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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) mol­ecule. The salicylate anions doubly bridge the MnII atoms to form one-dimensional polymeric chains. A comparison of Mn-O bond distances with the corresponding Mn-O-C angles suggests a significant electrostatic content in the Mn-O bonds. A face-to-face distance of 3.352 (7) Å between neighbouring parallel phen planes indicates [pi]-[pi] stacking inter­actions between polymeric chains.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270105011078/ob1227sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270105011078/ob1227Isup2.hkl
Contains datablock I

CCDC reference: 275491

Comment top

The structure and properties of multinuclear Mn complexes have attracted much scientific attention, due to their potentially 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, a series of Mn complexes have been synthesized and their crystal structures have been 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 for significant 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 has been determined.

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, with a distorted octahedral coordination geometry. The phen ligand lies on a twofold axis and chelates to the MnII with normal bond distances and angles. Crystallographically independent salicylate anions coordinate to the MnII atom with appreciably different Mn—O bond distances and Mn—O—C bond angles (Table 1). It is noteworthy that the shorter Mn—O1 bond corresponds to the larger Mn—O1—C1 bond angle, whereas the longer Mn—O2i bond corresponds to the smaller (normal) Mn—O2i—C1i bond angle [symmetry code: (i) 1 − x, 1 − y, 1 − z].

A similar situation is also observed in some reported MnII complexes incorporating non-chelating carboxylates. The Mn—O(carboxyl) bond distances and corresponding Mn—O—C bond angles found in those MnII complexes are summarized in Table 3. In these structures, the Mn—O—C bond angles range from 121.1 (2) to 170.10 (6)° and the Mn—O bond distances range from 2.050 (4) to 2.278 (2) Å. A comparison of the bond distances with the bond angles shows that the Mn—O bond distances are independent of the corresponding Mn—O—C bond angles. In some structures, even though the larger Mn—O—C bond angles imply poor overlap between the atomic orbitals of the Mn and the molecular orbitals of the ligand, the shorter Mn—O bond distances indicate a stronger interaction between them. This finding strongly suggests the existence of the significant electrostatic content in the Mn—O(carboxyl) bonds.

The salicylate anions play the role of bridging ligand in (I). Neighbouring 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 salicylate anions and two MnII atoms related by an inversion centre. The repeat unit of the eight-membered ring assumes a chair configuration, with the Mn atoms deviating from the basal plane formed by two carboxyl groups by 0.856 (3) Å. The Mn···Mn separation in the eight-membered ring is 4.8252 (5) Å.

A parallel arrangement of the phen ligands of neighbouring polymeric chains is illustrated in Fig. 2. The face-to-face distance of 3.352 (7) Å between parallel N11-phen and N11iv-phen planes [symmetry code: (iv) 1 − x, 2 − y, 1 − z] and a partially overlapped arrangement (Fig. 3) suggest a ππ interaction. The shortest distance between the centroids of the aromatic rings of neighbouring phen ligands is 3.8384 (12) Å.

The hydroxyl group of the salicylate is free from coordination in (I), which differs from the situation found in [Cu(C7H5O3)2(C7H6N2)2]n (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 C—H···O hydrogen bonds, both with the phen ligands (Fig. 2) and with salicylate anions of adjacent polymeric chains.

Experimental top

Each reagent was commercially available and of analytical grade. Mn(CH3COO)2·4H2O (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). The solution was refluxed for 5 h, then cooled to room temperature and filtered. Pale-yellow single crystals of (I) were obtained from the filtrate after 3 d.

Refinement top

The hydroxyl H atom was located in a difference Fourier map and refined riding in its as-found position, with a fixed isotropic displacement parameter of 0.05 Å2. Aromatic H atoms were placed in calculated positions, with C—H = 0.93 Å, and were included in the final cycles of refinement in riding mode, with Uiso(H) = 1.2Ueq(C).

