In the title compound, [Mn(C
8H
7O
2)
2(C
12H
9N
3)], the manganese(II) centre is surrounded by three bidentate chelating ligands, namely, one 2-(2-pyridyl)benzimidazole ligand [Mn-N = 2.1954 (13) and 2.2595 (14) Å] and two
p-toluate ligands [Mn-O = 2.1559 (13)-2.2748 (14) Å]. It displays a severely distorted octahedral geometry, with
cis angles ranging from 58.87 (4) to 106.49 (5)°. Intermolecular C-H
O hydrogen bonds between the
p-toluate ligands link the molecules into infinite chains, and every two neighbouring chains are further coupled by N-H
O and C-H
O hydrogen bonds between the 2-(2-pyridyl)benzimidazole and
p-toluate ligands, leading to an infinite ribbon-like double-chain packing mode. The complete solid-state structure can be described as a three-dimensional supramolecular framework, stabilized by these intermolecular hydrogen-bonding interactions and possible C-H
interactions, as well as stacking interactions involving the 2-(2-pyridyl)benzimidazole ligands.
Supporting information
CCDC reference: 672430
2-(2-Pyridyl)benzimidazole (1 mmol) dissolved in ethanol (15 ml) was dropwise
added to an ethanol–DMF solution (30 ml, ca 1:1 v/v)
containing manganese p-toluate tetrahydrate (1 mmol), with continuous
stirring. The mixture was refluxed for 1 h and then filtered. The yellow
filtrate was allowed to stand undisturbed for several weeks at room
temperature, during which time yellow crystals of (I) suitable for X-ray
diffraction analysis were deposited. Analysis calculated for
C28H23MnN3O4: C 64.62, H 4.45, N 8.07%; found C 64.47, H 4.55, N
8.11%. FT–IR (KBr, cm-1): 3066 (m), 2922(w), 1618 (s),
1587 (s), 1520 (vs), 1412 (vs), 1311 (m), 1299
(m), 1194 (m), 1058 (w), 980 (m), 863 (s),
787 (m), 774 (s), 746 (s), 622 (s), 544
(w), 486 (w).
H atoms on both phenyl/pyridyl rings and methyl groups were placed in calculated
positions, with C—H distances of 0.93 and 0.96 Å, respectively, and were
included in the final cycles of refinement as riding, with Uiso(H) =
1.2Ueq(C) and 1.5Ueq(C), respectively. The H atom on the
imidazole N atom was located from difference maps and refined isotropically.
Data collection: CrystalClear (Rigaku, 2000); cell refinement: CrystalClear (Rigaku, 2000); data reduction: CrystalClear (Rigaku, 2000); program(s) used to solve structure: SHELXTL (Sheldrick, 1997); program(s) used to refine structure: SHELXTL (Sheldrick, 1997); molecular graphics: SHELXTL (Sheldrick, 1997); software used to prepare material for publication: SHELXTL (Sheldrick, 1997) and PLATON (Spek, 2003).
[2-(2-Pyridyl)benzimidazole-
κ2N2,
N3]bis(
p-toluato-
κ2O,
O')manganese(II)
top
Crystal data top
[Mn(C8H7O2)2(C12H9N3)] | F(000) = 1076 |
Mr = 520.43 | Dx = 1.415 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 5667 reflections |
a = 7.582 (2) Å | θ = 2.2–27.5° |
b = 17.482 (5) Å | µ = 0.58 mm−1 |
c = 18.731 (5) Å | T = 295 K |
β = 100.368 (4)° | Prism, yellow |
V = 2442.3 (11) Å3 | 0.46 × 0.42 × 0.20 mm |
Z = 4 | |
Data collection top
Rigaku Mercury CCD Diffractometer | 5561 independent reflections |
Radiation source: fine-focus sealed tube | 4584 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.027 |
phi and ω scans | θmax = 27.5°, θmin = 2.2° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −9→9 |
Tmin = 0.760, Tmax = 0.890 | k = −22→22 |
18797 measured reflections | l = −24→20 |
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)] = 0.036 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.105 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.00 | w = 1/[σ2(Fo2) + (0.064P)2 + 0.2429P] where P = (Fo2 + 2Fc2)/3 |
