research communications
tert-butyl-10,15,20-triphenylporphyrin
of 5-aSchool of Chemistry, SFI Tetrapyrrole Laboratory, Trinity Biomedical Sciences Institute, 152-160 Pearse Street, Trinity College Dublin, The University of Dublin, Dublin 2, Ireland, and bCentre for Scientific and Applied Research, PSN College of Engineering and Technology, Melathediyoor, Tirunelveli 627 152, India
*Correspondence e-mail: sengem@tcd.ie
In the title free base porphyrin, C42H34N4, the neighbouring N⋯N distances in the center of the ring vary from 2.818 (8) to 2.998 (8) Å and the phenyl rings are tilted from the 24-atom mean plane at angles varying between 62.42 (2)–71.63 (2)°. The NH groups are involved in intramolecular bifurcated N—H⋯(N,N) hydrogen bonds. The Ca—Cm—Ca angles vary slightly for the phenyl rings, between 124.19 (18)–126.17 (18)°. The largest deviation from the mean plane of the 24-atom macrocycle is associated with the meso carbon at the substituted tert-butyl position, which is displaced from the mean plane by 0.44 (2) Å. The free base porphyrin is characterized by a significant degree of ruffled (B1u) distortion with contributions from domed (A2u) and wave [Eg(y) and Eg(x)] modes. In the crystal, molecules are linked by a number of weak C—H⋯π interactions, forming a three-dimensional framework. The structure was refined as a two-component inversion twin.
CCDC reference: 1444998
1. Chemical context
Unsymmetrically meso-substituted are of interest for a wide range of potential applications including non-linear optics (Notaras et al., 2007; Zawadzka et al., 2009), photodynamic therapy (Wiehe et al., 2005), and sensor and device applications (Scheicher et al., 2009). The synthesis of unsymmetrical porphyrin systems, such as the title compound, has been well documented (Senge et al., 2010; Senge, 2011). The title compound was first synthesized as part of a study on the identification of stable porphomethenes and porphodimethenes using sterically hindered (Senge et al., 2000). This was achieved through acid-catalyzed condensation of pyrroles with It was later synthesized as part of this publication through the bromination of 5-tert-butylporphyrin following a reported literature procedure for similar compounds (Fazekas et al., 2008) and subsequent Suzuki cross-coupling with phenylboronic acid, in excellent yield.
2. Structural commentary
The molecular structure of the title compound is illustrated in Fig. 1. The distance of neighbouring N⋯N atoms in the center of the ring shows a slight elongation of the porphyrin core along direction C5 to C15 [N1⋯N2 2.818 (8) Å, N2⋯N3 2.998 (8) Å, N3⋯N4 2.830 (8) Å, N4⋯N1 2.994 (7) Å]. The NH groups are involved in intramolecular bifurcated N—H⋯(N,N) hydrogen bonds (Table 1). The angles between the alpha carbons (Ca) and the meso carbon atoms (Cm) can be used to determine the structural differences between similar and differences within the individual porphyrin structure. In the title compound, the Ca—Cm—Ca angles vary slightly with the Ca—Cm(tert-butyl)—Ca angle of 120.55 (18)° at C5 representing the smallest. This is due to the nature of the tert-butyl substitution present. This angle is similar to that observed in the dication, 5,10,15,20-tetrakis(tert-butyl)-22H+,24H+-porphyrindiium ditrifluoroacetate (Senge, 2000), with an average Ca—Cm(tert-butyl)–Ca angle of 119.53° and 5-tert-butylporphyrin published (Ryppa et al., 2005), which shows an Ca–Cm(tert-butyl)–Ca angle of 119.86°. The Ca—Cm(phenyl)—Ca angle of the title compound at C10 and C20 are quite similar at 126.03 (18) and 126.17 (18)°, respectively. The Ca—Cm(phenyl)—Ca angles in 5,10,15,20-tetraphenylporphyrin, with an average angle of 125.35° (Silvers & Tulinsky, 1967), are comparable to that of the title compound, however, the Ca—Cm(phenyl)—Ca angle at C15 of the title compound is smaller [124.19 (18)°].
The tilt angles of the phenyl meso-substituents are 67.62 (2)° (C10), 71.63 (2)° (C15) and 62.42 (2)° (C20). These angles are larger than the tilt angles observed in 5,10,15,20-tetraphenylporphyrin, which are ca 60° (Silvers & Tulinsky, 1967). The tilt of the pyrrole rings against the 24-atom plane are 9.93 (2)° (N1), 172.68 (6)° (N2), 0.17 (2)° (N3) and 3.45 (1)° (N4), with the highest deviation from the mean plane associated with the pyrrole rings closest to the tert-butyl group at C5. The pyrrole ring N2 shows the largest deviation and this is visible in the overall conformation of the macrocycle rings (Fig. 2). A (Senge et al., 2015) was performed using the NSD (normal structural decomposition) method developed by Shelnutt and co-workers (Jentzen et al., 1997). The conformation is characterized by a significant degree of ruffled (B1u) distortion with contributions from domed (A2u) and wave [Eg(y) and Eg(x)] modes (Fig. 3). Contributions are also evident in the B2g in-plane distortion. A comparison with 5-tert-butylporphyrin (Ryppa et al., 2005) reveals a relatively similar composition of distortion modes for both compounds. This indicates that the tert-butyl group is the predominant contributor to the macrocycle distortion. There is, however, a noticeable difference between the NSD of both structures with regards to the B1u and Eg(y) out-of-plane distortions. The title compound exhibits similar contributions from both these modes whereas the free base 5-tert-butylporphyrin shows significantly more contributions in the B1u compared to the Eg(y) distortions. This can also be seen in the in-plane distortions as both compounds show significant contributions from the B2g and smaller contributions from the A1g mode, the title compound shows much larger contributions towards the B1g in-plane distortions compared to that of the 5-tert-butylporphyrin.
The maximum deviations from the 24-atom mean plane are associated with carbon and nitrogen atoms surrounding the tert-butyl substitution at C5. Atom C5 deviates from the mean plane by 0.440 (2) Å, whereas atoms C8, C2, C4, C20, N2 and C7 deviate from the mean plane by −0.361 (2), −0.244 (2), 0.232 (2), −0.217 (2), 0.203 (2) and −0.203 (2) Å, respectively. The smallest deviations are for the atoms associated with the pyrrole ring at the N3 position; atoms C11 C12, C13, C14 and N3 deviate from the mean plane by −0.003 (2), −0.027 (2), 0.027 (2), 0.009 (2) and −0.007 (2), respectively. This ring also shows the least tilt in the porphyrin structure.
3. Supramolecular features
In the crystal, the four molecules stack with a 90° rotation with regards to the tert-butyl-substituted group. The centroid–centroid distance of the 24-atom mean planes of the porphyrin rings are between 8.762 (2) and 7.758 (2) Å. The rings that stack above each other are separated by 8.762 (2) Å and the rings that are orientated in an edge-on packing are separated by a centroid–centroid distance of 7.758 (2) Å (Fig. 4). The orientation of the molecules in the shows that the Cb-hydrogen atoms between the tert-butyl group at C5 and the phenyl group at C10 are pointing towards the center of the neighbouring ring. Molecules are linked by a number of weak C—H⋯π interactions (Table 1), forming a three-dimensional framework. There are no solvent molecules contained within the overall structure, as seen in Fig. 5.
4. Database survey
A search of the Cambridge Structural Database (CSD, Version 5.36, update November 2014; Groom & Allen, 2014) gave several hits for unsymmetrically meso-substituted similar to the title compound. Speck et al. (1997) reported the structure of 5-(3,5-di-tert-butylmuconic acid anhydride)-10,15,20-triphenylporphyrin in which they reported phenyl tilt angles of 59.07–78.15° from the 24-atom mean plane, with the largest deviation on the phenyl group opposite the alternative meso-substituted position. In this structure there was a larger variance of the Ca—Cm(phenyl)—Ca angle of 123.88–125.51° and a Ca—Cm(C5)—Ca larger than the title compound of 127.35°. Senge et al. (1999) published the structure of 5-(2,5-dimethoxybenzyl)-10,15,20-triphenylporphyrin. The tilt angle of the phenyl rings from the 24-atom mean plane was larger and more varied compared to the title compound (73.47–87.56°). The Ca—Cm(phenyl)—Ca angle is similar to the title compound with an angle range of 125.46–125.78°. The structure of 5-(3,5-dihydroxyphenyl)-10,15,20-triphenylporphyrin pyridine clathrate has been reported by Tanaka et al. (2001). This compound displayed a phenyl tilt angle of 65.87–73.97° from the 24-atom mean plane and all Ca—Cm—Ca angles are of a similar size, 124.68–125.97°. Wojaczyński et al. (2002) reported the structure of 5,10,15-triphenylporphyrin which displays similar properties to the title compound with regards to the Ca—Cm(phenyl)—Ca angle either side of the unsubstituted meso position being almost equal to each other (123.78–123.95°). The Ca—Cm(phenyl)—Ca opposite the unsubstituted meso position is smaller than the Ca—Cm(H)—Ca angle, 126.20 and 127.93°, respectively. The phenyl tilt angle from the 24-atom mean plane shows a larger tilt angle (73.56–78.16°) associated with the phenyl rings. However, there is a narrower variance in these angle than in the title compound. Ryppa et al. (2005) published the structure of 5-tert-butylporphyrin which presents Ca—Cm(H)—Ca angles of 129.00–129.23° for the C10 and C15 positions and 125.23° for the C15 position which are all larger than in the title compound. The Ca—Cm(tert-butyl)—Ca angle (C5 in both structures) are of similar size at 119.86° (120.28° for the title compound). The overall pyrrole tilt against the mean 24-atom plane shows similar results to that of the title compound. The pyrrole rings (N1 and N2) closest to the tert-butyl meso substitute show significantly higher tilts (11.68 and 14.33°, respectively) compared to the pyrrole rings (N3 and N4) closest to the unsubstituted position at C15 (4.04 and 5.26°, respectively). Yang et al. (2011) reported the structure ethyl 8-(10,15,20-triphenylporphyrin-5-yl)-1-naphthoate exhibiting a phenyl tilt angle from the 24-atom mean plane of 59.13° for the phenyl opposite the naphthanote substitute and between 74.91–76.38° for the other phenyl groups. A similar angle for all Ca—Cm—Ca is observed, 125.36–125.82°. Ma et al. (2013) published the structure of 2-hydroxyphenyl 8-(10,15,20-triphenylporphyrin-5-yl)-1-naphthoate which exhibited a Ca—Cm(phenyl)—Ca angle of 124.36–124.68° similar to the title compound and a Ca—Cm(naphthoate)—Ca angle of 125.25° which is slightly larger compared to the title compound. The tilt angle of the phenyl rings from the 24-atom mean plane is 60.46–83.15° which shows a larger variance than for the title compound.
