catena-Poly[[[triaqua­cadmium(II)]-μ-2,2′-[oxalylbis(azanediyl)]diacetato-κ2O,O′] dihydrate]

Zhou, F.

doi:10.1107/S1600536809052015

metal-organic compounds

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ISSN: 2056-9890

Volume 66| Part 1| January 2010| Page m35

doi:10.1107/S1600536809052015

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catena-Poly[[[triaquacadmium(II)]-μ-2,2′-[oxalylbis(azanediyl)]diacetato-κ²O,O′] dihydrate]

Fangxia Zhou ^a ^*

^aDepartment of Chemistry , Jining University, Shandong 273155, People's Republic of China
^*Correspondence e-mail: fangxiazhou@yahoo.cn

(Received 17 November 2009; accepted 3 December 2009; online 9 December 2009)

The structure of the polymeric title complex, {[Cd(C₆H₆N₂O₆)(H₂O)₃]·2H₂O}_n, consists of chains running parallel to [ $[\overline{1}]$ 01] 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 ).

Experimental

Crystal data

[Cd(C₆H₆N₂O₆)(H₂O)₃]·2H₂O
M_r = 404.61
Monoclinic, C 2/c
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 ) 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[F² > 2σ(F²)] = 0.023
wR(F²) = 0.058
S = 1.07
1214 reflections
93 parameters
H-atom parameters constrained
Δρ_max = 0.50 e Å⁻³
Δρ_min = −0.53 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O6ⁱ	0.86	2.31	3.024 (3)	141
O4—H4W1⋯O1ⁱⁱ	0.88	1.78	2.654 (2)	171
O6—H6W2⋯O2ⁱⁱⁱ	0.93	2.03	2.869 (3)	150
O5—H5W⋯O4^iv	0.83	1.89	2.717 (3)	170
O4—H4W2⋯O6	0.91	1.83	2.733 (3)	170
O6—H6W1⋯O3	0.88	1.97	2.839 (3)	170
Symmetry codes: (i) x+1, y, z; (ii) $[x-{\script{1\over 2}}, y-{\script{1\over 2}}, z]$ ; (iii) $[x-{\script{1\over 2}}, y+{\script{1\over 2}}, z]$ ; (iv) $[x+{\script{1\over 2}}, y-{\script{1\over 2}}, z]$ .

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

Supporting information

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

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

checkCIF report

Comment top

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).

Related literature top

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

Experimental top

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%.

Computing details top

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

Figures top

	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.

catena-Poly[[[triaquacadmium(II)]-µ₂-2,2'- [oxalylbis(azanediyl)]diacetato-κ²O:O'] dihydrate] top

Crystal data top

[Cd(C₆H₆N₂O₆)(H₂O)₃]·2H₂O	F(000) = 808
M_r = 404.61	D_x = 2.019 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 3445 reflections
a = 7.0898 (14) Å	θ = 3.5–25.2°
b = 8.0306 (16) Å	µ = 1.70 mm⁻¹
c = 23.396 (5) Å	T = 293 K
β = 92.06 (3)°	Block, green
V = 1331.2 (5) Å³	0.23 × 0.18 × 0.15 mm
Z = 4

Data collection top

Bruker SMART CCD diffractometer	1214 independent reflections
Radiation source: fine-focus sealed tube	1171 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.038
ϕ and ω scans	θ_max = 25.2°, θ_min = 3.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −7→8
T_min = 0.696, T_max = 0.785	k = −9→9
3445 measured reflections	l = −25→28

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.023	H-atom parameters constrained
wR(F²) = 0.058	w = 1/[σ²(F_o²) + (0.032P)² + 1.2127P] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max < 0.001
1214 reflections	Δρ_max = 0.50 e Å⁻³
93 parameters	Δρ_min = −0.53 e Å⁻³
0 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0057 (5)

Crystal data top

[Cd(C₆H₆N₂O₆)(H₂O)₃]·2H₂O	V = 1331.2 (5) Å³
M_r = 404.61	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 7.0898 (14) Å	µ = 1.70 mm⁻¹
b = 8.0306 (16) Å	T = 293 K
c = 23.396 (5) Å	0.23 × 0.18 × 0.15 mm
β = 92.06 (3)°

