Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S010827010803182X/av3161sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S010827010803182X/av3161Isup2.hkl |
CCDC reference: 710743
A mixture of CdCl2.2.5H2O (0.114 g, 0.5 mmol), H2adip (0.073 g, 0.5 mmol) and L (0.148 g, 0.5 mmol) were dissolved in 12 ml of distilled water, followed by addition of triethylamine until the pH value of the system was adjusted to about 5.5. The resulting solution was stirred for about 1 h at room temperature, sealed in a 23 ml Teflon-lined stainless steel autoclave and heated at 185° for 10 days under autogenous pressure. Afterwards, the reaction system was cooled slowly to room temperature. Pale-yellow block crystals of (I) suitable for single-crystal X-ray diffraction analysis were collected from the final reaction system by filtration, washed several times with distilled water and dried in air at ambient temperature (yield 28% based on CdII).
All H atoms were positioned geometrically (N—H = 0.86 Å, and C—H = 0.93 and 0.97 Å) and refined as riding, with Uiso(H) values of 1.2Ueq(carrier).
Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO (Rigaku, 1998); data reduction: PROCESS-AUTO (Rigaku, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL-Plus (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
[Cd3(C6H8O4)3(C19H12N4)2] | Z = 1 |
Mr = 1362.28 | F(000) = 680 |
Triclinic, P1 | Dx = 1.815 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 8.321 (1) Å | Cell parameters from 9709 reflections |
b = 10.977 (2) Å | θ = 3.0–27.5° |
c = 15.365 (3) Å | µ = 1.35 mm−1 |
α = 71.62 (2)° | T = 293 K |
β = 75.16 (3)° | Block, pale yellow |
γ = 71.89 (2)° | 0.27 × 0.24 × 0.21 mm |
V = 1246.3 (4) Å3 |
Rigaku R-AXIS RAPID diffractometer | 5634 independent reflections |
Radiation source: rotating anode | 4583 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.030 |
Detector resolution: 10.0 pixels mm-1 | θmax = 27.5°, θmin = 3.0° |
ω scans | h = −10→10 |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | k = −14→14 |
Tmin = 0.685, Tmax = 0.751 | l = −19→19 |
12314 measured reflections |
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)] = 0.031 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.069 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0255P)2 + 1.2155P] where P = (Fo2 + 2Fc2)/3 |
5634 reflections | (Δ/σ)max = 0.001 |
358 parameters | Δρmax = 0.48 e Å−3 |
0 restraints | Δρmin = −0.72 e Å−3 |
[Cd3(C6H8O4)3(C19H12N4)2] | γ = 71.89 (2)° |
Mr = 1362.28 | V = 1246.3 (4) Å3 |
Triclinic, P1 | Z = 1 |
a = 8.321 (1) Å | Mo Kα radiation |
b = 10.977 (2) Å | µ = 1.35 mm−1 |
c = 15.365 (3) Å | T = 293 K |
α = 71.62 (2)° | 0.27 × 0.24 × 0.21 mm |
β = 75.16 (3)° |
Rigaku R-AXIS RAPID diffractometer | 5634 independent reflections |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | 4583 reflections with I > 2σ(I) |
