In the title complex, [Mn(C
5H
4NO)
2(C
5H
5NO)
2]
n or [Mn(μ-3-PyO)
2(3-PyOH)
2]
n (3-PyO
− is the pyridin-3-olate anion and 3-PyOH is pyridin-3-ol), the Mn
II atom lies on an inversion centre and has octahedral geometry, defined by two N atoms and two deprotonated exocyclic O atoms of symmetry-related pyridin-3-olate ligands [Mn—N = 2.3559 (14) Å and Mn—O = 2.1703 (11) Å], as well as two N atoms of terminal 3-PyOH ligands [Mn—N = 2.3482 (13) Å]. The Mn
II atoms are bridged by the deprotonated pyridin-3-olate anion into a layer structure, generating sheets in the (
01) plane. These sheets are linked by O—H
O hydrogen bonds. There are also π–π and C—H
π interactions in the crystal structure.
Supporting information
CCDC reference: 268082
Complex (I) was synthesized by the addition of manganese diacetate tetrahydrate (10 mmol) to an aqueous solution of 3-hydroxypyridine (20 mmol). The solution was allowed to evaporate at room temperature, and yellow crystals were obtained after several days. Analysis calculated for C20H18N4O4Mn: C 55.44, H 4.19, N 12.93%; found: C 55.47, H 4.25, N 12.95%.
H atoms attached to C atoms were placed in calculated positions [C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C)] using the riding-model approximation. The hydroxy atom H1 was located in a difference map and refined with an O—H distance restraint of 0.85 (1) Å and with Uiso(H) = 1.5Ueq(O).
Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976) and PLATON (Spek 2003); software used to prepare material for publication: SHELXL97.
Poly[[bis(pyridin-3-ol)manganese(II)]-di-µ-pyridin-3-olato]
top
Crystal data top
[Mn(C5H4NO)2(C5H5NO)2] | F(000) = 446 |
Mr = 433.32 | Dx = 1.639 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 7874 reflections |
a = 9.4512 (19) Å | θ = 3.0–27.5° |
b = 10.583 (2) Å | µ = 0.79 mm−1 |
c = 9.5998 (19) Å | T = 296 K |
β = 113.90 (3)° | Prism, yellow |
V = 877.9 (4) Å3 | 0.36 × 0.24 × 0.18 mm |
Z = 2 | |
Data collection top
Rigaku R-AXIS RAPID diffractometer | 2012 independent reflections |
Radiation source: fine-focus sealed tube | 1870 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.019 |
Detector resolution: 10 pixels mm-1 | θmax = 27.5°, θmin = 3.0° |
ω scans | h = −12→12 |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | k = −13→13 |
Tmin = 0.764, Tmax = 0.871 | l = −12→12 |
8483 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)] = 0.029 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.095 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0688P)2 + 0.2628P] where P = (Fo2 + 2Fc2)/3 |
2012 reflections | (Δ/σ)max = 0.001 |
136 parameters | Δρmax = 0.43 e Å−3 |
1 restraint | Δρmin = −0.25 e Å−3 |
Crystal data top
[Mn(C5H4NO)2(C5H5NO)2] | V = 877.9 (4) Å3 |
Mr = 433.32 | Z = 2 |
Monoclinic, P21/n | Mo Kα radiation |
a = 9.4512 (19) Å | µ = 0.79 mm−1 |
