Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270104012387/gg1221sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270104012387/gg1221Isup2.hkl |
CCDC reference: 245858
Crystals of the title compound were obtained by the direct reaction of pure powdered manganese with phthalonitrile (Kubiak & Janczak, 1993) under a stream of iodine vapour at 493 K.
H atoms were placed in calculated positions and treated as riding, with C—H distances of 0.93 Å and with Uiso(H) = 1.2Ueq(C). Please check added text.
Data collection: KM-4 CCD Software (Kuma, 2001); cell refinement: KM-4 CCD Software; data reduction: KM-4 CCD Software; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Sheldrick, 1990); software used to prepare material for publication: SHELXL97.
[Mn(C32H16MnN8)I]·0.5I2 | Z = 2 |
Mr = 821.27 | F(000) = 790 |
Triclinic, P1 | Dx = 1.931 Mg m−3 Dm = 1.93 Mg m−3 Dm measured by flotation in a mixture of CHBr3/CHCl3 |
Hall symbol: -P 1 | Melting point: loses the I2 molecule K |
a = 8.447 (2) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 13.051 (2) Å | Cell parameters from 2544 reflections |
c = 13.218 (2) Å | θ = 3.0–28° |
α = 102.11 (2)° | µ = 2.69 mm−1 |
β = 91.61 (2)° | T = 293 K |
γ = 96.81 (2)° | Parallelepiped, black-violet |
V = 1412.6 (5) Å3 | 0.24 × 0.21 × 0.17 mm |
Kuma KM-4 with CCD area-detector diffractometer | 6769 independent reflections |
Radiation source: fine-focus sealed tube | 4580 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.045 |
Detector resolution: 1024x1024 with blocks 2x2 pixels mm-1 | θmax = 28.0°, θmin = 3.0° |
ω scans | h = −8→11 |
Absorption correction: analytical face-indexed (SHELXTL; Sheldrick, 1990) | k = −17→16 |
Tmin = 0.563, Tmax = 0.656 | l = −17→17 |
16124 measured reflections |
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)] = 0.056 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.079 | H-atom parameters constrained |
S = 1.00 | w = 1/[σ2(Fo2) + (0.0162P)2] where P = (Fo2 + 2Fc2)/3 |
6769 reflections | (Δ/σ)max < 0.001 |
388 parameters | Δρmax = 0.82 e Å−3 |
0 restraints | Δρmin = −1.07 e Å−3 |
[Mn(C32H16MnN8)I]·0.5I2 | γ = 96.81 (2)° |
Mr = 821.27 | V = 1412.6 (5) Å3 |
Triclinic, P1 | Z = 2 |
a = 8.447 (2) Å | Mo Kα radiation |
b = 13.051 (2) Å | µ = 2.69 mm−1 |
c = 13.218 (2) Å | T = 293 K |
α = 102.11 (2)° | 0.24 × 0.21 × 0.17 mm |
β = 91.61 (2)° |
Kuma KM-4 with CCD area-detector diffractometer | 6769 independent reflections |
Absorption correction: analytical face-indexed (SHELXTL; Sheldrick, 1990) | 4580 reflections with I > 2σ(I) |
