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The title compounds, [Mn(C10H8O6)]n and [Zn(C10H8O6)]n, are isomorphous coordination polymers prepared from 2,5-dimeth­oxy­terephthalic acid (H2dmt) and the respective metal(II) salts. Both complexes form three-dimensional metal–organic frameworks with each MII centre bridged by four 2,5-dimeth­oxy­terephthalate (dmt2−) anions, resulting in the same type of network topology. The asymmetric unit consists of one MII cation on a twofold axis and one half of a dmt2− anion (located on a centre of inversion). In the crystal structure, the MII centres are coordinated in a rather unusual way, as there is a distorted tetra­hedral inner coordination sphere formed by four carboxyl­ate O atoms of four different dmt2− anions, and an additional outer coordination sphere formed by two meth­oxy and two carboxyl­ate O atoms, with each of the O atoms belonging to one of the four different dmt2− anions forming the inner coordination sphere. Consideration of both coordination spheres results in a super-dodeca­hedral coordination geometry for the MII centres. Besides the numerous MII...O inter­actions, both structures are further stabilized by weak C—H...O contacts.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270110046950/gg3245sup1.cif
Contains datablocks I, II, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270110046950/gg3245Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270110046950/gg3245IIsup3.hkl
Contains datablock II

CCDC references: 813469; 813470

Comment top

Metal–organic coordination polymers (MOCPs) are crystalline frameworks composed of metal ions or clusters of metal ions called secondary building units (SBUs) and organic molecules called linkers, to form one-, two- or three-dimensional structures possessing cavities (Li et al., 1999). In specific cases, knowledge of the SBU and linker geometries, in conjunction with their interaction principles, allows the prediction of network topologies and thus supports rational framework design. It is known that specific reaction conditions such as temperature, solvent and moisture can influence SBU formation (Hausdorf et al., 2008). Nevertheless, generation of SBUs subject to linker properties has only rarely been investigated (Choi et al., 2009).

While the reaction of 2,5-dihydroxyterephthalic acid and Zn(NO3)2.4H2O [carried out under conditions (Tranchemontagne et al., 2008) comparable with those used here] leads to MOF-74 (Rosi et al., 2005) type networks, the reaction of 2,5-di-n-propoxyterephthalic acid and Zn(NO3)2.4H2O gives rise to IRMOF (Eddaoudi et al., 2002) type structures. However, three-dimensional coordination polymers containing the dmt2- anion as a linker with ZnII or MnII as metal ions for the SBU have not been reported so far. This prompted us to use the dmt2- anion as a rigid dicarboxylate with small weakly coordinating substituents for our investigations to form appropriate new types of MOCPs.

The title compounds, [Mn(dmt)]n, (I), and [Zn(dmt)]n, (II), crystallize in the monoclinic space group C2/c with asymmetric units containing one MII cation (M = Mn or Zn) and one half of a dmt2- anion (Fig. 1). Indeed, the two compounds are isomorphous, which is shown in the molecular overlay plot in Fig. 2. Besides a slight difference in the monoclinic angle β, the unit-cell dimensions do not differ significantly from each other.

As shown in Fig. 1, each of the MII cations adopts a distorted MIIO4 tetrahedral geometry, coordinated by four O atoms from four different dmt2- anions. The Mn1—O1 and Mn1—O2 bond lengths of 2.1391 (6) and 2.0761 (5) Å, respectively, in (I) are in accordance with those reported for related manganese(II) terephthalates [Mn—O = 2.100 (4)–2.188 (3) Å; Xu et al., 2010; Luo et al., 2008]. The corresponding O—Mn—O angles range from 93.73 (2) to 141.52 (3)°, thus deviating considerably from the ideal value of 109.4° for a tetrahedral coordination sphere. The Zn—O bond lengths in (II) range from 2.0023 (13) Å for Zn1—O1 to 1.9547 (13) Å for Zn1—O2 and do not vary significantly from literature values for related zinc(II) terephthalate-based MOCPs [1.935 (2)–2.104 (5) Å; Higuchi et al., 2009; Wang et al., 2008]. However, the distortion of the O—Zn—O angles from ideal tetrahedral geometry in (II), ranging from 99.51 (5) to 137.03 (8)°, is smaller than in (I). These structural differences between (I) and (II) may be caused by the different sizes of the MnII and ZnII cations (0.91 and 0.83 Å, respectively; Reference for standard values?).

