Literature DB >> 21579204

5,10,15,20-Tetra-2-furylporphyrin.

Avijit Ghosh, Ray J Butcher, Shaikh M Mobin, M Ravikanth.   

Abstract

Mol-ecules of the title macrocycle, C(36)H(22)N(4)O(4), are located on an inversion center. The porphyrin ring shows a wave-like conformation with adjacent pyrrole rings tilted above the porphyrin plane and the inter-porphyrin distance is 3.584 (3) Å. The dihedral angles between the meso-furyl groups and the porphyrin plane are 38.87 (7) and 48.29 (7)°; these are much smaller than those observed for meso-tetra-phenyl-porphyrin, indicating that the meso-furyl groups are more inclined towards the porphyrin plane. The decrease in the dihedral angle is due to the presence of intra-molecular hydro-den bonding between the meso-fury O atom and the β-pyrrole CH group. Intra-molecular N-H⋯N hydrogen bonds are also present.

Entities:  

Year:  2010        PMID： 21579204      PMCID： PMC2979040          DOI： 10.1107/S1600536810014285

Source DB:  PubMed          Journal:  Acta Crystallogr Sect E Struct Rep Online        ISSN： 1600-5368


Related literature

The electronic properties of porphyrin macrocycles can be altered by selectively introducing substituents at meso- or β-positions, see: Lindsey (2000 ▶). For the effect on the electronic properties of introducing five-membered heterocycles such as thio­phene and furan at the meso-position in place of six-membered aryl groups, see: Bhavana & Bhyrappa (2001 ▶); Purushothaman et al., (2001 ▶); Gupta & Ravikanth (2002 ▶, 2003a ▶,b ▶, 2005 ▶). For the structure of 5,10,15,20-tetra­kis(phen­yl)porphyrin, see: Senge (2000 ▶).

Experimental

Crystal data

C36H22N4O4 M = 574.58 Monoclinic, a = 9.6068 (4) Å b = 7.3956 (3) Å c = 18.1770 (7) Å β = 97.419 (4)° V = 1280.63 (9) Å3 Z = 2 Mo Kα radiation μ = 0.10 mm−1 T = 150 K 0.28 × 0.23 × 0.17 mm

Data collection

Oxford Diffraction Xcalibur-S diffractometer Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009 ▶) T min = 0.973, T max = 0.983 14627 measured reflections 4350 independent reflections 2596 reflections with I > 2σ(I) R int = 0.050

