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Acta Crystallogr Sect E Struct Rep Online. 2010 November 1; 66(Pt 11): m1431–m1432.
Published online 2010 October 23. doi:  10.1107/S1600536810041139
PMCID: PMC3009275

catena-Poly[[[tetraaqua(3,5-dinitro-4-oxidopyridine N-oxide-κO 1)neodymium(III)]-μ-oxalato-κ4 O 1,O 2:O 1′,O 2′] tetrahydrate]

Abstract

In the title coordination polymer, {[Nd(C5H2N3O6)(C2O4)(H2O)4]·4H2O}n, the oxalate dianions link adjacent nine-coordinate, tricapped trigonal-prismatic Nd(III) atoms into a chain running along the b axis. The 3,5-dinitropyridin-4-oxido N-oxide ligand is formally a zwitterionic anion; the anion binds to the metal atom through the N-oxide O atom. The chains are connected into a three-dimensional network by O—H(...)O hydrogen bonds involving the coordinated and uncoordinated water mol­ecules.

Related literature

For a related Nd(III) structure, see: Wang et al. (2010 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-m1431-scheme1.jpg

Experimental

Crystal data

  • [Nd(C5H2N3O6)(C2O4)(H2O)4]·4H2O
  • M r = 576.48
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-m1431-efi1.jpg
  • a = 6.7695 (7) Å
  • b = 9.9695 (11) Å
  • c = 14.6269 (16) Å
  • α = 73.719 (1)°
  • β = 88.137 (1)°
  • γ = 76.693 (1)°
  • V = 921.58 (17) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 2.92 mm−1
  • T = 293 K
  • 0.35 × 0.25 × 0.05 mm

Data collection

  • Bruker SMART APEX diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996 [triangle]) T min = 0.429, T max = 0.868
  • 7952 measured reflections
  • 4147 independent reflections
  • 4005 reflections with I > 2σ(I)
  • R int = 0.015

Refinement

  • R[F 2 > 2σ(F 2)] = 0.019
  • wR(F 2) = 0.050
  • S = 1.06
  • 4147 reflections
  • 262 parameters
  • H-atom parameters constrained
  • Δρmax = 0.48 e Å−3
  • Δρmin = −0.94 e Å−3

Data collection: SMART (Bruker, 2003 [triangle]); cell refinement: SAINT (Bruker, 2003 [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: X-SEED (Barbour, 2001 [triangle]); software used to prepare material for publication: publCIF (Westrip, 2010 [triangle]).

Table 1
Selected bond lengths (Å)
Table 2
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810041139/xu5029sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810041139/xu5029Isup2.hkl

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

Acknowledgments

We thank Baoji University of Arts and Sciences (Key Research Project No. ZK08114) and the University of Malaya for supporting this study.

supplementary crystallographic information

Comment

Lanthanum(III) oxalates adopt open-framework architectures whose cavities are occupied by the templating agent, typically an ammonium counterion. The reaction of neodymium nitrate and adipic acid in the presence of 3,5-dinitro-4-hydroxypyridine N-oxide gave an unexpected neodymium oxalate, whose positive charge is balanced by the deprotonated 3,5-dinitropyridin-4-olate-N-oxide unit. The oxalate part of the coordination polymer, [Nd(H2O)4(C5H2N3O6)(C2O4).H2O]n (Scheme I, Fig. 1), links adjacent nine-coordinate, tricapped-trigonal-prismatic Nd(III) centers (Fig. 2) into a linear chain running along the b axis of the triclinic unit cell. The 3,5-dinitropyridin-4-olate-N-oxide part is formally a zwitterionic anion; the anion binds through the N-oxide O atom. The chains are connected by O–H···O hydrogen bonds that involve the coordinated and lattice water molecules into a three-dimensional network.

This study continues from the only report of a metal derivative of 3,5-dinitro-4-hydroxypyridine N-oxide; the deprotonated ligand is also unidentate in the tris-ethanol adduct of the same metal (Wang et al., 2010).