The uncommon values for the O—MII—O bond angles mentioned above can be explained by the existence of a second coordination sphere formed by weak interactions between the MII cations and O atoms of the methoxy and carboxylate groups (Fig. 1). This leads to a distorted [MIIO4(O)2(OMe)2] super dodecahedron (Fig. 3), where the methoxy O atoms are located in trans positions to each other, while the two bidentate and two monodentate carboxylates coordinate in a cis position to each other (Fig. 4).

The bond lengths for M—OMe [Mn1—O3 = 2.5596 (6) Å and Zn1—O3 = 2.6224 (17) Å] and M—O2' [Mn1—O2' = 2.7570 (6) Å and Zn1—O2' = 2.8772 (16) Å] reveal that these bonds are much weaker than the M—O bonds of the inner coordination sphere. Similar coordination modes have already been reported for CdII complexes (Li et al., 2008). The MIIO8 super dodecahedra are edge-sharing, to give a one-dimensional chain along the c axis (Fig. 3). Two adjacent one-dimensional chains are interconnected by dmt2- anions to obtain a three-dimensional coordination network, with shortest Mn1A···Mn1B and Zn1A···Zn1B distances between the one-dimensional chains of 8.0793 (3) and 8.0552 (2) Å, respectively. Apart from these MII—O interactions, there are weak intermolecular C—H···O hydrogen-bonding interactions in both networks, involving C3—H3···O1i and C5—H5B···O2ii for both (I) and (II), contributing to the stabilization of the crystal structures (symmetry codes are given in Tables 1 and 2).

One dimensional rhombic channels of 9.1 × 13.1 Å in diameter (measured between atoms in opposite corners) are located along the c axis in the networks of (I) and (II). The methoxy groups point inside these channels and subdivide them into two smaller pores, shown as balls in the network structure (Fig. 5). Taking the van der Waals radii into account, their size is reduced to about 1.2 Å, which is much too small for the uptake of any solvent molecules or nitrogen. A better understanding of the network structures of (I) and (II) can be achieved by a topological investigation, reducing complex network structures to simple SBU-and-linker networks (Rosi et al., 2005) (Fig. 6). To derive the nets of (I) and (II), the SBUs were reduced to rods of shaded quadrangles linked by sharing opposite edges, which leads to a ladder-like conformation of the one-dimensional SBU chains. The linkers are represented by rungs to form a 4-connected net with parallel rungs, analogous to the Al net in SrAl2. This is called a network with sra12 topology, also found in metal–organic frameworks such as MIL-47 (Barthelet et al., 2002), MIL-53 (Loiseau et al., 2004) and MOF-71 (Rosi et al., 2005).

The main reason for the generation of the more or less unusual isomorphous structures of (I) and (II) may be the formation of metal centres with high coordination numbers. The reaction of Zn(NO3)2.4H2O and a rigid dicarboxylic acid in N,N-dimethyl formamide usually leads to an IRMOF-type framework (Eddaoudi et al., 2002) containing a four-coordinated Zn metal centre. Performing these reactions with 2,5-dihydroxyterephthalic acid instead leads to MOF-74-type frameworks, caused by the linker molecule facilitating the formation of a much more stable five-coordinated metal species. The frameworks of (I) and (II) discussed here exhibit eight-coordinated metal centres, which seems to be the most stable coordination geometry under these conditions.

