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The title compound [systematic name: 3,10,13,20-tetra­bromo-4,9,14,19-tetrapropyl-21,22,23,24-tetraazapentacyclo[16.2.1.12,5.18,11.112,15]tetracosa-2(22),3,5,7,9,11,13,15(24),16,18,20-undecaene], C32H34Br4N4, crystallizes in two distinct crystalline forms, viz. monoclinic prisms and triclinic plates, and the first of these is described here. The molecule of the prismatic form has a centre of symmetry and a more warped structure than that of the triclinic plate-like form. The shape of the central N4 cavity is rectanglar, enlarged in the direction of the methine-bridge C atoms, and the N...N distances are 2.713 (3) and 2.818 (3) Å.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270102013483/ob1071sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270102013483/ob1071Isup2.hkl
Contains datablock I

CCDC reference: 195623

Comment top

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.

Experimental top

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.

Refinement top

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.

Computing details top

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.

Figures top
[Figure 1] Fig. 1. A view of the molecular structure of (I), with the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii. Atoms labelled with a suffix A are at symmetry position (-x, -y, 2 - z). Is this correct?
[Figure 2] Fig. 2. A side view of (I).
3,6,13,16-tetrabromo-2,7,12,17-tetrapropylporphycene top
Crystal data top
C32H34Br4N4F(000) = 788
Mr = 794.27Dx = 1.731 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 5386 reflections
a = 13.6720 (8) Åθ = 2.9–30.4°
b = 8.0201 (5) ŵ = 5.31 mm1
c = 14.4687 (9) ÅT = 90 K
β = 106.101 (1)°Prism, purple
V = 1524.27 (16) Å30.24 × 0.19 × 0.15 mm
Z = 2
Data collection top
Make and model CCD area-detector
diffractometer
3111 independent reflections
Radiation source: fine-focus sealed tube2751 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.028
Detector resolution: 8.366 pixels mm-1θmax = 26.4°, θmin = 1.6°
ϕ and ω scansh = 1716
Absorption correction: empirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
k = 710
Tmin = 0.325, Tmax = 0.451l = 1718
9484 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.031Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.082H-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 parametersΔρmax = 1.34 e Å3
0 restraintsΔρmin = 0.61 e Å3
Crystal data top
C32H34Br4N4V = 1524.27 (16) Å3
Mr = 794.27Z = 2
Monoclinic, P21/cMo Kα radiation
a = 13.6720 (8) ŵ = 5.31 mm1
b = 8.0201 (5) ÅT = 90 K
c = 14.4687 (9) Å0.24 × 0.19 × 0.15 mm
β = 106.101 (1)°
Data collection top
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 = 0.451Rint = 0.028
9484 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0310 restraints
wR(F2) = 0.082H-atom parameters constrained
S = 1.07Δρmax = 1.34 e Å3
3111 reflectionsΔρmin = 0.61 e Å3
183 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
xyzUiso*/UeqOcc. (<1)
Br10.334097 (19)0.13390 (4)0.870019 (19)0.02008 (10)
Br20.392981 (19)0.19846 (4)1.017372 (19)0.02292 (11)
C10.02930 (19)0.0692 (3)0.79563 (17)0.0151 (5)
C20.1240 (2)0.1025 (3)0.77112 (19)0.0162 (5)
C30.19834 (19)0.0659 (3)0.85206 (18)0.0151 (5)
C40.15133 (19)0.0043 (3)0.92394 (18)0.0148 (5)
C50.19426 (19)0.0530 (3)1.01895 (18)0.0145 (5)
C60.29139 (19)0.1174 (3)1.07029 (19)0.0155 (5)
C70.2941 (2)0.1449 (3)1.16450 (18)0.0152 (5)
C80.19590 (19)0.1009 (3)1.17272 (18)0.0145 (5)
C90.1629 (2)0.1156 (3)1.25596 (19)0.0172 (6)
H90.21550.13771.31310.021*
C100.0667 (2)0.1035 (4)1.26876 (19)0.0179 (5)
H100.06480.12161.33310.021*
C110.1352 (2)0.1669 (3)0.67736 (18)0.0169 (5)
H11A0.07270.22810.64330.020*
H11B0.19300.24600.69000.020*
C120.1537 (2)0.0253 (4)0.6129 (2)0.0214 (6)
H12A0.09630.05440.60100.026*
H12B0.21650.03530.64700.026*
C130.1644 (2)0.0882 (4)0.5172 (2)0.0266 (7)
H13A0.21850.17230.52870.040*
