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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 66| Part 5| May 2010| Pages o1160-o1161
https://doi.org/10.1107/S1600536810014285

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

Avijit Ghosh,a Ray J. Butcher,b Shaikh M. Mobinc and M. Ravikantha*

aDepartment of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai 400 076, India, bDepartment of Chemistry, Howard University, 525 College Street NW, Washington, DC 20059, USA, and cNational Single Crystal X-ray Diffraction Facility, Indian Institute of Technology Bombay, Powai, Mumbai 400 076, India
*Correspondence e-mail: ravikanth@chem.iitb.ac.in

(Received 17 March 2010; accepted 19 April 2010; online 24 April 2010)

Mol­ecules of the title macrocycle, C36H22N4O4, 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 inter­porphyrin 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-tetra­phenyl­porphyrin, 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 intra­molecular hydro­den bonding between the meso-fury O atom and the β-pyrrole CH group. Intra­molecular N—H⋯N hydrogen bonds are also present.

Related literature

The electronic properties of porphyrin macrocycles can be altered by selectively introducing substituents at meso- or β-positions, see: Lindsey (2000[Lindsey, J. S. (2000). The Porphyrin Handbook, Vol. 1, edited by K. M. Kadish, K. M. Smith & R. Guilard, pp. 45-118. San Diego: Academic Press.]). 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[Bhavana, P. & Bhyrappa, P. (2001). Chem. Phys. Lett. 349, 399-404.]); Purushothaman et al., (2001[Purushothaman, B., Varghese, B. & Bhyrappa, P. (2001). Acta Cryst. C57, 252-253.]); Gupta & Ravikanth (2002[Gupta, I. & Ravikanth, M. (2002). Tetrahedron Lett. 43, 9453-9455.], 2003a[Gupta, I. & Ravikanth, M. (2003a). Eur. J. Org. Chem. pp. 4392-4400.],b[Gupta, I. & Ravikanth, M. (2003b). Tetrahedron, 43, 6131-6139.], 2005[Gupta, I. & Ravikanth, M. (2005). J. Chem. Sci. 117, 161-166.]). For the structure of 5,10,15,20-tetra­kis(phen­yl)porphyrin, see: Senge (2000[Senge, M. O. (2000). The Porphyrin Handbook, Vol. 1, edited by K. M. Kadish, K. M. Smith & R. Guilard, pp. 239-347. New York: Academic Press.]).

[Scheme 1]

Experimental

Crystal data

  • C36H22N4O4

  • Mr = 574.58

  • Monoclinic, P 21 /c

  • 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[Oxford Diffraction (2009). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.]) Tmin = 0.973, Tmax = 0.983

  • 14627 measured reflections

  • 4350 independent reflections

  • 2596 reflections with I > 2σ(I)

  • Rint = 0.050
Refinement

  • R[F2 > 2σ(F2)] = 0.057

  • wR(F2) = 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

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A D⋯A D—H⋯A
N2—H2N⋯N1 0.92 (2) 2.29 (2) 2.886 (2) 121.5 (16)
N2—H2N⋯N1i 0.92 (2) 2.41 (2) 2.9618 (19) 118.1 (15)
C16—H16A⋯O2 0.95 2.35 2.855 (2) 113
C17—H17A⋯O1i 0.95 2.39 2.906 (2) 114
Symmetry code: (i) -x, -y+1, -z+1.

Data collection: CrysAlis CCD (Oxford Diffraction, 2009[Oxford Diffraction (2009). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.]); cell refinement: CrysAlis CCD; data reduction: CrysAlis RED (Oxford Diffraction, 2009[Oxford Diffraction (2009). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536810014285/bt5220sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810014285/bt5220Isup2.hkl

checkCIF report


Comment top

Porphyrin macrocycles are synthetically flexible and by selectively introducing substituents at meso- or β-positions, the electronic properties of the porphyrin ring can be altered at will for any application (Lindsey, 2000). Recently we, and others, have shown that introducing five membered heterocycles such as thiophene and furan at the meso-position in place of six membered aryl groups alter the electronic properties significantly (Bhavana & Bhyrappa, 2001; Purushothaman et al., 2001; Gupta & Ravikanth, 2002, 2003a, 2003b, and 2005). In the crystal structure of the Zn(II) derivative of 5,10,15,20-tetrathienylporphyrin, the structure was shown to correlate with the observed electronic properties (Purushothaman et al., 2001).

