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Acta Cryst. (2007). E63, m2443    [ doi:10.1107/S160053680704202X ]

Poly[[[(2,2'-bipyridine)cadmium(II)]-[mu]3-pyridine-2,4-dicarboxylato] monohydrate]

X.-M. Li, Q.-W. Wang and B. Liu

Abstract top

In the title compound, {[Cd(C7H3NO4)(C10H8N2)]·H2O}n, each CdII atom is octahedrally coordinated by one N,N-bidentate 2,2'-bipyridine (bpy) molecule and three pyridine-2,4-dicarboxylate (pydc2-) dianions (one N,O-bidentate and two O-monodentate). The pydc species serve as bridges in a layered polymeric network. The crystal structure features [pi]-[pi] stacking interactions between the bpy molecules [closest atomic separation = 3.721 (4) Å] and probable O-H...O hydrogen bonds between the solvent water molecule and the uncoordinated carboxylate O atoms of the pydc2- dianions.

Comment top

In the title compound, (I), each CdII atom is six-coordinated in an octahedral geometry (Table 1) by two N atom from the 2,2'-bipyridine (bpy) ligand, and one N atom and three O atoms from three pyridine-2,4-dicarboxylate (pydc2-) dianions (one N,O-bidentate, two O-monodentate) (Fig. 1). The bridging pydc2- species result in a layered, polymeric network propagating in (100). Aromatic π–π interactions between the bpy molecules, with a shortest atom-to-atom distance of 3.721 (4) Å, and probable O—H···O hydrogen bonds (Fig. 2 and Table 2) complete the structure.

For related structures, see: Gu et al. (2004); Wang et al. (2004); Zhang & Chen (2003).

Related literature top

For related literature, see: Gu et al. (2004); Wang et al. (2004); Zhang & Chen (2003).

Experimental top

A mixture of Cd(NO3)2.4H2O (0.150 g, 0.5 mmol), H2pydc (0.167 g, 1.0 mmol), bpy (0.156 g, 1.0 mmol) and H2O (18 ml) in a 30 ml Teflon-lined autoclave were heated under autogenous pressure at 413 K for five days. After cooling to room temperature, colorless blocks of (I) were obtained. Elemental analysis calculated for C17H13N3O5Cd: C 45.2, H 2.9, N 9.3%; found: C 45.0, H 2.8, N 9.2%.

Refinement top

All the C-bound H atoms were generated geometrically (C—H = 0.93 Å) and refined as riding with Uiso(H) = 1.2Ueq(C). The H atoms of the water molecule were located in a difference Fourier map and refined as riding in their as-found relative positions with free refinement of Uiso. The water H-atom positions reported here should be regarded as tentative.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (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: SHELXL97 (Sheldrick, 1997).