Data collection top

Bruker SMART CCD diffractometer	1214 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1171 reflections with I > 2σ(I)
T_min = 0.696, T_max = 0.785	R_int = 0.038
3445 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.023	0 restraints
wR(F²) = 0.058	H-atom parameters constrained
S = 1.07	Δρ_max = 0.50 e Å⁻³
1214 reflections	Δρ_min = −0.53 e Å⁻³
93 parameters

Special details top

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) top

	x	y	z	U_iso*/U_eq
C1	0.6801 (3)	0.3969 (3)	0.15103 (10)	0.0264 (5)
C2	0.7678 (4)	0.4894 (3)	0.10180 (11)	0.0300 (6)
H1A	0.6764	0.5681	0.0859	0.036*
H1B	0.8756	0.5525	0.1166	0.036*
C3	0.7039 (4)	0.3045 (3)	0.02244 (11)	0.0272 (6)
N1	0.8284 (3)	0.3821 (3)	0.05672 (9)	0.0308 (5)
H1	0.9470	0.3680	0.0519	0.037*
O1	0.5996 (2)	0.4896 (2)	0.18701 (8)	0.0328 (4)
O2	0.6869 (3)	0.2444 (3)	0.15559 (9)	0.0407 (5)
O3	0.5325 (3)	0.3144 (2)	0.02483 (9)	0.0377 (5)
O4	0.2191 (3)	0.3021 (2)	0.19554 (8)	0.0304 (4)
H4W1	0.1704	0.2020	0.1897	0.080*
H4W2	0.2397	0.3493	0.1608	0.080*
O5	0.5000	0.0250 (3)	0.2500	0.0437 (7)
H5W	0.5695	−0.0341	0.2305	0.080*
O6	0.2377 (2)	0.4466 (2)	0.09015 (8)	0.0362 (4)
H6W1	0.3381	0.4129	0.0726	0.080*
H6W2	0.2583	0.5541	0.1036	0.080*
Cd	0.5000	0.29781 (3)	0.2500	0.02762 (15)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0266 (12)	0.0301 (13)	0.0225 (12)	−0.0053 (10)	−0.0004 (9)	−0.0037 (11)
C2	0.0376 (14)	0.0280 (13)	0.0250 (13)	−0.0056 (11)	0.0073 (11)	−0.0049 (11)
C3	0.0346 (14)	0.0277 (14)	0.0198 (13)	0.0017 (10)	0.0074 (11)	0.0004 (10)
N1	0.0326 (11)	0.0351 (12)	0.0253 (11)	−0.0017 (9)	0.0091 (9)	−0.0060 (10)
O1	0.0391 (10)	0.0324 (10)	0.0277 (10)	−0.0058 (8)	0.0108 (8)	−0.0048 (8)
O2	0.0580 (13)	0.0273 (10)	0.0375 (12)	0.0003 (10)	0.0107 (10)	0.0027 (9)
O3	0.0310 (11)	0.0460 (12)	0.0364 (11)	0.0035 (8)	0.0058 (9)	−0.0099 (9)
O4	0.0337 (10)	0.0260 (10)	0.0316 (11)	−0.0015 (7)	0.0027 (8)	−0.0023 (7)
O5	0.0417 (15)	0.0282 (14)	0.063 (2)	0.000	0.0247 (14)	0.000
O6	0.0353 (10)	0.0368 (11)	0.0368 (11)	0.0000 (8)	0.0055 (8)	−0.0020 (8)
Cd	0.0324 (2)	0.02517 (19)	0.02557 (19)	0.000	0.00427 (11)	0.000

Geometric parameters (Å, º) top

C1—O2	1.230 (3)	O1—Cd	2.2621 (18)
C1—O1	1.274 (3)	O4—Cd	2.326 (2)
C1—C2	1.522 (3)	O4—H4W1	0.8839
C2—N1	1.440 (3)	O4—H4W2	0.9134
C2—H1A	0.9700	O5—Cd	2.191 (3)
C2—H1B	0.9700	O5—H5W	0.8320
C3—O3	1.221 (3)	O6—H6W1	0.8775
C3—O3	1.221 (3)	O6—H6W2	0.9280
C3—N1	1.326 (4)	Cd—O1ⁱⁱ	2.2621 (18)
C3—C3ⁱ	1.531 (5)	Cd—O4ⁱⁱ	2.326 (2)
N1—H1	0.8600

