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The title complex, [Mn(C5H4NCO2)2(C5H4NCOOH)]OH, consists of a cation and a hydroxide ion. The Mn atom is coordinated by three N atoms and three O atoms from three pyridinecarboxylate ligands, and has a distorted octahedral geometry, with Mn-N distances ranging from 2.157 (1) to 2.233 (1) Å and Mn-O distances from 1.910 (1) to 1.927 (4) Å. One ligand is protonated as the acid form. This forms one of two independent hydrogen bonds, to the anion.
Supporting information
 | Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100012245/qa0380sup1.cif |
 | Structure factor file (CIF format) https://doi.org/10.1107/S0108270100012245/qa0380Isup2.hkl |
CCDC reference: 152658
S2. Experimental top
Mn(OAc)2(H2O)4 and pyridinecarboxylic acid were dissolved in pyridine and absolute EtOH, and solid (nBu4N)[MnO4] was added in small portions with stirring, affording a bronze precipitate that was filtered, washed with a mixture solvent comprising pyridine and absolute EtOH, and dried in a desiccator containing silica gel. Well shaped single crystals of the title complex were obtained by a diffusion method.
Computing details top
Data collection: KappaCCD Server Software (Nonius, 1997); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); software used to prepare material for publication: SHELXL97.
Bis(pyridinecarboxylato-O,N)(pyridinecarboxylic acid-O,N)manganese(III) hydroxide top
Crystal data top
| [Mn(C6H4NO2)2(C6H5NO2)]·OH | F(000) = 1792 |
| Mr = 439.26 | Dx = 1.638 Mg m−3 |
| Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
| a = 30.523 (6) Å | Cell parameters from 4099 reflections |
| b = 8.4111 (17) Å | θ = 1–27° |
| c = 13.914 (3) Å | µ = 0.79 mm−1 |
| β = 94.40 (3)° | T = 293 K |
| V = 3561.6 (12) Å3 | Plate, brown |
| Z = 8 | 0.16 × 0.10 × 0.08 mm |
Data collection top
| KappaCCD diffractometer | 3882 reflections with I > 2σ(I) |
| Radiation source: fine-focus sealed tube | Rint = 0.076 |
| Graphite monochromator | θmax = 27.5°, θmin = 1.3° |
| ϕ and ω scans with κ offsets | h = −39→39 |
| 6842 measured reflections | k = 0→10 |
| 4099 independent reflections | l = 0→17 |
Refinement top
| Refinement on F2 | Secondary atom site location: difference Fourier map |
| Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
| R[F2 > 2σ(F2)] = 0.029 | H-atom parameters constrained |
| wR(F2) = 0.067 | w = 1/[σ2(Fo2) + (0.060P)2 + 0.550P] where P = (Fo2 + 2Fc2)/3 |
| S = 0.86 | (Δ/σ)max = 0.001 |
| 4099 reflections | Δρmax = 0.88 e Å−3 |
| 263 parameters | Δρmin = −0.80 e Å−3 |
| 0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
| Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0139 (4) |
Crystal data top
| [Mn(C6H4NO2)2(C6H5NO2)]·OH | V = 3561.6 (12) Å3 |
| Mr = 439.26 | Z = 8 |