Computing details top

Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku, 2002); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top
[Figure 1] Fig. 1. A segment of the polymeric structure of (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms have been omitted for clarity. [Symmetry codes: (i) 1 − x, 1 − y, 1 − z; (ii) 1 − x, y, 1/2 − z; (iii) x, 1 − y, z − 1/2.]
[Figure 2] Fig. 2. A unit-cell packing diagram for (I), showing the parallel arrangement of the phen rings and the interchain C—H···O hydrogen bonds (dashed lines).
[Figure 3] Fig. 3. The ππ stacking between the phen rings of (I). [Symmetry code: (iv) 1 − x, 2 − y, 1 − z.]
Poly[bis(µ-salicylato-κ2O:O')(1,10-phenanthroline-κ2N,N')manganese(II)] top
Crystal data top
[Mn(C7H5O3)2(C12H8N2)]F(000) = 1044
Mr = 509.36Dx = 1.540 Mg m3
Orthorhombic, PbcnMo Kα radiation, λ = 0.71069 Å
Hall symbol: -P 2n 2abCell parameters from 10105 reflections
a = 23.5785 (5) Åθ = 2.7–24.4°
b = 12.1715 (3) ŵ = 0.65 mm1
c = 7.6545 (2) ÅT = 295 K
V = 2196.73 (9) Å3Platelet, pale yellow
Z = 40.20 × 0.18 × 0.03 mm
Data collection top
Rigaku R-AXIS RAPID
diffractometer
1965 independent reflections
Radiation source: fine-focus sealed tube1544 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.043
Detector resolution: 10.0 pixels mm-1θmax = 25.2°, θmin = 1.7°
ω scansh = 2828
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)
k = 1414
Tmin = 0.875, Tmax = 0.976l = 98
13706 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)] = 0.035Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.081H-atom parameters constrained
S = 1.04 w = 1/[σ2(Fo2) + (0.0411P)2 + 0.6755P]
where P = (Fo2 + 2Fc2)/3
1965 reflections(Δ/σ)max = 0.001
159 parametersΔρmax = 0.21 e Å3
0 restraintsΔρmin = 0.24 e Å3
Crystal data top
[Mn(C7H5O3)2(C12H8N2)]V = 2196.73 (9) Å3
Mr = 509.36Z = 4
Orthorhombic, PbcnMo Kα radiation
a = 23.5785 (5) ŵ = 0.65 mm1
b = 12.1715 (3) ÅT = 295 K
c = 7.6545 (2) Å0.20 × 0.18 × 0.03 mm
Data collection top
Rigaku R-AXIS RAPID
diffractometer
1965 independent reflections
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)
1544 reflections with I > 2σ(I)
Tmin = 0.875, Tmax = 0.976Rint = 0.043
13706 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0350 restraints
wR(F2) = 0.081H-atom parameters constrained
S = 1.04Δρmax = 0.21 e Å3
1965 reflectionsΔρmin = 0.24 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*/Ueq
Mn0.50000.62071 (3)0.25000.03329 (15)
O10.55843 (6)0.52049 (12)0.3759 (2)0.0561 (5)
O20.55714 (6)0.36152 (11)0.5183 (2)0.0417 (4)
O30.63914 (7)0.22927 (12)0.4902 (3)0.0570 (5)
H30.60770.26080.53500.050*
N110.45111 (7)0.77275 (13)0.1565 (2)0.0347 (4)
C10.57995 (9)0.43099 (16)0.4165 (3)0.0362 (5)
C20.63737 (8)0.40402 (16)0.3457 (3)0.0349 (5)
C30.66428 (9)0.30514 (18)0.3867 (3)0.0412 (5)
C40.71836 (11)0.2837 (2)0.3206 (4)0.0616 (8)
H40.73600.21720.34550.074*
C50.74537 (11)0.3598 (3)0.2197 (4)0.0726 (9)
H50.78150.34510.17730.087*
C60.71973 (11)0.4581 (3)0.1799 (4)0.0707 (9)
H60.73850.50960.11120.085*
C70.66629 (10)0.4799 (2)0.2422 (3)0.0526 (6)
H70.64910.54650.21490.063*
C120.40254 (9)0.77245 (17)0.0693 (3)0.0423 (6)
H120.38750.70530.03430.051*
C130.37291 (10)0.86805 (19)0.0274 (3)0.0475 (6)
H130.33850.86410.03180.057*
C140.39489 (10)0.96747 (18)0.0743 (3)0.0453 (6)