5561 reflections | (Δ/σ)max = 0.001 |
331 parameters | Δρmax = 0.22 e Å−3 |
0 restraints | Δρmin = −0.30 e Å−3 |
Crystal data top
[Mn(C8H7O2)2(C12H9N3)] | V = 2442.3 (11) Å3 |
Mr = 520.43 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 7.582 (2) Å | µ = 0.58 mm−1 |
b = 17.482 (5) Å | T = 295 K |
c = 18.731 (5) Å | 0.46 × 0.42 × 0.20 mm |
β = 100.368 (4)° | |
Data collection top
Rigaku Mercury CCD Diffractometer | 5561 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 4584 reflections with I > 2σ(I) |
Tmin = 0.760, Tmax = 0.890 | Rint = 0.027 |
18797 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.036 | 0 restraints |
wR(F2) = 0.105 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.00 | Δρmax = 0.22 e Å−3 |
5561 reflections | Δρmin = −0.30 e Å−3 |
331 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 | 0.30440 (3) | 0.391974 (13) | 0.631563 (13) | 0.03934 (10) | |
O1 | 0.23328 (16) | 0.26835 (7) | 0.62196 (7) | 0.0531 (3) | |
O2 | 0.01969 (15) | 0.35321 (6) | 0.62093 (6) | 0.0421 (3) | |
O3 | 0.58797 (16) | 0.38591 (6) | 0.67383 (6) | 0.0441 (3) | |
O4 | 0.40767 (16) | 0.38786 (7) | 0.75329 (7) | 0.0512 (3) | |
N1 | 0.29988 (17) | 0.42932 (7) | 0.51934 (7) | 0.0396 (3) | |
N2 | 0.23004 (18) | 0.51722 (8) | 0.62917 (7) | 0.0420 (3) | |
N3 | 0.22728 (19) | 0.51832 (8) | 0.43451 (7) | 0.0443 (3) | |
H3B | 0.185 (3) | 0.5603 (12) | 0.4115 (11) | 0.067 (6)* | |
C1 | −0.0622 (2) | 0.22119 (8) | 0.62098 (7) | 0.0371 (3) | |
C2 | −0.0055 (2) | 0.14537 (9) | 0.62936 (8) | 0.0414 (4) | |
H2A | 0.1159 | 0.1337 | 0.6353 | 0.050* | |
C3 | −0.1308 (3) | 0.08734 (9) | 0.62883 (9) | 0.0477 (4) | |
H3A | −0.0920 | 0.0369 | 0.6346 | 0.057* | |
C4 | −0.3120 (3) | 0.10306 (9) | 0.61988 (9) | 0.0473 (4) | |
C5 | −0.3676 (2) | 0.17867 (10) | 0.61226 (10) | 0.0509 (4) | |
H5A | −0.4891 | 0.1903 | 0.6065 | 0.061* | |
C6 | −0.2434 (2) | 0.23713 (10) | 0.61314 (9) | 0.0463 (4) | |
H6A | −0.2824 | 0.2876 | 0.6084 | 0.056* | |
C7 | 0.0710 (2) | 0.28391 (9) | 0.62111 (8) | 0.0377 (3) | |
C8 | −0.4480 (3) | 0.03972 (12) | 0.61898 (12) | 0.0699 (6) | |
H8A | −0.5378 | 0.0553 | 0.6461 | 0.105* | |
H8B | −0.3890 | −0.0055 | 0.6405 | 0.105* | |
H8C | −0.5034 | 0.0290 | 0.5698 | 0.105* | |
C9 | 0.7228 (2) | 0.37799 (8) | 0.79847 (8) | 0.0369 (3) | |
C10 | 0.8933 (2) | 0.37288 (9) | 0.78208 (9) | 0.0428 (4) | |
H10A | 0.9077 | 0.3704 | 0.7339 | 0.051* | |
C11 | 1.0432 (2) | 0.37141 (10) | 0.83699 (9) | 0.0459 (4) | |
H11A | 1.1569 | 0.3680 | 0.8251 | 0.055* | |
C12 | 1.0254 (2) | 0.37493 (9) | 0.90913 (9) | 0.0445 (4) | |
C13 | 0.8537 (2) | 0.37857 (10) | 0.92542 (9) | 0.0469 (4) | |
H13A | 0.8394 | 0.3805 | 0.9737 | 0.056* | |
C14 | 0.7036 (2) | 0.37933 (9) | 0.87083 (8) | 0.0421 (4) | |
H14A | 0.5897 | 0.3807 | 0.8827 | 0.050* | |
C15 | 0.5632 (2) | 0.38360 (8) | 0.73887 (8) | 0.0383 (3) | |
C16 | 1.1882 (3) | 0.37569 (13) | 0.96872 (11) | 0.0668 (6) | |
H16A | 1.2947 | 0.3742 | 0.9477 | 0.100* | |
H16B | 1.1855 | 0.3319 | 0.9994 | 0.100* | |
H16C | 1.1881 | 0.4215 | 0.9970 | 0.100* | |
C17 | 0.3176 (2) | 0.39839 (9) | 0.45318 (9) | 0.0417 (4) | |
C18 | 0.3685 (3) | 0.32505 (11) | 0.43601 (10) | 0.0553 (4) | |
H18A | 0.3996 | 0.2880 | 0.4717 | 0.066* | |
C19 | 0.3709 (3) | 0.30942 (13) | 0.36400 (11) | 0.0643 (5) | |
H19A | 0.4036 | 0.2609 | 0.3508 | 0.077* | |
C20 | 0.3250 (3) | 0.36530 (13) | 0.31047 (11) | 0.0634 (5) | |