Refinement

R[F 2 > 2σ(F 2)] = 0.057 wR(F 2) = 0.140 S = 0.94 4350 reflections 203 parameters H atoms treated by a mixture of independent and constrained refinement Δρmax = 0.38 e Å−3 Δρmin = −0.30 e Å−3 Data collection: CrysAlis CCD (Oxford Diffraction, 2009 ▶); cell refinement: CrysAlis CCD; data reduction: CrysAlis RED (Oxford Diffraction, 2009 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL. Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810014285/bt5220sup1.cif Structure factors: contains datablocks I. DOI: 10.1107/S1600536810014285/bt5220Isup2.hkl Additional supplementary materials: crystallographic information; 3D view; checkCIF report
C36H22N4O4F(000) = 596
Mr = 574.58Dx = 1.490 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 1578 reflections
a = 9.6068 (4) Åθ = 2.6–25.1°
b = 7.3956 (3) ŵ = 0.10 mm−1
c = 18.1770 (7) ÅT = 150 K
β = 97.419 (4)°Block, black
V = 1280.63 (9) Å30.28 × 0.23 × 0.17 mm
Z = 2
Oxford Diffraction Xcalibur-S diffractometer2596 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.050
graphiteθmax = 32.7°, θmin = 3.3°
ω scansh = −11→14
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009)k = −11→10
Tmin = 0.973, Tmax = 0.983l = −27→27
14627 measured reflections2 standard reflections every 50 reflections
4350 independent reflections intensity decay: <2%
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.057Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.140H atoms treated by a mixture of independent and constrained refinement
S = 0.94w = 1/[σ2(Fo2) + (0.0704P)2] where P = (Fo2 + 2Fc2)/3
4350 reflections(Δ/σ)max < 0.001
203 parametersΔρmax = 0.38 e Å−3
0 restraintsΔρmin = −0.30 e Å−3
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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.
xyzUiso*/Ueq
O10.12370 (14)0.14955 (18)0.78524 (7)0.0328 (3)
O20.28868 (13)1.19097 (16)0.53303 (7)0.0277 (3)
N10.14624 (14)0.57702 (18)0.58457 (7)0.0182 (3)
N20.04097 (14)0.74030 (19)0.44418 (8)0.0181 (3)
H2N0.018 (2)0.644 (3)0.4727 (11)0.033 (6)*
C10.17490 (17)0.4903 (2)0.65124 (9)0.0190 (3)
C20.25816 (18)0.6045 (2)0.70508 (9)0.0228 (4)
H2A0.28960.57540.75540.027*
C30.28217 (18)0.7587 (2)0.67017 (9)0.0223 (4)
H3A0.33280.86080.69100.027*
C40.21545 (17)0.7390 (2)0.59420 (9)0.0182 (3)
C50.12791 (17)0.3159 (2)0.66826 (9)0.0183 (3)
C60.19861 (19)0.2322 (2)0.73637 (9)0.0211 (3)
C70.33718 (18)0.2124 (2)0.75868 (9)0.0232 (4)
H7A0.41160.25660.73400.028*
C80.3506 (2)0.1135 (3)0.82580 (11)0.0320 (4)
H8A0.43580.08000.85510.038*
C90.2214 (2)0.0765 (3)0.84007 (11)0.0334 (5)
H9A0.19920.00980.88170.040*
C100.22148 (16)0.8718 (2)0.53867 (9)0.0184 (3)
C110.32446 (18)1.0178 (2)0.55473 (9)0.0199 (3)
C120.45911 (18)1.0137 (2)0.58713 (9)0.0227 (4)
H12A0.50960.91030.60680.027*
C130.51107 (19)1.1943 (3)0.58618 (10)0.0287 (4)
