Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270102013483/ob1071sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270102013483/ob1071Isup2.hkl |
CCDC reference: 195623
The title compound was synthesized using the method published by Will et al. (1990). Crystals suitable for X-ray diffraction were obtained by slow evaporation from a saturated dichoromethane-n-hexane solution. Distinct crystals, both prisms and plates, grew within 3 d. The former crystal form, (I), was used in this study.
H atoms were located in calculated positions and allowed to ride on the corresponding parent atoms, with C—H distances in the range 095–0.99 Å and N—H = 0.88 Å. Are these the correct constraints? The two imino H atoms are distributed with half occupancy over each of the four possible positions because of intramolecular tautomerization.
Data collection: SMART (Bruker, 2001); cell refinement: SMART; data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2001); software used to prepare material for publication: SHELXTL.
C32H34Br4N4 | F(000) = 788 |
Mr = 794.27 | Dx = 1.731 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 5386 reflections |
a = 13.6720 (8) Å | θ = 2.9–30.4° |
b = 8.0201 (5) Å | µ = 5.31 mm−1 |
c = 14.4687 (9) Å | T = 90 K |
β = 106.101 (1)° | Prism, purple |
V = 1524.27 (16) Å3 | 0.24 × 0.19 × 0.15 mm |
Z = 2 |
Make and model CCD area-detector diffractometer | 3111 independent reflections |
Radiation source: fine-focus sealed tube | 2751 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.028 |
Detector resolution: 8.366 pixels mm-1 | θmax = 26.4°, θmin = 1.6° |
ϕ and ω scans | h = −17→16 |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | k = −7→10 |
Tmin = 0.325, Tmax = 0.451 | l = −17→18 |
9484 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)] = 0.031 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.082 | H-atom parameters constrained |
S = 1.07 | w = 1/[σ2(Fo2) + (0.0494P)2 + 0.7118P] where P = (Fo2 + 2Fc2)/3 |
3111 reflections | (Δ/σ)max = 0.002 |
183 parameters | Δρmax = 1.34 e Å−3 |
0 restraints | Δρmin = −0.61 e Å−3 |
C32H34Br4N4 | V = 1524.27 (16) Å3 |
Mr = 794.27 | Z = 2 |
Monoclinic, P21/c | Mo Kα radiation |
a = 13.6720 (8) Å | µ = 5.31 mm−1 |
b = 8.0201 (5) Å | T = 90 K |
c = 14.4687 (9) Å | 0.24 × 0.19 × 0.15 mm |
β = 106.101 (1)° |
Make and model CCD area-detector diffractometer | 3111 independent reflections |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | 2751 reflections with I > 2σ(I) |
Tmin = 0.325, Tmax = 0.451 | Rint = 0.028 |
9484 measured reflections |
R[F2 > 2σ(F2)] = 0.031 | 0 restraints |
wR(F2) = 0.082 | H-atom parameters constrained |
S = 1.07 | Δρmax = 1.34 e Å−3 |
3111 reflections | Δρmin = −0.61 e Å−3 |
183 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 | Occ. (<1) | |
Br1 | 0.334097 (19) | −0.13390 (4) | 0.870019 (19) | 0.02008 (10) | |
Br2 | 0.392981 (19) | 0.19846 (4) | 1.017372 (19) | 0.02292 (11) | |
C1 | 0.02930 (19) | −0.0692 (3) | 0.79563 (17) | 0.0151 (5) | |
C2 | 0.1240 (2) | −0.1025 (3) | 0.77112 (19) | 0.0162 (5) | |
C3 | 0.19834 (19) | −0.0659 (3) | 0.85206 (18) | 0.0151 (5) | |
C4 | 0.15133 (19) | −0.0043 (3) | 0.92394 (18) | 0.0148 (5) | |
C5 | 0.19426 (19) | 0.0530 (3) | 1.01895 (18) | 0.0145 (5) | |
