Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270199015358/br1271sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270199015358/br1271Isup2.hkl |
CCDC reference: 143224
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.
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).
[Mn(C6H4NO2)2(H2O)2] | F(000) = 342 |
Mr = 335.18 | Dx = 1.778 Mg m−3 Dm = 1.780 (3) Mg m−3 Dm measured by by flotation in CCl4/ C2H4Br2 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71069 Å |
a = 8.730 (2) Å | Cell parameters from 25 reflections |
b = 10.189 (2) Å | θ = 5–12.5° |
c = 7.147 (1) Å | µ = 1.09 mm−1 |
β = 100.02 (3)° | T = 293 K |
V = 626.0 (2) Å3 | Lamellar, colorless |
Z = 2 | 0.7 × 0.3 × 0.15 mm |
AFC6S diffractometer | 1527 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.026 |
Graphite monochromator | θmax = 30.0°, θmin = 2.4° |
2θ scans | h = −12→12 |
Absorption correction: psi scan (Coppens et al., 1965) | k = −14→0 |
Tmin = 0.630, Tmax = 0.850 | l = 0→10 |
1961 measured reflections | 3 standard reflections every 150 reflections |
1826 independent reflections | intensity decay: 0.9% |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.038 | All H-atom parameters refined |
wR(F2) = 0.108 | Calculated w = 1/[σ2(Fo2) + (0.0619P)2 + 0.1001P] where P = (Fo2 + 2Fc2)/3 |
S = 1.07 | (Δ/σ)max < 0.001 |
1826 reflections | Δρmax = 0.47 e Å−3 |
122 parameters | Δρmin = −0.75 e Å−3 |
0 restraints | Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.071 (6) |
[Mn(C6H4NO2)2(H2O)2] | V = 626.0 (2) Å3 |
Mr = 335.18 | Z = 2 |
Monoclinic, P21/c | Mo Kα radiation |
a = 8.730 (2) Å | µ = 1.09 mm−1 |
b = 10.189 (2) Å | T = 293 K |
c = 7.147 (1) Å | 0.7 × 0.3 × 0.15 mm |
β = 100.02 (3)° |
AFC6S diffractometer | 1527 reflections with I > 2σ(I) |
Absorption correction: psi scan (Coppens et al., 1965) | Rint = 0.026 |
Tmin = 0.630, Tmax = 0.850 | 3 standard reflections every 150 reflections |
1961 measured reflections | intensity decay: 0.9% |
1826 independent reflections |
R[F2 > 2σ(F2)] = 0.038 | 0 restraints |
wR(F2) = 0.108 | All H-atom parameters refined |
S = 1.07 | Δρmax = 0.47 e Å−3 |
1826 reflections | Δρmin = −0.75 e Å−3 |
122 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Mn | 0.5000 | 0.5000 | 0.0000 | 0.01773 (15) | |
O1 | 0.58420 (18) | 0.54475 (14) | 0.29566 (19) | 0.0261 (3) | |
O2 | 0.73856 (17) | 0.62313 (13) | 0.55220 (19) | 0.0251 (3) | |
O3W | 0.32055 (19) | 0.37035 (15) | 0.0739 (2) | 0.0276 (3) | |
N | 0.68087 (19) | 0.16293 (15) | 0.5043 (2) | 0.0203 (3) | |
C1 | 0.6383 (2) | 0.28655 (17) | 0.4551 (2) | 0.0193 (3) | |
C2 | 0.7343 (2) | 0.39390 (17) | 0.5054 (2) | 0.0181 (3) | |
C3 | 0.8814 (2) | 0.37218 (19) | 0.6100 (3) | 0.0232 (4) | |
C4 | 0.9298 (2) | 0.2443 (2) | 0.6528 (3) | 0.0263 (4) | |
C5 | 0.8263 (2) | 0.14336 (19) | 0.5963 (3) | 0.0232 (4) | |
C6 | 0.6811 (2) | 0.53071 (18) | 0.4461 (2) | 0.0182 (3) | |
H1 | 0.534 (3) | 0.298 (2) | 0.386 (3) | 0.022 (6)* | |
H2 | 0.944 (3) | 0.440 (3) | 0.641 (4) | 0.028 (6)* | |
H3 | 1.032 (3) | 0.228 (3) | 0.723 (4) | 0.040 (7)* | |
H4 | 0.857 (3) | 0.053 (3) | 0.624 (4) | 0.026 (6)* | |
H5 | 0.303 (4) | 0.378 (3) | 0.195 (5) | 0.052 (9)* | |
H6 | 0.306 (4) | 0.293 (3) | 0.033 (5) | 0.051 (9)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Mn | 0.0222 (2) | 0.0119 (2) | 0.0176 (2) | 0.00056 (13) | −0.00093 (14) | −0.00061 (12) |