Tmin = 0.563, Tmax = 0.656 | Rint = 0.045 |
16124 measured reflections |
R[F2 > 2σ(F2)] = 0.056 | 0 restraints |
wR(F2) = 0.079 | H-atom parameters constrained |
S = 1.00 | Δρmax = 0.82 e Å−3 |
6769 reflections | Δρmin = −1.07 e Å−3 |
388 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
I1 | 0.07453 (5) | 0.19823 (3) | 0.85243 (3) | 0.05760 (14) | |
Mn1 | 0.34004 (10) | 0.33739 (6) | 0.84499 (6) | 0.0442 (2) | |
I2 | 0.02352 (6) | 0.05696 (4) | 0.60189 (4) | 0.1008 (2) | |
N1 | 0.4907 (5) | 0.2497 (3) | 0.8913 (3) | 0.0432 (12) | |
N2 | 0.4788 (5) | 0.3026 (3) | 1.0777 (3) | 0.0476 (13) | |
N3 | 0.3392 (5) | 0.4156 (3) | 0.9896 (3) | 0.0430 (12) | |
N4 | 0.1817 (5) | 0.5554 (3) | 0.9678 (3) | 0.0481 (13) | |
N5 | 0.2406 (5) | 0.4512 (3) | 0.8013 (3) | 0.0428 (12) | |
N6 | 0.2595 (5) | 0.4001 (3) | 0.6138 (3) | 0.0492 (13) | |
N7 | 0.3941 (5) | 0.2860 (3) | 0.7021 (3) | 0.0396 (12) | |
N8 | 0.5606 (5) | 0.1502 (3) | 0.7252 (4) | 0.0485 (13) | |
C1 | 0.5602 (6) | 0.1695 (4) | 0.8259 (5) | 0.0447 (15) | |
C2 | 0.6335 (6) | 0.1079 (4) | 0.8905 (5) | 0.0468 (16) | |
C3 | 0.7208 (7) | 0.0210 (4) | 0.8640 (5) | 0.0631 (19) | |
H3 | 0.7398 | −0.0076 | 0.7955 | 0.076* | |
C4 | 0.7757 (7) | −0.0186 (4) | 0.9440 (5) | 0.069 (2) | |
H4 | 0.8329 | −0.0762 | 0.9299 | 0.083* | |
C5 | 0.7484 (7) | 0.0244 (4) | 1.0441 (5) | 0.0604 (18) | |
H5 | 0.7858 | −0.0064 | 1.0960 | 0.072* | |
C6 | 0.6668 (7) | 0.1126 (4) | 1.0730 (5) | 0.0606 (18) | |
H6 | 0.6513 | 0.1413 | 1.1421 | 0.073* | |
C7 | 0.6131 (6) | 0.1530 (4) | 0.9969 (4) | 0.0417 (15) | |
C8 | 0.5189 (6) | 0.2415 (4) | 0.9921 (5) | 0.0425 (15) | |
C9 | 0.3984 (6) | 0.3848 (4) | 1.0771 (4) | 0.0423 (15) | |
C10 | 0.3558 (6) | 0.4535 (4) | 1.1685 (4) | 0.0451 (16) | |
C11 | 0.3862 (6) | 0.4564 (4) | 1.2763 (4) | 0.0423 (15) | |
H11 | 0.4482 | 0.4096 | 1.2974 | 0.051* | |
C12 | 0.3218 (7) | 0.5296 (4) | 1.3474 (5) | 0.0628 (19) | |
H12 | 0.3398 | 0.5322 | 1.4177 | 0.075* | |
C13 | 0.2260 (7) | 0.6032 (4) | 1.3153 (5) | 0.0627 (19) | |
H13 | 0.1819 | 0.6519 | 1.3648 | 0.075* | |
C14 | 0.1998 (6) | 0.6014 (4) | 1.2101 (4) | 0.0513 (17) | |
H14 | 0.1438 | 0.6510 | 1.1889 | 0.062* | |
C15 | 0.2575 (6) | 0.5258 (4) | 1.1398 (4) | 0.0470 (16) | |
C16 | 0.2560 (6) | 0.5018 (4) | 1.0238 (4) | 0.0424 (15) | |
C17 | 0.1805 (6) | 0.5339 (4) | 0.8638 (4) | 0.0448 (15) | |
C18 | 0.1175 (7) | 0.5986 (4) | 0.7991 (4) | 0.0528 (17) | |
C19 | 0.0449 (7) | 0.6931 (4) | 0.8234 (4) | 0.0575 (18) | |