| Monoclinic, C2/c | Mo Kα radiation |
| a = 30.523 (6) Å | µ = 0.79 mm−1 |
| b = 8.4111 (17) Å | T = 293 K |
| c = 13.914 (3) Å | 0.16 × 0.10 × 0.08 mm |
| β = 94.40 (3)° |
Data collection top
| KappaCCD diffractometer | 3882 reflections with I > 2σ(I) |
| 6842 measured reflections | Rint = 0.076 |
| 4099 independent reflections |
Refinement top
| R[F2 > 2σ(F2)] = 0.029 | 0 restraints |
| wR(F2) = 0.067 | H-atom parameters constrained |
| S = 0.86 | Δρmax = 0.88 e Å−3 |
| 4099 reflections | Δρmin = −0.80 e Å−3 |
| 263 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 | ||
| Mn1 | 0.614124 (4) | 0.217414 (16) | 0.116907 (9) | 0.04042 (7) | |
| O1 | 0.65559 (2) | 0.38753 (10) | 0.11856 (5) | 0.05395 (17) | |
| O2 | 0.70201 (3) | 0.51880 (12) | 0.03362 (6) | 0.0714 (2) | |
| O3 | 0.61673 (2) | 0.22286 (9) | 0.25571 (6) | 0.05266 (18) | |
| O4 | 0.65768 (3) | 0.17416 (13) | 0.39219 (5) | 0.0732 (2) | |
| H4A | 0.6378 | 0.2326 | 0.4131 | 0.080* | |
| O5 | 0.57350 (2) | 0.04351 (7) | 0.10354 (5) | 0.04533 (15) | |
| O6 | 0.50603 (2) | −0.04327 (10) | 0.11845 (7) | 0.0664 (2) | |
| N1 | 0.61955 (2) | 0.24168 (10) | −0.03602 (6) | 0.04430 (17) | |
| N2 | 0.66947 (2) | 0.05081 (10) | 0.15712 (6) | 0.04671 (17) | |
| N3 | 0.54979 (2) | 0.34168 (9) | 0.11297 (5) | 0.04137 (16) | |
| C1 | 0.64966 (3) | 0.35425 (11) | −0.04899 (6) | 0.04342 (18) | |
| C2 | 0.65633 (3) | 0.39359 (13) | −0.14210 (7) | 0.0510 (2) | |
| H2A | 0.6777 | 0.4730 | −0.1546 | 0.080* | |
| C3 | 0.63283 (4) | 0.31487 (14) | −0.21723 (7) | 0.0561 (2) | |
| H3A | 0.6378 | 0.3399 | −0.2828 | 0.080* | |
| C4 | 0.60261 (4) | 0.20621 (12) | −0.19908 (7) | 0.0521 (2) | |
| H4B | 0.5855 | 0.1539 | −0.2505 | 0.080* | |
| C5 | 0.59554 (3) | 0.16963 (12) | −0.10229 (7) | 0.04510 (19) | |
| H5A | 0.5743 | 0.0904 | −0.0885 | 0.080* | |
| C6 | 0.67098 (3) | 0.42812 (12) | 0.03573 (7) | 0.0499 (2) | |
| C7 | 0.67961 (3) | 0.06377 (11) | 0.25243 (6) | 0.04094 (18) | |
| C8 | 0.71693 (3) | −0.01414 (12) | 0.29548 (7) | 0.0515 (2) | |
| H8A | 0.7241 | −0.0032 | 0.3636 | 0.080* | |
| C9 | 0.74276 (3) | −0.10262 (15) | 0.24163 (10) | 0.0651 (3) | |
| H9A | 0.7684 | −0.1549 | 0.2705 | 0.080* | |
| C10 | 0.73194 (3) | −0.11889 (16) | 0.14399 (10) | 0.0660 (3) | |
| H10A | 0.7495 | −0.1826 | 0.1045 | 0.080* | |
| C11 | 0.69538 (3) | −0.04053 (14) | 0.10287 (8) | 0.0560 (2) | |
| H11A | 0.6878 | −0.0516 | 0.0350 | 0.080* | |
| C12 | 0.65057 (3) | 0.15824 (11) | 0.30665 (6) | 0.04570 (19) | |
| C13 | 0.51797 (3) | 0.23231 (9) | 0.11744 (6) | 0.03862 (17) | |
| C14 | 0.47432 (3) | 0.27869 (13) | 0.12834 (8) | 0.0517 (2) | |
| H14A | 0.4519 | 0.1996 | 0.1325 | 0.080* | |
| C15 | 0.46470 (3) | 0.43743 (12) | 0.13160 (8) | 0.0518 (2) | |
| H15A | 0.4351 | 0.4717 | 0.1385 | 0.080* | |
