catena-Poly[[[aqua­copper(II)]-bis­[μ-N,N′-bis­(pyridin-4-yl)isophthalamide]-[aqua­copper(II)]-di-μ-sulfato] dimethyl­formamide disolvate]

Er-Peng Zhang; Li-Ping Wang; Yu-Fei Wang

doi:10.1107/S1600536813003413

. 2013 Feb 16;69(Pt 3):m150–m151. doi: 10.1107/S1600536813003413

catena-Poly[[[aquacopper(II)]-bis[μ-N,N′-bis(pyridin-4-yl)isophthalamide]-[aquacopper(II)]-di-μ-sulfato] dimethylformamide disolvate]

Er-Peng Zhang ^a,^*, Li-Ping Wang ^b, Yu-Fei Wang ^b

PMCID: PMC3588534 PMID: 23476497

Abstract

In the title coordination polymer, {[Cu(SO₄)(C₁₈H₁₄N₄O₂)(H₂O)]·C₃H₇NO}_n, the Cu^II ion is coordinated by two N atoms of two briding N,N′-bis(pyridin-4-yl)isophthalamide ligands, two O atoms of two bridging SO₄ ²⁻ anions and a water molecule, giving a distorted CuN₂O₃ square-pyramidal geometry. The whole repeating molecular unit is generated by inversion symmetry. This leads to the formation of a looped-chain one-dimensional coordination polymer propagating along [110]. The dimethylformamide (DMF) molecules are linked to the chains via O—H⋯O hydrogen bonds. The chains are linked via N—H⋯O hydrogen bonds, forming two-dimensional networks parallel to (001). There are also a number of C—H⋯O interactions present and a parallel slipped π–π interaction. The latter involves inversion-related pyridine rings with a centroid–centroid distance of 3.594 (2) Å [normal distance = 3.3338 (13) and slippage = 1.341 Å]. These interactions lead to the formation of a three-dimensional structure.

Related literature

For background to metal complexes with a N,N′-bis-(4-pyridyl)isophthalamide ligand, see: Adarsh et al. (2009 ▶); Gong et al. (2010 ▶, 2011 ▶); Kim et al. (2011 ▶).

Experimental

Crystal data

[Cu(SO₄)(C₁₈H₁₄N₄O₂)(H₂O)]·C₃H₇NO
M _r = 569.06
Triclinic,
a = 10.389 (2) Å
b = 11.092 (1) Å
c = 12.105 (2) Å
α = 63.47 (3)°
β = 79.75 (2)°
γ = 71.08 (3)°
V = 1179.8 (4) Å³
Z = 2
Mo Kα radiation
μ = 1.07 mm⁻¹
T = 293 K
0.28 × 0.24 × 0.20 mm

Data collection

Rigaku Saturn 724 diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.753, T _max = 0.814
14785 measured reflections
5581 independent reflections
4622 reflections with I > 2σ(I)
R _int = 0.039

Refinement

R[F ² > 2σ(F ²)] = 0.052
wR(F ²) = 0.124
S = 1.07
5581 reflections
339 parameters
4 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.44 e Å⁻³
Δρ_min = −0.48 e Å⁻³

Data collection: CrystalClear (Rigaku/MSC, 2006 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Supplementary Material

Click here for additional data file.^{(30.9KB, cif)}

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536813003413/su2555sup1.cif

e-69-0m150-sup1.cif^{(30.9KB, cif)}

Click here for additional data file.^{(273.2KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813003413/su2555Isup2.hkl

e-69-0m150-Isup2.hkl^{(273.2KB, 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
N3—H3A⋯O2ⁱ	0.86 (3)	2.03 (3)	2.867 (3)	164 (3)
N4—H4A⋯O3ⁱ	0.87 (3)	2.25 (3)	3.103 (4)	168 (3)
O5—H5A⋯O8ⁱⁱ	0.82 (3)	1.81 (3)	2.626 (4)	179 (4)
O5—H5B⋯O2	0.81 (3)	1.90 (3)	2.684 (3)	164 (4)
C4—H4⋯O8	0.93	2.45	3.325 (4)	157
C18—H18⋯O6ⁱⁱⁱ	0.93	2.55	3.277 (4)	136
C19—H19⋯O4^iv	0.93	2.47	3.286 (4)	146
C20—H20C⋯O3^v	0.96	2.58	3.226 (6)	125

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

Acknowledgments

The authors are grateful to the Henan Center for Disease Control and Prevention for financial support and thank Professor Hong-Wei Hou of Zhengzhou University for his help.

supplementary crystallographic information

Comment

The bis-pyridyl-bis-amide ligands have been used to construct various metal-organic frameworks (MOFs), not only due to their conformational flexibility but also due to the multiple hydrogen bonding sites in the ligand backbone (Adarsh et al., 2009; Gong et al., 2010, 2011; Kim et al., 2011). In this work, the bis-pyridyl-bis-amide ligand, N,N'-bis-(4-pyridyl)isophthalamide (bppa), has been used to generate the title coordination polymer whose crystal structure is reported on herein.

The coordination enviroment of the Cu^II center in the title complex is shown in Fig. 1. In the distorted square pyramidal geometry of the Cu^II ion the basal positions are occupied by two pyridyl N atoms of briding bppa ligands (N1 and N2ⁱ), an O atom (O1) of a briding SO₄^2- anion and the O atom (O5) of a coordinated water molecule, while the axial position is occupied by the O atom (O4ⁱⁱ) of a second briding SO₄^2- anion. The Cu^II ions are connected by a pair of bridging SO₄^2- anions, yielding a centrosymmetric Cu₂(SO₄)₂ binuclear unit with a Cu···Cu distance of 4.772( ) Å. The binuclear units are further linked by two bppa ligands to give a looped-chain coordination polymer extending along [1 1 0], as shown in Fig. 2. The distance between two Cu^II ions bridged by the bppa ligands is ca. 13.87 Å.

In the crystal, the chains are linked via N-H···O to form two-dimensional networks extending in the a and b directions. The dimethyl formamide (DMF) molecules are linked to the chains via O-H···O hydrogen bonds (Table 1). There are also a number of C-H···O interactions present and a parallel slipped π-π interaction. The latter involves inversion related N2/C14-C18 pyridine rings with a centroid-to-centroid distance 3.594 (2) Å [normal distance 3.3338 (13) Å, slippage 1.341 Å]. These interactions lead to the formatin of a three-diemnsional structure.

Experimental

The ligand N,N'-bis-(4-pyridyl)isophthalamide (0.03 mmol, 10 mg) in DMF (5 ml) was added dropwise to a methanol solution (5 ml) of CuSO₄^.5H₂O; (0.03 mmol, 7.5 mg) in methanol. The resulting solution was allowed to stand at room temperature. After one week good quality blue crystals were obtained.