Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807047575/rk2042sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807047575/rk2042Isup2.hkl |
CCDC reference: 1259402
A mixture of palladium acetate (1 mmol), pyridine-2,4-dicarboxylic acid (1 mmol), and 2,2-bipyridine (2 mmol) in mixed 1:1 solvent of H2O and ethanol in a 25 ml teflon-lined stainless steel autoclave was kept at 473 K for 10 days. Red crystals were obtained after cooling to room temperature with a yield of 22%. Anal. Calc. for C17H13N3O5Pd: C 45.77, H 2.47, N 9.42%; Found: 45.71, H 2.52, N 9.40%.
The H atoms of the water molecule were located from difference density maps and were refined with distance restraints of d(H···H) = 1.38 (2) Å, d(O–H) = 0.82 (1) Å, and refined freely. All other H atoms were placed in calculated positions with a C–H bond distance of 0.93%A and Uiso(H) = 1.2Ueq(C).
Complexes containing carboxyl acids have been the interest of chemists these years due to their potential applications, such as catalysis, optics, information storage, medicine, molecular electrochemistry, biochemistry and biological pharmaceutics (Li et al. (1993); Go et al. (2004)). Thus far, N-containing aromatic carboxyl acid has been widely used in dye intermediate, organic synthesis, sensitization material, functional pigment, adipiodone and acetrizoic acid (An et al. (2000). Pyridine carboxylic acid is also a good ligand in coordination chemistry due to its strong coordination ability and versatile coordination modes, so much attention has been paid to it in these decades (Baroni et al. (1996); Hundal et al. (2002)). Herein, we report the new complex - poly[(2,2'-bipyridine)palladium(II)(pyridine-2,4-dicarboxylato)acqua].
The title compound contains one palladium cation chelated by one 2,2'-bipyridine ligand and one pyridine-2,4-dicarboxylate ligand, further coordinated by two carboxylate groups belonging to two neighboring independent pyridine-2,4-dicarboxylate ligands (Fig. 1). Pd atom is hexa-coordinated exhibiting octahedron geometry containing three N and three O atoms. Each two neighboring Pd2+-cations are bridged by two independent pyridine-2,4-dicarboxylate ligands, which are further coordinated to the third Pd2+-cation with carboxylate oxygen atom to form corrugated layers parallel to the (1 0 1) plane (Fig. 2).
For related literature, see: An et al. (2000); Baroni et al. (1996); Go et al. (2004); Hundal et al. (2002); Li et al. (1993)
Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2001); software used to prepare material for publication: SHELXTL (Bruker, 2001).
[Pd(C7H3NO4)(C10H8N2)]·H2O | F(000) = 888 |
Mr = 445.72 | Dx = 1.826 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 2958 reflections |
a = 11.8236 (2) Å | θ = 2.6–25.5° |
b = 14.7796 (5) Å | µ = 1.18 mm−1 |
c = 9.9352 (5) Å | T = 293 K |
β = 110.987 (1)° | Block, red |
V = 1620.98 (10) Å3 | 0.43 × 0.28 × 0.22 mm |
Z = 4 |