H20A | 0.3283 | 0.3528 | 0.2625 | 0.076* | |
C21 | 0.2752 (3) | 0.43798 (12) | 0.32643 (9) | 0.0568 (5) | |
H21A | 0.2452 | 0.4749 | 0.2905 | 0.068* | |
C22 | 0.2719 (2) | 0.45368 (10) | 0.39896 (9) | 0.0438 (4) | |
C23 | 0.24584 (19) | 0.50072 (9) | 0.50566 (8) | 0.0378 (3) | |
C24 | 0.2108 (2) | 0.55194 (9) | 0.56406 (8) | 0.0387 (3) | |
C25 | 0.1633 (3) | 0.62781 (10) | 0.55485 (10) | 0.0520 (4) | |
H25A | 0.1503 | 0.6505 | 0.5093 | 0.062* | |
C26 | 0.1351 (3) | 0.66971 (10) | 0.61452 (11) | 0.0582 (5) | |
H26A | 0.1023 | 0.7210 | 0.6094 | 0.070* | |
C27 | 0.1556 (3) | 0.63541 (11) | 0.68080 (11) | 0.0563 (5) | |
H27A | 0.1387 | 0.6627 | 0.7216 | 0.068* | |
C28 | 0.2021 (3) | 0.55922 (10) | 0.68577 (9) | 0.0526 (4) | |
H28A | 0.2149 | 0.5357 | 0.7309 | 0.063* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Mn1 | 0.03876 (16) | 0.04196 (15) | 0.03671 (15) | 0.00085 (10) | 0.00515 (10) | 0.00634 (9) |
O1 | 0.0395 (7) | 0.0473 (6) | 0.0740 (8) | 0.0020 (5) | 0.0142 (6) | 0.0015 (6) |
O2 | 0.0426 (6) | 0.0389 (6) | 0.0464 (6) | 0.0013 (5) | 0.0122 (5) | 0.0041 (5) |
O3 | 0.0409 (6) | 0.0564 (7) | 0.0347 (6) | 0.0028 (5) | 0.0061 (5) | 0.0019 (5) |
O4 | 0.0364 (7) | 0.0741 (8) | 0.0436 (7) | 0.0055 (5) | 0.0088 (5) | 0.0031 (6) |
N1 | 0.0375 (7) | 0.0444 (7) | 0.0371 (6) | 0.0001 (6) | 0.0066 (5) | 0.0055 (6) |
N2 | 0.0418 (7) | 0.0444 (7) | 0.0390 (7) | 0.0000 (6) | 0.0050 (5) | 0.0041 (6) |
N3 | 0.0484 (8) | 0.0439 (7) | 0.0382 (7) | −0.0069 (6) | 0.0008 (6) | 0.0084 (6) |
C1 | 0.0417 (8) | 0.0385 (7) | 0.0314 (7) | −0.0005 (6) | 0.0074 (6) | −0.0003 (6) |
C2 | 0.0417 (9) | 0.0433 (8) | 0.0388 (8) | 0.0048 (7) | 0.0059 (7) | 0.0024 (7) |
C3 | 0.0603 (11) | 0.0374 (8) | 0.0444 (9) | 0.0031 (8) | 0.0068 (8) | 0.0048 (7) |
C4 | 0.0523 (10) | 0.0458 (9) | 0.0418 (9) | −0.0088 (7) | 0.0033 (7) | 0.0036 (7) |
C5 | 0.0403 (9) | 0.0503 (9) | 0.0615 (11) | −0.0018 (8) | 0.0080 (8) | 0.0039 (8) |
C6 | 0.0433 (9) | 0.0408 (8) | 0.0558 (10) | 0.0038 (7) | 0.0115 (7) | 0.0030 (7) |
C7 | 0.0396 (8) | 0.0436 (8) | 0.0306 (7) | 0.0016 (6) | 0.0080 (6) | 0.0017 (6) |
C8 | 0.0665 (13) | 0.0597 (12) | 0.0783 (14) | −0.0189 (10) | −0.0005 (11) | 0.0112 (10) |
C9 | 0.0397 (8) | 0.0368 (7) | 0.0344 (7) | 0.0032 (6) | 0.0071 (6) | 0.0002 (6) |
C10 | 0.0421 (9) | 0.0534 (9) | 0.0341 (8) | 0.0008 (7) | 0.0101 (7) | 0.0003 (7) |
C11 | 0.0373 (9) | 0.0566 (9) | 0.0445 (9) | 0.0000 (7) | 0.0097 (7) | 0.0042 (7) |
C12 | 0.0446 (9) | 0.0454 (8) | 0.0419 (9) | −0.0028 (7) | 0.0034 (7) | 0.0043 (7) |
C13 | 0.0513 (10) | 0.0560 (9) | 0.0343 (8) | 0.0074 (8) | 0.0098 (7) | 0.0012 (7) |
C14 | 0.0405 (9) | 0.0496 (9) | 0.0380 (8) | 0.0084 (7) | 0.0123 (7) | 0.0025 (7) |
C15 | 0.0401 (9) | 0.0361 (7) | 0.0389 (8) | 0.0022 (6) | 0.0080 (6) | 0.0009 (6) |
C16 | 0.0513 (12) | 0.0947 (15) | 0.0497 (11) | −0.0034 (10) | −0.0035 (9) | 0.0086 (10) |
C17 | 0.0338 (8) | 0.0510 (9) | 0.0401 (8) | −0.0042 (7) | 0.0063 (6) | 0.0035 (7) |
C18 | 0.0569 (11) | 0.0571 (10) | 0.0521 (10) | 0.0090 (9) | 0.0107 (8) | 0.0013 (8) |
C19 | 0.0636 (13) | 0.0698 (12) | 0.0609 (12) | 0.0066 (10) | 0.0151 (10) | −0.0124 (10) |
C20 | 0.0633 (13) | 0.0851 (14) | 0.0442 (10) | −0.0108 (11) | 0.0159 (9) | −0.0101 (10) |
C21 | 0.0630 (12) | 0.0672 (12) | 0.0398 (9) | −0.0139 (9) | 0.0082 (8) | 0.0043 (8) |
C22 | 0.0394 (9) | 0.0519 (9) | 0.0396 (8) | −0.0108 (7) | 0.0055 (6) | 0.0030 (7) |
C23 | 0.0320 (8) | 0.0426 (8) | 0.0374 (7) | −0.0071 (6) | 0.0024 (6) | 0.0070 (6) |
