PMCCPMCCPMCC

Search tips
Search criteria 

Advanced

 
Logo of actaeInternational Union of Crystallographysearchopen accessarticle submissionjournal home pagethis article
 
Acta Crystallogr Sect E Struct Rep Online. 2010 January 1; 66(Pt 1): m35.
Published online 2009 December 9. doi:  10.1107/S1600536809052015
PMCID: PMC2980082

catena-Poly[[[triaqua­cadmium(II)]-μ-2,2′-[oxalylbis(azanediyl)]diacetato-κ2 O,O′] dihydrate]

Abstract

The structure of the polymeric title complex, {[Cd(C6H6N2O6)(H2O)3]·2H2O}n, consists of chains running parallel to [An external file that holds a picture, illustration, etc.
Object name is e-66-00m35-efi3.jpg01] in which the oxamidato ligand, deprotonated only at the carboxyl­ate groups, acts as a bridging bis-monodentate ligand. The Cd atom and the O atom of a coordinated water mol­ecule are located on a twofold axis. The coordination geometry around the Cd atom is distorted trigonal-pyramidal. In the crystal structure, neighbouring chains are linked into a three-dimensional network by inter­chain O—H(...)O and N—H(...)O hydrogen bonds.

Related literature

For the crystal structure of the corresponding copper(II) compound, see: Lloret et al. (1992 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-00m35-scheme1.jpg

Experimental

Crystal data

  • [Cd(C6H6N2O6)(H2O)3]·2H2O
  • M r = 404.61
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-00m35-efi4.jpg
  • a = 7.0898 (14) Å
  • b = 8.0306 (16) Å
  • c = 23.396 (5) Å
  • β = 92.06 (3)°
  • V = 1331.2 (5) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 1.70 mm−1
  • T = 293 K
  • 0.23 × 0.18 × 0.15 mm

Data collection

  • Bruker SMART CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996 [triangle]) T min = 0.696, T max = 0.785
  • 3445 measured reflections
  • 1214 independent reflections
  • 1171 reflections with I > 2σ(I)
  • R int = 0.038

Refinement

  • R[F 2 > 2σ(F 2)] = 0.023
  • wR(F 2) = 0.058
  • S = 1.07
  • 1214 reflections
  • 93 parameters
  • H-atom parameters constrained
  • Δρmax = 0.50 e Å−3
  • Δρmin = −0.53 e Å−3

Data collection: SMART (Bruker, 1998 [triangle]); cell refinement: SAINT (Bruker, 1998 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809052015/rz2395sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809052015/rz2395Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

The financial support of the Science Foundation of Shandong is gratefully acknowledged.

supplementary crystallographic information

Comment

N-Substituted and N,N'-disubstituted oxamides have played an important role in the design of new polymetallic systems. The versatility of these ligands is based on the wide variety of substituted derivatives which can be synthesized, yielding different numbers of chelate rings with different donor atoms, and on their easy cis-trans conformational change affording symmetric and asymmetric oxamidato bridges. A new polymeric cadmium(II) complex bridged by a symmetrical oxamide-N,N'-diacetic acid ligand has been synthesized and its crystal structure is reported herein.

The title compound (Fig. 1) is a polymeric cadmium(II) complex forming one-dimensional chains parallel to [1 0 1]. The Cd and the oxygen atom of a coordinated water molecules are located on a two-fold axis and the midpoint of the oxamide C—C bond on an inversion centre. The ligand is deprotonated only at the terminal carboxylate groups and acts as a bis-monodentate bridge. The coordination geometry around the Cd atom is distorted trigonal pyramidal, with atoms O5, O1 and O1i [symmetry code: (i) 1-x, y, 1/2-z] at the equatorial plane and atoms O4 and O4i at the apical positions [O4—Co1—O4i = 178.29 (8)°]. The sum of the O—Cd—O angles within the equatorial plane is 359.99 (9)°. The structure is similar to that previously reported for the copper(II) complex (Lloret et al., 1992). The cadmium-cadmium separation within the chain 12.369 (4) Å. Strong interchain N—H···O and O—H···O hydrogen bonds (Table 1) result in the formation of a three-dimensional network (Fig. 2).

