catena-Poly[[aquabis[N-(pyridin-3-yl)isonicotinamide-κN 1]copper(II)]-μ-fumarato-κ2 O 1:O 4]

Sultan H Qiblawi; Robert L LaDuca

doi:10.1107/S1600536812047101

. 2012 Nov 24;68(Pt 12):m1514. doi: 10.1107/S1600536812047101

catena-Poly[[aquabis[N-(pyridin-3-yl)isonicotinamide-κN ¹]copper(II)]-μ-fumarato-κ² O ¹:O ⁴]

Sultan H Qiblawi ^a, Robert L LaDuca ^a,^*

PMCID: PMC3588761 PMID: 23468726

Abstract

In the title compound, [Cu(C₄H₂O₄)(C₁₁H₉N₃O)₂(H₂O)]_n, Cu^II ions on crystallographic twofold rotation axes are coordinated in a square pyramidal environment by two trans O atoms belonging to two monodentate fumarate anions, two trans isonicotinamide pyridyl N-donor atoms from monodentate, pendant 3-pyridylisonicotinamide (3-pina) ligands, and one apical aqua ligand, also sited on the crystallographic twofold rotation axis. The exobidentate fumarate ligands form [Cu(fumarate)(3-pina)₂(H₂O)]_n coordination polymer chains that are arranged parallel to [001]. In the crystal, these polymeric chains are anchored into supramolecular layers parallel to (100) by O—H⋯O hydrogen bonds between aqua ligands and unligating fumarate O atoms, and N—H⋯O(=C) hydrogen bonds between 3-pina ligands. In turn, the layers aggregate by weak C—H⋯N and C—H⋯O hydrogen bonds, affording a three-dimensional network.

Related literature

For the preparation of 3-pyridylisonicotinamide, see: Gardner et al. (1954 ▶). For the preparation of other dicarboxylate coordination polymers containing 3-pyridylisonicotinamide, see: Kumar (2009 ▶). graphic file with name e-68-m1514-scheme1.jpg

Experimental

Crystal data

[Cu(C₄H₂O₄)(C₁₁H₉N₃O)₂(H₂O)]
M _r = 594.04
Monoclinic,
a = 29.854 (4) Å
b = 5.3535 (7) Å
c = 17.353 (2) Å
β = 118.686 (2)°
V = 2433.0 (6) Å³
Z = 4
Mo Kα radiation
μ = 0.96 mm⁻¹
T = 173 K
0.25 × 0.13 × 0.09 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.794, T _max = 0.919
9406 measured reflections
2240 independent reflections
1758 reflections with I > 2σ(I)
R _int = 0.053

Refinement

R[F ² > 2σ(F ²)] = 0.036
wR(F ²) = 0.083
S = 1.04
2240 reflections
188 parameters
5 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.34 e Å⁻³
Δρ_min = −0.36 e Å⁻³

Data collection: APEX2 (Bruker, 2006 ▶); cell refinement: SAINT (Bruker, 2006 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: Crystal Maker (Palmer, 2007 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Click here for additional data file.^{(23.8KB, cif)}

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812047101/lh5556sup1.cif

e-68-m1514-sup1.cif^{(23.8KB, cif)}

Click here for additional data file.^{(110.2KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812047101/lh5556Isup2.hkl

e-68-m1514-Isup2.hkl^{(110.2KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3O⋯O1ⁱ	0.84 (1)	1.83 (1)	2.660 (2)	169 (3)
N2—H2N⋯O2ⁱ	0.88 (2)	2.33 (2)	3.153 (3)	155 (3)
C2—H2⋯O4ⁱⁱ	0.95	2.48	3.360 (4)	153
C7—H7⋯O1ⁱⁱⁱ	0.95	2.48	3.430 (4)	178
C9—H9⋯N1^iv	0.95	2.39	3.263 (4)	153
C12—H12⋯O1^v	0.95	2.43	3.374 (4)	171

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) ; (v) .

Acknowledgments

We gratefully acknowledge the donors of the American Chemical Society Petroleum Research Fund for funding this work.

supplementary crystallographic information

Comment

In comparison to divalent metal coordination polymers containing rigid rod dipyridine ligands such as 4,4'-bipyridine, related materials containing the kinked dipodal ligand 3-pyridylisonicotinamide (3-pina) are much less common (Kumar, 2009). The title compound was obtained as blue crystals through the hydrothermal reaction of copper nitrate, fumaric acid, and 3-pina.

The asymmetric unit of the title compound contains a divalent copper atom and an aqua ligand on a crystallographic twofold rotation axis, a 3-pina ligand, and one half of a fumarate ligand whose centroid rests on a crystallographic inversion centre. The copper atom is square pyramidally coordinated (Fig. 1), with the basal plane containing trans isonicotinamide pyridyl N atom donors from two 3-pina ligands and trans O atom donors from monodentate carboxylate groups belonging to two fumarate ligands. The aqua ligand is located in the apical position.

The Cu atoms are linked by exobidentate, bis(monodentate) fumarate ligands to form [Cu(fumarate)(3-pina)₂(H₂O)]_n coordination polymer chains that are oriented parallel to [0 0 1] (Fig. 2). Each individual chain is anchored to two others via O—H···O pairwise hydrogen bonding (Table 1) between aqua ligands and unligated fumarate O atoms, thereby constructing supramolecular two-dimensional layers arranged parallel to the bc crystal planes (Fig. 3). The stability of the layer motifs is enhanced by N—H···O hydrogen bonding between amide groups of adjacent 3-pina ligands (Fig. 4). In turn the layers stack along [1 0 0] in an AAA pattern via C—H···N interactions mediated by unligated 3-pyridyl N atoms belonging to the pendant 3-pina ligands (Fig. 5), thus forming the three-dimensional structure of the title compound which is also stabilized by weak C—H···O interactions.

Experimental

Copper(II) nitrate hydrate and fumaric acid were obtained commercially. 3-Pyridylisonicotinamide (3-pina) was prepared via a published procedure (Gardner et al., 1954). A mixture of copper nitrate hydrate (86 mg, 0.37 mmol), fumaric acid (42 mg, 0.36 mmol), 3-pina (74 mg, 0.37 mmol) and 10.0 g water (550 mmol) was placed into a 23 ml Teflon-lined Parr acid digestion bomb, which was then heated under autogenous pressure at 393 K for 24 h. Blue needles of the title compound were obtained.