Experimental

3,5-Dinitro-4-hydroxypyridine N-oxide (0.183 g), a commercially available chemical, was dissolved in water (25 ml) at 333 K. Neodymium nitrate hexahydrate (0.441 g) was added and the mixture heated for 6 h. Adipic acid (0.091 g) was added and the mixture heated for another 2 h. The solution was filtered and the water removed by evaporation. The residue was recrystallzed from ethanol solution to furnish violet-colored prisms. These were washed with water.

Refinement

Carbon-bound H-atoms were placed in calculated positions (C–H 0.93 Å) and were included in the refinement in the riding model approximation, with U(H) set to 1.2U(C).

The water H atoms were placed in chemically sensible positions on the basis of hydrogen bonding (O–H 0.82–0.85 Å) and their temperature factors tied by a factor of 1.5 times.

Figures

Fig. 1.
Thermal ellipsoid plot (Barbour, 2001) of a portion of the chain motif of [Nd(H2O)4(C5H2N3O6)(C2O4).H2O]n at the 50% probability level; hydrogen atoms are shown as spheres of arbitrary radius. Symmetry codes: i = 1 - x, 1 - y, 1 - z; ii = 1 - y, 2 - y, ...
Fig. 2.
Nine-coordinate geometry of Nd.

Crystal data

[Nd(C5H2N3O6)(C2O4)(H2O)4]·4H2OZ = 2
Mr = 576.48F(000) = 570
Triclinic, P1Dx = 2.077 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 6.7695 (7) ÅCell parameters from 6995 reflections
b = 9.9695 (11) Åθ = 2.3–28.2°
c = 14.6269 (16) ŵ = 2.92 mm1
α = 73.719 (1)°T = 293 K
β = 88.137 (1)°Prism, violet
γ = 76.693 (1)°0.35 × 0.25 × 0.05 mm
V = 921.58 (17) Å3

Data collection

Bruker SMART APEX diffraractometer diffractometer4147 independent reflections
Radiation source: fine-focus sealed tube4005 reflections with I > 2σ(I)
graphiteRint = 0.015
[var phi] and ω scansθmax = 27.5°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)h = −8→8
Tmin = 0.429, Tmax = 0.868k = −12→12
7952 measured reflectionsl = −18→18

