Bis(4-amino-pyridinium) bis-(oxalato-κO,O')cuprate(II) dihydrate.

The Cu(II) atom in the title salt, (C(5)H(7)N(2))(2)[Cu(C(2)O(4))(2)]·2H(2)O, 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 mol-ecules inter-act 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 = 465.86

Monoclinic,

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[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 ▶); 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 ▶).

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

(C5H7N2)2[Cu(C2O4)2]·2H2O	F000 = 478
Mr = 465.86	Dx = 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 = 2.0–25.1º
b = 20.311 (1) Å	µ = 1.28 mm−1
c = 11.9261 (9) Å	T = 295 (2) K
β = 90.450 (1)º	Block, blue
V = 898.8 (1) Å3	0.14 × 0.10 × 0.08 mm
Z = 2

Bruker SMART area-detector diffractometer	1590 independent reflections
Radiation source: fine-focus sealed tube	1498 reflections with I > 2σ(I)
Monochromator: graphite	Rint = 0.016
T = 295(2) K	θmax = 25.1º
φ and ω scans	θmin = 2.0º
Absorption correction: multi-scan(SADABS; Sheldrick, 1996)	h = −4→4
Tmin = 0.764, Tmax = 0.905	k = −21→24
2623 measured reflections	l = −8→14

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)] = 0.037	H 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 reflections	Δρmax = 0.23 e Å−3
153 parameters	Δρmin = −0.49 e Å−3
5 restraints	Extinction correction: none
Primary atom site location: structure-invariant direct methods

	x	y	z	Uiso*/Ueq
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)*

	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)

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)

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···O1wiv	0.85 (3)	2.02 (3)	2.867 (4)	176 (4)

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) ; (ii) ; (iii) .