Figures top
[Figure 1] Fig. 1. The asymmetric unit of (I), expanded to show the Cd coordination, with displacement ellipsoids drawn at the 30% probability level (arbitrary spheres for the H atoms). Symmetry codes: (i) -x, 1/2 + y, 3/2 - z; (ii) -x, -y, 1 - z.
[Figure 2] Fig. 2. The packing for (I), viewed along the c axis. Dashed lines indicate hydrogen bonds.
Poly[[[(2,2'-bipyridine)cadmium(II)]-µ3-pyridine-2,4-dicarboxylato] monohydrate] top
Crystal data top
[Cd(C7H3NO4)(C10H8N2)]·H2OF(000) = 896
Mr = 451.70Dx = 1.810 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 3238 reflections
a = 12.0969 (6) Åθ = 2.3–26.0°
b = 14.4457 (7) ŵ = 1.35 mm−1
c = 10.1629 (5) ÅT = 292 K
β = 111.045 (1)°Block, colourless
V = 1657.49 (14) Å30.43 × 0.33 × 0.23 mm
Z = 4
Data collection top
Bruker SMART CCD area-detector
diffractometer		3249 independent reflections
Radiation source: fine-focus sealed tube2842 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.060
ω scansθmax = 26.0°, θmin = 2.3°
Absorption correction: multi-scan
(SADABS; Bruker, 2001)		h = −14→14
Tmin = 0.591, Tmax = 0.731k = −17→17
13935 measured reflectionsl = −12→12
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)] = 0.023Hydrogen site location: difmap and geom
wR(F2) = 0.061H atoms treated by a mixture of independent and constrained refinement
S = 1.04 w = 1/[σ2(Fo2) + (0.0309P)2]
where P = (Fo2 + 2Fc2)/3
3249 reflections(Δ/σ)max = 0.001
237 parametersΔρmax = 0.43 e Å−3
0 restraintsΔρmin = −0.72 e Å−3
Crystal data top
[Cd(C7H3NO4)(C10H8N2)]·H2OV = 1657.49 (14) Å3
Mr = 451.70Z = 4
Monoclinic, P21/cMo Kα radiation
a = 12.0969 (6) ŵ = 1.35 mm−1
b = 14.4457 (7) ÅT = 292 K
c = 10.1629 (5) Å0.43 × 0.33 × 0.23 mm
β = 111.045 (1)°
Data collection top
Bruker SMART CCD area-detector
diffractometer		3249 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2001)		2842 reflections with I > 2σ(I)
Tmin = 0.591, Tmax = 0.731Rint = 0.060
13935 measured reflectionsθmax = 26.0°
Refinement top
R[F2 > 2σ(F2)] = 0.023H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.061Δρmax = 0.43 e Å−3
S = 1.04Δρmin = −0.72 e Å−3
3249 reflectionsAbsolute structure: ?
237 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
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 > 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cd10.244494 (14)0.182255 (10)0.898812 (16)0.02916 (8)
C14−0.0973 (2)−0.14669 (16)0.7861 (2)0.0343 (5)
H14A−0.0901−0.18720.85990.041*
C40.5261 (3)0.00825 (19)1.2185 (3)0.0503 (7)
H4A0.60830.01151.25720.060*
C100.4989 (3)0.27229 (19)0.9184 (3)0.0485 (7)
H10A0.44960.31120.84920.058*
O20.07129 (15)0.10789 (11)0.86810 (16)0.0410 (4)
N3−0.16050 (18)−0.17299 (11)0.65473 (19)0.0296 (4)
