Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270111055454/qs3010sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270111055454/qs3010Isup2.hkl |
CCDC reference: 867003
Into a 25 ml Teflon-lined stainless steel autoclave were loaded Cd(NO3)2.4H2O (154 mg, 0.5 mmol), 1,4-phenylenediacetic acid (97 mg, 0.5 mmol), 1,3-bis(pyridin-4-yl)propane (99 mg, 0.5 mmol), H2O (8 ml) and EtOH (8 ml). The autoclave was sealed and heated in an oven to 433 K for 3 d, and then cooled to ambient temperature at a rate of 5 K h-1 to form colourless crystals of (I), which were washed with ethanol and dried in air (yield 188 mg, 75% based on Cd). Analysis, calculated for C23H22CdN2O4: C 54.94, H 4.41, N 5.57%; found: C 54.62, H 4.18, N 5.75%. Spectroscopic analysis: IR (KBr, ν, cm-1): 1606 (s), 1590 (s), 1541 (s), 1506 (m), 1494 (m), 1401 (s), 1376 (s), 1226 (m), 1168 (m), 1069 (m), 1013 (s), 853 (s), 829 (s), 771 (s), 683 (m), 548 (s).
All H atoms were placed in geometrically idealized positions, with C—H = 0.95 Å for phenyl and pyridyl groups or 0.98 Å for methylene groups, and constrained to ride on their parent atoms, with Uiso(H) = 1.2Ueq(C) for phenyl and pyridyl groups or 1.5Ueq(C) for methylene groups.
Data collection: CrystalClear (Rigaku, 2001); cell refinement: CrystalClear (Rigaku, 2001); data reduction: CrystalStructure (Rigaku/MSC, 2004); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).
[Cd(C10H8O4)(C13H14N2)] | F(000) = 1016 |
Mr = 502.84 | Dx = 1.618 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 8184 reflections |
a = 10.022 (2) Å | θ = 3.5–27.5° |
b = 22.316 (5) Å | µ = 1.09 mm−1 |
c = 10.316 (2) Å | T = 223 K |
β = 116.51 (3)° | Block, colourless |
V = 2064.6 (9) Å3 | 0.30 × 0.30 × 0.10 mm |
Z = 4 |
Rigaku Mercury CCD area-detector diffractometer | 4699 independent reflections |
Radiation source: fine-focus sealed tube | 3702 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.035 |
ω scans | θmax = 27.5°, θmin = 3.5° |
Absorption correction: multi-scan (REQAB; Jacobson, 1998) | h = −11→13 |
Tmin = 0.736, Tmax = 0.899 | k = −28→23 |
11710 measured reflections | l = −13→9 |
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)] = 0.047 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.099 | H-atom parameters constrained |
S = 1.10 | w = 1/[σ2(Fo2) + (0.0414P)2 + 0.6308P] where P = (Fo2 + 2Fc2)/3 |
