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Acta Cryst. (2007). E63, m2079    [ doi:10.1107/S1600536807032035 ]

catena-Poly[[diaqua(2,2'-bipyridine-[kappa]2N,N')cadmium(II)]-[mu]-phthalato-[kappa]2O:O']

X.-Y. Wang, C.-C. Dong, X.-T. Deng, C.-G. Wang and B. Hu

Abstract top

In the title compound, [Cd(C8H4O4)(C10H8N2)(H2O)2]n, the Cd atom has a distorted trigonal-prismatic coordination geometry, bonded to two N atoms from the 2,2'-bipyridine ligand, two water O atoms and two O atoms from two different phthalate ligands, thereby producing a linear coordination polymer. The crystal structure is stabilized by [pi]-[pi] interactions [centroid-to-centroid distance = 3.766 (3) Å] and hydrogen bonds.

Comment top

The phthalate ligand was successfully used to design and synthesize a wide variety of metal complexes, those containing Cd(II) complexes are less considered (Sun et al., 2005). Several structures of Cd(II) complexes with phth have been reported, for example, [Cd(phth)2(4,4'-bpy)]n (4,4'-bpy = 4,4'-bipyridine; Wang et al., 2005), [Cd(4,4'-bpy)(phth)(H2O)]n × 2H2O (Suresh et al., 2001). These structures were found to be two-dimensional or three-dimensional coordination polymers with the phth and 4,4'-bpy ligands serving as bridging units. In contrast [Cd2(phen)4(phth)2]

× 4H2O (phen = 1,10-phenanthroline; Sun et al., 2005) is a binuclear complex. There have been no reports of one-dimensional Cd-bipy complexes in which phth ligands act as bridging ligands. The molecular structure of title compound is shown in Fig.1. The Cd II cation is in a distorted trigonal prismatic Cd N2O4 geometry coordinated by two N atomes of the bipy ligand and four O atoms of two bridging phth ligands and two coordinated water molecules. π-π stacking is observed between neighbouring parallel pyridine rings along 001 direction as shown in Fig.2. The distance between centroids is 3.766 (3) Å for N1 and N2i-containing rings [symmetry code: (i) –X, –Y, 1-Z]. These interactions together with hydrogen bonds stabilize the crystal structure.

Related literature top

For related literature, see: Sun et al. (2005); Suresh et al. (2001); Wang et al. (2005).

Experimental top

A mixture of Cd(CH3COO)2 × 2(H2O) (1 mmol, 0.266 g), phthalic acid (1 mmol, 0.168 g), bipy (2 mmol, 0.312 g) and H2O (10 ml) was heated in a 23 ml stainless steel reactor with a teflon liner at 453 K for 72 h. Colorless block-shaped crystals of the title complex were obtained.

Refinement top

H atoms bonded to O atoms were located in difference maps and then included in the refinement with restraints for bond-length of O–H = 0.82 (2) Å and Uiso(H) = 1.5Ueq(O). H atoms bonded to C atoms were placed in calculated positions and included in the riding- model approximation, with C–H = 0.93 Å and U iso(H) = 1.2U eq (C of aromatic).

