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In the title one-dimensional complex, {[MnIII(C9H10NO2)2]Cl}n, the Schiff base ligand 2-[(2-hydroxy­ethyl)­imino­methyl]­phenolate (Hsae) functions as both a bridging and a chelating ligand. The MnIII ion is six-coordinated by two N and four O atoms from four different Hsae ligands, yielding a distorted MnO4N2 octahedral environment. Each [MnIII(Hsae)2]+ cationic unit has the Mn atom on an inversion centre and each [MnIII(Hsae)2]+ cation lies about another inversion centre. The chain-like complex is further extended into a three-dimensional network structure through Cl...H—O hydrogen bonds and C—H...π contacts involving the Hsae rings.

Supporting information


Crystallographic Information File (CIF)
Contains datablocks I, global


Structure factor file (CIF format)
Contains datablock I

CCDC reference: 294345

Comment top

Recently, the Schiff base proligand 2-[(2-hydroxyethyl)iminomethyl]phenol (H2sae) and its derivatives have been employed to assembly discrete alkoxo- or phenoxo-bridged complexes with interesting magnetic properties in the field of coordination chemistry (Oshio et al., 2000, 2003; Koizumi et al., 2003). After deprotonation, H2sae yields the potentially tridentate Hsae or sae2− ligands, which possess a ONO donor set and are able to bind in both bridging and chelating modes (Basler et al., 2003). In addition, the favourable flexibility of the –N CH2—CH2—OH or [–NCH2—CH2—O] moiety and the appropriate rigidity of the benzene ring structure in Hsae or sae2− ligands can lead to unexpected complexes with beautiful molecular structures and interesting properties (Koizumi et al., 2005). To date, more than 20 complexes involving NiII, CuII, FeII, FeIII, MnII and MnIII ions have been reported featuring Hsae or sae2− ligands and their derivatives (Dey et al., 2002; Nihei et al., 2003; Oshio, Nihei, Yoshida et al., 2005; Boskovic et al., 2003, 2005). It is noteworthy that several of them exhibit the behavior of single-molecule magnets (SMMs) (Oshio, Nihei, Yoshida et al., 2005; Oshio et al., 2004; Oshio, Nihei, Koizumi et al., 2005; Boskovic et al., 2003). However, to the best of our knowledge, all such reported complexes are zero-dimensional, including mono- or binuclear complexes as well as polynuclear clusters. We report here the synthesis and crystal structure of a novel one-dimensional chain-like complex {[MnIII(Hsae)2]Cl}n, (I), which represents a new topology containing Hsae ligand.

The one-dimensional structure of (I) is depicted in Fig. 1, and selected bond lengths and angles are listed in Table 1. The crystal structure consists of a one-dimensional cationic polymer [MnIII(Hsae)2]nn+ and free Cl anions. Each [MnIII(Hsae)2]+ cationic unit is centrosymmetric. The Mn atom is six-coordinated symmetrically by two phenoxy O atoms and two N atoms from two Hsae ligands, and two alkoxy O atoms from the adjacent two [MnIII(Hsae)2]+ units, yielding a distorted MnO4N2 octahedral surrounding. The Mn—O and Mn—N bond lengths are in accordance with the corresponding bonds in bi- or polynuclear complexes involving H2sae or its derivatives (Table 2). In one Hsae ligand, the phenoxo O atom and the N atom coordinate to the same Mn atom, whereas the alkoxo O atom coordinates to the next adjacent Mn atom. Alternatively, the complex can be simply considered as doubly linked by two O—C—CN bridging groups (Fig. 1), which makes the one-dimensional structure look like an infinite `8'-shaped chain. The `8'-shaped chains are linked by Cl ions through O2—H200···Cl1(x + 1/2, y + 1/2, −z + 1/2) hydrogen bonds to form a two-dimensional network structure. Then the networks are further connected by C—H···π contacts between the Hsae rings with a shortest CH/C distance [C3—H3···C4(−x + 1/2, y + 1/2, −z + 1/2); Umezawa et al., 1998] of 2.726 Å to yield a three-dimensional non-covalent network structure.