C6 | 0.29139 (19) | 0.1174 (3) | 1.07029 (19) | 0.0155 (5) | |
C7 | 0.2941 (2) | 0.1449 (3) | 1.16450 (18) | 0.0152 (5) | |
C8 | 0.19590 (19) | 0.1009 (3) | 1.17272 (18) | 0.0145 (5) | |
C9 | 0.1629 (2) | 0.1156 (3) | 1.25596 (19) | 0.0172 (6) | |
H9 | 0.2155 | 0.1377 | 1.3131 | 0.021* | |
C10 | 0.0667 (2) | 0.1035 (4) | 1.26876 (19) | 0.0179 (5) | |
H10 | 0.0648 | 0.1216 | 1.3331 | 0.021* | |
C11 | 0.1352 (2) | −0.1669 (3) | 0.67736 (18) | 0.0169 (5) | |
H11A | 0.0727 | −0.2281 | 0.6433 | 0.020* | |
H11B | 0.1930 | −0.2460 | 0.6900 | 0.020* | |
C12 | 0.1537 (2) | −0.0253 (4) | 0.6129 (2) | 0.0214 (6) | |
H12A | 0.0963 | 0.0544 | 0.6010 | 0.026* | |
H12B | 0.2165 | 0.0353 | 0.6470 | 0.026* | |
C13 | 0.1644 (2) | −0.0882 (4) | 0.5172 (2) | 0.0266 (7) | |
H13A | 0.2185 | −0.1723 | 0.5287 | 0.040* | |
H13B | 0.1817 | 0.0051 | 0.4809 | 0.040* | |
H13C | 0.1000 | −0.1381 | 0.4803 | 0.040* | |
C14 | 0.38107 (19) | 0.2160 (3) | 1.24189 (19) | 0.0176 (6) | |
H14A | 0.3535 | 0.2761 | 1.2889 | 0.021* | |
H14B | 0.4178 | 0.2980 | 1.2127 | 0.021* | |
C15 | 0.4559 (2) | 0.0849 (4) | 1.2946 (2) | 0.0338 (8) | |
H15A | 0.4758 | 0.0137 | 1.2469 | 0.041* | |
H15B | 0.4220 | 0.0129 | 1.3320 | 0.041* | |
C16 | 0.5515 (2) | 0.1602 (4) | 1.3626 (2) | 0.0289 (7) | |
H16A | 0.5895 | 0.2217 | 1.3252 | 0.043* | |
H16B | 0.5944 | 0.0708 | 1.3988 | 0.043* | |
H16C | 0.5322 | 0.2363 | 1.4075 | 0.043* | |
N1 | 0.04833 (16) | −0.0117 (3) | 0.88738 (15) | 0.0142 (4) | |
H1 | 0.0027 | 0.0155 | 0.9174 | 0.017* | 0.50 |
N2 | 0.13820 (16) | 0.0501 (3) | 1.08445 (15) | 0.0139 (4) | |
H2 | 0.0740 | 0.0197 | 1.0713 | 0.017* | 0.50 |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br1 | 0.01577 (15) | 0.02661 (18) | 0.01909 (16) | 0.00405 (10) | 0.00688 (11) | −0.00023 (10) |
Br2 | 0.01722 (16) | 0.0333 (2) | 0.01986 (16) | −0.00726 (11) | 0.00783 (11) | −0.00278 (11) |
C1 | 0.0176 (12) | 0.0177 (13) | 0.0110 (12) | −0.0010 (11) | 0.0056 (10) | 0.0018 (10) |
C2 | 0.0202 (13) | 0.0145 (13) | 0.0159 (13) | 0.0008 (11) | 0.0085 (10) | 0.0010 (10) |
C3 | 0.0142 (12) | 0.0166 (13) | 0.0160 (12) | 0.0023 (10) | 0.0067 (10) | 0.0015 (10) |
C4 | 0.0145 (12) | 0.0163 (13) | 0.0135 (12) | −0.0001 (10) | 0.0037 (10) | 0.0023 (10) |
C5 | 0.0159 (12) | 0.0140 (13) | 0.0144 (12) | 0.0023 (10) | 0.0053 (9) | 0.0019 (10) |
C6 | 0.0145 (12) | 0.0167 (13) | 0.0157 (13) | −0.0003 (10) | 0.0052 (10) | 0.0000 (10) |
C7 | 0.0152 (12) | 0.0140 (13) | 0.0153 (13) | 0.0016 (10) | 0.0022 (10) | 0.0010 (10) |
C8 | 0.0151 (12) | 0.0136 (13) | 0.0142 (12) | 0.0009 (10) | 0.0027 (10) | 0.0000 (10) |
C9 | 0.0176 (13) | 0.0201 (14) | 0.0121 (12) | −0.0004 (11) | 0.0011 (10) | −0.0011 (10) |
C10 | 0.0210 (13) | 0.0209 (14) | 0.0116 (12) | −0.0004 (11) | 0.0042 (10) | −0.0005 (10) |
C11 | 0.0181 (13) | 0.0183 (13) | 0.0151 (13) | −0.0017 (11) | 0.0061 (10) | −0.0032 (10) |
C12 | 0.0279 (14) | 0.0211 (15) | 0.0164 (13) | −0.0011 (12) | 0.0082 (11) | −0.0008 (11) |
C13 | 0.0322 (16) | 0.0330 (17) | 0.0156 (14) | −0.0032 (14) | 0.0084 (12) | −0.0018 (12) |
C14 | 0.0147 (12) | 0.0205 (14) | 0.0162 (13) | −0.0001 (11) | 0.0020 (10) | −0.0030 (11) |
C15 | 0.0255 (15) | 0.0266 (17) | 0.0360 (18) | 0.0020 (14) | −0.0137 (13) | −0.0005 (14) |
C16 | 0.0193 (14) | 0.0371 (18) | 0.0235 (15) | 0.0023 (13) | −0.0057 (12) | −0.0016 (13) |