b = 10.583 (2) Å | T = 296 K |
c = 9.5998 (19) Å | 0.36 × 0.24 × 0.18 mm |
β = 113.90 (3)° | |
Data collection top
Rigaku R-AXIS RAPID diffractometer | 2012 independent reflections |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | 1870 reflections with I > 2σ(I) |
Tmin = 0.764, Tmax = 0.871 | Rint = 0.019 |
8483 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.029 | 1 restraint |
wR(F2) = 0.095 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | Δρmax = 0.43 e Å−3 |
2012 reflections | Δρmin = −0.25 e Å−3 |
136 parameters | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Mn1 | 0.5000 | 0.5000 | 0.5000 | 0.01678 (13) | |
O1 | 0.85038 (13) | 0.72041 (12) | 0.21408 (13) | 0.0306 (3) | |
H11 | 0.860 (3) | 0.757 (2) | 0.140 (2) | 0.046* | |
O2 | 0.62536 (12) | 0.32396 (9) | 0.52332 (11) | 0.0210 (2) | |
N1 | 0.55242 (15) | 0.55947 (12) | 0.29002 (14) | 0.0233 (3) | |
N2 | 0.76736 (14) | 0.09055 (11) | 0.82708 (14) | 0.0215 (3) | |
C1 | 0.68904 (18) | 0.60598 (15) | 0.30248 (17) | 0.0246 (3) | |
H1 | 0.7757 | 0.5909 | 0.3921 | 0.030* | |
C2 | 0.70793 (17) | 0.67588 (14) | 0.18786 (16) | 0.0226 (3) | |
C3 | 0.57901 (18) | 0.69633 (15) | 0.05301 (17) | 0.0268 (3) | |
H3 | 0.5868 | 0.7428 | −0.0258 | 0.032* | |
C4 | 0.43910 (19) | 0.64611 (16) | 0.03874 (18) | 0.0286 (3) | |
H4 | 0.3514 | 0.6572 | −0.0510 | 0.034* | |
C5 | 0.42991 (18) | 0.57945 (15) | 0.15803 (18) | 0.0262 (3) | |
H5 | 0.3345 | 0.5468 | 0.1466 | 0.031* | |
C6 | 0.76141 (16) | 0.18774 (13) | 0.73456 (16) | 0.0206 (3) | |
H6 | 0.8529 | 0.2307 | 0.7518 | 0.025* | |
C7 | 0.62522 (16) | 0.22854 (13) | 0.61321 (15) | 0.0187 (3) | |
C8 | 0.49016 (17) | 0.16188 (14) | 0.59220 (17) | 0.0257 (3) | |
H8 | 0.3967 | 0.1843 | 0.5137 | 0.031* | |
C9 | 0.49555 (18) | 0.06302 (15) | 0.6878 (2) | 0.0292 (3) | |
H9 | 0.4057 | 0.0191 | 0.6745 | 0.035* | |
C10 | 0.63513 (19) | 0.02940 (15) | 0.80342 (18) | 0.0243 (3) | |
H10 | 0.6375 | −0.0377 | 0.8668 | 0.029* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Mn1 | 0.01824 (19) | 0.01568 (19) | 0.01650 (19) | −0.00002 (9) | 0.00712 (13) | 0.00035 (9) |
O1 | 0.0262 (6) | 0.0430 (7) | 0.0232 (5) | −0.0072 (5) | 0.0108 (4) | 0.0029 (5) |
O2 | 0.0244 (5) | 0.0189 (5) | 0.0208 (5) | 0.0027 (4) | 0.0102 (4) | 0.0025 (4) |
N1 | 0.0276 (6) | 0.0226 (6) | 0.0226 (6) | 0.0012 (5) | 0.0131 (5) | 0.0020 (5) |
N2 | 0.0217 (6) | 0.0219 (6) | 0.0198 (5) | 0.0025 (5) | 0.0074 (5) | 0.0009 (5) |
C1 | 0.0251 (7) | 0.0286 (7) | 0.0206 (7) | 0.0025 (6) | 0.0096 (6) | 0.0035 (6) |
C2 | 0.0244 (7) | 0.0235 (7) | 0.0223 (7) | −0.0003 (5) | 0.0119 (6) | −0.0020 (5) |
C3 | 0.0304 (8) | 0.0303 (8) | 0.0218 (7) | 0.0003 (6) | 0.0129 (6) | 0.0059 (6) |
C4 | 0.0257 (7) | 0.0348 (8) | 0.0231 (7) | 0.0014 (6) | 0.0077 (6) | 0.0049 (6) |
C5 | 0.0251 (7) | 0.0272 (7) | 0.0278 (7) | −0.0012 (6) | 0.0124 (6) | 0.0023 (6) |
