Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229614015137/yp3067sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S2053229614015137/yp3067Isup2.hkl | |
Portable Document Format (PDF) file https://doi.org/10.1107/S2053229614015137/yp3067sup3.pdf |
CCDC reference: 1010687
Manganese carboxylate cluster chemistry is now widely recognized as a field from which materials suitable for qubit-based computation could emerge. That chemistry was pioneered by George Christou and David Hendrickson, among others, with the fruitful Mn12 line of compounds, including the emblematic cluster [Mn12O12(O2CPh)16(H2O)4] (Boyd et al., 1988; Sessoli et al., 1993). This mixed-valence cluster displays the two essential features required for a single-molecule magnet (SMM), i.e. a high-spin ground state and a large negative magnetic anisotropy. However, the most impressive behaviour reported for these clusters is the resonant quantum tunnelling of magnetization, which is a key property for molecular spintronics (Perenboom et al., 1998; Hill et al., 2003, 2010). Like SMM clusters, some chain-shaped molecules also exhibit bistability and slow relaxation of their magnetization. These compounds, termed single-chain magnets (SCM), have their magnetic behaviour affected not only by the magnetic anisotropy of the spins but also by their intrachain magnetic interactions (Coronado et al., 2003; Brooker & Kitchen, 2009; Zhang et al., 2013).
Although many synthetic approaches have been described in the literature, the rational design of a synthesis for a given manganese carboxylate cluster is hindered by the fine tuning of the following parameters: the oxidation states of the metal centres; the suitability of the symmetry of the ligand field for the 3d orbitals centred on the metals; the coordination modes of the carboxylate ligands; and competition with ancillary ligands. Moreover, both the nuclearity and dimensionality of the resulting structure are quite unpredictable, with a large range of possibilities, from isolated SMMs, which may be described as zero-dimensional nanoparticles, to three-dimensional polymeric architectures, which may be considered as bulk materials.
While working on the synthesis of such compounds, we obtained a one-dimensional polymer, namely [Mn3(OAc)6(py)2(H2O)2]n (OAc is acetate and py is pyridine), (I), which is a candidate for a new SCM.
Although the synthesis of (I) was carried out under aerobic conditions, the complex is an MnII species with the formula [Mn3(OAc)6(H2O)2(py)2]∞, where OAc and py are acetate and pyridine ligands, respectively. One manganese ion, Mn1, is located on an inversion centre in the triclinic unit cell, and the other, Mn2, is located in a general position, close to an inversion centre. Three acetate ligands are bonded to Mn1, using three coordination modes (Fig. 1). The first acetate (atoms O1/O2) bridges independent Mn centres in the common 2.11 syn–syn mode [for Harris coordination nomenclature, see Coxall et al. (2000)], found, for example, in the starting material manganese diacetate, Mn(OAc)2.4H2O (Bertaut et al., 1974; Nicolaï et al., 2001), and also in Co(OAc)2.H2O (Zhang et al., 2010) and other simple divalent metal salts. Acetate O5/O6 bridges the same metal centres Mn1 and Mn2 in the 2.20 coordination mode, which is much less frequently observed. For Mn-based polymers, only two cases have been reported to date including this coordination mode for OAc, viz. [Mn3(OAc)6(H2O)4].2H2O (Cheng & Wang, 1991) and a complex polymer with a chain-like structure (Xu et al., 2009). Finally, the polymeric nature of (I) is fixed by the third acetate, O3/O4, in the 3.12 coordination mode, between Mn1 and Mn2 in the asymmetric unit and a symmetry-related Mn2i site [symmetry code: (i) -x + 1, -y + 1, -z + 1]. This arrangement for polymerization is identical to that found in Mn(OAc)2.4H2O (Bertaut et al., 1974) and α-Mn(OAc)2 (Lin et al., 2009), and in more complex polymeric compounds with various dimensionalities (e.g. Zartilas et al., 2008; Weng et al., 2008; Wan et al., 2010). These different µ2- and µ3-bridging modes are reflected in the IR spectrum of (I): the νasym and νsym vibration modes for the COO- groups are split into two or three bands around 1557 and 1414 cm-1, respectively.