O1 | 0.0355 (8) | 0.0212 (6) | 0.0179 (6) | 0.0061 (6) | −0.0053 (5) | −0.0002 (5) |
O2 | 0.0316 (7) | 0.0157 (6) | 0.0250 (6) | −0.0022 (5) | −0.0029 (5) | −0.0014 (5) |
O3W | 0.0393 (8) | 0.0173 (6) | 0.0265 (7) | −0.0080 (6) | 0.0065 (6) | −0.0032 (5) |
N | 0.0217 (7) | 0.0158 (7) | 0.0220 (7) | −0.0005 (5) | −0.0001 (5) | 0.0020 (5) |
C1 | 0.0204 (8) | 0.0168 (8) | 0.0191 (7) | −0.0008 (6) | −0.0011 (6) | 0.0021 (6) |
C2 | 0.0210 (8) | 0.0164 (8) | 0.0161 (7) | −0.0008 (6) | 0.0011 (6) | 0.0006 (6) |
C3 | 0.0212 (8) | 0.0212 (9) | 0.0244 (8) | −0.0037 (7) | −0.0040 (6) | 0.0009 (7) |
C4 | 0.0204 (8) | 0.0271 (9) | 0.0284 (9) | 0.0031 (7) | −0.0040 (7) | 0.0050 (7) |
C5 | 0.0238 (9) | 0.0185 (8) | 0.0260 (8) | 0.0030 (7) | 0.0001 (7) | 0.0035 (7) |
C6 | 0.0223 (8) | 0.0156 (7) | 0.0166 (7) | −0.0011 (6) | 0.0031 (6) | 0.0005 (6) |
Mn—O1 | 2.1617 (14) | N—C5 | 1.339 (2) |
Mn—O1i | 2.1617 (14) | N—C1 | 1.343 (2) |
Mn—O3W | 2.1830 (15) | N—Mniv | 2.2876 (16) |
Mn—O3Wi | 2.1830 (15) | C1—C2 | 1.387 (2) |
Mn—Nii | 2.2876 (16) | C2—C3 | 1.387 (2) |
Mn—Niii | 2.2876 (16) | C2—C6 | 1.507 (2) |
O1—C6 | 1.255 (2) | C3—C4 | 1.387 (3) |
O2—C6 | 1.257 (2) | C4—C5 | 1.382 (3) |
O1—Mn—O1i | 180.0 | C6—O1—Mn | 151.30 (13) |
O1—Mn—O3W | 91.58 (6) | C5—N—C1 | 117.62 (16) |
O1i—Mn—O3W | 88.42 (6) | C5—N—Mniv | 119.45 (12) |
O1—Mn—O3Wi | 88.42 (6) | C1—N—Mniv | 121.23 (12) |
O1i—Mn—O3Wi | 91.58 (6) | N—C1—C2 | 123.01 (16) |
O3W—Mn—O3Wi | 180.0 | C3—C2—C1 | 118.37 (17) |
O1—Mn—Nii | 91.35 (6) | C3—C2—C6 | 120.70 (16) |
O1i—Mn—Nii | 88.65 (6) | C1—C2—C6 | 120.93 (15) |
O3W—Mn—Nii | 94.61 (6) | C2—C3—C4 | 119.10 (17) |
O3Wi—Mn—Nii | 85.39 (6) | C5—C4—C3 | 118.44 (17) |
O1—Mn—Niii | 88.65 (6) | N—C5—C4 | 123.25 (17) |
O1i—Mn—Niii | 91.35 (6) | O1—C6—O2 | 124.74 (17) |
O3W—Mn—Niii | 85.39 (6) | O1—C6—C2 | 118.37 (16) |
O3Wi—Mn—Niii | 94.61 (6) | O2—C6—C2 | 116.89 (16) |
Nii—Mn—Niii | 180.0 |
Symmetry codes: (i) −x+1, −y+1, −z; (ii) x, −y+1/2, z−1/2; (iii) −x+1, y+1/2, −z+1/2; (iv) −x+1, y−1/2, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | [Mn(C6H4NO2)2(H2O)2] |
Mr | 335.18 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 8.730 (2), 10.189 (2), 7.147 (1) |
β (°) | 100.02 (3) |
V (Å3) | 626.0 (2) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.09 |
Crystal size (mm) | 0.7 × 0.3 × 0.15 |
Data collection | |
Diffractometer | AFC6S diffractometer |
Absorption correction | Psi scan (Coppens et al., 1965) |
Tmin, Tmax | 0.630, 0.850 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 1961, 1826, 1527 |
Rint | 0.026 |
(sin θ/λ)max (Å−1) | 0.703 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.038, 0.108, 1.07 |
No. of reflections | 1826 |
No. of parameters | 122 |
H-atom treatment | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 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).
Mn—O1 | 2.1617 (14) | Mn—Ni | 2.2876 (16) |
Mn—O3W | 2.1830 (15) | ||
O1—Mn—O3W | 91.58 (6) | O3W—Mn—Ni | 94.61 (6) |
O1ii—Mn—O3W | 88.42 (6) | O3Wii—Mn—Ni | 85.39 (6) |
O1—Mn—Ni | 91.35 (6) | O3W—Mn—Niii | 85.39 (6) |
O1ii—Mn—Ni | 88.65 (6) |
Symmetry codes: (i) x, −y+1/2, z−1/2; (ii) −x+1, −y+1, −z; (iii) −x+1, y+1/2, −z+1/2. |
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.