Comparing with the reported alkoxo- or phenoxo-bridged polynuclear complexes containing the Hsae or sae2− ligand, we found that the key factor favoring the formation of a one-dimensional structure in the title complex, instead of a polynuclear structure, is that the phenoxo or alkoxo O atom does not act as a bridging atom, while the whole Hsae ligand functions as a bridging group. The synthesis of the title complex is similar to that of the tetranuclear [Mn4(Hsae)4Cl4] complex (Boskovic et al., 2003), except that a different solvent is used; this fact demonstrates that the molecular structures of complexes are strongly dependent on the solvent employed for this system.

Experimental top

MnCl2·4H2O (0.61 g, 3.09 mmol) was added to a solution of H2sae (0.51 g, 3.09 mmol) in EtOH (40 ml), and the resulting mixture was stirred overnight and filtered. The filtrate was evaperated to dryness and then dissolved in a mixed solvent of MeOH/MeCN (volume ratio about 1:4). The resulted solution was evaporated at room temperature until dark-brown needles formed.

Refinement top

The coordinates of the H atoms of the alkoxo-group were found from difference Fourier maps and normalized to an O—H distance of 0.85 Å. H atoms bound to C atoms were also visible in difference maps and were positioned using the HFIX commands in SHELXL97 (Sheldrick, 1997) and refined as riding atoms (0.97 Å or 0.93 Å).

Computing details top

Data collection: CrystalStructure (Rigaku/MSC & Rigaku Corporation, 2004); cell refinement: CrystalStructure; data reduction: CrystalStructure; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP (Sheldrick, 1998); software used to prepare material for publication: XP.