5. Synthesis and crystallization
The title compound was prepared previously by Senge et al. (2000) using a condensation approach. Here, 5-tert-butylporphyrin (100 mg, 0.27 mmol, 1 eq) was dissolved in dry CHCl3 (50 ml) and cooled to 273 K. N-Bromosuccinimide (145 mg, 0.81 mmol, 3 eq) was added and the solution was stirred for 5 h. The resulting solution was quenched with acetone and the crude product was purified via on silica gel (hexane/CH2Cl2 = 4:1, v/v). The solvent was removed in vacuo yielding 5-tert-butyl-10,15,20-tribromoporphyrin as purple crystals (yield: 45 mg, 0.075 mmol, 28%). Rf = 0.44 (hexane:CH2Cl2, 2:1); 1H NMR (400 MHz, CDCl3) δ: 9.45 (d, 3JH-H = 4.76 Hz, 2H, Hβ), 9.36 (d, 3JH-H = 4.76 Hz, 2H, Hβ), 9.31 (d, 3JH-H = 5.04 Hz, 2H, Hβ), 9.25 (d, 3JH-H = 5 Hz, 2H, Hβ), 2.33 (s, 9H, CH3), −1.72 p.p.m. (brs, 2H, NH); HRMS (MALDI): m/z calculated for C24H19N4Br3 600.9238 [M + H]+; found 600.9248.
A Schlenk tube was charged with 5-tert-butyl-10,15,20-tribromoporphyrin (20 mg, 0.033 mmol, 1 eq), phenylboronic acid (121.93 mg, 1 mmol, 30 eq), tetrakis(triphenylphosphine)palladium(0) (7.63 mg, 0.0066 mmol, 0.2 eq), cesium carbonate (651.64 mg, 2 mmol, 60 eq) and dried under vacuum. The mixture was dissolved in anhydrous THF (5 ml) and was degassed via three freeze–pump–thaw cycles and left under argon. The solution was heated to 353 K under an argon atmosphere for 48 h. The solvent was removed under reduced pressure and the residue was dissolved in CH2Cl2 (10 ml). The crude product was washed sequentially with sat. aq. NaHCO3 (20 ml) and deionized H2O (20 ml). The organic phase was dried over Na2SO4 and filtered. The crude product was purified via on silica gel (hexane/CH2Cl2 = 1:1, v/v). The solvent was removed in vacuo, yielding the title compound as purple crystals (yield: 15 mg, 0.025 mmol, 76%). The compound was recrystallized from CH2Cl2 layered with methanol to yield single crystals suitable for X-ray diffraction analysis.
6. Refinement
Crystal data, data collection and structure . The structure was refined as a two-component The NH and C-bound H atoms were placed in their expected calculated positions and refined using a standard riding model: N—H = 0.88 Å, C—H = 0.95–0.98 Å, with Uiso(H) = 1.5Ueq(C-methyl) and 1.2Ueq(N,C) for other H atoms.
details are summarized in Table 2
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Supporting information
CCDC reference: 1444998
10.1107/S2056989016000025/su5266sup1.cif
contains datablocks I, Global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S2056989016000025/su5266Isup2.hkl
Unsymmetrically meso-substituted
are of interest for a wide range of potential applications including non-linear optics (Notaras et al., 2007; Zawadzka et al., 2009), photodynamic therapy (Wiehe et al., 2005), and sensor and device applications (Scheicher et al., 2009). The synthesis of unsymmetrical porphyrin systems, such as the title compound, has been well documented (Senge et al., 2010; Senge, 2011). The title compound was first synthesized as part of a study on the identification of stable porphomethenes and porphodimethenes using sterically hindered (Senge et al., 2000). This was achieved through acid-catalyzed condensation of pyrroles with It was later synthesized as part of this publication through the bromination of 5-tert-butylporphyrin following a reported literature procedure for similar compounds (Fazekas et al., 2008) and subsequent Suzuki cross-coupling with phenylboronic acid, in excellent yield.The molecular structure of the title compound is illustrated in Fig. 1. The distance of neighbouring N···N atoms in the center of the ring shows a slight elongation of the porphyrin core along direction C5 to C15 [N1···N2 2.818 (8) Å, N2···N3 2.998 (8) Å, N3···N4 2.830 (8) Å, N4···N1 2.994 (7) Å]. The NH groups are involved in intramolecular bifurcated N—H···(N,N) hydrogen bonds (Table 1). The angles between the alpha carbons (Ca) and the meso carbon atoms (Cm) can be used to determine the structural differences between similar
and differences within the individual porphyrin structure. In the title compound, the Ca—Cm-–Ca angles vary slightly with the Ca—Cm(tert-butyl)—Ca angle of 120.55 (18)° at C5 representing the smallest. This is due to the nature of the tert-butyl substitution present. This angle is similar to that observed in the dication, 5,10,15,20-tetrakis(tert-butyl)-22H+,24H+-porphyrindiium ditrifluoroacetate (Senge, 2000), with an average Ca—Cm(tert-butyl)–Ca angle of 119.53° and 5-tert-butylporphyrin published (Ryppa et al., 2005), which shows an Ca–Cm(tert-butyl)–Ca angle of 119.86°. The Ca—Cm(phenyl)—Ca angle of the title compound at C10 and C20 are quite similar at 126.03 (18) and 126.17 (18)°, respectively. The Ca—Cm(phenyl)—Ca angles in 5,10,15,20-tetraphenylporphyrin, with an average angle of 125.35° (Silvers & Tulinsky, 1967), are comparable to that of the title compound, however, the Ca—Cm(phenyl)—Ca angle at C15 of the title compound is smaller [124.19 (18)°].The tilt angles of the phenyl meso substituents are 67.62 (2)° (C10), 71.63 (2)° (C15) and 62.42 (2)° (C20), respectively. These angles are larger than the tilt angles observed in 5,10,15,20-tetraphenylporphyrin, which are ca 60° (Silvers & Tulinsky, 1967). The tilt of the pyrrole rings against the 24-atom plane are 9.93 (2)° (N1), 172.68 (6)° (N2), 0.17 (2)° (N3) and 3.45 (1)° (N4), with the highest deviation from the mean plane associated with the pyrrole rings closest to the tert-butyl group at C5. The pyrrole ring N2 shows the largest deviation and this is visible in the overall conformation of the macrocycle rings (Fig. 2). A
(Senge et al., 2015) was performed using the NSD (normal structural decomposition) method developed by Shelnutt and co-workers (Jentzen et al., 1997). The conformation is characterized by a significant degree of ruffled (B1u) distortion with contributions from domed (A2u) and wave [Eg(y) and Eg(x)] modes (Fig. 3). Contributions are also evident in the B2g in-plane distortion. A comparison with 5-tert-butyl-porphyrin (Ryppa et al., 2005) reveals a relatively similar composition of distortion modes for both compounds. This indicates that the tert-butyl group is the predominant contributor to the macrocycle distortion. There is, however, a noticeable difference between the NSD of both structures with regards to the B1u and Eg(y) out-of-plane distortions. The title compound exhibits similar contributions from both these modes whereas the free base 5-tert-butyl-porphyrin shows significantly more contributions in the B1u compared to the Eg(y) distortions. This can also be seen in the in-plane distortions as both compounds show significant contributions from the B2g and smaller contributions from the A1g mode, the title compound shows much larger contributions towards the B1g in-plane distortions compared to that of the 5-tert-butyl-porphyrin.The maximum deviations from the 24-atom mean plane are associated with carbon and nitrogen atoms surrounding the tert-butyl substitution at C5. Atom C5 deviates from the mean plane by 0.440 (2) Å, whereas atoms C8, C2, C4, C20, N2 and C7 deviate from the mean plane by −0.361 (2), −0.244 (2), 0.232 (2), −0.217 (2), 0.203 (2) and −0.203 (2) Å, respectively. The smallest deviations are for the atoms associated with the pyrrole ring at the N3 position; atoms C11 C12, C13, C14 and N3 deviate from the mean plane by −0.003 (2), −0.027 (2), 0.027 (2), 0.009 (2) and −0.007 (2), respectively. This ring also shows the least tilt in the porphyrin structure.