N1 | 0.0137 (10) | 0.0173 (11) | 0.0126 (10) | 0.0008 (9) | 0.0050 (8) | −0.0008 (8) |
N2 | 0.0157 (10) | 0.0159 (11) | 0.0100 (10) | 0.0014 (9) | 0.0033 (8) | 0.0000 (8) |
Br1—C3 | 1.882 (2) | C11—C12 | 1.534 (4) |
Br2—C6 | 1.878 (3) | C11—H11A | 0.9900 |
C1—N1 | 1.360 (3) | C11—H11B | 0.9900 |
C1—C10i | 1.410 (4) | C12—C13 | 1.519 (4) |
C1—C2 | 1.458 (4) | C12—H12A | 0.9900 |
C2—C3 | 1.353 (4) | C12—H12B | 0.9900 |
C2—C11 | 1.499 (4) | C13—H13A | 0.9800 |
C3—C4 | 1.452 (3) | C13—H13B | 0.9800 |
C4—N1 | 1.361 (3) | C13—H13C | 0.9800 |
C4—C5 | 1.413 (4) | C14—C15 | 1.517 (4) |
C5—N2 | 1.374 (3) | C14—H14A | 0.9900 |
C5—C6 | 1.426 (4) | C14—H14B | 0.9900 |
C6—C7 | 1.371 (4) | C15—C16 | 1.526 (4) |
C7—C8 | 1.425 (4) | C15—H15A | 0.9900 |
C7—C14 | 1.501 (4) | C15—H15B | 0.9900 |
C8—N2 | 1.364 (3) | C16—H16A | 0.9800 |
C8—C9 | 1.404 (4) | C16—H16B | 0.9800 |
C9—C10 | 1.382 (4) | C16—H16C | 0.9800 |
C9—H9 | 0.9500 | N1—H1 | 0.8800 |
C10—C1i | 1.410 (4) | N2—H2 | 0.8800 |
C10—H10 | 0.9500 | ||
N1—C1—C10i | 127.0 (2) | C13—C12—C11 | 112.5 (2) |
N1—C1—C2 | 110.9 (2) | C13—C12—H12A | 109.1 |
C10i—C1—C2 | 122.0 (2) | C11—C12—H12A | 109.1 |
C3—C2—C1 | 104.7 (2) | C13—C12—H12B | 109.1 |
C3—C2—C11 | 128.1 (2) | C11—C12—H12B | 109.1 |
C1—C2—C11 | 127.2 (2) | H12A—C12—H12B | 107.8 |
C2—C3—C4 | 108.5 (2) | C12—C13—H13A | 109.5 |
C2—C3—Br1 | 122.1 (2) | C12—C13—H13B | 109.5 |
C4—C3—Br1 | 127.95 (19) | H13A—C13—H13B | 109.5 |
N1—C4—C5 | 119.9 (2) | C12—C13—H13C | 109.5 |
N1—C4—C3 | 108.8 (2) | H13A—C13—H13C | 109.5 |
C5—C4—C3 | 131.3 (2) | H13B—C13—H13C | 109.5 |
N2—C5—C4 | 120.3 (2) | C7—C14—C15 | 113.3 (2) |
N2—C5—C6 | 105.3 (2) | C7—C14—H14A | 108.9 |
C4—C5—C6 | 134.4 (2) | C15—C14—H14A | 108.9 |
C7—C6—C5 | 109.9 (2) | C7—C14—H14B | 108.9 |
C7—C6—Br2 | 122.0 (2) | C15—C14—H14B | 108.9 |
C5—C6—Br2 | 126.86 (19) | H14A—C14—H14B | 107.7 |
C6—C7—C8 | 106.1 (2) | C14—C15—C16 | 112.8 (3) |
C6—C7—C14 | 126.9 (2) | C14—C15—H15A | 109.0 |
C8—C7—C14 | 127.0 (2) | C16—C15—H15A | 109.0 |
N2—C8—C9 | 126.0 (2) | C14—C15—H15B | 109.0 |
N2—C8—C7 | 108.0 (2) | C16—C15—H15B | 109.0 |
C9—C8—C7 | 125.9 (2) | H15A—C15—H15B | 107.8 |
C10—C9—C8 | 130.8 (2) | C15—C16—H16A | 109.5 |
C10—C9—H9 | 114.6 | C15—C16—H16B | 109.5 |
C8—C9—H9 | 114.6 | H16A—C16—H16B | 109.5 |
C9—C10—C1i | 132.2 (3) | C15—C16—H16C | 109.5 |
C9—C10—H10 | 113.9 | H16A—C16—H16C | 109.5 |
C1i—C10—H10 | 113.9 | H16B—C16—H16C | 109.5 |
C2—C11—C12 | 111.8 (2) | C1—N1—C4 | 106.9 (2) |
C2—C11—H11A | 109.3 | C1—N1—H1 | 126.5 |
C12—C11—H11A | 109.3 | C4—N1—H1 | 126.5 |
C2—C11—H11B | 109.3 | C8—N2—C5 | 110.6 (2) |
C12—C11—H11B | 109.3 | C8—N2—H2 | 124.7 |
H11A—C11—H11B | 107.9 | C5—N2—H2 | 124.7 |
Symmetry code: (i) −x, −y, −z+2. |
Experimental details
Crystal data | |
Chemical formula | C32H34Br4N4 |
Mr | 794.27 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 90 |
a, b, c (Å) | 13.6720 (8), 8.0201 (5), 14.4687 (9) |
β (°) | 106.101 (1) |
V (Å3) | 1524.27 (16) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 5.31 |
Crystal size (mm) | 0.24 × 0.19 × 0.15 |
Data collection | |
Diffractometer | Make and model CCD area-detector diffractometer |