C24 | 0.0307 (7) | 0.0412 (8) | 0.0429 (8) | −0.0059 (6) | 0.0027 (6) | 0.0029 (6) |
C25 | 0.0543 (11) | 0.0455 (9) | 0.0539 (10) | −0.0015 (8) | 0.0036 (8) | 0.0110 (8) |
C26 | 0.0606 (12) | 0.0426 (9) | 0.0707 (12) | 0.0024 (8) | 0.0096 (9) | −0.0027 (9) |
C27 | 0.0576 (12) | 0.0534 (10) | 0.0583 (11) | 0.0011 (9) | 0.0118 (9) | −0.0095 (9) |
C28 | 0.0597 (11) | 0.0544 (10) | 0.0440 (9) | 0.0029 (8) | 0.0102 (8) | −0.0007 (8) |
Geometric parameters (Å, º) top
Mn1—O3 | 2.1559 (13) | C9—C10 | 1.384 (2) |
Mn1—N1 | 2.1954 (13) | C9—C14 | 1.389 (2) |
Mn1—O1 | 2.2268 (13) | C9—C15 | 1.495 (2) |
Mn1—O2 | 2.2370 (13) | C10—C11 | 1.389 (2) |
Mn1—N2 | 2.2595 (14) | C10—H10A | 0.9300 |
Mn1—O4 | 2.2748 (14) | C11—C12 | 1.383 (2) |
Mn1—C15 | 2.5478 (17) | C11—H11A | 0.9300 |
Mn1—C7 | 2.5720 (16) | C12—C13 | 1.391 (3) |
O1—C7 | 1.2576 (19) | C12—C16 | 1.508 (2) |
O2—C7 | 1.2722 (18) | C13—C14 | 1.386 (2) |
O3—C15 | 1.2663 (19) | C13—H13A | 0.9300 |
O4—C15 | 1.258 (2) | C14—H14A | 0.9300 |
N1—C23 | 1.324 (2) | C16—H16A | 0.9600 |
N1—C17 | 1.381 (2) | C16—H16B | 0.9600 |
N2—C28 | 1.337 (2) | C16—H16C | 0.9600 |
N2—C24 | 1.347 (2) | C17—C18 | 1.393 (2) |
N3—C23 | 1.3501 (19) | C17—C22 | 1.400 (2) |
N3—C22 | 1.384 (2) | C18—C19 | 1.379 (3) |
N3—H3B | 0.88 (2) | C18—H18A | 0.9300 |
C1—C6 | 1.383 (2) | C19—C20 | 1.398 (3) |
C1—C2 | 1.394 (2) | C19—H19A | 0.9300 |
C1—C7 | 1.490 (2) | C20—C21 | 1.374 (3) |
C2—C3 | 1.389 (2) | C20—H20A | 0.9300 |
C2—H2A | 0.9300 | C21—C22 | 1.391 (2) |
C3—C4 | 1.381 (3) | C21—H21A | 0.9300 |
C3—H3A | 0.9300 | C23—C24 | 1.474 (2) |
C4—C5 | 1.387 (2) | C24—C25 | 1.377 (2) |
C4—C8 | 1.511 (2) | C25—C26 | 1.385 (3) |
C5—C6 | 1.388 (2) | C25—H25A | 0.9300 |
C5—H5A | 0.9300 | C26—C27 | 1.362 (3) |
C6—H6A | 0.9300 | C26—H26A | 0.9300 |
C8—H8A | 0.9600 | C27—C28 | 1.377 (3) |
C8—H8B | 0.9600 | C27—H27A | 0.9300 |
C8—H8C | 0.9600 | C28—H28A | 0.9300 |
| | | |
O3—Mn1—N1 | 102.06 (5) | C12—C11—C10 | 120.78 (16) |
O3—Mn1—O1 | 101.12 (4) | C12—C11—H11A | 119.6 |
N1—Mn1—O1 | 104.44 (5) | C10—C11—H11A | 119.6 |
O3—Mn1—O2 | 154.21 (4) | C11—C12—C13 | 118.44 (16) |
N1—Mn1—O2 | 98.99 (4) | C11—C12—C16 | 120.82 (17) |
O1—Mn1—O2 | 58.87 (4) | C13—C12—C16 | 120.74 (16) |
O3—Mn1—N2 | 106.49 (5) | C14—C13—C12 | 121.00 (15) |
N1—Mn1—N2 | 74.45 (5) | C14—C13—H13A | 119.5 |
O1—Mn1—N2 | 152.00 (5) | C12—C13—H13A | 119.5 |
O2—Mn1—N2 | 93.35 (5) | C13—C14—C9 | 120.21 (15) |
O3—Mn1—O4 | 59.32 (4) | C13—C14—H14A | 119.9 |
N1—Mn1—O4 | 155.83 (5) | C9—C14—H14A | 119.9 |
O1—Mn1—O4 | 94.87 (5) | O4—C15—O3 | 120.79 (15) |
O2—Mn1—O4 | 103.43 (4) | O4—C15—C9 | 120.51 (15) |
N2—Mn1—O4 | 95.17 (5) | O3—C15—C9 | 118.68 (14) |
C23—N1—C17 | 105.79 (13) | C12—C16—H16A | 109.5 |
C23—N1—Mn1 | 114.62 (10) | C12—C16—H16B | 109.5 |
C17—N1—Mn1 | 139.09 (11) | H16A—C16—H16B | 109.5 |
C28—N2—C24 | 117.63 (14) | C12—C16—H16C | 109.5 |
C28—N2—Mn1 | 126.21 (11) | H16A—C16—H16C | 109.5 |
C24—N2—Mn1 | 116.15 (10) | H16B—C16—H16C | 109.5 |
C23—N3—C22 | 107.32 (14) | N1—C17—C18 | 130.04 (15) |
C23—N3—H3B | 129.5 (13) | N1—C17—C22 | 109.23 (14) |
C22—N3—H3B | 122.9 (13) | C18—C17—C22 | 120.72 (16) |
C6—C1—C2 | 118.94 (15) | C19—C18—C17 | 117.45 (18) |
C6—C1—C7 | 120.77 (14) | C19—C18—H18A | 121.3 |
C2—C1—C7 | 120.28 (14) | C17—C18—H18A | 121.3 |
C3—C2—C1 | 119.81 (16) | C18—C19—C20 | 121.16 (19) |
C3—C2—H2A | 120.1 | C18—C19—H19A | 119.4 |
C1—C2—H2A | 120.1 | C20—C19—H19A | 119.4 |
C4—C3—C2 | 121.32 (15) | C21—C20—C19 | 122.19 (18) |
C4—C3—H3A | 119.3 | C21—C20—H20A | 118.9 |