In the crystal, the four molecules stack with a 90° rotation with regards to the tert-butyl-substituted group. The centroid–centroid distance of the 24-atom mean planes of the porphyrin rings are between 8.762 (2) and 7.758 (2) Å. The rings that stack above each other are separated by 8.762 (2) Å and the rings that are orientated in an edge-on packing are separated by a centroid–centroid distance of 7.758 (2) Å (Fig. 4). The orientation of the molecules in the π interactions (Table 1), forming a three-dimensional framework. There are no solvent molecules contained within the overall structure, as seen in Fig. 5.
shows that the Cb-hydrogen atoms between the tert-butyl group at C5 and the phenyl group at C10 are pointing towards the center of the neighbouring ring. Molecules are linked by a number of weak C—H···A search of the Cambridge Structural Database (CSD, Version 5.36, update November 2014; Groom & Allen, 2014) gave several hits for unsymmetrically meso-substituted
similar to the title compound. Speck et al. (1997) reported the structure of 5-(3,5-di-tert-butylmuconic acid anhydride)-10,15,20-triphenylporphyrin in which they reported phenyl tilt angles of 59.07–78.15° from the 24-atom mean plane, with the largest deviation on the phenyl group opposite the alternative meso-substituted position. In this structure there was a larger variance of the Ca-–Cm(phenyl)—Ca angle of 123.88–125.51° and a Ca-–Cm(C5)—Ca larger than the title compound of 127.35°. Senge et al. (1999) published the structure of 5-(2,5-dimethoxybenzyl)-10,15,20-triphenylporphyrin. The tilt angle of the phenyl rings from the 24-atom mean plane was larger and more varied compared to the title compound (73.47–87.56°). The Ca—Cm(phenyl)—Ca angle is similar to the title compound with an angle range of 125.46–125.78°. The structure of 5-(3,5-dihydroxyphenyl)-10,15,20-triphenylporphyrin pyridine clathrate has been reported by Tanaka et al. (2001). This compound displayed a phenyl tilt angle of 65.87–73.97° from the 24-atom mean plane and all Ca-–Cm-–Ca angles are of a similar size, 124.68–125.97°. Wojaczyński et al. (2002) reported the structure of 5,10,15-triphenylporphyrin which displays similar properties to the title compound with regards to the Ca-–Cm(phenyl)—Ca angle either side of the unsubstituted meso position being almost equal to each other (123.78–123.95°). The Ca—Cm(phenyl)—Ca opposite the unsubstituted meso position is smaller than the Ca—Cm(H)—Ca angle, 126.20 and 127.93°, respectively. The phenyl tilt angle from the 24-atom mean plane shows a larger tilt angle (73.56–78.16°) associated with the phenyl rings. However, there is a narrower variance in these angle than in the title compound. Ryppa et al. (2005) published the structure of 5-tert-butylporphyrin which presents Ca-–Cm(H)—Ca angles of 129.00–129.23° for the C10 and C15 positions and 125.23° for the C15 position which are all larger than in the title compound. The Ca—Cm(tert-butyl)—Ca angle (C5 in both structures) are of similar size at 119.86° (120.28° for the title compound). The overall pyrrole tilt against the mean 24-atom plane shows similar results to that of the title compound. The pyrrole rings (N1 and N2) closest to the tert-butyl meso substitute show significantly higher tilts (11.68 and 14.33°, respectively) compared to the pyrrole rings (N3 and N4) closest to the unsubstituted position at C15 (4.04 and 5.26°, respectively). Yang et al. (2011) reported the structure ethyl 8-(10,15,20-triphenylporphyrin-5-yl)-1-naphthoate exhibiting a phenyl tilt angle from the 24-atom mean plane of 59.13° for the phenyl opposite the naphthanote substitute and between 74.91–76.38° for the other phenyl groups. A similar angle for all Ca—Cm-–Ca is observed, 125.36–125.82°. Ma et al. (2013) published the structure of 2-hydroxyphenyl 8-(10,15,20-triphenylporphyrin-5-yl)-1-naphthoate which exhibited a Ca—Cm(phenyl)—Ca angle of 124.36–124.68° similar to the title compound and a Ca—Cm(naphthoate)—Ca angle of 125.25° which is slightly larger compared to the title compound. The tilt angle of the phenyl rings from the 24-atom mean plane is 60.46–83.15° which shows a larger variance than for the title compound.The title compound was prepared previously by Senge et al. (2000) using a condensation approach. Here, 5-(tert-butyl)-porphyrin (100 mg, 0.27 mmol, 1 eq) was dissolved in dry CHCl3 (50 ml) and cooled to 273 K. N-Bromosuccinimide (145 mg, 0.81 mmol, 3 eq) was added and the solution was stirred for 5 h. The resulting solution was quenched with acetone and the crude product was purified via δ: 9.45 (d, 3JH—H = 4.76 Hz, 2H, Hβ), 9.36 (d, 3JH—H = 4.76 Hz, 2H, Hβ), 9.31 (d, 3JH—H = 5.04 Hz, 2H, Hβ), 9.25 (d, 3JH—H = 5 Hz, 2H, Hβ), 2.33 (s, 9H, CH3), −1.72 p.p.m. (brs, 2H, NH); HRMS (MALDI): m/z calculated for C24H19N4Br3 600.9238 [M + H]+; found 600.9248.
on silica gel (hexane/CH2Cl2 = 4:1, v/v). The solvent was removed in vacuo yielding 5-(tert-butyl)-10,15,20-tribromoporphyrin as purple crystals (yield: 45 mg, 0.075 mmol, 28%). Rf = 0.44 (hexane:CH2Cl2, 2:1); 1H NMR (400 MHz, CDCl3)A Schlenk tube was charged with 5-(tert-butyl)-10,15,20-tribromoporphyrin (20 mg, 0.033 mmol, 1 eq), phenylboronic acid (121.93 mg, 1 mmol, 30 eq), tetrakis(triphenylphosphine)palladium(0) (7.63 mg, 0.0066 mmol, 0.2 eq), caesium carbonate (651.64 mg, 2 mmol, 60 eq) and dried under vacuum. The mixture was dissolved in anhydrous THF (5 ml) and was degassed via three freeze–pump–thaw cycles and left under argon. The solution was heated to 353 K under an argon atmosphere for 48 h. The solvent was removed under reduced pressure and the residue was dissolved in CH2Cl2 (10 ml). The crude product was washed sequentially with sat. aq. NaHCO3 (20 ml) and deionized H2O (20 ml). The organic phase was dried over Na2SO4 and filtered. The crude product was purified via
on silica gel (hexane/CH2Cl2 = 1:1, v/v). The solvent was removed in vacuo, yielding the title compound as purple crystals (yield: 15 mg, 0.025 mmol, 76%). The compound was recrystallized from CH2Cl2 layered with methanol to yield single crystals suitable for X-ray diffraction analysis.Crystal data, data collection and structure
details are summarized in Table 2. The structure was refined as a two-component The NH and C-bound H atoms were placed in their expected calculated positions and refined using a standard riding model: N—H = 0.88 Å, C—H = 0.95–0.98 Å, with Uiso(H) = 1.5Ueq(C-methyl) and 1.2Ueq(N,C) for other H atoms.Unsymmetrically meso-substituted
are of interest for a wide range of potential applications including non-linear optics (Notaras et al., 2007; Zawadzka et al., 2009), photodynamic therapy (Wiehe et al., 2005), and sensor and device applications (Scheicher et al., 2009). The synthesis of unsymmetrical porphyrin systems, such as the title compound, has been well documented (Senge et al., 2010; Senge, 2011). The title compound was first synthesized as part of a study on the identification of stable porphomethenes and porphodimethenes using sterically hindered (Senge et al., 2000). This was achieved through acid-catalyzed condensation of pyrroles with It was later synthesized as part of this publication through the bromination of 5-tert-butylporphyrin following a reported literature procedure for similar compounds (Fazekas et al., 2008) and subsequent Suzuki cross-coupling with phenylboronic acid, in excellent yield.The molecular structure of the title compound is illustrated in Fig. 1. The distance of neighbouring N···N atoms in the center of the ring shows a slight elongation of the porphyrin core along direction C5 to C15 [N1···N2 2.818 (8) Å, N2···N3 2.998 (8) Å, N3···N4 2.830 (8) Å, N4···N1 2.994 (7) Å]. The NH groups are involved in intramolecular bifurcated N—H···(N,N) hydrogen bonds (Table 1). The angles between the alpha carbons (Ca) and the meso carbon atoms (Cm) can be used to determine the structural differences between similar
and differences within the individual porphyrin structure. In the title compound, the Ca—Cm-–Ca angles vary slightly with the Ca—Cm(tert-butyl)—Ca angle of 120.55 (18)° at C5 representing the smallest. This is due to the nature of the tert-butyl substitution present. This angle is similar to that observed in the dication, 5,10,15,20-tetrakis(tert-butyl)-22H+,24H+-porphyrindiium ditrifluoroacetate (Senge, 2000), with an average Ca—Cm(tert-butyl)–Ca angle of 119.53° and 5-tert-butylporphyrin published (Ryppa et al., 2005), which shows an Ca–Cm(tert-butyl)–Ca angle of 119.86°. The Ca—Cm(phenyl)—Ca angle of the title compound at C10 and C20 are quite similar at 126.03 (18) and 126.17 (18)°, respectively. The Ca—Cm(phenyl)—Ca angles in 5,10,15,20-tetraphenylporphyrin, with an average angle of 125.35° (Silvers & Tulinsky, 1967), are comparable to that of the title compound, however, the Ca—Cm(phenyl)—Ca angle at C15 of the title compound is smaller [124.19 (18)°].The tilt angles of the phenyl meso substituents are 67.62 (2)° (C10), 71.63 (2)° (C15) and 62.42 (2)° (C20), respectively. These angles are larger than the tilt angles observed in 5,10,15,20-tetraphenylporphyrin, which are ca 60° (Silvers & Tulinsky, 1967). The tilt of the pyrrole rings against the 24-atom plane are 9.93 (2)° (N1), 172.68 (6)° (N2), 0.17 (2)° (N3) and 3.45 (1)° (N4), with the highest deviation from the mean plane associated with the pyrrole rings closest to the tert-butyl group at C5. The pyrrole ring N2 shows the largest deviation and this is visible in the overall conformation of the macrocycle rings (Fig. 2). A
(Senge et al., 2015) was performed using the NSD (normal structural decomposition) method developed by Shelnutt and co-workers (Jentzen et al., 1997). The conformation is characterized by a significant degree of ruffled (B1u) distortion with contributions from domed (A2u) and wave [Eg(y) and Eg(x)] modes (Fig. 3). Contributions are also evident in the B2g in-plane distortion. A comparison with 5-tert-butyl-porphyrin (Ryppa et al., 2005) reveals a relatively similar composition of distortion modes for both compounds. This indicates that the tert-butyl group is the predominant contributor to the macrocycle distortion. There is, however, a noticeable difference between the NSD of both structures with regards to the B1u and Eg(y) out-of-plane distortions. The title compound exhibits similar contributions from both these modes whereas the free base 5-tert-butyl-porphyrin shows significantly more contributions in the B1u compared to the Eg(y) distortions. This can also be seen in the in-plane distortions as both compounds show significant contributions from the B2g and smaller contributions from the A1g mode, the title compound shows much larger contributions towards the B1g in-plane distortions compared to that of the 5-tert-butyl-porphyrin.The maximum deviations from the 24-atom mean plane are associated with carbon and nitrogen atoms surrounding the tert-butyl substitution at C5. Atom C5 deviates from the mean plane by 0.440 (2) Å, whereas atoms C8, C2, C4, C20, N2 and C7 deviate from the mean plane by −0.361 (2), −0.244 (2), 0.232 (2), −0.217 (2), 0.203 (2) and −0.203 (2) Å, respectively. The smallest deviations are for the atoms associated with the pyrrole ring at the N3 position; atoms C11 C12, C13, C14 and N3 deviate from the mean plane by −0.003 (2), −0.027 (2), 0.027 (2), 0.009 (2) and −0.007 (2), respectively. This ring also shows the least tilt in the porphyrin structure.