Tmin = 0.685, Tmax = 0.751 | Rint = 0.030 |
12314 measured reflections |
R[F2 > 2σ(F2)] = 0.031 | 0 restraints |
wR(F2) = 0.069 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.48 e Å−3 |
5634 reflections | Δρmin = −0.72 e Å−3 |
358 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
C1 | −0.1982 (4) | 0.6489 (3) | 0.3215 (2) | 0.0252 (6) | |
C2 | −0.3385 (4) | 0.7668 (3) | 0.3391 (3) | 0.0355 (8) | |
H2A | −0.3812 | 0.8159 | 0.2815 | 0.043* | |
H2B | −0.2901 | 0.8241 | 0.3560 | 0.043* | |
C3 | −0.4901 (4) | 0.7358 (4) | 0.4150 (3) | 0.0457 (9) | |
H3A | −0.4509 | 0.6995 | 0.4744 | 0.055* | |
H3B | −0.5763 | 0.8182 | 0.4179 | 0.055* | |
C4 | 0.2947 (4) | 0.5726 (3) | 0.2984 (2) | 0.0291 (7) | |
C5 | 0.3889 (5) | 0.6631 (4) | 0.3081 (2) | 0.0438 (9) | |
H5A | 0.4971 | 0.6547 | 0.2648 | 0.053* | |
H5B | 0.3219 | 0.7538 | 0.2895 | 0.053* | |
C6 | 0.4257 (5) | 0.6399 (4) | 0.4025 (2) | 0.0428 (9) | |
H6A | 0.4993 | 0.5512 | 0.4192 | 0.051* | |
H6B | 0.3184 | 0.6421 | 0.4464 | 0.051* | |
C7 | 0.1360 (4) | 0.2078 (3) | 0.4588 (2) | 0.0305 (7) | |
C8 | 0.1907 (5) | 0.0621 (3) | 0.5092 (2) | 0.0361 (7) | |
H8A | 0.1673 | 0.0532 | 0.5758 | 0.043* | |
H8B | 0.3135 | 0.0295 | 0.4907 | 0.043* | |
C9 | 0.0970 (4) | −0.0226 (3) | 0.4879 (2) | 0.0344 (7) | |
H9A | 0.1290 | −0.0198 | 0.4221 | 0.041* | |
H9B | 0.1345 | −0.1140 | 0.5226 | 0.041* | |
C10 | −0.2702 (4) | 0.3275 (3) | 0.3213 (2) | 0.0340 (7) | |
H10 | −0.2870 | 0.3484 | 0.3776 | 0.041* | |
C11 | −0.3885 (4) | 0.2714 (4) | 0.3075 (2) | 0.0383 (8) | |
H11 | −0.4825 | 0.2558 | 0.3536 | 0.046* | |
C12 | −0.3630 (4) | 0.2400 (3) | 0.2251 (2) | 0.0331 (7) | |
H12 | −0.4402 | 0.2026 | 0.2147 | 0.040* | |
C13 | −0.2206 (4) | 0.2639 (3) | 0.1560 (2) | 0.0258 (6) | |
C14 | −0.1081 (4) | 0.3216 (3) | 0.1757 (2) | 0.0244 (6) | |
C15 | 0.0451 (4) | 0.3468 (3) | 0.1072 (2) | 0.0233 (6) | |
C16 | 0.0806 (4) | 0.3174 (3) | 0.0210 (2) | 0.0249 (6) | |
C17 | 0.2297 (4) | 0.3412 (3) | −0.0414 (2) | 0.0321 (7) | |
H17 | 0.2549 | 0.3237 | −0.0995 | 0.038* | |
C18 | 0.3378 (4) | 0.3904 (3) | −0.0159 (2) | 0.0357 (8) | |
H18 | 0.4385 | 0.4056 | −0.0557 | 0.043* | |
C19 | 0.2934 (4) | 0.4172 (3) | 0.0708 (2) | 0.0337 (7) | |
H19 | 0.3667 | 0.4514 | 0.0876 | 0.040* | |
C20 | −0.0385 (4) | 0.2606 (3) | 0.00450 (19) | 0.0242 (6) | |
C21 | −0.1795 (4) | 0.2316 (3) | 0.0686 (2) | 0.0264 (6) | |
C22 | −0.1706 (4) | 0.1600 (3) | −0.0466 (2) | 0.0278 (6) | |
C23 | −0.2030 (4) | 0.0944 (3) | −0.1075 (2) | 0.0285 (6) | |
C24 | −0.3625 (4) | 0.0683 (3) | −0.0922 (2) | 0.0342 (7) | |
H24 | −0.4490 | 0.0972 | −0.0458 | 0.041* | |
C25 | −0.3940 (5) | −0.0005 (3) | −0.1454 (2) | 0.0407 (8) | |
H25 | −0.5001 | −0.0196 | −0.1337 | 0.049* | |
C26 | −0.2657 (5) | −0.0404 (3) | −0.2161 (2) | 0.0405 (8) | |