C6 | 0.0189 (6) | 0.0209 (7) | 0.0212 (6) | 0.0003 (5) | 0.0073 (5) | −0.0007 (5) |
C7 | 0.0213 (6) | 0.0169 (6) | 0.0184 (6) | 0.0015 (5) | 0.0084 (5) | −0.0023 (5) |
C8 | 0.0198 (7) | 0.0263 (7) | 0.0259 (7) | 0.0002 (6) | 0.0040 (6) | 0.0028 (6) |
C9 | 0.0223 (7) | 0.0275 (8) | 0.0353 (8) | −0.0040 (6) | 0.0091 (7) | 0.0035 (6) |
C10 | 0.0271 (8) | 0.0211 (6) | 0.0257 (8) | 0.0009 (6) | 0.0116 (6) | 0.0045 (6) |
Geometric parameters (Å, º) top
Mn1—N1 | 2.3482 (13) | C1—H1 | 0.9300 |
Mn1—N2i | 2.3559 (14) | C2—C3 | 1.389 (2) |
Mn1—O2ii | 2.1703 (11) | C3—C4 | 1.379 (2) |
O1—C2 | 1.3503 (18) | C3—H3 | 0.9300 |
O2—C7 | 1.3287 (17) | C4—C5 | 1.377 (2) |
Mn1—N1ii | 2.3483 (13) | C4—H4 | 0.9300 |
Mn1—N2iii | 2.3559 (14) | C5—H5 | 0.9300 |
Mn1—O2 | 2.1703 (11) | C6—C7 | 1.409 (2) |
N1—C1 | 1.341 (2) | C6—H6 | 0.9300 |
N1—C5 | 1.342 (2) | C7—C8 | 1.400 (2) |
N2—C10 | 1.342 (2) | C8—C9 | 1.379 (2) |
N2—C6 | 1.3452 (19) | C8—H8 | 0.9300 |
N2—Mn1iv | 2.3559 (14) | C9—C10 | 1.383 (2) |
O1—H11 | 0.85 (3) | C9—H9 | 0.9300 |
C1—C2 | 1.396 (2) | C10—H10 | 0.9300 |
| | | |
N1ii—Mn1—N1 | 180.0 | C2—O1—H11 | 116.3 (17) |
N1ii—Mn1—N2i | 88.02 (5) | C7—O2—Mn1 | 125.12 (9) |
N1—Mn1—N2i | 91.98 (5) | C1—N1—C5 | 117.22 (12) |
N2iii—Mn1—N2i | 180.0 | C1—N1—Mn1 | 123.52 (10) |
O2ii—Mn1—O2 | 180.0 | C2—C1—H1 | 118.3 |
O2ii—Mn1—N1ii | 91.28 (4) | C2—C3—H3 | 120.8 |
O2—Mn1—N1ii | 88.72 (4) | C3—C2—C1 | 118.23 (14) |
O2ii—Mn1—N2iii | 87.82 (4) | C3—C4—H4 | 120.1 |
O2—Mn1—N2iii | 92.18 (4) | C4—C3—C2 | 118.44 (14) |
N1ii—Mn1—N2iii | 91.98 (5) | C4—C3—H3 | 120.8 |
N1—Mn1—N2iii | 88.02 (5) | C4—C5—H5 | 118.5 |
N1—C1—C2 | 123.37 (14) | C5—N1—Mn1 | 116.82 (10) |
N1—C1—H1 | 118.3 | C5—C4—C3 | 119.71 (15) |
N1—C5—C4 | 123.00 (14) | C5—C4—H4 | 120.1 |
N1—C5—H5 | 118.5 | C6—N2—Mn1iv | 123.62 (10) |
N2—C6—C7 | 124.06 (13) | C7—C6—H6 | 118.0 |
N2—C6—H6 | 118.0 | C7—C8—H8 | 120.0 |
N2—C10—C9 | 122.11 (14) | C8—C7—C6 | 116.04 (13) |
N2—C10—H10 | 118.9 | C8—C9—C10 | 119.70 (14) |
O1—C2—C3 | 123.46 (13) | C8—C9—H9 | 120.2 |
O1—C2—C1 | 118.31 (13) | C9—C8—C7 | 120.06 (14) |
O2ii—Mn1—N1 | 88.72 (4) | C9—C8—H8 | 120.0 |
O2—Mn1—N1 | 91.28 (4) | C9—C10—H10 | 118.9 |
O2ii—Mn1—N2i | 92.18 (4) | C10—N2—C6 | 118.02 (13) |
O2—Mn1—N2i | 87.82 (4) | C10—N2—Mn1iv | 117.53 (10) |
O2—C7—C6 | 121.93 (13) | C10—C9—H9 | 120.2 |
O2—C7—C8 | 122.03 (13) | | |
| | | |
Mn1—N1—C1—C2 | −159.86 (11) | N2i—Mn1—N1—C5 | −151.96 (11) |
Mn1—N1—C5—C4 | 161.93 (13) | N2—C6—C7—O2 | −178.98 (12) |
Mn1iv—N2—C6—C7 | 168.59 (10) | N2—C6—C7—C8 | 0.5 (2) |
Mn1iv—N2—C10—C9 | −169.66 (12) | O1—C2—C3—C4 | 179.92 (15) |
Mn1—O2—C7—C8 | 62.97 (16) | O2ii—Mn1—N1—C5 | −59.82 (11) |
Mn1—O2—C7—C6 | −117.61 (13) | O2—Mn1—N1—C5 | 120.18 (11) |
N1ii—Mn1—O2—C7 | 10.35 (11) | O2—C7—C8—C9 | 179.65 (14) |
N1—Mn1—O2—C7 | −169.65 (11) | C1—N1—C5—C4 | −1.0 (2) |
N1—C1—C2—O1 | 178.60 (14) | C1—C2—C3—C4 | −0.3 (2) |
