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Acta Crystallogr Sect E Struct Rep Online. 2008 January 1; 64(Pt 1): m221.
Published online 2007 December 18. doi:  10.1107/S160053680706117X
PMCID: PMC2915147

Bis(4-amino­pyridinium) bis­(oxalato-κ2 O,O′)cuprate(II) dihydrate

Abstract

The CuII atom in the title salt, (C5H7N2)2[Cu(C2O4)2]·2H2O, is located on a center of inversion and is chelated by two oxalate groups in a square-planar coordination geometry. The cation, anion and water mol­ecules inter­act through hydrogen bonds, forming a three-dimensional hydrogen-bonded network.

Related literature

See Geiser et al. (1987 [triangle]) for the square-planar pyridinium dioxalatocuprate(II) oxalic acid co-crystal. See Sun et al. (2004 [triangle]) for 2,6-bis­(4′-pyridyl-1′-pyridinium)pyrazine bis­(bis­(oxalato)cuprate(II), which is also square planar. In bis­(2-amino­anilinium) bis­(oxalato)cuprate(II), the amino groups coordinate to the metal atom, which exhibits octa­hedral coordination (Keene et al., 2003 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-64-0m221-scheme1.jpg

Experimental

Crystal data

  • (C5H7N2)2[Cu(C2O4)2]·2H2O
  • M r = 465.86
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-0m221-efi1.jpg
  • a = 3.7105 (3) Å
  • b = 20.311 (1) Å
  • c = 11.9261 (9) Å
  • β = 90.450 (1)°
  • V = 898.8 (1) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 1.28 mm−1
  • T = 295 (2) K
  • 0.14 × 0.10 × 0.08 mm

Data collection

  • Bruker SMART area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996 [triangle]) T min = 0.764, T max = 0.905
  • 2623 measured reflections
  • 1590 independent reflections
  • 1498 reflections with I > 2σ(I)
  • R int = 0.016

Refinement

  • R[F 2 > 2σ(F 2)] = 0.037
  • wR(F 2) = 0.109
  • S = 1.12
  • 1590 reflections
  • 153 parameters
  • 5 restraints
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.23 e Å−3
  • Δρmin = −0.49 e Å−3

Data collection: SMART (Bruker, 2000 [triangle]); cell refinement: SAINT (Bruker, 2000 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997 [triangle]); molecular graphics: X-SEED (Barbour, 2001 [triangle]); software used to prepare material for publication: publCIF (Westrip, 2008 [triangle]).

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

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053680706117X/xu2384sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053680706117X/xu2384Isup2.hkl

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

Acknowledgments

We thank the Foundation of Jiangsu Provincial Key Program of Physical Chemistry in Yangzhou University, China, and the University of Malaya for supporting this study.

supplementary crystallographic information

Comment

There are many crystallographic studies of coordination compounds of oxalic acid (Cambridge Structural Database, Version 5.28, Nov. 2006). The copper(II) center in the title compound shows square-planar coordination (Table 1); the cations, anions and lattice water molecules interact through hydrogen bonds (Table 2) to give rise to a three-dimensional network motif.

Experimental

Potassium oxalate monohydrate (0.036 g, 0.2 mmol) dissolved in water (5 ml) was reacted with copper nitrate trihydrate (0.048 g, 0.2 mmol) in water (5 ml). To this solution was added 4-C5H4N–NH–C(O)–C(O)–NH–4–C5H4N (0.048 g, 0.2 mmol) dissolved in methanol (15 ml). Blue crystals separated after a few days in 60% yield. CH&N elemental analysis. Calc. for C14H18CuN4O10: C 36.09, H 3.89, N 12.02%. Found: C 36.43, H 3.74, N 12.18%.

Refinement

The carbon-bound H atoms were placed in calculated positions and were allowed to ride on the parent atoms. The oxygen- and nitrogen-bound H atoms were refined with a distance restraint O–H = N–H = 0.85±0.01 Å. Their temperature factors were freely refined.

Figures

Fig. 1.
Thermal ellipsoid plot of 2[C5H7N2]+[Cu(C2O4)2]2-.2H2O; Displacement ellipsoids are drawn at the 50% probability level, and H atoms as spheres of arbitrary radii.