H26 | −0.2859 | −0.0859 | −0.2524 | 0.049* | |
C27 | −0.1094 (5) | −0.0129 (3) | −0.2324 (2) | 0.0384 (8) | |
H27 | −0.0244 | −0.0390 | −0.2803 | 0.046* | |
C28 | −0.0764 (4) | 0.0534 (3) | −0.1783 (2) | 0.0347 (7) | |
H28 | 0.0308 | 0.0705 | −0.1894 | 0.042* | |
N1 | −0.1345 (3) | 0.3523 (2) | 0.25708 (17) | 0.0272 (5) | |
N2 | 0.1523 (3) | 0.3968 (2) | 0.13115 (17) | 0.0270 (5) | |
N3 | −0.0334 (3) | 0.2143 (2) | −0.06913 (17) | 0.0278 (6) | |
H3 | 0.0413 | 0.2185 | −0.1197 | 0.033* | |
N4 | −0.2618 (3) | 0.1682 (3) | 0.03641 (18) | 0.0297 (6) | |
O1 | −0.1143 (3) | 0.6519 (2) | 0.24133 (15) | 0.0385 (6) | |
O2 | −0.1656 (3) | 0.5454 (2) | 0.38768 (15) | 0.0332 (5) | |
O3 | 0.3030 (3) | 0.5584 (3) | 0.22032 (17) | 0.0460 (6) | |
O4 | 0.2067 (3) | 0.5132 (2) | 0.36927 (17) | 0.0402 (6) | |
O5 | 0.1721 (3) | 0.2371 (2) | 0.37212 (17) | 0.0423 (6) | |
O6 | 0.0577 (4) | 0.2854 (2) | 0.50925 (19) | 0.0483 (7) | |
Cd1 | 0.08006 (3) | 0.43806 (2) | 0.277754 (15) | 0.02549 (7) | |
Cd2 | 0.0000 | 0.5000 | 0.5000 | 0.02473 (8) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0242 (14) | 0.0318 (15) | 0.0254 (15) | −0.0114 (13) | −0.0062 (12) | −0.0093 (12) |
C2 | 0.0303 (17) | 0.0352 (17) | 0.051 (2) | −0.0114 (14) | −0.0079 (15) | −0.0210 (16) |
C3 | 0.0326 (18) | 0.065 (2) | 0.056 (2) | −0.0151 (18) | 0.0003 (17) | −0.042 (2) |
C4 | 0.0272 (15) | 0.0284 (15) | 0.0331 (17) | −0.0096 (13) | −0.0047 (13) | −0.0080 (13) |
C5 | 0.060 (2) | 0.0447 (19) | 0.037 (2) | −0.0316 (19) | −0.0161 (17) | −0.0012 (16) |
C6 | 0.0376 (19) | 0.067 (2) | 0.0337 (19) | −0.0246 (19) | −0.0001 (15) | −0.0208 (18) |
C7 | 0.0329 (16) | 0.0264 (15) | 0.0387 (18) | −0.0129 (13) | −0.0058 (14) | −0.0122 (13) |
C8 | 0.0436 (19) | 0.0305 (16) | 0.0386 (19) | −0.0135 (15) | −0.0141 (15) | −0.0051 (14) |
C9 | 0.0421 (19) | 0.0246 (15) | 0.0391 (19) | −0.0095 (14) | −0.0109 (15) | −0.0077 (13) |
C10 | 0.0400 (18) | 0.0396 (17) | 0.0269 (16) | −0.0150 (15) | 0.0001 (14) | −0.0147 (14) |
C11 | 0.0353 (18) | 0.054 (2) | 0.0295 (17) | −0.0212 (17) | 0.0066 (14) | −0.0154 (15) |
C12 | 0.0314 (17) | 0.0448 (18) | 0.0312 (17) | −0.0203 (15) | −0.0034 (14) | −0.0118 (14) |
C13 | 0.0282 (15) | 0.0270 (14) | 0.0245 (15) | −0.0110 (13) | −0.0044 (12) | −0.0057 (12) |
C14 | 0.0292 (15) | 0.0244 (14) | 0.0230 (15) | −0.0089 (12) | −0.0062 (12) | −0.0071 (11) |
C15 | 0.0275 (15) | 0.0222 (13) | 0.0222 (14) | −0.0076 (12) | −0.0064 (12) | −0.0055 (11) |
C16 | 0.0277 (15) | 0.0265 (14) | 0.0214 (14) | −0.0104 (13) | −0.0044 (12) | −0.0038 (11) |
C17 | 0.0348 (17) | 0.0378 (17) | 0.0266 (16) | −0.0138 (15) | −0.0017 (13) | −0.0107 (13) |
C18 | 0.0333 (17) | 0.0484 (19) | 0.0301 (17) | −0.0208 (16) | 0.0029 (14) | −0.0127 (15) |
C19 | 0.0339 (17) | 0.0414 (18) | 0.0331 (17) | −0.0208 (15) | −0.0018 (14) | −0.0116 (14) |
