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In the title polymeric complex, [Mn(C
7H
5O
3)
2(C
12H
8N
2)]
n, the Mn
II 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 Mn
II 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
-
stacking interactions between polymeric chains.
Supporting information
CCDC reference: 275491
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.
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).
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).
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 = 509.36 | Dx = 1.540 Mg m−3 |
Orthorhombic, Pbcn | Mo Kα radiation, λ = 0.71069 Å |
Hall symbol: -P 2n 2ab | Cell parameters from 10105 reflections |
a = 23.5785 (5) Å | θ = 2.7–24.4° |
b = 12.1715 (3) Å | µ = 0.65 mm−1 |
c = 7.6545 (2) Å | T = 295 K |
V = 2196.73 (9) Å3 | Platelet, pale yellow |
Z = 4 | 0.20 × 0.18 × 0.03 mm |
Data collection top
Rigaku R-AXIS RAPID diffractometer | 1965 independent reflections |
Radiation source: fine-focus sealed tube | 1544 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.043 |
Detector resolution: 10.0 pixels mm-1 | θmax = 25.2°, θmin = 1.7° |
ω scans | h = −28→28 |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | k = −14→14 |
Tmin = 0.875, Tmax = 0.976 | l = −9→8 |
13706 measured reflections | |
Refinement top
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)] = 0.035 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.081 | H-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 parameters | Δρmax = 0.21 e Å−3 |
0 restraints | Δρmin = −0.24 e Å−3 |
Crystal data top
[Mn(C7H5O3)2(C12H8N2)] | V = 2196.73 (9) Å3 |
Mr = 509.36 | Z = 4 |
Orthorhombic, Pbcn | Mo Kα radiation |
a = 23.5785 (5) Å | µ = 0.65 mm−1 |
b = 12.1715 (3) Å | T = 295 K |
c = 7.6545 (2) Å | 0.20 × 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 = 0.976 | Rint = 0.043 |
13706 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.035 | 0 restraints |
wR(F2) = 0.081 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.21 e Å−3 |
1965 reflections | Δρmin = −0.24 e Å−3 |
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 | x | y | z | Uiso*/Ueq | |
Mn | 0.5000 | 0.62071 (3) | 0.2500 | 0.03329 (15) | |
O1 | 0.55843 (6) | 0.52049 (12) | 0.3759 (2) | 0.0561 (5) | |
O2 | 0.55714 (6) | 0.36152 (11) | 0.5183 (2) | 0.0417 (4) | |
O3 | 0.63914 (7) | 0.22927 (12) | 0.4902 (3) | 0.0570 (5) | |
H3 | 0.6077 | 0.2608 | 0.5350 | 0.050* | |
N11 | 0.45111 (7) | 0.77275 (13) | 0.1565 (2) | 0.0347 (4) | |
C1 | 0.57995 (9) | 0.43099 (16) | 0.4165 (3) | 0.0362 (5) | |