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.019Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.050H-atom parameters constrained
S = 1.06w = 1/[σ2(Fo2) + (0.031P)2 + 0.4577P] where P = (Fo2 + 2Fc2)/3
4147 reflections(Δ/σ)max = 0.001
262 parametersΔρmax = 0.48 e Å3
0 restraintsΔρmin = −0.94 e Å3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/Ueq
Nd10.671311 (14)0.671999 (10)0.625076 (7)0.01518 (5)
N10.3029 (3)0.7237 (2)0.78523 (13)0.0226 (4)
N20.2172 (3)0.3827 (2)0.93382 (15)0.0299 (4)
N30.2733 (4)0.8438 (2)1.00008 (16)0.0403 (6)
O10.3422 (3)0.77791 (18)0.69178 (11)0.0261 (3)
O1W0.7817 (3)0.69793 (18)0.77798 (11)0.0292 (4)
H110.78670.63120.82830.044*
H120.77570.77440.79300.044*
O20.2029 (5)0.3315 (3)0.86815 (16)0.0645 (8)
O2W0.9719 (3)0.75337 (19)0.54317 (15)0.0383 (4)
H211.09370.70910.55500.057*
H220.96570.82510.49580.057*
O30.2085 (4)0.3157 (2)1.01719 (14)0.0471 (5)
O3W1.0000 (3)0.48281 (19)0.66002 (13)0.0340 (4)
H311.06490.48020.60980.051*
H321.00390.39780.69270.051*
O40.2421 (3)0.5451 (2)1.07188 (12)0.0361 (4)
O4W0.6382 (3)0.44826 (18)0.75126 (12)0.0284 (4)
H410.68310.42300.80780.043*
H420.60510.37900.73990.043*
O50.2961 (8)0.7979 (3)1.08425 (18)0.1165 (17)
O5W0.7576 (5)0.9490 (3)0.82384 (19)0.0745 (9)
H510.67531.02480.79450.112*
H520.74930.92880.88200.112*
O60.2434 (7)0.9714 (3)0.96151 (19)0.0894 (12)
O6W0.5130 (3)1.2177 (2)0.70856 (15)0.0448 (5)
H610.51061.21410.65180.067*
H620.40161.20310.73310.067*
O70.7357 (2)0.5438 (2)0.49783 (13)0.0303 (4)
O7W0.9661 (3)0.98025 (19)0.37762 (14)0.0361 (4)
H710.87191.05400.36190.054*
H721.07791.00300.37390.054*
O80.6186 (2)0.41980 (19)0.41502 (13)0.0270 (3)
O8W0.9041 (4)0.8190 (2)0.25538 (16)0.0513 (6)
H810.87350.87590.19990.077*
H820.95350.85690.29080.077*
O90.6495 (2)0.93475 (16)0.60571 (11)0.0248 (3)
O100.5087 (3)1.16112 (17)0.52372 (12)0.0306 (4)
C10.2625 (3)0.5922 (2)0.81517 (16)0.0227 (4)
H10.24760.54350.77100.027*
C20.2433 (3)0.5296 (2)0.91041 (16)0.0222 (4)
C30.2536 (3)0.6000 (2)0.98472 (16)0.0236 (4)
C40.2774 (4)0.7458 (2)0.94198 (16)0.0260 (5)
C50.3056 (4)0.8018 (2)0.84657 (17)0.0260 (5)
H50.32660.89430.82430.031*
C60.6016 (3)0.4897 (2)0.47487 (15)0.0197 (4)
C70.5458 (3)1.0272 (2)0.53784 (15)0.0209 (4)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Nd10.01768 (7)0.01469 (7)0.01310 (6)−0.00390 (4)−0.00032 (4)−0.00356 (4)
N10.0235 (9)0.0255 (9)0.0170 (8)−0.0038 (7)0.0025 (7)−0.0049 (7)
N20.0405 (11)0.0271 (10)0.0236 (10)−0.0120 (9)0.0007 (8)−0.0063 (8)
N30.0708 (17)0.0278 (11)0.0241 (11)−0.0114 (11)−0.0001 (11)−0.0096 (9)
O10.0309 (8)0.0277 (8)0.0163 (7)−0.0035 (7)0.0063 (6)−0.0041 (6)
O1W0.0431 (10)0.0254 (8)0.0193 (8)−0.0061 (7)−0.0061 (7)−0.0071 (6)
O20.131 (3)0.0454 (13)0.0338 (11)−0.0453 (15)0.0084 (13)−0.0179 (10)
O2W0.0260 (8)0.0279 (9)0.0506 (12)−0.0042 (7)0.0098 (8)0.0028 (8)
O30.0825 (16)0.0360 (11)0.0251 (9)−0.0260 (11)0.0002 (10)−0.0019 (8)
O3W0.0295 (9)0.0278 (9)0.0340 (9)0.0009 (7)0.0082 (7)0.0015 (7)
O40.0581 (12)0.0327 (10)0.0181 (8)−0.0146 (9)−0.0014 (8)−0.0045 (7)
O4W0.0374 (9)0.0250 (8)0.0223 (8)−0.0126 (7)−0.0011 (7)−0.0011 (6)
O50.289 (6)0.0440 (15)0.0247 (12)−0.051 (2)−0.018 (2)−0.0095 (10)
O5W0.143 (3)0.0332 (12)0.0434 (14)−0.0063 (15)−0.0147 (16)−0.0135 (10)
O60.196 (4)0.0310 (13)0.0439 (14)−0.0246 (17)0.0042 (19)−0.0161 (11)
O6W0.0596 (13)0.0429 (11)0.0366 (11)−0.0140 (10)−0.0045 (10)−0.0163 (9)
O70.0230 (8)0.0416 (10)0.0379 (10)−0.0121 (7)0.0062 (7)−0.0264 (8)
O7W0.0364 (10)0.0282 (9)0.0418 (10)−0.0110 (7)−0.0046 (8)−0.0035 (8)
O80.0240 (8)0.0359 (9)0.0300 (9)−0.0120 (7)0.0066 (7)−0.0200 (7)
O8W0.0771 (16)0.0401 (12)0.0403 (12)−0.0189 (11)−0.0021 (11)−0.0123 (9)
O90.0309 (8)0.0195 (7)0.0222 (8)−0.0056 (6)−0.0070 (6)−0.0022 (6)
O100.0488 (10)0.0176 (8)0.0240 (8)−0.0041 (7)−0.0123 (7)−0.0049 (6)
C10.0215 (10)0.0253 (11)0.0215 (10)−0.0038 (8)0.0016 (8)−0.0083 (8)
C20.0223 (10)0.0236 (11)0.0207 (10)−0.0055 (8)0.0008 (8)−0.0061 (8)
C30.0250 (10)0.0254 (11)0.0198 (10)−0.0041 (8)−0.0006 (8)−0.0067 (8)
C40.0333 (12)0.0242 (11)0.0218 (11)−0.0055 (9)0.0002 (9)−0.0095 (9)
C50.0312 (11)0.0216 (11)0.0256 (11)−0.0062 (9)0.0028 (9)−0.0071 (9)
C60.0191 (10)0.0205 (10)0.0202 (10)−0.0034 (8)0.0015 (8)−0.0078 (8)
C70.0238 (10)0.0197 (10)0.0187 (10)−0.0053 (8)−0.0011 (8)−0.0043 (8)