The arrangement of the acetate ligands completes the octahedral coordination environment for the Mn1 centre. This metal centre presents an [MnO6] ligand field with the symmetry lowered from octahedral to Ci, because the Mn1—O bond lengths for each acetate are significantly different: Mn1—O1 = 2.1369 (9), Mn1—O3 = 2.1997 (8) and Mn1—O5 = 2.2277 (8) Å. The coordination environment for Mn2, which is in a general position, is completed with neutral ligands, H2O and pyridine, present in the reaction media. Mn2 thus has an [MnO5N] coordination, with a ligand field probably slightly stronger than that for Mn1, and a large deviation from octahedral symmetry: the coordination bond lengths for Mn2 are in the range 2.0995 (9)–2.2946 (10) Å and the trans angles are in the range 164.84 (4)–176.87 (4)°.
The one-dimensional polymeric chain of (I), formed via inversion centres, runs in the [010] direction (Fig. 2). Within the asymmetric unit, the Mn1···Mn2 separation is 3.36180 (18) Å and the Mn2···Mn2i distance, allowing polymerization, is longer, at 4.4804 (3) Å. Both distances are unexceptional, considering that, in Mn–acetate-based polymers, they span a large range, ca 2.5–5.2 Å, allowing a variety of magnetic ground states for these materials. In the present case, long metal–metal separations alternate along the chain with dimers of short separation. Parallel chains are packed in the crystal structure, and the cohesion is maintained through O—H···O hydrogen bonds of moderate strength, using the coordinated water molecules as donors (Fig. 2 and Table 2). The graph set (Bernstein et al., 1995) resulting from two inversion-related interchain hydrogen bonds is R22(8), common in water–acetate systems. The metal–metal distance in the R(8) [Should this be R22(8)?] ring is Mn2···Mn2ii = 5.3752 (3) Å [symmetry code: (ii) -x + 2, -y + 1, -z + 1]. Since this distance is much longer than the metal–metal interactions along the chain, (I) should be considered as a true low-dimensional one-dimensional polymer, rather than a two-dimensional material. In spite of its low dimensionality, this material is a densely packed system, reaching a high Kitaigorodski packing coefficient of CK = 0.733 (PLATON; Spek, 2009).
The above-described geometric features are encouraging and make (I) a candidate for being an Ising one-dimensional system behaving as a ferri- or ferromagnet. Assuming a weak enough crystal-field splitting, high-spin d5 electronic configurations may be expected for the MnII centres. The anisotropic trinuclear units (Mn1···Mn2···Mn2i) have distances between the magnetic sites that are suitable for ferromagnetic interactions. Indeed, these distances, of 3.36 and 4.48 Å, may be compared with those observed in the first heterometallic MnIII–NiII polymeric SCM synthesized in 2002: MnIII···MnIII = 3.42 Å and MnIII···NiII = 5.06 Å (Clérac et al., 2002). Thus, the actual nature of the magnetic behaviour for the title MnII polymer should be defined mainly by interchain contacts resulting from the R(8) [Should this be R22(8)?] ring motifs. A search of the Cambridge Structural Database (Version 5.35, updated May 2014; Allen, 2002) retrieved 139 similar R22(8) rings in Mn compounds, with coordinated water molecules as donors and carboxylate O atoms as acceptors. Most of them are associated with first-level centrosymmetric patterns R(aa), as in (I), and the others belong to second-level patterns R(ab), in Motherwell's graph-set nomenclature (Motherwell et al., 2000). The important feature to be considered, bearing the magnetic properties in mind, is the poor flexibility of this ring: for R(aa) patterns, the ring has a chair conformation and the metal–metal interaction is determined mainly by the puckering parameters, while R(ab) patterns may adopt a folded conformation, allowing shorter metal–metal interactions. In the subset of 139 hits, regardless of the Mn oxidation state and the dimensionality of the crystal structure, the Mn···Mn separation in R22(8) rings is in the range 4.77–6.32 Å. Interestingly, the shortest separation was reported for a complex Mn22 cluster, in which the R(8) [Should this be R22(8)?] ring links two molecules. This mixed-valence compound is an SMM with quantum tunnelling of magnetization (Brockman et al., 2007). Thus, it may be inferred that the R(8) [Should this be R22(8)?] ring in (I) is not an efficient exchange pathway, making a strong antiferromagnetic interchain coupling unlikely.