C2 | 0.63737 (8) | 0.40402 (16) | 0.3457 (3) | 0.0349 (5) | |
C3 | 0.66428 (9) | 0.30514 (18) | 0.3867 (3) | 0.0412 (5) | |
C4 | 0.71836 (11) | 0.2837 (2) | 0.3206 (4) | 0.0616 (8) | |
H4 | 0.7360 | 0.2172 | 0.3455 | 0.074* | |
C5 | 0.74537 (11) | 0.3598 (3) | 0.2197 (4) | 0.0726 (9) | |
H5 | 0.7815 | 0.3451 | 0.1773 | 0.087* | |
C6 | 0.71973 (11) | 0.4581 (3) | 0.1799 (4) | 0.0707 (9) | |
H6 | 0.7385 | 0.5096 | 0.1112 | 0.085* | |
C7 | 0.66629 (10) | 0.4799 (2) | 0.2422 (3) | 0.0526 (6) | |
H7 | 0.6491 | 0.5465 | 0.2149 | 0.063* | |
C12 | 0.40254 (9) | 0.77245 (17) | 0.0693 (3) | 0.0423 (6) | |
H12 | 0.3875 | 0.7053 | 0.0343 | 0.051* | |
C13 | 0.37291 (10) | 0.86805 (19) | 0.0274 (3) | 0.0475 (6) | |
H13 | 0.3385 | 0.8641 | −0.0318 | 0.057* | |
C14 | 0.39489 (10) | 0.96747 (18) | 0.0743 (3) | 0.0453 (6) | |
H14 | 0.3754 | 1.0318 | 0.0480 | 0.054* | |
C15 | 0.44694 (9) | 0.97203 (15) | 0.1623 (3) | 0.0363 (5) | |
C16 | 0.47493 (10) | 1.07284 (16) | 0.2089 (3) | 0.0437 (6) | |
H16 | 0.4578 | 1.1395 | 0.1814 | 0.052* | |
C17 | 0.47352 (9) | 0.87126 (15) | 0.2032 (3) | 0.0308 (5) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Mn | 0.0269 (2) | 0.0251 (2) | 0.0479 (3) | 0.000 | 0.0033 (2) | 0.000 |
O1 | 0.0443 (9) | 0.0456 (9) | 0.0783 (13) | 0.0173 (8) | 0.0091 (10) | 0.0191 (9) |
O2 | 0.0358 (8) | 0.0374 (7) | 0.0520 (10) | 0.0035 (6) | 0.0111 (8) | 0.0067 (7) |
O3 | 0.0481 (10) | 0.0381 (8) | 0.0849 (14) | 0.0135 (7) | −0.0007 (9) | 0.0049 (9) |
N11 | 0.0313 (10) | 0.0323 (9) | 0.0406 (12) | −0.0020 (7) | 0.0020 (8) | −0.0002 (8) |
C1 | 0.0321 (12) | 0.0355 (11) | 0.0410 (14) | 0.0056 (9) | −0.0005 (10) | −0.0004 (10) |
C2 | 0.0275 (11) | 0.0443 (12) | 0.0330 (13) | 0.0048 (9) | −0.0016 (10) | −0.0018 (9) |
C3 | 0.0355 (12) | 0.0468 (12) | 0.0412 (15) | 0.0085 (10) | −0.0047 (11) | −0.0077 (11) |
C4 | 0.0420 (15) | 0.0817 (19) | 0.0610 (19) | 0.0293 (14) | −0.0052 (14) | −0.0156 (16) |
C5 | 0.0344 (14) | 0.133 (3) | 0.050 (2) | 0.0184 (16) | 0.0088 (13) | −0.0093 (19) |
C6 | 0.0399 (15) | 0.122 (3) | 0.0496 (18) | −0.0031 (16) | 0.0119 (13) | 0.0162 (18) |
C7 | 0.0405 (13) | 0.0714 (16) | 0.0458 (16) | 0.0021 (12) | 0.0030 (13) | 0.0135 (13) |
C12 | 0.0372 (13) | 0.0409 (12) | 0.0488 (16) | −0.0020 (10) | −0.0022 (11) | −0.0017 (10) |
C13 | 0.0381 (13) | 0.0544 (14) | 0.0500 (16) | 0.0049 (11) | −0.0051 (11) | 0.0041 (12) |
C14 | 0.0439 (14) | 0.0450 (13) | 0.0470 (15) | 0.0132 (10) | 0.0038 (11) | 0.0076 (11) |
C15 | 0.0440 (13) | 0.0319 (11) | 0.0332 (13) | 0.0059 (9) | 0.0058 (11) | 0.0032 (9) |