In the crystal, the four molecules stack with a 90° rotation with regards to the tert-butyl-substituted group. The centroid–centroid distance of the 24-atom mean planes of the porphyrin rings are between 8.762 (2) and 7.758 (2) Å. The rings that stack above each other are separated by 8.762 (2) Å and the rings that are orientated in an edge-on packing are separated by a centroid–centroid distance of 7.758 (2) Å (Fig. 4). The orientation of the molecules in the π interactions (Table 1), forming a three-dimensional framework. There are no solvent molecules contained within the overall structure, as seen in Fig. 5.
shows that the Cb-hydrogen atoms between the tert-butyl group at C5 and the phenyl group at C10 are pointing towards the center of the neighbouring ring. Molecules are linked by a number of weak C—H···A search of the Cambridge Structural Database (CSD, Version 5.36, update November 2014; Groom & Allen, 2014) gave several hits for unsymmetrically meso-substituted
similar to the title compound. Speck et al. (1997) reported the structure of 5-(3,5-di-tert-butylmuconic acid anhydride)-10,15,20-triphenylporphyrin in which they reported phenyl tilt angles of 59.07–78.15° from the 24-atom mean plane, with the largest deviation on the phenyl group opposite the alternative meso-substituted position. In this structure there was a larger variance of the Ca-–Cm(phenyl)—Ca angle of 123.88–125.51° and a Ca-–Cm(C5)—Ca larger than the title compound of 127.35°. Senge et al. (1999) published the structure of 5-(2,5-dimethoxybenzyl)-10,15,20-triphenylporphyrin. The tilt angle of the phenyl rings from the 24-atom mean plane was larger and more varied compared to the title compound (73.47–87.56°). The Ca—Cm(phenyl)—Ca angle is similar to the title compound with an angle range of 125.46–125.78°. The structure of 5-(3,5-dihydroxyphenyl)-10,15,20-triphenylporphyrin pyridine clathrate has been reported by Tanaka et al. (2001). This compound displayed a phenyl tilt angle of 65.87–73.97° from the 24-atom mean plane and all Ca-–Cm-–Ca angles are of a similar size, 124.68–125.97°. Wojaczyński et al. (2002) reported the structure of 5,10,15-triphenylporphyrin which displays similar properties to the title compound with regards to the Ca-–Cm(phenyl)—Ca angle either side of the unsubstituted meso position being almost equal to each other (123.78–123.95°). The Ca—Cm(phenyl)—Ca opposite the unsubstituted meso position is smaller than the Ca—Cm(H)—Ca angle, 126.20 and 127.93°, respectively. The phenyl tilt angle from the 24-atom mean plane shows a larger tilt angle (73.56–78.16°) associated with the phenyl rings. However, there is a narrower variance in these angle than in the title compound. Ryppa et al. (2005) published the structure of 5-tert-butylporphyrin which presents Ca-–Cm(H)—Ca angles of 129.00–129.23° for the C10 and C15 positions and 125.23° for the C15 position which are all larger than in the title compound. The Ca—Cm(tert-butyl)—Ca angle (C5 in both structures) are of similar size at 119.86° (120.28° for the title compound). The overall pyrrole tilt against the mean 24-atom plane shows similar results to that of the title compound. The pyrrole rings (N1 and N2) closest to the tert-butyl meso substitute show significantly higher tilts (11.68 and 14.33°, respectively) compared to the pyrrole rings (N3 and N4) closest to the unsubstituted position at C15 (4.04 and 5.26°, respectively). Yang et al. (2011) reported the structure ethyl 8-(10,15,20-triphenylporphyrin-5-yl)-1-naphthoate exhibiting a phenyl tilt angle from the 24-atom mean plane of 59.13° for the phenyl opposite the naphthanote substitute and between 74.91–76.38° for the other phenyl groups. A similar angle for all Ca—Cm-–Ca is observed, 125.36–125.82°. Ma et al. (2013) published the structure of 2-hydroxyphenyl 8-(10,15,20-triphenylporphyrin-5-yl)-1-naphthoate which exhibited a Ca—Cm(phenyl)—Ca angle of 124.36–124.68° similar to the title compound and a Ca—Cm(naphthoate)—Ca angle of 125.25° which is slightly larger compared to the title compound. The tilt angle of the phenyl rings from the 24-atom mean plane is 60.46–83.15° which shows a larger variance than for the title compound.The title compound was prepared previously by Senge et al. (2000) using a condensation approach. Here, 5-(tert-butyl)-porphyrin (100 mg, 0.27 mmol, 1 eq) was dissolved in dry CHCl3 (50 ml) and cooled to 273 K. N-Bromosuccinimide (145 mg, 0.81 mmol, 3 eq) was added and the solution was stirred for 5 h. The resulting solution was quenched with acetone and the crude product was purified via δ: 9.45 (d, 3JH—H = 4.76 Hz, 2H, Hβ), 9.36 (d, 3JH—H = 4.76 Hz, 2H, Hβ), 9.31 (d, 3JH—H = 5.04 Hz, 2H, Hβ), 9.25 (d, 3JH—H = 5 Hz, 2H, Hβ), 2.33 (s, 9H, CH3), −1.72 p.p.m. (brs, 2H, NH); HRMS (MALDI): m/z calculated for C24H19N4Br3 600.9238 [M + H]+; found 600.9248.