Related literature top

For related literature, see: Barthelet et al. (2002); Choi et al. (2009); Eddaoudi et al. (2002); Hausdorf et al. (2008); Higuchi et al. (2009); Li et al. (1999, 2008); Loiseau et al. (2004); Luo et al. (2008); Passaniti et al. (2002); Rosi et al. (2005); Tranchemontagne et al. (2008); Wang et al. (2008); Xu et al. (2010).

Experimental top

All chemicals and solvents were commercially available and used without further purification. 2,5-Dimethoxyterephthalic acid was synthesized according to the procedure published by Passaniti et al. (2002).

For the synthesis of [Mn(dmt)]n, (I), MnCl2.4H2O (105 mg, 0.53 mmol) and 2,5-dimethoxyterephthalic acid (40 mg, 0.18 mmol) were dissolved in N,N-dimethyl formamide (40 ml) and heated in a sealed tube for 24 h at 373 K. Yellow crystals of (I) [Colourless given in CIF tables - please clarify] precipitated after 24 h (yield 72%).

For the synthesis of [Zn(dmt)]n, (II), the same procedure was used as for (I), using Zn(NO3)2.4H2O (140 mg, 0.53 mmol) instead of MnCl2.4H2O. Colourless crystals of (II) precipitated after 18 h (yield 79%).

Refinement top

For both compounds, H atoms were positioned geometrically and allowed to ride on their respective parent atoms, with C—H = 0.98 Å and Uiso(H) = 1.5Ueq(C) for methyl H, and C—H = 0.95 Å and Uiso(H) = 1.2Ueq(C) for aryl H atoms.