H13B0.18170.00510.48090.040*
H13C0.10000.13810.48030.040*
C140.38107 (19)0.2160 (3)1.24189 (19)0.0176 (6)
H14A0.35350.27611.28890.021*
H14B0.41780.29801.21270.021*
C150.4559 (2)0.0849 (4)1.2946 (2)0.0338 (8)
H15A0.47580.01371.24690.041*
H15B0.42200.01291.33200.041*
C160.5515 (2)0.1602 (4)1.3626 (2)0.0289 (7)
H16A0.58950.22171.32520.043*
H16B0.59440.07081.39880.043*
H16C0.53220.23631.40750.043*
N10.04833 (16)0.0117 (3)0.88738 (15)0.0142 (4)
H10.00270.01550.91740.017*0.50
N20.13820 (16)0.0501 (3)1.08445 (15)0.0139 (4)
H20.07400.01971.07130.017*0.50
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br10.01577 (15)0.02661 (18)0.01909 (16)0.00405 (10)0.00688 (11)0.00023 (10)
Br20.01722 (16)0.0333 (2)0.01986 (16)0.00726 (11)0.00783 (11)0.00278 (11)
C10.0176 (12)0.0177 (13)0.0110 (12)0.0010 (11)0.0056 (10)0.0018 (10)
C20.0202 (13)0.0145 (13)0.0159 (13)0.0008 (11)0.0085 (10)0.0010 (10)
C30.0142 (12)0.0166 (13)0.0160 (12)0.0023 (10)0.0067 (10)0.0015 (10)
C40.0145 (12)0.0163 (13)0.0135 (12)0.0001 (10)0.0037 (10)0.0023 (10)
C50.0159 (12)0.0140 (13)0.0144 (12)0.0023 (10)0.0053 (9)0.0019 (10)
C60.0145 (12)0.0167 (13)0.0157 (13)0.0003 (10)0.0052 (10)0.0000 (10)
C70.0152 (12)0.0140 (13)0.0153 (13)0.0016 (10)0.0022 (10)0.0010 (10)
C80.0151 (12)0.0136 (13)0.0142 (12)0.0009 (10)0.0027 (10)0.0000 (10)
C90.0176 (13)0.0201 (14)0.0121 (12)0.0004 (11)0.0011 (10)0.0011 (10)
C100.0210 (13)0.0209 (14)0.0116 (12)0.0004 (11)0.0042 (10)0.0005 (10)
C110.0181 (13)0.0183 (13)0.0151 (13)0.0017 (11)0.0061 (10)0.0032 (10)
C120.0279 (14)0.0211 (15)0.0164 (13)0.0011 (12)0.0082 (11)0.0008 (11)
C130.0322 (16)0.0330 (17)0.0156 (14)0.0032 (14)0.0084 (12)0.0018 (12)
C140.0147 (12)0.0205 (14)0.0162 (13)0.0001 (11)0.0020 (10)0.0030 (11)
C150.0255 (15)0.0266 (17)0.0360 (18)0.0020 (14)0.0137 (13)0.0005 (14)
C160.0193 (14)0.0371 (18)0.0235 (15)0.0023 (13)0.0057 (12)0.0016 (13)
N10.0137 (10)0.0173 (11)0.0126 (10)0.0008 (9)0.0050 (8)0.0008 (8)
N20.0157 (10)0.0159 (11)0.0100 (10)0.0014 (9)0.0033 (8)0.0000 (8)
Geometric parameters (Å, º) top
Br1—C31.882 (2)C11—C121.534 (4)
Br2—C61.878 (3)C11—H11A0.9900
C1—N11.360 (3)C11—H11B0.9900
C1—C10i1.410 (4)C12—C131.519 (4)
C1—C21.458 (4)C12—H12A0.9900
C2—C31.353 (4)C12—H12B0.9900
C2—C111.499 (4)C13—H13A0.9800
C3—C41.452 (3)C13—H13B0.9800
C4—N11.361 (3)C13—H13C0.9800
C4—C51.413 (4)C14—C151.517 (4)
C5—N21.374 (3)C14—H14A0.9900
C5—C61.426 (4)C14—H14B0.9900
C6—C71.371 (4)C15—C161.526 (4)
C7—C81.425 (4)C15—H15A0.9900
C7—C141.501 (4)C15—H15B0.9900
C8—N21.364 (3)C16—H16A0.9800
C8—C91.404 (4)C16—H16B0.9800
C9—C101.382 (4)C16—H16C0.9800
C9—H90.9500N1—H10.8800
C10—C1i1.410 (4)N2—H20.8800
C10—H100.9500
N1—C1—C10i127.0 (2)C13—C12—C11112.5 (2)
N1—C1—C2110.9 (2)C13—C12—H12A109.1
C10i—C1—C2122.0 (2)C11—C12—H12A109.1
C3—C2—C1104.7 (2)C13—C12—H12B109.1
C3—C2—C11128.1 (2)C11—C12—H12B109.1
C1—C2—C11127.2 (2)H12A—C12—H12B107.8
C2—C3—C4108.5 (2)C12—C13—H13A109.5
C2—C3—Br1122.1 (2)C12—C13—H13B109.5
C4—C3—Br1127.95 (19)H13A—C13—H13B109.5
N1—C4—C5119.9 (2)C12—C13—H13C109.5
N1—C4—C3108.8 (2)H13A—C13—H13C109.5
C5—C4—C3131.3 (2)H13B—C13—H13C109.5
N2—C5—C4120.3 (2)C7—C14—C15113.3 (2)
N2—C5—C6105.3 (2)C7—C14—H14A108.9
C4—C5—C6134.4 (2)C15—C14—H14A108.9
C7—C6—C5109.9 (2)C7—C14—H14B108.9
C7—C6—Br2122.0 (2)C15—C14—H14B108.9
C5—C6—Br2126.86 (19)H14A—C14—H14B107.7
C6—C7—C8106.1 (2)C14—C15—C16112.8 (3)
C6—C7—C14126.9 (2)C14—C15—H15A109.0
C8—C7—C14127.0 (2)C16—C15—H15A109.0
N2—C8—C9126.0 (2)C14—C15—H15B109.0
N2—C8—C7108.0 (2)C16—C15—H15B109.0
C9—C8—C7125.9 (2)H15A—C15—H15B107.8
C10—C9—C8130.8 (2)C15—C16—H16A109.5
C10—C9—H9114.6C15—C16—H16B109.5
C8—C9—H9114.6H16A—C16—H16B109.5
C9—C10—C1i132.2 (3)C15—C16—H16C109.5
C9—C10—H10113.9H16A—C16—H16C109.5
C1i—C10—H10113.9H16B—C16—H16C109.5
C2—C11—C12111.8 (2)C1—N1—C4106.9 (2)
C2—C11—H11A109.3C1—N1—H1126.5
C12—C11—H11A109.3C4—N1—H1126.5
C2—C11—H11B109.3C8—N2—C5110.6 (2)
C12—C11—H11B109.3C8—N2—H2124.7
H11A—C11—H11B107.9C5—N2—H2124.7
Symmetry code: (i) x, y, z+2.

