Catena-poly[[(1,10-phenanthroline-κ 2N,N′)manganese(II)]-di-μ-salicylato-κ 4O:O′]

Full text of DOI:10.1107/S0108270105011078

metal-organic compounds
Acta Crystallographica Section C
Crystal Structure
Communications
signi®cant electrostatic content in the coordination bond
between the MnII atom and the ligand (Nie et al., 2001; Liu et
al., 2003), which may play an important role for oxygen release
during photosynthesis. As part of our ongoing investigation,
the title polymeric MnII complex, (I), has been prepared and
its structure determined.
ISSN 0108-2701
catena-Poly[[(1,10-phenanthroline-
j2N,N0)manganese(II)]-di-l-salicylato-
j4O:O0]
A segment of the polymeric structure of (I) is illustrated in
Fig. 1. The MnII atom is located on a twofold axis and is
coordinated by four salicylate anions and one phenanthroline
(phen) molecule, displaying distorted octahedral coordination
geometry. The phen ligand lies on a twofold axis and chelates
to the MnII atom with normal bond distances and angles.
Crystallographically independent salicylate anions coordinate
to the MnII atom with appreciably different MnÐO bond
distances and MnÐOÐC angles (Table 1). It is noteworthy
that the shorter MnÐO1 bond corresponds to the larger MnÐ
O1ÐC1 angle, whereas the longer MnÐO2i bond corresponds
to the smaller (normal) MnÐO2iÐC1i angle [symmetry code:
(i) 1 x, 1 y, 1 z].
Jian-Rong Su and Duan-Jun Xu*
Department of Chemistry, Zhejiang University, People's Republic of China
Correspondence e-mail: xudj@mail.hz.zj.cn
Received 29 March 2005
Accepted 8 April 2005
Online 13 May 2005
A similar situation is observed in some reported MnII
complexes incorporating non-chelating carboxylates. The
MnÐO(carboxyl) bond distances and corresponding MnÐ
OÐC angles found in these MnII complexes are summarized
in Table 3. In these structures, the MnÐOÐC angles range
from 121.1 (2) to 170.10 (6)ꢀ and the MnÐO bond distances
In the title polymeric complex, [Mn(C7H5O3)2(C12H8N2)]n,
the MnII atom is located on a twofold axis and displays a
distorted octahedral coordination geometry, formed by four
salicylate anions and one 1,10-phenanthroline (phen) mol-
ecule. The salicylate anions doubly bridge the MnII atoms to
form one-dimensional polymeric chains. A comparison of
MnÐO bond distances with the corresponding MnÐOÐC
angles suggests a signi®cant electrostatic content in the MnÐ
Ê
range from 2.050 (4) to 2.278 (2) A. A comparison of the bond
distances with the bond angles shows that the MnÐO bond
Ê
O bonds. A face-to-face distance of 3.352 (7) A between
neighbouring parallel phen planes indicates ꢀ±ꢀ stacking
interactions between polymeric chains.
Comment
The structure and properties of multinuclear Mn complexes
have attracted much scienti®c attention due to their poten-
tially useful electronic or magnetic properties and their
presence in various biosystems (Yachandra et al., 1996),
especially in the oxygen-evolving complex of photosystem II
(PSII). The process of water splitting is generally believed to
occur at an Mn cluster located in the reaction centre of PSII
(Vincent & Christou, 1989). In order to mimic the Mn cluster,
Figure 1
A segment of the polymeric structure of (I), showing the atom-numbering
a series of Mn complexes have been synthesized and their
crystal structures determined in our laboratory (Xu et al.,
1997; Li et al., 2002; Su et al., 2004). Among these, the X-ray
structures of several MnII complexes showed evidence of
scheme. Displacement ellipsoids are drawn at the 30% probability level
and H atoms have been omitted for clarity. [Symmetry codes: (i) 1 x,
1
2
1
y, 1 z; (ii) 1 x, y,
z; (iii) x, 1 y, z 12.]
m256 # 2005 International Union of Crystallography
DOI: 10.1107/S0108270105011078
Acta Cryst. (2005). C61, m256±m258

metal-organic compounds
distances are independent of the corresponding MnÐOÐC
angles. In some structures, even though the larger MnÐOÐC
angles imply poor overlap between the atomic orbitals of the
Mn atom and the molecular orbitals of the ligand, the shorter
MnÐO bond distances indicate a stronger interaction
between them. This ®nding strongly suggests the existence of a
signi®cant electrostatic content in the MnÐO(carboxyl)
bonds.