O2—C1—O1	122.8 (2)	C1—O1—Cd	100.97 (15)
O2—C1—C2	122.4 (2)	Cd—O4—H4W1	113.2
O1—C1—C2	114.8 (2)	Cd—O4—H4W2	109.4
N1—C2—C1	113.7 (2)	H4W1—O4—H4W2	108.3
N1—C2—H1A	108.8	Cd—O5—H5W	124.8
C1—C2—H1A	108.8	H6W1—O6—H6W2	109.0
N1—C2—H1B	108.8	O5—Cd—O1ⁱⁱ	132.90 (4)
C1—C2—H1B	108.8	O5—Cd—O1	132.90 (4)
H1A—C2—H1B	107.7	O1ⁱⁱ—Cd—O1	94.19 (9)
O3—C3—N1	125.7 (2)	O5—Cd—O4	90.86 (4)
O3—C3—N1	125.7 (2)	O1ⁱⁱ—Cd—O4	93.76 (7)
O3—C3—C3ⁱ	121.3 (3)	O1—Cd—O4	85.08 (7)
O3—C3—C3ⁱ	121.3 (3)	O5—Cd—O4ⁱⁱ	90.86 (4)
N1—C3—C3ⁱ	113.1 (3)	O1ⁱⁱ—Cd—O4ⁱⁱ	85.08 (7)
C3—N1—C2	121.0 (2)	O1—Cd—O4ⁱⁱ	93.76 (7)
C3—N1—H1	119.5	O4—Cd—O4ⁱⁱ	178.29 (8)
C2—N1—H1	119.5

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O6ⁱⁱⁱ	0.86	2.31	3.024 (3)	141
O4—H4W1···O1^iv	0.88	1.78	2.654 (2)	171
O6—H6W2···O2^v	0.93	2.03	2.869 (3)	150
O5—H5W···O4^vi	0.83	1.89	2.717 (3)	170
O4—H4W2···O6	0.91	1.83	2.733 (3)	170
O6—H6W1···O3	0.88	1.97	2.839 (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.

Experimental details

Crystal data
Chemical formula	[Cd(C₆H₆N₂O₆)(H₂O)₃]·2H₂O
M_r	404.61
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	293
a, b, c (Å)	7.0898 (14), 8.0306 (16), 23.396 (5)
β (°)	92.06 (3)
V (Å³)	1331.2 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.70
Crystal size (mm)	0.23 × 0.18 × 0.15

Data collection
Diffractometer	Bruker SMART CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.696, 0.785
No. of measured, independent and observed [I > 2σ(I)] reflections	3445, 1214, 1171
R_int	0.038
(sin θ/λ)_max (Å⁻¹)	0.600

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.023, 0.058, 1.07
No. of reflections	1214
No. of parameters	93
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.50, −0.53

Computer programs: SMART (Bruker 1998), SAINT (Bruker 1998), SHELXS97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O6ⁱ	0.86	2.31	3.024 (3)	141.2
O4—H4W1···O1ⁱⁱ	0.88	1.78	2.654 (2)	170.5
O6—H6W2···O2ⁱⁱⁱ	0.93	2.03	2.869 (3)	149.7
O5—H5W···O4^iv	0.83	1.89	2.717 (3)	170.0
O4—H4W2···O6	0.91	1.83	2.733 (3)	170.4
O6—H6W1···O3	0.88	1.97	2.839 (3)	170.1

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

Acknowledgements

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

References

Bruker, (1998). SMART and SAINT. Bruker AXS, Madison, Wisconsin, USA. Google Scholar
Lloret, F., Sletten, J., Ruiz, R., Julve, M., Faus, J. & Verdaguer, M. (1992). Inorg. Chem. 31, 778–784. CSD CrossRef CAS Web of Science Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar

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