Geometric parameters (Å, °)

Nd1—O12.5266 (16)O4—C31.246 (3)
Nd1—O72.5124 (16)O4W—H410.8391
Nd1—O8i2.4972 (16)O4W—H420.8323
Nd1—O92.5243 (16)O5W—H510.8401
Nd1—O10ii2.4897 (16)O5W—H520.8205
Nd1—O1W2.4798 (16)O6W—H610.8420
Nd1—O2W2.5080 (17)O6W—H620.8503
Nd1—O3W2.5241 (17)O7—C61.255 (3)
Nd1—O4W2.5153 (16)O7W—H710.8363
N1—C51.346 (3)O7W—H720.8351
N1—C11.350 (3)O8—C61.251 (3)
N1—O11.364 (2)O8W—H810.8498
N2—O21.223 (3)O8W—H820.8376
N2—O31.222 (3)O9—C71.250 (3)
N2—C21.459 (3)O10—C71.258 (3)
N3—O51.189 (3)C1—C21.373 (3)
N3—O61.210 (3)C1—H10.9300
N3—C41.459 (3)C2—C31.461 (3)
O1W—H110.8381C3—C41.456 (3)
O1W—H120.8435C4—C51.375 (3)
O2W—H210.8386C5—H50.9300
O2W—H220.8392C6—C6i1.538 (4)
O3W—H310.8474C7—C7ii1.563 (4)
O3W—H320.8431
O1W—Nd1—O10ii135.33 (5)O6—N3—C4119.1 (2)
O1W—Nd1—O8i131.00 (6)N1—O1—Nd1119.90 (12)
O10ii—Nd1—O8i70.29 (6)Nd1—O1W—H11120.2
O1W—Nd1—O2W91.36 (6)Nd1—O1W—H12127.9
O10ii—Nd1—O2W81.90 (6)H11—O1W—H12108.0
O8i—Nd1—O2W137.49 (6)Nd1—O2W—H21125.7
O1W—Nd1—O7148.48 (6)Nd1—O2W—H22125.1
O10ii—Nd1—O772.57 (6)H21—O2W—H22108.9
O8i—Nd1—O764.62 (5)Nd1—O3W—H31111.6
O2W—Nd1—O776.89 (6)Nd1—O3W—H32121.7
O1W—Nd1—O4W73.70 (6)H31—O3W—H32108.4
O10ii—Nd1—O4W139.35 (6)Nd1—O4W—H41126.0
O8i—Nd1—O4W69.18 (6)Nd1—O4W—H42123.9
O2W—Nd1—O4W132.51 (6)H41—O4W—H42108.6
O7—Nd1—O4W92.70 (6)H51—O5W—H52114.0
O1W—Nd1—O971.57 (5)H61—O6W—H62108.1
O10ii—Nd1—O965.01 (5)C6—O7—Nd1120.14 (14)
O8i—Nd1—O9122.97 (6)H71—O7W—H72110.0
O2W—Nd1—O967.67 (6)C6—O8—Nd1i121.03 (14)
O7—Nd1—O9127.25 (6)H81—O8W—H82111.9
O4W—Nd1—O9140.03 (6)C7—O9—Nd1119.52 (14)
O1W—Nd1—O3W79.37 (6)C7—O10—Nd1ii121.18 (14)
O10ii—Nd1—O3W134.04 (6)N1—C1—C2120.4 (2)
O8i—Nd1—O3W112.90 (6)N1—C1—H1119.8
O2W—Nd1—O3W65.61 (6)C2—C1—H1119.8
O7—Nd1—O3W69.13 (6)C1—C2—N2114.8 (2)
O4W—Nd1—O3W67.38 (6)C1—C2—C3123.9 (2)
O9—Nd1—O3W123.39 (6)N2—C2—C3121.22 (19)
O1W—Nd1—O176.77 (6)O4—C3—C4124.5 (2)
O10ii—Nd1—O179.67 (6)O4—C3—C2125.6 (2)
O8i—Nd1—O167.82 (6)C4—C3—C2109.93 (19)
O2W—Nd1—O1138.53 (6)C5—C4—N3115.0 (2)
O7—Nd1—O1130.56 (5)C5—C4—C3124.1 (2)
O4W—Nd1—O182.50 (6)N3—C4—C3120.9 (2)
O9—Nd1—O170.89 (5)N1—C5—C4120.4 (2)
O3W—Nd1—O1145.78 (5)N1—C5—H5119.8
C5—N1—C1120.8 (2)C4—C5—H5119.8
C5—N1—O1119.60 (19)O8—C6—O7125.9 (2)
C1—N1—O1119.60 (18)O8—C6—C6i116.9 (2)
O2—N2—O3122.3 (2)O7—C6—C6i117.2 (2)
O2—N2—C2118.1 (2)O9—C7—O10126.3 (2)
O3—N2—C2119.6 (2)O9—C7—C7ii117.4 (2)
O5—N3—O6121.0 (3)O10—C7—C7ii116.2 (2)
O5—N3—C4119.9 (2)