H140.37541.03180.04800.054*
C150.44694 (9)0.97203 (15)0.1623 (3)0.0363 (5)
C160.47493 (10)1.07284 (16)0.2089 (3)0.0437 (6)
H160.45781.13950.18140.052*
C170.47352 (9)0.87126 (15)0.2032 (3)0.0308 (5)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Mn0.0269 (2)0.0251 (2)0.0479 (3)0.0000.0033 (2)0.000
O10.0443 (9)0.0456 (9)0.0783 (13)0.0173 (8)0.0091 (10)0.0191 (9)
O20.0358 (8)0.0374 (7)0.0520 (10)0.0035 (6)0.0111 (8)0.0067 (7)
O30.0481 (10)0.0381 (8)0.0849 (14)0.0135 (7)0.0007 (9)0.0049 (9)
N110.0313 (10)0.0323 (9)0.0406 (12)0.0020 (7)0.0020 (8)0.0002 (8)
C10.0321 (12)0.0355 (11)0.0410 (14)0.0056 (9)0.0005 (10)0.0004 (10)
C20.0275 (11)0.0443 (12)0.0330 (13)0.0048 (9)0.0016 (10)0.0018 (9)
C30.0355 (12)0.0468 (12)0.0412 (15)0.0085 (10)0.0047 (11)0.0077 (11)
C40.0420 (15)0.0817 (19)0.0610 (19)0.0293 (14)0.0052 (14)0.0156 (16)
C50.0344 (14)0.133 (3)0.050 (2)0.0184 (16)0.0088 (13)0.0093 (19)
C60.0399 (15)0.122 (3)0.0496 (18)0.0031 (16)0.0119 (13)0.0162 (18)
C70.0405 (13)0.0714 (16)0.0458 (16)0.0021 (12)0.0030 (13)0.0135 (13)
C120.0372 (13)0.0409 (12)0.0488 (16)0.0020 (10)0.0022 (11)0.0017 (10)
C130.0381 (13)0.0544 (14)0.0500 (16)0.0049 (11)0.0051 (11)0.0041 (12)
C140.0439 (14)0.0450 (13)0.0470 (15)0.0132 (10)0.0038 (11)0.0076 (11)
C150.0440 (13)0.0319 (11)0.0332 (13)0.0059 (9)0.0058 (11)0.0032 (9)
C160.0588 (14)0.0292 (10)0.0430 (15)0.0068 (9)0.0082 (12)0.0025 (9)
C170.0351 (10)0.0290 (9)0.0282 (12)0.0002 (8)0.0080 (9)0.0011 (8)
Geometric parameters (Å, º) top
Mn—O12.0774 (15)C4—H40.9300
Mn—O2i2.2375 (15)C5—C61.374 (4)
Mn—N112.2946 (17)C5—H50.9300
Mn—O2ii2.2375 (15)C6—C71.373 (3)
Mn—O1iii2.0774 (15)C6—H60.9300
Mn—N11iii2.2946 (17)C7—H70.9300
O1—C11.241 (2)C12—C131.395 (3)
O2—C11.270 (3)C12—H120.9300
O2—Mni2.2375 (15)C13—C141.364 (3)
O3—C31.353 (3)C13—H130.9300
O3—H30.9027C14—C151.401 (3)
N11—C121.326 (3)C14—H140.9300
N11—C171.358 (2)C15—C171.413 (3)
C1—C21.495 (3)C15—C161.438 (3)
C2—C71.395 (3)C16—C16iii1.339 (5)
C2—C31.396 (3)C16—H160.9300
C3—C41.397 (3)C17—C17iii1.440 (4)
C4—C51.365 (4)
O1—Mn—O1iii108.08 (9)C4—C5—C6120.8 (2)
O1—Mn—O2ii91.44 (6)C4—C5—H5119.6
O1—Mn—O2i95.07 (6)C6—C5—H5119.6
O2ii—Mn—O2i168.90 (7)C7—C6—C5119.7 (3)
O1—Mn—N11162.07 (7)C7—C6—H6120.2
O1—Mn—N11iii89.76 (6)C5—C6—H6120.2
O2ii—Mn—N1188.71 (6)C6—C7—C2121.2 (2)
O2i—Mn—N1182.33 (6)C6—C7—H7119.4
N11—Mn—N11iii72.49 (8)C2—C7—H7119.4
Mn—O1—C1154.50 (16)N11—C12—C13123.1 (2)
C1—O2—Mni132.62 (13)N11—C12—H12118.4
C3—O3—H3107.0C13—C12—H12118.4
C12—N11—C17118.10 (18)C14—C13—C12119.3 (2)
C12—N11—Mn126.07 (14)C14—C13—H13120.4
C17—N11—Mn115.76 (14)C12—C13—H13120.4
O1—C1—O2124.4 (2)C13—C14—C15119.6 (2)
O1—C1—C2118.18 (19)C13—C14—H14120.2
O2—C1—C2117.38 (17)C15—C14—H14120.2
C7—C2—C3118.4 (2)C14—C15—C17117.44 (19)
C7—C2—C1120.20 (19)C14—C15—C16123.73 (19)
C3—C2—C1121.30 (19)C17—C15—C16118.8 (2)
O3—C3—C2121.4 (2)C16iii—C16—C15121.45 (13)
O3—C3—C4119.0 (2)C16iii—C16—H16119.3
C2—C3—C4119.7 (2)C15—C16—H16119.3
C5—C4—C3120.3 (3)N11—C17—C15122.4 (2)
C5—C4—H4119.9N11—C17—C17iii117.92 (11)
C3—C4—H4119.9C15—C17—C17iii119.68 (13)
Symmetry codes: (i) x+1, y+1, z+1; (ii) x, y+1, z1/2; (iii) x+1, y, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O3—H3···O20.901.712.525 (2)148
C5—H5···O3iv0.932.523.417 (3)161
C14—H14···O3v0.932.453.323 (3)157
Symmetry codes: (iv) x+3/2, y+1/2, z1/2; (v) x+1, y+1, z+1/2.