4699 reflections | (Δ/σ)max = 0.001 |
271 parameters | Δρmax = 0.60 e Å−3 |
0 restraints | Δρmin = −0.53 e Å−3 |
[Cd(C10H8O4)(C13H14N2)] | V = 2064.6 (9) Å3 |
Mr = 502.84 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 10.022 (2) Å | µ = 1.09 mm−1 |
b = 22.316 (5) Å | T = 223 K |
c = 10.316 (2) Å | 0.30 × 0.30 × 0.10 mm |
β = 116.51 (3)° |
Rigaku Mercury CCD area-detector diffractometer | 4699 independent reflections |
Absorption correction: multi-scan (REQAB; Jacobson, 1998) | 3702 reflections with I > 2σ(I) |
Tmin = 0.736, Tmax = 0.899 | Rint = 0.035 |
11710 measured reflections |
R[F2 > 2σ(F2)] = 0.047 | 0 restraints |
wR(F2) = 0.099 | H-atom parameters constrained |
S = 1.10 | Δρmax = 0.60 e Å−3 |
4699 reflections | Δρmin = −0.53 e Å−3 |
271 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 | ||
Cd1 | 0.50810 (3) | 0.437184 (11) | −0.37266 (3) | 0.03559 (11) | |
N1 | 0.6340 (3) | 0.50732 (14) | −0.1898 (3) | 0.0380 (7) | |
N2 | 0.6275 (4) | 0.86966 (14) | 0.0545 (3) | 0.0410 (7) | |
O1 | 0.7236 (3) | 0.36904 (14) | −0.2451 (3) | 0.0556 (8) | |
O2 | 0.5297 (3) | 0.36719 (13) | −0.1990 (3) | 0.0486 (7) | |
O3 | 0.6325 (3) | 0.47537 (13) | 0.5028 (3) | 0.0479 (7) | |
O4 | 0.7351 (3) | 0.52707 (11) | 0.3915 (3) | 0.0434 (6) | |
C1 | 0.7734 (4) | 0.52475 (19) | −0.1540 (5) | 0.0467 (10) | |
H1 | 0.8258 | 0.5056 | −0.1985 | 0.056* | |
C2 | 0.8441 (5) | 0.56950 (19) | −0.0551 (5) | 0.0495 (10) | |
H2 | 0.9437 | 0.5791 | −0.0316 | 0.059* | |
C3 | 0.7711 (4) | 0.60046 (19) | 0.0101 (5) | 0.0469 (10) | |
C4 | 0.6267 (5) | 0.5805 (2) | −0.0240 (5) | 0.0562 (12) | |
H4 | 0.5731 | 0.5982 | 0.0211 | 0.067* | |
C5 | 0.5627 (5) | 0.5351 (2) | −0.1231 (4) | 0.0507 (11) | |
H5 | 0.4650 | 0.5231 | −0.1451 | 0.061* | |
C6 | 0.8407 (5) | 0.6546 (2) | 0.1070 (5) | 0.0588 (12) | |
H6A | 0.9488 | 0.6533 | 0.1400 | 0.071* | |
H6B | 0.8033 | 0.6909 | 0.0485 | 0.071* | |
C7 | 0.8123 (5) | 0.65966 (17) | 0.2364 (5) | 0.0486 (10) | |
H7A | 0.8622 | 0.6266 | 0.3032 | 0.058* | |
H7B | 0.7050 | 0.6563 | 0.2062 | 0.058* | |
C8 | 0.8689 (5) | 0.71924 (18) | 0.3148 (5) | 0.0521 (11) | |
H8A | 0.8607 | 0.7184 | 0.4060 | 0.062* | |
H8B | 0.9747 | 0.7234 | 0.3389 | 0.062* | |
C9 | 0.7869 (4) | 0.77270 (17) | 0.2294 (4) | 0.0424 (9) | |
C10 | 0.8506 (4) | 0.81248 (19) | 0.1719 (5) | 0.0498 (10) | |