H19 | 0.0252 | 0.7228 | 0.8915 | 0.069* | |
C20 | 0.0046 (7) | 0.7395 (4) | 0.7435 (5) | 0.068 (2) | |
H20 | −0.0398 | 0.8025 | 0.7578 | 0.081* | |
C21 | 0.0298 (7) | 0.6928 (4) | 0.6418 (5) | 0.0598 (18) | |
H21 | −0.0025 | 0.7246 | 0.5892 | 0.072* | |
C22 | 0.0994 (6) | 0.6029 (4) | 0.6154 (4) | 0.0525 (17) | |
H22 | 0.1197 | 0.5742 | 0.5472 | 0.063* | |
C23 | 0.1387 (6) | 0.5561 (4) | 0.6978 (4) | 0.0484 (16) | |
C24 | 0.2166 (7) | 0.4614 (4) | 0.6992 (5) | 0.0496 (16) | |
C25 | 0.3394 (7) | 0.3182 (4) | 0.6133 (4) | 0.0494 (16) | |
C26 | 0.3943 (7) | 0.2569 (4) | 0.5222 (5) | 0.0499 (16) | |
C27 | 0.3861 (7) | 0.2604 (4) | 0.4184 (5) | 0.066 (2) | |
H27 | 0.3269 | 0.3082 | 0.3966 | 0.080* | |
C28 | 0.4632 (8) | 0.1951 (4) | 0.3475 (5) | 0.070 (2) | |
H28 | 0.4532 | 0.1970 | 0.2777 | 0.084* | |
C29 | 0.5578 (8) | 0.1248 (4) | 0.3798 (5) | 0.076 (2) | |
H29 | 0.6093 | 0.0801 | 0.3309 | 0.092* | |
C30 | 0.5751 (7) | 0.1215 (4) | 0.4845 (5) | 0.0599 (18) | |
H30 | 0.6397 | 0.0759 | 0.5053 | 0.072* | |
C31 | 0.4954 (6) | 0.1867 (4) | 0.5574 (4) | 0.0457 (15) | |
C32 | 0.4893 (7) | 0.2043 (4) | 0.6664 (5) | 0.0503 (17) |
U11 | U22 | U33 | U12 | U13 | U23 | |
I1 | 0.0650 (3) | 0.0376 (2) | 0.0730 (3) | 0.0074 (2) | −0.0011 (2) | 0.0184 (2) |
Mn1 | 0.0584 (6) | 0.0310 (4) | 0.0468 (6) | 0.0129 (4) | −0.0014 (5) | 0.0122 (4) |
I2 | 0.0904 (4) | 0.1021 (4) | 0.0988 (5) | 0.0039 (3) | 0.0008 (3) | 0.0020 (3) |
N1 | 0.060 (3) | 0.025 (2) | 0.044 (3) | 0.008 (2) | 0.003 (3) | 0.004 (2) |
N2 | 0.062 (3) | 0.033 (2) | 0.054 (3) | 0.023 (2) | −0.001 (3) | 0.015 (2) |
N3 | 0.067 (3) | 0.027 (2) | 0.040 (3) | 0.018 (2) | 0.006 (2) | 0.011 (2) |
N4 | 0.066 (3) | 0.042 (2) | 0.044 (3) | 0.022 (2) | 0.008 (3) | 0.020 (2) |
N5 | 0.055 (3) | 0.028 (2) | 0.048 (3) | 0.015 (2) | 0.001 (3) | 0.009 (2) |
N6 | 0.058 (3) | 0.044 (3) | 0.051 (3) | 0.013 (2) | 0.002 (3) | 0.018 (2) |
N7 | 0.048 (3) | 0.033 (2) | 0.038 (3) | 0.008 (2) | 0.005 (2) | 0.008 (2) |
N8 | 0.064 (3) | 0.042 (3) | 0.042 (3) | 0.015 (2) | −0.005 (3) | 0.008 (2) |
C1 | 0.050 (4) | 0.037 (3) | 0.050 (4) | 0.002 (3) | 0.002 (3) | 0.017 (3) |
C2 | 0.046 (4) | 0.036 (3) | 0.063 (4) | 0.001 (3) | 0.009 (3) | 0.024 (3) |
C3 | 0.092 (5) | 0.053 (4) | 0.058 (4) | 0.033 (4) | 0.032 (4) | 0.026 (3) |
C4 | 0.096 (5) | 0.028 (3) | 0.090 (5) | 0.031 (3) | 0.009 (4) | 0.011 (3) |
C5 | 0.069 (4) | 0.052 (3) | 0.076 (5) | 0.031 (3) | 0.006 (4) | 0.036 (3) |
C6 | 0.083 (5) | 0.047 (3) | 0.057 (4) | 0.016 (3) | −0.011 (4) | 0.019 (3) |