C20 | 0.0305 (15) | 0.0270 (14) | 0.0197 (14) | −0.0109 (13) | −0.0058 (12) | −0.0074 (11) |
C21 | 0.0307 (16) | 0.0295 (15) | 0.0245 (15) | −0.0142 (13) | −0.0051 (12) | −0.0077 (12) |
C22 | 0.0333 (16) | 0.0312 (15) | 0.0231 (15) | −0.0135 (14) | −0.0079 (13) | −0.0051 (12) |
C23 | 0.0400 (17) | 0.0284 (14) | 0.0219 (15) | −0.0139 (14) | −0.0080 (13) | −0.0057 (12) |
C24 | 0.047 (2) | 0.0392 (17) | 0.0248 (16) | −0.0224 (16) | −0.0056 (14) | −0.0086 (14) |
C25 | 0.057 (2) | 0.0428 (19) | 0.0341 (18) | −0.0299 (18) | −0.0096 (16) | −0.0071 (15) |
C26 | 0.069 (3) | 0.0348 (17) | 0.0280 (17) | −0.0196 (18) | −0.0150 (17) | −0.0105 (14) |
C27 | 0.050 (2) | 0.0375 (18) | 0.0275 (17) | −0.0055 (16) | −0.0067 (15) | −0.0133 (14) |
C28 | 0.0370 (18) | 0.0388 (17) | 0.0307 (17) | −0.0094 (15) | −0.0067 (14) | −0.0115 (14) |
N1 | 0.0323 (14) | 0.0307 (13) | 0.0242 (13) | −0.0122 (11) | −0.0036 (11) | −0.0111 (10) |
N2 | 0.0297 (13) | 0.0308 (13) | 0.0267 (13) | −0.0126 (11) | −0.0045 (11) | −0.0111 (11) |
N3 | 0.0350 (14) | 0.0349 (13) | 0.0188 (12) | −0.0166 (12) | −0.0017 (11) | −0.0086 (10) |
N4 | 0.0351 (14) | 0.0376 (14) | 0.0239 (13) | −0.0171 (12) | −0.0049 (11) | −0.0104 (11) |
O1 | 0.0448 (14) | 0.0405 (13) | 0.0275 (12) | −0.0157 (11) | 0.0044 (10) | −0.0087 (10) |
O2 | 0.0374 (12) | 0.0351 (12) | 0.0300 (12) | −0.0109 (10) | −0.0128 (10) | −0.0047 (10) |
O3 | 0.0597 (16) | 0.0601 (16) | 0.0329 (13) | −0.0328 (14) | −0.0071 (12) | −0.0151 (12) |
O4 | 0.0407 (13) | 0.0473 (14) | 0.0390 (14) | −0.0270 (12) | 0.0088 (11) | −0.0167 (11) |
O5 | 0.0655 (17) | 0.0289 (11) | 0.0360 (14) | −0.0147 (12) | −0.0141 (12) | −0.0059 (10) |
O6 | 0.0654 (18) | 0.0263 (12) | 0.0515 (16) | −0.0162 (12) | 0.0018 (13) | −0.0126 (11) |
Cd1 | 0.03053 (12) | 0.02833 (11) | 0.02298 (12) | −0.01158 (9) | −0.00432 (9) | −0.01008 (9) |
Cd2 | 0.03343 (17) | 0.02485 (15) | 0.01876 (15) | −0.00966 (13) | −0.00413 (12) | −0.00750 (12) |
C1—O1 | 1.246 (4) | C16—C17 | 1.400 (4) |
C1—O2 | 1.273 (4) | C16—C20 | 1.431 (4) |
C1—C2 | 1.493 (4) | C17—C18 | 1.367 (4) |
C2—C3 | 1.527 (5) | C17—H17 | 0.9300 |
C2—H2A | 0.9700 | C18—C19 | 1.388 (4) |
C2—H2B | 0.9700 | C18—H18 | 0.9300 |
C3—C6i | 1.513 (4) | C19—N2 | 1.328 (4) |
C3—H3A | 0.9700 | C19—H19 | 0.9300 |
C3—H3B | 0.9700 | C20—N3 | 1.365 (4) |
C4—O3 | 1.239 (4) | C20—C21 | 1.375 (4) |
C4—O4 | 1.260 (4) | C21—N4 | 1.373 (4) |
C4—C5 | 1.504 (4) | C22—N4 | 1.321 (4) |
C5—C6 | 1.487 (5) | C22—N3 | 1.367 (4) |
C5—H5A | 0.9700 | C22—C23 | 1.464 (4) |
C5—H5B | 0.9700 | C23—C28 | 1.387 (4) |
C6—C3ii | 1.513 (4) | C23—C24 | 1.390 (4) |
C6—H6A | 0.9700 | C24—C25 | 1.388 (4) |
C6—H6B | 0.9700 | C24—H24 | 0.9300 |
C7—O5 | 1.245 (4) | C25—C26 | 1.389 (5) |
C7—O6 | 1.251 (4) | C25—H25 | 0.9300 |
C7—C8 | 1.520 (4) | C26—C27 | 1.370 (5) |