H10 | 0.9509 | 0.8075 | 0.1910 | 0.060* | |
C11 | 0.7697 (4) | 0.85949 (19) | 0.0868 (5) | 0.0477 (10) | |
H11 | 0.8174 | 0.8858 | 0.0495 | 0.057* | |
C12 | 0.5672 (5) | 0.8322 (2) | 0.1147 (6) | 0.0710 (15) | |
H12 | 0.4678 | 0.8388 | 0.0967 | 0.085* | |
C13 | 0.6410 (5) | 0.7848 (2) | 0.2008 (6) | 0.0690 (15) | |
H13 | 0.5925 | 0.7603 | 0.2407 | 0.083* | |
C14 | 0.7670 (4) | 0.34242 (16) | 0.0973 (4) | 0.0370 (8) | |
C15 | 0.8127 (4) | 0.40199 (16) | 0.1199 (4) | 0.0384 (8) | |
H15 | 0.8234 | 0.4229 | 0.0459 | 0.046* | |
C16 | 0.8428 (4) | 0.43119 (16) | 0.2476 (4) | 0.0359 (8) | |
H16 | 0.8741 | 0.4714 | 0.2597 | 0.043* | |
C17 | 0.8271 (4) | 0.40150 (16) | 0.3597 (4) | 0.0345 (8) | |
C18 | 0.7820 (4) | 0.34232 (16) | 0.3375 (4) | 0.0386 (8) | |
H18 | 0.7716 | 0.3214 | 0.4116 | 0.046* | |
C19 | 0.7516 (4) | 0.31305 (17) | 0.2090 (4) | 0.0418 (9) | |
H19 | 0.7203 | 0.2729 | 0.1970 | 0.050* | |
C20 | 0.7417 (5) | 0.31138 (18) | −0.0420 (4) | 0.0456 (10) | |
H20A | 0.6840 | 0.2747 | −0.0527 | 0.055* | |
H20B | 0.8381 | 0.3000 | −0.0374 | 0.055* | |
C21 | 0.6588 (4) | 0.35144 (16) | −0.1734 (4) | 0.0388 (9) | |
C22 | 0.8510 (4) | 0.43454 (16) | 0.4975 (4) | 0.0371 (8) | |
H22A | 0.8459 | 0.4061 | 0.5675 | 0.045* | |
H22B | 0.9502 | 0.4530 | 0.5409 | 0.045* | |
C23 | 0.7333 (4) | 0.48234 (16) | 0.4634 (4) | 0.0351 (8) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cd1 | 0.03852 (17) | 0.03556 (16) | 0.03327 (16) | 0.00254 (12) | 0.01652 (12) | 0.00252 (11) |
N1 | 0.0406 (17) | 0.0404 (17) | 0.0354 (17) | 0.0019 (15) | 0.0191 (14) | 0.0034 (13) |
N2 | 0.0416 (17) | 0.0412 (18) | 0.0407 (18) | 0.0010 (15) | 0.0189 (15) | 0.0033 (14) |
O1 | 0.0570 (18) | 0.0632 (19) | 0.0559 (19) | 0.0120 (16) | 0.0334 (16) | 0.0153 (15) |
O2 | 0.0479 (16) | 0.0511 (17) | 0.0479 (17) | 0.0077 (14) | 0.0222 (13) | 0.0108 (13) |
O3 | 0.0472 (15) | 0.0573 (18) | 0.0500 (17) | 0.0096 (14) | 0.0314 (14) | 0.0125 (13) |
O4 | 0.0520 (16) | 0.0380 (14) | 0.0466 (16) | 0.0066 (13) | 0.0276 (13) | 0.0078 (12) |
C1 | 0.042 (2) | 0.052 (2) | 0.051 (3) | 0.008 (2) | 0.0249 (19) | −0.0014 (19) |
C2 | 0.036 (2) | 0.060 (3) | 0.055 (3) | −0.006 (2) | 0.0225 (19) | −0.011 (2) |
C3 | 0.042 (2) | 0.053 (2) | 0.048 (2) | −0.005 (2) | 0.0229 (19) | −0.0078 (19) |
C4 | 0.043 (2) | 0.077 (3) | 0.054 (3) | −0.001 (2) | 0.026 (2) | −0.019 (2) |