Bruker APEXII CCD area-detector diffractometer | 2958 independent reflections |
Radiation source: fine-focus sealed tube | 2620 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.060 |
φ and ω scans | θmax = 25.5°, θmin = 2.6° |
Absorption correction: multi-scan (SADABS; Bruker, 2001) | h = −14→14 |
Tmin = 0.631, Tmax = 0.781 | k = −17→17 |
12911 measured reflections | l = −12→12 |
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)] = 0.020 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.046 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.00 | w = 1/[σ2(Fo2) + (0.0184P)2] where P = (Fo2 + 2Fc2)/3 |
2958 reflections | (Δ/σ)max = 0.007 |
241 parameters | Δρmax = 0.36 e Å−3 |
3 restraints | Δρmin = −0.61 e Å−3 |
[Pd(C7H3NO4)(C10H8N2)]·H2O | V = 1620.98 (10) Å3 |
Mr = 445.72 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 11.8236 (2) Å | µ = 1.18 mm−1 |
b = 14.7796 (5) Å | T = 293 K |
c = 9.9352 (5) Å | 0.43 × 0.28 × 0.22 mm |
β = 110.987 (1)° |
Bruker APEXII CCD area-detector diffractometer | 2958 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2001) | 2620 reflections with I > 2σ(I) |
Tmin = 0.631, Tmax = 0.781 | Rint = 0.060 |
12911 measured reflections |
R[F2 > 2σ(F2)] = 0.020 | 3 restraints |
wR(F2) = 0.046 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.00 | Δρmax = 0.36 e Å−3 |
2958 reflections | Δρmin = −0.61 e Å−3 |
241 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 > 2σ(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 | ||
Pd1 | 0.255492 (13) | 0.317737 (9) | 0.101199 (14) | 0.02804 (6) | |
C1 | 0.33154 (16) | 0.11459 (12) | 0.04854 (18) | 0.0294 (4) | |
C2 | 0.40267 (19) | 0.14676 (14) | 0.28598 (19) | 0.0374 (5) | |
H2 | 0.4112 | 0.1862 | 0.3619 | 0.045* | |
C3 | 0.45769 (19) | 0.06187 (13) | 0.3168 (2) | 0.0368 (5) | |
H3 | 0.5044 | 0.0475 | 0.4116 | 0.044* | |
C4 | 0.38032 (17) | 0.02680 (13) | 0.07263 (19) | 0.0321 (4) | |
H4 | 0.3690 | −0.0122 | −0.0046 | 0.039* | |
C5 | 0.44442 (17) | −0.00109 (12) | 0.20991 (19) | 0.0318 (4) | |
C6 | 0.49924 (19) | −0.09614 (14) | 0.2425 (2) | 0.0384 (5) | |
C7 | 0.27151 (17) | 0.15279 (14) | −0.09911 (19) | 0.0309 (4) | |
C8 | 0.0011 (2) | 0.22777 (17) | 0.0816 (2) | 0.0513 (6) | |
H8 | 0.0522 | 0.1895 | 0.1512 | 0.062* | |
C9 | −0.1189 (3) | 0.2124 (2) | 0.0344 (3) | 0.0650 (7) | |
H9 | −0.1508 | 0.1647 | 0.0704 | 0.078* | |
C10 | −0.1918 (3) | 0.2688 (2) | −0.0673 (3) | 0.0691 (8) | |
H10 | −0.2751 | 0.2594 | −0.1030 | 0.083* | |
C11 | −0.1428 (2) | 0.3405 (2) | −0.1186 (3) | 0.0585 (7) | |
H11 | −0.1930 | 0.3796 | −0.1877 | 0.070* | |
C12 | −0.02156 (19) | 0.35290 (15) | −0.06706 (19) | 0.0386 (5) | |
C13 | 0.03749 (19) | 0.42873 (14) | −0.11791 (19) | 0.0375 (5) | |
C14 | −0.0261 (2) | 0.49206 (17) | −0.2185 (2) | 0.0538 (6) | |
H14 | −0.1102 | 0.4888 | −0.2581 | 0.065* | |
C15 | 0.0332 (3) | 0.55996 (18) | −0.2608 (3) | 0.0673 (8) | |
H15 | −0.0099 | 0.6024 | −0.3290 | 0.081* | |