Experimental details

Crystal data
Chemical formula[Mn(C7H5O3)2(C12H8N2)]
Mr509.36
Crystal system, space groupOrthorhombic, Pbcn
Temperature (K)295
a, b, c (Å)23.5785 (5), 12.1715 (3), 7.6545 (2)
V3)2196.73 (9)
Z4
Radiation typeMo Kα
µ (mm1)0.65
Crystal size (mm)0.20 × 0.18 × 0.03
Data collection
DiffractometerRigaku R-AXIS RAPID
diffractometer
Absorption correctionMulti-scan
(ABSCOR; Higashi, 1995)
Tmin, Tmax0.875, 0.976
No. of measured, independent and
observed [I > 2σ(I)] reflections
13706, 1965, 1544
Rint0.043
(sin θ/λ)max1)0.599
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.035, 0.081, 1.04
No. of reflections1965
No. of parameters159
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.21, 0.24

Computer programs: PROCESS-AUTO (Rigaku, 1998), PROCESS-AUTO, CrystalStructure (Rigaku, 2002), SIR92 (Altomare et al., 1993), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Selected geometric parameters (Å, º) top
Mn—O12.0774 (15)Mn—N112.2946 (17)
Mn—O2i2.2375 (15)
O1—Mn—O1ii108.08 (9)O2iii—Mn—N1188.71 (6)
O1—Mn—O2iii91.44 (6)O2i—Mn—N1182.33 (6)
O1—Mn—O2i95.07 (6)N11—Mn—N11ii72.49 (8)
O2iii—Mn—O2i168.90 (7)Mn—O1—C1154.50 (16)
O1—Mn—N11162.07 (7)C1—O2—Mni132.62 (13)
O1—Mn—N11ii89.76 (6)
Symmetry codes: (i) x+1, y+1, z+1; (ii) x+1, y, z+1/2; (iii) x, y+1, z1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O3—H3···O20.901.712.525 (2)148
C5—H5···O3iv0.932.523.417 (3)161
C14—H14···O3v0.932.453.323 (3)157
Symmetry codes: (iv) x+3/2, y+1/2, z1/2; (v) x+1, y+1, z+1/2.
A comparison of the Mn—O(carboxyl) bond distances (Å) and corresponding Mn—O—C bond angles (°) for selected MnII complexes incorporating non-chelating carboxylate ligands top
Carboxylate ligandMn—OMn—O—C
Benzoatea2.050 (4)165.8 (4)
Salicylateb2.0774 (15)154.50 (16)
Salicylatec2.087 (2)152.94 (16)
Isophthalated2.104 (2)161.8 (2)
Succinatee2.117 (3)136.8 (3)
DL-Malatef2.1174 (17)146.76 (14)
Salicylateg2.1227 (18)170.10 (6)
Isophthalateh2.141 (2)148.3 (2)
Aspantatej2.1593 (19)147.09 (19)
Hydrogen phthalatek2.171 (4)156.8 (4)
Salicylatel2.200 (12)124.4 (6)
Benzoatem2.201 (4)125.9 (4)
Salicylaten2.219 (3)121.1 (2)
Benzoatep2.224 (14)121.9 (12)
Dihydro-orotateq2.2352 (16)125.37 (16)
Salicylateb2.2375 (15)132.62 (13)
Glutarater2.278 (2)128.47 (18)
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).
 

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