C5 | 0.041 (2) | 0.072 (3) | 0.042 (2) | −0.013 (2) | 0.0215 (19) | −0.010 (2) |
C6 | 0.060 (3) | 0.058 (3) | 0.059 (3) | −0.014 (2) | 0.027 (2) | −0.010 (2) |
C7 | 0.054 (2) | 0.040 (2) | 0.050 (2) | −0.0007 (19) | 0.022 (2) | 0.0033 (18) |
C8 | 0.063 (3) | 0.041 (2) | 0.046 (2) | −0.001 (2) | 0.018 (2) | −0.0027 (18) |
C9 | 0.046 (2) | 0.042 (2) | 0.035 (2) | −0.0035 (19) | 0.0143 (17) | −0.0070 (16) |
C10 | 0.034 (2) | 0.051 (2) | 0.057 (3) | −0.0060 (19) | 0.0138 (19) | 0.001 (2) |
C11 | 0.037 (2) | 0.053 (2) | 0.052 (3) | −0.007 (2) | 0.0188 (19) | 0.006 (2) |
C12 | 0.049 (3) | 0.085 (4) | 0.085 (4) | 0.016 (3) | 0.036 (3) | 0.033 (3) |
C13 | 0.058 (3) | 0.072 (3) | 0.084 (4) | 0.003 (3) | 0.038 (3) | 0.035 (3) |
C14 | 0.0395 (19) | 0.0347 (19) | 0.035 (2) | 0.0082 (17) | 0.0152 (16) | 0.0016 (15) |
C15 | 0.043 (2) | 0.039 (2) | 0.036 (2) | 0.0055 (18) | 0.0208 (17) | 0.0077 (16) |
C16 | 0.0377 (19) | 0.0337 (19) | 0.039 (2) | −0.0032 (16) | 0.0195 (16) | 0.0031 (16) |
C17 | 0.0318 (18) | 0.0357 (19) | 0.0350 (19) | 0.0065 (16) | 0.0140 (15) | 0.0046 (15) |
C18 | 0.044 (2) | 0.0339 (19) | 0.042 (2) | 0.0024 (17) | 0.0225 (18) | 0.0075 (16) |
C19 | 0.046 (2) | 0.0298 (18) | 0.049 (2) | 0.0010 (18) | 0.0212 (18) | 0.0047 (17) |
C20 | 0.056 (2) | 0.036 (2) | 0.041 (2) | 0.012 (2) | 0.0184 (19) | 0.0048 (17) |
C21 | 0.048 (2) | 0.0299 (18) | 0.036 (2) | 0.0040 (18) | 0.0162 (18) | 0.0001 (15) |
C22 | 0.0392 (19) | 0.038 (2) | 0.0324 (19) | 0.0052 (17) | 0.0144 (15) | 0.0056 (15) |
C23 | 0.0358 (19) | 0.039 (2) | 0.0274 (18) | 0.0024 (16) | 0.0109 (15) | −0.0045 (15) |
Cd1—O2 | 2.313 (3) | C7—C8 | 1.528 (5) |
Cd1—O3i | 2.315 (3) | C7—H7A | 0.9800 |
Cd1—N2ii | 2.315 (3) | C7—H7B | 0.9800 |
Cd1—N1 | 2.340 (3) | C8—C9 | 1.493 (6) |
Cd1—O3iii | 2.430 (3) | C8—H8A | 0.9800 |
Cd1—O1 | 2.484 (3) | C8—H8B | 0.9800 |
Cd1—O4iii | 2.488 (3) | C9—C10 | 1.372 (6) |
Cd1—C21 | 2.719 (4) | C9—C13 | 1.383 (6) |
N1—C1 | 1.334 (5) | C10—C11 | 1.376 (6) |
N1—C5 | 1.345 (5) | C10—H10 | 0.9400 |
N2—C11 | 1.331 (5) | C11—H11 | 0.9400 |
N2—C12 | 1.336 (6) | C12—C13 | 1.367 (6) |
N2—Cd1iv | 2.315 (3) | C12—H12 | 0.9400 |
O1—C21 | 1.246 (5) | C13—H13 | 0.9400 |
O2—C21 | 1.250 (5) | C14—C15 | 1.391 (5) |
O3—C23 | 1.256 (4) | C14—C19 | 1.392 (5) |
O3—Cd1v | 2.315 (3) | C14—C20 | 1.512 (5) |
O3—Cd1iii | 2.430 (3) | C15—C16 | 1.377 (5) |