| C16 | 0.49811 (4) | 0.54807 (14) | 0.12634 (8) | 0.0571 (2) | |
| H16A | 0.4918 | 0.6598 | 0.1283 | 0.080* | |
| C17 | 0.53983 (3) | 0.49588 (12) | 0.11596 (7) | 0.0494 (2) | |
| H17A | 0.5629 | 0.5729 | 0.1124 | 0.080* | |
| C18 | 0.53185 (3) | 0.06829 (12) | 0.11369 (7) | 0.0477 (2) | |
| O7 | 0.60981 (5) | 0.26293 (15) | 0.54448 (12) | 0.1074 (4) | |
| H7A | 0.5842 | 0.2122 | 0.5664 | 0.080* |
Atomic displacement parameters (Å2) top
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Mn1 | 0.03257 (9) | 0.05178 (11) | 0.03600 (10) | 0.00273 (4) | −0.00336 (6) | −0.00100 (5) |
| O1 | 0.0473 (3) | 0.0682 (4) | 0.0451 (3) | −0.0108 (3) | −0.0045 (3) | −0.0093 (3) |
| O2 | 0.0599 (5) | 0.0889 (6) | 0.0629 (5) | −0.0340 (4) | −0.0117 (4) | 0.0046 (4) |
| O3 | 0.0403 (3) | 0.0668 (4) | 0.0504 (4) | 0.0104 (3) | 0.0003 (3) | 0.0006 (3) |
| O4 | 0.0855 (6) | 0.0959 (6) | 0.0371 (4) | 0.0205 (5) | −0.0033 (4) | −0.0120 (4) |
| O5 | 0.0378 (3) | 0.0401 (3) | 0.0577 (4) | 0.0033 (2) | 0.0011 (3) | 0.0031 (3) |
| O6 | 0.0477 (4) | 0.0574 (4) | 0.0940 (6) | −0.0126 (3) | 0.0046 (4) | 0.0073 (4) |
| N1 | 0.0304 (3) | 0.0498 (4) | 0.0520 (4) | 0.0016 (3) | −0.0017 (3) | 0.0005 (3) |
| N2 | 0.0395 (4) | 0.0565 (4) | 0.0435 (4) | 0.0010 (3) | −0.0013 (3) | −0.0005 (3) |
| N3 | 0.0376 (3) | 0.0500 (4) | 0.0357 (3) | 0.0010 (3) | −0.0021 (3) | −0.0023 (3) |
| C1 | 0.0366 (4) | 0.0498 (4) | 0.0425 (4) | 0.0021 (3) | −0.0063 (3) | −0.0013 (4) |
| C2 | 0.0457 (5) | 0.0669 (6) | 0.0410 (4) | 0.0019 (4) | 0.0067 (4) | 0.0056 (4) |
| C3 | 0.0624 (6) | 0.0698 (6) | 0.0370 (4) | 0.0164 (5) | 0.0108 (4) | 0.0080 (4) |
| C4 | 0.0594 (6) | 0.0557 (5) | 0.0389 (5) | 0.0087 (4) | −0.0115 (4) | −0.0068 (4) |
| C5 | 0.0384 (4) | 0.0516 (4) | 0.0452 (5) | −0.0007 (3) | 0.0031 (3) | −0.0062 (4) |
| C6 | 0.0372 (4) | 0.0577 (5) | 0.0535 (5) | −0.0024 (3) | −0.0058 (4) | 0.0046 (4) |
| C7 | 0.0325 (4) | 0.0511 (4) | 0.0388 (4) | −0.0080 (3) | −0.0004 (3) | −0.0024 (3) |
| C8 | 0.0429 (5) | 0.0607 (5) | 0.0485 (5) | 0.0035 (4) | −0.0130 (4) | 0.0038 (4) |
| C9 | 0.0393 (5) | 0.0709 (6) | 0.0827 (8) | 0.0099 (4) | −0.0103 (5) | 0.0036 (6) |
| C10 | 0.0430 (5) | 0.0756 (7) | 0.0793 (8) | 0.0124 (5) | 0.0038 (5) | −0.0115 (6) |
| C11 | 0.0430 (5) | 0.0753 (6) | 0.0491 (5) | 0.0082 (4) | 0.0003 (4) | −0.0102 (5) |
| C12 | 0.0512 (5) | 0.0450 (4) | 0.0402 (4) | −0.0068 (3) | −0.0012 (4) | 0.0060 (3) |
| C13 | 0.0371 (4) | 0.0392 (4) | 0.0392 (4) | −0.0024 (3) | 0.0005 (3) | 0.0048 (3) |
| C14 | 0.0319 (4) | 0.0683 (6) | 0.0547 (6) | 0.0006 (3) | 0.0030 (4) | 0.0025 (4) |
| C15 | 0.0379 (4) | 0.0551 (5) | 0.0617 (6) | 0.0101 (4) | −0.0011 (4) | −0.0014 (4) |
| C16 | 0.0608 (6) | 0.0619 (6) | 0.0477 (5) | 0.0126 (5) | −0.0023 (4) | −0.0034 (4) |