In the present paper, we report the crystal structure of 5,10,15,20-tetrakis(2-furyl)porphyrin (I) and compare it with the crystal structure of 5,10,15,20-tetrakis(phenyl)porphyrin (II) (Senge, 2000). The molecular structure of (I) is presented in Fig. 1. The porphyrin plane of (I) displays a wave like conformation with an interplanar porphyrin separation of 3.488 (Å). The aromatic nature of (I) is evident from the observation that the Cα-Cβ distance is greater than the Cβ-Cβ bond distance. The four inner pyrrole N atoms are almost in plane with four meso carbons. The bond distances and bond angles of (I) are altered relative to those of (II) revealing replacing phenyl groups with furyl groups at meso positions changes the porphyrin π-electron delocalization pathway. The dihedral angles of meso-furyl groups with respect to porphyrin plane in (I) are 38.87 (7)° and 48.29 (7)° and those of meso-phenyl groups in (II) are 61.0° and 61.3°. This significant decrease in the dihedral angle in case of (I) is due to presence of intramolecular hydroden bonding between meso-furyl "O" and β-pyrrole "CH". As is clear from Figure 1, the four meso-furyl"O" are involved in hydrogen bonding with two β-pyrrole "CH" which are opposite to each other. This bonding helps in the significant reduction of dihedral angle of meso-furyl groups with the plane of the porphyrin. As a result the meso-furyl groups are inclined more towards the porphyrin plane resulting in extension of π-delocalization of the porphyrin ring to the furyl groups. The observed spectroscopic properties of (I), such as large red shifts in absorption and emission maxima and significant downfield shifts of NH and \b-pyrrole protons in NMR as compared to (II) also in agreement with the enhanced π-delocalization in (I). Thus, the crystal structure presented here indicates that the porphyrin (I) adopts more planar structure as compared to porphyrin (II).

Related literature top

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 top

In a 500 ml one necked round bottom flask fitted an with argon bubbler, furan-2-aldehyde (286 mg, 2.98 mmol) and pyrrole (210 ml, 2.98 mmol) in 300 ml of CH2Cl2 were condensed in the presence of BF3.OEt2 (120 ml of 2.5 M stock solution) under argon atmosphere for 1 h followed by oxidation with DDQ (674 mg, 2.98 mmol) in open air for additional 45 min. The solvent was removed under reduced pressure and the crude compound was purified by silica gel column chromatography using CH2Cl2 (62 mg, 12%). M. P. 300°C. Single crystals of (I) suitable for X-ray analysis were obtained by slow evaporation of a dichloromethane/n-hexane solution over a period of one week. Spectroscopic analysis, 1HNMR (300 MHz, CDCl3, δ in p.p.m.): -2.59 (s, 2H, NH), 7.04 (m, 4H, furyl), 7.32 (m, 4H, furyl), 8.14 (s, 4H, furyl), 9.16 (s, 8H, β-pyrrole); elemental analysis calculated for C36H22N4O4: C,75.25; H, 3.86; N, 9.75%; found: C,75.31; H, 3.92; N, 9.65%: 574.6; found: 574.7(M+).

Refinement top

H atoms bonded to C were placed in geometrically idealized positions and constrained to ride on their parent atoms with a C—H distance of 0.95 Å [Uiso(H) = 1.2Ueq(C)]. The H attached to N was refined isotropically.

Structure description top

Porphyrin macrocycles are synthetically flexible and by selectively introducing substituents at meso- or β-positions, the electronic properties of the porphyrin ring can be altered at will for any application (Lindsey, 2000). Recently we, and others, have shown that introducing five membered heterocycles such as thiophene and furan at the meso-position in place of six membered aryl groups alter the electronic properties significantly (Bhavana & Bhyrappa, 2001; Purushothaman et al., 2001; Gupta & Ravikanth, 2002, 2003a, 2003b, and 2005). In the crystal structure of the Zn(II) derivative of 5,10,15,20-tetrathienylporphyrin, the structure was shown to correlate with the observed electronic properties (Purushothaman et al., 2001).

In the present paper, we report the crystal structure of 5,10,15,20-tetrakis(2-furyl)porphyrin (I) and compare it with the crystal structure of 5,10,15,20-tetrakis(phenyl)porphyrin (II) (Senge, 2000). The molecular structure of (I) is presented in Fig. 1. The porphyrin plane of (I) displays a wave like conformation with an interplanar porphyrin separation of 3.488 (Å). The aromatic nature of (I) is evident from the observation that the Cα-Cβ distance is greater than the Cβ-Cβ bond distance. The four inner pyrrole N atoms are almost in plane with four meso carbons. The bond distances and bond angles of (I) are altered relative to those of (II) revealing replacing phenyl groups with furyl groups at meso positions changes the porphyrin π-electron delocalization pathway. The dihedral angles of meso-furyl groups with respect to porphyrin plane in (I) are 38.87 (7)° and 48.29 (7)° and those of meso-phenyl groups in (II) are 61.0° and 61.3°. This significant decrease in the dihedral angle in case of (I) is due to presence of intramolecular hydroden bonding between meso-furyl "O" and β-pyrrole "CH". As is clear from Figure 1, the four meso-furyl"O" are involved in hydrogen bonding with two β-pyrrole "CH" which are opposite to each other. This bonding helps in the significant reduction of dihedral angle of meso-furyl groups with the plane of the porphyrin. As a result the meso-furyl groups are inclined more towards the porphyrin plane resulting in extension of π-delocalization of the porphyrin ring to the furyl groups. The observed spectroscopic properties of (I), such as large red shifts in absorption and emission maxima and significant downfield shifts of NH and \b-pyrrole protons in NMR as compared to (II) also in agreement with the enhanced π-delocalization in (I). Thus, the crystal structure presented here indicates that the porphyrin (I) adopts more planar structure as compared to porphyrin (II).