C16 | 0.1545 (3) | 0.56407 (17) | −0.2021 (3) | 0.0643 (7) | |
H16 | 0.1979 | 0.6087 | −0.2287 | 0.077* | |
C17 | 0.2120 (2) | 0.49978 (16) | −0.1013 (2) | 0.0502 (6) | |
H17 | 0.2959 | 0.5028 | −0.0589 | 0.060* | |
N1 | 0.33959 (16) | 0.17305 (10) | 0.15486 (16) | 0.0329 (4) | |
N2 | 0.04991 (17) | 0.29603 (12) | 0.03223 (17) | 0.0394 (4) | |
N3 | 0.15557 (16) | 0.43315 (11) | −0.06002 (17) | 0.0392 (4) | |
O1 | 0.57118 (13) | −0.10790 (10) | 0.36799 (14) | 0.0448 (4) | |
O2 | 0.46972 (18) | −0.15543 (11) | 0.14916 (18) | 0.0658 (5) | |
O3 | 0.23331 (13) | 0.23406 (10) | −0.11209 (13) | 0.0414 (4) | |
O4 | 0.26788 (13) | 0.10078 (9) | −0.19922 (13) | 0.0400 (3) | |
O5 | 0.3824 (2) | 0.7288 (3) | 0.3790 (3) | 0.1309 (11) | |
H1W | 0.406 (5) | 0.693 (3) | 0.447 (4) | 0.196* | |
H2W | 0.437 (3) | 0.749 (4) | 0.354 (5) | 0.196* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Pd1 | 0.02882 (10) | 0.02435 (9) | 0.02583 (9) | 0.00097 (6) | 0.00355 (7) | 0.00026 (5) |
C1 | 0.0268 (10) | 0.0330 (10) | 0.0274 (9) | −0.0022 (8) | 0.0085 (8) | −0.0001 (8) |
C2 | 0.0477 (13) | 0.0372 (11) | 0.0248 (9) | 0.0067 (10) | 0.0100 (9) | −0.0001 (8) |
C3 | 0.0425 (12) | 0.0403 (12) | 0.0263 (9) | 0.0072 (9) | 0.0107 (9) | 0.0061 (8) |
C4 | 0.0321 (10) | 0.0341 (10) | 0.0292 (9) | −0.0002 (8) | 0.0099 (8) | −0.0023 (8) |
C5 | 0.0304 (10) | 0.0327 (10) | 0.0329 (10) | 0.0035 (8) | 0.0118 (9) | 0.0040 (8) |
C6 | 0.0361 (12) | 0.0360 (11) | 0.0424 (12) | 0.0050 (9) | 0.0131 (10) | 0.0020 (9) |
C7 | 0.0279 (10) | 0.0337 (11) | 0.0294 (10) | −0.0060 (8) | 0.0081 (8) | 0.0001 (8) |
C8 | 0.0525 (15) | 0.0548 (15) | 0.0444 (12) | −0.0103 (12) | 0.0147 (12) | 0.0050 (11) |
C9 | 0.0555 (17) | 0.0892 (19) | 0.0515 (15) | −0.0251 (16) | 0.0205 (14) | −0.0021 (14) |
C10 | 0.0431 (15) | 0.110 (2) | 0.0526 (15) | −0.0217 (16) | 0.0156 (13) | −0.0082 (16) |
C11 | 0.0391 (14) | 0.092 (2) | 0.0397 (12) | 0.0044 (13) | 0.0090 (11) | 0.0014 (12) |
C12 | 0.0368 (12) | 0.0492 (12) | 0.0284 (10) | 0.0046 (10) | 0.0099 (9) | −0.0048 (9) |
C13 | 0.0392 (12) | 0.0433 (12) | 0.0280 (9) | 0.0121 (9) | 0.0096 (9) | −0.0008 (8) |
C14 | 0.0501 (14) | 0.0592 (15) | 0.0459 (13) | 0.0177 (12) | 0.0096 (11) | 0.0087 (11) |
C15 | 0.076 (2) | 0.0638 (18) | 0.0600 (16) | 0.0267 (15) | 0.0218 (15) | 0.0285 (14) |
C16 | 0.072 (2) | 0.0581 (16) | 0.0673 (16) | 0.0076 (14) | 0.0310 (15) | 0.0253 (13) |
C17 | 0.0493 (14) | 0.0469 (14) | 0.0575 (13) | 0.0045 (11) | 0.0230 (12) | 0.0138 (11) |
N1 | 0.0384 (10) | 0.0313 (9) | 0.0277 (8) | 0.0023 (7) | 0.0103 (8) | 0.0012 (6) |
N2 | 0.0373 (10) | 0.0458 (10) | 0.0324 (9) | −0.0016 (8) | 0.0091 (8) | −0.0011 (8) |
N3 | 0.0404 (10) | 0.0388 (10) | 0.0373 (9) | 0.0068 (8) | 0.0127 (8) | 0.0054 (7) |
O1 | 0.0462 (9) | 0.0494 (9) | 0.0357 (8) | 0.0193 (7) | 0.0110 (7) | 0.0093 (6) |
O2 | 0.0705 (13) | 0.0407 (9) | 0.0629 (10) | 0.0143 (9) | −0.0043 (9) | −0.0124 (8) |
O3 | 0.0512 (10) | 0.0362 (8) | 0.0293 (7) | 0.0036 (7) | 0.0054 (7) | 0.0043 (6) |
