Bis(4-amino­pyridinium) bis­(oxalato-κ2O,O′)cuprate(II) dihydrate

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

doi:10.1107/S160053680706117X

metal-organic compounds

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Volume 64| Part 1| January 2008| Page m221

https://doi.org/10.1107/S160053680706117X

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Bis(4-aminopyridinium) bis(oxalato-κ²O,O′)cuprate(II) dihydrate

Zi-Cai Pan,^a Kou-Lin Zhang ^a and Seik Weng Ng ^b ^*

^aCollege of Chemistry and Chemical Engineering, Yangzhou University, Yangzhou 225002, People's Republic of China, and ^bDepartment of Chemistry, University of Malaya, 50603, Kuala Lumpur, Malaysia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 19 November 2007; accepted 20 November 2007; online 18 December 2007)

The Cu^II 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 ) for the square-planar pyridinium dioxalatocuprate(II) oxalic acid co-crystal. See Sun et al. (2004 ) 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 ).

Experimental

Crystal data

(C₅H₇N₂)₂[Cu(C₂O₄)₂]·2H₂O
M_r = 465.86
Monoclinic, P 2₁ /c
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 ) 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[F² > 2σ(F²)] = 0.037
wR(F²) = 0.109
S = 1.12
1590 reflections
153 parameters
5 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.23 e Å⁻³
Δρ_min = −0.49 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

Cu1—O1	1.932 (2)
Cu1—O3	1.927 (2)

O1—Cu1—O3	85.4 (1)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1w—H11⋯O1	0.85 (3)	2.03 (2)	2.852 (3)	164 (5)
O1w—H12⋯O3ⁱ	0.85 (3)	2.12 (5)	2.931 (3)	160 (5)
N1—H1⋯O2	0.85 (3)	2.12 (2)	2.858 (4)	146 (4)
N2—H21⋯O4ⁱⁱ	0.85 (1)	2.07 (1)	2.906 (4)	168 (4)
N2—H22⋯O1wⁱⁱⁱ	0.85 (3)	2.02 (3)	2.867 (4)	176 (4)
Symmetry codes: (i) -x+2, -y+1, -z+1; (ii) $[x+1, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (iii) -x+3, -y+1, -z.

Data collection: SMART (Bruker, 2000 ); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; 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, 2008 ).

Supporting information

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

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S160053680706117X/xu2384Isup2.hkl

checkCIF report

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%.

Structure description top

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

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]·2H₂O	F(000) = 478
M_r = 465.86	D_x = 1.721 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2198 reflections
a = 3.7105 (3) Å	θ = 2.0–25.1°
b = 20.311 (1) Å	µ = 1.28 mm⁻¹
c = 11.9261 (9) Å	T = 295 K
β = 90.450 (1)°	Block, blue
V = 898.8 (1) Å³	0.14 × 0.10 × 0.08 mm
Z = 2

Data collection top

Bruker SMART area-detector diffractometer	1590 independent reflections
Radiation source: fine-focus sealed tube	1498 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.016
φ and ω scans	θ_max = 25.1°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −4→4
T_min = 0.764, T_max = 0.905	k = −21→24
2623 measured reflections	l = −8→14

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.109	H atoms treated by a mixture of independent and constrained refinement
S = 1.12	w = 1/[σ²(F_o²) + (0.0536P)² + 1.2237P] where P = (F_o² + 2F_c²)/3
1590 reflections	(Δ/σ)_max = 0.001
153 parameters	Δρ_max = 0.23 e Å⁻³
5 restraints	Δρ_min = −0.49 e Å⁻³

Crystal data top

(C₅H₇N₂)₂[Cu(C₂O₄)₂]·2H₂O	V = 898.8 (1) Å³
M_r = 465.86	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 3.7105 (3) Å	µ = 1.28 mm⁻¹
b = 20.311 (1) Å	T = 295 K
c = 11.9261 (9) Å	0.14 × 0.10 × 0.08 mm
β = 90.450 (1)°

Data collection top

Bruker SMART area-detector diffractometer	1590 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1498 reflections with I > 2σ(I)
T_min = 0.764, T_max = 0.905	R_int = 0.016
2623 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	5 restraints
wR(F²) = 0.109	H atoms treated by a mixture of independent and constrained refinement
S = 1.12	Δρ_max = 0.23 e Å⁻³
1590 reflections	Δρ_min = −0.49 e Å⁻³
153 parameters