Experimental details

Crystal data
Chemical formulaC32H34Br4N4
Mr794.27
Crystal system, space groupMonoclinic, P21/c
Temperature (K)90
a, b, c (Å)13.6720 (8), 8.0201 (5), 14.4687 (9)
β (°) 106.101 (1)
V3)1524.27 (16)
Z2
Radiation typeMo Kα
µ (mm1)5.31
Crystal size (mm)0.24 × 0.19 × 0.15
Data collection
DiffractometerMake and model CCD area-detector
diffractometer
Absorption correctionEmpirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.325, 0.451
No. of measured, independent and
observed [I > 2σ(I)] reflections
9484, 3111, 2751
Rint0.028
(sin θ/λ)max1)0.625
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.031, 0.082, 1.07
No. of reflections3111
No. of parameters183
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)1.34, 0.61

Computer programs: SMART (Bruker, 2001), SMART, SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2001), SHELXTL.

Selected geometric parameters (Å, º) top
Br1—C31.882 (2)C8—C91.404 (4)
Br2—C61.878 (3)C9—C101.382 (4)
C4—C51.413 (4)
C4—C3—Br1127.95 (19)C5—C6—Br2126.86 (19)
N1—C4—C5119.9 (2)C6—C7—C8106.1 (2)
C5—C4—C3131.3 (2)N2—C8—C9126.0 (2)
N2—C5—C4120.3 (2)C9—C8—C7125.9 (2)
C4—C5—C6134.4 (2)C10—C9—C8130.8 (2)
 

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