C8—C9 | 1.534 (4) | C26—H26 | 0.9300 |
C8—H8A | 0.9700 | C27—C28 | 1.385 (5) |
C8—H8B | 0.9700 | C27—H27 | 0.9300 |
C9—C9iii | 1.517 (7) | C28—H28 | 0.9300 |
C9—H9A | 0.9700 | N3—H3 | 0.8600 |
C9—H9B | 0.9700 | Cd1—N1 | 2.387 (2) |
C10—N1 | 1.331 (4) | Cd1—N2 | 2.328 (3) |
C10—C11 | 1.400 (5) | Cd1—O1 | 2.391 (3) |
C10—H10 | 0.9300 | Cd1—O2 | 2.532 (2) |
C11—C12 | 1.363 (4) | Cd1—O3 | 2.431 (2) |
C11—H11 | 0.9300 | Cd1—O4 | 2.408 (2) |
C12—C13 | 1.406 (4) | Cd1—O5 | 2.249 (2) |
C12—H12 | 0.9300 | Cd2—O2 | 2.318 (2) |
C13—C14 | 1.416 (4) | Cd2—O4 | 2.284 (2) |
C13—C21 | 1.426 (4) | Cd2—O6 | 2.218 (2) |
C14—N1 | 1.344 (4) | Cd2—O6iv | 2.218 (2) |
C14—C15 | 1.469 (4) | Cd2—O4iv | 2.284 (2) |
C15—N2 | 1.353 (4) | Cd2—O2iv | 2.318 (2) |
C15—C16 | 1.398 (4) | ||
O1—C1—O2 | 120.1 (3) | N4—C21—C13 | 128.6 (3) |
O1—C1—C2 | 119.6 (3) | C20—C21—C13 | 120.7 (2) |
O2—C1—C2 | 120.2 (3) | N4—C22—N3 | 112.6 (3) |
C1—C2—C3 | 115.3 (3) | N4—C22—C23 | 125.2 (3) |
C1—C2—H2A | 108.4 | N3—C22—C23 | 122.2 (3) |
C3—C2—H2A | 108.4 | C28—C23—C24 | 119.1 (3) |
C1—C2—H2B | 108.4 | C28—C23—C22 | 121.5 (3) |
C3—C2—H2B | 108.4 | C24—C23—C22 | 119.4 (3) |
H2A—C2—H2B | 107.5 | C25—C24—C23 | 120.8 (3) |
C6i—C3—C2 | 115.4 (3) | C25—C24—H24 | 119.6 |
C6i—C3—H3A | 108.4 | C23—C24—H24 | 119.6 |
C2—C3—H3A | 108.4 | C26—C25—C24 | 119.3 (3) |
C6i—C3—H3B | 108.4 | C26—C25—H25 | 120.3 |
C2—C3—H3B | 108.4 | C24—C25—H25 | 120.3 |
H3A—C3—H3B | 107.5 | C27—C26—C25 | 120.0 (3) |
O3—C4—O4 | 120.7 (3) | C27—C26—H26 | 120.0 |
O3—C4—C5 | 119.5 (3) | C25—C26—H26 | 120.0 |
O4—C4—C5 | 119.8 (3) | C26—C27—C28 | 120.8 (3) |
C6—C5—C4 | 116.1 (3) | C26—C27—H27 | 119.6 |
C6—C5—H5A | 108.3 | C28—C27—H27 | 119.6 |
C4—C5—H5A | 108.3 | C27—C28—C23 | 120.0 (3) |
C6—C5—H5B | 108.3 | C27—C28—H28 | 120.0 |
C4—C5—H5B | 108.3 | C23—C28—H28 | 120.0 |
H5A—C5—H5B | 107.4 | C10—N1—C14 | 119.1 (2) |
C5—C6—C3ii | 116.7 (3) | C10—N1—Cd1 | 124.8 (2) |
C5—C6—H6A | 108.1 | C14—N1—Cd1 | 115.96 (18) |
C3ii—C6—H6A | 108.1 | C19—N2—C15 | 118.4 (3) |
C5—C6—H6B | 108.1 | C19—N2—Cd1 | 123.8 (2) |
C3ii—C6—H6B | 108.1 | C15—N2—Cd1 | 117.73 (18) |
H6A—C6—H6B | 107.3 | C20—N3—C22 | 106.4 (2) |
O5—C7—O6 | 127.0 (3) | C20—N3—H3 | 126.8 |
O5—C7—C8 | 117.0 (3) | C22—N3—H3 | 126.8 |
O6—C7—C8 | 116.1 (3) | C22—N4—C21 | 104.4 (2) |
C7—C8—C9 | 112.1 (3) | C1—O1—Cd1 | 97.3 (2) |
C7—C8—H8A | 109.2 | C1—O2—Cd2 | 129.29 (18) |
C9—C8—H8A | 109.2 | C1—O2—Cd1 | 89.94 (18) |
C7—C8—H8B | 109.2 | Cd2—O2—Cd1 | 93.91 (8) |
C9—C8—H8B | 109.2 | C4—O3—Cd1 | 92.36 (18) |
H8A—C8—H8B | 107.9 | C4—O4—Cd2 | 154.8 (2) |
C9iii—C9—C8 | 113.4 (3) | C4—O4—Cd1 | 92.9 (2) |
C9iii—C9—H9A | 108.9 | Cd2—O4—Cd1 | 98.20 (8) |
C8—C9—H9A | 108.9 | C7—O5—Cd1 | 125.2 (2) |
C9iii—C9—H9B | 108.9 | C7—O6—Cd2 | 138.3 (2) |
C8—C9—H9B | 108.9 | O5—Cd1—N2 | 103.07 (9) |
H9A—C9—H9B | 107.7 | O5—Cd1—N1 | 86.65 (9) |