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).

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2009); cell refinement: CrysAlis CCD (Oxford Diffraction, 2009); 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 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of C36H22N4O4 the showing the atom numbering scheme and 50% probability displacement ellipsoids. The weak C—H···O intramolecular interactions between C—H and O are shown by dashed lines.
[Figure 2] Fig. 2. The molecular packing for C36H22N4O4 viewed down the a axis. The weak C—H···O intramolecular interactions between C—H and O are shown by dashed lines.
5,10,15,20-Tetra-2-furylporphyrin top
Crystal data top
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
Data collection top
Oxford Diffraction Xcalibur-S
diffractometer		2596 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.050
Graphite monochromatorθmax = 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 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)] = 0.057Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.140H atoms treated by a mixture of independent and constrained refinement
S = 0.94 w = 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
Crystal data top
C36H22N4O4V = 1280.63 (9) Å3
Mr = 574.58Z = 2
Monoclinic, P21/cMo Kα radiation
a = 9.6068 (4) ŵ = 0.10 mm−1
b = 7.3956 (3) ÅT = 150 K
c = 18.1770 (7) Å0.28 × 0.23 × 0.17 mm
β = 97.419 (4)°
Data collection top
Oxford Diffraction Xcalibur-S
diffractometer		2596 reflections with I > 2σ(I)
Absorption correction: multi-scan
(CrysAlis RED; Oxford Diffraction, 2009)		Rint = 0.050
Tmin = 0.973, Tmax = 0.9832 standard reflections every 50 reflections
14627 measured reflections intensity decay: <2%
4350 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0570 restraints
wR(F2) = 0.140H atoms treated by a mixture of independent and constrained refinement
S = 0.94Δρmax = 0.38 e Å−3
4350 reflectionsΔρmin = −0.30 e Å−3
203 parameters
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
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)
Atomic displacement parameters (Å2) top
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)
Geometric parameters (Å, º) top
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)
Symmetry code: (i) −x, −y+1, −z+1.
Hydrogen-bond geometry (Å, º) top
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) −x, −y+1, −z+1.

Experimental details

Crystal data
Chemical formulaC36H22N4O4
Mr574.58
Crystal system, space groupMonoclinic, P21/c
Temperature (K)150
a, b, c (Å)9.6068 (4), 7.3956 (3), 18.1770 (7)
β (°) 97.419 (4)
V (Å3)1280.63 (9)
Z2
Radiation typeMo Kα
µ (mm−1)0.10
Crystal size (mm)0.28 × 0.23 × 0.17
Data collection
DiffractometerOxford Diffraction Xcalibur-S
Absorption correctionMulti-scan
(CrysAlis RED; Oxford Diffraction, 2009)
Tmin, Tmax0.973, 0.983
No. of measured, independent and
observed [I > 2σ(I)] reflections		14627, 4350, 2596
Rint0.050
(sin θ/λ)max (Å−1)0.759
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.057, 0.140, 0.94
No. of reflections4350
No. of parameters203
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å−3)0.38, −0.30

Computer programs: CrysAlis CCD (Oxford Diffraction, 2009), CrysAlis RED (Oxford Diffraction, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top
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)112.8
C17—H17A···O1i0.952.392.906 (2)114.1
Symmetry code: (i) −x, −y+1, −z+1.
 

Acknowledgements

Financial support from the DST and CSIR, Goverment of India, to MR is gratefully acknowledged.

References

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 First citationOxford Diffraction (2009). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.  Google Scholar
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 First citationSenge, M. O. (2000). The Porphyrin Handbook, Vol. 1, edited by K. M. Kadish, K. M. Smith & R. Guilard, pp. 239–347. New York: Academic Press.  Google Scholar
 First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar

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ISSN: 2056-9890
Volume 66| Part 5| May 2010| Pages o1160-o1161
https://doi.org/10.1107/S1600536810014285
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