C7 | 0.034 (3) | 0.042 (3) | 0.058 (4) | 0.017 (3) | 0.007 (3) | 0.023 (3) |
C8 | 0.050 (4) | 0.023 (3) | 0.055 (4) | 0.004 (3) | 0.000 (3) | 0.010 (3) |
C9 | 0.048 (4) | 0.036 (3) | 0.045 (4) | 0.002 (3) | 0.004 (3) | 0.017 (3) |
C10 | 0.044 (4) | 0.030 (3) | 0.059 (4) | 0.007 (3) | −0.003 (3) | 0.004 (3) |
C11 | 0.046 (4) | 0.040 (3) | 0.042 (4) | 0.002 (3) | 0.005 (3) | 0.014 (3) |
C12 | 0.071 (5) | 0.058 (3) | 0.064 (5) | 0.007 (3) | 0.010 (4) | 0.020 (3) |
C13 | 0.071 (5) | 0.047 (4) | 0.073 (5) | 0.031 (3) | 0.018 (4) | 0.006 (3) |
C14 | 0.066 (4) | 0.033 (3) | 0.059 (4) | 0.003 (3) | −0.006 (4) | 0.020 (3) |
C15 | 0.059 (4) | 0.030 (3) | 0.054 (4) | −0.001 (3) | −0.002 (3) | 0.017 (3) |
C16 | 0.053 (4) | 0.033 (3) | 0.046 (4) | 0.009 (3) | 0.000 (3) | 0.016 (3) |
C17 | 0.055 (4) | 0.035 (3) | 0.053 (4) | 0.015 (3) | 0.016 (3) | 0.022 (3) |
C18 | 0.065 (4) | 0.040 (3) | 0.056 (4) | 0.018 (3) | 0.004 (4) | 0.011 (3) |
C19 | 0.078 (5) | 0.053 (3) | 0.046 (4) | 0.015 (3) | 0.002 (4) | 0.017 (3) |
C20 | 0.076 (5) | 0.062 (3) | 0.070 (5) | 0.026 (3) | −0.011 (4) | 0.016 (3) |
C21 | 0.077 (5) | 0.054 (4) | 0.059 (4) | 0.024 (4) | 0.006 (4) | 0.027 (3) |
C22 | 0.066 (4) | 0.044 (3) | 0.058 (4) | 0.021 (3) | −0.002 (3) | 0.029 (3) |
C23 | 0.064 (4) | 0.035 (3) | 0.050 (4) | 0.017 (3) | 0.002 (3) | 0.014 (3) |
C24 | 0.059 (4) | 0.034 (3) | 0.061 (4) | 0.010 (3) | −0.001 (4) | 0.021 (3) |
C25 | 0.070 (4) | 0.028 (3) | 0.044 (4) | 0.023 (3) | −0.008 (3) | 0.008 (3) |
C26 | 0.061 (4) | 0.027 (3) | 0.054 (4) | 0.011 (3) | 0.008 (4) | 0.011 (3) |
C27 | 0.097 (5) | 0.046 (3) | 0.061 (5) | 0.022 (3) | 0.018 (4) | 0.010 (3) |
C28 | 0.099 (6) | 0.059 (4) | 0.051 (4) | 0.003 (4) | 0.002 (4) | 0.011 (3) |
C29 | 0.098 (6) | 0.057 (4) | 0.074 (5) | 0.023 (4) | 0.003 (5) | 0.004 (4) |
C30 | 0.088 (5) | 0.049 (3) | 0.052 (4) | 0.026 (3) | 0.013 (4) | 0.020 (3) |
C31 | 0.049 (4) | 0.043 (3) | 0.049 (4) | 0.005 (3) | 0.014 (3) | 0.017 (3) |
C32 | 0.061 (4) | 0.037 (3) | 0.056 (4) | 0.005 (3) | −0.003 (4) | 0.016 (3) |
I1—Mn1 | 2.7312 (11) | C10—C15 | 1.429 (6) |
Mn1—N7 | 1.953 (4) | C10—C11 | 1.434 (7) |
Mn1—N5 | 1.969 (4) | C11—C12 | 1.366 (7) |
Mn1—N3 | 1.969 (4) | C11—H11 | 0.9300 |
Mn1—N1 | 1.974 (4) | C12—C13 | 1.447 (7) |
I2—I2i | 2.7827 (12) | C12—H12 | 0.9300 |
I1—I2 | 3.4238 (10) | C13—C14 | 1.396 (7) |
N1—C8 | 1.375 (6) | C13—H13 | 0.9300 |
N1—C1 | 1.408 (6) | C14—C15 | 1.353 (7) |
N2—C8 | 1.318 (6) | C14—H14 | 0.9300 |