C2—C3—H3A | 119.3 | C19—C20—H20A | 118.9 |
C3—C4—C5 | 118.66 (15) | C20—C21—C22 | 116.69 (17) |
C3—C4—C8 | 121.14 (16) | C20—C21—H21A | 121.7 |
C5—C4—C8 | 120.19 (18) | C22—C21—H21A | 121.7 |
C4—C5—C6 | 120.48 (17) | N3—C22—C21 | 132.84 (16) |
C4—C5—H5A | 119.8 | N3—C22—C17 | 105.36 (14) |
C6—C5—H5A | 119.8 | C21—C22—C17 | 121.79 (17) |
C1—C6—C5 | 120.78 (15) | N1—C23—N3 | 112.30 (14) |
C1—C6—H6A | 119.6 | N1—C23—C24 | 121.30 (13) |
C5—C6—H6A | 119.6 | N3—C23—C24 | 126.39 (14) |
O1—C7—O2 | 120.26 (14) | N2—C24—C25 | 122.06 (15) |
O1—C7—C1 | 120.15 (14) | N2—C24—C23 | 113.19 (13) |
O2—C7—C1 | 119.59 (14) | C25—C24—C23 | 124.75 (15) |
C4—C8—H8A | 109.5 | C24—C25—C26 | 118.91 (17) |
C4—C8—H8B | 109.5 | C24—C25—H25A | 120.5 |
H8A—C8—H8B | 109.5 | C26—C25—H25A | 120.5 |
C4—C8—H8C | 109.5 | C27—C26—C25 | 119.59 (17) |
H8A—C8—H8C | 109.5 | C27—C26—H26A | 120.2 |
H8B—C8—H8C | 109.5 | C25—C26—H26A | 120.2 |
C10—C9—C14 | 118.92 (15) | C26—C27—C28 | 118.25 (17) |
C10—C9—C15 | 120.11 (14) | C26—C27—H27A | 120.9 |
C14—C9—C15 | 120.96 (15) | C28—C27—H27A | 120.9 |
C9—C10—C11 | 120.62 (15) | N2—C28—C27 | 123.56 (17) |
C9—C10—H10A | 119.7 | N2—C28—H28A | 118.2 |
C11—C10—H10A | 119.7 | C27—C28—H28A | 118.2 |
| | | |
O3—Mn1—O1—C7 | 159.95 (9) | N1—Mn1—C7—O2 | −82.31 (9) |
N1—Mn1—O1—C7 | −94.36 (9) | O1—Mn1—C7—O2 | −175.73 (14) |
O2—Mn1—O1—C7 | −2.46 (8) | N2—Mn1—C7—O2 | −1.52 (10) |
N2—Mn1—O1—C7 | −10.39 (16) | O4—Mn1—C7—O2 | 100.88 (8) |
O4—Mn1—O1—C7 | 100.29 (9) | C15—Mn1—C7—O2 | 126.55 (8) |
C15—Mn1—O1—C7 | 129.83 (9) | C14—C9—C10—C11 | −1.9 (2) |
O3—Mn1—O2—C7 | −40.52 (14) | C15—C9—C10—C11 | 176.84 (14) |
N1—Mn1—O2—C7 | 103.94 (9) | C9—C10—C11—C12 | 0.1 (3) |
O1—Mn1—O2—C7 | 2.44 (8) | C10—C11—C12—C13 | 1.1 (2) |
N2—Mn1—O2—C7 | 178.72 (9) | C10—C11—C12—C16 | −178.18 (17) |
O4—Mn1—O2—C7 | −85.15 (9) | C11—C12—C13—C14 | −0.5 (3) |
C15—Mn1—O2—C7 | −71.07 (10) | C16—C12—C13—C14 | 178.79 (17) |
N1—Mn1—O3—C15 | 164.61 (9) | C12—C13—C14—C9 | −1.3 (3) |
O1—Mn1—O3—C15 | −87.81 (9) | C10—C9—C14—C13 | 2.5 (2) |
O2—Mn1—O3—C15 | −51.34 (14) | C15—C9—C14—C13 | −176.23 (14) |
N2—Mn1—O3—C15 | 87.47 (9) | Mn1—O4—C15—O3 | 2.18 (14) |
O4—Mn1—O3—C15 | 1.27 (8) | Mn1—O4—C15—C9 | −179.61 (12) |
C7—Mn1—O3—C15 | −75.49 (10) | Mn1—O3—C15—O4 | −2.30 (15) |
O3—Mn1—O4—C15 | −1.28 (8) | Mn1—O3—C15—C9 | 179.46 (12) |
N1—Mn1—O4—C15 | −44.50 (16) | C10—C9—C15—O4 | 179.63 (14) |
O1—Mn1—O4—C15 | 98.77 (9) | C14—C9—C15—O4 | −1.7 (2) |
O2—Mn1—O4—C15 | 157.90 (8) | C10—C9—C15—O3 | −2.1 (2) |
N2—Mn1—O4—C15 | −107.40 (9) | C14—C9—C15—O3 | 176.58 (14) |
C7—Mn1—O4—C15 | 127.94 (9) | O3—Mn1—C15—O4 | 177.78 (14) |
O3—Mn1—N1—C23 | −108.61 (11) | N1—Mn1—C15—O4 | 157.83 (9) |
O1—Mn1—N1—C23 | 146.39 (10) | O1—Mn1—C15—O4 | −84.76 (9) |
O2—Mn1—N1—C23 | 86.37 (11) | O2—Mn1—C15—O4 | −28.66 (11) |
N2—Mn1—N1—C23 | −4.62 (10) | N2—Mn1—C15—O4 | 77.28 (9) |
O4—Mn1—N1—C23 | −71.58 (16) | C7—Mn1—C15—O4 | −60.06 (10) |
C15—Mn1—N1—C23 | −98.63 (11) | N1—Mn1—C15—O3 | −19.95 (11) |
C7—Mn1—N1—C23 | 116.13 (11) | O1—Mn1—C15—O3 | 97.46 (9) |
O3—Mn1—N1—C17 | 81.06 (16) | O2—Mn1—C15—O3 | 153.56 (8) |
O1—Mn1—N1—C17 | −23.93 (17) | N2—Mn1—C15—O3 | −100.50 (9) |
O2—Mn1—N1—C17 | −83.95 (16) | O4—Mn1—C15—O3 | −177.78 (14) |
N2—Mn1—N1—C17 | −174.94 (17) | C7—Mn1—C15—O3 | 122.16 (9) |
O4—Mn1—N1—C17 | 118.10 (17) | C23—N1—C17—C18 | −179.15 (18) |
C15—Mn1—N1—C17 | 91.04 (17) | Mn1—N1—C17—C18 | −8.3 (3) |
C7—Mn1—N1—C17 | −54.19 (17) | C23—N1—C17—C22 | −0.16 (17) |
O3—Mn1—N2—C28 | −79.41 (15) | Mn1—N1—C17—C22 | 170.70 (12) |