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Bruker, 2000); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), with displacement ellipsoids drawn at the 50% probability level. The H atoms have been omitted for clarity [symmety code:(b) x + 1, y, z].
[Figure 2] Fig. 2. The molecular structure of compound (I), showing the formation of π-π stacking. Packing diagram of one-dimensional chains structure along 001 direction.
catena-Poly[[diaqua(2,2'-bipyridine-κ2N,N')cadmium(II)]- µ-phthalato-κ2O:O'] top
Crystal data top
[Cd(C8H4O4)(C10H8N2)(H2O)2]Z = 2
Mr = 468.73F(000) = 468
Triclinic, P1Dx = 1.807 Mg m−3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 7.1268 (5) ÅCell parameters from 4016 reflections
b = 10.0900 (8) Åθ = 2.6–28.3°
c = 12.2110 (9) ŵ = 1.31 mm−1
α = 92.676 (1)°T = 293 K
β = 100.809 (1)°Block, colorless
γ = 90.382 (1)°0.40 × 0.32 × 0.22 mm
V = 861.5 (1) Å3
Data collection top
Bruker SMART CCD area-detector
diffractometer		3237 independent reflections
Radiation source: fine-focus sealed tube2993 reflections with I > 2σ(I)
graphiteRint = 0.053
φ and ω scansθmax = 25.8°, θmin = 1.7°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2001)		h = −7→8
Tmin = 0.623, Tmax = 0.972k = −12→9
5178 measured reflectionsl = −14→14
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)] = 0.034Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.106H atoms treated by a mixture of independent and constrained refinement
S = 1.17 w = 1/[σ2(Fo2) + (0.0547P)2 + 0.8703P]
where P = (Fo2 + 2Fc2)/3
3237 reflections(Δ/σ)max < 0.001
256 parametersΔρmax = 0.77 e Å−3
6 restraintsΔρmin = −1.11 e Å−3
Crystal data top
[Cd(C8H4O4)(C10H8N2)(H2O)2]γ = 90.382 (1)°
Mr = 468.73V = 861.5 (1) Å3
Triclinic, P1Z = 2
a = 7.1268 (5) ÅMo Kα radiation
b = 10.0900 (8) ŵ = 1.31 mm−1
c = 12.2110 (9) ÅT = 293 K
α = 92.676 (1)°0.40 × 0.32 × 0.22 mm
β = 100.809 (1)°
Data collection top
Bruker SMART CCD area-detector
diffractometer		3237 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2001)		2993 reflections with I > 2σ(I)
Tmin = 0.623, Tmax = 0.972Rint = 0.053
5178 measured reflectionsθmax = 25.8°
Refinement top
R[F2 > 2σ(F2)] = 0.034H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.106Δρmax = 0.77 e Å−3
S = 1.17Δρmin = −1.11 e Å−3
3237 reflectionsAbsolute structure: ?
256 parametersFlack parameter: ?
6 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
Cd20.17038 (4)0.02430 (3)0.23625 (2)0.02881 (13)
N10.1757 (5)−0.1635 (4)0.3463 (3)0.0335 (8)
N20.2500 (5)0.0849 (4)0.4289 (3)0.0358 (8)
O1−0.0341 (4)0.1911 (3)0.2320 (3)0.0367 (7)
O1W0.3260 (5)−0.1045 (3)0.1228 (3)0.0368 (7)
O2W−0.1092 (5)−0.0851 (3)0.1248 (3)0.0378 (7)