N2—C9 | 1.337 (6) | C15—C16 | 1.499 (7) |
N3—C16 | 1.398 (6) | C17—C18 | 1.454 (7) |
N3—C9 | 1.401 (6) | C18—C23 | 1.363 (7) |
N4—C16 | 1.315 (6) | C18—C19 | 1.423 (7) |
N4—C17 | 1.343 (6) | C19—C20 | 1.376 (7) |
N5—C17 | 1.372 (6) | C19—H19 | 0.9300 |
N5—C24 | 1.395 (6) | C20—C21 | 1.388 (7) |
N6—C24 | 1.327 (6) | C20—H20 | 0.9300 |
N6—C25 | 1.329 (6) | C21—C22 | 1.359 (6) |
N7—C25 | 1.411 (6) | C21—H21 | 0.9300 |
N7—C32 | 1.421 (6) | C22—C23 | 1.406 (7) |
N8—C1 | 1.302 (6) | C22—H22 | 0.9300 |
N8—C32 | 1.331 (6) | C23—C24 | 1.470 (6) |
C1—C2 | 1.461 (7) | C25—C26 | 1.421 (7) |
C2—C3 | 1.414 (7) | C26—C27 | 1.382 (7) |
C2—C7 | 1.429 (7) | C26—C31 | 1.458 (7) |
C3—C4 | 1.364 (7) | C27—C28 | 1.363 (7) |
C3—H3 | 0.9300 | C27—H27 | 0.9300 |
C4—C5 | 1.362 (7) | C28—C29 | 1.407 (7) |
C4—H4 | 0.9300 | C28—H28 | 0.9300 |
C5—C6 | 1.402 (7) | C29—C30 | 1.398 (8) |
C5—H5 | 0.9300 | C29—H29 | 0.9300 |
C6—C7 | 1.323 (7) | C30—C31 | 1.390 (7) |
C6—H6 | 0.9300 | C30—H30 | 0.9300 |
C7—C8 | 1.489 (6) | C31—C32 | 1.414 (7) |
C9—C10 | 1.428 (7) | ||
N7—Mn1—N5 | 89.51 (17) | C13—C12—H12 | 119.4 |
N7—Mn1—N3 | 164.40 (17) | C14—C13—C12 | 120.1 (5) |
N5—Mn1—N3 | 88.61 (17) | C14—C13—H13 | 120.0 |
N7—Mn1—N1 | 89.30 (17) | C12—C13—H13 | 120.0 |
N5—Mn1—N1 | 165.03 (17) | C15—C14—C13 | 118.6 (5) |
N3—Mn1—N1 | 88.54 (17) | C15—C14—H14 | 120.7 |
N7—Mn1—I1 | 99.69 (12) | C13—C14—H14 | 120.7 |
N5—Mn1—I1 | 100.08 (12) | C14—C15—C10 | 122.8 (5) |
N3—Mn1—I1 | 95.89 (12) | C14—C15—C16 | 133.2 (5) |
N1—Mn1—I1 | 94.83 (12) | C10—C15—C16 | 103.8 (5) |
I1—I2—I2i | 178.97 (3) | N4—C16—N3 | 128.2 (5) |
C8—N1—C1 | 108.2 (4) | N4—C16—C15 | 122.2 (5) |
C8—N1—Mn1 | 125.4 (3) | N3—C16—C15 | 109.5 (4) |
C1—N1—Mn1 | 125.1 (4) | N4—C17—N5 | 127.0 (5) |
C8—N2—C9 | 122.7 (5) | N4—C17—C18 | 124.2 (5) |
C16—N3—C9 | 107.8 (4) | N5—C17—C18 | 108.7 (5) |
C16—N3—Mn1 | 125.3 (3) | C23—C18—C19 | 118.7 (5) |
C9—N3—Mn1 | 126.1 (3) | C23—C18—C17 | 109.2 (5) |
C16—N4—C17 | 122.2 (4) | C19—C18—C17 | 132.1 (5) |
C17—N5—C24 | 107.2 (4) | C20—C19—C18 | 118.3 (5) |
C17—N5—Mn1 | 127.2 (4) | C20—C19—H19 | 120.9 |
C24—N5—Mn1 | 125.6 (3) | C18—C19—H19 | 120.9 |
C24—N6—C25 | 124.0 (5) | C19—C20—C21 | 120.5 (5) |
C25—N7—C32 | 106.3 (4) | C19—C20—H20 | 119.8 |
C25—N7—Mn1 | 126.9 (3) | C21—C20—H20 | 119.8 |
C32—N7—Mn1 | 126.6 (4) | C22—C21—C20 | 123.0 (5) |
C1—N8—C32 | 124.0 (5) | C22—C21—H21 | 118.5 |
N8—C1—N1 | 127.6 (5) | C20—C21—H21 | 118.5 |
N8—C1—C2 | 124.1 (5) | C21—C22—C23 | 115.8 (5) |
N1—C1—C2 | 108.2 (5) | C21—C22—H22 | 122.1 |