Computing details top

For both compounds, data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top
[Figure 1] Fig. 1. The asymmetric units of (a) (I) and (b) (II), showing the atom-labelling schemes. Displacement ellipsoids are drawn at the 50% probability level. Singly, doubly and triply primed atoms are at the symmetry positions ? [Please complete]
[Figure 2] Fig. 2. A molecular overlay of the asymmetric units of (I) and (II), showing only minor differences in the atom positions. The atoms of (I) are shown as shaded balls and the atoms of (II) as white balls with shaded borders. H atoms have been omitted for clarity.
[Figure 3] Fig. 3. The one-dimensional chains of (a) [Mn-(µ-CO2)2-Mn]n and (b) [Zn-(µ-CO2)2-Zn]n. The MII—O bonds of the second coordination spheres are shown as dashed lines. The inorganic MIIO8 SBUs are chains of edge-sharing dodecahedra [in the electronic version of the journal, purple for Mn in (a), turquoise for Zn in (b)], in which the C atoms can be connected to form a zigzag ladder (c).
[Figure 4] Fig. 4. The super-dodecahedral coordination spheres (a) MnO4(O)2(OMe)2 and (b) ZnO4(O)2(OMe)2, showing the coordination modes of the anions. The MII—O bonds of the second coordination spheres are shown as dashed lines.
[Figure 5] Fig. 5. A view of the network of (I) and (II) along the c, axis with shaded MIIO4(O)2(OMe)2 super dodecahedrons. The large balls show the accessible pores. The atom coordinates from (I) were used as the example to create the diagram.
[Figure 6] Fig. 6. The topology of the network, reduced to a simple SBU-and-linker geometry model. The MIIO4(OMe)2 SBUs are reduced to rods of shaded quadrangles and the dmt2- linkers are represented by thin grey rods.
(I) Poly[(µ4-2,5-dimethoxybenzene-1,4-dicarboxylato)manganese(II)] top
Crystal data top
[Mn(C10H8O6)]F(000) = 564
Mr = 279.10Dx = 1.776 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 8637 reflections
a = 16.7686 (6) Åθ = 2.5–34.5°
b = 8.4646 (3) ŵ = 1.28 mm1
c = 7.4464 (3) ÅT = 153 K
β = 99.093 (1)°Block, yellow
V = 1043.66 (7) Å30.52 × 0.35 × 0.33 mm
Z = 4
Data collection top
Bruker Kappa APEXII CCD area-detector
diffractometer
2156 independent reflections
Radiation source: fine-focus sealed tube2084 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.019
ϕ and ω scansθmax = 34.5°, θmin = 2.5°
Absorption correction: multi-scan
(SADABS; Bruker, 2007)
h = 2626
Tmin = 0.633, Tmax = 0.747k = 1313
11427 measured reflectionsl = 1111
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)] = 0.019Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.052H-atom parameters constrained
S = 1.09 w = 1/[σ2(Fo2) + (0.0264P)2 + 0.4525P]
where P = (Fo2 + 2Fc2)/3
2156 reflections(Δ/σ)max = 0.001
79 parametersΔρmax = 0.42 e Å3
0 restraintsΔρmin = 0.34 e Å3
Crystal data top
[Mn(C10H8O6)]V = 1043.66 (7) Å3
Mr = 279.10Z = 4
Monoclinic, C2/cMo Kα radiation
a = 16.7686 (6) ŵ = 1.28 mm1
b = 8.4646 (3) ÅT = 153 K
c = 7.4464 (3) Å0.52 × 0.35 × 0.33 mm
β = 99.093 (1)°
Data collection top
Bruker Kappa APEXII CCD area-detector
diffractometer
2156 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2007)
2084 reflections with I > 2σ(I)
Tmin = 0.633, Tmax = 0.747Rint = 0.019
11427 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0190 restraints
wR(F2) = 0.052H-atom parameters constrained
S = 1.09Δρmax = 0.42 e Å3
2156 reflectionsΔρmin = 0.34 e Å3
79 parameters
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
Mn11.00000.076459 (18)0.25000.01459 (5)
O10.88960 (4)0.05007 (7)0.25036 (9)0.02221 (11)