N1—C1—C2—C3 | −1.2 (2) | C2—C3—C4—C5 | 1.1 (2) |
N2iii—Mn1—O2—C7 | −81.58 (11) | C3—C4—C5—N1 | −0.4 (2) |
N2i—Mn1—O2—C7 | 98.42 (11) | C5—N1—C1—C2 | 1.8 (2) |
O2ii—Mn1—N1—C1 | 101.92 (12) | C6—N2—C10—C9 | 0.3 (2) |
O2—Mn1—N1—C1 | −78.08 (12) | C6—C7—C8—C9 | 0.2 (2) |
N2iii—Mn1—N1—C1 | −170.22 (12) | C7—C8—C9—C10 | −0.6 (2) |
N2i—Mn1—N1—C1 | 9.78 (12) | C8—C9—C10—N2 | 0.3 (3) |
N2iii—Mn1—N1—C5 | 28.04 (11) | C10—N2—C6—C7 | −0.7 (2) |
Symmetry codes: (i) −x+3/2, y+1/2, −z+3/2; (ii) −x+1, −y+1, −z+1; (iii) x−1/2, −y+1/2, z−1/2; (iv) −x+3/2, y−1/2, −z+3/2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H11···O2v | 0.85 (3) | 1.78 (3) | 2.621 (3) | 176 (2) |
C5—H5···Cg2iii | 0.93 | 2.91 | 3.773 (2) | 155 |
Symmetry codes: (iii) x−1/2, −y+1/2, z−1/2; (v) −x+3/2, y+1/2, −z+1/2. |
Experimental details
Crystal data |
Chemical formula | [Mn(C5H4NO)2(C5H5NO)2] |
Mr | 433.32 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 296 |
a, b, c (Å) | 9.4512 (19), 10.583 (2), 9.5998 (19) |
β (°) | 113.90 (3) |
V (Å3) | 877.9 (4) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.79 |
Crystal size (mm) | 0.36 × 0.24 × 0.18 |
|
Data collection |
Diffractometer | Rigaku R-AXIS RAPID diffractometer |
Absorption correction | Multi-scan (ABSCOR; Higashi, 1995) |
Tmin, Tmax | 0.764, 0.871 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8483, 2012, 1870 |
Rint | 0.019 |
(sin θ/λ)max (Å−1) | 0.649 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.029, 0.095, 1.04 |
No. of reflections | 2012 |
No. of parameters | 136 |
No. of restraints | 1 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.43, −0.25 |
Selected geometric parameters (Å, º) topMn1—N1 | 2.3482 (13) | Mn1—O2ii | 2.1703 (11) |
Mn1—N2i | 2.3559 (14) | | |
| | | |
N1—Mn1—N2i | 91.98 (5) | O2—Mn1—N2iii | 92.18 (4) |
O2—Mn1—N1ii | 88.72 (4) | | |
Symmetry codes: (i) −x+3/2, y+1/2, −z+3/2; (ii) −x+1, −y+1, −z+1; (iii) x−1/2, −y+1/2, z−1/2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H11···O2iv | 0.85 (3) | 1.78 (3) | 2.621 (3) | 176 (2) |
C5—H5···Cg2iii | 0.93 | 2.91 | 3.773 (2) | 155 |
Symmetry codes: (iii) x−1/2, −y+1/2, z−1/2; (iv) −x+3/2, y+1/2, −z+1/2. |
Molecular self-assembly of coordination architecture has been a rapidly developing research area within supramolecular chemistry in recent years (Liu et al., 2003). The choice of ligand is an important factor, since it greatly influences the structure of the coordination architecture and the functionality of the complex formed. Bifunctional hydroxypyridine (PyOH) molecules, including 2-OH, 3-OH and 4-OH, are good candidates for the construction of supramolecular systems, which are not only capable of binding to metal centres, but can also form regular hydrogen bonds by functioning as both a hydrogen donor and an acceptor (Breeze & Wang, 1993). Among the isomers of PyOH molecules, 2- or 