Crystal data

(C5H7N2)2[Cu(C2O4)2]·2H2OF000 = 478
Mr = 465.86Dx = 1.721 Mg m3
Monoclinic, P21/cMo Kα radiation λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 2198 reflections
a = 3.7105 (3) Åθ = 2.0–25.1º
b = 20.311 (1) ŵ = 1.28 mm1
c = 11.9261 (9) ÅT = 295 (2) K
β = 90.450 (1)ºBlock, blue
V = 898.8 (1) Å30.14 × 0.10 × 0.08 mm
Z = 2

Data collection

Bruker SMART area-detector diffractometer1590 independent reflections
Radiation source: fine-focus sealed tube1498 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.016
T = 295(2) Kθmax = 25.1º
[var phi] and ω scansθmin = 2.0º
Absorption correction: multi-scan(SADABS; Sheldrick, 1996)h = −4→4
Tmin = 0.764, Tmax = 0.905k = −21→24
2623 measured reflectionsl = −8→14

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.037H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.109  w = 1/[σ2(Fo2) + (0.0536P)2 + 1.2237P] where P = (Fo2 + 2Fc2)/3
S = 1.12(Δ/σ)max = 0.001
1590 reflectionsΔρmax = 0.23 e Å3
153 parametersΔρmin = −0.49 e Å3
5 restraintsExtinction correction: none
Primary atom site location: structure-invariant direct methods

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

xyzUiso*/Ueq
Cu10.50000.50000.50000.0283 (2)
O10.8063 (6)0.52464 (11)0.37661 (18)0.0352 (5)
O21.0084 (7)0.48225 (12)0.21648 (19)0.0399 (6)
O30.4985 (6)0.41370 (10)0.43287 (17)0.0313 (5)
O40.7190 (7)0.36328 (11)0.28166 (19)0.0386 (5)
O1w1.1418 (8)0.65099 (13)0.3772 (2)0.0477 (6)
N11.1417 (8)0.37249 (17)0.0727 (2)0.0439 (7)
N21.5342 (8)0.27528 (14)−0.1995 (2)0.0365 (6)
C10.8457 (8)0.47791 (15)0.3044 (2)0.0275 (6)
C20.6748 (8)0.41168 (14)0.3400 (2)0.0275 (6)
C31.1500 (8)0.3067 (2)0.0721 (3)0.0411 (8)
H31.06740.28370.13430.049*
C41.2757 (8)0.27283 (17)−0.0171 (3)0.0354 (7)
H41.27760.2270−0.01600.043*
C51.4040 (7)0.30699 (15)−0.1115 (2)0.0266 (6)
C61.3848 (8)0.37643 (16)−0.1090 (3)0.0344 (7)
H61.46090.4011−0.17020.041*
C71.2545 (9)0.40679 (17)−0.0167 (3)0.0428 (8)
H71.24290.4525−0.01510.051*
H111.045 (13)0.6140 (13)0.363 (4)0.084 (17)*
H121.268 (11)0.642 (3)0.434 (3)0.077 (17)*
H11.068 (10)0.3915 (18)0.132 (2)0.046 (11)*
H211.563 (10)0.2337 (6)−0.199 (3)0.042 (10)*
H221.621 (11)0.2979 (18)−0.253 (2)0.055 (12)*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Cu10.0380 (3)0.0234 (3)0.0237 (3)−0.00362 (19)0.0082 (2)−0.00456 (18)
O10.0493 (13)0.0257 (11)0.0309 (11)−0.0074 (10)0.0139 (10)−0.0061 (9)
O20.0526 (14)0.0358 (12)0.0314 (12)−0.0023 (11)0.0165 (11)−0.0029 (10)
O30.0416 (12)0.0258 (11)0.0265 (11)−0.0047 (9)0.0058 (9)−0.0030 (8)
O40.0550 (14)0.0256 (11)0.0354 (12)−0.0043 (10)0.0117 (10)−0.0088 (9)
O1w0.0663 (17)0.0358 (14)0.0411 (14)−0.0106 (12)−0.0018 (13)0.0083 (11)
N10.0379 (15)0.064 (2)0.0295 (15)0.0085 (14)−0.0009 (12)−0.0171 (14)
N20.0476 (16)0.0320 (15)0.0300 (14)0.0043 (12)0.0065 (12)−0.0016 (12)
C10.0325 (15)0.0265 (15)0.0236 (15)0.0023 (12)0.0016 (12)−0.0007 (11)
C20.0310 (14)0.0277 (15)0.0240 (14)0.0019 (11)0.0004 (12)−0.0020 (12)
C30.0321 (16)0.065 (2)0.0265 (16)0.0059 (15)−0.0001 (13)0.0060 (16)
C40.0328 (15)0.0393 (17)0.0342 (16)0.0024 (13)−0.0023 (13)0.0077 (14)
C50.0248 (13)0.0307 (15)0.0244 (14)0.0030 (11)−0.0051 (11)−0.0015 (12)
C60.0353 (16)0.0330 (16)0.0348 (17)0.0010 (13)0.0012 (13)0.0021 (13)
C70.0436 (18)0.0353 (18)0.049 (2)0.0056 (14)−0.0018 (16)−0.0133 (16)