Absorption correction | Empirical (using intensity measurements) (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.325, 0.451 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9484, 3111, 2751 |
Rint | 0.028 |
(sin θ/λ)max (Å−1) | 0.625 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.031, 0.082, 1.07 |
No. of reflections | 3111 |
No. of parameters | 183 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.34, −0.61 |
Computer programs: SMART (Bruker, 2001), SMART, SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2001), SHELXTL.
Br1—C3 | 1.882 (2) | C8—C9 | 1.404 (4) |
Br2—C6 | 1.878 (3) | C9—C10 | 1.382 (4) |
C4—C5 | 1.413 (4) | ||
C4—C3—Br1 | 127.95 (19) | C5—C6—Br2 | 126.86 (19) |
N1—C4—C5 | 119.9 (2) | C6—C7—C8 | 106.1 (2) |
C5—C4—C3 | 131.3 (2) | N2—C8—C9 | 126.0 (2) |
N2—C5—C4 | 120.3 (2) | C9—C8—C7 | 125.9 (2) |
C4—C5—C6 | 134.4 (2) | C10—C9—C8 | 130.8 (2) |
Porphycene is one of the unique isomers of porphyrin first synthesized in 1986 (Vogel et al., 1986). This isomer exhibits geometries of the N4 coordination site which deviate noticeably from the ideal square shape of the porphyrin core, and its unique structural properties result in interesting catalysis in the complexes it forms with metals (Hayashi et al., 2001). We have found that the title porphycene, (I), exists in the solid state in two crystalline forms, namely prisms and plates, with distinct structures. The triclinic plate form has a rectangular N4 coordination site, enlarged in the bromo-substituted direction (Will et al., 1990). The monoclinic prismatic form is discussed in detail here. \sch
The molecular structure of (I) and the atom-numbering scheme are shown in Fig. 1. The monoclinic form, (I), is a more warped structure than the triclinic form, which has an almost planar structure caused by π···π stacking between the aromatic rings; the closest distance between rings is about 3.2 Å (Will et al., 1990).
The angle between adjacent pyrrole planes is 21.8 (1)° for (I), but only 6.6 (5)° for the triclinic structure. The maximum shift of the 24 peripheral atoms from the least-squares plane of the C20N4 porphycene core is 0.309 (2) Å For which atom?. The shape of the N4 central cavity is rectangular, enlarged in the direction of the methine-bridge C atoms, with N1···N2 (-x, -y, 2 - z) and N1···N2 distances of 2.709 (3) and 2.818 (3) Å, respectively. This shape is different from that of the triclinic form, in which the core is lengthened vertically (Will et al., 1990).
The macrocycle of (I) chelates with various transition metal ions, such as Co2+, Cu2+ and Ni2+, to form divalent metal complexes in moderate yield. Metalloporphyrins containing halogenated substitutents at the pyrrole ring exhibit a high efficiency for catalysis in the oxidation of organic substrates, due to saddling of the macrocyclic structure and a large positive shift in the central metal redox couple (Grinstaff et al., 1994). Similarly, the CoIII/CoII redox couple for the cobalt complex of (I) is observed at -0.14 V versus Ag/AgCl in pyridine, with a considerable positive shift due to the tetrabromo substituents; the value is -0.35 V versus Ag/AgCl for the un-substituted analogue (Reference?). Studies of the catalytic properties of various metal complexes with bromo-subsutituted porphycene are currently in progress in our laboratory.