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Acta Cryst. (2007). E63, m1331-m1332    [ doi:10.1107/S1600536807015851 ]

Bis(2-aminopyridinium) diaquabis(malonato-[kappa]2O,O')cuprate(II)

S. R. Choudhury, J. Bhattacharyya, S. Das, B. Dey, S. Mukhopadhyay, L.-P. Lu and M.-L. Zhu

Abstract top

The CuII ion in the title compound, (C5H7N2)2[Cu(C3H2O4)2(H2O)2], is located on an inversion centre and coordinated by four O atoms from two bidentate malonate (mal) ligands in the equatorial plane and two O atoms from two coordinated water molecules in the axial positions, forming an elongated octahedral geometry. Each [Cu(mal)2(H2O)2]2- anion bridges two 2-aminopyridinium cations via N-H...O hydrogen bonds and symmetry-related anions via O-H...O hydrogen bonds, to form an infinite one-dimensional chain. Additional O-H...O and C-H...O hydrogen bonds generate two-dimensional sheets that are joined into a three-dimensional network via N-H...O, C-H...O and interlayer [pi]-[pi] interactions between aminopyridinium cations (symmetry code: 1-x,1-y,2-z).

Comment top

The title complex, (I), (C5H5N2H)2[Cu(mal)2(H2O)2] (Fig. 1), was synthesized from purely aqueous media by mixing the reactants in stoichiometric

ratio and adjusting the pH of the mixture with dilute NaOH. Selected geometric data are listed in Table 1.

The asymmetric unit of (I) consists of one diaquabis(malonato)cuprate(II) anion

and two protonated 2-aminopyridine cations. The coordination around Cu in the mononuclear unit is elongated octahedral, forming a CuO6 chromophore. Four carboxylate O atoms from two bidentate malonate anions build the equatorial plane, with Cu—O bonds nearly identical [1.929 (15) and 1.933 (15) Å for Cu1—O3 and Cu1—O1, respectively], whereas two water molecules occupy the axial sites [2.665 (2) Å for Cu1—O5]. The values of the Cu—O(malonate) bonds and bond angles around Cu1 agree well with those previously reported for other malonate-containing CuII complexes. The axial Cu1—O5 bond is somewhat longer than that in the similar unit reported by other authors, e.g. [Cu(H2O)4][Cu(mal)2(H2O)2] (Chattopadhyay et al., 1993), {[Cu(H2O)4]2[Cu(mal)2(H2O)2]} (Reference?), [Cu(mal)2(H2O)2]{[Cu(H2O)4][Cu(mal)2(H2O)2]} (Ruiz-Pérez et al. 2000) and [MII(H2O)6][CuII(mal)2(H2O)2] (Rodríguez-Martin et al. 2002).

Compound (I) is in form of a dianion. A comparison of the geometry of the current anion with that of the related neutral complex [Cu(Hmal)2(H2O)2] (Lenstra & Kataeva, 2001) indicates shorter Cu—O bonds in the equatorial plane and longer axial bonds in (I), consistent with a Jahn–Teller effect. The

malonate ligands show a twist–boat conformation, with the methylene C atom out

of the chelate ring plane.

The supramolecular interactions in (I) are listed in Table 2. The monomeric anionic units link to one another via strong complementary O5—H5A···O2 hydrogen bonds generating an R22(12) (Bernstein et al., 1995) hydrogen-bonded supramolecular synthon, to give an infinite one-dimensional tape along the a axis (Fig. 2). Each monomeric unit also binds two 2-aminopyridine ligands via N2—H2C···O2 and N1—H1···O1 hydrogen bonds through the formation of an R22(8) hydrogen-bonding synthon (Fig. 2). Each such layer links adjacent layers along the b axis via O5—H5B···O4 hydrogen bonds, generating an R22(12) cyclic motif (Fig. 3). The aminopyridine unit from one layer also participates in hydrogen bonding via a C7—H7···O2 hydrogen bond with the adjacent layer to give a two-dimensional sheet. It is interesting to note that one H atom (H5A) of the coordinated water molecule helps the monomeric unit to grow one-dimensionally and the other H atom (H5B) helps the one-dimensional chains to grow two-dimensionally. These two-dimensional sheets propagate along the c axis direction through interlayer N2—H2D···O4 and C5—H5···O3 hydrogen bonds. Interlayer π–π (Fig. 4) stacking between aminopyridine moieties also provides additional stabilization of the ultimate three-dimensional structure (Fig. 5).

Related literature top

For related literature, see: Chattopadhyay et al. (1993); Lenstra & Kataeva (2001); Rodríguez-Martin et al. (2002); Ruiz-Pérez et al. (2000); Bernstein et al. (1995).

