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The title complex, [MnII(nic)2(H2O)2]n [nic is 3-pyridine­carboxyl­ate (also called nicotinate), C6H4NO2], has a two-dimensional layer structure with the unique Mn atom on an inversion centre. In each layer, all nicotinate ligands are coordinated to Mn atoms in a bridging/bidentate mode, thus linking the {MnII(nic)2(H2O)2} monomeric units together to form a dative-bond-based layered polymer. The intra-layer hydrogen bonds involving all water mol­ecules and the carboxyl­ate groups may play an auxiliary part in stabilizing the layer. The layers are arranged in an ordered manner along the a axis through van der Waals forces so as to complete the solid-state structure of the crystal.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270199015358/br1271sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270199015358/br1271Isup2.hkl
Contains datablock I

CCDC reference: 143224

Comment top

In recent years, polymer-based materials have received much attention owing to their novel magnetic properties (Manriquez et al., 1991; Mallah et al., 1993). The main preparation strategy adopted by most inorganic chemists is to assemble metal ions with multidentate ligands to molecular-based inorganic polymers (Kahn, 1987 and references therein). These inorganic and organic hybrid materials, classified as Type II MMC (Macromolecular Metal Complexes) according to Ciardelli, Tsuchida & Wöhrle's scheme, may exhibit properties of multifunctionality and processability (Ciardelli et al., 1996). Following the strategy above, we have succeeded in isolating three crystals of Type II MMC: {[Mn(Hheidi)(H2O)]·(H2O)}n [Hheidi is N-(2-hydroxyethyl)-iminodiacetate] (Liu et al., 1999); [Mn(pyz)2(SCN)2]n and [Fe(pyz)2(SCN)2]n (pyz is pyrazine) (Wei et al., in preparation). Variable-temperature magnetic susceptibility studies revealed that the third one could exhibit magnetic-ordering phase transition at the temperature of 7.7 K. In this paper, we report another polymeric complex of Type II MMC, i.e. [Mn(nic)2(H2O)2]n, (I). \sch

As shown in Fig. 1, the Mn atom resides on the centre of symmetry of the octahedron and is coordinated by two N atoms of the pyridine rings, two O atoms of the carboxylate groups and two O atoms of the water molecules; all of the corresponding pairs of the ligand atoms lie in trans positions and the two ligands of each pair are related by the center of symmetry. According to the bond-valence theory (Brown, 1981), the sum of the bond-valences is equal to 1.998, which is in nice agreement with the valence of the Mn2+ ion. As shown in Table 1, 12 of 15 bond angles around the Mn atom are slightly distorted from the ideal octahedral values of 90°.

In the polymeric layer (see Fig. 2), each nicotinate ligand connects two Mn atoms through one O atom of its carboxylate group and the N atom of its pyridine ring, respectively, i.e. the coordination mode of the nicotinate ligand is bridging/bidentate. Acting as the adhesives, the nicotinate ligands link the monomeric units {Mn(nic)2(H2O)2} together to form an extended dative-bond-based layer. All water molecules and the uncoordinated O atoms of the carboxylate groups participate in constituting the intralayer hydrogen bonds which may play an auxiliary part in stabilizing the layer [O3w—H6···O2iv 2.695 (2) Å, 176.3°; O3w—H5···O2v 2.809 (2) Å, 174 (3)°][symmetry codes: (iv) 1 - x, y - 1/2, 1/2 - z; (v) 1 - x, 1 - y, 1 - z]. If all ligands are omitted from the layer for clarity, an Mn-only layer will be obtained. It can be even clear to notice that this layer is just the yz plane, viz. bc plane in monoclinic system (see Fig. 3). Moreover, all Mn atoms of this layer are related by the 21 screw axes (parallel to the b axis, and z = 1/4) and c glide planes (perpendicular to the b axis, and y = 1/4). The shortest distance between the two Mn atoms of this layer is 6.223 (1) Å. The perpendicular distance and Mn···Mn distance between the two adjacent Mn-only layers are 8.597 (2) Å and 8.730 (2) Å, respectively. Fig. 3 is the packing diagram of the unit cell for (I). As it shows, the layers are arranged in an orderly manner along the a axis through the van der Waals force so as to complete the solid-state structure of the crystal.

It is interesting to compare the two related manganese(II) pyridinecarboxylates, when the carboxylate group is in ortho position (Okabe & Koizumi, 1998) and in meta position [the title complex, (I)]. In the former situation, each 2-pyridinecarboxylate ligand is coordinated to the Mn atom as the chelating mode, thus giving rise to the simple mononuclear complex; whereas in the latter situation, the coordination mode of the 3-pyridinecarboxylate ligand is bridging/ bidentate, hence leading to the two-dimensional layer structure.

Experimental top

The solution of MnSO4·H2O (0.17 g, 1.0 mmol) dissolved in distilled water (5 ml) was layered, in a culture tube, with the solution of nicotinic acid (0.12 g, 1.0 mmol) and KOH (56 mg, 1.0 mmol) dissolved in distilled water (3 ml) and ethanol (2 ml). After a month's diffusion, colorless lamellar crystals were precipitated in 29% yield (based on Mn). The chemicals used were all of analytical purity and obtained from commercial sources.