C3—C2—C7 | 120.1 (5) | C23—C22—H22 | 122.1 |
C3—C2—C1 | 131.0 (5) | C18—C23—C22 | 123.7 (5) |
C7—C2—C1 | 108.8 (5) | C18—C23—C24 | 105.3 (5) |
C4—C3—C2 | 116.6 (5) | C22—C23—C24 | 131.0 (5) |
C4—C3—H3 | 121.7 | N6—C24—N5 | 127.7 (5) |
C2—C3—H3 | 121.7 | N6—C24—C23 | 122.7 (5) |
C5—C4—C3 | 121.3 (5) | N5—C24—C23 | 109.6 (5) |
C5—C4—H4 | 119.4 | N6—C25—N7 | 125.4 (5) |
C3—C4—H4 | 119.4 | N6—C25—C26 | 123.8 (5) |
C4—C5—C6 | 123.4 (6) | N7—C25—C26 | 110.6 (4) |
C4—C5—H5 | 118.3 | C27—C26—C25 | 134.3 (5) |
C6—C5—H5 | 118.3 | C27—C26—C31 | 119.2 (5) |
C7—C6—C5 | 116.4 (6) | C25—C26—C31 | 106.0 (5) |
C7—C6—H6 | 121.8 | C28—C27—C26 | 121.3 (6) |
C5—C6—H6 | 121.8 | C28—C27—H27 | 119.3 |
C6—C7—C2 | 122.0 (5) | C26—C27—H27 | 119.3 |
C6—C7—C8 | 134.2 (5) | C27—C28—C29 | 120.0 (6) |
C2—C7—C8 | 103.7 (5) | C27—C28—H28 | 120.0 |
N2—C8—N1 | 128.2 (5) | C29—C28—H28 | 120.0 |
N2—C8—C7 | 120.7 (5) | C30—C29—C28 | 120.7 (6) |
N1—C8—C7 | 111.1 (5) | C30—C29—H29 | 119.6 |
N2—C9—N3 | 126.5 (5) | C28—C29—H29 | 119.6 |
N2—C9—C10 | 124.1 (5) | C31—C30—C29 | 119.7 (6) |
N3—C9—C10 | 109.4 (4) | C31—C30—H30 | 120.1 |
C9—C10—C15 | 109.3 (5) | C29—C30—H30 | 120.1 |
C9—C10—C11 | 131.8 (5) | C30—C31—C32 | 134.1 (6) |
C15—C10—C11 | 118.8 (5) | C30—C31—C26 | 118.8 (5) |
C12—C11—C10 | 118.4 (5) | C32—C31—C26 | 107.1 (5) |
C12—C11—H11 | 120.8 | N8—C32—C31 | 124.2 (5) |
C10—C11—H11 | 120.8 | N8—C32—N7 | 125.9 (5) |
C11—C12—C13 | 121.2 (6) | C31—C32—N7 | 109.9 (5) |
C11—C12—H12 | 119.4 |
Symmetry code: (i) −x, −y, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [Mn(C32H16MnN8)I]·0.5I2 |
Mr | 821.27 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 8.447 (2), 13.051 (2), 13.218 (2) |
α, β, γ (°) | 102.11 (2), 91.61 (2), 96.81 (2) |
V (Å3) | 1412.6 (5) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 2.69 |
Crystal size (mm) | 0.24 × 0.21 × 0.17 |
Data collection | |
Diffractometer | Kuma KM-4 with CCD area-detector diffractometer |
Absorption correction | Analytical face-indexed (SHELXTL; Sheldrick, 1990) |
Tmin, Tmax | 0.563, 0.656 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 16124, 6769, 4580 |
Rint | 0.045 |
(sin θ/λ)max (Å−1) | 0.661 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.056, 0.079, 1.00 |
No. of reflections | 6769 |
No. of parameters | 388 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.82, −1.07 |
Computer programs: KM-4 CCD Software (Kuma, 2001), KM-4 CCD Software, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), SHELXTL (Sheldrick, 1990), SHELXL97.
