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The asymmetric unit of the title compound, {[Pd(C7H3NO4)(C10H8N2)]·H2O}n, contains one palladium cation chelated by one 2,2′-bipyridine ligand and one pyridine-2,4-dicarboxyl­ate ligand, further coordinated by two carboxyl­ate O atoms belonging to two neighbouring independent pyridine-2,4-dicarboxyl­ate ligands. The Pd atom exhibits octa­hedral geometry involving three N and three O atoms. Each pair of neighbouring Pd2+ cations is bridged by two independent pyridine-2,4-dicarboxyl­ate ligands, which are further coordinated to a third Pd2+ cation via a carboxyl­ate O atom to form corrugated layers parallel to the (101) plane.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807047575/rk2042sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807047575/rk2042Isup2.hkl
Contains datablock I

CCDC reference: 1259402

Key indicators

  • Single-crystal X-ray study
  • T = 293 K
  • Mean [sigma](C-C) = 0.003 Å
  • R factor = 0.020
  • wR factor = 0.046
  • Data-to-parameter ratio = 12.3

checkCIF/PLATON results

No syntax errors found



Alert level B PLAT420_ALERT_2_B D-H Without Acceptor O5 - H2W ... ?
Alert level C PLAT062_ALERT_4_C Rescale T(min) & T(max) by ..................... 0.99 PLAT369_ALERT_2_C Long C(sp2)-C(sp2) Bond C5 - C6 ... 1.53 Ang.
Alert level G PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature 293 K PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature . 293 K PLAT794_ALERT_5_G Check Predicted Bond Valency for Pd1 (2) 1.46 PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 3
0 ALERT level A = In general: serious problem 1 ALERT level B = Potentially serious problem 2 ALERT level C = Check and explain 4 ALERT level G = General alerts; check 2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 2 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check

Comment top

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).

Related literature top

For related literature, see: An et al. (2000); Baroni et al. (1996); Go et al. (2004); Hundal et al. (2002); Li et al. (1993)

Experimental top

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%.

Refinement top

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).

Structure description top

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)

Computing details top

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).