Computing details top

Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1994); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: TEXSAN (Molecular Structure Corporation, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP in SHELXTL (Siemens, 1990); software used to prepare material for publication: CIFTAB in SHELXL97 (Sheldrick, 1997).

Figures top
[Figure 1] Fig. 1. Structure of the monomeric unit of the title polymer with the atom- numbering scheme (50% probability ellipsoids).
[Figure 2] Fig. 2. Structure of one layer of the title polymer (view along the a axis). Hydrogen bonds are indicated by broken lines and H atoms are omitted for clarity. Mn atoms are criss-crossed, O atoms are striped, N atoms are dotted and C atoms are ticked on one side.
[Figure 3] Fig. 3. Packing diagram of the title polymer in the unit cell (view along the c axis). The way of labelling atoms is the same to that of Fig. 2.
Poly[trans-diaquamanganese(II)-µ-(3-pyridinecarboxylato-N:O)-µ-(3-pyridine- carboxylato-O:N)] top
Crystal data top
[Mn(C6H4NO2)2(H2O)2]F(000) = 342
Mr = 335.18Dx = 1.778 Mg m3
Dm = 1.780 (3) Mg m3
Dm measured by by flotation in CCl4/ C2H4Br2
Monoclinic, P21/cMo Kα radiation, λ = 0.71069 Å
a = 8.730 (2) ÅCell parameters from 25 reflections
b = 10.189 (2) Åθ = 5–12.5°
c = 7.147 (1) ŵ = 1.09 mm1
β = 100.02 (3)°T = 293 K
V = 626.0 (2) Å3Lamellar, colorless
Z = 20.7 × 0.3 × 0.15 mm
Data collection top
AFC6S
diffractometer
1527 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.026
Graphite monochromatorθmax = 30.0°, θmin = 2.4°
2θ scansh = 1212
Absorption correction: psi scan
(Coppens et al., 1965)
k = 140
Tmin = 0.630, Tmax = 0.850l = 010
1961 measured reflections3 standard reflections every 150 reflections
1826 independent reflections intensity decay: 0.9%
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.038All H-atom parameters refined
wR(F2) = 0.108Calculated w = 1/[σ2(Fo2) + (0.0619P)2 + 0.1001P]
where P = (Fo2 + 2Fc2)/3
S = 1.07(Δ/σ)max < 0.001
1826 reflectionsΔρmax = 0.47 e Å3
122 parametersΔρmin = 0.75 e Å3
0 restraintsExtinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.071 (6)
Crystal data top
[Mn(C6H4NO2)2(H2O)2]V = 626.0 (2) Å3
Mr = 335.18Z = 2
Monoclinic, P21/cMo Kα radiation
a = 8.730 (2) ŵ = 1.09 mm1
b = 10.189 (2) ÅT = 293 K
c = 7.147 (1) Å0.7 × 0.3 × 0.15 mm
β = 100.02 (3)°
Data collection top
AFC6S
diffractometer
1527 reflections with I > 2σ(I)
Absorption correction: psi scan
(Coppens et al., 1965)
Rint = 0.026
Tmin = 0.630, Tmax = 0.8503 standard reflections every 150 reflections
1961 measured reflections intensity decay: 0.9%
1826 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0380 restraints
wR(F2) = 0.108All H-atom parameters refined
S = 1.07Δρmax = 0.47 e Å3
1826 reflectionsΔρmin = 0.75 e Å3
122 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. All H atoms were located from difference Fourier maps and included in the refinement calculations isotropically.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Mn0.50000.50000.00000.01773 (15)
O10.58420 (18)0.54475 (14)0.29566 (19)0.0261 (3)
O20.73856 (17)0.62313 (13)0.55220 (19)0.0251 (3)
O3W0.32055 (19)0.37035 (15)0.0739 (2)0.0276 (3)
N0.68087 (19)0.16293 (15)0.5043 (2)0.0203 (3)
C10.6383 (2)0.28655 (17)0.4551 (2)0.0193 (3)
C20.7343 (2)0.39390 (17)0.5054 (2)0.0181 (3)
C30.8814 (2)0.37218 (19)0.6100 (3)0.0232 (4)
C40.9298 (2)0.2443 (2)0.6528 (3)0.0263 (4)
C50.8263 (2)0.14336 (19)0.5963 (3)0.0232 (4)
C60.6811 (2)0.53071 (18)0.4461 (2)0.0182 (3)
H10.534 (3)0.298 (2)0.386 (3)0.022 (6)*
H20.944 (3)0.440 (3)0.641 (4)0.028 (6)*
H31.032 (3)0.228 (3)0.723 (4)0.040 (7)*
H40.857 (3)0.053 (3)0.624 (4)0.026 (6)*
H50.303 (4)0.378 (3)0.195 (5)0.052 (9)*
H60.306 (4)0.293 (3)0.033 (5)0.051 (9)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Mn0.0222 (2)0.0119 (2)0.0176 (2)0.00056 (13)0.00093 (14)0.00061 (12)
O10.0355 (8)0.0212 (6)0.0179 (6)0.0061 (6)0.0053 (5)0.0002 (5)
O20.0316 (7)0.0157 (6)0.0250 (6)0.0022 (5)0.0029 (5)0.0014 (5)
O3W0.0393 (8)0.0173 (6)0.0265 (7)0.0080 (6)0.0065 (6)0.0032 (5)
N0.0217 (7)0.0158 (7)0.0220 (7)0.0005 (5)0.0001 (5)0.0020 (5)
C10.0204 (8)0.0168 (8)0.0191 (7)0.0008 (6)0.0011 (6)0.0021 (6)
C20.0210 (8)0.0164 (8)0.0161 (7)0.0008 (6)0.0011 (6)0.0006 (6)
C30.0212 (8)0.0212 (9)0.0244 (8)0.0037 (7)0.0040 (6)0.0009 (7)
C40.0204 (8)0.0271 (9)0.0284 (9)0.0031 (7)0.0040 (7)0.0050 (7)
C50.0238 (9)0.0185 (8)0.0260 (8)0.0030 (7)0.0001 (7)0.0035 (7)
C60.0223 (8)0.0156 (7)0.0166 (7)0.0011 (6)0.0031 (6)0.0005 (6)
Geometric parameters (Å, º) top
Mn—O12.1617 (14)N—C51.339 (2)
Mn—O1i2.1617 (14)N—C11.343 (2)
Mn—O3W2.1830 (15)N—Mniv2.2876 (16)
Mn—O3Wi2.1830 (15)C1—C21.387 (2)
Mn—Nii2.2876 (16)C2—C31.387 (2)
Mn—Niii2.2876 (16)C2—C61.507 (2)
O1—C61.255 (2)C3—C41.387 (3)
O2—C61.257 (2)C4—C51.382 (3)
O1—Mn—O1i180.0C6—O1—Mn151.30 (13)
O1—Mn—O3W91.58 (6)C5—N—C1117.62 (16)
O1i—Mn—O3W88.42 (6)C5—N—Mniv119.45 (12)
O1—Mn—O3Wi88.42 (6)C1—N—Mniv121.23 (12)
O1i—Mn—O3Wi91.58 (6)N—C1—C2123.01 (16)
O3W—Mn—O3Wi180.0C3—C2—C1118.37 (17)
O1—Mn—Nii91.35 (6)C3—C2—C6120.70 (16)
O1i—Mn—Nii88.65 (6)C1—C2—C6120.93 (15)
O3W—Mn—Nii94.61 (6)C2—C3—C4119.10 (17)
O3Wi—Mn—Nii85.39 (6)C5—C4—C3118.44 (17)
O1—Mn—Niii88.65 (6)N—C5—C4123.25 (17)
O1i—Mn—Niii91.35 (6)O1—C6—O2124.74 (17)
O3W—Mn—Niii85.39 (6)O1—C6—C2118.37 (16)
O3Wi—Mn—Niii94.61 (6)O2—C6—C2116.89 (16)
Nii—Mn—Niii180.0
Symmetry codes: (i) x+1, y+1, z; (ii) x, y+1/2, z1/2; (iii) x+1, y+1/2, z+1/2; (iv) x+1, y1/2, z+1/2.