N20.44967 (18)0.20406 (14)0.9674 (2)0.0361 (4)
N10.34439 (18)0.06681 (13)1.05976 (19)0.0362 (5)
C15−0.16857 (18)−0.11471 (14)0.5488 (2)0.0262 (4)
O1−0.0301 (2)0.15522 (13)0.6491 (2)0.0621 (6)
C90.6189 (3)0.2877 (2)0.9654 (3)0.0604 (8)
H9A0.64980.33590.92860.072*
C50.4627 (2)0.07151 (16)1.1180 (2)0.0338 (5)
C12−0.05572 (19)0.00095 (14)0.7100 (2)0.0286 (5)
C20.3452 (3)−0.0643 (2)1.2019 (3)0.0607 (8)
H2A0.3030−0.10941.22940.073*
C16−0.11956 (19)−0.02688 (15)0.5725 (2)0.0294 (5)
H16A−0.12920.01300.49740.035*
C13−0.0424 (2)−0.06178 (15)0.8165 (2)0.0334 (5)
H13A0.0036−0.04680.90900.040*
C60.5212 (2)0.14681 (17)1.0671 (2)0.0354 (5)
C11−0.0009 (2)0.09652 (16)0.7424 (2)0.0358 (5)
C10.2879 (3)0.00001 (19)1.1009 (3)0.0474 (6)
H1A0.2058−0.00321.05930.057*
C70.6434 (3)0.1597 (2)1.1185 (3)0.0546 (7)
H7A0.69210.12021.18740.066*
C30.4659 (3)−0.0600 (2)1.2609 (3)0.0645 (9)
H3A0.5073−0.10281.32910.077*
C80.6921 (3)0.2310 (3)1.0671 (3)0.0645 (9)
H8A0.77360.24041.10130.077*
O3−0.26657 (15)−0.23395 (12)0.38788 (15)0.0384 (4)
C17−0.22854 (19)−0.15273 (16)0.4008 (2)0.0282 (5)
O4−0.23259 (15)−0.10070 (10)0.30068 (15)0.0363 (4)
O5−0.1177 (3)0.2292 (3)0.3783 (3)0.1224 (12)
H1W−0.10440.19010.43860.088 (15)*
H2W−0.04170.25600.36270.23 (3)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cd10.03122 (11)0.02280 (10)0.02797 (11)0.00096 (6)0.00396 (8)0.00026 (6)
C140.0464 (14)0.0303 (11)0.0239 (11)−0.0063 (11)0.0099 (10)0.0006 (9)
C40.0481 (16)0.0513 (16)0.0446 (15)0.0176 (13)0.0083 (13)0.0086 (12)
C100.0527 (17)0.0474 (16)0.0425 (14)−0.0086 (13)0.0137 (13)0.0044 (12)
O20.0447 (10)0.0408 (10)0.0343 (9)−0.0184 (8)0.0104 (8)−0.0086 (7)
N30.0367 (11)0.0245 (9)0.0250 (9)−0.0024 (8)0.0081 (9)−0.0014 (7)
N20.0361 (11)0.0383 (11)0.0307 (10)−0.0022 (9)0.0079 (9)−0.0018 (9)
N10.0407 (12)0.0317 (11)0.0358 (10)0.0073 (9)0.0131 (9)0.0051 (8)
C150.0253 (11)0.0279 (11)0.0241 (10)0.0024 (9)0.0073 (9)0.0005 (8)
O10.0675 (14)0.0331 (10)0.0621 (13)−0.0128 (10)−0.0054 (11)0.0116 (9)
C90.0538 (19)0.078 (2)0.0511 (17)−0.0243 (17)0.0214 (16)−0.0022 (16)
C50.0372 (13)0.0360 (13)0.0264 (11)0.0118 (10)0.0094 (10)−0.0012 (9)
C120.0287 (11)0.0256 (11)0.0315 (11)−0.0033 (9)0.0110 (10)−0.0045 (9)
C20.071 (2)0.0491 (17)0.0670 (19)0.0080 (15)0.0302 (17)0.0243 (14)
C160.0313 (12)0.0271 (11)0.0291 (11)−0.0004 (9)0.0100 (10)0.0011 (9)
C130.0413 (13)0.0340 (12)0.0233 (10)−0.0068 (10)0.0096 (10)−0.0058 (9)
C60.0350 (13)0.0419 (13)0.0271 (11)0.0042 (11)0.0086 (10)−0.0054 (10)
C110.0358 (13)0.0285 (12)0.0432 (14)−0.0055 (10)0.0143 (11)−0.0033 (10)
C10.0473 (15)0.0411 (15)0.0562 (16)0.0039 (12)0.0217 (13)0.0124 (12)
C70.0381 (15)0.082 (2)0.0386 (15)0.0047 (15)0.0078 (13)0.0008 (14)