| C17 | 0.0503 (5) | 0.0525 (5) | 0.0441 (5) | 0.0027 (4) | −0.0054 (4) | −0.0030 (4) |
| C18 | 0.0400 (4) | 0.0566 (5) | 0.0461 (5) | 0.0012 (4) | 0.0001 (3) | 0.0047 (4) |
| O7 | 0.0967 (8) | 0.0904 (7) | 0.1355 (12) | −0.0040 (6) | 0.0122 (8) | −0.0251 (8) |
Geometric parameters (Å, º) top
| Mn1—O1 | 1.9094 (8) | C3—H3A | 0.9602 |
| Mn1—O5 | 1.9174 (7) | C4—C5 | 1.4139 (14) |
| Mn1—O3 | 1.9274 (9) | C4—H4B | 0.9602 |
| Mn1—N1 | 2.1566 (10) | C5—H5A | 0.9600 |
| Mn1—N3 | 2.2215 (8) | C7—C8 | 1.4075 (13) |
| Mn1—N2 | 2.2328 (9) | C7—C12 | 1.4455 (13) |
| O1—C6 | 1.3223 (13) | C8—C9 | 1.3518 (17) |
| O2—C6 | 1.2183 (12) | C8—H8A | 0.9600 |
| O3—C12 | 1.3237 (12) | C9—C10 | 1.3801 (19) |
| O4—C12 | 1.2009 (12) | C9—H9A | 0.9601 |
| O4—H4A | 0.8500 | C10—C11 | 1.3818 (16) |
| O5—C18 | 1.3066 (11) | C10—H10A | 0.9600 |
| O6—C18 | 1.2303 (13) | C11—H11A | 0.9602 |
| N1—C5 | 1.2849 (12) | C13—C14 | 1.4074 (13) |
| N1—C1 | 1.3412 (12) | C13—C18 | 1.4453 (13) |
| N2—C7 | 1.3429 (12) | C14—C15 | 1.3687 (15) |
| N2—C11 | 1.3700 (13) | C14—H14A | 0.9601 |
| N3—C17 | 1.3334 (12) | C15—C16 | 1.3867 (16) |
| N3—C13 | 1.3427 (11) | C15—H15A | 0.9600 |
| C1—C2 | 1.3674 (13) | C16—C17 | 1.3652 (15) |
| C1—C6 | 1.4427 (13) | C16—H16A | 0.9599 |
| C2—C3 | 1.3895 (16) | C17—H17A | 0.9599 |
| C2—H2A | 0.9599 | O7—H7A | 0.9600 |
| C3—C4 | 1.3364 (17) | ||
| O1—Mn1—O5 | 174.91 (3) | N1—C5—H5A | 122.8 |
| O1—Mn1—O3 | 89.64 (4) | C4—C5—H5A | 119.8 |
| O5—Mn1—O3 | 95.28 (4) | O2—C6—O1 | 120.75 (10) |
| O1—Mn1—N1 | 80.79 (4) | O2—C6—C1 | 123.56 (10) |
| O5—Mn1—N1 | 94.27 (3) | O1—C6—C1 | 115.66 (8) |
| O3—Mn1—N1 | 170.41 (3) | N2—C7—C8 | 120.03 (9) |
| O1—Mn1—N3 | 103.39 (3) | N2—C7—C12 | 117.12 (8) |
| O5—Mn1—N3 | 78.04 (3) | C8—C7—C12 | 122.85 (8) |
| O3—Mn1—N3 | 88.97 (4) | C9—C8—C7 | 120.51 (10) |
| N1—Mn1—N3 | 93.77 (4) | C9—C8—H8A | 120.1 |
| O1—Mn1—N2 | 88.81 (4) | C7—C8—H8A | 119.4 |
| O5—Mn1—N2 | 90.96 (3) | C8—C9—C10 | 119.64 (10) |
| O3—Mn1—N2 | 77.96 (4) | C8—C9—H9A | 120.8 |
| N1—Mn1—N2 | 101.12 (4) | C10—C9—H9A | 119.5 |
| N3—Mn1—N2 | 162.14 (3) | C9—C10—C11 | 119.01 (11) |
| C6—O1—Mn1 | 117.54 (6) | C9—C10—H10A | 121.1 |
| C12—O3—Mn1 | 119.83 (7) | C11—C10—H10A | 119.9 |
| C12—O4—H4A | 108.9 | N2—C11—C10 | 121.42 (10) |
| C18—O5—Mn1 | 119.68 (6) | N2—C11—H11A | 119.3 |
| C5—N1—C1 | 126.54 (9) | C10—C11—H11A | 119.2 |
| C5—N1—Mn1 | 125.50 (7) | O4—C12—O3 | 124.01 (10) |
| C1—N1—Mn1 | 107.74 (6) | O4—C12—C7 | 120.47 (9) |
| C7—N2—C11 | 119.37 (8) | O3—C12—C7 | 115.52 (8) |
| C7—N2—Mn1 | 108.02 (6) | N3—C13—C14 | 120.61 (8) |
| C11—N2—Mn1 | 132.18 (7) | N3—C13—C18 | 115.93 (8) |
| C17—N3—C13 | 119.84 (8) | C14—C13—C18 | 123.43 (8) |
| C17—N3—Mn1 | 131.30 (6) | C15—C14—C13 | 118.77 (9) |
| C13—N3—Mn1 | 108.52 (6) | C15—C14—H14A | 121.2 |
| N1—C1—C2 | 116.85 (9) | C13—C14—H14A | 120.0 |