O20.96699 (3)0.15728 (7)0.48546 (7)0.01809 (10)
O30.89455 (3)0.29664 (7)0.73532 (8)0.02100 (11)
C10.82337 (4)0.19593 (8)0.45428 (9)0.01336 (10)
C20.82294 (4)0.27479 (8)0.62019 (9)0.01438 (10)
C30.74941 (4)0.32770 (8)0.66249 (9)0.01502 (11)
H30.74880.38150.77420.018*
C40.89808 (4)0.13108 (8)0.39354 (9)0.01460 (11)
C50.89157 (6)0.38382 (13)0.89920 (15)0.0369 (2)
H5A0.86890.48890.86850.055*
H5B0.94630.39450.96750.055*
H5C0.85750.32760.97360.055*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Mn10.00888 (7)0.02125 (8)0.01397 (7)0.0000.00279 (4)0.000
O10.0159 (2)0.0270 (3)0.0246 (3)0.00280 (19)0.00613 (19)0.0088 (2)
O20.0104 (2)0.0248 (2)0.0194 (2)0.00177 (17)0.00324 (16)0.00496 (18)
O30.0127 (2)0.0239 (3)0.0241 (2)0.00429 (18)0.00405 (18)0.0099 (2)
C10.0106 (2)0.0138 (2)0.0157 (2)0.00215 (18)0.00227 (18)0.00033 (18)
C20.0106 (2)0.0149 (2)0.0169 (2)0.00198 (19)0.00020 (19)0.0019 (2)
C30.0121 (3)0.0171 (3)0.0155 (2)0.0033 (2)0.00114 (19)0.0026 (2)
C40.0123 (3)0.0144 (2)0.0179 (3)0.00228 (19)0.0048 (2)0.0022 (2)
C50.0255 (4)0.0425 (5)0.0370 (5)0.0149 (4)0.0124 (3)0.0265 (4)
Geometric parameters (Å, º) top
Mn1—O2i2.0761 (5)C1—C3iv1.3965 (9)
Mn1—O2ii2.0761 (5)C1—C21.4052 (9)
Mn1—O1iii2.1391 (6)C1—C41.5015 (9)
Mn1—O12.1391 (6)C2—C31.3938 (9)
O1—C41.2567 (9)C3—C1iv1.3965 (9)
O2—C41.2660 (8)C3—H30.9500
O2—Mn1ii2.0761 (5)C5—H5A0.9800
O3—C21.3733 (8)C5—H5B0.9800
O3—C51.4337 (10)C5—H5C0.9800
O2i—Mn1—O2ii141.52 (3)C3—C2—C1118.61 (6)
O2i—Mn1—O1iii105.36 (2)C2—C3—C1iv122.04 (6)
O2ii—Mn1—O1iii93.73 (2)C2—C3—H3119.0
O2i—Mn1—O193.73 (2)C1iv—C3—H3119.0
O2ii—Mn1—O1105.36 (2)O1—C4—O2121.70 (6)
O1iii—Mn1—O1119.91 (4)O1—C4—C1117.85 (6)
C4—O1—Mn1107.00 (5)O2—C4—C1120.45 (6)
C4—O2—Mn1ii122.61 (4)O3—C5—H5A109.5
C2—O3—C5117.13 (6)O3—C5—H5B109.5
C3iv—C1—C2119.35 (6)H5A—C5—H5B109.5
C3iv—C1—C4116.66 (6)O3—C5—H5C109.5
C2—C1—C4123.98 (6)H5A—C5—H5C109.5
O3—C2—C3122.21 (6)H5B—C5—H5C109.5
O3—C2—C1119.17 (6)
O2i—Mn1—O1—C4171.27 (5)C1—C2—C3—C1iv0.28 (11)
O2ii—Mn1—O1—C442.48 (5)Mn1—O1—C4—O216.20 (8)
O1iii—Mn1—O1—C461.16 (5)Mn1—O1—C4—C1163.40 (5)
C5—O3—C2—C32.96 (11)Mn1ii—O2—C4—O1116.47 (7)
C5—O3—C2—C1177.31 (8)Mn1ii—O2—C4—C163.11 (8)
C3iv—C1—C2—O3179.47 (6)C3iv—C1—C4—O15.41 (9)
C4—C1—C2—O30.65 (10)C2—C1—C4—O1173.44 (7)
C3iv—C1—C2—C30.27 (11)C3iv—C1—C4—O2174.99 (6)
C4—C1—C2—C3179.09 (6)C2—C1—C4—O26.16 (10)
O3—C2—C3—C1iv179.45 (6)
Symmetry codes: (i) x, y, z1/2; (ii) x+2, y, z+1; (iii) x+2, y, z+1/2; (iv) x+3/2, y+1/2, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C3—H3···O1iv0.952.372.7209 (8)101
C5—H5B···O2v0.982.473.0654 (11)119
Symmetry codes: (iv) x+3/2, y+1/2, z+1; (v) x+2, y, z+3/2.
(II) Poly[(µ4-2,5-dimethoxybenzene-1,4-dicarboxylato)zinc(II)] top
Crystal data top
[Zn(C10H8O6)]F(000) = 584
Mr = 289.53Dx = 1.851 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 2923 reflections
a = 16.5936 (6) Åθ = 2.5–26.0°
b = 8.4438 (3) ŵ = 2.38 mm1
c = 7.4838 (3) ÅT = 153 K
β = 97.649 (2)°Block, colourless
V = 1039.25 (7) Å30.21 × 0.15 × 0.13 mm
Z = 4
Data collection top
Bruker Kappa APEXII CCD area-detector
diffractometer
1005 independent reflections
Radiation source: fine-focus sealed tube898 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.032
ϕ and ω scansθmax = 25.8°, θmin = 2.5°
Absorption correction: multi-scan
(SADABS; Bruker, 2007)
h = 1920
Tmin = 0.695, Tmax = 0.746k = 910
6781 measured reflectionsl = 98
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)] = 0.022Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.049H-atom parameters constrained
