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ISSN: 2056-9890

2-{[(Bi­phenyl-2-yl)diazen­yl]methyl­­idene}-1,3,3-tri­methyl­indoline

aIndustrial Research Limited, PO Box 31-310, Lower Hutt, New Zealand
*Correspondence e-mail: g.gainsford@irl.cri.nz

(Received 22 February 2011; accepted 8 March 2011; online 15 March 2011)

The title mol­ecule, C24H23N3, shows some delocalization of charge based on the small [8.0 (2)°] angle between the indolin-2-yl­idene ring system and the link methyl­diazene C2N2 atom plane. A further twist of 17.2 (3)° is subtended between the C2N2 plane and its attached benzene ring. The dihedral angle between the biphenyl rings is 47.96(14)°. In the crystal, the mol­ecules pack via C—H⋯π attractive inter­actions.

Related literature

For applications of azo compounds, see: Möhlmann & van der Vorst (1989[Möhlmann, G. & van der Vorst, C. (1989). Side Chain Liquid Crystal Polymers, edited by C. Mcardle. Glasgow: Plenum and Hall.]); Zollinger (1987[Zollinger, H. (1987). In Colour Chemistry, Synthesis, Properties and Applications of Organic Dyes. Weinheim: VCH.]). For related compounds, see Jones (2004[Jones, P. G. (2004). Private Communication to the Cambridge Structural Database (Refcodes EZUCUX and EZUDAE). CCDC, Union Road, Cambridge, England.]); Jones & Chrapkowski (2004[Jones, P. G. & Chrapkowski, A. (2004). Private Communication to the Cambridge Structural Database (Refcode YADTIH). CCDC, Union Road, Cambridge, England.]); Gainsford et al. (2008[Gainsford, G. J., Bhuiyan, M. D. H. & Kay, A. J. (2008). Acta Cryst. C64, o616-o619.]). For a description of the Cambridge Structural Database, see: Allen (2002[Allen, F. H. (2002). Acta Cryst. B58, 380-388.]).

[Scheme 1]

Experimental

Crystal data
  • C24H23N3

  • Mr = 353.45

  • Orthorhombic, P c a 21

  • a = 14.2968 (17) Å

  • b = 8.2407 (10) Å

  • c = 16.2671 (17) Å

  • V = 1916.5 (4) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 0.07 mm−1

  • T = 116 K

  • 0.70 × 0.20 × 0.10 mm

Data collection
  • Bruker APEXII CCD diffractometer

  • Absorption correction: multi-scan [Blessing (1995[Blessing, R. H. (1995). Acta Cryst. A51, 33-38.]) and SADABS (Bruker, 2005[Bruker (2005). APEX2 and SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.])] Tmin = 0.640, Tmax = 0.746

  • 34258 measured reflections

  • 1783 independent reflections

  • 1764 reflections with I > 2σ(I)

  • Rint = 0.041

Refinement
  • R[F2 > 2σ(F2)] = 0.037

  • wR(F2) = 0.086

  • S = 1.23

  • 1783 reflections

  • 247 parameters

  • 1 restraint

  • H-atom parameters constrained

  • Δρmax = 0.19 e Å−3

  • Δρmin = −0.16 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

Cg1, Cg2 and Cg3 are the centroids of the C19–C24, C4–C9 and C13–C18 rings, respectively.

D—H⋯A D—H H⋯A DA D—H⋯A
C1—H1CCg1i 0.98 2.86 3.582 (3) 131
C11—H11BCg3ii 0.98 2.74 3.721 (3) 179
C22—H22⋯Cg2iii 0.95 2.76 3.645 (3) 155
Symmetry codes: (i) [x+{\script{1\over 2}}, -y+2, z]; (ii) [x+{\script{1\over 2}}, -y+1, z]; (iii) [-x+1, -y+2, z-{\script{1\over 2}}].

Data collection: APEX2 (Bruker, 2005[Bruker (2005). APEX2 and SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2005[Bruker (2005). APEX2 and SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; 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: ORTEP-3 (Farrugia, 1997[Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.]) and Mercury (Macrae et al., 2008[Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466-470.]); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009[Spek, A. L. (2009). Acta Cryst. D65, 148-155.]).

Supporting information


Comment top

Azo compounds are integral to a number of fields of organic chemistry. While they played a key part in the development of the dye industry (Zollinger, 1987) they are also finding application as the enabling materials for a range of fields including nonlinear optics, photochromism and holographic recording. Dyes based on azobenzene typically exhibit high extinction coefficients and their absorption maxima can usually be tailored to lie anywhere in the visible region via appropriate substitution onto the phenyl rings. Furthermore due to their geometrically rigid structures and large aspect ratios, azobenzene compounds are ideal as mesogens (Möhlmann & van der Vorst, 1989).