Figures top
[Figure 1] Fig. 1. A view of the title compound with the numbering scheme. Displacement ellipsoids are drawn with 30% probability. H atoms are presented as a spheres of arbitrary radius. Symmetry codes: (i) -x + 1, y + 1/2, -z + 1/2; (ii) x, -y + 1/2, z + 1/2.
[Figure 2] Fig. 2. A view of corrugated layers parallel to the (1 0 1) plane.
Poly[aqua(2,2'-bipyridine)(µ3-pyridine-2,4-dicarboxylato)palladium(II)] top
Crystal data top
[Pd(C7H3NO4)(C10H8N2)]·H2OF(000) = 888
Mr = 445.72Dx = 1.826 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 2958 reflections
a = 11.8236 (2) Åθ = 2.6–25.5°
b = 14.7796 (5) ŵ = 1.18 mm1
c = 9.9352 (5) ÅT = 293 K
β = 110.987 (1)°Block, red
V = 1620.98 (10) Å30.43 × 0.28 × 0.22 mm
Z = 4
Data collection top
Bruker APEXII CCD area-detector
diffractometer
2958 independent reflections
Radiation source: fine-focus sealed tube2620 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.060
φ and ω scansθmax = 25.5°, θmin = 2.6°
Absorption correction: multi-scan
(SADABS; Bruker, 2001)
h = 1414
Tmin = 0.631, Tmax = 0.781k = 1717
12911 measured reflectionsl = 1212
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.020Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.046H 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 parametersΔρmax = 0.36 e Å3
3 restraintsΔρmin = 0.61 e Å3
Crystal data top
[Pd(C7H3NO4)(C10H8N2)]·H2OV = 1620.98 (10) Å3
Mr = 445.72Z = 4
Monoclinic, P21/cMo Kα radiation
a = 11.8236 (2) ŵ = 1.18 mm1
b = 14.7796 (5) ÅT = 293 K
c = 9.9352 (5) Å0.43 × 0.28 × 0.22 mm
β = 110.987 (1)°
Data collection top
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 = 0.781Rint = 0.060
12911 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0203 restraints
wR(F2) = 0.046H atoms treated by a mixture of independent and constrained refinement
S = 1.00Δρmax = 0.36 e Å3
2958 reflectionsΔρmin = 0.61 e Å3
241 parameters
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 > 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Pd10.255492 (13)0.317737 (9)0.101199 (14)0.02804 (6)
C10.33154 (16)0.11459 (12)0.04854 (18)0.0294 (4)
C20.40267 (19)0.14676 (14)0.28598 (19)0.0374 (5)
H20.41120.18620.36190.045*
C30.45769 (19)0.06187 (13)0.3168 (2)0.0368 (5)
H30.50440.04750.41160.044*
C40.38032 (17)0.02680 (13)0.07263 (19)0.0321 (4)
H40.36900.01220.00460.039*
C50.44442 (17)0.00109 (12)0.20991 (19)0.0318 (4)
C60.49924 (19)0.09614 (14)0.2425 (2)0.0384 (5)
C70.27151 (17)0.15279 (14)0.09911 (19)0.0309 (4)
C80.0011 (2)0.22777 (17)0.0816 (2)0.0513 (6)
H80.05220.18950.15120.062*
C90.1189 (3)0.2124 (2)0.0344 (3)0.0650 (7)
H90.15080.16470.07040.078*
C100.1918 (3)0.2688 (2)0.0673 (3)0.0691 (8)
H100.27510.25940.10300.083*
C110.1428 (2)0.3405 (2)0.1186 (3)0.0585 (7)
H110.19300.37960.18770.070*
C120.02156 (19)0.35290 (15)0.06706 (19)0.0386 (5)
C130.03749 (19)0.42873 (14)0.11791 (19)0.0375 (5)
C140.0261 (2)0.49206 (17)0.2185 (2)0.0538 (6)
H140.11020.48880.25810.065*