Preliminary magnetic measurements of (I) are in agreement with this structural description. At room temperature, the title complex shows a χmT value of 13.15 cm3 mol-1 K, which is very close to that calculated for three non-interacting Si = 5/2 centres, 13.12 cm3 mol-1 K, assuming a spin-only model (gMn = 2.00; Christian et al., 2004). A plot of M versus T shows different magnetization pathways below a critical temperature TC = 50 K, pointing to superparamagnetic behaviour [Might it help the reader to have this plot available in the supporting information?]. On the other hand, a hysteresis loop in the M(H) plot is observed (Fig. 3), indicative of ferromagnetic exchange interactions (Bertotti, 1998). Experimentally, an SCM shows both superparamagnet-like properties with frequency-dependent out-of-phase signals in AC susceptibility measurements, and hysteresis in M versus applied DC field measurements (King et al., 2004; Brockman et al., 2007). Therefore, AC magnetic susceptibility measurements are currently being carried out, in order to characterize further the potential SCM behaviour of this new polymer.
All synthetic and post-synthetic work was carried out under aerobic conditions. The reagents and solvents were obtained from commercial sources and used without further purification. IR analyses were performed using a Nicolet Nexus 6700 FT–IR spectrometer in the 4000–600 cm-1 range. Compound (I) was prepared by the addition of excess pyridine (12.41 mmol, 1 ml) to a hot solution of Mn(OAc)2.4H2O (1 mmol, 0.245 g) in EtOH (95%; 5 ml). The solution was stirred for 30 min and filtered, [and then layered with Et2O?]. After 1 d, colourless crystals of (I) were obtained from this solution by slow diffusion of Et2O (yield 48%). Spectroscopic analysis: IR ([Medium?], νmax, cm-1): 3252 (br), 2943 (s), 2878 (s), 1557 (m), 1414 (m), 1004 (st), 877 (m), 658 (m), 606 (m). Magnetic susceptibility measurements on powdered crystals were carried out using a Quantum Design SQUID magnetometer at 2 K under an applied field H of -50000 to 50000 Oe, and in the temperature range 2–300 K at H = 1000 Oe. Correction for the diamagnetic contribution of the constituent atoms was applied using Pascal's constants.
Crystal data, data collection and structure refinement details are summarized in Table 1. The collection of diffraction data (work done in Canada) and the final structure refinement (work done in Mexico) were routine works. All C-bound H atoms were placed in calculated positions, with C—H = 0.95 (pyridine) or 0.98 Å (methyl acetate). Methyl groups were considered as rigid tetrahedral groups free to rotate about their C—C bonds. Isotropic displacement parameters for these H atoms were calculated as Uiso(H) = 1.2Ueq(C) for the pyridine molecule and Uiso(H) = 1.5Ueq(C) for the methyl groups. Atoms H71 and H72 of the water molecule were clearly detected in a difference map and were refined with free coordinates and isotropic displacement parameters.
Data collection: APEX2 (Bruker, 2009); cell refinement: APEX2 (Bruker, 2009); data reduction: XPREP (Bruker, 2009); program(s) used to solve structure: SHELXS2013 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL2013 (Sheldrick, 2008).