N1—C10—C11 | 122.8 (3) | N2—Cd1—N1 | 70.66 (8) |
N1—C10—H10 | 118.6 | O5—Cd1—O1 | 153.45 (9) |
C11—C10—H10 | 118.6 | N2—Cd1—O1 | 98.78 (9) |
C12—C11—C10 | 118.6 (3) | N1—Cd1—O1 | 86.53 (9) |
C12—C11—H11 | 120.7 | O5—Cd1—O4 | 84.01 (9) |
C10—C11—H11 | 120.7 | N2—Cd1—O4 | 136.70 (8) |
C11—C12—C13 | 120.2 (3) | N1—Cd1—O4 | 152.51 (8) |
C11—C12—H12 | 119.9 | O1—Cd1—O4 | 90.38 (9) |
C13—C12—H12 | 119.9 | O5—Cd1—O3 | 111.41 (10) |
C12—C13—C14 | 117.4 (3) | N2—Cd1—O3 | 85.23 (8) |
C12—C13—C21 | 124.7 (3) | N1—Cd1—O3 | 152.91 (8) |
C14—C13—C21 | 117.9 (3) | O1—Cd1—O3 | 85.10 (9) |
N1—C14—C13 | 121.9 (3) | O4—Cd1—O3 | 53.32 (8) |
N1—C14—C15 | 117.9 (2) | O5—Cd1—O2 | 101.13 (9) |
C13—C14—C15 | 120.1 (3) | N2—Cd1—O2 | 142.84 (8) |
N2—C15—C16 | 121.3 (3) | N1—Cd1—O2 | 83.13 (8) |
N2—C15—C14 | 117.7 (2) | O1—Cd1—O2 | 52.56 (7) |
C16—C15—C14 | 121.0 (2) | O4—Cd1—O2 | 73.45 (8) |
C15—C16—C17 | 118.9 (3) | O3—Cd1—O2 | 111.39 (8) |
C15—C16—C20 | 116.4 (2) | O6—Cd2—O6iv | 180.00 (14) |
C17—C16—C20 | 124.7 (3) | O6—Cd2—O4 | 86.90 (9) |
C18—C17—C16 | 119.3 (3) | O6iv—Cd2—O4 | 93.10 (9) |
C18—C17—H17 | 120.4 | O6—Cd2—O4iv | 93.10 (9) |
C16—C17—H17 | 120.4 | O6iv—Cd2—O4iv | 86.90 (9) |
C17—C18—C19 | 118.4 (3) | O4—Cd2—O4iv | 180.0 |
C17—C18—H18 | 120.8 | O6—Cd2—O2 | 89.51 (10) |
C19—C18—H18 | 120.8 | O6iv—Cd2—O2 | 90.49 (10) |
N2—C19—C18 | 123.8 (3) | O4—Cd2—O2 | 79.91 (9) |
N2—C19—H19 | 118.1 | O4iv—Cd2—O2 | 100.09 (9) |
C18—C19—H19 | 118.1 | O6—Cd2—O2iv | 90.49 (10) |
N3—C20—C21 | 105.9 (2) | O6iv—Cd2—O2iv | 89.51 (10) |
N3—C20—C16 | 130.1 (3) | O4—Cd2—O2iv | 100.09 (9) |
C21—C20—C16 | 123.8 (3) | O4iv—Cd2—O2iv | 79.91 (9) |
N4—C21—C20 | 110.7 (3) | O2—Cd2—O2iv | 180.0 |
Symmetry codes: (i) x−1, y, z; (ii) x+1, y, z; (iii) −x, −y, −z+1; (iv) −x, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3···O1v | 0.86 | 2.04 | 2.770 (3) | 142 |
Symmetry code: (v) −x, −y+1, −z. |
Experimental details
Crystal data | |
Chemical formula | [Cd3(C6H8O4)3(C19H12N4)2] |
Mr | 1362.28 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 8.321 (1), 10.977 (2), 15.365 (3) |
α, β, γ (°) | 71.62 (2), 75.16 (3), 71.89 (2) |
V (Å3) | 1246.3 (4) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 1.35 |
Crystal size (mm) | 0.27 × 0.24 × 0.21 |
Data collection | |
Diffractometer | Rigaku R-AXIS RAPID diffractometer |
Absorption correction | Multi-scan (ABSCOR; Higashi, 1995) |
Tmin, Tmax | 0.685, 0.751 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 12314, 5634, 4583 |
Rint | 0.030 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.031, 0.069, 1.03 |
No. of reflections | 5634 |
No. of parameters | 358 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.48, −0.72 |
Computer programs: PROCESS-AUTO (Rigaku, 1998), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL-Plus (Sheldrick, 2008).