C30.077 (2)0.0557 (19)0.0583 (19)0.0268 (16)0.0206 (17)0.0266 (15)
C80.0436 (17)0.099 (3)0.0504 (17)−0.0219 (18)0.0163 (15)−0.0099 (18)
O30.0495 (11)0.0301 (9)0.0281 (8)−0.0037 (7)0.0049 (8)−0.0044 (6)
C170.0250 (11)0.0291 (12)0.0285 (11)0.0052 (9)0.0072 (9)−0.0023 (9)
O40.0456 (10)0.0368 (9)0.0232 (7)−0.0004 (7)0.0084 (7)0.0026 (7)
O50.0634 (18)0.224 (4)0.0726 (18)−0.003 (2)0.0149 (15)0.053 (2)
Geometric parameters (Å, º) top
Cd1—O22.2742 (16)C9—C81.366 (5)
Cd1—N3i2.3030 (17)C9—H9A0.9300
Cd1—O4ii2.3042 (14)C5—C61.488 (3)
Cd1—N12.3446 (18)C12—C131.376 (3)
Cd1—N22.346 (2)C12—C161.391 (3)
Cd1—O3i2.4125 (15)C12—C111.516 (3)
C14—N31.333 (3)C2—C31.366 (4)
C14—C131.376 (3)C2—C11.373 (4)
C14—H14A0.9300C2—H2A0.9300
C4—C51.379 (3)C16—H16A0.9300
C4—C31.384 (4)C13—H13A0.9300
C4—H4A0.9300C6—C71.392 (4)
C10—N21.337 (3)C1—H1A0.9300
C10—C91.374 (4)C7—C81.379 (4)
C10—H10A0.9300C7—H7A0.9300
O2—C111.273 (3)C3—H3A0.9300
N3—C151.342 (3)C8—H8A0.9300
N3—Cd1iii2.3030 (17)O3—C171.250 (3)
N2—C61.353 (3)O3—Cd1iii2.4125 (15)
N1—C11.334 (3)C17—O41.252 (3)
N1—C51.340 (3)O4—Cd1ii2.3042 (14)
C15—C161.384 (3)O5—H1W0.8068
C15—C171.519 (3)O5—H2W1.0603
O1—C111.226 (3)
O2—Cd1—N3i95.16 (7)N1—C5—C4121.0 (2)
O2—Cd1—O4ii82.78 (6)N1—C5—C6116.69 (19)
N3i—Cd1—O4ii111.93 (6)C4—C5—C6122.3 (2)
O2—Cd1—N188.76 (7)C13—C12—C16117.74 (19)
N3i—Cd1—N1152.10 (6)C13—C12—C11120.72 (19)
O4ii—Cd1—N195.96 (6)C16—C12—C11121.54 (19)
O2—Cd1—N2158.22 (7)C3—C2—C1118.0 (3)
N3i—Cd1—N2106.15 (7)C3—C2—H2A121.0
O4ii—Cd1—N293.16 (6)C1—C2—H2A121.0
N1—Cd1—N270.31 (7)C15—C16—C12119.22 (19)
O2—Cd1—O3i99.18 (6)C15—C16—H16A120.4
N3i—Cd1—O3i69.74 (6)C12—C16—H16A120.4
O4ii—Cd1—O3i177.36 (6)C12—C13—C14120.0 (2)
N1—Cd1—O3i82.36 (6)C12—C13—H13A120.0
N2—Cd1—O3i84.37 (6)C14—C13—H13A120.0
N3—C14—C13122.4 (2)N2—C6—C7120.5 (2)
N3—C14—H14A118.8N2—C6—C5116.8 (2)
C13—C14—H14A118.8C7—C6—C5122.7 (2)
C5—C4—C3119.2 (3)O1—C11—O2126.2 (2)
C5—C4—H4A120.4O1—C11—C12118.7 (2)
C3—C4—H4A120.4O2—C11—C12115.1 (2)
N2—C10—C9123.1 (3)N1—C1—C2123.1 (3)
N2—C10—H10A118.4N1—C1—H1A118.5
C9—C10—H10A118.4C2—C1—H1A118.5
C11—O2—Cd1117.70 (14)C8—C7—C6119.9 (3)
C14—N3—C15118.34 (18)C8—C7—H7A120.1
C14—N3—Cd1iii122.74 (14)C6—C7—H7A120.1
C15—N3—Cd1iii118.76 (13)C2—C3—C4119.7 (3)
C10—N2—C6118.6 (2)C2—C3—H3A120.2
C10—N2—Cd1123.63 (17)C4—C3—H3A120.2
C6—N2—Cd1117.67 (16)C9—C8—C7119.1 (3)
C1—N1—C5119.0 (2)C9—C8—H8A120.5
C1—N1—Cd1122.66 (17)C7—C8—H8A120.5
C5—N1—Cd1118.26 (15)C17—O3—Cd1iii117.30 (12)
N3—C15—C16122.14 (18)O3—C17—O4124.93 (19)
N3—C15—C17116.02 (18)O3—C17—C15118.07 (18)
C16—C15—C17121.75 (18)O4—C17—C15117.0 (2)
C8—C9—C10118.9 (3)C17—O4—Cd1ii112.35 (14)
C8—C9—H9A120.6H1W—O5—H2W115.0
C10—C9—H9A120.6
N3i—Cd1—O2—C1173.72 (17)C3—C4—C5—C6−179.9 (2)
