Structure and Conformation of Photosynthetic Pigments and Related Compounds 9 On the Structure and Macrocycle Conformation of Two Copper(II) Rhodochlorin Derivatives and Two Related Rhodoporphyrins

Mathias O. Senge, Karin Ruhlandt, Shwn Ji H Lee, Kevin M. Smith

Research output: Contribution to journalArticle

8 Citations (Scopus)

Abstract

Crystal structure analyses of (rhodochlorinato-15-acetic trimethyl ester)copper(II) 3 and (31,32-didehydro-rhodochlorinato-15-formic acid trimethyl ester)copper(II) 4 reveal intriguing multiple macrocycle conformations of the metallochlorins in the crystal. The observed conformations range from almost planar macrocycles to distorted macrocycles with individual atoms being displaced up to 0.72 A from the mean plane. The nonplanar macrocycles show a S4-ruttled macrocycle distortion with significant distortions for the weso-carbons and tilting of the Cb–Cb axes. A comparison with the related free base porphyrins rhodoporphyrin-15-acetic acid trimethyl ester 5 and rhodoporphyrin dimethyl ester 6 shows that the conformational distortion is due to the mixing of metal and substituent effects, hydroporphyrin character, and packing forces. Crystal data: 3, monoclinic, P21, a = 12.096(4) A, b = 14.307(4) Å, c = 22.343(9) A, β = 104.94(4)°, Z = 4 (2 indep. mol.), R = 0,069 for 8141 reflections with I > 2.0a(I); 4, triclinic, P1, a = 10.528(3) A, b = 10.646(4) A, c = 34.026(13) A, a = 89.81(4)°, β = 88.72(3)°, y = 60.38(2)°, Z = 4 (4 indep. mol.), R = 0.073 for 9446 reflections with I > 2.5 σ(I); 5, triclinic, PĪ, a = 9.591(2) A, b = 12.959(4) A, c = 13.453(4) A, a = 105.86(2)°, β = 92.67(2)°, γ = 96.12(2)°, Z = 2. R = 0.060 for 4990 reflections with I > 2.5 σ(I); 6, triclinic, PĪ, a = 8.908(4) A, b = 12.895(5) A, c = 13.482(6) A, a = 102.74(3)°,β = 90.38(4)°, y = 91.84(3)°, Z = 2, R = 0.089 for 3369 reflections with I > 2.0σ(I).

Original languageEnglish (US)
Pages (from-to)969-981
Number of pages13
JournalZeitschrift fur Naturforschung - Section B Journal of Chemical Sciences
Volume50
Issue number6
DOIs
StatePublished - Jun 1 1995

Fingerprint

Pigments
Conformations
Copper
Esters
Derivatives
formic acid
Acetic Acid
Crystals
Porphyrins
Carbon
Crystal structure
Metals
Atoms

Keywords

  • Copper(II)chlorins
  • Metallochlorins
  • Metalloporphyrins
  • Rhodochlorin
  • Tetrapyrroles

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

@article{c3388d0d550247e48196017ad9abce8c,
title = "Structure and Conformation of Photosynthetic Pigments and Related Compounds 9 On the Structure and Macrocycle Conformation of Two Copper(II) Rhodochlorin Derivatives and Two Related Rhodoporphyrins",
abstract = "Crystal structure analyses of (rhodochlorinato-15-acetic trimethyl ester)copper(II) 3 and (31,32-didehydro-rhodochlorinato-15-formic acid trimethyl ester)copper(II) 4 reveal intriguing multiple macrocycle conformations of the metallochlorins in the crystal. The observed conformations range from almost planar macrocycles to distorted macrocycles with individual atoms being displaced up to 0.72 A from the mean plane. The nonplanar macrocycles show a S4-ruttled macrocycle distortion with significant distortions for the weso-carbons and tilting of the Cb–Cb axes. A comparison with the related free base porphyrins rhodoporphyrin-15-acetic acid trimethyl ester 5 and rhodoporphyrin dimethyl ester 6 shows that the conformational distortion is due to the mixing of metal and substituent effects, hydroporphyrin character, and packing forces. Crystal data: 3, monoclinic, P21, a = 12.096(4) A, b = 14.307(4) {\AA}, c = 22.343(9) A, β = 104.94(4)°, Z = 4 (2 indep. mol.), R = 0,069 for 8141 reflections with I > 2.0a(I); 4, triclinic, P1, a = 10.528(3) A, b = 10.646(4) A, c = 34.026(13) A, a = 89.81(4)°, β = 88.72(3)°, y = 60.38(2)°, Z = 4 (4 indep. mol.), R = 0.073 for 9446 reflections with I > 2.5 σ(I); 5, triclinic, PĪ, a = 9.591(2) A, b = 12.959(4) A, c = 13.453(4) A, a = 105.86(2)°, β = 92.67(2)°, γ = 96.12(2)°, Z = 2. R = 0.060 for 4990 reflections with I > 2.5 σ(I); 6, triclinic, PĪ, a = 8.908(4) A, b = 12.895(5) A, c = 13.482(6) A, a = 102.74(3)°,β = 90.38(4)°, y = 91.84(3)°, Z = 2, R = 0.089 for 3369 reflections with I > 2.0σ(I).",
keywords = "Copper(II)chlorins, Metallochlorins, Metalloporphyrins, Rhodochlorin, Tetrapyrroles",
author = "Senge, {Mathias O.} and Karin Ruhlandt and Lee, {Shwn Ji H} and Smith, {Kevin M.}",
year = "1995",
month = "6",
day = "1",
doi = "10.1515/znb-1995-0620",
language = "English (US)",
volume = "50",
pages = "969--981",
journal = "Zeitschrift fur Naturforschung - Section B Journal of Chemical Sciences",
issn = "0932-0776",
publisher = "Verlag der Zeitschrift fur Naturforschung",
number = "6",

}

TY - JOUR

T1 - Structure and Conformation of Photosynthetic Pigments and Related Compounds 9 On the Structure and Macrocycle Conformation of Two Copper(II) Rhodochlorin Derivatives and Two Related Rhodoporphyrins

AU - Senge, Mathias O.