Experimental top

Copper(II) acetate monohydrate (0.199 g, 1 mmol) was dissolved in water (20 ml) and allowed to react with malonic acid (0.208 g, 2 mmol) in water (10 ml) to give a clear blue solution. A warm aqueous solution (10 ml) of 2-aminopyridine (0.188 g, 2 mmol) was added dropwise to the above blue solution with continuous

stirring. The pH of this solution was adjusted to 5.20 by dropwise addition of dilute NaOH. This solution was heated at 323 K for 1 h with continuous stirring

and then filtered and kept for crystallization. Flat blue single crystals of (I) suitable for X-ray analysis were separated after several weeks from the mother liquor by slow evaporation at room temperature. The crystals were filtered off, washed with cold water and dried on filter paper (yield 0.24 g, 48%). Analysis, calculated for C16H22N4O10Cu: C 38.91, H 4.49, N 11.34%; found: C 38.22, H 3.89, N 10.91%.

Refinement top

H atoms attached to C and N atoms were placed in geometrically idealized positions, with Csp2—H = 0.93, Csp3—H = 0.97 and Nsp2—H = 0.86 Å, and constrained to ride on their parent atoms, with Uiso(H) = 1.2Ueq(C,N). H atoms attached to O (water) were located in a difference Fourier map and refined freely.

Computing details top

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: SHELXTL/PC (Sheldrick, 1999); software used to prepare material for publication: SHELXTL/PC.

Figures top
[Figure 1] Fig. 1. The structure of (I), with displacement ellipsoids drawn at the 30% probability level. Dotted lines indicate hydrogen bonds. Unlabelled atoms are generated by the inversion operation (1 - x, 1 - y, 1 - z).
[Figure 2] Fig. 2. The one-dimensional assembly of monomeric units along the a axis with 2-aminopyridinium. Dashed lines indicate hydrogen bonds.
[Figure 3] Fig. 3. The two-dimensional assembly of monomeric units. Aminopyridinium ligands have been omitted for clarity. Dashed lines indicate hydrogen bonds.
[Figure 4] Fig. 4. The π–π stacking (blue dotted line) between aminopyridine units. N2—H2D···O4 and C5—H5···O3 hydrogen bonds (dashed lines) help to grow the structure along c axis.
[Figure 5] Fig. 5. The packing of complex (I), resulting in the three-dimensional assembly. Dotted lines indicate hydrogen bonds.
Bis(2-aminopyridinium) diaquabis(malonato-κ2O,O')cuprate(II) top
Crystal data top
(C5H7N2)2[Cu(C3H2O4)2(H2O)2]Z = 1
Mr = 493.92F(000) = 255
Triclinic, P1Dx = 1.694 Mg m−3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 7.0433 (13) ÅCell parameters from 1903 reflections
b = 7.9116 (15) Åθ = 3.2–26.9°
c = 9.5767 (18) ŵ = 1.19 mm−1
α = 96.096 (2)°T = 298 K
β = 107.865 (2)°Block, blue
γ = 103.743 (2)°0.50 × 0.40 × 0.30 mm
V = 484.03 (16) Å3
Data collection top
Bruker SMART 1K CCD area-detector
diffractometer		1659 independent reflections
Radiation source: fine-focus sealed tube1616 reflections with I > 2σ(I)
graphiteRint = 0.013
ω scansθmax = 25.0°, θmin = 2.3°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2000)		h = −8→8
Tmin = 0.587, Tmax = 0.716k = −7→9
1987 measured reflectionsl = −11→10
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.028Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.075H atoms treated by a mixture of independent and constrained refinement
S = 1.14 w = 1/[σ2(Fo2) + (0.0298P)2 + 0.2343P]
where P = (Fo2 + 2Fc2)/3
1659 reflections(Δ/σ)max = 0.001
150 parametersΔρmax = 0.21 e Å−3
0 restraintsΔρmin = −0.27 e Å−3
Crystal data top
(C5H7N2)2[Cu(C3H2O4)2(H2O)2]γ = 103.743 (2)°
Mr = 493.92V = 484.03 (16) Å3
Triclinic, P1Z = 1
a = 7.0433 (13) ÅMo Kα radiation
b = 7.9116 (15) ŵ = 1.19 mm−1
c = 9.5767 (18) ÅT = 298 K
α = 96.096 (2)°0.50 × 0.40 × 0.30 mm
β = 107.865 (2)°
Data collection top
Bruker SMART 1K CCD area-detector
diffractometer		1659 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2000)		1616 reflections with I > 2σ(I)
Tmin = 0.587, Tmax = 0.716Rint = 0.013
1987 measured reflectionsθmax = 25.0°
Refinement top
R[F2 > 2σ(F2)] = 0.028H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.075Δρmax = 0.21 e Å−3
S = 1.14Δρmin = −0.27 e Å−3
1659 reflectionsAbsolute structure: ?
150 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Special details top