S = 1.05 w = 1/[σ2(Fo2) + (0.0227P)2 + 0.9295P]
where P = (Fo2 + 2Fc2)/3
1005 reflections(Δ/σ)max < 0.001
79 parametersΔρmax = 0.31 e Å3
0 restraintsΔρmin = 0.28 e Å3
Crystal data top
[Zn(C10H8O6)]V = 1039.25 (7) Å3
Mr = 289.53Z = 4
Monoclinic, C2/cMo Kα radiation
a = 16.5936 (6) ŵ = 2.38 mm1
b = 8.4438 (3) ÅT = 153 K
c = 7.4838 (3) Å0.21 × 0.15 × 0.13 mm
β = 97.649 (2)°
Data collection top
Bruker Kappa APEXII CCD area-detector
diffractometer
1005 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2007)
898 reflections with I > 2σ(I)
Tmin = 0.695, Tmax = 0.746Rint = 0.032
6781 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0220 restraints
wR(F2) = 0.049H-atom parameters constrained
S = 1.05Δρmax = 0.31 e Å3
1005 reflectionsΔρmin = 0.28 e Å3
79 parameters
Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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
Zn11.00000.07765 (4)0.25000.01735 (12)
O10.89943 (8)0.04802 (17)0.27162 (18)0.0206 (3)
O20.97106 (7)0.16244 (16)0.50689 (17)0.0175 (3)
O30.88909 (8)0.29952 (17)0.74397 (19)0.0223 (3)
C10.82575 (11)0.1943 (2)0.4642 (3)0.0161 (4)
C20.81990 (11)0.2758 (2)0.6249 (3)0.0167 (4)
C30.74429 (11)0.3298 (2)0.6580 (3)0.0173 (4)
H30.74010.38480.76720.021*
C40.90393 (11)0.1308 (2)0.4121 (3)0.0157 (4)
C50.88121 (14)0.3818 (3)0.9077 (3)0.0407 (7)
H5A0.86020.48870.87950.061*
H5B0.93450.38900.98140.061*
H5C0.84350.32430.97450.061*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Zn10.01064 (17)0.0276 (2)0.01397 (18)0.0000.00223 (12)0.000
O10.0149 (7)0.0303 (9)0.0166 (7)0.0026 (6)0.0023 (6)0.0049 (6)
O20.0116 (6)0.0232 (8)0.0177 (7)0.0003 (5)0.0020 (6)0.0025 (6)
O30.0140 (7)0.0305 (8)0.0210 (8)0.0039 (6)0.0025 (6)0.0093 (7)
C10.0144 (9)0.0172 (10)0.0170 (10)0.0000 (8)0.0030 (8)0.0027 (8)
C20.0131 (9)0.0176 (10)0.0186 (10)0.0001 (8)0.0014 (8)0.0009 (8)
C30.0165 (10)0.0196 (11)0.0157 (10)0.0014 (8)0.0024 (8)0.0013 (8)
C40.0147 (10)0.0179 (10)0.0148 (10)0.0007 (8)0.0030 (8)0.0051 (8)
C50.0272 (13)0.0553 (17)0.0352 (14)0.0159 (11)0.0120 (10)0.0260 (12)
Geometric parameters (Å, º) top
Zn1—O2i1.9547 (13)C1—C3iv1.395 (3)
Zn1—O2ii1.9547 (13)C1—C21.401 (3)
Zn1—O1iii2.0023 (13)C1—C41.502 (3)
Zn1—O12.0023 (13)C2—C31.388 (3)
O1—C41.256 (2)C3—C1iv1.395 (3)
O2—C41.267 (2)C3—H30.9500
O2—Zn1ii1.9547 (13)C5—H5A0.9800
O3—C21.371 (2)C5—H5B0.9800
O3—C51.430 (3)C5—H5C0.9800
O2i—Zn1—O2ii137.03 (8)C3—C2—C1118.85 (17)
O2i—Zn1—O1iii102.89 (5)C2—C3—C1iv121.94 (19)
O2ii—Zn1—O1iii99.51 (5)C2—C3—H3119.0
O2i—Zn1—O199.51 (5)C1iv—C3—H3119.0
O2ii—Zn1—O1102.89 (5)O1—C4—O2122.41 (17)
O1iii—Zn1—O1116.00 (8)O1—C4—C1117.28 (17)
C4—O1—Zn1113.89 (12)O2—C4—C1120.30 (17)
C4—O2—Zn1ii122.20 (12)O3—C5—H5A109.5
C2—O3—C5117.63 (15)O3—C5—H5B109.5
C3iv—C1—C2119.21 (17)H5A—C5—H5B109.5
C3iv—C1—C4116.79 (18)O3—C5—H5C109.5
C2—C1—C4124.00 (17)H5A—C5—H5C109.5
O3—C2—C3122.32 (18)H5B—C5—H5C109.5
O3—C2—C1118.83 (16)
O2i—Zn1—O1—C4173.31 (13)C1—C2—C3—C1iv0.2 (3)
O2ii—Zn1—O1—C443.62 (14)Zn1—O1—C4—O216.5 (2)
O1iii—Zn1—O1—C463.84 (12)Zn1—O1—C4—C1164.29 (13)
C5—O3—C2—C30.6 (3)Zn1ii—O2—C4—O1112.14 (18)
C5—O3—C2—C1179.4 (2)Zn1ii—O2—C4—C168.6 (2)
C3iv—C1—C2—O3179.77 (17)C3iv—C1—C4—O16.6 (3)
C4—C1—C2—O30.3 (3)C2—C1—C4—O1173.91 (18)
C3iv—C1—C2—C30.2 (3)C3iv—C1—C4—O2172.60 (17)
C4—C1—C2—C3179.64 (18)C2—C1—C4—O26.8 (3)
O3—C2—C3—C1iv179.76 (17)
Symmetry codes: (i) x, y, z1/2; (ii) x+2, y, z+1; (iii) x+2, y, z+1/2; (iv) x+3/2, y+1/2, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C3—H3···O1iv0.952.362.713 (2)101
C5—H5B···O2v0.982.473.071 (3)120
Symmetry codes: (iv) x+3/2, y+1/2, z+1; (v) x+2, y, z+3/2.