C1−0.0826 (6)0.2393 (4)0.1376 (4)0.0318 (9)
C2−0.2245 (6)0.3485 (4)0.1321 (3)0.0272 (8)
C3−0.1681 (7)0.4770 (4)0.1130 (4)0.0371 (10)
H3−0.04720.49190.09730.045*
C4−0.2906 (8)0.5825 (5)0.1172 (4)0.0511 (13)
H4−0.25240.66740.10320.061*
C5−0.4691 (8)0.5617 (5)0.1420 (4)0.0480 (12)
H5−0.54980.63300.14620.058*
C6−0.5291 (7)0.4355 (5)0.1608 (4)0.0388 (10)
H6−0.64950.42190.17770.047*
C7−0.4064 (6)0.3275 (4)0.1542 (3)0.0300 (8)
C8−0.4824 (6)0.1897 (4)0.1651 (3)0.0290 (8)
C90.1466 (7)−0.2885 (5)0.3006 (4)0.0436 (11)
H90.1229−0.30070.22320.052*
C100.1505 (8)−0.3987 (5)0.3640 (5)0.0520 (13)
H100.1322−0.48350.33010.062*
C110.1822 (9)−0.3802 (5)0.4781 (5)0.0537 (13)
H110.1841−0.45250.52290.064*
C120.2110 (8)−0.2535 (5)0.5255 (4)0.0462 (11)
H120.2329−0.23970.60270.055*
C130.2073 (6)−0.1463 (4)0.4578 (3)0.0321 (9)
C140.2451 (6)−0.0068 (4)0.5035 (3)0.0314 (9)
C150.2745 (7)0.0255 (5)0.6174 (4)0.0392 (10)
H150.2672−0.03940.66810.047*
C160.3146 (7)0.1553 (5)0.6536 (4)0.0440 (11)
H160.33620.17900.72950.053*
C170.3227 (7)0.2497 (5)0.5776 (4)0.0436 (11)
H170.35080.33800.60070.052*
C180.2879 (7)0.2104 (5)0.4658 (4)0.0423 (11)
H180.29110.27440.41380.051*
O2−0.0222 (5)0.2038 (4)0.0518 (3)0.0463 (8)
O3−0.6024 (5)0.1793 (3)0.2278 (3)0.0413 (7)
O4−0.4241 (4)0.0953 (3)0.1102 (3)0.0391 (7)
H1WA0.399 (7)−0.051 (5)0.104 (4)0.059*
H2WA−0.191 (6)−0.029 (4)0.118 (4)0.059*
H2WB−0.097 (8)−0.110 (5)0.062 (2)0.059*
H1WB0.257 (7)−0.134 (5)0.065 (3)0.059*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cd20.02976 (19)0.03001 (19)0.02768 (19)0.00116 (12)0.00831 (12)0.00022 (12)
N10.0322 (18)0.036 (2)0.0335 (19)0.0057 (15)0.0087 (15)−0.0001 (15)
N20.042 (2)0.036 (2)0.0293 (18)−0.0033 (16)0.0057 (15)0.0006 (15)
O10.0343 (16)0.0360 (17)0.0393 (17)0.0116 (13)0.0054 (13)0.0012 (13)
O1W0.0405 (18)0.0376 (17)0.0347 (16)0.0052 (14)0.0138 (14)−0.0025 (13)
O2W0.0354 (17)0.0392 (18)0.0403 (17)0.0083 (13)0.0114 (14)−0.0014 (14)
C10.029 (2)0.032 (2)0.034 (2)−0.0082 (17)0.0063 (17)−0.0033 (17)
C20.031 (2)0.027 (2)0.0227 (18)−0.0014 (16)0.0054 (15)−0.0027 (15)
C30.039 (2)0.034 (2)0.037 (2)−0.0018 (18)0.0064 (19)0.0031 (18)
C40.071 (4)0.029 (2)0.050 (3)−0.009 (2)0.004 (3)0.005 (2)
C50.054 (3)0.032 (2)0.056 (3)0.015 (2)0.007 (2)−0.002 (2)
C60.034 (2)0.039 (2)0.043 (3)0.0064 (19)0.0091 (19)−0.0056 (19)
C70.032 (2)0.030 (2)0.028 (2)0.0008 (17)0.0066 (16)−0.0004 (16)
C80.0262 (19)0.030 (2)0.030 (2)−0.0011 (16)0.0053 (16)0.0014 (16)
C90.050 (3)0.037 (3)0.044 (3)0.002 (2)0.010 (2)−0.002 (2)
C100.056 (3)0.032 (3)0.069 (4)0.003 (2)0.015 (3)0.000 (2)
C110.071 (4)0.036 (3)0.055 (3)−0.003 (2)0.010 (3)0.012 (2)
C120.055 (3)0.044 (3)0.040 (3)0.000 (2)0.006 (2)0.011 (2)