on silica gel (hexane/CH2Cl2 = 4:1, v/v). The solvent was removed in vacuo yielding 5-(tert-butyl)-10,15,20-tribromoporphyrin as purple crystals (yield: 45 mg, 0.075 mmol, 28%). Rf = 0.44 (hexane:CH2Cl2, 2:1); 1H NMR (400 MHz, CDCl3)A Schlenk tube was charged with 5-(tert-butyl)-10,15,20-tribromoporphyrin (20 mg, 0.033 mmol, 1 eq), phenylboronic acid (121.93 mg, 1 mmol, 30 eq), tetrakis(triphenylphosphine)palladium(0) (7.63 mg, 0.0066 mmol, 0.2 eq), caesium carbonate (651.64 mg, 2 mmol, 60 eq) and dried under vacuum. The mixture was dissolved in anhydrous THF (5 ml) and was degassed via three freeze–pump–thaw cycles and left under argon. The solution was heated to 353 K under an argon atmosphere for 48 h. The solvent was removed under reduced pressure and the residue was dissolved in CH2Cl2 (10 ml). The crude product was washed sequentially with sat. aq. NaHCO3 (20 ml) and deionized H2O (20 ml). The organic phase was dried over Na2SO4 and filtered. The crude product was purified via
on silica gel (hexane/CH2Cl2 = 1:1, v/v). The solvent was removed in vacuo, yielding the title compound as purple crystals (yield: 15 mg, 0.025 mmol, 76%). The compound was recrystallized from CH2Cl2 layered with methanol to yield single crystals suitable for X-ray diffraction analysis. detailsCrystal data, data collection and structure
details are summarized in Table 2. The structure was refined as a two-component The NH and C-bound H atoms were placed in their expected calculated positions and refined using a standard riding model: N—H = 0.88 Å, C—H = 0.95–0.98 Å, with Uiso(H) = 1.5Ueq(C-methyl) and 1.2Ueq(N,C) for other H atoms.Data collection: APEX2 (Bruker, 2014); cell
SAINT-Plus (Bruker, 2014); data reduction: SAINT-Plus (Bruker, 2014); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014/7 (Sheldrick, 2015b); molecular graphics: XP (Sheldrick, 2008); software used to prepare material for publication: publCIF (Westrip, 2010).Fig. 1. The molecular structure of the title compound, with atom labelling. Displacement ellipsoids are drawn at the 50% probability level. The bifurcated N—H···(N,N) hydrogen bonds are shown as dashed lines (see Table 1). | |
Fig. 2. Side view of the structure of the title compound looking down the C5 meso-position, showing the tilt angle of the macrocycle rings. Displacement ellipsoids are drawn at the 50% probability level. | |
Fig. 3. NSD analysis of the title compound and comparison with 5-(tert-butyl)porphyrin. NSD gives a graphical representation of the displacements along the lowest frequency coordinates that best simulate the structures. | |
Fig. 4. Unit cell of the title compound viewed along the a axis, showing four complete molecular units. | |
Fig. 5. Crystal packing of the title compound, viewed along the b axis. |
C42H34N4 | Dx = 1.250 Mg m−3 |
Mr = 594.73 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, P212121 | Cell parameters from 9394 reflections |
a = 11.3373 (4) Å | θ = 2.4–27.6° |
b = 12.6936 (5) Å | µ = 0.07 mm−1 |
c = 21.9616 (8) Å | T = 100 K |
V = 3160.5 (2) Å3 | Block, purple |
Z = 4 | 0.34 × 0.30 × 0.30 mm |
F(000) = 1256 |
Bruker SMART APEX2 area detector diffractometer | 7377 independent reflections |
Radiation source: sealed tube | 7039 reflections with I > 2σ(I) |
Detector resolution: 8.258 pixels mm-1 | Rint = 0.029 |
φ and ω scans | θmax = 27.7°, θmin = 1.9° |
Absorption correction: multi-scan (SADABS; Bruker, 2014) | h = −14→14 |
Tmin = 0.697, Tmax = 0.746 | k = −16→16 |
124779 measured reflections | l = −28→28 |
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.038 | w = 1/[σ2(Fo2) + (0.0624P)2 + 0.8289P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.106 | (Δ/σ)max < 0.001 |
S = 1.06 | Δρmax = 0.30 e Å−3 |
7377 reflections | Δρmin = −0.22 e Å−3 |
419 parameters | Absolute structure: Refined as an inversion twin |
0 restraints |
C42H34N4 | V = 3160.5 (2) Å3 |
Mr = 594.73 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 11.3373 (4) Å | µ = 0.07 mm−1 |
b = 12.6936 (5) Å | T = 100 K |
c = 21.9616 (8) Å | 0.34 × 0.30 × 0.30 mm |
Bruker SMART APEX2 area detector diffractometer | 7377 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2014) | 7039 reflections with I > 2σ(I) |
Tmin = 0.697, Tmax = 0.746 | Rint = 0.029 |
124779 measured reflections |
R[F2 > 2σ(F2)] = 0.038 | 0 restraints |
wR(F2) = 0.106 | H-atom parameters constrained |
S = 1.06 | Δρmax = 0.30 e Å−3 |
7377 reflections | Δρmin = −0.22 e Å−3 |
419 parameters | Absolute structure: Refined as an inversion twin |
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. Refined as a 2-component inversion twin. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.62591 (17) | 0.45488 (15) | 0.12493 (9) | 0.0203 (4) | |
C2 | 0.59743 (18) | 0.55211 (16) | 0.09532 (9) | 0.0229 (4) | |
H32 | 0.6114 | 0.6207 | 0.1110 | 0.027* | |
C3 | 0.54693 (19) | 0.52918 (16) | 0.04083 (10) | 0.0239 (4) | |
H33 | 0.5204 | 0.5793 | 0.0117 | 0.029* | |
C4 | 0.54015 (17) | 0.41647 (15) | 0.03442 (9) | 0.0204 (4) | |
C5 | 0.48857 (17) | 0.35700 (16) | −0.01260 (9) | 0.0209 (4) | |
C6 | 0.45205 (17) | 0.25105 (16) | −0.00211 (9) | 0.0196 (4) | |
C7 | 0.35626 (19) | 0.19968 (16) | −0.03491 (9) | 0.0227 (4) | |
H7 | 0.3092 | 0.2299 | −0.0662 | 0.027* | |
C8 | 0.34703 (18) | 0.10171 (16) | −0.01265 (9) | 0.0228 (4) | |
H8 | 0.2923 | 0.0493 | −0.0251 | 0.027* | |
C9 | 0.43661 (17) | 0.09110 (15) | 0.03413 (9) | 0.0197 (4) | |
C10 | 0.45654 (18) | −0.00410 (16) | 0.06508 (9) | 0.0212 (4) | |
C11 | 0.52777 (18) | −0.01752 (16) | 0.11669 (9) | 0.0229 (4) | |
C12 | 0.5508 (2) | −0.11397 (17) | 0.14810 (10) | 0.0289 (5) | |
H14 | 0.5230 | −0.1817 | 0.1366 | 0.035* | |
C13 | 0.6196 (2) | −0.09202 (17) | 0.19738 (11) | 0.0286 (5) | |
H15 | 0.6477 | −0.1415 | 0.2264 | 0.034* | |
C14 | 0.64198 (18) | 0.01871 (16) | 0.19762 (9) | 0.0220 (4) | |
C15 | 0.71165 (17) | 0.07601 (16) | 0.23872 (9) | 0.0213 (4) | |
C16 | 0.73131 (18) | 0.18453 (16) | 0.23489 (9) | 0.0220 (4) | |
C17 | 0.8031 (2) | 0.24329 (18) | 0.27767 (9) | 0.0269 (4) | |
H17 | 0.8470 | 0.2152 | 0.3108 | 0.032* | |
C18 | 0.7955 (2) | 0.34552 (17) | 0.26138 (10) | 0.0265 (4) | |
H16 | 0.8332 | 0.4034 | 0.2807 | 0.032* | |