C16 | 0.0588 (14) | 0.0292 (10) | 0.0430 (15) | 0.0068 (9) | 0.0082 (12) | 0.0025 (9) |
C17 | 0.0351 (10) | 0.0290 (9) | 0.0282 (12) | 0.0002 (8) | 0.0080 (9) | 0.0011 (8) |
Geometric parameters (Å, º) top
Mn—O1 | 2.0774 (15) | C4—H4 | 0.9300 |
Mn—O2i | 2.2375 (15) | C5—C6 | 1.374 (4) |
Mn—N11 | 2.2946 (17) | C5—H5 | 0.9300 |
Mn—O2ii | 2.2375 (15) | C6—C7 | 1.373 (3) |
Mn—O1iii | 2.0774 (15) | C6—H6 | 0.9300 |
Mn—N11iii | 2.2946 (17) | C7—H7 | 0.9300 |
O1—C1 | 1.241 (2) | C12—C13 | 1.395 (3) |
O2—C1 | 1.270 (3) | C12—H12 | 0.9300 |
O2—Mni | 2.2375 (15) | C13—C14 | 1.364 (3) |
O3—C3 | 1.353 (3) | C13—H13 | 0.9300 |
O3—H3 | 0.9027 | C14—C15 | 1.401 (3) |
N11—C12 | 1.326 (3) | C14—H14 | 0.9300 |
N11—C17 | 1.358 (2) | C15—C17 | 1.413 (3) |
C1—C2 | 1.495 (3) | C15—C16 | 1.438 (3) |
C2—C7 | 1.395 (3) | C16—C16iii | 1.339 (5) |
C2—C3 | 1.396 (3) | C16—H16 | 0.9300 |
C3—C4 | 1.397 (3) | C17—C17iii | 1.440 (4) |
C4—C5 | 1.365 (4) | | |
| | | |
O1—Mn—O1iii | 108.08 (9) | C4—C5—C6 | 120.8 (2) |
O1—Mn—O2ii | 91.44 (6) | C4—C5—H5 | 119.6 |
O1—Mn—O2i | 95.07 (6) | C6—C5—H5 | 119.6 |
O2ii—Mn—O2i | 168.90 (7) | C7—C6—C5 | 119.7 (3) |
O1—Mn—N11 | 162.07 (7) | C7—C6—H6 | 120.2 |
O1—Mn—N11iii | 89.76 (6) | C5—C6—H6 | 120.2 |
O2ii—Mn—N11 | 88.71 (6) | C6—C7—C2 | 121.2 (2) |
O2i—Mn—N11 | 82.33 (6) | C6—C7—H7 | 119.4 |
N11—Mn—N11iii | 72.49 (8) | C2—C7—H7 | 119.4 |
Mn—O1—C1 | 154.50 (16) | N11—C12—C13 | 123.1 (2) |
C1—O2—Mni | 132.62 (13) | N11—C12—H12 | 118.4 |
C3—O3—H3 | 107.0 | C13—C12—H12 | 118.4 |
C12—N11—C17 | 118.10 (18) | C14—C13—C12 | 119.3 (2) |
C12—N11—Mn | 126.07 (14) | C14—C13—H13 | 120.4 |
C17—N11—Mn | 115.76 (14) | C12—C13—H13 | 120.4 |
O1—C1—O2 | 124.4 (2) | C13—C14—C15 | 119.6 (2) |
O1—C1—C2 | 118.18 (19) | C13—C14—H14 | 120.2 |
O2—C1—C2 | 117.38 (17) | C15—C14—H14 | 120.2 |
C7—C2—C3 | 118.4 (2) | C14—C15—C17 | 117.44 (19) |
C7—C2—C1 | 120.20 (19) | C14—C15—C16 | 123.73 (19) |
C3—C2—C1 | 121.30 (19) | C17—C15—C16 | 118.8 (2) |
O3—C3—C2 | 121.4 (2) | C16iii—C16—C15 | 121.45 (13) |
O3—C3—C4 | 119.0 (2) | C16iii—C16—H16 | 119.3 |
C2—C3—C4 | 119.7 (2) | C15—C16—H16 | 119.3 |
C5—C4—C3 | 120.3 (3) | N11—C17—C15 | 122.4 (2) |
C5—C4—H4 | 119.9 | N11—C17—C17iii | 117.92 (11) |
C3—C4—H4 | 119.9 | C15—C17—C17iii | 119.68 (13) |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x, −y+1, z−1/2; (iii) −x+1, y, −z+1/2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3···O2 | 0.90 | 1.71 | 2.525 (2) | 148 |
C5—H5···O3iv | 0.93 | 2.52 | 3.417 (3) | 161 |
C14—H14···O3v | 0.93 | 2.45 | 3.323 (3) | 157 |