N1—Mn1—N2—C28 | −177.68 (15) | N1—C17—C18—C19 | 178.60 (17) |
O1—Mn1—N2—C28 | 90.70 (17) | C22—C17—C18—C19 | −0.3 (3) |
O2—Mn1—N2—C28 | 83.91 (15) | C17—C18—C19—C20 | 0.4 (3) |
O4—Mn1—N2—C28 | −19.91 (15) | C18—C19—C20—C21 | −0.2 (3) |
C15—Mn1—N2—C28 | −48.80 (15) | C19—C20—C21—C22 | −0.2 (3) |
C7—Mn1—N2—C28 | 84.67 (15) | C23—N3—C22—C21 | 179.02 (18) |
O3—Mn1—N2—C24 | 101.25 (11) | O2i—N3—C22—C21 | 26.5 (3) |
N1—Mn1—N2—C24 | 2.98 (10) | C23—N3—C22—C17 | −0.28 (17) |
O1—Mn1—N2—C24 | −88.64 (15) | O2i—N3—C22—C17 | −152.80 (11) |
O2—Mn1—N2—C24 | −95.43 (11) | C20—C21—C22—N3 | −178.95 (18) |
O4—Mn1—N2—C24 | 160.75 (11) | C20—C21—C22—C17 | 0.3 (3) |
C15—Mn1—N2—C24 | 131.86 (11) | N1—C17—C22—N3 | 0.27 (18) |
C7—Mn1—N2—C24 | −94.67 (11) | C18—C17—C22—N3 | 179.37 (15) |
C6—C1—C2—C3 | 0.8 (2) | N1—C17—C22—C21 | −179.13 (15) |
C7—C1—C2—C3 | −179.70 (13) | C18—C17—C22—C21 | 0.0 (3) |
C1—C2—C3—C4 | 0.2 (2) | C17—N1—C23—N3 | −0.02 (17) |
C2—C3—C4—C5 | −0.8 (3) | Mn1—N1—C23—N3 | −173.45 (10) |
C2—C3—C4—C8 | 179.72 (16) | C17—N1—C23—C24 | 179.48 (13) |
C3—C4—C5—C6 | 0.4 (3) | Mn1—N1—C23—C24 | 6.05 (17) |
C8—C4—C5—C6 | 179.91 (17) | C22—N3—C23—N1 | 0.19 (18) |
C2—C1—C6—C5 | −1.2 (2) | O2i—N3—C23—N1 | 156.59 (10) |
C7—C1—C6—C5 | 179.32 (15) | C22—N3—C23—C24 | −179.28 (14) |
C4—C5—C6—C1 | 0.5 (3) | O2i—N3—C23—C24 | −22.87 (19) |
Mn1—O1—C7—O2 | 4.30 (14) | C28—N2—C24—C25 | −0.3 (2) |
Mn1—O1—C7—C1 | −175.14 (12) | Mn1—N2—C24—C25 | 179.06 (13) |
Mn1—O2—C7—O1 | −4.28 (14) | C28—N2—C24—C23 | 179.58 (14) |
Mn1—O2—C7—C1 | 175.16 (12) | Mn1—N2—C24—C23 | −1.02 (16) |
C6—C1—C7—O1 | −173.84 (14) | N1—C23—C24—N2 | −3.4 (2) |
C2—C1—C7—O1 | 6.6 (2) | N3—C23—C24—N2 | 176.04 (14) |
C6—C1—C7—O2 | 6.7 (2) | N1—C23—C24—C25 | 176.53 (15) |
C2—C1—C7—O2 | −172.79 (13) | N3—C23—C24—C25 | −4.0 (2) |
O3—Mn1—C7—O1 | −25.36 (11) | N2—C24—C25—C26 | 0.3 (3) |
N1—Mn1—C7—O1 | 93.42 (10) | C23—C24—C25—C26 | −179.66 (16) |
O2—Mn1—C7—O1 | 175.73 (14) | C24—C25—C26—C27 | 0.3 (3) |
N2—Mn1—C7—O1 | 174.21 (9) | C25—C26—C27—C28 | −0.8 (3) |
O4—Mn1—C7—O1 | −83.39 (9) | C24—N2—C28—C27 | −0.1 (3) |
C15—Mn1—C7—O1 | −57.72 (10) | Mn1—N2—C28—C27 | −179.48 (14) |
O3—Mn1—C7—O2 | 158.91 (8) | C26—C27—C28—N2 | 0.7 (3) |
Symmetry code: (i) −x, −y+1, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3B···O2i | 0.88 (2) | 2.18 (2) | 2.9882 (19) | 153.3 (18) |
C5—H5A···O1ii | 0.93 | 2.57 | 3.442 (2) | 157 |
C6—H6A···O3ii | 0.93 | 2.42 | 3.196 (2) | 141 |
C10—H10A···O2iii | 0.93 | 2.44 | 3.345 (2) | 166 |
C11—H11A···O4iii | 0.93 | 2.54 | 3.426 (2) | 158 |
C25—H25A···O2i | 0.93 | 2.55 | 3.351 (2) | 145 |
C13—H13A···Cg1iv | 0.93 | 2.90 | 3.794 (1) | 163 |
C26—H26A···Cg2v | 0.93 | 2.79 | 3.654 (3) | 155 |
C27—H27A···Cg3vi | 0.93 | 2.91 | 3.712 (1) | 145 |
Symmetry codes: (i) −x, −y+1, −z+1; (ii) x−1, y, z; (iii) x+1, y, z; (iv) x+1, −y−1/2, z−1/2; (v) −x+1, y−1/2, −z+1/2; (vi) −x, y−1/2, −z+1/2. |
Experimental details
Crystal data |
Chemical formula | [Mn(C8H7O2)2(C12H9N3)] |
Mr | 520.43 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 295 |
a, b, c (Å) | 7.582 (2), 17.482 (5), 18.731 (5) |
β (°) | 100.368 (4) |
V (Å3) | 2442.3 (11) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.58 |
Crystal size (mm) | 0.46 × 0.42 × 0.20 |
|
Data collection |
Diffractometer | Rigaku Mercury CCD Diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.760, 0.890 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 18797, 5561, 4584 |
Rint | 0.027 |