O4 | 0.0466 (9) | 0.0449 (8) | 0.0253 (6) | 0.0012 (7) | 0.0089 (6) | −0.0022 (6) |
O5 | 0.0622 (15) | 0.249 (4) | 0.0731 (16) | −0.003 (2) | 0.0136 (13) | 0.0545 (19) |
Pd1—O1i | 2.2476 (14) | C8—H8 | 0.9300 |
Pd1—O4ii | 2.2793 (13) | C9—C10 | 1.354 (4) |
Pd1—N2 | 2.2995 (18) | C9—H9 | 0.9300 |
Pd1—N1 | 2.3380 (15) | C10—C11 | 1.389 (4) |
Pd1—N3 | 2.3485 (16) | C10—H10 | 0.9300 |
Pd1—O3 | 2.3854 (13) | C11—C12 | 1.351 (3) |
C1—N1 | 1.341 (2) | C11—H11 | 0.9300 |
C1—C4 | 1.405 (3) | C12—N2 | 1.340 (3) |
C1—C7 | 1.493 (2) | C12—C13 | 1.501 (3) |
C2—N1 | 1.307 (2) | C13—N3 | 1.307 (3) |
C2—C3 | 1.396 (3) | C13—C14 | 1.379 (3) |
C2—H2 | 0.9300 | C14—C15 | 1.374 (4) |
C3—C5 | 1.378 (3) | C14—H14 | 0.9300 |
C3—H3 | 0.9300 | C15—C16 | 1.342 (4) |
C4—C5 | 1.365 (3) | C15—H15 | 0.9300 |
C4—H4 | 0.9300 | C16—C17 | 1.371 (3) |
C5—C6 | 1.532 (3) | C16—H16 | 0.9300 |
C6—O2 | 1.232 (2) | C17—N3 | 1.334 (3) |
C6—O1 | 1.244 (2) | C17—H17 | 0.9300 |
C7—O4 | 1.246 (2) | O1—Pd1iii | 2.2476 (14) |
C7—O3 | 1.274 (3) | O4—Pd1iv | 2.2793 (13) |
C8—N2 | 1.340 (3) | O5—H1W | 0.82 (4) |
C8—C9 | 1.344 (4) | O5—H2W | 0.83 (4) |
O1i—Pd1—O4ii | 81.48 (5) | C8—C9—H9 | 121.1 |
O1i—Pd1—N2 | 157.48 (6) | C10—C9—H9 | 121.1 |
O4ii—Pd1—N2 | 93.71 (5) | C9—C10—C11 | 120.4 (3) |
O1i—Pd1—N1 | 97.10 (6) | C9—C10—H10 | 119.8 |
O4ii—Pd1—N1 | 113.28 (5) | C11—C10—H10 | 119.8 |
N2—Pd1—N1 | 104.96 (6) | C12—C11—C10 | 119.3 (2) |
O1i—Pd1—N3 | 87.09 (6) | C12—C11—H11 | 120.4 |
O4ii—Pd1—N3 | 93.98 (5) | C10—C11—H11 | 120.4 |
N2—Pd1—N3 | 71.23 (6) | N2—C12—C11 | 119.9 (2) |
N1—Pd1—N3 | 152.73 (5) | N2—C12—C13 | 118.00 (19) |
O1i—Pd1—O3 | 100.33 (5) | C11—C12—C13 | 122.1 (2) |
O4ii—Pd1—O3 | 177.49 (5) | N3—C13—C14 | 120.3 (2) |
N2—Pd1—O3 | 83.96 (5) | N3—C13—C12 | 116.20 (17) |
N1—Pd1—O3 | 68.34 (5) | C14—C13—C12 | 123.5 (2) |
N3—Pd1—O3 | 84.39 (5) | C15—C14—C13 | 120.8 (2) |
N1—C1—C4 | 123.47 (16) | C15—C14—H14 | 119.6 |
N1—C1—C7 | 113.89 (16) | C13—C14—H14 | 119.6 |
C4—C1—C7 | 122.56 (16) | C16—C15—C14 | 118.9 (2) |
N1—C2—C3 | 122.70 (18) | C16—C15—H15 | 120.5 |
N1—C2—H2 | 118.6 | C14—C15—H15 | 120.5 |
C3—C2—H2 | 118.6 | C15—C16—C17 | 117.3 (2) |
C5—C3—C2 | 121.52 (17) | C15—C16—H16 | 121.4 |
C5—C3—H3 | 119.2 | C17—C16—H16 | 121.4 |
C2—C3—H3 | 119.2 | N3—C17—C16 | 124.4 (2) |
C5—C4—C1 | 119.74 (16) | N3—C17—H17 | 117.8 |
C5—C4—H4 | 120.1 | C16—C17—H17 | 117.8 |
C1—C4—H4 | 120.1 | C2—N1—C1 | 116.59 (16) |
C4—C5—C3 | 115.79 (17) | C2—N1—Pd1 | 122.92 (13) |
C4—C5—C6 | 121.96 (17) | C1—N1—Pd1 | 120.34 (12) |
C3—C5—C6 | 122.25 (16) | C8—N2—C12 | 120.1 (2) |
O2—C6—O1 | 124.2 (2) | C8—N2—Pd1 | 122.97 (15) |
O2—C6—C5 | 120.57 (18) | C12—N2—Pd1 | 116.90 (14) |
O1—C6—C5 | 115.17 (18) | C13—N3—C17 | 118.32 (18) |
O4—C7—O3 | 126.28 (16) | C13—N3—Pd1 | 117.44 (13) |
O4—C7—C1 | 114.81 (17) | C17—N3—Pd1 | 124.14 (15) |
O3—C7—C1 | 118.86 (16) | C6—O1—Pd1iii | 117.87 (13) |
N2—C8—C9 | 122.6 (2) | C7—O3—Pd1 | 118.48 (10) |
