Bis(4-carboxamido­pyridinium) diaqua­dioxalatocuprate(II)

In the title compound, (C₆H₇N₂O)₂[Cu(C₂O₄)₂(H₂O)₂], the Cu^II center (site symmetry ) exhibits an octa­hedral coordination geometry arising from four O atoms of two oxalate dianions and two O atoms of water mol­ecules. The protonated isonicotinamide cation inter­acts with the anion by O—H...O and N—H...O hydrogen bonds, generating a three-dimensional network.

Key indicators

• Single-crystal X-ray study
• T = 295 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.025
• wR factor = 0.067
• Data-to-parameter ratio = 12.5

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT232_ALERT_2_B Hirshfeld Test Diff (M-X)  Cu     -   OW1     ..      12.26 su

Alert level C
CRYSC01_ALERT_1_C The word below has not been recognised as a standard
            identifier.
            aquamarine
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ....       2.68
PLAT369_ALERT_2_C Long   C(sp2)-C(sp2) Bond  C1     -   C2     ...       1.55 Ang.
PLAT417_ALERT_2_C Short Inter D-H..H-D       HW2    ..  HN1     ..       2.11 Ang.
PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........          5
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          2
              C6 H7 N2 O

   0 ALERT level A = In general: serious problem
   1 ALERT level B = Potentially serious problem
   7 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   4 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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Computing details

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: SHELXL97.

Bis(4-carboxamidopyridinium) diaquadioxalatocopper(II)

Crystal data

(C6H7N2O)2[Cu(C2O4)2(H2O)2]	Z = 1
Mr = 521.89	F(000) = 267
Triclinic, P1	Dx = 1.817 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.788 (2) Å	Cell parameters from 1237 reflections
b = 6.957 (2) Å	θ = 2.1–27.3°
c = 10.849 (3) Å	µ = 1.23 mm^−1
α = 76.127 (2)°	T = 295 K
β = 75.198 (2)°	Block, aquamarine blue
γ = 79.483 (3)°	0.43 × 0.32 × 0.24 mm
V = 476.9 (2) Å^3

Data collection

Bruker SMART CCD APEX II diffractometer	1887 independent reflections
Radiation source: fine-focus sealed tube	1822 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.012
ω scans	θmax = 26.1°, θmin = 3.0°
Absorption correction: multi-scan (SADABS; Bruker, 2002)	h = −8→8
Tmin = 0.635, Tmax = 0.750	k = −8→8
4061 measured reflections	l = −13→13