H13A0.60251.23470.60530.034*
C140.4052 (2)1.2961 (2)0.55300 (10)0.0284 (4)
H14A0.41031.42260.54460.034*
C150.13864 (16)0.8702 (2)0.46911 (9)0.0185 (3)
C160.13469 (18)1.0021 (2)0.41186 (9)0.0231 (4)
H16A0.19321.10580.41250.028*
C170.03278 (18)0.9546 (2)0.35596 (10)0.0226 (4)
H17A0.00571.02140.31180.027*
C18−0.02633 (17)0.7862 (2)0.37546 (9)0.0183 (3)
U11U22U33U12U13U23
O10.0354 (8)0.0311 (7)0.0315 (7)−0.0065 (6)0.0025 (6)0.0025 (6)
O20.0274 (7)0.0201 (6)0.0345 (7)−0.0029 (5)0.0002 (5)−0.0029 (5)
N10.0185 (7)0.0161 (6)0.0193 (7)−0.0016 (5)−0.0006 (5)−0.0015 (5)
N20.0181 (7)0.0163 (7)0.0193 (7)−0.0023 (6)0.0005 (5)−0.0004 (5)
C10.0193 (8)0.0179 (8)0.0195 (8)−0.0011 (7)0.0010 (6)−0.0024 (6)
C20.0244 (9)0.0252 (9)0.0178 (8)−0.0035 (7)−0.0015 (6)−0.0026 (7)
C30.0222 (9)0.0231 (8)0.0204 (8)−0.0048 (7)−0.0015 (6)−0.0040 (7)
C40.0158 (8)0.0181 (8)0.0204 (8)0.0007 (6)0.0010 (6)−0.0024 (6)
C50.0171 (8)0.0191 (8)0.0183 (8)0.0003 (6)0.0011 (6)−0.0013 (6)
C60.0269 (9)0.0165 (8)0.0194 (8)−0.0013 (7)0.0013 (6)−0.0023 (6)
C70.0192 (8)0.0235 (9)0.0264 (9)0.0014 (7)0.0008 (7)0.0066 (7)
C80.0348 (11)0.0229 (9)0.0337 (10)−0.0003 (8)−0.0126 (8)0.0036 (8)
C90.0527 (14)0.0231 (9)0.0229 (9)−0.0074 (9)−0.0005 (9)0.0051 (8)
C100.0163 (8)0.0162 (7)0.0226 (8)0.0003 (6)0.0024 (6)−0.0024 (6)
C110.0230 (9)0.0166 (8)0.0205 (8)−0.0017 (7)0.0041 (6)−0.0019 (6)
C120.0200 (9)0.0233 (8)0.0243 (8)0.0014 (7)0.0010 (7)0.0008 (7)
C130.0206 (9)0.0346 (10)0.0311 (10)−0.0094 (8)0.0041 (7)−0.0100 (8)
C140.0331 (11)0.0193 (9)0.0340 (10)−0.0099 (8)0.0087 (8)−0.0073 (8)
C150.0143 (8)0.0178 (8)0.0234 (8)−0.0011 (6)0.0024 (6)−0.0013 (6)
C160.0230 (9)0.0198 (8)0.0258 (9)−0.0051 (7)0.0002 (7)0.0022 (7)
C170.0243 (9)0.0202 (8)0.0228 (8)−0.0021 (7)0.0010 (7)0.0040 (7)
C180.0186 (8)0.0178 (8)0.0181 (8)0.0005 (6)0.0008 (6)−0.0001 (6)
O1—C61.359 (2)C7—C81.414 (2)
O1—C91.387 (2)C7—H7A0.9500
O2—C111.371 (2)C8—C91.329 (3)
O2—C141.373 (2)C8—H8A0.9500
N1—C11.367 (2)C9—H9A0.9500
N1—C41.371 (2)C10—C151.404 (2)
N2—C181.373 (2)C10—C111.468 (2)
N2—C151.378 (2)C11—C121.351 (2)
N2—H2N0.92 (2)C12—C131.427 (3)
C1—C51.414 (2)C12—H12A0.9500
C1—C21.452 (2)C13—C141.344 (3)
C2—C31.340 (2)C13—H13A0.9500
C2—H2A0.9500C14—H14A0.9500
C3—C41.453 (2)C15—C161.423 (2)
C3—H3A0.9500C16—C171.363 (2)
C4—C101.415 (2)C16—H16A0.9500
C5—C18i1.398 (2)C17—C181.432 (2)
C5—C61.470 (2)C17—H17A0.9500
C6—C71.349 (2)C18—C5i1.398 (2)
C6—O1—C9106.18 (15)C8—C9—O1109.99 (17)
C11—O2—C14106.71 (14)C8—C9—H9A125.0
C1—N1—C4104.95 (13)O1—C9—H9A125.0
C18—N2—C15110.34 (14)C15—C10—C4124.46 (15)
C18—N2—H2N125.5 (13)C15—C10—C11118.31 (15)
C15—N2—H2N123.7 (13)C4—C10—C11117.21 (14)
N1—C1—C5126.03 (15)C12—C11—O2109.69 (15)
N1—C1—C2110.81 (14)C12—C11—C10130.76 (16)
C5—C1—C2123.13 (15)O2—C11—C10119.51 (14)
C3—C2—C1106.82 (15)C11—C12—C13106.88 (16)