Figures top
[Figure 1] Fig. 1. A fragment of the one-dimensional structure of (I), showing the atom-labeling scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms bonded to C atoms have been omitted. [symmetry codes: Mn (A) x, y − 1, z; (B) x, y + 1, z; (C) x, y − 2, z. N,O (A) x, y − 1, z; (B) −x, −y + 1, −z; (AA) −x, −y + 2, −z.]
[Figure 2] Fig. 2. The two-dimensional network of (I), formed by hydrogen-bond interactions (along the c axis). Hydrogen bonds are shown as dashed lines and H atoms have been omitted for clarity.
catena-poly[[manganese(III)-di-µ-2-[(2-hydroxyethyl)iminomethyl]phenolato- κ2O1,N:κO2;κO2:κ2O1] chloride] top
Crystal data top
[Mn(C9H10NO2)2]ClF(000) = 864
Mr = 418.76Dx = 1.547 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71070 Å
Hall symbol: -C 2ycCell parameters from 2054 reflections
a = 18.202 (8) Åθ = 3.8–27.5°
b = 5.700 (2) ŵ = 0.91 mm1
c = 18.703 (9) ÅT = 123 K
β = 112.091 (3)°Needle, brown
V = 1797.9 (13) Å30.30 × 0.10 × 0.03 mm
Z = 4
Data collection top
2054 independent reflections
Radiation source: fine-focus sealed tube1571 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.092
Detector resolution: 100x100 microns pixels mm-1θmax = 27.5°, θmin = 3.8°
Oscillation scansh = 2323
Absorption correction: multi scan
(ABSCOR; Higashi, 1995)
k = 76
Tmin = 0.802, Tmax = 0.928l = 1924
6807 measured reflections
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)] = 0.045Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.103H-atom parameters constrained
S = 0.96 w = 1/[σ2(Fo2) + (0.0254P)2]
where P = (Fo2 + 2Fc2)/3
2054 reflections(Δ/σ)max < 0.001
122 parametersΔρmax = 0.50 e Å3
0 restraintsΔρmin = 0.42 e Å3
Crystal data top
[Mn(C9H10NO2)2]ClV = 1797.9 (13) Å3
Mr = 418.76Z = 4
Monoclinic, C2/cMo Kα radiation
a = 18.202 (8) ŵ = 0.91 mm1
b = 5.700 (2) ÅT = 123 K
c = 18.703 (9) Å0.30 × 0.10 × 0.03 mm
β = 112.091 (3)°
Data collection top
2054 independent reflections
Absorption correction: multi scan
(ABSCOR; Higashi, 1995)
1571 reflections with I > 2σ(I)
Tmin = 0.802, Tmax = 0.928Rint = 0.092
6807 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0450 restraints
wR(F2) = 0.103H-atom parameters constrained
S = 0.96Δρmax = 0.50 e Å3
2054 reflectionsΔρmin = 0.42 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
Mn10.00000.50000.00000.01232 (18)
N10.08849 (10)0.7300 (3)0.01181 (11)0.0122 (4)
O10.05297 (9)0.4074 (3)0.10230 (8)0.0161 (4)
Cl10.25001.25000.00000.0246 (3)
C10.13670 (13)0.8080 (4)0.07785 (13)0.0137 (5)
C20.13578 (13)0.7442 (4)0.15201 (13)0.0139 (5)
C30.17832 (12)0.8837 (4)0.21678 (13)0.0159 (5)
C40.18058 (13)0.8262 (4)0.28877 (13)0.0185 (6)
C50.14221 (13)0.6237 (4)0.29834 (13)0.0177 (5)
C60.10030 (14)0.4843 (4)0.23607 (14)0.0166 (6)
C70.09493 (13)0.5434 (4)0.16174 (14)0.0133 (5)
C80.10016 (13)0.8184 (4)0.05735 (12)0.0134 (5)
C90.05010 (13)1.0349 (4)0.08921 (14)0.0149 (5)
O20.07193 (10)1.2272 (2)0.03563 (9)0.0168 (4)
H100.12151.25350.01900.026 (8)*
Atomic displacement parameters (Å2) top
Mn10.0136 (3)0.0080 (3)0.0147 (4)0.00376 (19)0.0046 (2)0.00051 (19)
N10.0131 (10)0.0072 (10)0.0162 (12)0.0007 (8)0.0054 (9)0.0003 (8)
O10.0189 (9)0.0116 (9)0.0146 (9)0.0066 (7)0.0026 (7)0.0004 (7)
Cl10.0147 (5)0.0313 (5)0.0226 (6)0.0093 (4)0.0009 (4)0.0024 (4)
C10.0146 (12)0.0076 (11)0.0188 (14)0.0006 (9)0.0062 (11)0.0015 (10)
C20.0123 (12)0.0112 (12)0.0169 (14)0.0003 (9)0.0039 (11)0.0005 (10)
C30.0129 (11)0.0124 (12)0.0211 (15)0.0031 (10)0.0049 (11)0.0015 (11)
C40.0180 (13)0.0160 (13)0.0172 (15)0.0020 (10)0.0019 (11)0.0048 (11)
C50.0202 (13)0.0188 (13)0.0153 (14)0.0017 (11)0.0079 (11)0.0002 (11)
C60.0184 (13)0.0143 (13)0.0183 (15)0.0035 (10)0.0082 (11)0.0018 (10)
C70.0104 (11)0.0102 (11)0.0169 (14)0.0011 (9)0.0025 (10)0.0002 (10)
C80.0166 (12)0.0097 (12)0.0162 (13)0.0054 (9)0.0088 (10)0.0036 (10)
C90.0173 (12)0.0103 (12)0.0169 (15)0.0027 (9)0.0063 (11)0.0008 (10)
O20.0145 (9)0.0087 (8)0.0267 (10)0.0030 (7)0.0071 (8)0.0045 (7)
Geometric parameters (Å, º) top
Mn1—O1i1.8659 (17)C4—C51.395 (3)
Mn1—O11.8659 (17)C4—H40.9300
Mn1—N12.0232 (18)C5—C61.379 (3)
Mn1—N1i2.0232 (18)C5—H50.9300
Mn1—O2ii2.2874 (15)C6—C71.398 (3)
Mn1—O2iii2.2874 (15)C6—H60.9300
N1—C11.295 (3)C8—C91.517 (3)
N1—C81.476 (3)C8—H8A0.9700
O1—C71.335 (3)C8—H8B0.9700
C1—C21.440 (3)C9—O21.437 (3)
C2—C31.412 (3)C9—H9B0.9700
C2—C71.413 (3)O2—Mn1iv2.2874 (15)
C3—C41.371 (3)O2—H100.8500
O1i—Mn1—O1180.00 (11)C3—C4—C5119.5 (2)
O1i—Mn1—N190.68 (7)C3—C4—H4120.3
O1—Mn1—N189.32 (7)C5—C4—H4120.3
O1i—Mn1—N1i89.32 (7)C6—C5—C4120.9 (2)
O1—Mn1—N1i90.68 (7)C6—C5—H5119.6
N1—Mn1—N1i180.00 (10)C4—C5—H5119.6
O1i—Mn1—O2ii88.56 (7)C5—C6—C7120.7 (2)
O1—Mn1—O2ii91.44 (7)C5—C6—H6119.6
N1—Mn1—O2ii92.71 (7)C7—C6—H6119.6
N1i—Mn1—O2ii87.29 (7)O1—C7—C6119.5 (2)
O1i—Mn1—O2iii91.44 (7)O1—C7—C2121.8 (2)
O1—Mn1—O2iii88.56 (7)C6—C7—C2118.7 (2)
N1—Mn1—O2iii87.29 (7)N1—C8—C9111.04 (17)
N1i—Mn1—O2iii92.71 (7)N1—C8—H8A109.4
O2ii—Mn1—O2iii180.00 (7)C9—C8—H8A109.4
C1—N1—C8116.69 (18)N1—C8—H8B109.4
C1—N1—Mn1123.54 (15)C9—C8—H8B109.4
C8—N1—Mn1119.78 (14)H8A—C8—H8B108.0
C7—O1—Mn1127.09 (15)O2—C9—C8112.27 (19)
N1—C1—C2125.6 (2)O2—C9—H9A109.2
C3—C2—C7119.4 (2)C8—C9—H9B109.2
C3—C2—C1118.9 (2)H9A—C9—H9B107.9
C7—C2—C1121.7 (2)C9—O2—Mn1iv133.10 (13)
C4—C3—C2120.8 (2)C9—O2—H10111.5
Symmetry codes: (i) x, y+1, z; (ii) x, y+2, z; (iii) x, y1, z; (iv) x, y+1, z.