(sin θ/λ)max (Å−1) | 0.649 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.036, 0.105, 1.00 |
No. of reflections | 5561 |
No. of parameters | 331 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.22, −0.30 |
Selected geometric parameters (Å, º) topMn1—O3 | 2.1559 (13) | Mn1—O2 | 2.2370 (13) |
Mn1—N1 | 2.1954 (13) | Mn1—N2 | 2.2595 (14) |
Mn1—O1 | 2.2268 (13) | Mn1—O4 | 2.2748 (14) |
| | | |
O3—Mn1—N1 | 102.06 (5) | O1—Mn1—N2 | 152.00 (5) |
O3—Mn1—O1 | 101.12 (4) | O2—Mn1—N2 | 93.35 (5) |
N1—Mn1—O1 | 104.44 (5) | O3—Mn1—O4 | 59.32 (4) |
O3—Mn1—O2 | 154.21 (4) | N1—Mn1—O4 | 155.83 (5) |
N1—Mn1—O2 | 98.99 (4) | O1—Mn1—O4 | 94.87 (5) |
O1—Mn1—O2 | 58.87 (4) | O2—Mn1—O4 | 103.43 (4) |
O3—Mn1—N2 | 106.49 (5) | N2—Mn1—O4 | 95.17 (5) |
N1—Mn1—N2 | 74.45 (5) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3B···O2i | 0.88 (2) | 2.18 (2) | 2.9882 (19) | 153.3 (18) |
C5—H5A···O1ii | 0.93 | 2.57 | 3.442 (2) | 156.6 |
C6—H6A···O3ii | 0.93 | 2.42 | 3.196 (2) | 140.8 |
C10—H10A···O2iii | 0.93 | 2.44 | 3.345 (2) | 165.7 |
C11—H11A···O4iii | 0.93 | 2.54 | 3.426 (2) | 158.3 |
C25—H25A···O2i | 0.93 | 2.55 | 3.351 (2) | 145.2 |
C13—H13A···Cg1iv | 0.93 | 2.90 | 3.794 (1) | 163 |
C26—H26A···Cg2v | 0.93 | 2.79 | 3.654 (3) | 155 |
C27—H27A···Cg3vi | 0.93 | 2.91 | 3.712 (1) | 145 |
Symmetry codes: (i) −x, −y+1, −z+1; (ii) x−1, y, z; (iii) x+1, y, z; (iv) x+1, −y−1/2, z−1/2; (v) −x+1, y−1/2, −z+1/2; (vi) −x, y−1/2, −z+1/2. |
Low molecular weight manganese carboxylate species play an important role at the active sites of various redox-based enzymes (Weighardt, 1989). Mn superoxide dismutase, Mn peroxidase and Mn dioxygenase are each believed to contain a mononuclear Mn site, which participates in the redox changes of biological systems (Law et al., 1999). X-ray crystallography reveals that the peripheral ligation around the Mn centre in these enzymes includes both the carboxylate groups of various binding modes and the imidazole rings from various amino acid residues (Pecoraro & Butler, 1986), and it suggests that changes in the carboxylate binding mode may be important to the action of these enzymes (Rardin et al., 1991). Carboxylic acid- and imidazole-containing molecule are often employed to prepare simple models for the active sites of these enzymes. Understanding the structural effects of imidazole ligation to the Mn centre and the different carboxylate binding modes in these models will undoubtedly be helpful in gaining insight into the structural aspects that may influence the mechanism of action of the enzyme active sites. As far as we are aware, for the great majority of six-coordinate Mn complexes with carboxylate ligation, the number of carboxylate ligands acting as a chelating ligand usually remains low so as to avoid (or reduce) the strain from small-angle chelation (the chelation angle is usually less than 60°), and thus far reports of mononuclear complexes with more than two carboxylate ligands chelating an octahedral Mn centre have been rare (Jha & Mishra, 1986; Chai et al., 2004; Moubaraki et al., 2003). In the present paper, we report the structure of the title compound, (I). Compound (I) is a rare example of a mononuclear manganese complex with three chelating ligands, including a pair of chelating carboxylate ligands and a third chelating imidazole-containing ligand, simultaneously in the coordination environment. A mononuclear seven-coordinate MnII complex with a similar chelating ligand situation has recently been reported (Viossat et al., 2003).