| N1—C1—C6 | 117.70 (9) | C14—C15—C16 | 119.49 (9) |
| C2—C1—C6 | 125.40 (9) | C14—C15—H15A | 120.1 |
| C1—C2—C3 | 119.46 (10) | C16—C15—H15A | 120.4 |
| C1—C2—H2A | 119.5 | C17—C16—C15 | 119.05 (10) |
| C3—C2—H2A | 121.0 | C17—C16—H16A | 120.6 |
| C4—C3—C2 | 120.51 (9) | C15—C16—H16A | 120.4 |
| C4—C3—H3A | 119.5 | N3—C17—C16 | 122.19 (10) |
| C2—C3—H3A | 120.0 | N3—C17—H17A | 119.0 |
| C3—C4—C5 | 119.13 (9) | C16—C17—H17A | 118.8 |
| C3—C4—H4B | 121.2 | O6—C18—O5 | 121.10 (9) |
| C5—C4—H4B | 119.7 | O6—C18—C13 | 122.37 (9) |
| N1—C5—C4 | 117.43 (9) | O5—C18—C13 | 116.52 (8) |
| O5—Mn1—O1—C6 | 7.6 (4) | Mn1—N1—C1—C6 | 0.89 (10) |
| O3—Mn1—O1—C6 | 173.00 (7) | N1—C1—C2—C3 | −1.25 (14) |
| N1—Mn1—O1—C6 | −6.43 (7) | C6—C1—C2—C3 | −178.62 (9) |
| N3—Mn1—O1—C6 | −98.14 (8) | C1—C2—C3—C4 | 2.77 (16) |
| N2—Mn1—O1—C6 | 95.03 (8) | C2—C3—C4—C5 | −1.45 (15) |
| O1—Mn1—O3—C12 | −77.70 (7) | C1—N1—C5—C4 | 3.12 (14) |
| O5—Mn1—O3—C12 | 101.02 (7) | Mn1—N1—C5—C4 | 177.14 (6) |
| N1—Mn1—O3—C12 | −74.3 (2) | C3—C4—C5—N1 | −1.37 (14) |
| N3—Mn1—O3—C12 | 178.90 (7) | Mn1—O1—C6—O2 | −169.17 (9) |
| N2—Mn1—O3—C12 | 11.16 (7) | Mn1—O1—C6—C1 | 8.82 (11) |
| O1—Mn1—O5—C18 | −117.5 (3) | N1—C1—C6—O2 | 171.79 (10) |
| O3—Mn1—O5—C18 | 77.18 (7) | C2—C1—C6—O2 | −10.86 (16) |
| N1—Mn1—O5—C18 | −103.60 (7) | N1—C1—C6—O1 | −6.14 (13) |
| N3—Mn1—O5—C18 | −10.64 (7) | C2—C1—C6—O1 | 171.21 (9) |
| N2—Mn1—O5—C18 | 155.18 (7) | C11—N2—C7—C8 | 0.92 (14) |
| O1—Mn1—N1—C5 | −172.18 (8) | Mn1—N2—C7—C8 | −172.40 (7) |
| O5—Mn1—N1—C5 | 9.05 (8) | C11—N2—C7—C12 | −178.45 (9) |
| O3—Mn1—N1—C5 | −175.59 (15) | Mn1—N2—C7—C12 | 8.22 (9) |
| N3—Mn1—N1—C5 | −69.21 (8) | N2—C7—C8—C9 | −0.12 (15) |
| N2—Mn1—N1—C5 | 100.87 (8) | C12—C7—C8—C9 | 179.23 (10) |
| O1—Mn1—N1—C1 | 2.78 (6) | C7—C8—C9—C10 | −1.20 (18) |
| O5—Mn1—N1—C1 | −175.99 (6) | C8—C9—C10—C11 | 1.7 (2) |
| O3—Mn1—N1—C1 | −0.6 (2) | C7—N2—C11—C10 | −0.43 (16) |
| N3—Mn1—N1—C1 | 105.75 (6) | Mn1—N2—C11—C10 | 170.99 (9) |
| N2—Mn1—N1—C1 | −84.17 (6) | C9—C10—C11—N2 | −0.88 (19) |
| O1—Mn1—N2—C7 | 79.77 (6) | Mn1—O3—C12—O4 | 169.92 (9) |
| O5—Mn1—N2—C7 | −105.31 (6) | Mn1—O3—C12—C7 | −10.18 (11) |
| O3—Mn1—N2—C7 | −10.12 (6) | N2—C7—C12—O4 | 179.73 (10) |
| N1—Mn1—N2—C7 | 160.14 (6) | C8—C7—C12—O4 | 0.37 (15) |
| N3—Mn1—N2—C7 | −53.94 (12) | N2—C7—C12—O3 | −0.17 (12) |
| O1—Mn1—N2—C11 | −92.37 (10) | C8—C7—C12—O3 | −179.53 (9) |
| O5—Mn1—N2—C11 | 82.55 (10) | C17—N3—C13—C14 | −2.01 (13) |
| O3—Mn1—N2—C11 | 177.75 (10) | Mn1—N3—C13—C14 | 172.03 (7) |
| N1—Mn1—N2—C11 | −12.00 (10) | C17—N3—C13—C18 | 179.99 (9) |
| N3—Mn1—N2—C11 | 133.92 (11) | Mn1—N3—C13—C18 | −5.97 (9) |
| O1—Mn1—N3—C17 | −3.24 (9) | N3—C13—C14—C15 | 1.79 (15) |
| O5—Mn1—N3—C17 | −178.24 (9) | C18—C13—C14—C15 | 179.62 (10) |