C3—C2—H2A126.6C11—C12—H12A126.6
C1—C2—H2A126.6C13—C12—H12A126.6
C2—C3—C4106.44 (15)C14—C13—C12106.52 (16)
C2—C3—H3A126.8C14—C13—H13A126.7
C4—C3—H3A126.8C12—C13—H13A126.7
N1—C4—C10125.42 (14)C13—C14—O2110.19 (16)
N1—C4—C3110.87 (14)C13—C14—H14A124.9
C10—C4—C3123.71 (15)O2—C14—H14A124.9
C18i—C5—C1125.99 (15)N2—C15—C10125.79 (15)
C18i—C5—C6117.66 (14)N2—C15—C16106.53 (14)
C1—C5—C6116.27 (14)C10—C15—C16127.66 (15)
C7—C6—O1109.88 (15)C17—C16—C15108.49 (15)
C7—C6—C5129.05 (16)C17—C16—H16A125.8
O1—C6—C5120.94 (15)C15—C16—H16A125.8
C6—C7—C8107.00 (16)C16—C17—C18108.02 (15)
C6—C7—H7A126.5C16—C17—H17A126.0
C8—C7—H7A126.5C18—C17—H17A126.0
C9—C8—C7106.94 (16)N2—C18—C5i126.57 (15)
C9—C8—H8A126.5N2—C18—C17106.56 (14)
C7—C8—H8A126.5C5i—C18—C17126.81 (15)
C4—N1—C1—C5−178.98 (16)N1—C4—C10—C11−167.21 (15)
C4—N1—C1—C22.96 (18)C3—C4—C10—C1113.4 (2)
N1—C1—C2—C3−1.3 (2)C14—O2—C11—C12−0.13 (18)
C5—C1—C2—C3−179.43 (16)C14—O2—C11—C10−178.14 (14)
C1—C2—C3—C4−0.86 (19)C15—C10—C11—C12−136.32 (19)
C1—N1—C4—C10177.00 (15)C4—C10—C11—C1242.0 (2)
C1—N1—C4—C3−3.52 (18)C15—C10—C11—O241.2 (2)
C2—C3—C4—N12.8 (2)C4—C10—C11—O2−140.43 (15)
C2—C3—C4—C10−177.70 (15)O2—C11—C12—C130.29 (19)
N1—C1—C5—C18i−11.1 (3)C10—C11—C12—C13177.99 (16)
C2—C1—C5—C18i166.76 (16)C11—C12—C13—C14−0.3 (2)
N1—C1—C5—C6165.50 (15)C12—C13—C14—O20.3 (2)
C2—C1—C5—C6−16.7 (2)C11—O2—C14—C13−0.09 (19)
C9—O1—C6—C70.23 (19)C18—N2—C15—C10176.59 (15)
C9—O1—C6—C5176.41 (15)C18—N2—C15—C16−1.62 (18)
C18i—C5—C6—C7126.53 (19)C4—C10—C15—N2−0.6 (3)
C1—C5—C6—C7−50.3 (2)C11—C10—C15—N2177.63 (15)
C18i—C5—C6—O1−48.8 (2)C4—C10—C15—C16177.22 (16)
C1—C5—C6—O1134.29 (16)C11—C10—C15—C16−4.5 (3)
O1—C6—C7—C8−0.7 (2)N2—C15—C16—C172.51 (19)
C5—C6—C7—C8−176.46 (17)C10—C15—C16—C17−175.66 (17)
C6—C7—C8—C90.9 (2)C15—C16—C17—C18−2.4 (2)
C7—C8—C9—O1−0.8 (2)C15—N2—C18—C5i177.44 (16)
C6—O1—C9—C80.4 (2)C15—N2—C18—C170.17 (18)
N1—C4—C10—C1511.0 (3)C16—C17—C18—N21.42 (19)
C3—C4—C10—C15−168.37 (16)C16—C17—C18—C5i−175.84 (16)
D—H···AD—HH···AD···AD—H···A
N2—H2N···N10.92 (2)2.29 (2)2.886 (2)121.5 (16)
N2—H2N···N1i0.92 (2)2.41 (2)2.9618 (19)118.1 (15)
C16—H16A···O20.952.352.855 (2)113
C17—H17A···O1i0.952.392.906 (2)114
Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯AD—HH⋯AD⋯AD—H⋯A
N2—H2N⋯N10.92 (2)2.29 (2)2.886 (2)121.5 (16)
N2—H2N⋯N1i0.92 (2)2.41 (2)2.9618 (19)118.1 (15)
C16—H16A⋯O20.952.352.855 (2)113
C17—H17A⋯O1i0.952.392.906 (2)114

Symmetry code: (i) .

  2 in total

1.  [5,10,15,20-Tetrakis(2-thienyl)-porphyrinato]zinc(II).

Authors:  B Purushothaman; B Varghese; P Bhyrappa
Journal:  Acta Crystallogr C       Date:  2001-03       Impact factor: 1.172

2.  A short history of SHELX.

Authors:  George M Sheldrick
Journal:  Acta Crystallogr A       Date:  2007-12-21       Impact factor: 2.290
  2 in total

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