Experimental details

(I)(II)
Crystal data
Chemical formula[Mn(C10H8O6)][Zn(C10H8O6)]
Mr279.10289.53
Crystal system, space groupMonoclinic, C2/cMonoclinic, C2/c
Temperature (K)153153
a, b, c (Å)16.7686 (6), 8.4646 (3), 7.4464 (3)16.5936 (6), 8.4438 (3), 7.4838 (3)
β (°) 99.093 (1) 97.649 (2)
V3)1043.66 (7)1039.25 (7)
Z44
Radiation typeMo KαMo Kα
µ (mm1)1.282.38
Crystal size (mm)0.52 × 0.35 × 0.330.21 × 0.15 × 0.13
Data collection
DiffractometerBruker Kappa APEXII CCD area-detector
diffractometer
Bruker Kappa APEXII CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2007)
Multi-scan
(SADABS; Bruker, 2007)
Tmin, Tmax0.633, 0.7470.695, 0.746
No. of measured, independent and
observed [I > 2σ(I)] reflections
11427, 2156, 2084 6781, 1005, 898
Rint0.0190.032
(sin θ/λ)max1)0.7970.613
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.019, 0.052, 1.09 0.022, 0.049, 1.05
No. of reflections21561005
No. of parameters7979
H-atom treatmentH-atom parameters constrainedH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.42, 0.340.31, 0.28

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
C3—H3···O1i0.952.372.7209 (8)101.3
C5—H5B···O2ii0.982.473.0654 (11)118.7
Symmetry codes: (i) x+3/2, y+1/2, z+1; (ii) x+2, y, z+3/2.
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
C3—H3···O1i0.952.362.713 (2)101.2
C5—H5B···O2ii0.982.473.071 (3)119.6
Symmetry codes: (i) x+3/2, y+1/2, z+1; (ii) x+2, y, z+3/2.
 

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