O4—C23 | 1.249 (4) | C15—H15 | 0.9400 |
O4—Cd1iii | 2.488 (3) | C16—C17 | 1.401 (5) |
C1—C2 | 1.376 (6) | C16—H16 | 0.9400 |
C1—H1 | 0.9400 | C17—C18 | 1.381 (5) |
C2—C3 | 1.380 (6) | C17—C22 | 1.522 (5) |
C2—H2 | 0.9400 | C18—C19 | 1.384 (5) |
C3—C4 | 1.401 (6) | C18—H18 | 0.9400 |
C3—C6 | 1.524 (6) | C19—H19 | 0.9400 |
C4—C5 | 1.377 (6) | C20—C21 | 1.524 (5) |
C4—H4 | 0.9400 | C20—H20A | 0.9800 |
C5—H5 | 0.9400 | C20—H20B | 0.9800 |
C6—C7 | 1.489 (6) | C22—C23 | 1.511 (5) |
C6—H6A | 0.9800 | C22—H22A | 0.9800 |
C6—H6B | 0.9800 | C22—H22B | 0.9800 |
O2—Cd1—O3i | 142.27 (10) | C6—C7—H7B | 109.3 |
O2—Cd1—N2ii | 90.36 (11) | C8—C7—H7B | 109.3 |
O3i—Cd1—N2ii | 93.24 (11) | H7A—C7—H7B | 108.0 |
O2—Cd1—N1 | 89.83 (11) | C9—C8—C7 | 114.0 (3) |
O3i—Cd1—N1 | 88.34 (11) | C9—C8—H8A | 108.8 |
N2ii—Cd1—N1 | 177.18 (11) | C7—C8—H8A | 108.8 |
O2—Cd1—O3iii | 143.22 (10) | C9—C8—H8B | 108.8 |
O3i—Cd1—O3iii | 73.79 (10) | C7—C8—H8B | 108.8 |
N2ii—Cd1—O3iii | 95.11 (11) | H8A—C8—H8B | 107.6 |
N1—Cd1—O3iii | 83.07 (11) | C10—C9—C13 | 115.6 (4) |
O2—Cd1—O1 | 54.39 (10) | C10—C9—C8 | 122.2 (4) |
O3i—Cd1—O1 | 87.88 (10) | C13—C9—C8 | 122.2 (4) |
N2ii—Cd1—O1 | 95.04 (11) | C9—C10—C11 | 120.9 (4) |
N1—Cd1—O1 | 87.36 (11) | C9—C10—H10 | 119.6 |
O3iii—Cd1—O1 | 159.49 (9) | C11—C10—H10 | 119.6 |
O2—Cd1—O4iii | 91.54 (9) | N2—C11—C10 | 123.4 (4) |
O3i—Cd1—O4iii | 126.15 (9) | N2—C11—H11 | 118.3 |
N2ii—Cd1—O4iii | 86.86 (10) | C10—C11—H11 | 118.3 |
N1—Cd1—O4iii | 90.31 (10) | N2—C12—C13 | 124.1 (4) |
O3iii—Cd1—O4iii | 52.66 (9) | N2—C12—H12 | 118.0 |
O1—Cd1—O4iii | 145.82 (9) | C13—C12—H12 | 118.0 |
O2—Cd1—C21 | 27.26 (11) | C12—C13—C9 | 120.3 (4) |
O3i—Cd1—C21 | 115.05 (11) | C12—C13—H13 | 119.9 |
N2ii—Cd1—C21 | 94.68 (11) | C9—C13—H13 | 119.9 |
N1—Cd1—C21 | 86.76 (11) | C15—C14—C19 | 117.5 (3) |
O3iii—Cd1—C21 | 166.38 (11) | C15—C14—C20 | 120.0 (4) |
O1—Cd1—C21 | 27.22 (10) | C19—C14—C20 | 122.5 (3) |
O4iii—Cd1—C21 | 118.60 (11) | C16—C15—C14 | 121.8 (3) |
C1—N1—C5 | 117.0 (3) | C16—C15—H15 | 119.1 |
C1—N1—Cd1 | 122.6 (3) | C14—C15—H15 | 119.1 |
C5—N1—Cd1 | 120.1 (3) | C15—C16—C17 | 120.6 (3) |
C11—N2—C12 | 115.7 (4) | C15—C16—H16 | 119.7 |
C11—N2—Cd1iv | 119.3 (3) | C17—C16—H16 | 119.7 |
C12—N2—Cd1iv | 124.1 (3) | C18—C17—C16 | 117.7 (3) |
C21—O1—Cd1 | 87.0 (2) | C18—C17—C22 | 121.4 (3) |
C21—O2—Cd1 | 94.8 (2) | C16—C17—C22 | 120.8 (3) |
