Crystal structure of poly[(N,N-di­methyl­acetamide-κO)(μ4-5-methyl­isophthalato-κ5 O:O,O′:O′′:O′′′)manganese(II)]

Lan Jin; Li-Li Zha; San Gao; Shi-Yao Yang; Rong-Bin Huang

doi:10.1107/S2056989014025626

. 2015 Jan 1;71(Pt 1):m1–m2. doi: 10.1107/S2056989014025626

Crystal structure of poly[(N,N-dimethylacetamide-κO)(μ₄-5-methylisophthalato-κ⁵ O:O,O′:O′′:O′′′)manganese(II)]

Lan Jin ^a, Li-Li Zha ^a, San Gao ^a, Shi-Yao Yang ^a,^*, Rong-Bin Huang ^a

PMCID: PMC4331860 PMID: 25705469

Abstract

The title compound, poly[(N,N-dimethylacetamide-κO)(μ₄-5-methylisophthalato-κ⁵ O,O′:O′,O′′:O′′)manganese(II)], [Mn(C₉H₆O₄)(C₃H₇NO)]_n, was obtained from a mixture containing MnCl₂·4H₂O and 5-methylisophthalic acid in N,N-dimethylacetamide solution. The Mn²⁺ ion is coordinated by five O atoms from four bridging 5-methylisophthalate ligands and one O atom from one N,N-dimethylacetamide ligand, defining a considerably distorted coordination polyhedron with one very long Mn—O bond of 2.623 (2) Å. The Mn²⁺ ions are joined by carboxylate groups, forming rod-shaped secondary building units along the a axis. The rods are further connected by 5-methylisophthalate ligands to form the pcu (primitive cubic net) structure.

Keywords: crystal structure; manganese(II) coordination polymer; pcu structure; N,N-dimethylacetamide; 5-methylisophthalate

Related literature

For the structures of coordination polymers comprising first-row transition metal ions and benzene dicarboxylates, see: Deng et al. (2013 ▸); Jin et al. (2012 ▸); Li et al. (2010 ▸); Yang et al. (2013 ▸); Zhou et al. (2009 ▸). For the nomenclature for metal-organic frameworks, see: Rosi et al. (2005 ▸);. A very closely related crystal structure, poly[(dimethylformamide)(5-methoxybenzene-1,3-dicarboxylato)manganese(II)], was reported recently (Huang, 2013 ▸). The author described the structure in a PtS (cooperite) topology according to a different analytical approach (Carlucci et al., 2003 ▸; Hill et al., 2005 ▸). graphic file with name e-71-000m1-scheme1.jpg

Experimental

Crystal data

[Mn(C₉H₆O₄)(C₃H₇NO)]
M _r = 306.17
Orthorhombic,
a = 7.281 (5) Å
b = 15.148 (11) Å
c = 10.903 (8) Å
V = 1202.5 (15) Å³
Z = 4
Mo Kα radiation
μ = 1.11 mm⁻¹
T = 200 K
0.15 × 0.10 × 0.10 mm

Data collection

Bruker APEX area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2004 ▸) T _min = 0.851, T _max = 0.897
10159 measured reflections
2874 independent reflections
2768 reflections with I > 2σ(I)
R _int = 0.025

Refinement

R[F ² > 2σ(F ²)] = 0.024
wR(F ²) = 0.059
S = 1.07
2874 reflections
175 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.29 e Å⁻³
Absolute structure: Flack (1983 ▸), 0 Friedel pairs
Absolute structure parameter: 0.025 (14)

Data collection: SMART (Bruker, 2002 ▸); cell refinement: SAINT (Bruker, 2002 ▸); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▸); program(s) used to refine structure: SHELXTL; molecular graphics: DIAMOND (Brandenburg, 2007 ▸); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablock(s) I, AE2. DOI: 10.1107/S2056989014025626/fk2084sup1.cif

e-71-000m1-sup1.cif^{(22.2KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989014025626/fk2084Isup2.hkl

e-71-000m1-Isup2.hkl^{(141.1KB, hkl)}

Click here for additional data file.^{(1.6MB, tif)}

x y z x y z x y z x y z x y z x y z . DOI: 10.1107/S2056989014025626/fk2084fig1.tif

Coordination modes in (I). Anisotropic displacement ellipsoids are drawn at the 50% probability level. Symmetry codes: i −x, −y + 2, z + Inline graphic ; ii −x + , y − , z + ; iii x − , −y + , z; iv x + , −y + , z; v −x + , y + , z − ; vi −x, −y + 2, z − .

Click here for additional data file.^{(3.4MB, tif)}

a 6 . DOI: 10.1107/S2056989014025626/fk2084fig2.tif

The packing of (I), viewed down the a axis, showing MnO₆ in polyhedra.

CCDC reference: 1035658

Additional supporting information: crystallographic information; 3D view; checkCIF report

Table 1. Selected geometric parameters (, ).

Mn1O4ⁱ	2.0609(19)
Mn1O3ⁱⁱ	2.0855(15)
Mn1O1	2.0885(16)
Mn1O5	2.1342(18)
Mn1O2ⁱⁱⁱ	2.1378(16)

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O4ⁱMn1O3ⁱⁱ	131.59(6)
O4ⁱMn1O1	83.59(6)
O3ⁱⁱMn1O1	98.77(7)
O4ⁱMn1O5	83.95(6)
O3ⁱⁱMn1O5	84.88(7)
O1Mn1O5	166.04(5)
O4ⁱMn1O2ⁱⁱⁱ	135.70(6)
O3ⁱⁱMn1O2ⁱⁱⁱ	92.23(7)
O1Mn1O2ⁱⁱⁱ	97.51(7)
O5Mn1O2ⁱⁱⁱ	95.80(7)

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

Acknowledgments

We are grateful for financial support by the National Natural Science Foundation of China (grant Nos. 21071117 and 21471125).

supplementary crystallographic information

S1. Structural commentary

We have reported the structures of dozens of coordination polymers comprising first-row transition metal ions and benzene dicarboxylates (Deng et al., 2013; Jin et al., 2012; Li et al. 2010; Yang et al., 2013; Zhou et al., 2009). We found that metal ion is the most important factor that influences the structure of coordination polymer.

The title compound, [Mn(C₉H₆O₄)(C₃H₇O)]_n, (I) was obtained with the same method reported in our previous paper (Yang et al., 2013). The structure feature of I is quite similar to those manganese analogs reported in that paper. The Mn²⁺ ions are joined by carboxyl groups to form rod-shaped secondary building units (SBUs) along the a axis. Each rod is further connected to four adjacent rods by 5-methylisophthalates to form the rod packing type 2 pcu (primitive cubic net) structure according to the nomenclature for metal-organic frameworks (Rosi et al., 2005). A very closely related molecular structure, poly[(dimethylformamide)(5-methoxybenzene-1,3-dicarboxylato)manganese(II)], was reported recently (Huang, 2013). The author described the structure in PtS (cooperite) topology according to a different analysis approach (Carlucci et al., 2003; Hill et al., 2005).

S2. Synthesis and crystallization

A mixture containing MnCl₂.4H₂O (0.039 g, 0.20 mmol) and 5-methylisophthalic acid (H₂mip, 0.036 g, 0.20 mmol) in 10 mL N,N-dimethylacetamide (DMF) was heated at 100 °C for 5000 min. Colourless block crystals were generated (0.025 g, 41%).

S3. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. H atoms bonded to C atoms were positioned geometrically and refined using a riding model (including free rotation about the C—C bond), with C—H = 0.95–0.99 Å and with U_iso(H) = 1.2 (1.5 for methyl groups) times U_eq(C).