Experimental details

Crystal data
Chemical formula[Mn(C9H10NO2)2]Cl
Crystal system, space groupMonoclinic, C2/c
Temperature (K)123
a, b, c (Å)18.202 (8), 5.700 (2), 18.703 (9)
β (°) 112.091 (3)
V3)1797.9 (13)
Radiation typeMo Kα
µ (mm1)0.91
Crystal size (mm)0.30 × 0.10 × 0.03
Data collection
DiffractometerRigaku R-AXIS RAPID IP
Absorption correctionMulti scan
(ABSCOR; Higashi, 1995)
Tmin, Tmax0.802, 0.928
No. of measured, independent and
observed [I > 2σ(I)] reflections
6807, 2054, 1571
(sin θ/λ)max1)0.649
R[F2 > 2σ(F2)], wR(F2), S 0.045, 0.103, 0.96
No. of reflections2054
No. of parameters122
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.50, 0.42

Computer programs: CrystalStructure (Rigaku/MSC & Rigaku Corporation, 2004), CrystalStructure, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), XP (Sheldrick, 1998), XP.

Selected geometric parameters (Å, º) top
Mn1—O11.8659 (17)Mn1—O2i2.2874 (15)
Mn1—N12.0232 (18)
O1—Mn1—N189.32 (7)N1—Mn1—O2i87.29 (7)
O1—Mn1—O2i88.56 (7)
Symmetry code: (i) x, y1, z.
Comparative geometrical parameters (Å) for complexes involving similar ligands top
(I)a1.8659 (17)2.2874 (15)2.0232 (18)
(II)b1.856 (2)–1.866 (2)1.972 (3)–1.994 (3)
(III)c2.214 (2)–2.223 (3)
(IV)d1.882 (4)–2.100 (4)1.968 (2)–2.228 (4)
(V)e1.860 (5)2.021 (7)
Notes: (a) this work; (b) Mn4Cl4L4 (H2L is salicylidene-2-ethanolamine; Boskovic et al., 2003); (c) MnII2(H2L)2Cl2 [H3L is N-(2-hydroxy-5-nitrobenzyl)iminodiethanol; Koizumi et al., 2004]; (d) [MnII4MnIII2(sae)6(CH3OH)2Cl2]·2CH3OH (H2sae is 2-salicylideneaminoethanol; Hoshino et al., 2003); (e) MnIII2NiII2Cl2(salpa)2 [salpa is N-(2-hydroxybenzyl)-3-amino-1-propanol; Oshio, Nihei, Koizumi et al., 2005].

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