I1—Mn1 | 2.7312 (11) | Mn1—N1 | 1.974 (4) |
Mn1—N7 | 1.953 (4) | I2—I2i | 2.7827 (12) |
Mn1—N5 | 1.969 (4) | I1—I2 | 3.4238 (10) |
Mn1—N3 | 1.969 (4) | ||
N7—Mn1—N5 | 89.51 (17) | N7—Mn1—I1 | 99.69 (12) |
N7—Mn1—N3 | 164.40 (17) | N5—Mn1—I1 | 100.08 (12) |
N5—Mn1—N3 | 88.61 (17) | N3—Mn1—I1 | 95.89 (12) |
N7—Mn1—N1 | 89.30 (17) | N1—Mn1—I1 | 94.83 (12) |
N5—Mn1—N1 | 165.03 (17) | I1—I2—I2i | 178.97 (3) |
N3—Mn1—N1 | 88.54 (17) |
Symmetry code: (i) −x, −y, −z+1. |
The present study continues our investigations into the synthesis, characterization and stereochemistry of metallophthalocyaninate complexes, which have been obtained under oxidation conditions of iodine vapour. The I atoms in most iodine-doped metallophthalocyanines form linear chains of symmetrical I3− ions, which are usually disordered in the crystal (Janczak & Idemori, 2001). The I atoms can also be bonded directly to the central metal, yielding mono- or diiodo-metallophthalocyaninate complexes (Janczak & Kubiak, 1999a; Schweiger et al., 1998). Additionally, it has been stated that, besides these disordered and symmetrical triiodide ions, I atoms can form ordered but unsymmetrical I3− ions (Janczak & Kubiak, 1999b; Janczak & Idemori, 2002a). Against this background, we present here the crystal structure of the title compound, (I). \sch
Refinement of the crystal structure of (I), supported by a Raman experiment, clearly shows that this iodo[phthalocyaninato(2-)]manganese(III) complex (Fig. 1) crystallizes as a dimer, with a neutral I2 molecule forming a bridge (Fig. 2). The Raman spectrum exhibits, in the frequency region of 100–500 cm−1, one expected band at \v ~180 cm−1, for an I2 molecule which interacts weakly with the axial I atoms of neighbouring MnPcI molecules, forming a dimeric structure, (MnPcI)2·I2. The absence of any observable peak at ~200 cm−1 eliminates pure iodine as an impurity (Anderson & Sun, 1970). The interaction of the I2 molecule with two I atoms axially bonded to the central Mn results in the population of molecular orbitals with I—I antibonding character, hence a slight increase in the I—I bond length, a decrease in bond order and constant stretching forces are observed (Cowie et al., 1979; Marks et al., 1976). This Raman spectrum is characteristic of complexes containing weakly interacting I2 molecules (Teitelbaum et al., 1978, 1980; Mizuno et al., 1981).