Experimental details

Crystal data
Chemical formula[Mn(C6H4NO2)2(H2O)2]
Mr335.18
Crystal system, space groupMonoclinic, P21/c
Temperature (K)293
a, b, c (Å)8.730 (2), 10.189 (2), 7.147 (1)
β (°) 100.02 (3)
V3)626.0 (2)
Z2
Radiation typeMo Kα
µ (mm1)1.09
Crystal size (mm)0.7 × 0.3 × 0.15
Data collection
DiffractometerAFC6S
diffractometer
Absorption correctionPsi scan
(Coppens et al., 1965)
Tmin, Tmax0.630, 0.850
No. of measured, independent and
observed [I > 2σ(I)] reflections
1961, 1826, 1527
Rint0.026
(sin θ/λ)max1)0.703
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.038, 0.108, 1.07
No. of reflections1826
No. of parameters122
H-atom treatmentAll H-atom parameters refined
Δρmax, Δρmin (e Å3)0.47, 0.75

Computer programs: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1994), MSC/AFC Diffractometer Control Software, TEXSAN (Molecular Structure Corporation, 1997), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), XP in SHELXTL (Siemens, 1990), CIFTAB in SHELXL97 (Sheldrick, 1997).

Selected geometric parameters (Å, º) top
Mn—O12.1617 (14)Mn—Ni2.2876 (16)
Mn—O3W2.1830 (15)
O1—Mn—O3W91.58 (6)O3W—Mn—Ni94.61 (6)
O1ii—Mn—O3W88.42 (6)O3Wii—Mn—Ni85.39 (6)
O1—Mn—Ni91.35 (6)O3W—Mn—Niii85.39 (6)
O1ii—Mn—Ni88.65 (6)
Symmetry codes: (i) x, y+1/2, z1/2; (ii) x+1, y+1, z; (iii) x+1, y+1/2, z+1/2.
 

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