[Mn3(C2H3O2)6(C6H5N)2(H2O)2] | F(000) = 365 |
Mr = 713.31 | Dx = 1.665 Mg m−3 |
Triclinic, P1 | Melting point: 493 K |
a = 8.1153 (2) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 9.0404 (2) Å | Cell parameters from 9432 reflections |
c = 10.0759 (2) Å | θ = 2.3–28.3° |
α = 83.160 (1)° | µ = 1.38 mm−1 |
β = 81.994 (1)° | T = 200 K |
γ = 77.423 (1)° | Block, colourless |
V = 711.43 (3) Å3 | 0.15 × 0.12 × 0.12 mm |
Z = 1 |
Bruker APEXII CCD area-detector diffractometer | 3514 independent reflections |
Radiation source: fine-focus sealed tube | 3269 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.012 |
ϕ and ω scans | θmax = 28.3°, θmin = 2.3° |
Absorption correction: multi-scan (SADABS; Bruker, 2009) | h = −10→10 |
Tmin = 0.820, Tmax = 0.852 | k = −12→12 |
11780 measured reflections | l = −13→13 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.020 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.057 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | w = 1/[σ2(Fo2) + (0.031P)2 + 0.2663P] where P = (Fo2 + 2Fc2)/3 |
3514 reflections | (Δ/σ)max = 0.001 |
198 parameters | Δρmax = 0.31 e Å−3 |
0 restraints | Δρmin = −0.35 e Å−3 |
0 constraints |
[Mn3(C2H3O2)6(C6H5N)2(H2O)2] | γ = 77.423 (1)° |
Mr = 713.31 | V = 711.43 (3) Å3 |
Triclinic, P1 | Z = 1 |
a = 8.1153 (2) Å | Mo Kα radiation |
b = 9.0404 (2) Å | µ = 1.38 mm−1 |
c = 10.0759 (2) Å | T = 200 K |
α = 83.160 (1)° | 0.15 × 0.12 × 0.12 mm |
β = 81.994 (1)° |
Bruker APEXII CCD area-detector diffractometer | 3514 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2009) | 3269 reflections with I > 2σ(I) |
Tmin = 0.820, Tmax = 0.852 | Rint = 0.012 |
11780 measured reflections |
R[F2 > 2σ(F2)] = 0.020 | 0 restraints |
wR(F2) = 0.057 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | Δρmax = 0.31 e Å−3 |
3514 reflections | Δρmin = −0.35 e Å−3 |
198 parameters |
Experimental. Data collection was performed with four batch runs at phi = 0.00° (600 frames), at phi = 90.00° (600 frames), at phi = 180.00° (600 frames) and at phi = 270.00° (600 frames). A fifth batch run was collected at phi = 0.00° (50 frames) to monitor crystal and diffractometer stability. Frame width = 0.30° in omega. Data were merged, corrected for decay (if any), and treated with multi-scan absorption corrections (if required). |