4-PyOH exhibit tautomerization to their pyridone isomers, viz. 2- or 4-pyridone (Yang & Craven, 1998; Wheeler & Ammon, 1974; Trikoupis et al., 2002). For example, 4-PyOH would be expected to coordinate, if at all, through the pyridone O atom, which has only weak donor properties because the N atom is protonated (Gao et al., 2004; Lu et al.,2004), whereas 3-PyOH does not have the corresponding tautomeric form, `3-pyridone', and so is a true hydroxypyridine (Flakus et al., 2003). Therefore, 3-PyOH is able to construct high-dimensional coordination polymers, in contrast with 2- or 4-PyOH. To date, only two such extended structures of CuII coordination polymers by means of covalent bonds have been reported, namely [Cu(3-pyO-N,O)2(3-pyOH)(H2O)]n (chain; Castillo et al., 2000) and [Cu(3-PyOH)2(O2CCF3)2]n (layer; Kawata et al., 1997). As a contribution to this study, we report here the structure of the title novel two-dimensional manganese(II) coordination polymer, (I), [Mn(µ-3-PyO-N,O)2(3-PyOH)2]n.
As shown in Fig. 1, the asymmetric unit of (I) is composed of one MnII atom, one neutral 3-PyOH molecule and one deprotonated pyridin-3-onate anion. The MnII atom lies on an inversion centre [chosen for convenience to be at (1/2,1/2,1/2)] and is six-coordinated by two N atoms and two deprotonated exocyclic O atoms of symmetry-related pyridin-3-onate ligands, as well as by two N atoms of the terminal 3-PyOH molecules. The Mn1—N1 bond is slightly shorter than the Mn1—N2i(3-PyO−) bond (Table 1) and the Mn1—O2ii bond is shorter than the Mn—N bonds.
Compound (I) has a two-dimensional layer structure (Figs. 2a and 2 b) with sheets in the (101) plane; the shortest Mn···Mn separation is 7.4156 (15) Å [e.g. between Mn1 at (1/2,1/2,1/2) and (0,0,0)]. In contrast, in the reported one-dimensional copper(II) polymer [Cu(3-pyO-N,O)2(3-pyOH)(H2O)]n (Castillo et al., 2000), the CuII atoms are bridged by the deprotonated pyridin-3-onate anion, to produce a one-dimensional chain with a Cu···Cu separation of 7.03 Å, while in the reported two-dimensional copper(II) polymer [Cu(3-PyOH)2(O2CCF3)2]n (Kawata et al., 1997), the Cu centres are linked by neutral 3-hydroxypyridine ligands, with a shortest Cu···Cu separation of 7.23 Å.
The sheets of (I) are linked by O—H···O hydrogen bonds (Table 2) between the neutral 3-py—OH hydroxy group (O1—H1) and a screw-axis related deprotonated phenolate atom O2. In addition to these strong hydrogen bonds, there are also π–π interactions between the neutral and symmetry-related deprotonated 3-PyOH ligands. The centroid···centroid separation between the N1–C5 ring at (x,y,z) and the N2–C10 ring at (1 − x, 1 − y, 1 − z) is 3.631 Å, with an interplanar angle of 19.25°. There is also a C—H···π interaction, C5—H5···Cg2 (Table 2), where Cg2 is the centroid of the N2—C10 ring at (x − 1/2, 1/2 − y, z − 1/2).