The salicylate anions act as bridging ligands in (I). Neigh-
bouring MnII atoms are bridged by two salicylate anions to
form zigzag polymeric chains along the c axis, as shown in Fig.
2. The polymeric chain has a repeat unit formed by two sali-
cylate anions and two MnII atoms related by an inversion
centre. The repeat unit of the eight-membered ring assumes a
chair con®guration, with the Mn atoms deviating from the
A parallel arrangement of the phen ligands of neighbouring
polymeric chains is illustrated in Fig. 2. The face-to-face
iv
distance of 3.352 (7) A between parallel N11-phen and N11 -
Ê
phen planes [symmetry code: (iv) 1 x, 2 y, 1 z], and a
partially overlapped arrangement (Fig. 3) suggest a ꢀ±ꢀ
interaction. The shortest distance between the centroids of the
Ê
aromatic rings of neighbouring phen ligands is 3.8384 (12) A.
The hydroxyl group of the salicylate is free from
coordination in (I), which differs from the situation found
in catena-poly[[bis(1H-benzimidazole)salicylatocopper(II)]-ꢁ-
salicylato] (Li et al., 2005). However, the hydroxyl group is
involved in an intramolecular hydrogen bond with the
carboxyl O atom (Table 2), which also forms weak CÐHÁ Á ÁO
hydrogen bonds, both with the phen ligands (Fig. 2) and with
the salicylate anions of adjacent polymeric chains.
Ê
basal plane formed by two carboxyl groups by 0.856 (3) A.
The MnÁ Á ÁMn separation in the eight-membered ring is
Experimental
Ê
4.8252 (5) A.
Each reagent was commercially available and of analytical grade.
Mn(CH3COO)2Á4H2O (0.25 g, 1 mmol), salicylic acid (0.14 g,
1 mmol), 1,10-phenanthroline (0.20 g, 1 mmol) and Na2CO3 (0.05 g,
1 mmol) were dissolved in a water±ethanol solution (20 ml, 1:1 v/v).
The resulting solution was re¯uxed for 5 h, then cooled to room
temperature and ®ltered. Pale-yellow single crystals of (I) were
obtained from the ®ltrate after 3 d.
Crystal data
[Mn(C7H5O3)2(C12H8N2)]
Mr = 509.36
Orthorhombic, Pbcn
a = 23.5785 (5) A
Ê
b = 12.1715 (3) A
Mo Kꢂ radiation
Cell parameters from 10 105
re¯ections
ꢃ = 2.7±24.4ꢀ
Ê
1
ꢁ = 0.65 mm
T = 295 (2) K
Ê
c = 7.6545 (2) A
Ê
V = 2196.73 (9) A
3
Platelet, pale yellow
0.20 Â 0.18 Â 0.03 mm
Z = 4
Dx = 1.540 Mg m
3
Data collection
Rigaku R-AXIS RAPID
diffractometer
! scans
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)
Tmin = 0.875, Tmax = 0.976
13 706 measured re¯ections
1965 independent re¯ections
1544 re¯ections with I > 2ꢄ(I)
Rint = 0.043
Figure 2
A unit-cell packing diagram for (I), showing the parallel arrangement of
the phen rings and the interchain CÐHÁ Á ÁO hydrogen bonds (dashed
lines).
ꢃmax = 25.2ꢀ
h = 28 ! 28
k = 14 ! 14
l = 9 ! 8
Re®nement
Re®nement on F2
R[F2 > 2ꢄ(F2)] = 0.035
wR(F2) = 0.081
w = 1/[ꢄ2(Fo2) + (0.0411P)2
+ 0.6755P]
2
where P = (Fo + 2Fc2)/3
S = 1.04
1965 re¯ections
159 parameters
H-atom parameters constrained
(Á/ꢄ)max = 0.001
3
Ê
Áꢅmax = 0.21 e A
3
Ê
0.24 e A
Áꢅmin
=
Table 1
Selected geometric parameters (A, ).