C19 | 0.71826 (18) | 0.34990 (17) | 0.20853 (9) | 0.0222 (4) | |
C20 | 0.68693 (17) | 0.44495 (16) | 0.17978 (9) | 0.0207 (4) | |
C51 | 0.4682 (2) | 0.40954 (17) | −0.07592 (10) | 0.0258 (4) | |
C52 | 0.5728 (3) | 0.4822 (2) | −0.09285 (11) | 0.0416 (6) | |
H26 | 0.5619 | 0.5091 | −0.1343 | 0.062* | |
H28 | 0.6466 | 0.4422 | −0.0907 | 0.062* | |
H27 | 0.5762 | 0.5415 | −0.0643 | 0.062* | |
C53 | 0.3523 (2) | 0.4725 (2) | −0.07555 (12) | 0.0379 (6) | |
H25 | 0.3423 | 0.5081 | −0.1148 | 0.057* | |
H23 | 0.3547 | 0.5251 | −0.0429 | 0.057* | |
H24 | 0.2859 | 0.4245 | −0.0687 | 0.057* | |
C54 | 0.4670 (2) | 0.32888 (19) | −0.12892 (10) | 0.0328 (5) | |
H30 | 0.3922 | 0.2902 | −0.1286 | 0.049* | |
H29 | 0.5325 | 0.2793 | −0.1240 | 0.049* | |
H31 | 0.4754 | 0.3662 | −0.1677 | 0.049* | |
C101 | 0.39426 (18) | −0.10025 (16) | 0.04186 (10) | 0.0237 (4) | |
C102 | 0.3099 (2) | −0.15159 (18) | 0.07717 (11) | 0.0309 (5) | |
H11 | 0.2940 | −0.1273 | 0.1173 | 0.037* | |
C103 | 0.2487 (2) | −0.2378 (2) | 0.05445 (12) | 0.0376 (5) | |
H12 | 0.1914 | −0.2718 | 0.0792 | 0.045* | |
C104 | 0.2698 (2) | −0.27463 (18) | −0.00350 (12) | 0.0355 (5) | |
H2 | 0.2257 | −0.3321 | −0.0194 | 0.043* | |
C105 | 0.3566 (2) | −0.22658 (19) | −0.03835 (12) | 0.0349 (5) | |
H10 | 0.3742 | −0.2533 | −0.0777 | 0.042* | |
C106 | 0.4181 (2) | −0.13967 (18) | −0.01629 (11) | 0.0305 (5) | |
H9 | 0.4765 | −0.1070 | −0.0409 | 0.037* | |
C151 | 0.76452 (18) | 0.01846 (16) | 0.29167 (9) | 0.0224 (4) | |
C152 | 0.8858 (2) | 0.00258 (18) | 0.29672 (11) | 0.0296 (5) | |
H22 | 0.9363 | 0.0245 | 0.2646 | 0.035* | |
C153 | 0.9336 (2) | −0.04490 (17) | 0.34815 (11) | 0.0308 (5) | |
H21 | 1.0165 | −0.0550 | 0.3509 | 0.037* | |
C154 | 0.8620 (2) | −0.07733 (18) | 0.39504 (10) | 0.0303 (5) | |
H20 | 0.8952 | −0.1086 | 0.4304 | 0.036* | |
C155 | 0.7411 (2) | −0.0641 (3) | 0.39028 (11) | 0.0439 (7) | |
H19 | 0.6910 | −0.0871 | 0.4223 | 0.053* | |
C156 | 0.6928 (2) | −0.0172 (2) | 0.33863 (10) | 0.0376 (6) | |
H18 | 0.6097 | −0.0095 | 0.3355 | 0.045* | |
C201 | 0.72236 (19) | 0.54413 (16) | 0.21163 (10) | 0.0240 (4) | |
C202 | 0.6685 (2) | 0.56983 (18) | 0.26648 (10) | 0.0315 (5) | |
H4 | 0.6079 | 0.5260 | 0.2823 | 0.038* | |
C203 | 0.7030 (3) | 0.65957 (19) | 0.29837 (11) | 0.0376 (6) | |
H5 | 0.6658 | 0.6771 | 0.3358 | 0.045* | |
C204 | 0.7912 (3) | 0.72280 (18) | 0.27563 (12) | 0.0394 (6) | |
H1 | 0.8155 | 0.7834 | 0.2977 | 0.047* | |
C205 | 0.8445 (2) | 0.69838 (19) | 0.22084 (13) | 0.0379 (6) | |
H34 | 0.9050 | 0.7425 | 0.2052 | 0.045* | |
C206 | 0.8097 (2) | 0.60957 (18) | 0.18865 (11) | 0.0309 (5) | |
H3 | 0.8459 | 0.5935 | 0.1507 | 0.037* | |
N1 | 0.58622 (15) | 0.37541 (13) | 0.08755 (7) | 0.0195 (3) | |
H1A | 0.5897 | 0.3078 | 0.0963 | 0.023* | |
N2 | 0.49590 (15) | 0.18454 (13) | 0.04146 (8) | 0.0194 (3) | |
N3 | 0.58505 (15) | 0.06048 (13) | 0.14814 (7) | 0.0206 (3) | |
H3A | 0.5852 | 0.1276 | 0.1380 | 0.025* | |
N4 | 0.68278 (15) | 0.25104 (13) | 0.19218 (7) | 0.0207 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0194 (8) | 0.0195 (9) | 0.0221 (9) | 0.0008 (7) | 0.0007 (7) | −0.0005 (7) |
C2 | 0.0248 (9) | 0.0176 (9) | 0.0263 (9) | 0.0017 (7) | −0.0015 (8) | −0.0013 (7) |
C3 | 0.0287 (10) | 0.0171 (9) | 0.0260 (9) | 0.0009 (8) | −0.0027 (8) | 0.0024 (7) |
C4 | 0.0178 (8) | 0.0203 (9) | 0.0230 (9) | 0.0019 (7) | 0.0005 (7) | 0.0012 (7) |
C5 | 0.0185 (8) | 0.0215 (9) | 0.0227 (9) | 0.0018 (7) | −0.0010 (7) | 0.0005 (7) |
C6 | 0.0193 (8) | 0.0212 (9) | 0.0183 (8) | 0.0015 (7) | 0.0002 (7) | −0.0026 (7) |
C7 | 0.0239 (9) | 0.0227 (9) | 0.0214 (9) | −0.0014 (7) | −0.0042 (8) | −0.0013 (7) |
C8 | 0.0234 (9) | 0.0223 (9) | 0.0228 (9) | −0.0011 (7) | −0.0041 (8) | −0.0009 (8) |
C9 | 0.0197 (9) | 0.0208 (9) | 0.0186 (9) | 0.0004 (7) | 0.0001 (7) | −0.0011 (7) |
C10 | 0.0223 (9) | 0.0204 (9) | 0.0208 (9) | 0.0013 (7) | −0.0012 (7) | −0.0007 (7) |
C11 | 0.0237 (9) | 0.0198 (9) | 0.0251 (9) | 0.0021 (7) | −0.0027 (8) | 0.0010 (8) |
C12 | 0.0348 (11) | 0.0200 (10) | 0.0320 (11) | 0.0012 (9) | −0.0100 (9) | 0.0025 (8) |
C13 | 0.0336 (11) | 0.0219 (9) | 0.0305 (11) | 0.0002 (9) | −0.0091 (9) | 0.0049 (8) |
C14 | 0.0235 (9) | 0.0204 (9) | 0.0221 (9) | 0.0015 (7) | −0.0027 (7) | 0.0036 (7) |
C15 | 0.0199 (9) | 0.0232 (9) | 0.0207 (9) | 0.0024 (7) | −0.0021 (7) | 0.0013 (7) |
C16 | 0.0228 (9) | 0.0232 (9) | 0.0199 (9) | 0.0017 (7) | −0.0017 (7) | 0.0016 (7) |
C17 | 0.0303 (10) | 0.0283 (10) | 0.0220 (10) | 0.0021 (9) | −0.0087 (8) | 0.0002 (8) |
C18 | 0.0316 (11) | 0.0231 (10) | 0.0248 (10) | 0.0011 (8) | −0.0081 (9) | −0.0020 (8) |
C19 | 0.0208 (9) | 0.0247 (10) | 0.0213 (9) | 0.0005 (8) | −0.0002 (8) | −0.0011 (8) |
C20 | 0.0201 (9) | 0.0204 (9) | 0.0215 (9) | −0.0004 (7) | 0.0011 (7) | −0.0008 (7) |
C51 | 0.0293 (10) | 0.0221 (9) | 0.0260 (10) | −0.0005 (8) | −0.0052 (8) | 0.0042 (8) |
C52 | 0.0548 (16) | 0.0427 (14) | 0.0274 (11) | −0.0190 (13) | −0.0019 (11) | 0.0082 (10) |
C53 | 0.0417 (13) | 0.0336 (12) | 0.0385 (12) | 0.0135 (11) | −0.0096 (11) | 0.0046 (10) |
C54 | 0.0441 (13) | 0.0330 (12) | 0.0213 (10) | −0.0018 (10) | 0.0011 (9) | 0.0016 (8) |
C101 | 0.0259 (10) | 0.0196 (9) | 0.0255 (10) | 0.0028 (8) | −0.0049 (8) | 0.0002 (8) |
C102 | 0.0344 (11) | 0.0281 (11) | 0.0302 (11) | −0.0039 (9) | 0.0025 (9) | −0.0032 (9) |
C103 | 0.0380 (12) | 0.0307 (12) | 0.0443 (14) | −0.0073 (10) | 0.0028 (10) | −0.0021 (10) |
C104 | 0.0408 (13) | 0.0218 (10) | 0.0440 (13) | −0.0002 (9) | −0.0103 (11) | −0.0040 (9) |
C105 | 0.0476 (14) | 0.0243 (10) | 0.0328 (12) | 0.0053 (10) | −0.0051 (11) | −0.0071 (9) |
C106 | 0.0402 (12) | 0.0233 (10) | 0.0279 (10) | 0.0027 (9) | −0.0014 (9) | −0.0017 (8) |
C151 | 0.0254 (10) | 0.0206 (9) | 0.0212 (9) | 0.0004 (8) | −0.0042 (7) | 0.0010 (7) |
C152 | 0.0256 (10) | 0.0269 (10) | 0.0362 (11) | −0.0030 (8) | −0.0019 (9) | 0.0117 (9) |
C153 | 0.0260 (10) | 0.0250 (10) | 0.0414 (12) | −0.0022 (9) | −0.0108 (9) | 0.0083 (9) |
C154 | 0.0394 (12) | 0.0274 (11) | 0.0242 (10) | 0.0065 (9) | −0.0096 (9) | 0.0011 (8) |
C155 | 0.0403 (13) | 0.0683 (19) | 0.0231 (11) | 0.0171 (13) | 0.0068 (10) | 0.0140 (11) |
C156 | 0.0275 (11) | 0.0577 (16) | 0.0277 (11) | 0.0117 (11) | 0.0035 (9) | 0.0128 (11) |