C150.0332 (3)0.55996 (18)0.2608 (3)0.0673 (8)
H150.00990.60240.32900.081*
C160.1545 (3)0.56407 (17)0.2021 (3)0.0643 (7)
H160.19790.60870.22870.077*
C170.2120 (2)0.49978 (16)0.1013 (2)0.0502 (6)
H170.29590.50280.05890.060*
N10.33959 (16)0.17305 (10)0.15486 (16)0.0329 (4)
N20.04991 (17)0.29603 (12)0.03223 (17)0.0394 (4)
N30.15557 (16)0.43315 (11)0.06002 (17)0.0392 (4)
O10.57118 (13)0.10790 (10)0.36799 (14)0.0448 (4)
O20.46972 (18)0.15543 (11)0.14916 (18)0.0658 (5)
O30.23331 (13)0.23406 (10)0.11209 (13)0.0414 (4)
O40.26788 (13)0.10078 (9)0.19922 (13)0.0400 (3)
O50.3824 (2)0.7288 (3)0.3790 (3)0.1309 (11)
H1W0.406 (5)0.693 (3)0.447 (4)0.196*
H2W0.437 (3)0.749 (4)0.354 (5)0.196*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Pd10.02882 (10)0.02435 (9)0.02583 (9)0.00097 (6)0.00355 (7)0.00026 (5)
C10.0268 (10)0.0330 (10)0.0274 (9)0.0022 (8)0.0085 (8)0.0001 (8)
C20.0477 (13)0.0372 (11)0.0248 (9)0.0067 (10)0.0100 (9)0.0001 (8)
C30.0425 (12)0.0403 (12)0.0263 (9)0.0072 (9)0.0107 (9)0.0061 (8)
C40.0321 (10)0.0341 (10)0.0292 (9)0.0002 (8)0.0099 (8)0.0023 (8)
C50.0304 (10)0.0327 (10)0.0329 (10)0.0035 (8)0.0118 (9)0.0040 (8)
C60.0361 (12)0.0360 (11)0.0424 (12)0.0050 (9)0.0131 (10)0.0020 (9)
C70.0279 (10)0.0337 (11)0.0294 (10)0.0060 (8)0.0081 (8)0.0001 (8)
C80.0525 (15)0.0548 (15)0.0444 (12)0.0103 (12)0.0147 (12)0.0050 (11)
C90.0555 (17)0.0892 (19)0.0515 (15)0.0251 (16)0.0205 (14)0.0021 (14)
C100.0431 (15)0.110 (2)0.0526 (15)0.0217 (16)0.0156 (13)0.0082 (16)
C110.0391 (14)0.092 (2)0.0397 (12)0.0044 (13)0.0090 (11)0.0014 (12)
C120.0368 (12)0.0492 (12)0.0284 (10)0.0046 (10)0.0099 (9)0.0048 (9)
C130.0392 (12)0.0433 (12)0.0280 (9)0.0121 (9)0.0096 (9)0.0008 (8)
C140.0501 (14)0.0592 (15)0.0459 (13)0.0177 (12)0.0096 (11)0.0087 (11)
C150.076 (2)0.0638 (18)0.0600 (16)0.0267 (15)0.0218 (15)0.0285 (14)
C160.072 (2)0.0581 (16)0.0673 (16)0.0076 (14)0.0310 (15)0.0253 (13)
C170.0493 (14)0.0469 (14)0.0575 (13)0.0045 (11)0.0230 (12)0.0138 (11)
N10.0384 (10)0.0313 (9)0.0277 (8)0.0023 (7)0.0103 (8)0.0012 (6)
N20.0373 (10)0.0458 (10)0.0324 (9)0.0016 (8)0.0091 (8)0.0011 (8)
N30.0404 (10)0.0388 (10)0.0373 (9)0.0068 (8)0.0127 (8)0.0054 (7)
O10.0462 (9)0.0494 (9)0.0357 (8)0.0193 (7)0.0110 (7)0.0093 (6)
O20.0705 (13)0.0407 (9)0.0629 (10)0.0143 (9)0.0043 (9)0.0124 (8)
O30.0512 (10)0.0362 (8)0.0293 (7)0.0036 (7)0.0054 (7)0.0043 (6)
O40.0466 (9)0.0449 (8)0.0253 (6)0.0012 (7)0.0089 (6)0.0022 (6)
O50.0622 (15)0.249 (4)0.0731 (16)0.003 (2)0.0136 (13)0.0545 (19)
Geometric parameters (Å, º) top
Pd1—O1i2.2476 (14)C8—H80.9300
Pd1—O4ii2.2793 (13)C9—C101.354 (4)
Pd1—N22.2995 (18)C9—H90.9300
Pd1—N12.3380 (15)C10—C111.389 (4)
Pd1—N32.3485 (16)C10—H100.9300
Pd1—O32.3854 (13)C11—C121.351 (3)
C1—N11.341 (2)C11—H110.9300
C1—C41.405 (3)C12—N21.340 (3)
C1—C71.493 (2)C12—C131.501 (3)
C2—N11.307 (2)C13—N31.307 (3)
C2—C31.396 (3)C13—C141.379 (3)
C2—H20.9300C14—C151.374 (4)
C3—C51.378 (3)C14—H140.9300
C3—H30.9300C15—C161.342 (4)
C4—C51.365 (3)C15—H150.9300