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 (Å2) top
xyzUiso*/Ueq
Cu10.50000.50000.50000.03666 (15)
O10.3286 (2)0.5451 (2)0.61517 (16)0.0376 (3)
O20.1202 (3)0.6770 (2)0.68071 (18)0.0439 (4)
O30.3648 (2)0.6104 (2)0.34319 (15)0.0369 (3)
O40.2336 (3)0.8215 (2)0.26013 (18)0.0486 (4)
O50.7799 (3)0.8175 (3)0.6047 (2)0.0528 (5)
C10.2326 (3)0.6633 (3)0.6054 (2)0.0303 (4)
C20.2668 (4)0.7969 (3)0.5094 (2)0.0390 (5)
H2A0.39170.89110.56790.047*
H2B0.15170.84870.48990.047*
C30.2884 (3)0.7385 (3)0.3595 (2)0.0325 (4)
C40.2435 (3)0.4109 (3)0.9537 (2)0.0338 (4)
C50.2439 (3)0.3007 (3)1.0592 (2)0.0403 (5)
H50.23260.34101.15030.048*
C60.2608 (4)0.1344 (3)1.0272 (3)0.0494 (6)
H60.26030.06081.09670.059*
C70.2791 (4)0.0732 (3)0.8911 (3)0.0497 (6)
H70.2896−0.04080.86900.060*
C80.2810 (4)0.1815 (3)0.7930 (3)0.0439 (5)
H80.29330.14250.70190.053*
N10.2655 (3)0.3464 (2)0.82503 (19)0.0355 (4)
H10.26970.41380.76060.043*
N20.2258 (3)0.5744 (2)0.9738 (2)0.0424 (4)
H2C0.22850.63660.90570.051*
H2D0.21170.61801.05500.051*
H5A0.889 (6)0.788 (5)0.630 (4)0.076 (11)*
H5B0.803 (5)0.908 (4)0.651 (3)0.056 (10)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.0490 (2)0.0496 (3)0.0299 (2)0.03156 (18)0.02295 (17)0.01711 (16)
O10.0514 (9)0.0448 (8)0.0358 (8)0.0291 (7)0.0264 (7)0.0181 (6)
O20.0540 (9)0.0571 (10)0.0429 (9)0.0338 (8)0.0308 (8)0.0194 (7)
O30.0502 (9)0.0432 (8)0.0275 (7)0.0250 (7)0.0175 (6)0.0102 (6)
O40.0646 (11)0.0630 (11)0.0404 (9)0.0396 (9)0.0268 (8)0.0283 (8)
O50.0483 (11)0.0505 (12)0.0596 (12)0.0219 (9)0.0138 (9)0.0073 (10)
C10.0349 (10)0.0336 (10)0.0250 (9)0.0146 (9)0.0108 (8)0.0036 (8)
C20.0555 (13)0.0354 (11)0.0379 (11)0.0233 (10)0.0233 (10)0.0116 (9)
C30.0341 (10)0.0373 (11)0.0308 (10)0.0143 (9)0.0133 (8)0.0107 (8)
C40.0303 (10)0.0374 (11)0.0307 (10)0.0056 (9)0.0100 (8)0.0057 (8)
C50.0471 (12)0.0443 (13)0.0305 (11)0.0103 (10)0.0156 (9)0.0103 (9)
C60.0576 (15)0.0451 (14)0.0442 (13)0.0100 (11)0.0160 (11)0.0183 (11)
C70.0602 (15)0.0338 (12)0.0541 (15)0.0132 (11)0.0196 (12)0.0057 (10)
C80.0500 (13)0.0419 (12)0.0383 (12)0.0106 (10)0.0176 (10)−0.0001 (10)
N10.0394 (9)0.0397 (10)0.0288 (9)0.0101 (8)0.0137 (7)0.0093 (7)
N20.0559 (12)0.0402 (10)0.0381 (10)0.0170 (9)0.0229 (9)0.0095 (8)
Geometric parameters (Å, °) top
Cu1—O3i1.9293 (14)C4—N21.328 (3)
Cu1—O31.9293 (14)C4—N11.350 (3)
Cu1—O11.9336 (14)C4—C51.403 (3)
Cu1—O1i1.9336 (14)C5—C61.360 (3)
Cu1—O52.665 (2)C5—H50.9300
O1—C11.273 (2)C6—C71.396 (4)
O2—C11.238 (2)C6—H60.9300
O3—C31.272 (2)C7—C81.338 (3)
O4—C31.230 (3)C7—H70.9300
O5—H5A0.83 (4)C8—N11.347 (3)
O5—H5B0.76 (3)C8—H80.9300
C1—C21.498 (3)N1—H10.8600
C2—C31.524 (3)N2—H2C0.8600
C2—H2A0.9700N2—H2D0.8600
C2—H2B0.9700
O3i—Cu1—O3180.0O4—C3—C2117.50 (18)