The structure of (I) consists of two iodo[phthalocyaninato(2-)manganese(III) molecules bridged by an I2 molecule to form a dimer. The Mn atom is five-coordinate, four of which are the N-isoindole atoms while the fifth is an axial I atom, resulting in a distorted square-pyramidal geometry for the metal. The Mn atom lies 0.262 (2) Å above the weighted mean plane defined by the four N-isoindole atoms of Pc macroring. The phthalocyaninate ring is not strictly planar but has a saucer shape, since the I atom axially bound to the central Mn atom leads to a deviation of the macroring from planarity.
The Pc(2-) macrorings in the dimer are related by an inversion centre located at the centre of the I—I bond of the bridged I2 molecule. The I—I bond length in the bridging I2 molecule provides evidence for the existence of neutral I2 molecules in the crystal that only weakly interact with the axial I atoms of the MnPcI molecules, since it is slightly longer than the I—I distance observed in pure iodine; in the solid-state, this is 2.715 (6) Å (van Bolhuis et al., 1967).
A search of the Cambridge Structural Database (Version?; Allen, 2002) shows that relatively few structures have been reported having a neutral I2 molecule coordinated between two I atoms, and only three are metallophthalocyanine structures: GePcI2·I2 (Janczak Razik & Kubiak, 1999) and CrPcI2·I2 (Janczak & Idemori, 2002b), in which the neutral I2 molecules develop polymeric structures, and (FePcI)2·I2 (Janczak Kubiak & Hahn, 1999), which is isostructural with the present Mn complex, (I).
The I—I distance of the bridging I2 molecule in (I) is comparable with those found in the GePcI2·I2 [2.770 (2) Å], CrPcI2·I2 [2.773 (1) Å] and (FePcI)2I2 [2.766 (2) Å] systems, three phthalocyaninate complexes with a bridging I2 molecule between the two I atoms. Besides these complexes, a new iodine-doped phthalocyaninate complex has been reported in which the neutral I2 molecules interact with unsymmetrical I3− ions, forming zigzag ···I3−···I2···I3−···I2··· chains (Janczak, 2003). An interesting example of an I2 molecule interacting with two I3− ions and forming I3−···I2···I3− aggregates is in the crystal structure of iodine-doped bis(phthalocyaninato)niobium(IV) (Donzello et al., 1998). A neutral I2 molecule acting as a bridge can also be found in the iodine-doped chloro[phthalocyaninato(2-)]iron(III) complex (FePcCl)2·I2 (Palmer et al., 1985). Additionally, the I2 molecule is present and `stapled' by two inter-ring C—C σ bonds in the (diphthalocyaninato)niobium(V) complex obtained in an IBr2 atmosphere. However, in that crystal, the I2 molecule interacts with the Br atom of the IBr2− ion via only one I atom, forming [I—I···Br—I—Br]− aggregates (Janczak & Kubiak, 2003).
The I···I distance between the neutral I2 molecule and the I atom coordinated to the central Mn atom in (I) is a little shorter than the intermolecular distance (~3.50 Å) in pure iodine in the solid-state (van Bolhuis et al., 1967). This value demonstrates the interaction between the I2 molecule and the two MnPcI molecules, which are related by an inversion centre to formi a dimeric structure. The I1···I2—I2i···I1i sequence is almost linear. The Mn···Mn distance in the dimer is 12.045 (2) Å, while the shortest Mn···Mn distance of 5.610 (2) Å is observed between back-to-back partially overlapping neighbouring iodo[phthalocyaninato(2-)]manganese(III) molecules.
The two distances of ~3.25 and ~3.45 Å indicate the presence of π–π interactions between the back-to-back and face-to-face oriented and partially overlapping phthalocyaninato(2-) units (Fig. 2), since these values are comparable with the van der Waals distance of ~3.4 Å for an aromatic ring system (Pauling, 1960). The Pc—Pc interactions overlapping with π–π interactions is a common feature in such structures (Nevin et al., 1987; Terekhov et al., 1996; Isago et al., 1997). The overlapping of π electrons between the Pc(2-) rings which form the conduction band (Ibers et al., 1982) is responsible for the observed relatively high electrical conductivity measured on a polycrystalline sample pressed into pellets (at room temperature, the conductivity is 3.3–4.8 × 10−4 Ω−1cm−1). Anisotropy of the conductivity and investigations of the magnetic and spectroscopic properties of (I) are in progress.