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.025	Hydrogen site location: difmap and geom
wR(F^2) = 0.067	H-atom parameters constrained
S = 1.00	w = 1/[σ^2(Fo^2) + (0.0362P)^2 + 0.3522P] where P = (Fo^2 + 2Fc^2)/3
1887 reflections	(Δ/σ)max < 0.001
151 parameters	Δρmax = 0.25 e Å^−3
0 restraints	Δρmin = −0.46 e Å^−3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq
Cu	0.5000	0.5000	0.5000	0.02653 (11)
O1	0.45175 (19)	0.5222 (2)	0.68074 (12)	0.0307 (3)
O2	0.77472 (18)	0.3627 (2)	0.52514 (12)	0.0285 (3)
O3	0.6141 (2)	0.4445 (2)	0.84317 (12)	0.0348 (3)
O4	0.94742 (19)	0.2818 (2)	0.68471 (13)	0.0343 (3)
O5	−0.4341 (2)	0.9738 (2)	0.76881 (13)	0.0351 (3)
OW1	0.3523 (2)	0.1789 (2)	0.57731 (13)	0.0358 (3)
HW1	0.4074	0.1062	0.6361	0.043*
HW2	0.2355	0.2024	0.6116	0.043*
N1	0.0745 (2)	0.7147 (2)	1.03957 (15)	0.0301 (3)
H1	0.1403	0.6798	1.1011	0.036*
N2	−0.1707 (3)	0.8455 (3)	0.62584 (15)	0.0333 (4)
HN1	−0.2376	0.8773	0.5648	0.040*
HN2	−0.0470	0.7857	0.6117	0.040*
C1	0.6056 (3)	0.4476 (3)	0.73055 (16)	0.0242 (3)
C2	0.7954 (3)	0.3550 (3)	0.63944 (16)	0.0237 (3)
C5	−0.1300 (3)	0.7562 (3)	1.07003 (18)	0.0342 (4)
H5	−0.1992	0.7461	1.1567	0.041*
C6	−0.2377 (3)	0.8136 (3)	0.97335 (18)	0.0304 (4)
H6	−0.3800	0.8434	0.9941	0.036*
C7	−0.1332 (3)	0.8269 (2)	0.84455 (16)	0.0226 (3)
C8	0.0786 (3)	0.7824 (3)	0.81641 (18)	0.0306 (4)
H8	0.1518	0.7909	0.7306	0.037*
C9	0.1795 (3)	0.7255 (3)	0.9168 (2)	0.0334 (4)
H9	0.3218	0.6945	0.8990	0.040*
C10	−0.2580 (3)	0.8886 (3)	0.74106 (17)	0.0248 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu	0.02067 (16)	0.04032 (19)	0.01783 (16)	0.00801 (12)	−0.00852 (11)	−0.00892 (12)
O1	0.0230 (6)	0.0465 (8)	0.0214 (6)	0.0092 (5)	−0.0085 (5)	−0.0109 (5)
O2	0.0226 (6)	0.0400 (7)	0.0208 (6)	0.0065 (5)	−0.0071 (5)	−0.0080 (5)
O3	0.0297 (7)	0.0535 (9)	0.0215 (6)	0.0061 (6)	−0.0111 (5)	−0.0110 (6)
O4	0.0214 (6)	0.0508 (8)	0.0283 (7)	0.0059 (6)	−0.0108 (5)	−0.0062 (6)
O5	0.0260 (7)	0.0474 (8)	0.0300 (7)	0.0074 (6)	−0.0126 (5)	−0.0064 (6)
OW1	0.0277 (7)	0.0512 (8)	0.0266 (7)	0.0066 (6)	−0.0097 (5)	−0.0092 (6)
N1	0.0345 (8)	0.0325 (8)	0.0280 (8)	−0.0016 (6)	−0.0192 (7)	−0.0037 (6)
N2	0.0325 (8)	0.0459 (9)	0.0237 (8)	0.0029 (7)	−0.0131 (6)	−0.0099 (7)
C1	0.0210 (8)	0.0311 (9)	0.0198 (8)	−0.0007 (7)	−0.0061 (6)	−0.0043 (7)
C2	0.0207 (8)	0.0282 (8)	0.0206 (8)	−0.0005 (6)	−0.0059 (6)	−0.0027 (6)
C5	0.0364 (10)	0.0461 (11)	0.0208 (9)	−0.0061 (9)	−0.0078 (8)	−0.0062 (8)
C6	0.0232 (8)	0.0426 (10)	0.0244 (9)	−0.0003 (8)	−0.0063 (7)	−0.0072 (8)
C7	0.0242 (8)	0.0220 (8)	0.0223 (8)	0.0001 (6)	−0.0085 (7)	−0.0047 (6)
C8	0.0253 (9)	0.0412 (10)	0.0240 (9)	0.0016 (7)	−0.0058 (7)	−0.0086 (8)
C9	0.0235 (9)	0.0414 (11)	0.0366 (10)	0.0032 (8)	−0.0130 (8)	−0.0096 (8)
C10	0.0252 (8)	0.0269 (8)	0.0227 (8)	−0.0018 (7)	−0.0094 (7)	−0.0023 (7)

Geometric parameters (Å, º)