O3i—Cu1—O187.80 (6)O3—C3—C2119.42 (17)
O3—Cu1—O192.20 (6)N2—C4—N1118.51 (19)
O3i—Cu1—O1i92.20 (6)N2—C4—C5124.0 (2)
O3—Cu1—O1i87.80 (6)N1—C4—C5117.5 (2)
O1—Cu1—O1i180.0C6—C5—C4119.5 (2)
O3—Cu1—O584.65 (6)C6—C5—H5120.3
O3i—Cu1—O595.35 (6)C4—C5—H5120.3
O1i—Cu1—O584.96 (7)C5—C6—C7120.6 (2)
O1—Cu1—O595.04 (7)C5—C6—H6119.7
C1—O1—Cu1126.40 (13)C7—C6—H6119.7
C3—O3—Cu1126.18 (13)C8—C7—C6118.8 (2)
H5A—O5—H5B107 (3)C8—C7—H7120.6
O2—C1—O1121.31 (18)C6—C7—H7120.6
O2—C1—C2118.82 (18)C7—C8—N1120.5 (2)
O1—C1—C2119.74 (17)C7—C8—H8119.7
C1—C2—C3119.44 (18)N1—C8—H8119.7
C1—C2—H2A107.5C8—N1—C4123.03 (19)
C3—C2—H2A107.5C8—N1—H1118.5
C1—C2—H2B107.5C4—N1—H1118.5
C3—C2—H2B107.5C4—N2—H2C120.0
H2A—C2—H2B107.0C4—N2—H2D120.0
O4—C3—O3123.06 (18)H2C—N2—H2D120.0
O3i—Cu1—O1—C1157.70 (18)C1—C2—C3—O4151.5 (2)
O3—Cu1—O1—C1−22.30 (18)C1—C2—C3—O3−29.9 (3)
O1—Cu1—O3—C331.54 (17)N2—C4—C5—C6179.4 (2)
O1i—Cu1—O3—C3−148.46 (17)N1—C4—C5—C6−1.6 (3)
Cu1—O1—C1—O2177.25 (15)C4—C5—C6—C70.4 (4)
Cu1—O1—C1—C2−7.0 (3)C5—C6—C7—C80.5 (4)
O2—C1—C2—C3−145.0 (2)C6—C7—C8—N1−0.1 (4)
O1—C1—C2—C339.2 (3)C7—C8—N1—C4−1.2 (3)
Cu1—O3—C3—O4168.22 (16)N2—C4—N1—C8−178.8 (2)
Cu1—O3—C3—C2−10.4 (3)C5—C4—N1—C82.0 (3)
Symmetry codes: (i) −x+1, −y+1, −z+1.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O10.861.912.756 (2)168
N2—H2C···O20.862.142.930 (3)152
N2—H2D···O4ii0.862.353.172 (3)161
O5—H5A···O2iii0.83 (4)1.99 (4)2.807 (3)171 (3)
O5—H5B···O4iv0.76 (3)2.31 (3)3.043 (3)161 (3)
C5—H5···O3ii0.932.453.209 (3)139
C6—H6···O4v0.932.593.514 (3)172
C7—H7···O2vi0.932.493.278 (3)142
Symmetry codes: (ii) x, y, z+1; (iii) x+1, y, z; (iv) −x+1, −y+2, −z+1; (v) x, y−1, z+1; (vi) x, y−1, z.
Table 1
Selected geometric parameters (Å, °) top
Cu1—O31.9293 (14)Cu1—O52.665 (2)
Cu1—O11.9336 (14)
O3—Cu1—O192.20 (6)O1—Cu1—O595.04 (7)
O3—Cu1—O584.65 (6)
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O10.861.912.756 (2)168
N2—H2C···O20.862.142.930 (3)152
N2—H2D···O4i0.862.353.172 (3)161
O5—H5A···O2ii0.83 (4)1.99 (4)2.807 (3)171 (3)
O5—H5B···O4iii0.76 (3)2.31 (3)3.043 (3)161 (3)
C5—H5···O3i0.932.453.209 (3)139
C6—H6···O4iv0.932.593.514 (3)172
C7—H7···O2v0.932.493.278 (3)142
Symmetry codes: (i) x, y, z+1; (ii) x+1, y, z; (iii) −x+1, −y+2, −z+1; (iv) x, y−1, z+1; (v) x, y−1, z.
Acknowledgements top

SM is grateful to Jadavpur University for partial financial support of this work. MLZ acknowledges the National Natural Science Foundation of China (grant No. 20471033), the Provincial Natural Science Foundation of Shanxi Province of China (grant No. 20051013) and the Overseas Returned Scholar Foundation of Shanxi Province of China in 2006 for financial support.

references
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