x | y | z | Uiso*/Ueq | ||
Mn1 | 0.5000 | 1.0000 | 0.5000 | 0.01484 (6) | |
Mn2 | 0.67310 (2) | 0.63019 (2) | 0.56849 (2) | 0.01492 (6) | |
N1 | 0.49468 (13) | 0.58131 (12) | 0.75859 (11) | 0.0203 (2) | |
O1 | 0.69813 (11) | 0.93862 (10) | 0.34097 (9) | 0.02220 (18) | |
O2 | 0.81744 (11) | 0.69304 (9) | 0.38176 (9) | 0.02006 (17) | |
O3 | 0.43984 (10) | 0.77516 (9) | 0.49460 (9) | 0.01721 (16) | |
O4 | 0.30799 (13) | 0.58516 (10) | 0.49762 (11) | 0.0290 (2) | |
O5 | 0.66602 (11) | 0.85585 (9) | 0.64449 (9) | 0.01837 (17) | |
O6 | 0.83746 (14) | 0.78614 (12) | 0.80527 (11) | 0.0335 (2) | |
O7 | 0.89280 (13) | 0.53570 (12) | 0.67585 (11) | 0.0269 (2) | |
H71 | 0.908 (3) | 0.601 (3) | 0.718 (2) | 0.046 (6)* | |
H72 | 0.980 (3) | 0.482 (2) | 0.659 (2) | 0.041 (5)* | |
C1 | 0.80320 (14) | 0.81979 (13) | 0.31196 (12) | 0.0176 (2) | |
C2 | 0.92106 (19) | 0.83031 (17) | 0.18292 (15) | 0.0327 (3) | |
H2A | 1.0210 | 0.7471 | 0.1864 | 0.049* | |
H2B | 0.9572 | 0.9281 | 0.1719 | 0.049* | |
H2C | 0.8615 | 0.8225 | 0.1066 | 0.049* | |
C3 | 0.30526 (14) | 0.72234 (13) | 0.49728 (11) | 0.0164 (2) | |
C4 | 0.13774 (16) | 0.83251 (15) | 0.50462 (17) | 0.0306 (3) | |
H4A | 0.0509 | 0.7845 | 0.4793 | 0.046* | |
H4B | 0.1475 | 0.9232 | 0.4427 | 0.046* | |
H4C | 0.1053 | 0.8619 | 0.5967 | 0.046* | |
C5 | 0.72135 (15) | 0.87587 (13) | 0.75330 (12) | 0.0192 (2) | |
C6 | 0.6347 (2) | 1.01701 (16) | 0.82145 (15) | 0.0323 (3) | |
H6A | 0.7028 | 1.0322 | 0.8898 | 0.048* | |
H6B | 0.5218 | 1.0051 | 0.8644 | 0.048* | |
H6C | 0.6232 | 1.1054 | 0.7544 | 0.048* | |
C7 | 0.50630 (18) | 0.43829 (15) | 0.81537 (14) | 0.0264 (3) | |
H7A | 0.6018 | 0.3634 | 0.7860 | 0.032* | |
C8 | 0.3863 (2) | 0.39423 (17) | 0.91456 (15) | 0.0332 (3) | |
H8A | 0.3998 | 0.2916 | 0.9527 | 0.040* | |
C9 | 0.2468 (2) | 0.5017 (2) | 0.95705 (15) | 0.0371 (3) | |
H9A | 0.1618 | 0.4746 | 1.0246 | 0.044* | |
C10 | 0.23278 (19) | 0.6499 (2) | 0.89948 (15) | 0.0356 (3) | |
H10A | 0.1372 | 0.7262 | 0.9261 | 0.043* | |
C11 | 0.36003 (17) | 0.68556 (15) | 0.80251 (13) | 0.0259 (3) | |
H11A | 0.3516 | 0.7883 | 0.7655 | 0.031* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Mn1 | 0.01447 (12) | 0.00843 (11) | 0.01996 (12) | −0.00059 (8) | 0.00022 (9) | −0.00054 (8) |
Mn2 | 0.01320 (9) | 0.00939 (9) | 0.02067 (10) | −0.00066 (6) | 0.00036 (6) | −0.00119 (6) |
N1 | 0.0203 (5) | 0.0181 (5) | 0.0210 (5) | −0.0024 (4) | −0.0005 (4) | −0.0009 (4) |
O1 | 0.0210 (4) | 0.0158 (4) | 0.0257 (4) | 0.0004 (3) | 0.0040 (3) | −0.0012 (3) |
O2 | 0.0184 (4) | 0.0155 (4) | 0.0233 (4) | −0.0004 (3) | 0.0024 (3) | −0.0013 (3) |
O3 | 0.0136 (4) | 0.0121 (4) | 0.0250 (4) | −0.0018 (3) | −0.0013 (3) | −0.0009 (3) |
O4 | 0.0309 (5) | 0.0144 (4) | 0.0435 (6) | −0.0071 (4) | −0.0014 (4) | −0.0084 (4) |
O5 | 0.0205 (4) | 0.0134 (4) | 0.0210 (4) | −0.0016 (3) | −0.0036 (3) | −0.0026 (3) |
O6 | 0.0365 (6) | 0.0294 (5) | 0.0333 (5) | 0.0076 (4) | −0.0169 (4) | −0.0090 (4) |
O7 | 0.0199 (5) | 0.0234 (5) | 0.0353 (5) | 0.0055 (4) | −0.0067 (4) | −0.0077 (4) |
C1 | 0.0148 (5) | 0.0180 (5) | 0.0196 (5) | −0.0031 (4) | −0.0002 (4) | −0.0030 (4) |
C2 | 0.0317 (7) | 0.0305 (7) | 0.0275 (7) | 0.0002 (6) | 0.0113 (6) | 0.0015 (5) |
C3 | 0.0173 (5) | 0.0139 (5) | 0.0181 (5) | −0.0030 (4) | −0.0016 (4) | −0.0023 (4) |
C4 | 0.0151 (6) | 0.0221 (6) | 0.0538 (9) | −0.0011 (5) | −0.0061 (6) | −0.0023 (6) |
C5 | 0.0206 (6) | 0.0163 (5) | 0.0202 (5) | −0.0039 (4) | −0.0003 (4) | −0.0018 (4) |
C6 | 0.0425 (8) | 0.0253 (7) | 0.0275 (7) | 0.0034 (6) | −0.0074 (6) | −0.0115 (5) |
C7 | 0.0326 (7) | 0.0196 (6) | 0.0253 (6) | −0.0049 (5) | 0.0002 (5) | −0.0003 (5) |
C8 | 0.0452 (8) | 0.0298 (7) | 0.0267 (7) | −0.0178 (6) | −0.0018 (6) | 0.0047 (5) |
C9 | 0.0303 (7) | 0.0543 (10) | 0.0262 (7) | −0.0171 (7) | 0.0027 (6) | 0.0065 (6) |
C10 | 0.0250 (7) | 0.0472 (9) | 0.0264 (7) | 0.0041 (6) | 0.0042 (5) | 0.0007 (6) |
C11 | 0.0248 (6) | 0.0257 (6) | 0.0217 (6) | 0.0026 (5) | 0.0000 (5) | 0.0018 (5) |
Mn1—O1 | 2.1369 (9) | O7—H72 | 0.78 (2) |
Mn1—O1i | 2.1369 (9) | C1—C2 | 1.5094 (17) |
Mn1—O3 | 2.1997 (8) | C2—H2A | 0.9800 |
Mn1—O3i | 2.1997 (8) | C2—H2B | 0.9800 |
Mn1—O5i | 2.2277 (8) | C2—H2C | 0.9800 |
Mn1—O5 | 2.2277 (8) | C3—C4 | 1.4985 (17) |
Mn2—O4ii | 2.0995 (9) | C4—H4A | 0.9800 |
Mn2—O2 | 2.1579 (9) | C4—H4B | 0.9800 |
Mn2—O7 | 2.1755 (10) | C4—H4C | 0.9800 |
Mn2—O3 | 2.2215 (8) | C5—C6 | 1.5092 (17) |
Mn2—O5 | 2.2494 (8) | C6—H6A | 0.9800 |
Mn2—N1 | 2.2946 (10) | C6—H6B | 0.9800 |
N1—C7 | 1.3392 (16) | C6—H6C | 0.9800 |
N1—C11 | 1.3395 (16) | C7—C8 | 1.3819 (19) |
O1—C1 | 1.2542 (14) | C7—H7A | 0.9500 |
O2—C1 | 1.2625 (14) | C8—C9 | 1.376 (2) |
O3—C3 | 1.2796 (14) | C8—H8A | 0.9500 |
O4—C3 | 1.2352 (14) | C9—C10 | 1.383 (2) |
O4—Mn2ii | 2.0995 (9) | C9—H9A | 0.9500 |
O5—C5 | 1.2870 (15) | C10—C11 | 1.3833 (19) |
O6—C5 | 1.2343 (16) | C10—H10A | 0.9500 |
O7—H71 | 0.81 (2) | C11—H11A | 0.9500 |
O1—Mn1—O1i | 180.0 | H71—O7—H72 | 108 (2) |
O1—Mn1—O3 | 86.76 (3) | O1—C1—O2 | 125.21 (11) |
O1i—Mn1—O3 | 93.24 (3) | O1—C1—C2 | 116.92 (11) |
O1—Mn1—O3i | 93.24 (3) | O2—C1—C2 | 117.87 (11) |
O1i—Mn1—O3i | 86.76 (3) | C1—C2—H2A | 109.5 |
O3—Mn1—O3i | 180.0 | C1—C2—H2B | 109.5 |
O1—Mn1—O5i | 91.39 (3) | H2A—C2—H2B | 109.5 |
O1i—Mn1—O5i | 88.61 (3) | C1—C2—H2C | 109.5 |
O3—Mn1—O5i | 101.79 (3) | H2A—C2—H2C | 109.5 |
O3i—Mn1—O5i | 78.21 (3) | H2B—C2—H2C | 109.5 |
O1—Mn1—O5 | 88.61 (3) | O4—C3—O3 | 122.80 (11) |
O1i—Mn1—O5 | 91.39 (3) | O4—C3—C4 | 119.24 (11) |
O3—Mn1—O5 | 78.21 (3) | O3—C3—C4 | 117.94 (10) |
O3i—Mn1—O5 | 101.79 (3) | C3—C4—H4A | 109.5 |
O5i—Mn1—O5 | 180.0 | C3—C4—H4B | 109.5 |
O4ii—Mn2—O2 | 88.84 (4) | H4A—C4—H4B | 109.5 |
O4ii—Mn2—O7 | 88.67 (4) | C3—C4—H4C | 109.5 |
O2—Mn2—O7 | 95.57 (4) | H4A—C4—H4C | 109.5 |
O4ii—Mn2—O3 | 105.82 (4) | H4B—C4—H4C | 109.5 |
O2—Mn2—O3 | 89.30 (3) | O6—C5—O5 | 124.09 (11) |
O7—Mn2—O3 | 164.84 (4) | O6—C5—C6 | 118.89 (12) |
O4ii—Mn2—O5 | 176.87 (4) | O5—C5—C6 | 117.01 (11) |
O2—Mn2—O5 | 91.19 (3) | C5—C6—H6A | 109.5 |
O7—Mn2—O5 | 88.22 (4) | C5—C6—H6B | 109.5 |
O3—Mn2—O5 | 77.31 (3) | H6A—C6—H6B | 109.5 |
O4ii—Mn2—N1 | 93.24 (4) | C5—C6—H6C | 109.5 |
O2—Mn2—N1 | 173.79 (3) | H6A—C6—H6C | 109.5 |
O7—Mn2—N1 | 90.33 (4) | H6B—C6—H6C | 109.5 |
O3—Mn2—N1 | 84.51 (3) | N1—C7—C8 | 123.28 (13) |
O5—Mn2—N1 | 87.05 (3) | N1—C7—H7A | 118.4 |
C7—N1—C11 | 117.44 (11) | C8—C7—H7A | 118.4 |
C7—N1—Mn2 | 119.52 (9) | C9—C8—C7 | 118.76 (13) |
C11—N1—Mn2 | 122.07 (8) | C9—C8—H8A | 120.6 |
C1—O1—Mn1 | 135.91 (8) | C7—C8—H8A | 120.6 |
C1—O2—Mn2 | 129.37 (8) | C8—C9—C10 | 118.72 (13) |
C3—O3—Mn1 | 136.43 (7) | C8—C9—H9A | 120.6 |
C3—O3—Mn2 | 120.89 (7) | C10—C9—H9A | 120.6 |
Mn1—O3—Mn2 | 98.99 (3) | C9—C10—C11 | 119.02 (14) |
C3—O4—Mn2ii | 161.58 (10) | C9—C10—H10A | 120.5 |
C5—O5—Mn1 | 135.62 (7) | C11—C10—H10A | 120.5 |
C5—O5—Mn2 | 126.01 (7) | N1—C11—C10 | 122.75 (13) |
Mn1—O5—Mn2 | 97.33 (3) | N1—C11—H11A | 118.6 |
Mn2—O7—H71 | 107.7 (15) | C10—C11—H11A | 118.6 |
Mn2—O7—H72 | 134.9 (15) | ||
Mn1—O1—C1—O2 | −1.0 (2) | Mn2—O5—C5—O6 | 27.84 (17) |
Mn1—O1—C1—C2 | 178.82 (10) | Mn1—O5—C5—C6 | 14.66 (17) |
Mn2—O2—C1—O1 | 0.83 (18) | Mn2—O5—C5—C6 | −150.87 (9) |
Mn2—O2—C1—C2 | −178.99 (9) | C11—N1—C7—C8 | 0.8 (2) |
Mn2ii—O4—C3—O3 | −85.5 (3) | Mn2—N1—C7—C8 | −168.22 (11) |
Mn2ii—O4—C3—C4 | 96.5 (3) | N1—C7—C8—C9 | 0.5 (2) |
Mn1—O3—C3—O4 | −177.30 (9) | C7—C8—C9—C10 | −0.4 (2) |
Mn2—O3—C3—O4 | −24.02 (16) | C8—C9—C10—C11 | −0.8 (2) |
Mn1—O3—C3—C4 | 0.76 (18) | C7—N1—C11—C10 | −2.0 (2) |
Mn2—O3—C3—C4 | 154.04 (9) | Mn2—N1—C11—C10 | 166.62 (11) |
Mn1—O5—C5—O6 | −166.63 (10) | C9—C10—C11—N1 | 2.1 (2) |
Symmetry codes: (i) −x+1, −y+2, −z+1; (ii) −x+1, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
O7—H71···O6 | 0.81 (2) | 1.92 (2) | 2.6694 (15) | 154 (2) |
O7—H72···O2iii | 0.78 (2) | 2.05 (2) | 2.8162 (13) | 169 (2) |
Symmetry code: (iii) −x+2, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [Mn3(C2H3O2)6(C6H5N)2(H2O)2] |
Mr | 713.31 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 200 |
a, b, c (Å) | 8.1153 (2), 9.0404 (2), 10.0759 (2) |
α, β, γ (°) | 83.160 (1), 81.994 (1), 77.423 (1) |
V (Å3) | 711.43 (3) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 1.38 |
Crystal size (mm) | 0.15 × 0.12 × 0.12 |
Data collection | |
Diffractometer | Bruker APEXII CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2009) |
Tmin, Tmax | 0.820, 0.852 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 11780, 3514, 3269 |
Rint | 0.012 |
(sin θ/λ)max (Å−1) | 0.667 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.020, 0.057, 1.06 |
No. of reflections | 3514 |
No. of parameters | 198 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.31, −0.35 |
Computer programs: APEX2 (Bruker, 2009), XPREP (Bruker, 2009), SHELXS2013 (Sheldrick, 2008), SHELXL2013 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2008).
D—H···A | D—H | H···A | D···A | D—H···A |
O7—H71···O6 | 0.81 (2) | 1.92 (2) | 2.6694 (15) | 154 (2) |
O7—H72···O2i | 0.78 (2) | 2.05 (2) | 2.8162 (13) | 169 (2) |
Symmetry code: (i) −x+2, −y+1, −z+1. |