Cu—O1	1.9428 (13)	N1—H1	0.8600
Cu—O1^i	1.9428 (13)	N2—C10	1.319 (2)
Cu—O2	1.9873 (13)	N2—HN1	0.8600
Cu—O2^i	1.9873 (13)	N2—HN2	0.8600
Cu—OW1^i	2.4872 (16)	C1—C2	1.551 (2)
Cu—OW1	2.4872 (16)	C5—C6	1.371 (3)
O1—C1	1.268 (2)	C5—H5	0.9300
O2—C2	1.271 (2)	C6—C7	1.386 (2)
O3—C1	1.233 (2)	C6—H6	0.9300
O4—C2	1.230 (2)	C7—C8	1.384 (3)
O5—C10	1.230 (2)	C7—C10	1.511 (2)
OW1—HW1	0.8369	C8—C9	1.374 (3)
OW1—HW2	0.7908	C8—H8	0.9300
N1—C9	1.332 (3)	C9—H9	0.9300
N1—C5	1.336 (3)
O1—Cu—O1^i	180.0	HN1—N2—HN2	120.0
O1—Cu—O2	84.67 (5)	O3—C1—O1	125.24 (16)
O1^i—Cu—O2	95.33 (5)	O3—C1—C2	119.00 (15)
O1—Cu—O2^i	95.33 (5)	O1—C1—C2	115.76 (14)
O1^i—Cu—O2^i	84.67 (5)	O4—C2—O2	127.19 (16)
O2—Cu—O2^i	180.0	O4—C2—C1	117.39 (15)
O1—Cu—OW1^i	91.69 (5)	O2—C2—C1	115.41 (14)
O1^i—Cu—OW1^i	88.31 (5)	N1—C5—C6	119.92 (17)
O2—Cu—OW1^i	88.84 (5)	N1—C5—H5	120.0
O2^i—Cu—OW1^i	91.16 (5)	C6—C5—H5	120.0
O1—Cu—OW1	88.31 (5)	C5—C6—C7	119.57 (17)
O1^i—Cu—OW1	91.69 (5)	C5—C6—H6	120.2
O2—Cu—OW1	91.16 (5)	C7—C6—H6	120.2
O2^i—Cu—OW1	88.84 (5)	C8—C7—C6	119.02 (16)
OW1^i—Cu—OW1	180.0	C8—C7—C10	123.09 (16)
C1—O1—Cu	112.74 (11)	C6—C7—C10	117.89 (15)
C2—O2—Cu	111.40 (11)	C9—C8—C7	119.18 (17)
Cu—OW1—HW1	109.8	C9—C8—H8	120.4
Cu—OW1—HW2	107.9	C7—C8—H8	120.4
HW1—OW1—HW2	105.0	N1—C9—C8	120.27 (17)
C9—N1—C5	122.03 (16)	N1—C9—H9	119.9
C9—N1—H1	119.0	C8—C9—H9	119.9
C5—N1—H1	119.0	O5—C10—N2	123.88 (16)
C10—N2—HN1	120.0	O5—C10—C7	118.68 (15)
C10—N2—HN2	120.0	N2—C10—C7	117.44 (15)
O2—Cu—O1—C1	0.85 (13)	O3—C1—C2—O2	179.58 (16)
O2^i—Cu—O1—C1	−179.15 (13)	O1—C1—C2—O2	−0.6 (2)
OW1^i—Cu—O1—C1	−87.83 (13)	C9—N1—C5—C6	−0.6 (3)
OW1—Cu—O1—C1	92.17 (13)	N1—C5—C6—C7	0.4 (3)
O1—Cu—O2—C2	−1.19 (12)	C5—C6—C7—C8	−0.2 (3)
O1^i—Cu—O2—C2	178.81 (12)	C5—C6—C7—C10	179.36 (17)
OW1^i—Cu—O2—C2	90.62 (12)	C6—C7—C8—C9	0.2 (3)
OW1—Cu—O2—C2	−89.38 (12)	C10—C7—C8—C9	−179.34 (17)
Cu—O1—C1—O3	179.39 (15)	C5—N1—C9—C8	0.6 (3)
Cu—O1—C1—C2	−0.41 (19)	C7—C8—C9—N1	−0.4 (3)
Cu—O2—C2—O4	−179.26 (16)	C8—C7—C10—O5	−161.49 (18)
Cu—O2—C2—C1	1.25 (18)	C6—C7—C10—O5	18.9 (3)
O3—C1—C2—O4	0.0 (3)	C8—C7—C10—N2	19.1 (3)
O1—C1—C2—O4	179.85 (16)	C6—C7—C10—N2	−160.47 (17)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
OW1—HW1···O5^ii	0.84	1.97	2.7959 (19)	170
OW1—HW2···O4^iii	0.79	1.94	2.733 (2)	175
N1—H1···O3^iv	0.86	1.91	2.675 (2)	148
N1—H1···O4^iv	0.86	2.31	2.963 (2)	132
N2—HN1···OW1^v	0.86	2.04	2.837 (2)	154
N2—HN2···O2^i	0.86	2.31	3.078 (2)	149

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