Experimental

To a stirred methanol solution (10 ml) containing Cd(NO3)2.3H2O (0.0581 g, 0.2 mmol) was added dropwise a methanol solution (10 ml) of oxamide-N,N'-diacetic acid (0.0408 g, 0.2 mmol) and piperidine. The mixture was stirred quickly at 323 K for 5 h. The resulting solution at pH = 3 was filtered and the filtrate was kept at room temperature. Green crystals suitable for X-ray analysis were obtained from the filtrate by slow evaporation for 3 days (yield: 65%) Analysis, calculated for C6H16N2O11Cd: C 17.81, H 3.99; N 6.92%; found: C 17.89, H 3.97, N, 6.96%.

Refinement

Water H atoms were located in a difference Fourier map and isotropically refined with Uiso(H) = 0.08 Å2. All other H atoms were positioned geometrically and constrained to ride on their parent atoms, with C—H = 0.97 Å, N—H = 0.86 Å, and with Uiso(H) = 1.2Ueq(C, N).

Figures

Fig. 1.
The polymeric structure of the title compound, with displacement ellipsoids drawn at the 30% probability level. Lattice water molecules generated by symmetry are omitted. [Symmetry codes: (A) 3/2-x, 1/2-y, -z; (B) 1-x, y, 1/2-z; (C) 1/2+x, 1/2-y, -1/2+z]. ...
Fig. 2.
Packing diagram of the title compound viewed along the a axis. Interchain H bonds are shown as dashed lines.

Crystal data

[Cd(C6H6N2O6)(H2O)3]·2H2OF(000) = 808
Mr = 404.61Dx = 2.019 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 3445 reflections
a = 7.0898 (14) Åθ = 3.5–25.2°
b = 8.0306 (16) ŵ = 1.70 mm1
c = 23.396 (5) ÅT = 293 K
β = 92.06 (3)°Block, green
V = 1331.2 (5) Å30.23 × 0.18 × 0.15 mm
Z = 4

Data collection

Bruker SMART CCD diffractometer1214 independent reflections
Radiation source: fine-focus sealed tube1171 reflections with I > 2σ(I)
graphiteRint = 0.038
[var phi] and ω scansθmax = 25.2°, θmin = 3.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)h = −7→8
Tmin = 0.696, Tmax = 0.785k = −9→9
3445 measured reflectionsl = −25→28

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.023H-atom parameters constrained
wR(F2) = 0.058w = 1/[σ2(Fo2) + (0.032P)2 + 1.2127P] where P = (Fo2 + 2Fc2)/3
S = 1.07(Δ/σ)max < 0.001
1214 reflectionsΔρmax = 0.50 e Å3
93 parametersΔρmin = −0.53 e Å3
0 restraintsExtinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0057 (5)

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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)

xyzUiso*/Ueq
C10.6801 (3)0.3969 (3)0.15103 (10)0.0264 (5)
C20.7678 (4)0.4894 (3)0.10180 (11)0.0300 (6)
H1A0.67640.56810.08590.036*
H1B0.87560.55250.11660.036*
C30.7039 (4)0.3045 (3)0.02244 (11)0.0272 (6)
N10.8284 (3)0.3821 (3)0.05672 (9)0.0308 (5)
H10.94700.36800.05190.037*
O10.5996 (2)0.4896 (2)0.18701 (8)0.0328 (4)
O20.6869 (3)0.2444 (3)0.15559 (9)0.0407 (5)
O30.5325 (3)0.3144 (2)0.02483 (9)0.0377 (5)
O40.2191 (3)0.3021 (2)0.19554 (8)0.0304 (4)
H4W10.17040.20200.18970.080*
H4W20.23970.34930.16080.080*
O50.50000.0250 (3)0.25000.0437 (7)
H5W0.5695−0.03410.23050.080*
O60.2377 (2)0.4466 (2)0.09015 (8)0.0362 (4)
H6W10.33810.41290.07260.080*
H6W20.25830.55410.10360.080*
Cd0.50000.29781 (3)0.25000.02762 (15)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C10.0266 (12)0.0301 (13)0.0225 (12)−0.0053 (10)−0.0004 (9)−0.0037 (11)
C20.0376 (14)0.0280 (13)0.0250 (13)−0.0056 (11)0.0073 (11)−0.0049 (11)
C30.0346 (14)0.0277 (14)0.0198 (13)0.0017 (10)0.0074 (11)0.0004 (10)
N10.0326 (11)0.0351 (12)0.0253 (11)−0.0017 (9)0.0091 (9)−0.0060 (10)
O10.0391 (10)0.0324 (10)0.0277 (10)−0.0058 (8)0.0108 (8)−0.0048 (8)
O20.0580 (13)0.0273 (10)0.0375 (12)0.0003 (10)0.0107 (10)0.0027 (9)
O30.0310 (11)0.0460 (12)0.0364 (11)0.0035 (8)0.0058 (9)−0.0099 (9)
O40.0337 (10)0.0260 (10)0.0316 (11)−0.0015 (7)0.0027 (8)−0.0023 (7)
O50.0417 (15)0.0282 (14)0.063 (2)0.0000.0247 (14)0.000
O60.0353 (10)0.0368 (11)0.0368 (11)0.0000 (8)0.0055 (8)−0.0020 (8)
Cd0.0324 (2)0.02517 (19)0.02557 (19)0.0000.00427 (11)0.000