| O3—Mn1—N3—C17 | 86.14 (9) | C13—C14—C15—C16 | −1.45 (16) |
| N1—Mn1—N3—C17 | −84.66 (9) | C14—C15—C16—C17 | 1.36 (16) |
| N2—Mn1—N3—C17 | 128.77 (11) | C13—N3—C17—C16 | 1.95 (14) |
| O1—Mn1—N3—C13 | −176.36 (6) | Mn1—N3—C17—C16 | −170.52 (7) |
| O5—Mn1—N3—C13 | 8.65 (6) | C15—C16—C17—N3 | −1.62 (15) |
| O3—Mn1—N3—C13 | −86.97 (6) | Mn1—O5—C18—O6 | −170.13 (8) |
| N1—Mn1—N3—C13 | 102.22 (6) | Mn1—O5—C18—C13 | 10.79 (11) |
| N2—Mn1—N3—C13 | −44.34 (12) | N3—C13—C18—O6 | 179.00 (9) |
| C5—N1—C1—C2 | −1.80 (14) | C14—C13—C18—O6 | 1.07 (16) |
| Mn1—N1—C1—C2 | −176.69 (7) | N3—C13—C18—O5 | −1.93 (13) |
| C5—N1—C1—C6 | 175.78 (9) | C14—C13—C18—O5 | −179.86 (9) |
Hydrogen-bond geometry (Å, º) top
| D—H···A | D—H | H···A | D···A | D—H···A |
| O4—H4A···O7 | 0.85 | 2.09 | 2.7672 (19) | 136 |
| O7—H7A···O5i | 0.96 | 2.24 | 2.9473 (17) | 130 |
| Symmetry code: (i) x, −y, z+1/2. |
Experimental details
| Crystal data | |
| Chemical formula | [Mn(C6H4NO2)2(C6H5NO2)]·OH |
| Mr | 439.26 |
| Crystal system, space group | Monoclinic, C2/c |
| Temperature (K) | 293 |
| a, b, c (Å) | 30.523 (6), 8.4111 (17), 13.914 (3) |
| β (°) | 94.40 (3) |
| V (Å3) | 3561.6 (12) |
| Z | 8 |
| Radiation type | Mo Kα |
| µ (mm−1) | 0.79 |
| Crystal size (mm) | 0.16 × 0.10 × 0.08 |
| Data collection | |
| Diffractometer | KappaCCD diffractometer |
| Absorption correction | – |
| No. of measured, independent and observed [I > 2σ(I)] reflections | 6842, 4099, 3882 |
| Rint | 0.076 |
| (sin θ/λ)max (Å−1) | 0.650 |
| Refinement | |
| R[F2 > 2σ(F2)], wR(F2), S | 0.029, 0.067, 0.86 |
| No. of reflections | 4099 |
| No. of parameters | 263 |
| H-atom treatment | H-atom parameters constrained |
| Δρmax, Δρmin (e Å−3) | 0.88, −0.80 |
Computer programs: KappaCCD Server Software (Nonius, 1997), DENZO-SMN (Otwinowski & Minor, 1997), DENZO-SMN, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXL97.
Selected geometric parameters (Å, º) top
| Mn1—O1 | 1.9094 (8) | N3—C13 | 1.3427 (11) |
| Mn1—O5 | 1.9174 (7) | C1—C2 | 1.3674 (13) |
| Mn1—O3 | 1.9274 (9) | C1—C6 | 1.4427 (13) |
| Mn1—N1 | 2.1566 (10) | C2—C3 | 1.3895 (16) |
| Mn1—N3 | 2.2215 (8) | C3—C4 | 1.3364 (17) |
| Mn1—N2 | 2.2328 (9) | C4—C5 | 1.4139 (14) |
| O1—C6 | 1.3223 (13) | C7—C8 | 1.4075 (13) |
| O2—C6 | 1.2183 (12) | C7—C12 | 1.4455 (13) |
| O3—C12 | 1.3237 (12) | C8—C9 | 1.3518 (17) |
| O4—C12 | 1.2009 (12) | C9—C10 | 1.3801 (19) |
| O5—C18 | 1.3066 (11) | C10—C11 | 1.3818 (16) |
| O6—C18 | 1.2303 (13) | C13—C14 | 1.4074 (13) |
| N1—C5 | 1.2849 (12) | C13—C18 | 1.4453 (13) |
| N1—C1 | 1.3412 (12) | C14—C15 | 1.3687 (15) |
| N2—C7 | 1.3429 (12) | C15—C16 | 1.3867 (16) |
| N2—C11 | 1.3700 (13) | C16—C17 | 1.3652 (15) |
| N3—C17 | 1.3334 (12) | ||
| O1—Mn1—O5 | 174.91 (3) | C2—C1—C6 | 125.40 (9) |
| O1—Mn1—O3 | 89.64 (4) | C1—C2—C3 | 119.46 (10) |