Symmetry codes: (iv) −x+3/2, −y+1/2, z−1/2; (v) −x+1, y+1, −z+1/2. |
Experimental details
Crystal data |
Chemical formula | [Mn(C7H5O3)2(C12H8N2)] |
Mr | 509.36 |
Crystal system, space group | Orthorhombic, Pbcn |
Temperature (K) | 295 |
a, b, c (Å) | 23.5785 (5), 12.1715 (3), 7.6545 (2) |
V (Å3) | 2196.73 (9) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.65 |
Crystal size (mm) | 0.20 × 0.18 × 0.03 |
|
Data collection |
Diffractometer | Rigaku R-AXIS RAPID diffractometer |
Absorption correction | Multi-scan (ABSCOR; Higashi, 1995) |
Tmin, Tmax | 0.875, 0.976 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 13706, 1965, 1544 |
Rint | 0.043 |
(sin θ/λ)max (Å−1) | 0.599 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.035, 0.081, 1.04 |
No. of reflections | 1965 |
No. of parameters | 159 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.21, −0.24 |
Selected geometric parameters (Å, º) topMn—O1 | 2.0774 (15) | Mn—N11 | 2.2946 (17) |
Mn—O2i | 2.2375 (15) | | |
| | | |
O1—Mn—O1ii | 108.08 (9) | O2iii—Mn—N11 | 88.71 (6) |
O1—Mn—O2iii | 91.44 (6) | O2i—Mn—N11 | 82.33 (6) |
O1—Mn—O2i | 95.07 (6) | N11—Mn—N11ii | 72.49 (8) |
O2iii—Mn—O2i | 168.90 (7) | Mn—O1—C1 | 154.50 (16) |
O1—Mn—N11 | 162.07 (7) | C1—O2—Mni | 132.62 (13) |
O1—Mn—N11ii | 89.76 (6) | | |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, y, −z+1/2; (iii) x, −y+1, z−1/2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3···O2 | 0.90 | 1.71 | 2.525 (2) | 148 |
C5—H5···O3iv | 0.93 | 2.52 | 3.417 (3) | 161 |
C14—H14···O3v | 0.93 | 2.45 | 3.323 (3) | 157 |
Symmetry codes: (iv) −x+3/2, −y+1/2, z−1/2; (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 topCarboxylate ligand | Mn—O | Mn—O—C |
Benzoatea | 2.050 (4) | 165.8 (4) |
Salicylateb | 2.0774 (15) | 154.50 (16) |
Salicylatec | 2.087 (2) | 152.94 (16) |
Isophthalated | 2.104 (2) | 161.8 (2) |
Succinatee | 2.117 (3) | 136.8 (3) |
DL-Malatef | 2.1174 (17) | 146.76 (14) |
Salicylateg | 2.1227 (18) | 170.10 (6) |
Isophthalateh | 2.141 (2) | 148.3 (2) |
Aspantatej | 2.1593 (19) | 147.09 (19) |
Hydrogen phthalatek | 2.171 (4) | 156.8 (4) |
Salicylatel | 2.200 (12) | 124.4 (6) |
Benzoatem | 2.201 (4) | 125.9 (4) |
Salicylaten | 2.219 (3) | 121.1 (2) |
Benzoatep | 2.224 (14) | 121.9 (12) |
Dihydro-orotateq | 2.2352 (16) | 125.37 (16) |
Salicylateb | 2.2375 (15) | 132.62 (13) |
Glutarater | 2.278 (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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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 π–π 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.