Compound (I) consists of neutral [Mn(ptl)2(pybim)] monomers [ptl is p-toluate and pybim is 2-(2-pyridyl)benzimidazole] lying in a crystallographic general position. The MnII atom is coordinated to one bidentate chelating pybim ligand via atoms N1 and N2, and a pair of anionic bidentate chelating ptl ligands via atoms O1, O2, O3 and O4, as shown in Fig. 1. The complex displays a highly distorted octahedral geometry around the Mn centre (Table 1), in which three O atoms (O1, O2 and O3) of the tpl ligands and one pyridyl N atom (N2) of the pybim ligand define the equatorial plane, with atom Mn1 displaced from the least-squares O1–O3/N2 plane by 0.163 (2) Å. Imidazole atom N1 of the pybim ligand and atom O4 of the tpl ligand complete the distorted octahedron through coordination in the axial positions, with an N1—Mn1—O4 angle of 155.83 (5)°.
The Mn—N distances and N—Mn—N pybim chelate angle (Table 1) are comparable to those observed in the only reported pybim-containing MnII complex [Mn3(AcO)6(pybim)2] [2.197 (2) and 2.394 (2) Å, and 72.72 (6)°, respectively; Tangoulis et al., 1996], and the Mn–N(imidazole) distance in both compounds, perceptibly shorter than the Mn—N(pyridine) distance, indicates that the imidazole N of the pybim ligand is a stronger donor, since the phenyl group in ortho position enhances the electron density on this N atom. The Mn—O distances and O—Mn—O carboxylate chelate angles are as expected for MnII complexes with a similar coordination environment (Chai et al., 2004; Moubaraki et al., 2003; Viossat et al., 2003; Baumeister & Hartung 1997; Jha & Mishra, 1986).
The two chelate ring planes formed by the ptl ligands, O1/C7/O2/Mn1 and O3/C15/O4/Mn1, with a maximum out-of-plane deviation of 0.027 (1) Å for atom C7, are each almost coplanar with the respective attaching methylphenyl plane [C1–C6/C8 and C9–C14/C16, respectively], as indicated by the small dihedral angles of 7.9 (6) and 3.4 (1)°, respectively, observed between them. The pybim ligand and the pybim chelate ring (N1/C23/C24/N2/Mn1) are each reasonably planar, with a maximum out-of-plane deviation of 0.096 (6) Å for atom H28A and a very small dihedral angle of 3.3 (1)° observed between them, suggesting that the pybim plane can be extended to involve atom Mn1. The three Mn1-containing mean planes, denoting P1 (C1–C8/O1/O2/Mn1), P2 (C9–C16/O3/O4/Mn1) and P3 (C17–C28/N1–N3/Mn1), with maximum out-of-plane deviations of 0.137 (6) Å for atom O1, 0.062 (1) Å for atom C10 and 0.085 (9) Å for atom Mn1, respectively, make dihedral angles (P1/P2, P3/P1 and P3/P2) of 87.2 (2), 83.8 (6) and 71.0 (4)°, respectively, showing a profile of the approximate perpendicularity to each other (Fig. 2).
The high-spin d5 Mn2+ ion usually favors the formation of the octahedral d2sp3 hybrid orbital, with cis angles regular and close to 90°. The chelating carboxylate group usually gives a narrow bite of less than 60° at the central Mn atom, thus resulting in the distortion of the coordination environment, and the higher the number of chelating carboxylate groups, the more distorted the central metal coordination sphere and the more unstable the complex in keeping an octahedral coordination. Thus far, mononuclear Mn complexes with more than two chelating carboxylates have therefore rarely been encountered. The strong distortion deviating from an ideal Mn octahedron in (I), with the cis angles subtended at the Mn atom ranging from 58.87 (4) to 106.49 (5)°, is obviously due to the triple narrow bite of the three chelating ligands. The title compound provides a rare example of six-coordinate Mn compounds with an added N,N'-chelating ligand besides two chelating carboxylate ligations, though several similar complexes are found to have two added monodentate ligands in a more regular octahedral Mn coordination (Jha & Mishra, 1986; Chai et al., 2004; Moubaraki et al., 2003). Two seven-coordinate complexes with a dinuclear or mononuclear Mn centre have also been previously reported to possess a similar chelating ligand set, in which the central Mn coordination environments are approximately described as distorted capped octahedra (Viossat et al., 2003; Baumeister & Hartung, 1997).
As listed in Table 2, one normal intermolecular N—H···O hydrogen bond and five nonclassic intermolecular C—H···O hydrogen bonds are observed in the crystal structure. Four phenyl C atoms (C5, C6, C10 and C11) in one molecule donate their H atoms to the carboxyl O atoms (O1, O3, O2 and O4, respectively) of two symmetry-related molecules to generate infinite one-dimensional chains with the pybim ligands located at the same side of the chain (Fig. 3). Two molecules of neighbouring chains are further coupled via the N3—H3B···O2i [symmetry code: (i) –x, –y + 1, –z + 1] hydrogen bond and a fifth weak C25—H25A···O2i hydrogen bond to generate a centrosymmetric dimer (Fig. 4), thus resulting in the formation of an infinite hydrogen-bonded ribbon-shaped double-chain network (Fig. 5). All the pybim ligands are located within the region of hydrogen-bonded ribbon network, in which a normal and a weaker π-π stacking interactions (3.4 Å; Bondi, 1964) between inversion-related pybim ligands are observed (Fig. 6), with perpendicular pybim plane separations of 3.498 (4) and 3.669 (7) Å, respectively.
Three C—H···π interactions, with H···Cg distances of less than 3 Å (Cg is the centroid of the π ring) and γ less than 30° (γ is the angle formed by the H···Cg vector and the normal to the π-ring plane) (Spek, 2003) are also observed within the structure of (I) (Table 2). These C—H···π interactions link the monomer to adjacent symmetry-related monomers (Fig. 7), and complete an overall three-dimensional supramolecular network (Fig. 8). These intermolecular interactions together with numerous other van der Waals contacts ensure the solid-state crystalline cohesion of the title compound.