| O5—Mn1—O3 | 95.28 (4) | C4—C3—C2 | 120.51 (9) |
| O1—Mn1—N1 | 80.79 (4) | C3—C4—C5 | 119.13 (9) |
| O5—Mn1—N1 | 94.27 (3) | N1—C5—C4 | 117.43 (9) |
| O3—Mn1—N1 | 170.41 (3) | O2—C6—O1 | 120.75 (10) |
| O1—Mn1—N3 | 103.39 (3) | O2—C6—C1 | 123.56 (10) |
| O5—Mn1—N3 | 78.04 (3) | O1—C6—C1 | 115.66 (8) |
| O3—Mn1—N3 | 88.97 (4) | N2—C7—C8 | 120.03 (9) |
| N1—Mn1—N3 | 93.77 (4) | N2—C7—C12 | 117.12 (8) |
| O1—Mn1—N2 | 88.81 (4) | C8—C7—C12 | 122.85 (8) |
| O5—Mn1—N2 | 90.96 (3) | C9—C8—C7 | 120.51 (10) |
| O3—Mn1—N2 | 77.96 (4) | C8—C9—C10 | 119.64 (10) |
| N1—Mn1—N2 | 101.12 (4) | C9—C10—C11 | 119.01 (11) |
| N3—Mn1—N2 | 162.14 (3) | N2—C11—C10 | 121.42 (10) |
| C6—O1—Mn1 | 117.54 (6) | O4—C12—O3 | 124.01 (10) |
| C12—O3—Mn1 | 119.83 (7) | O4—C12—C7 | 120.47 (9) |
| C18—O5—Mn1 | 119.68 (6) | O3—C12—C7 | 115.52 (8) |
| C5—N1—C1 | 126.54 (9) | N3—C13—C14 | 120.61 (8) |
| C5—N1—Mn1 | 125.50 (7) | N3—C13—C18 | 115.93 (8) |
| C1—N1—Mn1 | 107.74 (6) | C14—C13—C18 | 123.43 (8) |
| C7—N2—C11 | 119.37 (8) | C15—C14—C13 | 118.77 (9) |
| C7—N2—Mn1 | 108.02 (6) | C14—C15—C16 | 119.49 (9) |
| C11—N2—Mn1 | 132.18 (7) | C17—C16—C15 | 119.05 (10) |
| C17—N3—C13 | 119.84 (8) | N3—C17—C16 | 122.19 (10) |
| C17—N3—Mn1 | 131.30 (6) | O6—C18—O5 | 121.10 (9) |
| C13—N3—Mn1 | 108.52 (6) | O6—C18—C13 | 122.37 (9) |
| N1—C1—C2 | 116.85 (9) | O5—C18—C13 | 116.52 (8) |
| N1—C1—C6 | 117.70 (9) | ||
| O5—Mn1—O1—C6 | 7.6 (4) | Mn1—N1—C1—C6 | 0.89 (10) |
| O3—Mn1—O1—C6 | 173.00 (7) | N1—C1—C2—C3 | −1.25 (14) |
| N1—Mn1—O1—C6 | −6.43 (7) | C6—C1—C2—C3 | −178.62 (9) |
| N3—Mn1—O1—C6 | −98.14 (8) | C1—C2—C3—C4 | 2.77 (16) |
| N2—Mn1—O1—C6 | 95.03 (8) | C2—C3—C4—C5 | −1.45 (15) |
| O1—Mn1—O3—C12 | −77.70 (7) | C1—N1—C5—C4 | 3.12 (14) |
| O5—Mn1—O3—C12 | 101.02 (7) | Mn1—N1—C5—C4 | 177.14 (6) |
| N1—Mn1—O3—C12 | −74.3 (2) | C3—C4—C5—N1 | −1.37 (14) |
| N3—Mn1—O3—C12 | 178.90 (7) | Mn1—O1—C6—O2 | −169.17 (9) |
| N2—Mn1—O3—C12 | 11.16 (7) | Mn1—O1—C6—C1 | 8.82 (11) |
| O1—Mn1—O5—C18 | −117.5 (3) | N1—C1—C6—O2 | 171.79 (10) |
| O3—Mn1—O5—C18 | 77.18 (7) | C2—C1—C6—O2 | −10.86 (16) |
| N1—Mn1—O5—C18 | −103.60 (7) | N1—C1—C6—O1 | −6.14 (13) |
| N3—Mn1—O5—C18 | −10.64 (7) | C2—C1—C6—O1 | 171.21 (9) |
| N2—Mn1—O5—C18 | 155.18 (7) | C11—N2—C7—C8 | 0.92 (14) |
| O1—Mn1—N1—C5 | −172.18 (8) | Mn1—N2—C7—C8 | −172.40 (7) |
| O5—Mn1—N1—C5 | 9.05 (8) | C11—N2—C7—C12 | −178.45 (9) |
| O3—Mn1—N1—C5 | −175.59 (15) | Mn1—N2—C7—C12 | 8.22 (9) |
| N3—Mn1—N1—C5 | −69.21 (8) | N2—C7—C8—C9 | −0.12 (15) |
| N2—Mn1—N1—C5 | 100.87 (8) | C12—C7—C8—C9 | 179.23 (10) |
| O1—Mn1—N1—C1 | 2.78 (6) | C7—C8—C9—C10 | −1.20 (18) |
| O5—Mn1—N1—C1 | −175.99 (6) | C8—C9—C10—C11 | 1.7 (2) |
| O3—Mn1—N1—C1 | −0.6 (2) | C7—N2—C11—C10 | −0.43 (16) |
| N3—Mn1—N1—C1 | 105.75 (6) | Mn1—N2—C11—C10 | 170.99 (9) |