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

	x	y	z	U_iso*/U_eq
Cu1	0.5000	0.5000	0.5000	0.0283 (2)
O1	0.8063 (6)	0.52464 (11)	0.37661 (18)	0.0352 (5)
O2	1.0084 (7)	0.48225 (12)	0.21648 (19)	0.0399 (6)
O3	0.4985 (6)	0.41370 (10)	0.43287 (17)	0.0313 (5)
O4	0.7190 (7)	0.36328 (11)	0.28166 (19)	0.0386 (5)
O1w	1.1418 (8)	0.65099 (13)	0.3772 (2)	0.0477 (6)
N1	1.1417 (8)	0.37249 (17)	0.0727 (2)	0.0439 (7)
N2	1.5342 (8)	0.27528 (14)	−0.1995 (2)	0.0365 (6)
C1	0.8457 (8)	0.47791 (15)	0.3044 (2)	0.0275 (6)
C2	0.6748 (8)	0.41168 (14)	0.3400 (2)	0.0275 (6)
C3	1.1500 (8)	0.3067 (2)	0.0721 (3)	0.0411 (8)
H3	1.0674	0.2837	0.1343	0.049*
C4	1.2757 (8)	0.27283 (17)	−0.0171 (3)	0.0354 (7)
H4	1.2776	0.2270	−0.0160	0.043*
C5	1.4040 (7)	0.30699 (15)	−0.1115 (2)	0.0266 (6)
C6	1.3848 (8)	0.37643 (16)	−0.1090 (3)	0.0344 (7)
H6	1.4609	0.4011	−0.1702	0.041*
C7	1.2545 (9)	0.40679 (17)	−0.0167 (3)	0.0428 (8)
H7	1.2429	0.4525	−0.0151	0.051*
H11	1.045 (13)	0.6140 (13)	0.363 (4)	0.084 (17)*
H12	1.268 (11)	0.642 (3)	0.434 (3)	0.077 (17)*
H1	1.068 (10)	0.3915 (18)	0.132 (2)	0.046 (11)*
H21	1.563 (10)	0.2337 (6)	−0.199 (3)	0.042 (10)*
H22	1.621 (11)	0.2979 (18)	−0.253 (2)	0.055 (12)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0380 (3)	0.0234 (3)	0.0237 (3)	−0.00362 (19)	0.0082 (2)	−0.00456 (18)
O1	0.0493 (13)	0.0257 (11)	0.0309 (11)	−0.0074 (10)	0.0139 (10)	−0.0061 (9)
O2	0.0526 (14)	0.0358 (12)	0.0314 (12)	−0.0023 (11)	0.0165 (11)	−0.0029 (10)
O3	0.0416 (12)	0.0258 (11)	0.0265 (11)	−0.0047 (9)	0.0058 (9)	−0.0030 (8)
O4	0.0550 (14)	0.0256 (11)	0.0354 (12)	−0.0043 (10)	0.0117 (10)	−0.0088 (9)
O1w	0.0663 (17)	0.0358 (14)	0.0411 (14)	−0.0106 (12)	−0.0018 (13)	0.0083 (11)
N1	0.0379 (15)	0.064 (2)	0.0295 (15)	0.0085 (14)	−0.0009 (12)	−0.0171 (14)
N2	0.0476 (16)	0.0320 (15)	0.0300 (14)	0.0043 (12)	0.0065 (12)	−0.0016 (12)
C1	0.0325 (15)	0.0265 (15)	0.0236 (15)	0.0023 (12)	0.0016 (12)	−0.0007 (11)
C2	0.0310 (14)	0.0277 (15)	0.0240 (14)	0.0019 (11)	0.0004 (12)	−0.0020 (12)
C3	0.0321 (16)	0.065 (2)	0.0265 (16)	0.0059 (15)	−0.0001 (13)	0.0060 (16)
C4	0.0328 (15)	0.0393 (17)	0.0342 (16)	0.0024 (13)	−0.0023 (13)	0.0077 (14)
C5	0.0248 (13)	0.0307 (15)	0.0244 (14)	0.0030 (11)	−0.0051 (11)	−0.0015 (12)
C6	0.0353 (16)	0.0330 (16)	0.0348 (17)	0.0010 (13)	0.0012 (13)	0.0021 (13)
C7	0.0436 (18)	0.0353 (18)	0.049 (2)	0.0056 (14)	−0.0018 (16)	−0.0133 (16)

Geometric parameters (Å, º) top

Cu1—O1	1.932 (2)	N2—C5	1.325 (4)
Cu1—O3	1.927 (2)	N2—H21	0.85 (1)
Cu1—O3ⁱ	1.927 (2)	N2—H22	0.85 (3)
Cu1—O1ⁱ	1.932 (2)	C1—C2	1.548 (4)
O1—C1	1.290 (4)	C3—C4	1.352 (5)
O2—C1	1.217 (4)	C3—H3	0.9300
O3—C2	1.291 (4)	C4—C5	1.409 (4)
O4—C2	1.216 (4)	C4—H4	0.9300
O1w—H11	0.85 (3)	C5—C6	1.413 (4)
O1w—H12	0.85 (3)	C6—C7	1.355 (5)
N1—C3	1.337 (5)	C6—H6	0.9300
N1—C7	1.343 (5)	C7—H7	0.9300
N1—H1	0.85 (3)