O4ii—Cd1—O2—C11−37.78 (17)N3—C15—C16—C122.6 (3)
N1—Cd1—O2—C11−133.95 (17)C17—C15—C16—C12−173.8 (2)
N2—Cd1—O2—C11−118.2 (2)C13—C12—C16—C151.3 (3)
O3i—Cd1—O2—C11144.00 (17)C11—C12—C16—C15−179.5 (2)
C13—C14—N3—C151.2 (3)C16—C12—C13—C14−3.8 (3)
C13—C14—N3—Cd1iii176.65 (18)C11—C12—C13—C14177.0 (2)
C9—C10—N2—C6−0.6 (4)N3—C14—C13—C122.7 (4)
C9—C10—N2—Cd1176.1 (2)C10—N2—C6—C70.8 (3)
O2—Cd1—N2—C10162.49 (18)Cd1—N2—C6—C7−176.09 (18)
N3i—Cd1—N2—C10−29.8 (2)C10—N2—C6—C5−179.7 (2)
O4ii—Cd1—N2—C1084.1 (2)Cd1—N2—C6—C53.5 (3)
N1—Cd1—N2—C10179.3 (2)N1—C5—C6—N20.4 (3)
O3i—Cd1—N2—C10−96.8 (2)C4—C5—C6—N2179.4 (2)
O2—Cd1—N2—C6−20.8 (3)N1—C5—C6—C7180.0 (2)
N3i—Cd1—N2—C6146.84 (16)C4—C5—C6—C7−1.0 (4)
O4ii—Cd1—N2—C6−99.25 (16)Cd1—O2—C11—O1−45.6 (3)
N1—Cd1—N2—C6−4.04 (15)Cd1—O2—C11—C12135.58 (16)
O3i—Cd1—N2—C679.84 (16)C13—C12—C11—O1−168.4 (2)
O2—Cd1—N1—C1−5.54 (19)C16—C12—C11—O112.5 (3)
N3i—Cd1—N1—C193.2 (2)C13—C12—C11—O210.5 (3)
O4ii—Cd1—N1—C1−88.15 (19)C16—C12—C11—O2−168.6 (2)
N2—Cd1—N1—C1−179.4 (2)C5—N1—C1—C20.6 (4)
O3i—Cd1—N1—C193.90 (19)Cd1—N1—C1—C2−175.6 (2)
O2—Cd1—N1—C5178.17 (15)C3—C2—C1—N1−1.1 (4)
N3i—Cd1—N1—C5−83.1 (2)N2—C6—C7—C8−0.3 (4)
O4ii—Cd1—N1—C595.56 (15)C5—C6—C7—C8−179.8 (2)
N2—Cd1—N1—C54.33 (15)C1—C2—C3—C40.4 (5)
O3i—Cd1—N1—C5−82.39 (15)C5—C4—C3—C20.6 (4)
C14—N3—C15—C16−3.9 (3)C10—C9—C8—C70.6 (5)
Cd1iii—N3—C15—C16−179.49 (16)C6—C7—C8—C9−0.4 (5)
C14—N3—C15—C17172.7 (2)Cd1iii—O3—C17—O4179.41 (17)
Cd1iii—N3—C15—C17−2.9 (2)Cd1iii—O3—C17—C151.8 (3)
N2—C10—C9—C8−0.1 (5)N3—C15—C17—O30.6 (3)
C1—N1—C5—C40.4 (3)C16—C15—C17—O3177.2 (2)
Cd1—N1—C5—C4176.85 (18)N3—C15—C17—O4−177.16 (19)
C1—N1—C5—C6179.4 (2)C16—C15—C17—O4−0.5 (3)
Cd1—N1—C5—C6−4.2 (2)O3—C17—O4—Cd1ii−23.7 (3)
C3—C4—C5—N1−1.0 (4)C15—C17—O4—Cd1ii153.94 (14)
Symmetry codes: (i) −x, y+1/2, −z+3/2; (ii) −x, −y, −z+1; (iii) −x, y−1/2, −z+3/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O5—H1W···O10.812.062.783 (4)149
O5—H2W···O2iv1.062.383.308 (4)145
O5—H2W···O1iv1.062.573.333 (4)129
Symmetry code: (iv) x, −y+1/2, z−1/2.
Selected bond lengths (Å) top
Cd1—O22.2742 (16)Cd1—N12.3446 (18)
Cd1—N3i2.3030 (17)Cd1—N22.346 (2)
Cd1—O4ii2.3042 (14)Cd1—O3i2.4125 (15)
Symmetry codes: (i) −x, y+1/2, −z+3/2; (ii) −x, −y, −z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O5—H1W···O10.8072.0632.783 (4)148.48
O5—H2W···O2iii1.0602.3843.308 (4)144.84
O5—H2W···O1iii1.0602.5683.333 (4)128.48
Symmetry code: (iii) x, −y+1/2, z−1/2.
Acknowledgements top

The authors thank Professor Ning-Hai Hu and [Title?] Heng-Qing Jia of Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, for supporting this work.

references
References top

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