C130.027 (2)0.037 (2)0.032 (2)0.0065 (17)0.0055 (16)0.0013 (17)
C140.0217 (18)0.038 (2)0.035 (2)0.0072 (16)0.0071 (16)0.0049 (18)
C150.044 (3)0.044 (3)0.030 (2)0.010 (2)0.0092 (19)0.0020 (19)
C160.044 (3)0.051 (3)0.034 (2)0.005 (2)0.002 (2)−0.005 (2)
C170.050 (3)0.038 (3)0.040 (3)−0.007 (2)0.004 (2)−0.009 (2)
C180.050 (3)0.037 (2)0.041 (3)−0.004 (2)0.010 (2)0.0032 (19)
O20.0446 (19)0.052 (2)0.0456 (19)−0.0010 (16)0.0219 (16)−0.0116 (16)
O30.0431 (18)0.0395 (18)0.0457 (18)−0.0065 (14)0.0213 (15)−0.0042 (14)
O40.0381 (17)0.0321 (16)0.0505 (19)−0.0041 (13)0.0194 (15)−0.0047 (14)
Geometric parameters (Å, °) top
Cd2—O12.229 (3)C5—H50.9300
Cd2—O3i2.264 (3)C6—C71.410 (6)
Cd2—O1W2.295 (3)C6—H60.9300
Cd2—N22.364 (4)C7—C81.510 (6)
Cd2—N12.370 (4)C8—O41.256 (5)
Cd2—O2W2.419 (3)C8—O31.257 (5)
N1—C131.341 (6)C9—C101.382 (7)
N1—C91.353 (6)C9—H90.9300
N2—C181.333 (6)C10—C111.373 (8)
N2—C141.334 (5)C10—H100.9300
O1—C11.262 (5)C11—C121.376 (7)
O1W—H1WA0.817 (19)C11—H110.9300
O1W—H1WB0.821 (19)C12—C131.389 (6)
O2W—H2WA0.807 (19)C12—H120.9300
O2W—H2WB0.821 (19)C13—C141.494 (6)
C1—O21.243 (5)C14—C151.390 (6)
C1—C21.496 (6)C15—C161.373 (7)
C2—C71.389 (6)C15—H150.9300
C2—C31.398 (6)C16—C171.369 (7)
C3—C41.386 (7)C16—H160.9300
C3—H30.9300C17—C181.380 (7)
C4—C51.379 (8)C17—H170.9300
C4—H40.9300C18—H180.9300
C5—C61.383 (7)O3—Cd2ii2.264 (3)
O1—Cd2—O3i86.89 (12)C6—C5—H5119.7
O1—Cd2—O1W141.77 (11)C5—C6—C7119.5 (4)
O3i—Cd2—O1W85.07 (11)C5—C6—H6120.2
O1—Cd2—N284.07 (12)C7—C6—H6120.2
O3i—Cd2—N281.96 (12)C2—C7—C6120.1 (4)
O1W—Cd2—N2131.33 (12)C2—C7—C8121.6 (4)
O1—Cd2—N1125.60 (12)C6—C7—C8118.2 (4)
O3i—Cd2—N1131.22 (12)O4—C8—O3125.2 (4)
O1W—Cd2—N186.34 (12)O4—C8—C7118.2 (4)
N2—Cd2—N168.64 (12)O3—C8—C7116.6 (4)
O1—Cd2—O2W81.03 (11)N1—C9—C10122.8 (5)
O3i—Cd2—O2W141.92 (12)N1—C9—H9118.6
O1W—Cd2—O2W82.64 (11)C10—C9—H9118.6
N2—Cd2—O2W131.78 (12)C11—C10—C9118.5 (5)
N1—Cd2—O2W83.77 (12)C11—C10—H10120.8
C13—N1—C9118.3 (4)C9—C10—H10120.8
C13—N1—Cd2119.3 (3)C10—C11—C12119.2 (5)
C9—N1—Cd2122.3 (3)C10—C11—H11120.4
C18—N2—C14118.4 (4)C12—C11—H11120.4
C18—N2—Cd2121.9 (3)C11—C12—C13119.9 (5)
C14—N2—Cd2119.6 (3)C11—C12—H12120.0
C1—O1—Cd2114.5 (3)C13—C12—H12120.0
Cd2—O1W—H1WA102 (4)N1—C13—C12121.3 (4)
Cd2—O1W—H1WB114 (4)N1—C13—C14115.9 (4)
H1WA—O1W—H1WB107 (3)C12—C13—C14122.8 (4)
Cd2—O2W—H2WA105 (4)N2—C14—C15121.9 (4)
Cd2—O2W—H2WB115 (4)N2—C14—C13116.2 (4)
H2WA—O2W—H2WB107 (3)C15—C14—C13121.9 (4)
O2—C1—O1125.5 (4)C16—C15—C14118.7 (4)
O2—C1—C2119.2 (4)C16—C15—H15120.6
O1—C1—C2115.3 (4)C14—C15—H15120.6
C7—C2—C3119.0 (4)C17—C16—C15119.8 (4)
C7—C2—C1121.5 (4)C17—C16—H16120.1
C3—C2—C1119.2 (4)C15—C16—H16120.1
C4—C3—C2120.7 (4)C16—C17—C18118.1 (4)
C4—C3—H3119.7C16—C17—H17120.9
