Poly[bis­(μ3-5-nitro­isophthalato)bis­(1,10-phenanthroline)dimanganese(II)]

Hai-Dong Wang; Min-Min Li; Hong-Yin He; Fu-Bin Jiang

doi:10.1107/S1600536809009052

. 2009 Mar 19;65(Pt 4):m416. doi: 10.1107/S1600536809009052

Poly[bis(μ₃-5-nitroisophthalato)bis(1,10-phenanthroline)dimanganese(II)]

Hai-Dong Wang ^a, Min-Min Li ^a, Hong-Yin He ^a,^*, Fu-Bin Jiang ^b

PMCID: PMC2968954 PMID: 21582358

Abstract

The title complex, [Mn₂(C₈H₃NO₆)₂(C₁₂H₈N₂)₂]_n, was synthesized under hydrothermal conditions. The structure contains two independent Mn^II atoms, each coordinated in a distorted octahedral MnN₂O₄ geometry. [Mn₂(phen)₂] units (phen = 1,10-phenantroline) are bridged by 5-nitroisophthalate (nip) ligands into ladder-like chains parallel to [100]. Adjacent polymeric chains are linked by C—H⋯O and π–π interactions [centroid-to-centroid distance = 3.6369 (12) Å] into a two-dimensional framework parallel to (010).

Related literature

For related isophthalate complexes, see: He et al. (2004 ▶, 2005 ▶); Sun et al. (2003 ▶); Wu et al. (2002 ▶).

Experimental

Crystal data

[Mn₂(C₈H₃NO₆)₂(C₁₂H₈N₂)₂]
M _r = 888.52
Triclinic,
a = 10.0602 (1) Å
b = 14.3435 (2) Å
c = 14.6637 (2) Å
α = 104.052 (1)°
β = 102.633 (1)°
γ = 110.460 (1)°
V = 1812.69 (4) Å³
Z = 2
Mo Kα radiation
μ = 0.78 mm⁻¹
T = 293 K
0.28 × 0.23 × 0.19 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2002 ▶) T _min = 0.82, T _max = 0.90
19255 measured reflections
6733 independent reflections
5771 reflections with I > 2σ(I)
R _int = 0.021

Refinement

R[F ² > 2σ(F ²)] = 0.032
wR(F ²) = 0.082
S = 1.05
6733 reflections
541 parameters
H-atom parameters constrained
Δρ_max = 0.38 e Å⁻³
Δρ_min = −0.28 e Å⁻³

Data collection: SMART (Bruker, 2002 ▶); cell refinement: SAINT (Bruker, 2002 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809009052/wm2223sup1.cif

e-65-0m416-sup1.cif^{(38KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809009052/wm2223Isup2.hkl

e-65-0m416-Isup2.hkl^{(322.8KB, hkl)}

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

Table 1. Selected bond lengths (Å).

Mn1—O6ⁱ	2.1498 (15)
Mn1—O11	2.1508 (15)
Mn1—N2	2.2531 (18)
Mn1—N1	2.2584 (18)
Mn1—O1	2.2661 (15)
Mn1—O2	2.2879 (15)
Mn2—O5	2.1608 (15)
Mn2—O12ⁱⁱ	2.1652 (15)
Mn2—O7	2.1938 (16)
Mn2—N5	2.2411 (18)
Mn2—N6	2.2697 (19)
Mn2—O8	2.3830 (16)

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Symmetry codes: (i) Inline graphic ; (ii) .

Table 2. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3⋯O1ⁱⁱⁱ	0.93	2.50	3.267 (4)	140
C10—H10⋯O2^iv	0.93	2.54	3.210 (3)	129
C29—H29⋯O5	0.93	2.51	3.079 (3)	119
C31—H31⋯O3^v	0.93	2.38	2.888 (4)	114
C38—H38⋯O7^vi	0.93	2.45	3.121 (3)	129
C38—H38⋯O12^vii	0.93	2.60	3.351 (3)	139

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Symmetry codes: (iii) Inline graphic ; (iv) ; (v) ; (vi) ; (vii) .

supplementary crystallographic information

Comment

Coordination polymers with isophthalate and its derivatives, such as 5-nitroisophthalate (He et al., 2004), 5-sulfoisophthalate (Sun et al., 2003), 5-hydroisophthalate (He et al., 2005) or 5-aminoisophthalate (Wu et al., 2002), have been attracted interest in recent years because of their potential applications and intriguing architectures with new topologies. Here we reported a novel compound, (I), [Mn₂(nip)₂(phen)₂]_n (I), where nip = 5-nitroisophthalate and phen = 1,10-phenanthroline.

In the title compound (I), the coordination sphere of the two manganese ions can be best described as distorted octahedral (Fig.1). The carboxyl groups of the nip ligands with µ₂-chelating coordination mode to the metal centres show an average Mn—O distance of 2.288 Å, whereas the carboxyl groups with a µ₁-bridging mode have an average Mn—O distance of 2.158 Å. The Mn···Mn separation is 7.8156 (5) Å. A one-dimensional ladder-like framework is created by the bridging coordination mode of the nip ligands. Significant π–π stacking interactions exist between adjacent ladders, with a Cg10···Cg10(-x, -y, 1 - z) distance of 3.6369 (12) Å (Cg10 is the centroid of atoms C14–C19) (Fig. 2).

Experimental

A mixture of MnSO₄.H₂O (0.0840 g, 0.5 mmol), 1,10-phenanthroline (0.1980 g, 1 mmol), 5-nitroisophthalic acid (0.2100 g, 1 mmol), 8 ml H₂O and 8 ml EtOH was heated at 473 K for 5 d in a 20 ml Teflon-lined stainless-steel autoclave. After cooling, yellow plane-like crystals of the title compound were obtained.