AU - Ruhlandt, Karin

AU - Lee, Shwn Ji H

AU - Smith, Kevin M.

PY - 1995/6/1

Y1 - 1995/6/1

N2 - Crystal structure analyses of (rhodochlorinato-15-acetic trimethyl ester)copper(II) 3 and (31,32-didehydro-rhodochlorinato-15-formic acid trimethyl ester)copper(II) 4 reveal intriguing multiple macrocycle conformations of the metallochlorins in the crystal. The observed conformations range from almost planar macrocycles to distorted macrocycles with individual atoms being displaced up to 0.72 A from the mean plane. The nonplanar macrocycles show a S4-ruttled macrocycle distortion with significant distortions for the weso-carbons and tilting of the Cb–Cb axes. A comparison with the related free base porphyrins rhodoporphyrin-15-acetic acid trimethyl ester 5 and rhodoporphyrin dimethyl ester 6 shows that the conformational distortion is due to the mixing of metal and substituent effects, hydroporphyrin character, and packing forces. Crystal data: 3, monoclinic, P21, a = 12.096(4) A, b = 14.307(4) Å, c = 22.343(9) A, β = 104.94(4)°, Z = 4 (2 indep. mol.), R = 0,069 for 8141 reflections with I > 2.0a(I); 4, triclinic, P1, a = 10.528(3) A, b = 10.646(4) A, c = 34.026(13) A, a = 89.81(4)°, β = 88.72(3)°, y = 60.38(2)°, Z = 4 (4 indep. mol.), R = 0.073 for 9446 reflections with I > 2.5 σ(I); 5, triclinic, PĪ, a = 9.591(2) A, b = 12.959(4) A, c = 13.453(4) A, a = 105.86(2)°, β = 92.67(2)°, γ = 96.12(2)°, Z = 2. R = 0.060 for 4990 reflections with I > 2.5 σ(I); 6, triclinic, PĪ, a = 8.908(4) A, b = 12.895(5) A, c = 13.482(6) A, a = 102.74(3)°,β = 90.38(4)°, y = 91.84(3)°, Z = 2, R = 0.089 for 3369 reflections with I > 2.0σ(I).

AB - Crystal structure analyses of (rhodochlorinato-15-acetic trimethyl ester)copper(II) 3 and (31,32-didehydro-rhodochlorinato-15-formic acid trimethyl ester)copper(II) 4 reveal intriguing multiple macrocycle conformations of the metallochlorins in the crystal. The observed conformations range from almost planar macrocycles to distorted macrocycles with individual atoms being displaced up to 0.72 A from the mean plane. The nonplanar macrocycles show a S4-ruttled macrocycle distortion with significant distortions for the weso-carbons and tilting of the Cb–Cb axes. A comparison with the related free base porphyrins rhodoporphyrin-15-acetic acid trimethyl ester 5 and rhodoporphyrin dimethyl ester 6 shows that the conformational distortion is due to the mixing of metal and substituent effects, hydroporphyrin character, and packing forces. Crystal data: 3, monoclinic, P21, a = 12.096(4) A, b = 14.307(4) Å, c = 22.343(9) A, β = 104.94(4)°, Z = 4 (2 indep. mol.), R = 0,069 for 8141 reflections with I > 2.0a(I); 4, triclinic, P1, a = 10.528(3) A, b = 10.646(4) A, c = 34.026(13) A, a = 89.81(4)°, β = 88.72(3)°, y = 60.38(2)°, Z = 4 (4 indep. mol.), R = 0.073 for 9446 reflections with I > 2.5 σ(I); 5, triclinic, PĪ, a = 9.591(2) A, b = 12.959(4) A, c = 13.453(4) A, a = 105.86(2)°, β = 92.67(2)°, γ = 96.12(2)°, Z = 2. R = 0.060 for 4990 reflections with I > 2.5 σ(I); 6, triclinic, PĪ, a = 8.908(4) A, b = 12.895(5) A, c = 13.482(6) A, a = 102.74(3)°,β = 90.38(4)°, y = 91.84(3)°, Z = 2, R = 0.089 for 3369 reflections with I > 2.0σ(I).

KW - Copper(II)chlorins

KW - Metallochlorins

KW - Metalloporphyrins

KW - Rhodochlorin

KW - Tetrapyrroles

UR - http://www.scopus.com/inward/record.url?scp=21844493371&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=21844493371&partnerID=8YFLogxK

U2 - 10.1515/znb-1995-0620

DO - 10.1515/znb-1995-0620

M3 - Article

AN - SCOPUS:21844493371

VL - 50

SP - 969

EP - 981

JO - Zeitschrift fur Naturforschung - Section B Journal of Chemical Sciences

JF - Zeitschrift fur Naturforschung - Section B Journal of Chemical Sciences

SN - 0932-0776

IS - 6

ER -