Geometric parameters (Å, °)

C1—O21.230 (3)O1—Cd2.2621 (18)
C1—O11.274 (3)O4—Cd2.326 (2)
C1—C21.522 (3)O4—H4W10.8839
C2—N11.440 (3)O4—H4W20.9134
C2—H1A0.9700O5—Cd2.191 (3)
C2—H1B0.9700O5—H5W0.8320
C3—O31.221 (3)O6—H6W10.8775
C3—O31.221 (3)O6—H6W20.9280
C3—N11.326 (4)Cd—O1ii2.2621 (18)
C3—C3i1.531 (5)Cd—O4ii2.326 (2)
N1—H10.8600
O2—C1—O1122.8 (2)C1—O1—Cd100.97 (15)
O2—C1—C2122.4 (2)Cd—O4—H4W1113.2
O1—C1—C2114.8 (2)Cd—O4—H4W2109.4
N1—C2—C1113.7 (2)H4W1—O4—H4W2108.3
N1—C2—H1A108.8Cd—O5—H5W124.8
C1—C2—H1A108.8H6W1—O6—H6W2109.0
N1—C2—H1B108.8O5—Cd—O1ii132.90 (4)
C1—C2—H1B108.8O5—Cd—O1132.90 (4)
H1A—C2—H1B107.7O1ii—Cd—O194.19 (9)
O3—C3—N1125.7 (2)O5—Cd—O490.86 (4)
O3—C3—N1125.7 (2)O1ii—Cd—O493.76 (7)
O3—C3—C3i121.3 (3)O1—Cd—O485.08 (7)
O3—C3—C3i121.3 (3)O5—Cd—O4ii90.86 (4)
N1—C3—C3i113.1 (3)O1ii—Cd—O4ii85.08 (7)
C3—N1—C2121.0 (2)O1—Cd—O4ii93.76 (7)
C3—N1—H1119.5O4—Cd—O4ii178.29 (8)
C2—N1—H1119.5

Symmetry codes: (i) −x+3/2, −y+1/2, −z; (ii) −x+1, y, −z+1/2.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1···O6iii0.862.313.024 (3)141
O4—H4W1···O1iv0.881.782.654 (2)171
O6—H6W2···O2v0.932.032.869 (3)150
O5—H5W···O4vi0.831.892.717 (3)170
O4—H4W2···O60.911.832.733 (3)170
O6—H6W1···O30.881.972.839 (3)170

Symmetry codes: (iii) x+1, y, z; (iv) x−1/2, y−1/2, z; (v) x−1/2, y+1/2, z; (vi) x+1/2, y−1/2, z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: RZ2395).

References

  • Bruker, (1998). SMART and SAINT Bruker AXS, Madison, Wisconsin, USA.
  • Lloret, F., Sletten, J., Ruiz, R., Julve, M., Faus, J. & Verdaguer, M. (1992). Inorg. Chem.31, 778–784.
  • Sheldrick, G. M. (1996). SADABS University of Göttingen, Germany.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Spek, A. L. (2009). Acta Cryst. D65, 148–155. [PMC free article] [PubMed]

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography