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The crystal structure of a new form of dehydrated mang­a­nese(II) acetate, poly[[hexa-μ3-acetato-trimanganese(II)] aceto­nitrile solvate], {[Mn3(CH3COO)6]·CH3CN}n, (I), reveals a three-dimensional polymeric structure based on an {Mn3} trimer. The {Mn3} asymmetric unit contains three crystallographically independent Mn positions, comprising a seven-coordinate center sharing a mirror plane with a six-coordinate center, and another six-coordinate atom located on an inversion center. Two of the four crystallographically independent acetate (OAc) ligands, as well as the acetonitrile solvent mol­ecule, are also located on the mirror plane. The Mn atoms are connected by a mixture of Mn—O—Mn and Mn—OCO—Mn bridging modes, giving rise to face- and corner-sharing inter­actions between manganese polyhedra within the trimers, and edge- and corner-sharing connections between the trimers. The network contains substantial pores which are tightly filled by crystallographically located acetonitrile mol­ecules. This structure represents the first porous structurally characterized phase of anhydrous manganese(II) acetate and as such it is compared with the closely related densely packed anhydrous manganese(II) acetate phase, solvent-free β-Mn(OAc)2.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270109014693/eg3016sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270109014693/eg3016Isup2.hkl
Contains datablock I

CCDC reference: 742164

Comment top

Coordination networks constructed from rigid bis-carboxylate or amine ligand linkers, such as terephthalic acid (Li et al., 1999) or 4,4-dipyridyl (Zaworotko, 2000), have attracted great attention in recent years. In such substances, changing the length of the linker ligand allows adjustment of structural properties such as pore size (Zaworotko, 2000; Yaghi et al., 2003). However, simple mono-carboxylates, such as formate or acetate, are also able to generate complex extended structures, due to the many accessible carboxylate bridging coordination modes (Viertelhaus et al., 2003; Martin & Hess, 1996). Such structures more closely resemble metal oxides such as zeolites, as the small size of the ligands obliges the metal ions to play a structural role in the linkers as well as the nodes. The resulting short metal···metal distances can lead to interesting magnetic behaviour, driving investigation of a number of stable porous formate networks based on divalent metal ions (Wang, Zhang, Fujiwara et al., 2004; Wang, Zhang, Otsuka et al., 2004; Wang et al., 2005; Viertelhaus et al., 2005; Rood et al., 2006). Such formate-based materials can accommodate a range of guests and have potential as porous magnets (Wang, Zhang, Fujiwara et al., 2004; Dybtsev et al., 2004). However, anhydrous acetate-based frameworks have received less attention to date.

Our recent investigation of the coordination chemistry of the novel chiral ethanolamine ligand, (S)-N-phenylethyldiethanolamine [(S)-H2PEDEA], has resulted in the serendipitous isolation of a new anhydrous manganese(II) acetate coordination framework, the title compound, {[Mn3(O2CCH3)6].CH3CN}n, (I), which crystallizes in the space group Pnma. Compound (I) is the first structurally characterized porous anhydrous manganese(II) acetate phase, and was isolated as a minor product from the attempted reaction of the well known manganese(III) trimer, [Mn3O(O2CCH3)6(py)3](ClO4) (Vincent et al., 1987), with (S)-H2PEDEA in acetonitrile–methanol. In this way, reduction from MnIII to MnII occurs due to reaction with the alcohol groups provided by the solvent and (S)-H2PEDEA. Accommodation of acetonitrile molecules within the resulting framework leads to a porous structure with a substantially increased unit cell volume (by ca 9%) in comparison with the previously published densely packed β-Mn(OAc)2 (Martin & Hess, 1996) and γ-Mn(OAc)2 (Yang et al., 2005).

The three-dimensional network formed by compound (I) is based on assembly of an {Mn3} asymmetric unit, consisting of a central seven-coordinate Mn centre (Mn1) and two six-coordinate Mn atoms (Mn2 and Mn3), four crystallographically independent acetate ligands, and an acetonitrile molecule (Fig. 1). Two of the Mn atoms (Mn1 and Mn2), two acetate ligands (those containing atoms C1 and C3) and the acetonitrile molecule are located on a mirror plane, while atom Mn3 sits on an inversion centre. The C1 acetate ligand is bisected by the mirror, so that only C atoms C1 and C2 sit on the mirror plane and atom O7iii [symmetry code: (iii) x, 1/2 - y, z] is generated by mirror symmetry from atom O7. In the C3 acetate ligand, all four atoms are located on the mirror plane.

The four crystallographically independent acetate ligands show two different µ3 coordination modes. The C3, C5 and C7 acetates all have one O atom [O1, O2 and O5ii, respectively; symmetry code: (ii) x - 1/2, y, 3/2 - z] acting as a monoatomic bridge between two Mn sites, with the other connecting to a third Mn atom. For the C1 acetate, both O atoms (O7 and symmetry-related O7iii) act as monoatomic bridges coordinating to atom Mn1, so that atoms O7 and O7iii, respectively, link atom Mn1 to atom Mn3 and symmetry-related atom Mn3v (Fig. 3) [symmetry code: (v) -x, y + 1/2, 1 - z]. The overall result is that the Mn centres are connected through a mixture of Mn—O—Mn and Mn—OCO—Mn bridges, whereby atoms Mn1 and Mn2 are connected by three Mn—O—Mn bridges (e.g. face-sharing polyhedra), and atom Mn1 connects to atom Mn3 by a single Mn—O—Mn bridge supported by two Mn—OCO—Mn linkages (corner-sharing polyhedra). The Mn1···Mn2 face-sharing connection results in a short Mn···Mn contact of 3.170 (1) Å that may indicate a weak metal–metal interaction. This contrasts with the {Mn3} unit observed in β-Mn(OAc)2 [Martin & Hess, 1996; Cambridge Structural Database (Allen, 2002) refcode QQQFUV02], which exhibits one face-sharing and one edge-sharing interaction between the Mn centres (Fig. 1). However, both β-Mn(OAc)2 and compound (I) show the same overall level of condensation, as the four connections to other trimers comprise exclusively corner-sharing interactions in β-Mn(OAc)2, but two edge-sharing and two corner-sharing interactions in compound (I). The structure of γ-Mn(OAc)2 (Yang et al., 2005) is essentially the same as β-Mn(OAc)2. However, the presence of disorder in the acetate bridging ligands merges the Mn2 and Mn3 sites into one position. This results in an inversion centre at the seven-coordinate atom Mn1 and a higher symmetry space group (P41212, compared with P212121 for the β phase).

The simplest way of describing the network formed by compound (I) is as a diamondoid net of Mn centres (Fig. 2). Seven-coordinate atom Mn1 forms a tetrahedral node by connecting to four other Mn1 centres via two Mn2 and two Mn3 atoms, which combined with the acetate ligands act as linkers. As such, atom Mn1 sits at the centre of an {Mn5} tetrahedral unit with vertices described by two Mn2 and two Mn3 atoms (Figs. 2 and 4). This arrangement results in wavy chains of Mn1 and Mn2 atoms propagating parallel to the crystallographic a axis, formed by face-sharing intratrimer and edge-sharing intertrimer Mn1···Mn2 interactions. The chains are connected to form a three-dimensional network by the corner-sharing links provided by atom Mn3 between the Mn1 nodes, leading to pores which run along the crystallographic a axis and are occupied by the crystallographically located acetonitrile guests (one per {Mn3} formula unit; Fig. 3). Tight binding of the guest acetonitrile molecules is indicated by the zero solvent-accessible void space calculated by PLATON (Spek, 2003), and is illustrated by the space-filling diagram on the right-hand side of Fig. 3.

Note that the chiral literature compound β-Mn(OAc)2 (space group P212121; Martin & Hess, 1996) is also based on a diamondoid arrangement of Mn centres (Fig. 2). However, breaking the structure down again into chains of Mn1 and Mn2 connected by Mn3 atoms reveals that the nature of the intra- and interchain connections is different from that of compound (I). The Mn1···Mn2 chains in β-Mn(OAc)2 contain alternating face-sharing and corner-sharing connections [rather than the face-sharing and edge-sharing connections seen in compound (I)], and the Mn3 linkers connect to the chains through alternating edge-sharing and corner-sharing connections [compared with exclusively corner-sharing in compound (I)]. As a result, the β-Mn(OAc)2 network is less regular (as reflected in the chiral space group). This distortion probably occurs because it is `collapsed' compared with compound (I), filling the space left by the absent acetonitrile molecules. The chirality of β-Mn(OAc)2, observed in the helical axes described by Martin & Hess (1996), is also manifested in the subtly contrasting connectivity around the Mn1 node positions compared with compound (I) (Fig. 4). In compound (I), atom Mn1 and the two Mn2 atoms sit on a mirror plane between two crystallographically identical Mn3 positions (Fig. 3). In β-Mn(OAc)2, the equivalent Mn1 position is effectively a chiral centre, as all four combinations of connection mode (face-, edge- or corner-sharing) and linked atom (e.g. Mn2 or Mn3 sites) are different.

Experimental top

[Mn3(OAc)6(py)3](ClO4) was synthesized according to the published procedure (Vincent et al., 1987). (S)-H2PEDEA was synthesized by reacting (S)-N-phenylethylamine with ethylene oxide in ethanol. Full details will be published elsewhere. All other reagents were obtained commercially as ACS reagent grade and used as supplied. IR spectra were recorded on a Bruker TENSOR 27 spectrometer.

(S)-H2PEDEA (0.078 g, 0.373 mmol) in methanol (3 ml) was added to a solution of [Mn3(OAc)6(py)3](ClO4) (0.27 g, 0.310 mmol) in acetonitrile (7 ml). The resulting dark-brown mixture was stirred for 16 h at room temperature before filtration. Slow evaporation of the solvent produced a dark-brown microcrystalline solid (0.092 g). The X-ray powder pattern of this material matched neither compound (I) nor β/γ-Mn(OAc)2. However, elemental analysis on dried material indicated that it was a form of manganese(II) acetate. Further evaporation produced a small quantity of pale-yellow single-crystal X-ray diffraction quality crystals of compound (I). FT–IR (KBr disc, ν, cm-1): 3386 (s), 2936 (w), 2255 (w), 1577 (v), 1418 (v), 1344 (s), 1049 (m), 1026 (m), 940 (w), 660 (s), 615 (m), 502 (w).

Refinement top

All H atoms are bound to methyl C atoms and were placed in geometrically idealized positions. For both acetate ligands and acetonitrile solvent they were constrained to ride and rotate on their parent atoms, with C—H = 0.98 Å and Uiso = 1.5Ueq(C). The relatively large Ueq(max)/Ueq(min) for carbon on both acetate framework and acetonitrile solvent atoms is a consequence of slight thermal disorder on the terminal methyl positions.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SMART (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: publCIF (Westrip, 2009).

Figures top
[Figure 1] Fig. 1. (a) The asymmetric unit of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii. [Symmetry codes: (i) x, y, z + 1; (ii) x - 1/2, y, 3/2 - z; (iii) x, 1/2 - y, z; (iv) x - 1/2, 1/2 - y, 3/2 - y.] (b) Polyhedral representation of the {Mn3} units in (I) (top) and β-Mn(OAc)2 (bottom), showing the connectivity of the three Mn atoms.
[Figure 2] Fig. 2. Diamondoid networks of Mn atoms in (a) compound (I) and (b) β-Mn(OAc)2. In each network, one tetrahedral {Mn5} unit has been highlighted in black, with larger spheres.
[Figure 3] Fig. 3. The crystal packing in compound (I), viewed along the crystallographic a-axis. (a) Mn atoms are represented as polyhedra and the acetonitrile molecules located within the pores are highlighted with larger spheres. (b) Space-filling representation, illustrating the tight filling of the pores by acetonitrile.
[Figure 4] Fig. 4. (a) The symmetrical tetrahedral {Mn5} units in compound (I). (b) The chiral tetrahedral {Mn5} unit in β-Mn(OAc)2. Abbreviations denote corner-sharing (cs), edge-sharing (es) and face-sharing (fs) polyhedra. [Symmetry codes: (ii) x - 1/2, y, 3/2 - z; (v) -x, y + 1/2, 1 - z; (A) x + 1/2, 3/2 - y, 1 - z; (B) -x, y + 1/2, 3/2 - z.]
poly[[hexa-µ3-acetato-trimanganese(II)] acetonitrile solvate] top
Crystal data top
[Mn3(C2H3O2)6]·C2H3NDx = 1.720 Mg m3
Mr = 560.14Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, PnmaCell parameters from 926 reflections
a = 10.788 (2) Åθ = 3.0–28.2°
b = 12.702 (2) ŵ = 1.78 mm1
c = 15.784 (3) ÅT = 193 K
V = 2163.0 (7) Å3Prism, yellow
Z = 40.15 × 0.08 × 0.05 mm
F(000) = 1132
Data collection top
Bruker SMART ? CCD area-detector
diffractometer
2763 independent reflections
Radiation source: fine-focus sealed tube2307 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.037
ϕ and ω scansθmax = 28.3°, θmin = 2.1°
Absorption correction: multi-scan
(SADABS; Bruker, 2001)
h = 1314
Tmin = 0.692, Tmax = 0.915k = 1616
18714 measured reflectionsl = 2120
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)] = 0.027Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.071H-atom parameters constrained
S = 1.09 w = 1/[σ2(Fo2) + (0.0293P)2 + 1.7643P]
where P = (Fo2 + 2Fc2)/3
2763 reflections(Δ/σ)max = 0.001
159 parametersΔρmax = 0.48 e Å3
0 restraintsΔρmin = 0.40 e Å3
Crystal data top
[Mn3(C2H3O2)6]·C2H3NV = 2163.0 (7) Å3
Mr = 560.14Z = 4
Orthorhombic, PnmaMo Kα radiation
a = 10.788 (2) ŵ = 1.78 mm1
b = 12.702 (2) ÅT = 193 K
c = 15.784 (3) Å0.15 × 0.08 × 0.05 mm
Data collection top
Bruker SMART ? CCD area-detector
diffractometer
2763 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2001)
2307 reflections with I > 2σ(I)
Tmin = 0.692, Tmax = 0.915Rint = 0.037
18714 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0270 restraints
wR(F2) = 0.071H-atom parameters constrained
S = 1.09Δρmax = 0.48 e Å3
2763 reflectionsΔρmin = 0.40 e Å3
159 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*/UeqOcc. (<1)
C10.0434 (2)0.25000.47600 (16)0.0182 (5)
C20.0952 (4)0.25000.38807 (18)0.0380 (8)
H2A0.09600.32210.36600.057*0.50
H2B0.18000.22230.38910.057*0.50
H2C0.04370.20560.35150.057*0.50
C30.0836 (3)0.25000.84620 (16)0.0257 (6)
C40.1704 (3)0.25000.92162 (19)0.0502 (11)
H4A0.24760.21400.90650.075*0.50
H4B0.13100.21330.96910.075*0.50
H4C0.18870.32270.93810.075*0.50
C50.25158 (19)0.06295 (16)0.58784 (13)0.0272 (4)
C60.3797 (2)0.0202 (2)0.6025 (2)0.0538 (8)
H6A0.37640.05680.60480.081*
H6B0.41200.04750.65620.081*
H6C0.43410.04220.55600.081*
C70.1231 (2)0.04699 (16)0.67196 (12)0.0288 (4)
C80.2484 (3)0.0016 (2)0.6921 (2)0.0599 (9)
H8A0.29510.00860.63950.090*
H8B0.29370.05000.72920.090*
H8C0.23810.06630.72080.090*
Mn10.04447 (3)0.25000.63752 (2)0.01546 (10)
Mn20.31414 (3)0.25000.71722 (2)0.01686 (10)
Mn30.00000.00000.50000.01945 (10)
O10.12887 (17)0.25000.77135 (11)0.0240 (4)
O20.21410 (12)0.14233 (11)0.63072 (8)0.0230 (3)
O30.04932 (16)0.00827 (11)0.63187 (9)0.0339 (4)
O40.19026 (14)0.01826 (14)0.53218 (11)0.0397 (4)
O50.40082 (13)0.14224 (11)0.80605 (8)0.0238 (3)
O60.47080 (18)0.25000.63844 (12)0.0278 (5)
O70.02185 (16)0.16621 (11)0.51492 (8)0.0298 (3)
C90.2874 (9)0.25000.4265 (4)0.147 (4)
H9A0.22840.20730.39420.220*0.50
H9B0.25650.32230.43080.220*0.50
H9C0.29700.22040.48350.220*0.50
C100.4023 (8)0.25000.3853 (4)0.090 (2)
N10.4963 (7)0.25000.3513 (6)0.139 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0192 (12)0.0175 (12)0.0179 (11)0.0000.0009 (10)0.000
C20.058 (2)0.0354 (17)0.0204 (13)0.0000.0130 (14)0.000
C30.0185 (13)0.0415 (17)0.0171 (12)0.0000.0001 (10)0.000
C40.0200 (16)0.112 (4)0.0184 (14)0.0000.0016 (12)0.000
C50.0236 (10)0.0285 (10)0.0294 (10)0.0004 (8)0.0011 (8)0.0070 (8)
C60.0403 (15)0.0498 (16)0.0714 (18)0.0168 (12)0.0143 (13)0.0315 (14)
C70.0395 (12)0.0260 (10)0.0210 (9)0.0076 (9)0.0060 (8)0.0034 (8)
C80.0626 (19)0.0505 (16)0.0665 (18)0.0311 (14)0.0263 (15)0.0269 (14)
Mn10.01396 (19)0.01953 (19)0.01290 (17)0.0000.00045 (14)0.000
Mn20.01382 (19)0.0227 (2)0.01407 (18)0.0000.00219 (14)0.000
Mn30.0275 (2)0.01335 (19)0.01746 (18)0.00050 (15)0.00011 (16)0.00320 (14)
O10.0155 (9)0.0415 (11)0.0151 (8)0.0000.0006 (7)0.000
O20.0209 (7)0.0251 (7)0.0230 (6)0.0001 (5)0.0021 (5)0.0070 (5)
O30.0579 (11)0.0222 (7)0.0217 (7)0.0053 (7)0.0092 (7)0.0007 (6)
O40.0292 (9)0.0476 (10)0.0425 (9)0.0014 (7)0.0036 (7)0.0265 (8)
O50.0250 (7)0.0227 (7)0.0236 (6)0.0047 (5)0.0069 (5)0.0059 (5)
O60.0162 (10)0.0497 (13)0.0175 (9)0.0000.0011 (7)0.000
O70.0547 (10)0.0147 (7)0.0199 (7)0.0052 (6)0.0035 (6)0.0003 (5)
C90.278 (12)0.061 (4)0.102 (5)0.0000.108 (7)0.000
C100.148 (7)0.053 (3)0.069 (4)0.0000.019 (4)0.000
N10.114 (6)0.129 (6)0.174 (8)0.0000.032 (5)0.000
Geometric parameters (Å, º) top
C1—O7i1.2506 (19)Mn1—O2i2.2871 (14)
C1—O71.2506 (19)Mn1—O5iii2.2514 (13)
C1—C21.496 (4)Mn1—O5ii2.2514 (14)
C2—H2A0.9800Mn1—O72.3215 (14)
C2—H2B0.9800Mn1—O7i2.3215 (14)
C2—H2C0.9800Mn1—Mn23.1697 (7)
C3—O6ii1.241 (3)Mn2—O12.1737 (19)
C3—O11.278 (3)Mn2—O22.2134 (13)
C3—C41.514 (4)Mn2—O2i2.2135 (13)
C4—H4A0.9800Mn2—O52.1711 (13)
C4—H4B0.9800Mn2—O5i2.1710 (13)
C4—H4C0.9800Mn2—O62.0983 (19)
C5—O41.238 (2)Mn3—O32.1509 (14)
C5—O21.280 (2)Mn3—O3iv2.1510 (14)
C5—C61.502 (3)Mn3—O42.1273 (16)
C6—H6A0.9800Mn3—O4iv2.1273 (16)
C6—H6B0.9800Mn3—O72.1374 (14)
C6—H6C0.9800Mn3—O7iv2.1373 (14)
C7—O31.236 (3)O5—C7v1.285 (2)
C7—O5ii1.285 (2)O5—Mn1v2.2513 (13)
C7—C81.503 (3)O6—C3v1.241 (3)
C8—H8A0.9800C9—C101.400 (11)
C8—H8B0.9800C9—H9A0.9800
C8—H8C0.9800C9—H9B0.9800
Mn1—O12.3004 (18)C9—H9C0.9800
Mn1—O22.2871 (14)C10—N11.147 (10)
O7i—C1—O7116.6 (2)O1—Mn1—Mn243.30 (5)
O7i—C1—C2121.67 (12)O7—Mn1—Mn2127.86 (4)
O7—C1—C2121.67 (12)O7i—Mn1—Mn2127.86 (4)
C1—C2—H2A109.5O6—Mn2—O5i92.05 (6)
C1—C2—H2B109.5O6—Mn2—O592.05 (6)
H2A—C2—H2B109.5O5i—Mn2—O578.17 (7)
C1—C2—H2C109.5O6—Mn2—O1166.80 (7)
H2A—C2—H2C109.5O5i—Mn2—O198.18 (5)
H2B—C2—H2C109.5O5—Mn2—O198.18 (5)
O6ii—C3—O1123.7 (2)O6—Mn2—O291.56 (6)
O6ii—C3—C4116.9 (2)O5i—Mn2—O2176.27 (5)
O1—C3—C4119.4 (2)O5—Mn2—O2102.64 (5)
C3—C4—H4A109.5O1—Mn2—O278.12 (5)
C3—C4—H4B109.5O6—Mn2—O2i91.56 (6)
H4A—C4—H4B109.5O5i—Mn2—O2i102.64 (5)
C3—C4—H4C109.5O5—Mn2—O2i176.27 (5)
H4A—C4—H4C109.5O1—Mn2—O2i78.12 (5)
H4B—C4—H4C109.5O2—Mn2—O2i76.32 (7)
O4—C5—O2124.60 (19)O6—Mn2—Mn1120.27 (5)
O4—C5—C6115.80 (19)O5i—Mn2—Mn1130.67 (4)
O2—C5—C6119.58 (19)O5—Mn2—Mn1130.67 (4)
C5—C6—H6A109.5O1—Mn2—Mn146.53 (5)
C5—C6—H6B109.5O2—Mn2—Mn146.18 (4)
H6A—C6—H6B109.5O2i—Mn2—Mn146.18 (4)
C5—C6—H6C109.5O4—Mn3—O4iv180.0
H6A—C6—H6C109.5O4—Mn3—O7iv91.58 (6)
H6B—C6—H6C109.5O4iv—Mn3—O7iv88.42 (6)
O3—C7—O5ii122.9 (2)O4—Mn3—O788.42 (6)
O3—C7—C8118.0 (2)O4iv—Mn3—O791.58 (6)
O5ii—C7—C8119.0 (2)O7iv—Mn3—O7180.0
C7—C8—H8A109.5O4—Mn3—O390.74 (7)
C7—C8—H8B109.5O4iv—Mn3—O389.26 (7)
H8A—C8—H8B109.5O7iv—Mn3—O394.91 (5)
C7—C8—H8C109.5O7—Mn3—O385.09 (5)
H8A—C8—H8C109.5O4—Mn3—O3iv89.26 (7)
H8B—C8—H8C109.5O4iv—Mn3—O3iv90.74 (7)
O5ii—Mn1—O5iii74.88 (7)O7iv—Mn3—O3iv85.09 (5)
O5ii—Mn1—O2i158.89 (5)O7—Mn3—O3iv94.91 (5)
O5iii—Mn1—O2i101.88 (5)O3—Mn3—O3iv180.0
O5ii—Mn1—O2101.88 (5)C3—O1—Mn2135.60 (17)
O5iii—Mn1—O2158.89 (5)C3—O1—Mn1134.22 (17)
O2i—Mn1—O273.45 (7)Mn2—O1—Mn190.17 (7)
O5ii—Mn1—O184.79 (5)C5—O2—Mn2131.21 (13)
O5iii—Mn1—O184.79 (5)C5—O2—Mn1138.47 (13)
O2i—Mn1—O174.12 (5)Mn2—O2—Mn189.53 (5)
O2—Mn1—O174.12 (5)C7—O3—Mn3128.84 (14)
O5ii—Mn1—O780.73 (5)C5—O4—Mn3137.33 (14)
O5iii—Mn1—O7113.35 (6)C7v—O5—Mn2132.96 (13)
O2i—Mn1—O7118.79 (5)C7v—O5—Mn1v127.16 (12)
O2—Mn1—O786.18 (5)Mn2—O5—Mn1v99.71 (5)
O1—Mn1—O7152.56 (3)C3v—O6—Mn2132.40 (17)
O5ii—Mn1—O7i113.35 (6)C1—O7—Mn3143.80 (13)
O5iii—Mn1—O7i80.73 (5)C1—O7—Mn194.39 (12)
O2i—Mn1—O7i86.18 (5)Mn3—O7—Mn1120.71 (6)
O2—Mn1—O7i118.79 (5)C10—C9—H9A109.5
O1—Mn1—O7i152.56 (3)C10—C9—H9B109.5
O7—Mn1—O7i54.57 (7)H9A—C9—H9B109.5
O5ii—Mn1—Mn2118.35 (4)C10—C9—H9C109.5
O5iii—Mn1—Mn2118.34 (4)H9A—C9—H9C109.5
O2i—Mn1—Mn244.29 (3)H9B—C9—H9C109.5
O2—Mn1—Mn244.29 (3)N1—C10—C9179.8 (9)
Symmetry codes: (i) x, y+1/2, z; (ii) x1/2, y, z+3/2; (iii) x1/2, y+1/2, z+3/2; (iv) x, y, z+1; (v) x+1/2, y, z+3/2.

Experimental details

Crystal data
Chemical formula[Mn3(C2H3O2)6]·C2H3N
Mr560.14
Crystal system, space groupOrthorhombic, Pnma
Temperature (K)193
a, b, c (Å)10.788 (2), 12.702 (2), 15.784 (3)
V3)2163.0 (7)
Z4
Radiation typeMo Kα
µ (mm1)1.78
Crystal size (mm)0.15 × 0.08 × 0.05
Data collection
DiffractometerBruker SMART ? CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2001)
Tmin, Tmax0.692, 0.915
No. of measured, independent and
observed [I > 2σ(I)] reflections
18714, 2763, 2307
Rint0.037
(sin θ/λ)max1)0.667
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.027, 0.071, 1.09
No. of reflections2763
No. of parameters159
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.48, 0.40

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), publCIF (Westrip, 2009).

Selected bond lengths (Å) top
Mn1—O12.3004 (18)Mn2—O2i2.2135 (13)
Mn1—O22.2871 (14)Mn2—O52.1711 (13)
Mn1—O2i2.2871 (14)Mn2—O5i2.1710 (13)
Mn1—O5ii2.2514 (13)Mn2—O62.0983 (19)
Mn1—O5iii2.2514 (14)Mn3—O32.1509 (14)
Mn1—O72.3215 (14)Mn3—O3iv2.1510 (14)
Mn1—O7i2.3215 (14)Mn3—O42.1273 (16)
Mn1—Mn23.1697 (7)Mn3—O4iv2.1273 (16)
Mn2—O12.1737 (19)Mn3—O72.1374 (14)
Mn2—O22.2134 (13)Mn3—O7iv2.1373 (14)
Symmetry codes: (i) x, y+1/2, z; (ii) x1/2, y+1/2, z+3/2; (iii) x1/2, y, z+3/2; (iv) x, y, z+1.
 

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