C201 | 0.0256 (9) | 0.0213 (9) | 0.0251 (9) | 0.0004 (8) | −0.0058 (8) | −0.0008 (8) |
C202 | 0.0390 (12) | 0.0272 (11) | 0.0283 (11) | 0.0000 (9) | −0.0015 (9) | −0.0046 (9) |
C203 | 0.0562 (16) | 0.0270 (11) | 0.0297 (11) | 0.0092 (11) | −0.0103 (11) | −0.0074 (9) |
C204 | 0.0527 (15) | 0.0217 (10) | 0.0439 (14) | 0.0055 (10) | −0.0272 (12) | −0.0059 (9) |
C205 | 0.0335 (12) | 0.0240 (11) | 0.0561 (16) | −0.0016 (9) | −0.0128 (11) | 0.0019 (10) |
C206 | 0.0262 (10) | 0.0271 (11) | 0.0395 (12) | 0.0008 (9) | −0.0024 (9) | 0.0005 (9) |
N1 | 0.0204 (7) | 0.0165 (7) | 0.0217 (8) | 0.0001 (6) | −0.0010 (6) | 0.0015 (6) |
N2 | 0.0210 (8) | 0.0185 (8) | 0.0186 (7) | 0.0009 (6) | −0.0001 (6) | −0.0004 (6) |
N3 | 0.0232 (8) | 0.0174 (7) | 0.0213 (8) | 0.0004 (6) | −0.0032 (6) | 0.0032 (6) |
N4 | 0.0225 (8) | 0.0199 (8) | 0.0197 (8) | 0.0007 (7) | −0.0008 (6) | 0.0024 (6) |
C1—N1 | 1.376 (2) | C52—H28 | 0.9800 |
C1—C20 | 1.395 (3) | C52—H27 | 0.9800 |
C1—C2 | 1.432 (3) | C53—H25 | 0.9800 |
C2—C3 | 1.358 (3) | C53—H23 | 0.9800 |
C2—H32 | 0.9500 | C53—H24 | 0.9800 |
C3—C4 | 1.440 (3) | C54—H30 | 0.9800 |
C3—H33 | 0.9500 | C54—H29 | 0.9800 |
C4—N1 | 1.381 (2) | C54—H31 | 0.9800 |
C4—C5 | 1.407 (3) | C101—C102 | 1.393 (3) |
C5—C6 | 1.426 (3) | C101—C106 | 1.398 (3) |
C5—C51 | 1.559 (3) | C102—C103 | 1.388 (3) |
C6—N2 | 1.369 (3) | C102—H11 | 0.9500 |
C6—C7 | 1.457 (3) | C103—C104 | 1.377 (4) |
C7—C8 | 1.340 (3) | C103—H12 | 0.9500 |
C7—H7 | 0.9500 | C104—C105 | 1.387 (4) |
C8—C9 | 1.451 (3) | C104—H2 | 0.9500 |
C8—H8 | 0.9500 | C105—C106 | 1.392 (3) |
C9—N2 | 1.373 (2) | C105—H10 | 0.9500 |
C9—C10 | 1.405 (3) | C106—H9 | 0.9500 |
C10—C11 | 1.402 (3) | C151—C156 | 1.389 (3) |
C10—C101 | 1.499 (3) | C151—C152 | 1.394 (3) |
C11—N3 | 1.371 (3) | C152—C153 | 1.390 (3) |
C11—C12 | 1.429 (3) | C152—H22 | 0.9500 |
C12—C13 | 1.363 (3) | C153—C154 | 1.374 (3) |
C12—H14 | 0.9500 | C153—H21 | 0.9500 |
C13—C14 | 1.428 (3) | C154—C155 | 1.385 (4) |
C13—H15 | 0.9500 | C154—H20 | 0.9500 |
C14—N3 | 1.371 (2) | C155—C156 | 1.393 (3) |
C14—C15 | 1.403 (3) | C155—H19 | 0.9500 |
C15—C16 | 1.398 (3) | C156—H18 | 0.9500 |
C15—C151 | 1.499 (3) | C201—C206 | 1.388 (3) |
C16—N4 | 1.377 (2) | C201—C202 | 1.389 (3) |
C16—C17 | 1.450 (3) | C202—C203 | 1.393 (3) |
C17—C18 | 1.349 (3) | C202—H4 | 0.9500 |
C17—H17 | 0.9500 | C203—C204 | 1.376 (4) |
C18—C19 | 1.455 (3) | C203—H5 | 0.9500 |
C18—H16 | 0.9500 | C204—C205 | 1.382 (4) |
C19—N4 | 1.366 (3) | C204—H1 | 0.9500 |
C19—C20 | 1.407 (3) | C205—C206 | 1.388 (3) |
C20—C201 | 1.495 (3) | C205—H34 | 0.9500 |
C51—C53 | 1.539 (3) | C206—H3 | 0.9500 |
C51—C52 | 1.548 (3) | N1—H1A | 0.8800 |
C51—C54 | 1.550 (3) | N3—H3A | 0.8800 |
C52—H26 | 0.9800 | ||
N1—C1—C20 | 127.66 (18) | C51—C53—H23 | 109.5 |
N1—C1—C2 | 106.69 (16) | H25—C53—H23 | 109.5 |
C20—C1—C2 | 125.59 (18) | C51—C53—H24 | 109.5 |
C3—C2—C1 | 108.08 (18) | H25—C53—H24 | 109.5 |
C3—C2—H32 | 126.0 | H23—C53—H24 | 109.5 |
C1—C2—H32 | 126.0 | C51—C54—H30 | 109.5 |
C2—C3—C4 | 108.77 (18) | C51—C54—H29 | 109.5 |
C2—C3—H33 | 125.6 | H30—C54—H29 | 109.5 |
C4—C3—H33 | 125.6 | C51—C54—H31 | 109.5 |
N1—C4—C5 | 125.11 (17) | H30—C54—H31 | 109.5 |
N1—C4—C3 | 105.80 (17) | H29—C54—H31 | 109.5 |
C5—C4—C3 | 128.86 (19) | C102—C101—C106 | 118.3 (2) |
C4—C5—C6 | 120.55 (18) | C102—C101—C10 | 120.98 (19) |
C4—C5—C51 | 119.12 (18) | C106—C101—C10 | 120.7 (2) |
C6—C5—C51 | 120.31 (17) | C103—C102—C101 | 120.8 (2) |
N2—C6—C5 | 126.09 (17) | C103—C102—H11 | 119.6 |
N2—C6—C7 | 109.88 (17) | C101—C102—H11 | 119.6 |
C5—C6—C7 | 123.95 (18) | C104—C103—C102 | 120.9 (2) |
C8—C7—C6 | 107.04 (18) | C104—C103—H12 | 119.6 |
C8—C7—H7 | 126.5 | C102—C103—H12 | 119.6 |
C6—C7—H7 | 126.5 | C103—C104—C105 | 118.9 (2) |
C7—C8—C9 | 106.84 (18) | C103—C104—H2 | 120.5 |
C7—C8—H8 | 126.6 | C105—C104—H2 | 120.5 |
C9—C8—H8 | 126.6 | C104—C105—C106 | 120.8 (2) |
N2—C9—C10 | 127.43 (17) | C104—C105—H10 | 119.6 |
N2—C9—C8 | 110.22 (17) | C106—C105—H10 | 119.6 |
C10—C9—C8 | 122.34 (18) | C105—C106—C101 | 120.3 (2) |
C11—C10—C9 | 126.03 (18) | C105—C106—H9 | 119.8 |
C11—C10—C101 | 116.57 (18) | C101—C106—H9 | 119.8 |
C9—C10—C101 | 117.38 (17) | C156—C151—C152 | 118.1 (2) |
N3—C11—C10 | 126.33 (18) | C156—C151—C15 | 120.06 (19) |
N3—C11—C12 | 106.79 (17) | C152—C151—C15 | 121.78 (19) |
C10—C11—C12 | 126.84 (19) | C153—C152—C151 | 120.8 (2) |
C13—C12—C11 | 108.22 (19) | C153—C152—H22 | 119.6 |
C13—C12—H14 | 125.9 | C151—C152—H22 | 119.6 |
C11—C12—H14 | 125.9 | C154—C153—C152 | 120.5 (2) |
C12—C13—C14 | 107.81 (19) | C154—C153—H21 | 119.7 |
C12—C13—H15 | 126.1 | C152—C153—H21 | 119.7 |
C14—C13—H15 | 126.1 | C153—C154—C155 | 119.5 (2) |
N3—C14—C15 | 125.08 (18) | C153—C154—H20 | 120.3 |
N3—C14—C13 | 107.10 (18) | C155—C154—H20 | 120.3 |
C15—C14—C13 | 127.78 (19) | C154—C155—C156 | 120.1 (2) |
C16—C15—C14 | 124.19 (18) | C154—C155—H19 | 119.9 |
C16—C15—C151 | 117.60 (18) | C156—C155—H19 | 119.9 |
C14—C15—C151 | 118.16 (18) | C151—C156—C155 | 120.9 (2) |
N4—C16—C15 | 125.56 (18) | C151—C156—H18 | 119.5 |
N4—C16—C17 | 110.51 (18) | C155—C156—H18 | 119.5 |
C15—C16—C17 | 123.88 (18) | C206—C201—C202 | 119.2 (2) |
C18—C17—C16 | 106.69 (18) | C206—C201—C20 | 121.71 (19) |
C18—C17—H17 | 126.7 | C202—C201—C20 | 119.03 (19) |
C16—C17—H17 | 126.7 | C201—C202—C203 | 120.3 (2) |
C17—C18—C19 | 106.67 (19) | C201—C202—H4 | 119.9 |
C17—C18—H16 | 126.7 | C203—C202—H4 | 119.9 |
C19—C18—H16 | 126.7 | C204—C203—C202 | 119.9 (2) |
N4—C19—C20 | 126.54 (18) | C204—C203—H5 | 120.0 |
N4—C19—C18 | 110.60 (18) | C202—C203—H5 | 120.0 |
C20—C19—C18 | 122.86 (19) | C203—C204—C205 | 120.2 (2) |
C1—C20—C19 | 126.17 (18) | C203—C204—H1 | 119.9 |
C1—C20—C201 | 117.46 (18) | C205—C204—H1 | 119.9 |
C19—C20—C201 | 116.37 (17) | C204—C205—C206 | 120.1 (2) |
C53—C51—C52 | 110.2 (2) | C204—C205—H34 | 119.9 |
C53—C51—C54 | 109.82 (19) | C206—C205—H34 | 119.9 |
C52—C51—C54 | 102.74 (19) | C205—C206—C201 | 120.2 (2) |
C53—C51—C5 | 110.11 (18) | C205—C206—H3 | 119.9 |
C52—C51—C5 | 110.86 (18) | C201—C206—H3 | 119.9 |
C54—C51—C5 | 112.86 (17) | C1—N1—C4 | 110.55 (16) |
C51—C52—H26 | 109.5 | C1—N1—H1A | 124.7 |
C51—C52—H28 | 109.5 | C4—N1—H1A | 124.7 |
H26—C52—H28 | 109.5 | C6—N2—C9 | 105.85 (16) |
C51—C52—H27 | 109.5 | C14—N3—C11 | 110.07 (16) |
