (2) |
C9—N6—C3—N5 | 0.4 (2) | Cd1iii—N6—C9—C8 | 1.2 (3) |
Cd1iii—N6—C3—N5 | 177.62 (14) | Cd1i—O2—C10—O1 | −6.3 (3) |
C9—N6—C3—C2 | −179.8 (2) | Cd1i—O2—C10—C11 | 173.39 (17) |
Cd1iii—N6—C3—C2 | −2.6 (3) | Cd1—O1—C10—O2 | −96.3 (2) |
C4—N5—C3—N6 | −1.2 (3) | Cd1—O1—C10—C11 | 84.0 (2) |
C4—N5—C3—C2 | 178.99 (19) | O2—C10—C11—C11iv | 13.7 (4) |
N4—C2—C3—N6 | 130.2 (2) | O1—C10—C11—C11iv | −166.6 (3) |
N4—C2—C3—N5 | −50.0 (3) | Cd1—O3—C12—O4 | −0.7 (3) |
C3—N5—C4—C9 | 1.5 (2) | Cd1—O3—C12—C13 | 178.0 (2) |
C3—N5—C4—C5 | −175.3 (2) | Cd1—O4—C12—O3 | 0.7 (3) |
N5—C4—C5—C6 | 177.9 (2) | Cd1—O4—C12—C13 | −178.0 (2) |
C9—C4—C5—C6 | 1.6 (3) | O3—C12—C13—C13v | −12.0 (5) |
C4—C5—C6—C7 | 0.1 (4) | O4—C12—C13—C13v | 166.7 (3) |
Symmetry codes: (i) −x, −y, −z; (ii) x, y−1, z; (iii) x, y+1, z; (iv) −x+1, −y, −z; (v) −x+1, −y+1, −z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N5—H5B···N2vi | 0.86 | 2.27 | 3.089 (3) | 159 |
Symmetry code: (vi) −x, −y+1, −z+1. |