O3—Cu1—O3ⁱ	180	O4—C2—O3	126.0 (3)
O3—Cu1—O1ⁱ	94.7 (1)	O4—C2—C1	119.2 (3)
O3ⁱ—Cu1—O1ⁱ	85.4 (1)	O3—C2—C1	114.8 (2)
O1—Cu1—O3	85.4 (1)	N1—C3—C4	121.4 (3)
O3ⁱ—Cu1—O1	94.7 (1)	N1—C3—H3	119.3
O1ⁱ—Cu1—O1	180	C4—C3—H3	119.3
C1—O1—Cu1	112.83 (19)	C3—C4—C5	119.9 (3)
C2—O3—Cu1	112.66 (18)	C3—C4—H4	120.0
H11—O1w—H12	101 (5)	C5—C4—H4	120.0
C3—N1—C7	120.4 (3)	N2—C5—C4	121.4 (3)
C3—N1—H1	118 (3)	N2—C5—C6	121.4 (3)
C7—N1—H1	122 (3)	C4—C5—C6	117.2 (3)
C5—N2—H21	122 (3)	C7—C6—C5	119.3 (3)
C5—N2—H22	118 (3)	C7—C6—H6	120.3
H21—N2—H22	120 (4)	C5—C6—H6	120.3
O2—C1—O1	125.5 (3)	N1—C7—C6	121.7 (3)
O2—C1—C2	120.4 (3)	N1—C7—H7	119.2
O1—C1—C2	114.0 (2)	C6—C7—H7	119.2

O3—Cu1—O1—C1	5.3 (2)	O2—C1—C2—O3	−177.7 (3)
O3ⁱ—Cu1—O1—C1	−174.7 (2)	O1—C1—C2—O3	4.2 (4)
O1ⁱ—Cu1—O3—C2	177.2 (2)	C7—N1—C3—C4	1.0 (5)
O1—Cu1—O3—C2	−2.8 (2)	N1—C3—C4—C5	0.5 (5)
Cu1—O1—C1—O2	175.7 (3)	C3—C4—C5—N2	178.9 (3)
Cu1—O1—C1—C2	−6.3 (3)	C3—C4—C5—C6	−1.7 (4)
Cu1—O3—C2—O4	179.1 (3)	N2—C5—C6—C7	−179.1 (3)
Cu1—O3—C2—C1	0.2 (3)	C4—C5—C6—C7	1.6 (4)
O2—C1—C2—O4	3.3 (4)	C3—N1—C7—C6	−1.1 (5)
O1—C1—C2—O4	−174.8 (3)	C5—C6—C7—N1	−0.2 (5)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1w—H11···O1	0.85 (3)	2.03 (2)	2.852 (3)	164 (5)
O1w—H12···O3ⁱⁱ	0.85 (3)	2.12 (5)	2.931 (3)	160 (5)
N1—H1···O2	0.85 (3)	2.12 (2)	2.858 (4)	146 (4)
N2—H21···O4ⁱⁱⁱ	0.85 (1)	2.07 (1)	2.906 (4)	168 (4)
N2—H22···O1w^iv	0.85 (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.

Experimental details

Crystal data
Chemical formula	(C₅H₇N₂)₂[Cu(C₂O₄)₂]·2H₂O
M_r	465.86
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	295
a, b, c (Å)	3.7105 (3), 20.311 (1), 11.9261 (9)
β (°)	90.450 (1)
V (Å³)	898.8 (1)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.28
Crystal size (mm)	0.14 × 0.10 × 0.08

Data collection
Diffractometer	Bruker SMART area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.764, 0.905
No. of measured, independent and observed [I > 2σ(I)] reflections	2623, 1590, 1498
R_int	0.016
(sin θ/λ)_max (Å⁻¹)	0.596

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.109, 1.12
No. of reflections	1590
No. of parameters	153
No. of restraints	5
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.23, −0.49

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), X-SEED (Barbour, 2001), publCIF (Westrip, 2007).

Selected geometric parameters (Å, º) top

Cu1—O1	1.932 (2)	Cu1—O3	1.927 (2)

O1—Cu1—O3	85.4 (1)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1w—H11···O1	0.85 (3)	2.03 (2)	2.852 (3)	164 (5)
O1w—H12···O3ⁱ	0.85 (3)	2.12 (5)	2.931 (3)	160 (5)
N1—H1···O2	0.85 (3)	2.12 (2)	2.858 (4)	146 (4)
N2—H21···O4ⁱⁱ	0.85 (1)	2.07 (1)	2.906 (4)	168 (4)
N2—H22···O1wⁱⁱⁱ	0.85 (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

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

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