C23—O3—Cd1v | 159.3 (3) | C17—C18—C19 | 121.7 (4) |
C23—O3—Cd1iii | 94.2 (2) | C17—C18—H18 | 119.2 |
Cd1v—O3—Cd1iii | 106.21 (10) | C19—C18—H18 | 119.2 |
C23—O4—Cd1iii | 91.7 (2) | C18—C19—C14 | 120.8 (4) |
N1—C1—C2 | 123.1 (4) | C18—C19—H19 | 119.6 |
N1—C1—H1 | 118.5 | C14—C19—H19 | 119.6 |
C2—C1—H1 | 118.5 | C14—C20—C21 | 111.7 (3) |
C1—C2—C3 | 121.0 (4) | C14—C20—H20A | 109.3 |
C1—C2—H2 | 119.5 | C21—C20—H20A | 109.3 |
C3—C2—H2 | 119.5 | C14—C20—H20B | 109.3 |
C2—C3—C4 | 115.6 (4) | C21—C20—H20B | 109.3 |
C2—C3—C6 | 122.0 (4) | H20A—C20—H20B | 107.9 |
C4—C3—C6 | 122.4 (4) | O1—C21—O2 | 123.4 (3) |
C5—C4—C3 | 120.5 (4) | O1—C21—C20 | 119.4 (4) |
C5—C4—H4 | 119.8 | O2—C21—C20 | 117.1 (4) |
C3—C4—H4 | 119.8 | O1—C21—Cd1 | 65.8 (2) |
N1—C5—C4 | 122.7 (4) | O2—C21—Cd1 | 57.93 (19) |
N1—C5—H5 | 118.6 | C20—C21—Cd1 | 169.6 (3) |
C4—C5—H5 | 118.6 | C23—C22—C17 | 110.1 (3) |
C7—C6—C3 | 115.7 (4) | C23—C22—H22A | 109.6 |
C7—C6—H6A | 108.4 | C17—C22—H22A | 109.6 |
C3—C6—H6A | 108.4 | C23—C22—H22B | 109.6 |
C7—C6—H6B | 108.4 | C17—C22—H22B | 109.6 |
C3—C6—H6B | 108.4 | H22A—C22—H22B | 108.2 |
H6A—C6—H6B | 107.4 | O4—C23—O3 | 121.2 (3) |
C6—C7—C8 | 111.5 (4) | O4—C23—C22 | 119.1 (3) |
C6—C7—H7A | 109.3 | O3—C23—C22 | 119.6 (3) |
C8—C7—H7A | 109.3 |
Symmetry codes: (i) x, y, z−1; (ii) −x+1, y−1/2, −z−1/2; (iii) −x+1, −y+1, −z; (iv) −x+1, y+1/2, −z−1/2; (v) x, y, z+1. |
Experimental details
Crystal data | |
Chemical formula | [Cd(C10H8O4)(C13H14N2)] |
Mr | 502.84 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 223 |
a, b, c (Å) | 10.022 (2), 22.316 (5), 10.316 (2) |
β (°) | 116.51 (3) |
V (Å3) | 2064.6 (9) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.09 |
Crystal size (mm) | 0.30 × 0.30 × 0.10 |
Data collection | |
Diffractometer | Rigaku Mercury CCD area-detector diffractometer |
Absorption correction | Multi-scan (REQAB; Jacobson, 1998) |
Tmin, Tmax | 0.736, 0.899 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 11710, 4699, 3702 |
Rint | 0.035 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.047, 0.099, 1.10 |
No. of reflections | 4699 |
No. of parameters | 271 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.60, −0.53 |
Computer programs: CrystalClear (Rigaku, 2001), CrystalStructure (Rigaku/MSC, 2004), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).