N2—C8—H8 | 118.7 | C7—O4—Pd1iv | 109.98 (12) |
C9—C8—H8 | 118.7 | H1W—O5—H2W | 114 (3) |
C8—C9—C10 | 117.8 (3) |
Symmetry codes: (i) −x+1, y+1/2, −z+1/2; (ii) x, −y+1/2, z+1/2; (iii) −x+1, y−1/2, −z+1/2; (iv) x, −y+1/2, z−1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O5—H1W···O2ii | 0.82 (4) | 1.95 (2) | 2.731 (3) | 157 (6) |
Symmetry code: (ii) x, −y+1/2, z+1/2. |
Experimental details
Crystal data | |
Chemical formula | [Pd(C7H3NO4)(C10H8N2)]·H2O |
Mr | 445.72 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 11.8236 (2), 14.7796 (5), 9.9352 (5) |
β (°) | 110.987 (1) |
V (Å3) | 1620.98 (10) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.18 |
Crystal size (mm) | 0.43 × 0.28 × 0.22 |
Data collection | |
Diffractometer | Bruker APEXII CCD area-detector |
Absorption correction | Multi-scan (SADABS; Bruker, 2001) |
Tmin, Tmax | 0.631, 0.781 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 12911, 2958, 2620 |
Rint | 0.060 |
(sin θ/λ)max (Å−1) | 0.606 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.020, 0.046, 1.00 |
No. of reflections | 2958 |
No. of parameters | 241 |
No. of restraints | 3 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.36, −0.61 |
Computer programs: APEX2 (Bruker, 2004), SAINT-Plus (Bruker, 2001), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2001).
D—H···A | D—H | H···A | D···A | D—H···A |
O5—H1W···O2i | 0.82 (4) | 1.95 (2) | 2.731 (3) | 157 (6) |
Symmetry code: (i) x, −y+1/2, z+1/2. |
Complexes containing carboxyl acids have been the interest of chemists these years due to their potential applications, such as catalysis, optics, information storage, medicine, molecular electrochemistry, biochemistry and biological pharmaceutics (Li et al. (1993); Go et al. (2004)). Thus far, N-containing aromatic carboxyl acid has been widely used in dye intermediate, organic synthesis, sensitization material, functional pigment, adipiodone and acetrizoic acid (An et al. (2000). Pyridine carboxylic acid is also a good ligand in coordination chemistry due to its strong coordination ability and versatile coordination modes, so much attention has been paid to it in these decades (Baroni et al. (1996); Hundal et al. (2002)). Herein, we report the new complex - poly[(2,2'-bipyridine)palladium(II)(pyridine-2,4-dicarboxylato)acqua].
The title compound contains one palladium cation chelated by one 2,2'-bipyridine ligand and one pyridine-2,4-dicarboxylate ligand, further coordinated by two carboxylate groups belonging to two neighboring independent pyridine-2,4-dicarboxylate ligands (Fig. 1). Pd atom is hexa-coordinated exhibiting octahedron geometry containing three N and three O atoms. Each two neighboring Pd2+-cations are bridged by two independent pyridine-2,4-dicarboxylate ligands, which are further coordinated to the third Pd2+-cation with carboxylate oxygen atom to form corrugated layers parallel to the (1 0 1) plane (Fig. 2).