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Acta Cryst. (2008). E64, m221    [ doi:10.1107/S160053680706117X ]

Bis(4-aminopyridinium) bis(oxalato-[kappa]2O,O')cuprate(II) dihydrate

Z.-C. Pan, K.-L. Zhang and S. W. Ng

Abstract top

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.

Comment top

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.

Related literature top

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

Experimental top

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 top

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.

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2007).

Figures top
[Figure 1] 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.
Bis(4-aminopyridinium) bis(oxalato-κ2O,O')cuprate(II) dihydrate top
Crystal data top
(C5H7N2)2[Cu(C2O4)2]·2H2OF000 = 478
Mr = 465.86Dx = 1.721 Mg m−3
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 mm−1
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 top
Bruker SMART area-detector
diffractometer		1590 independent reflections
Radiation source: fine-focus sealed tube1498 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.016
T = 295(2) Kθmax = 25.1º
φ 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 top
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 Å−3
153 parametersΔρmin = −0.49 e Å−3
5 restraintsExtinction correction: none
Primary atom site location: structure-invariant direct methods
Crystal data top
(C5H7N2)2[Cu(C2O4)2]·2H2OV = 898.8 (1) Å3
Mr = 465.86Z = 2
Monoclinic, P21/cMo Kα
a = 3.7105 (3) ŵ = 1.28 mm−1
b = 20.311 (1) ÅT = 295 (2) K
c = 11.9261 (9) Å0.14 × 0.10 × 0.08 mm
β = 90.450 (1)º
Data collection top
Bruker SMART area-detector
diffractometer		1590 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		1498 reflections with I > 2σ(I)
Tmin = 0.764, Tmax = 0.905Rint = 0.016
2623 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0375 restraints
wR(F2) = 0.109H atoms treated by a mixture of
independent and constrained refinement
S = 1.12Δρmax = 0.23 e Å−3
1590 reflectionsΔρmin = −0.49 e Å−3
153 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
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) top
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, °) top
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, °) top
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.
Table 1
Selected geometric parameters (Å, °) top
Cu1—O11.932 (2)Cu1—O31.927 (2)
O1—Cu1—O385.4 (1)
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1w—H11···O10.85 (3)2.03 (2)2.852 (3)164 (5)
O1w—H12···O3i0.85 (3)2.12 (5)2.931 (3)160 (5)
N1—H1···O20.85 (3)2.12 (2)2.858 (4)146 (4)
N2—H21···O4ii0.85 (1)2.07 (1)2.906 (4)168 (4)
N2—H22···O1wiii0.85 (3)2.02 (3)2.867 (4)176 (4)
Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) x+1, −y+1/2, z−1/2; (iii) −x+3, −y+1, −z.
Acknowledgements top

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.

references
References top

Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191.

Bruker (2000). SAINT (Version 6.10A) and SAINT (Version 6.10A). 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. (2007). publCIF. In preparation.