The design and construction of coordination polymers based on transition metals and organic spacers are currently attracting considerable attention (Moulton & Zaworotko, 2001; Kitagawa et al., 2004). Flexible ligands such as 1,4-phenylenediacetate (1,4-PDA) and 1,3-bis(pyridin-4-yl)propane (bpp) are usually the typical building elements in coordination networks, since they can adopt varied coordination modes and geometries. For 1,4-PDA, the two carboxyl groups can exhibit various coordination modes. Furthermore, this flexible ligand can adopt either cis or trans conformations (Blake et al., 2010; Lan et al., 2011; Sposato et al., 2010; Yang et al., 2010). The bpp ligand is more flexible than 1,4-PDA due to its –CH2–CH2–CH2– moieties, and it can adopt anti–anti, anti–gauche or gauche–gauche conformations (Carlucci et al., 2000; Hulvey et al., 2010; Mao et al., 1999). To understand further the coordination chemistry of flexible dicarboxylate and dipyridyl ligands, we employed these two ligands to react with CdII ions under solvothermal conditions and obtained the title two-dimensional coordination polymer, [Cd(C10H8O4)(C13H14N2)]n, (I).
As shown in Fig. 1, each CdII ion of (I) has pentagonal–bipyramidal coordination, with five O atoms from three 1,4-PDA ligands occupying the basal sites and two N atoms from two bpp ligands located on the axial positions. The Cd—O bond lengths range from 2.313 (3) to 2.488 (3) Å, and the Cd—N distances are 2.340 (3) and 2.315 (3) Å. Two equivalent CdII ions related by a twofold axis with an interatomic distance of 3.7959 (9) Å are bridged by 1,4-PDA ligands to form a [Cd2(1,4-PDA)2] unit. Adjacent [Cd2(1,4-PDA)2] units are linked via Cd—O bonds to afford a one-dimensional [Cd2(1,4-PDA)2]n chain (Fig. 2). These chains are further interconnected through bridging bpp ligands to generate a rare two-dimensional 6-connected net. The size of each triangular grid in the two-dimensional net is 10.31 × 12.29 × 12.29 Å (Fig. 3). Different from that of the reported complex {[Cu4(1,4-PDA)3(OH)2(bpp)2]2H2O}n (Reference?) constructed from trans-1,4-PDA and anti–anti bpp ligands, the conformations of the 1,4-PDA and bpp ligands in (I) are cis–gauche and anti–gauche, respectively.
The aromatic rings of the organic ligands of (I) are not close. The closest ring–ring contact is between the N1/C1–C5 and N2/C9–C13 rings, at a distance of 3.944 (3) Å.
Considering previously reported coordination polymers constructed from rigid dicarboxylate and dipyridyl ligands, we found that the structures of these complexes are usually two-dimensional (4,4) nets or three-dimensional frameworks. The structural motif of (I) is not only different from the reported rectangular sheets generated by metal ions and mixed ligands (Yang et al., 2010), but also from the reported coordination polymers which are composed of three-dimensional networks (Tao et al., 2000). The reason may be related to the flexibility of the 1,4-PDA ligand, which means the infinite [Cd2(1,4-PDA)2]n units can not form a two-dimensional net. Furthermore, the flexibility of the bpp ligand also plays an important role in determining the final structure. In contrast with rigid dipyridyl ligands such as 4,4'-bipyridine (Liu et al., 2009; Yang et al., 2010), four flexible bpp ligands in (I) form bridges between four [Cd2(1,4-PDA)2] units and a central [Cd2(1,4-PDA)2] unit. These bridges complete links to two [Cd2(1,4-PDA)2] units in the [Cd2(1,4-PDA)2]n chain on one side of the central unit and a further two [Cd2(1,4-PDA)2] units in the chain on the other side of the central unit. Together with the intrachain links, these connections make each [Cd2(1,4-PDA)2] unit a 6-connecting node.
each pair of flexible bpp ligands in (I) can bridge four [Cd2(1,4-PDA)2] units to a central [Cd2(1,4-PDA)2] unit, which makes the [Cd2(1,4-PDA)2] unit a 6-connecting node.
In summary, a new two-dimensional coordination polymer, (I), constructed from flexible dicarboxylate and dipyridyl ligands has been presented. The structure is different from those constructed from mixed rigid ligands or a mixture of both rigid and flexible ligands. Thus, the flexibility of organic ligands plays an important role in constructing coordination networks. This work emphasizes the coordinative flexibility and versatility of mixed ligands and their synthetic utility in coordination chemistry. We are currently extending this study by preparing new ligands of this type with other substituted functional groups. We anticipate this approach to be useful for constructing novel coordination complexes.