| N2—Mn1—N1—C1 | −84.17 (6) | C9—C10—C11—N2 | −0.88 (19) |
| O1—Mn1—N2—C7 | 79.77 (6) | Mn1—O3—C12—O4 | 169.92 (9) |
| O5—Mn1—N2—C7 | −105.31 (6) | Mn1—O3—C12—C7 | −10.18 (11) |
| O3—Mn1—N2—C7 | −10.12 (6) | N2—C7—C12—O4 | 179.73 (10) |
| N1—Mn1—N2—C7 | 160.14 (6) | C8—C7—C12—O4 | 0.37 (15) |
| N3—Mn1—N2—C7 | −53.94 (12) | N2—C7—C12—O3 | −0.17 (12) |
| O1—Mn1—N2—C11 | −92.37 (10) | C8—C7—C12—O3 | −179.53 (9) |
| O5—Mn1—N2—C11 | 82.55 (10) | C17—N3—C13—C14 | −2.01 (13) |
| O3—Mn1—N2—C11 | 177.75 (10) | Mn1—N3—C13—C14 | 172.03 (7) |
| N1—Mn1—N2—C11 | −12.00 (10) | C17—N3—C13—C18 | 179.99 (9) |
| N3—Mn1—N2—C11 | 133.92 (11) | Mn1—N3—C13—C18 | −5.97 (9) |
| O1—Mn1—N3—C17 | −3.24 (9) | N3—C13—C14—C15 | 1.79 (15) |
| O5—Mn1—N3—C17 | −178.24 (9) | C18—C13—C14—C15 | 179.62 (10) |
| O3—Mn1—N3—C17 | 86.14 (9) | C13—C14—C15—C16 | −1.45 (16) |
| N1—Mn1—N3—C17 | −84.66 (9) | C14—C15—C16—C17 | 1.36 (16) |
| N2—Mn1—N3—C17 | 128.77 (11) | C13—N3—C17—C16 | 1.95 (14) |
| O1—Mn1—N3—C13 | −176.36 (6) | Mn1—N3—C17—C16 | −170.52 (7) |
| O5—Mn1—N3—C13 | 8.65 (6) | C15—C16—C17—N3 | −1.62 (15) |
| O3—Mn1—N3—C13 | −86.97 (6) | Mn1—O5—C18—O6 | −170.13 (8) |
| N1—Mn1—N3—C13 | 102.22 (6) | Mn1—O5—C18—C13 | 10.79 (11) |
| N2—Mn1—N3—C13 | −44.34 (12) | N3—C13—C18—O6 | 179.00 (9) |
| C5—N1—C1—C2 | −1.80 (14) | C14—C13—C18—O6 | 1.07 (16) |
| Mn1—N1—C1—C2 | −176.69 (7) | N3—C13—C18—O5 | −1.93 (13) |
| C5—N1—C1—C6 | 175.78 (9) | C14—C13—C18—O5 | −179.86 (9) |
Hydrogen-bond geometry (Å, º) top
| D—H···A | D—H | H···A | D···A | D—H···A |
| O4—H4A···O7 | 0.85 | 2.09 | 2.7672 (19) | 136.1 |
| O7—H7A···O5i | 0.96 | 2.24 | 2.9473 (17) | 129.5 |
| Symmetry code: (i) x, −y, z+1/2. |
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The chemistry of manganese in various oxidation states with primarily carboxylate ligation is currently receiving much attention (Christou, 1989). These studies have been stimulated partly because manganese plays an essential and specific role in many redox-active metalloenzymes, including the photosynthetic Oxygen Evolving Complex superoxide dismutase, pseudocatalase and ribonucleotide reductase (Dexheimer et al., 1989; Wieghardt, 1989). We report here a new type of crystal structure, a new synthetic route and a different oxidation state for manganese from what has been observed before in this area (Figgis et al., 1978).
The title complex, (I), consists of a cation and a hydroxide ion. The Mn atom is coordinated by three N atoms and three O atoms from three pyridinecarboxylate ligands, and has a distorted octahedral geometry, with Mn—N distances ranging from 2.157 (1) to 2.233 (1) Å and Mn—O distances from 1.910 (1) to 1.927 (4) Å. One ligand is protonated as the acid form. This forms one of two independent hydrogen bonds (Table 1), to the anion.