Cd1—N1 | 2.387 (2) | Cd1—O4 | 2.408 (2) |
Cd1—N2 | 2.328 (3) | Cd1—O5 | 2.249 (2) |
Cd1—O1 | 2.391 (3) | Cd2—O2 | 2.318 (2) |
Cd1—O2 | 2.532 (2) | Cd2—O4 | 2.284 (2) |
Cd1—O3 | 2.431 (2) | Cd2—O6 | 2.218 (2) |
O5—Cd1—N2 | 103.07 (9) | N1—Cd1—O3 | 152.91 (8) |
O5—Cd1—N1 | 86.65 (9) | O1—Cd1—O3 | 85.10 (9) |
N2—Cd1—N1 | 70.66 (8) | O4—Cd1—O3 | 53.32 (8) |
O5—Cd1—O1 | 153.45 (9) | O5—Cd1—O2 | 101.13 (9) |
N2—Cd1—O1 | 98.78 (9) | N2—Cd1—O2 | 142.84 (8) |
N1—Cd1—O1 | 86.53 (9) | N1—Cd1—O2 | 83.13 (8) |
O5—Cd1—O4 | 84.01 (9) | O1—Cd1—O2 | 52.56 (7) |
N2—Cd1—O4 | 136.70 (8) | O4—Cd1—O2 | 73.45 (8) |
N1—Cd1—O4 | 152.51 (8) | O3—Cd1—O2 | 111.39 (8) |
O1—Cd1—O4 | 90.38 (9) | O6—Cd2—O4 | 86.90 (9) |
O5—Cd1—O3 | 111.41 (10) | O6—Cd2—O2 | 89.51 (10) |
N2—Cd1—O3 | 85.23 (8) | O4—Cd2—O2 | 79.91 (9) |
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3···O1i | 0.86 | 2.04 | 2.770 (3) | 142 |
Symmetry code: (i) −x, −y+1, −z. |
Metal–organic coordination polymers built up from polynuclear metal clusters and multicarboxylate building blocks have become an attractive area of research in recent years, owing to their interesting molecular topologies and potential applications as functional materials (Eddaoudi et al., 2001; Hagrman et al., 1999; Noveron et al., 2002). Polynuclear metal clusters can be very versatile in terms of coordination properties and rigidity, as well as displaying intriguing physical properties that are not found in mononuclear species. So far, multi-carboxylate building blocks with special configurations have been selected for use in the design of a wide range of polynuclear metal clusters. Following this direction, a variety of coordination polymers based on polynuclear metal clusters have been obtained using multi-carboxylate building blocks. Typically, benzene-1,2-dicarboxylic acid and benzene-1,3-dicarboxylic acid (have been widely used for the design and synthesis of coordination polymers with polynuclear metal clusters (Yang, Li et al. 2007). However, far less effort has been expended on adipatic acid (H2adip; Yang, Ma et al., 2007). As a dicarboxylate ligand, H2adip possesses flexibility owing to the presence of –CH2– spacers between the two carboxylate groups, which is helpful for the formation of coordination polymers with polynuclear metal clusters.