C4—H40.9300C16—C171.371 (3)
C5—C61.532 (3)C16—H160.9300
C6—O21.232 (2)C17—N31.334 (3)
C6—O11.244 (2)C17—H170.9300
C7—O41.246 (2)O1—Pd1iii2.2476 (14)
C7—O31.274 (3)O4—Pd1iv2.2793 (13)
C8—N21.340 (3)O5—H1W0.82 (4)
C8—C91.344 (4)O5—H2W0.83 (4)
O1i—Pd1—O4ii81.48 (5)C8—C9—H9121.1
O1i—Pd1—N2157.48 (6)C10—C9—H9121.1
O4ii—Pd1—N293.71 (5)C9—C10—C11120.4 (3)
O1i—Pd1—N197.10 (6)C9—C10—H10119.8
O4ii—Pd1—N1113.28 (5)C11—C10—H10119.8
N2—Pd1—N1104.96 (6)C12—C11—C10119.3 (2)
O1i—Pd1—N387.09 (6)C12—C11—H11120.4
O4ii—Pd1—N393.98 (5)C10—C11—H11120.4
N2—Pd1—N371.23 (6)N2—C12—C11119.9 (2)
N1—Pd1—N3152.73 (5)N2—C12—C13118.00 (19)
O1i—Pd1—O3100.33 (5)C11—C12—C13122.1 (2)
O4ii—Pd1—O3177.49 (5)N3—C13—C14120.3 (2)
N2—Pd1—O383.96 (5)N3—C13—C12116.20 (17)
N1—Pd1—O368.34 (5)C14—C13—C12123.5 (2)
N3—Pd1—O384.39 (5)C15—C14—C13120.8 (2)
N1—C1—C4123.47 (16)C15—C14—H14119.6
N1—C1—C7113.89 (16)C13—C14—H14119.6
C4—C1—C7122.56 (16)C16—C15—C14118.9 (2)
N1—C2—C3122.70 (18)C16—C15—H15120.5
N1—C2—H2118.6C14—C15—H15120.5
C3—C2—H2118.6C15—C16—C17117.3 (2)
C5—C3—C2121.52 (17)C15—C16—H16121.4
C5—C3—H3119.2C17—C16—H16121.4
C2—C3—H3119.2N3—C17—C16124.4 (2)
C5—C4—C1119.74 (16)N3—C17—H17117.8
C5—C4—H4120.1C16—C17—H17117.8
C1—C4—H4120.1C2—N1—C1116.59 (16)
C4—C5—C3115.79 (17)C2—N1—Pd1122.92 (13)
C4—C5—C6121.96 (17)C1—N1—Pd1120.34 (12)
C3—C5—C6122.25 (16)C8—N2—C12120.1 (2)
O2—C6—O1124.2 (2)C8—N2—Pd1122.97 (15)
O2—C6—C5120.57 (18)C12—N2—Pd1116.90 (14)
O1—C6—C5115.17 (18)C13—N3—C17118.32 (18)
O4—C7—O3126.28 (16)C13—N3—Pd1117.44 (13)
O4—C7—C1114.81 (17)C17—N3—Pd1124.14 (15)
O3—C7—C1118.86 (16)C6—O1—Pd1iii117.87 (13)
N2—C8—C9122.6 (2)C7—O3—Pd1118.48 (10)
N2—C8—H8118.7C7—O4—Pd1iv109.98 (12)
C9—C8—H8118.7H1W—O5—H2W114 (3)
C8—C9—C10117.8 (3)
Symmetry codes: (i) x+1, y+1/2, z+1/2; (ii) x, y+1/2, z+1/2; (iii) x+1, y1/2, z+1/2; (iv) x, y+1/2, z1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O5—H1W···O2ii0.82 (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
Mr445.72
Crystal system, space groupMonoclinic, P21/c
Temperature (K)293
a, b, c (Å)11.8236 (2), 14.7796 (5), 9.9352 (5)
β (°) 110.987 (1)
V3)1620.98 (10)
Z4
Radiation typeMo Kα
µ (mm1)1.18
Crystal size (mm)0.43 × 0.28 × 0.22
Data collection
DiffractometerBruker APEXII CCD area-detector
Absorption correctionMulti-scan
(SADABS; Bruker, 2001)
Tmin, Tmax0.631, 0.781
No. of measured, independent and
observed [I > 2σ(I)] reflections
12911, 2958, 2620
Rint0.060
(sin θ/λ)max1)0.606
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.020, 0.046, 1.00
No. of reflections2958
No. of parameters241
No. of restraints3
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.36, 0.61

Computer programs: APEX2 (Bruker, 2004), SAINT-Plus (Bruker, 2001), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2001).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O5—H1W···O2i0.82 (4)1.95 (2)2.731 (3)157 (6)
Symmetry code: (i) x, y+1/2, z+1/2.
 

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