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

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O1w—H11···O4iii0.841.992.809 (2)166
O1w—H12···O5w0.841.892.736 (3)178
O2w—H21···O8iv0.842.062.890 (2)174
O2w—H22···O7w0.841.972.806 (3)174
O3w—H31···O7iv0.852.072.908 (2)170
O3w—H32···O8wiv0.842.032.841 (3)161
O4w—H41···O4iii0.841.972.759 (2)155
O4w—H42···O6wv0.832.022.851 (3)177
O5w—H51···O6w0.842.062.893 (3)171
O5w—H52···O3iii0.822.432.956 (3)123
O6w—H61···O100.842.092.915 (3)168
O6w—H62···O8wii0.852.132.942 (3)160
O7w—H71···O1ii0.841.932.766 (2)172
O7w—H72···O9vi0.842.132.953 (2)168
O8w—H81···O6ii0.852.463.310 (4)174
O8w—H82···O7w0.842.022.816 (3)160

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: XU5029).

References

  • Barbour, L. J. (2001). J. Supramol. Chem.1, 189–191.
  • Bruker (2003). SAINT and SMART Bruker AXS Inc., Madison, Wisconsin, USA.
  • Sheldrick, G. M. (1996). SADABS University of Göttingen, Germany.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Wang, J.-G., Zhou, Q.-P., Zhang, G.-F., Li, P., Chen, B.-H., Zhao, F.-Q., Li, J.-Z. & Fan, X.-Z. (2010). J. Coord. Chem.63, 1379–1389.
  • Westrip, S. P. (2010). J. Appl. Cryst.43, 920–925.

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