H26—C52—H27 | 109.5 | C14—N3—H3A | 125.0 |
H28—C52—H27 | 109.5 | C11—N3—H3A | 125.0 |
C51—C53—H25 | 109.5 | C19—N4—C16 | 105.46 (17) |
N1—C1—C2—C3 | −2.5 (2) | C6—C5—C51—C52 | −142.9 (2) |
C20—C1—C2—C3 | 174.9 (2) | C4—C5—C51—C54 | 153.5 (2) |
C1—C2—C3—C4 | 0.8 (2) | C6—C5—C51—C54 | −28.3 (3) |
C2—C3—C4—N1 | 1.2 (2) | C11—C10—C101—C102 | 63.5 (3) |
C2—C3—C4—C5 | 175.9 (2) | C9—C10—C101—C102 | −115.2 (2) |
N1—C4—C5—C6 | 16.6 (3) | C11—C10—C101—C106 | −117.5 (2) |
C3—C4—C5—C6 | −157.2 (2) | C9—C10—C101—C106 | 63.7 (3) |
N1—C4—C5—C51 | −165.28 (18) | C106—C101—C102—C103 | −1.8 (3) |
C3—C4—C5—C51 | 21.0 (3) | C10—C101—C102—C103 | 177.1 (2) |
C4—C5—C6—N2 | −24.7 (3) | C101—C102—C103—C104 | 0.0 (4) |
C51—C5—C6—N2 | 157.20 (19) | C102—C103—C104—C105 | 2.3 (4) |
C4—C5—C6—C7 | 151.72 (19) | C103—C104—C105—C106 | −2.7 (4) |
C51—C5—C6—C7 | −26.4 (3) | C104—C105—C106—C101 | 0.8 (4) |
N2—C6—C7—C8 | −2.7 (2) | C102—C101—C106—C105 | 1.4 (3) |
C5—C6—C7—C8 | −179.56 (19) | C10—C101—C106—C105 | −177.5 (2) |
C6—C7—C8—C9 | 0.0 (2) | C16—C15—C151—C156 | 107.2 (2) |
C7—C8—C9—N2 | 2.6 (2) | C14—C15—C151—C156 | −70.3 (3) |
C7—C8—C9—C10 | −176.48 (19) | C16—C15—C151—C152 | −70.3 (3) |
N2—C9—C10—C11 | 11.5 (3) | C14—C15—C151—C152 | 112.2 (2) |
C8—C9—C10—C11 | −169.67 (19) | C156—C151—C152—C153 | −1.8 (4) |
N2—C9—C10—C101 | −169.90 (19) | C15—C151—C152—C153 | 175.7 (2) |
C8—C9—C10—C101 | 9.0 (3) | C151—C152—C153—C154 | 0.1 (4) |
C9—C10—C11—N3 | 4.0 (3) | C152—C153—C154—C155 | 1.2 (4) |
C101—C10—C11—N3 | −174.65 (19) | C153—C154—C155—C156 | −0.8 (4) |
C9—C10—C11—C12 | −178.7 (2) | C152—C151—C156—C155 | 2.2 (4) |
C101—C10—C11—C12 | 2.6 (3) | C15—C151—C156—C155 | −175.4 (3) |
N3—C11—C12—C13 | 0.6 (3) | C154—C155—C156—C151 | −1.0 (5) |
C10—C11—C12—C13 | −177.1 (2) | C1—C20—C201—C206 | −70.1 (3) |
C11—C12—C13—C14 | −0.5 (3) | C19—C20—C201—C206 | 110.2 (2) |
C12—C13—C14—N3 | 0.2 (3) | C1—C20—C201—C202 | 111.6 (2) |
C12—C13—C14—C15 | −177.8 (2) | C19—C20—C201—C202 | −68.1 (3) |
N3—C14—C15—C16 | 0.7 (3) | C206—C201—C202—C203 | −0.8 (3) |
C13—C14—C15—C16 | 178.4 (2) | C20—C201—C202—C203 | 177.5 (2) |
N3—C14—C15—C151 | 178.04 (19) | C201—C202—C203—C204 | −0.3 (4) |
C13—C14—C15—C151 | −4.2 (3) | C202—C203—C204—C205 | 0.9 (4) |
C14—C15—C16—N4 | 2.4 (3) | C203—C204—C205—C206 | −0.3 (4) |
C151—C15—C16—N4 | −174.98 (19) | C204—C205—C206—C201 | −0.8 (4) |
C14—C15—C16—C17 | 179.8 (2) | C202—C201—C206—C205 | 1.4 (3) |
C151—C15—C16—C17 | 2.4 (3) | C20—C201—C206—C205 | −176.9 (2) |
N4—C16—C17—C18 | 1.3 (3) | C20—C1—N1—C4 | −174.01 (19) |
C15—C16—C17—C18 | −176.4 (2) | C2—C1—N1—C4 | 3.3 (2) |
C16—C17—C18—C19 | 0.3 (2) | C5—C4—N1—C1 | −177.77 (18) |
C17—C18—C19—N4 | −1.8 (3) | C3—C4—N1—C1 | −2.8 (2) |
C17—C18—C19—C20 | 178.2 (2) | C5—C6—N2—C9 | −179.02 (19) |
N1—C1—C20—C19 | −1.3 (3) | C7—C6—N2—C9 | 4.1 (2) |
C2—C1—C20—C19 | −178.2 (2) | C10—C9—N2—C6 | 174.85 (19) |
N1—C1—C20—C201 | 179.02 (19) | C8—C9—N2—C6 | −4.1 (2) |
C2—C1—C20—C201 | 2.2 (3) | C15—C14—N3—C11 | 178.23 (19) |
N4—C19—C20—C1 | −8.5 (3) | C13—C14—N3—C11 | 0.1 (2) |
C18—C19—C20—C1 | 171.5 (2) | C10—C11—N3—C14 | 177.3 (2) |
N4—C19—C20—C201 | 171.15 (19) | C12—C11—N3—C14 | −0.4 (2) |
C18—C19—C20—C201 | −8.8 (3) | C20—C19—N4—C16 | −177.4 (2) |
C4—C5—C51—C53 | −83.4 (2) | C18—C19—N4—C16 | 2.6 (2) |
C6—C5—C51—C53 | 94.8 (2) | C15—C16—N4—C19 | 175.3 (2) |
C4—C5—C51—C52 | 38.9 (3) | C17—C16—N4—C19 | −2.4 (2) |
Cg1, Cg2, Cg3, Cg4 and Cg6 are the centroids of rings N1/C1–C4, N2/C6–C9, N3/C11–C14, N4/C16–C19 and C151–C156, respectively. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···N2 | 0.88 | 2.24 | 2.818 (2) | 123 |
N1—H1A···N4 | 0.88 | 2.46 | 2.995 (2) | 119 |
N3—H3A···N2 | 0.88 | 2.46 | 2.998 (2) | 120 |
N3—H3A···N4 | 0.88 | 2.26 | 2.831 (2) | 123 |
C204—H1···Cg6i | 0.95 | 2.57 | 3.477 (3) | 160 |
C202—H4···Cg3ii | 0.95 | 2.61 | 3.511 (2) | 160 |
C8—H8···Cg1iii | 0.95 | 2.67 | 3.452 (2) | 140 |
C156—H18···Cg1iv | 0.95 | 2.90 | 3.610 (2) | 132 |
C154—H20···Cg2v | 0.95 | 2.78 | 3.654 (2) | 153 |
C54—H30···Cg4iii | 0.98 | 2.98 | 3.664 (2) | 128 |
Symmetry codes: (i) x, y+1, z; (ii) −x+1, y+1/2, −z+1/2; (iii) x−1/2, −y+1/2, −z; (iv) −x+1, y−1/2, −z+1/2; (v) −x+3/2, −y, z+1/2. |
Cg1, Cg2, Cg3, Cg4 and Cg6 are the centroids of rings N1/C1–C4, N2/C6–C9, N3/C11–C14, N4/C16–C19 and C151–C156, respectively. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···N2 | 0.88 | 2.24 | 2.818 (2) | 123 |
N1—H1A···N4 | 0.88 | 2.46 | 2.995 (2) | 119 |
N3—H3A···N2 | 0.88 | 2.46 | 2.998 (2) | 120 |
N3—H3A···N4 | 0.88 | 2.26 | 2.831 (2) | 123 |
C204—H1···Cg6i | 0.95 | 2.57 | 3.477 (3) | 160 |
C202—H4···Cg3ii | 0.95 | 2.61 | 3.511 (2) | 160 |
C8—H8···Cg1iii | 0.95 | 2.67 | 3.452 (2) | 140 |
C156—H18···Cg1iv | 0.95 | 2.90 | 3.610 (2) | 132 |
C154—H20···Cg2v | 0.95 | 2.78 | 3.654 (2) | 153 |
C54—H30···Cg4iii | 0.98 | 2.98 | 3.664 (2) | 128 |
Symmetry codes: (i) x, y+1, z; (ii) −x+1, y+1/2, −z+1/2; (iii) x−1/2, −y+1/2, −z; (iv) −x+1, y−1/2, −z+1/2; (v) −x+3/2, −y, z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C42H34N4 |
Mr | 594.73 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 100 |
a, b, c (Å) | 11.3373 (4), 12.6936 (5), 21.9616 (8) |
V (Å3) | 3160.5 (2) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.07 |
Crystal size (mm) | 0.34 × 0.30 × 0.30 |
Data collection | |
Diffractometer | Bruker SMART APEX2 area detector |
Absorption correction | Multi-scan (SADABS; Bruker, 2014) |
Tmin, Tmax | 0.697, 0.746 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 124779, 7377, 7039 |
Rint | 0.029 |
(sin θ/λ)max (Å−1) | 0.653 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.038, 0.106, 1.06 |
No. of reflections | 7377 |
No. of parameters | 419 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.30, −0.22 |
Absolute structure | Refined as an inversion twin |
Computer programs: APEX2 (Bruker, 2014), SAINT-Plus (Bruker, 2014), SHELXT (Sheldrick, 2015a), SHELXL2014/7 (Sheldrick, 2015b), XP (Sheldrick, 2008), publCIF (Westrip, 2010).
Acknowledgements
This work was supported by a grant from the Science Foundation Ireland (SFI IvP 13/IA/1894). EMM thanks SERB, India, for a research grant (SB/FT/CS-157/2012).
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