ꢀ
Ê
MnÐO1
MnÐO2i
2.0774 (15)
2.2375 (15)
MnÐN11
2.2946 (17)
O1ÐMnÐO1ii
O1ÐMnÐO2iii
O1ÐMnÐO2i
O2iiiÐMnÐO2i
O1ÐMnÐN11
O1ÐMnÐN11ii
108.08 (9)
91.44 (6)
95.07 (6)
168.90 (7)
162.07 (7)
89.76 (6)
O2iiiÐMnÐN11
O2iÐMnÐN11
N11ÐMnÐN11ii
MnÐO1ÐC1
88.71 (6)
82.33 (6)
72.49 (8)
154.50 (16)
132.62 (13)
C1ÐO2ÐMni
Figure 3
The ꢀ±ꢀ stacking between the phen rings of (I). [Symmetry code: (iv)
Symmetry codes: (i) 1 x; 1 y; 1 z; (ii) 1 x; y; 12 z; (iii) x; 1 y; z
1
.
1
x, 2 y, 1 z.]
2
ꢁ
Acta Cryst. (2005). C61, m256±m258
Su and Xu
[Mn(C7H5O3)2(C12H8N2)] m257

metal-organic compounds
Table 2
Hydrogen-bond geometry (A, ).
This project was supported by the National Natural Science
Foundation of China (grant No. 20443003).
ꢀ
Ê
DÐHÁ Á ÁA
DÐH
HÁ Á ÁA
DÁ Á ÁA
DÐHÁ Á ÁA
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: OB1227). Services for accessing these data are
described at the back of the journal.
O3ÐH3Á Á ÁO2
C5ÐH5Á Á ÁO3iv
C14ÐH14Á Á ÁO3v
0.90
0.93
0.93
1.71
2.52
2.45
2.525 (2)
3.417 (3)
3.323 (3)
148
161
157
3
2
Symmetry codes: (iv)
x; 12 y; z 12; (v) 1 x; y ‡ 1; 12 z.
References
Altomare, A., Cascarano, G., Giacovazzo, C. & Guagliardi, A. (1993). J. Appl.
Cryst. 26, 343±350.
Bermejo, M. R., Fondo, M., Garcia-Deibe, A., Gonzalez, A. M., Sousa, A.,
Sanmartin, J., McAuliffe, C. A., Pritchard, R. G., Watkinson, M. & Lukov, V.
(1999). Inorg. Chim. Acta, 293, 210±217.
Table 3
Ê
A comparison of the MnÐO(carboxyl) bond distances (A) and
corresponding MnÐOÐC angles (ꢀ) for selected MnII complexes
incorporating non-chelating carboxylate ligands.
Castan, P., Viala, C., Fabre, P.-L., Nepveu, F., Souchard, J.-P. & Bernardinelli,
G. (1998). Can. J. Chem. 76, 205±212.
Ciunik, Z. (1987). Pol. J. Chem. 61, 521±523.
Devereux, M., Curran, M., McCann, M., Casey, M. T. & McKee, V. (1996).
Polyhedron, 15, 2029±2033.
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837±838.
Fleck, M., Tillmanns, E. & Bohaty, L. (2001). Z. Kristallogr. 216, 633±645.
Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan.
Hu, M.-L., Xu, D.-J. & Cheng, D.-P. (2001). J. Coord. Chem. 55, 11±16.
Kim, Y. J., Park, Y. J. & Jung, D. Y. (2004). Inorg. Chem. Commun. 7, 347±
349.
Li, H., Yin, K.-L. & Xu, D.-J. (2005). Acta Cryst. C61, m19±m21.
Li, Z.-Y., Xu, D.-J., Nie, J.-J., Wu, Z.-Y., Wu, J.-Y. & Chiang, M. Y. (2002). J.
Coord. Chem. 55, 1155±1160.
Liu, Y., Xu, D.-J., Nie, J.-J., Wu, J.-Y. & Chiang, M. Y. (2003). J. Coord. Chem.
56, 155±159.
Milios, C. J., Kefalloniti, E., Raptopoulou, C. P., Terzis, A., Escuer, A., Vicente,
R. & Perlepes, S. P. (2004). Polyhedron, 23, 83±95.
Nie, J.-J., Liu, L.-J., Luo, Y. & Xu, D.-J. (2001). J. Coord. Chem. 53, 365±
371.