C2—C3—H3119.7C18—C17—H17120.9
C5—C4—C3120.0 (4)N2—C18—C17123.1 (4)
C5—C4—H4120.0N2—C18—H18118.5
C3—C4—H4120.0C17—C18—H18118.5
C4—C5—C6120.6 (4)C8—O3—Cd2ii132.5 (3)
C4—C5—H5119.7
O1—Cd2—N1—C13−61.5 (3)C1—C2—C7—C6172.8 (4)
O3i—Cd2—N1—C1361.1 (4)C3—C2—C7—C8174.3 (4)
O1W—Cd2—N1—C13141.3 (3)C1—C2—C7—C8−10.7 (6)
N2—Cd2—N1—C133.9 (3)C5—C6—C7—C21.9 (7)
O2W—Cd2—N1—C13−135.7 (3)C5—C6—C7—C8−174.7 (4)
O1—Cd2—N1—C9118.0 (3)C2—C7—C8—O4−30.1 (6)
O3i—Cd2—N1—C9−119.4 (3)C6—C7—C8—O4146.4 (4)
O1W—Cd2—N1—C9−39.2 (3)C2—C7—C8—O3150.9 (4)
N2—Cd2—N1—C9−176.6 (4)C6—C7—C8—O3−32.5 (6)
O2W—Cd2—N1—C943.8 (3)C13—N1—C9—C10−0.9 (7)
O1—Cd2—N2—C18−48.8 (4)Cd2—N1—C9—C10179.6 (4)
O3i—Cd2—N2—C1838.9 (4)N1—C9—C10—C111.1 (8)
O1W—Cd2—N2—C18115.0 (4)C9—C10—C11—C12−0.8 (9)
N1—Cd2—N2—C18179.2 (4)C10—C11—C12—C130.2 (8)
O2W—Cd2—N2—C18−121.1 (4)C9—N1—C13—C120.2 (6)
O1—Cd2—N2—C14126.7 (3)Cd2—N1—C13—C12179.8 (3)
O3i—Cd2—N2—C14−145.6 (3)C9—N1—C13—C14178.0 (4)
O1W—Cd2—N2—C14−69.5 (4)Cd2—N1—C13—C14−2.5 (5)
N1—Cd2—N2—C14−5.3 (3)C11—C12—C13—N10.1 (7)
O2W—Cd2—N2—C1454.4 (4)C11—C12—C13—C14−177.5 (5)
O3i—Cd2—O1—C174.7 (3)C18—N2—C14—C151.3 (6)
O1W—Cd2—O1—C1−3.3 (4)Cd2—N2—C14—C15−174.4 (3)
N2—Cd2—O1—C1157.0 (3)C18—N2—C14—C13−178.4 (4)
N1—Cd2—O1—C1−144.7 (3)Cd2—N2—C14—C136.0 (5)
O2W—Cd2—O1—C1−69.0 (3)N1—C13—C14—N2−2.3 (5)
Cd2—O1—C1—O2−2.1 (5)C12—C13—C14—N2175.5 (4)
Cd2—O1—C1—C2178.2 (2)N1—C13—C14—C15178.1 (4)
O2—C1—C2—C7118.2 (4)C12—C13—C14—C15−4.2 (6)
O1—C1—C2—C7−62.0 (5)N2—C14—C15—C16−1.7 (7)
O2—C1—C2—C3−66.8 (5)C13—C14—C15—C16177.9 (4)
O1—C1—C2—C3112.9 (4)C14—C15—C16—C170.7 (7)
C7—C2—C3—C40.8 (6)C15—C16—C17—C180.6 (8)
C1—C2—C3—C4−174.3 (4)C14—N2—C18—C170.1 (7)
C2—C3—C4—C51.0 (7)Cd2—N2—C18—C17175.7 (4)
C3—C4—C5—C6−1.3 (8)C16—C17—C18—N2−1.1 (8)
C4—C5—C6—C7−0.1 (8)O4—C8—O3—Cd2ii−21.6 (7)
C3—C2—C7—C6−2.2 (6)C7—C8—O3—Cd2ii157.3 (3)
Symmetry codes: (i) x+1, y, z; (ii) x−1, y, z.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1W—H1WA···O4i0.82 (2)1.92 (2)2.709 (4)161 (5)
O2W—H2WA···O40.81 (2)2.08 (2)2.884 (4)172 (6)
O2W—H2WB···O2iii0.82 (2)1.97 (2)2.738 (4)156 (5)
O1W—H1WB···O2iii0.82 (2)2.08 (2)2.877 (5)164 (5)
Symmetry codes: (i) x+1, y, z; (iii) −x, −y, −z.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1W—H1WA···O4i0.82 (2)1.92 (2)2.709 (4)161 (5)
O2W—H2WA···O40.81 (2)2.08 (2)2.884 (4)172 (6)
O2W—H2WB···O2ii0.82 (2)1.97 (2)2.738 (4)156 (5)
O1W—H1WB···O2ii0.82 (2)2.08 (2)2.877 (5)164 (5)
Symmetry codes: (i) x+1, y, z; (ii) −x, −y, −z.
Acknowledgements top

This work is supported by the Hubei Key Laboratory of Novel Chemical Reactor and Green Chemical Technology (No. RCT2004011).

references
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