On the other hand, the preparation of ordered functional crystalline solids, which display a variety of well defined supramolecular architectures mediated by supramolecular interactions, is currently of great interest and importance (Lehn, 1988, 2002). In this regard, 1,10-phenanthroline (phen) and 2,2-bipyridyl have been widely used to build supramolecular architectures owing to their excellent coordinating ability and large conjugated system that can easily form π–π interactions (Tong et al., 2000; Zheng et al., 2001). On this basis, a number of coordination polymers have been prepared from one-dimensional covalently bonded chains or layers, yielding extended two- or three-dimensional supramolecular structures through these interactions (Zhang et al., 2005). However, far less attention has been given to their derivatives (Yang, Li et al., 2007; Yang, Ma et al., 2007). For example, the rare phen derivative 2-phenyl-1H-1,3,7,8,-tetraazacyclopenta[l]phenanthrene (L) possesses a fruitful aromatic system and is a good candidate for construction of metal–organic supramolecular architectures (Steck & Day, 1943). In this contribution, we selected H2adip as a flexible linker and L as a secondary ligand, generating a new trinuclear CdII coordination polymer, namely [Cd3(C6H8O4)3(C19H12N4)2]n, (I). Compound (I) is a rare example of a two-dimensional structure with four-connected (4,4) topology based on trinuclear CdII nodes.
The asymmetric unit of (I) contains of two crystallographically independent CdII atoms. As shown in Fig. 1, atom Cd1 is in a distorted pentagonal–bipyramidal coordination environment consisting of five O atoms from three adip ligands and two N atoms from one L ligand. Atoms O2, O3, O4, N1, and N2 atoms form the basal plane, while atoms O1 and O5 occupy the apical positions. Atom Cd2 lies on an inversion center and is coordinated by six O atoms from six adip ligands in a distorted octahedral geometry, where atoms O2, O2i, O6 and O6i [symmetry code: (i) -x, -y + 1, -z + 1] form the basal plane, and atoms O4 and O4i occupy the apical positions. The Cd—N [2.328 (3) and 2.387 (2) Å] and Cd—O distances [2.218 (2)–2.532 (2) Å] in (I) (Table 1) are comparable to those found in another crystallographically characterized CdII complex, [Cd4(OH)2(H2O)2(sip)2(4,4'-bpy)4].H2O (sip is 5-sulfoisophthalate and 4,4'-bpy is 4,4'-bipyridyl; Li et al., 2005). Notably, in (I), two coordination modes for the adip ligands have been found. One type of adip linker coordinates to four CdII atoms in a bis-tridentate mode, while the other type of adip connects four CdII centers in a bis-bidentate mode. Interestingly, the carboxylate ends of adip ligands link the CdII atoms to form a unique trinuclear CdII cluster. These clusters are further bridged by the adip linkers to result in a two-dimensional layer structure (Fig. 2). It is noted that the L ligands are extended on both sides of the layers, and the planes of adjacent L ligands are nearly parallel. These parallel L ligands are paired to furnish strong aromatic π–π stacking interactions [with a centroid-to-centroid distance of 3.785 (2) Å, a vertical face-to-face distance of 3.442 (1) Å and a dihedral angle of 0.80 (3)°], which extend the layers into a three-dimensional supramolecular structure in the bc plane (Fig. 3).
A better insight into the structure of (I) can be achieved by the application of the topological approach, that is, reducing multidimensional structures to simple node-and-linker nets. As discussed above, each trinuclear CdII cluster is surrounded by eight organic ligands, namely six bridging adip and two chelating L ligands. Therefore, this defines a four-connected node. Each trinuclear CdII cluster core is further linked to four nearest neighbors through six adip ligands, thus resulting in a unique four-connected two-dimensional network (Fig. 4). Considering the trinuclear clusters as nodes and keeping the adip ligands as spacers, the overall topology of the two-dimensional framework is best described as a four-connected (4,4)-net (Yang et al., 2008). So far, occurances of the (4,4)-net have been extensively reported; however, a (4,4)-net based on a trinuclear metal node is rarely observed (Batten & Robson, 1998). Therefore, to our knowledge, (I) is the first example of a two-dimensional (4,4)-net based on a trinuclear CdII node. The flexibility of the L ligand may play an important role in the formation of the unusual structure.
It is noteworthy that the structure of (I) is entirely different from that of the related compound [Cd2(Dpq)2(BPDC)2].1.5H2O (Dpq is dipyrido[3,2-d:2',3'-f]quinoxaline and BPDC is biphenyl-4,4'-dicarboxylate; Wang et al., 2007), in which the BPDC ligands are linked the CdII centers to give an interesting six-connected twofold interpenetrated three-dimensional α-Po-related architecture.
Finally, an N—H···O hydrogen bond between the N atom of the L ligand and a carboxylate O atom further stabilizes the structure of (I) (Table 2).