Rigaku (1998). PROCESS-AUTO. Rigaku Corporation, Tokyo, Japan.
Rigaku (2002). CrystalStructure. Version 3.00. Rigaku Corporation, 3-9-12
Akishima, Tokyo, Japan.
Carboxylate ligand
MnÐO
MnÐOÐC
Benzoatea
2.050 (4)
165.8 (4)
Salicylateb
2.0774 (15)
2.087 (2)
2.104 (2)
154.50 (16)
152.94 (16)
161.8 (2)
Salicylatec
Isophthalated
Succinatee
2.117 (3)
136.8 (3)
dl-Malatef
Salicylateg
2.1174 (17)
2.1227 (18)
2.141 (2)
2.1593 (19)
2.171 (4)
2.200 (12)
2.201 (4)
2.219 (3)
2.224 (14)
2.2352 (16)
2.2375 (15)
2.278 (2)
146.76 (14)
170.10 (6)
148.3 (2)
147.09 (19)
156.8 (4)
124.4 (6)
125.9 (4)
121.1 (2)
121.9 (12)
125.37 (16)
132.62 (13)
128.47 (18)
Isophthalateh
Aspartatej
Hydrogen phthalatek
Salicylatel
Benzoatem
Salicylaten
Benzoatep
Dihydro-orotateq
Salicylateb
Glutarater
References: (a) Milios et al. (2004); (b) this work; (c) Devereux et al. (1996); (d) Nie et al.
(2001); (e) Liu et al. (2003); (f) Fleck et al. (2001); (g) Rissanen et al. (1987); (h) Hu et al.
(2001); (j) Ciunik (1987); (k) Bermejo et al. (1999); (l) Tan et al. (1997); (m) Wang et al.
(1994); (n) Tan et al. (1996); (p) Vincent et al. (1987); (q) Castan et al. (1998); (r) Kim et al.
(2004).
Rissanen, K., Valkonen, J., Kokkonen, P. & Leskela, M. (1987). Acta Chem.
Scand. Ser. A, 41, 299±303.
The hydroxyl H atom was located in a difference Fourier map and
re®ned riding in its as-found position, with a ®xed isotropic displa-
È
Sheldrick, G. M. (1997). SHELXL97. University of Gottingen, Germany.
Su, J.-R., Yin, K.-L. & Xu, D.-J. (2004). Acta Cryst. E60, m1063±m1065.
Tan, X.-S., Ma, Z.-S., Shi, N.-C., Fu, D.-G., Chen, J. & Tang, W.-X. (1996). J.
Chem. Soc. Dalton Trans. pp. 2735±2741.
2
cement parameter of 0.05 A . Aromatic H atoms were placed in
Ê
Ê
calculated positions (CÐH = 0.93 A) and were included in the ®nal
Tan, X.-S., Sun, J., Hu, C.-H., Fu, D.-G., Xiang, D.-F., Zheng, P.-J. & Tang, W.-X.
(1997). Inorg. Chim. Acta, 257, 203±210.
cycles of re®nement in riding mode, with Uiso(H) = 1.2Ueq(C).
Data collection: PROCESS-AUTO (Rigaku, 1998); cell re®ne-
ment: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku,
2002); program(s) used to solve structure: SIR92 (Altomare et al.,
1993); program(s) used to re®ne structure: SHELXL97 (Sheldrick,
1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997);
software used to prepare material for publication: WinGX (Farrugia,
1999).
Vincent, J. B., Chang, H. R., Folting, K., Huffman, J. C., Christou, G. &
Hendrickson, D. N. (1987). J. Am. Chem. Soc. 109, 5703±5711.
Vincent, J. B. & Christou, G. (1989). Adv. Inorg. Chem. 28, 197±205.
Wang, S.-Y., Tsai, H. L., Folting, K., Martin, J. D., Hendrickson, D. N. &
Christou, G. (1994). Chem. Commun. pp. 671±673.
Xu, D.-J., Zhang, C.-G., Xu, Y.-Z. & Huang, X.-Y. (1997). Polyhedron, 16, 71±
73.
Yachandra, V. K., Sauer, K. & Klein, M. P. (1996). Chem. Rev. 96, 2927±2950.
ꢁ
m258 Su and Xu [Mn(C7H5O3)2(C12H8N2)]
Acta Cryst. (2005). C61, m256±m258