Geometric parameters (Å, °)

Cu1—O11.932 (2)N2—C51.325 (4)
Cu1—O31.927 (2)N2—H210.85 (1)
Cu1—O3i1.927 (2)N2—H220.85 (3)
Cu1—O1i1.932 (2)C1—C21.548 (4)
O1—C11.290 (4)C3—C41.352 (5)
O2—C11.217 (4)C3—H30.9300
O3—C21.291 (4)C4—C51.409 (4)
O4—C21.216 (4)C4—H40.9300
O1w—H110.85 (3)C5—C61.413 (4)
O1w—H120.85 (3)C6—C71.355 (5)
N1—C31.337 (5)C6—H60.9300
N1—C71.343 (5)C7—H70.9300
N1—H10.85 (3)
O3—Cu1—O3i180O4—C2—O3126.0 (3)
O3—Cu1—O1i94.7 (1)O4—C2—C1119.2 (3)
O3i—Cu1—O1i85.4 (1)O3—C2—C1114.8 (2)
O1—Cu1—O385.4 (1)N1—C3—C4121.4 (3)
O3i—Cu1—O194.7 (1)N1—C3—H3119.3
O1i—Cu1—O1180C4—C3—H3119.3
C1—O1—Cu1112.83 (19)C3—C4—C5119.9 (3)
C2—O3—Cu1112.66 (18)C3—C4—H4120.0
H11—O1w—H12101 (5)C5—C4—H4120.0
C3—N1—C7120.4 (3)N2—C5—C4121.4 (3)
C3—N1—H1118 (3)N2—C5—C6121.4 (3)
C7—N1—H1122 (3)C4—C5—C6117.2 (3)
C5—N2—H21122 (3)C7—C6—C5119.3 (3)
C5—N2—H22118 (3)C7—C6—H6120.3
H21—N2—H22120 (4)C5—C6—H6120.3
O2—C1—O1125.5 (3)N1—C7—C6121.7 (3)
O2—C1—C2120.4 (3)N1—C7—H7119.2
O1—C1—C2114.0 (2)C6—C7—H7119.2
O3—Cu1—O1—C15.3 (2)O2—C1—C2—O3−177.7 (3)
O3i—Cu1—O1—C1−174.7 (2)O1—C1—C2—O34.2 (4)
O1i—Cu1—O3—C2177.2 (2)C7—N1—C3—C41.0 (5)
O1—Cu1—O3—C2−2.8 (2)N1—C3—C4—C50.5 (5)
Cu1—O1—C1—O2175.7 (3)C3—C4—C5—N2178.9 (3)
Cu1—O1—C1—C2−6.3 (3)C3—C4—C5—C6−1.7 (4)
Cu1—O3—C2—O4179.1 (3)N2—C5—C6—C7−179.1 (3)
Cu1—O3—C2—C10.2 (3)C4—C5—C6—C71.6 (4)
O2—C1—C2—O43.3 (4)C3—N1—C7—C6−1.1 (5)
O1—C1—C2—O4−174.8 (3)C5—C6—C7—N1−0.2 (5)

Symmetry codes: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O1w—H11···O10.85 (3)2.03 (2)2.852 (3)164 (5)
O1w—H12···O3ii0.85 (3)2.12 (5)2.931 (3)160 (5)
N1—H1···O20.85 (3)2.12 (2)2.858 (4)146 (4)
N2—H21···O4iii0.85 (1)2.07 (1)2.906 (4)168 (4)
N2—H22···O1wiv0.85 (3)2.02 (3)2.867 (4)176 (4)

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: XU2384).

References

  • Barbour, L. J. (2001). J. Supramol. Chem., 1, 189–191.
  • Bruker (2000). SMART and SAINT Bruker AXS Inc., Madison, Winconsin, USA.
  • Geiser, U., Ramakrishna, B. L., Willett, R. D., Hulsberg, F. B. & Reedijk, J. (1987). Inorg. Chem.26, 3750–3756.
  • Keene, T. D., Hursthouse, M. B. & Price, D. J. (2003). Acta Cryst. E59, m1131–m1133.
  • Sheldrick, G. M. (1996). SADABS University of Göttingen, Germany.
  • Sheldrick, G. M. (1997). SHELXS97 and SHELXL97 University of Göttingen, Germany.
  • Sun, Y.-Q., Zhang, J., Chen, J.-L. & Yang, G.-Y. (2004). Eur. J. Inorg. Chem. pp. 3837–3841.
  • Westrip, S. P. (2008). publCIF In preparation.

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