Recently, we have become interested in developing photoswitchable molecules in order to alter the refractive index of a given material via photo-induced rather than electrically induced means (as occurs in nonlinear optical materials). As part of this we have been exploring how the placement of different substituents (e.g. donors, acceptors or neutral) on the backbone of various azo dyes affects the speed and reversibility of the photo- and thermal isomerization processes. Included in these studies have been a suite of compounds containing an indoline donor, an azo linker and a variety of substituents attached to the terminal nitrogen atom of the azo moiety. The molecules are easily prepared via diazotization of the corresponding aryl amine of the terminal substituent and coupling of the resultant diazonium salt with Fisher's base. The reaction is exemplified in Fig. 1 using 2-aminobiphenyl, 1, as the aromatic amine and which yielded the title compound, 3, in 80% yield.

Compound REFCODES below are from the Cambridge Structural Database (Version 5.31, with Aug 2010 updates; Allen, 2002). The asymmetric unit contents and labels of 3 are shown in Fig. 2. The bond lengths and angles, with the exception of those involving atom C12, are essentially identical with those reported by Jones in 2004 [EZUCUX, EZUDAE (Jones, 2004)) and YADTIH (Jones & Chrapkowski (2004)]. In these latter three compounds, where only a phenyl (or para-substituted phenyl) ring was bound to N3, an additional indol-2-ylidene ring was bonded to C12 rather than the hydrogen here (H12). The mean C12—C2 and C12—N2 distances for the three structures were 1.386 (5) and 1.395 (2) Å compared with 1.361 (4) and 1.362 (4) Å here. There are smaller consistent, but barely significant, differences with the N1—C9 and N1—C2 average bond lengths being longer (0.11 (5) Å) and shorter (0.08 (5) °) than found here. These differences can be attributed to extended charge delocalization through the N1—C2—C12—N2 chain that is not observed in the three reference cationic structures.

There is minor buckling beteween the 5- & 6-membered rings in the indol-2-ylidene ring of 1.09 (14) ° compared with 0.46 (14) ° in EZUDAE. The interplanar angles confirm the consistent twist along the delocalization plane: 8.0 (2) ° between the indol-2-ylidene (N1, C2–C9) and the C2,C12,N2,N3 planes, and a further 17.2 (3) ° angle subtended between the latter and the phenyl ring (C14–C18). The biphenyl rings are at 47.96 (14) ° to each other. This is another point of difference with the related compounds, where the "out of plane" indol-2-ylidene ring bound to C12 is at ~80 ° to the mean plane through the phenyl ring bound to N3.

The molecules are held in the lattice by a concerted set of C–H···π interactions shown in Table 1 and Fig. 3. Entry 2 in Table 1 is included because the second methyl hydrogen on C1 (H1A) interacts with atoms C14 & C15 in an adjacent (Cg3) ring. We note that the acidic proton H12 is not positioned to interact with adjacent N2 or N3 acceptors as observed in related compounds with cyano N atoms (e.g. structure (II) in Gainsford et al., 2008). This packing highlights the main difference between this structure and the reference compounds which have extensive hydrogen bonding (C–H···O) to the perchlorate anion and no significant C–H···π interactions.

Related literature top

For applications of azo compounds, see: Möhlmann & van der Vorst (1989); Zollinger (1987). For related compounds, see Jones (2004); Jones & Chrapkowski (2004); Gainsford et al. (2008). For a description of the Cambridge Structural Database, see: Allen (2002).

Experimental top

To conc. sulfuric acid (4 ml) was added 2-aminobiphenyl 1 (5 mmol) and the reaction was stirred and cooled to 273–278 K. A solution of sodium nitrite (380 mg, 5.5 mol) in 10 ml of water was added slowly and the reaction stirred at 273–278 K for 30 min. To this mixture, was added a solution of Fisher's base, 2, (865 mg, 5 mmol) in 20 ml of glacial acetic acid and the reaction was then stirred for a further 2 h at 273–278 K. The reaction mixture was then poured into water and neutralized with aqueous sodium carbonate. The resulting precipitate was collected by filtration, washed with water and dried over sodium sulfate. Recrystallization (ethanol) gave the title compound 3 as a deep red solid; Yield: 80%. Crystals were prepared by slow evaporation in methanol. m.p. 417.8–419.3 K. 1H NMR (DMSO-d6, 500 MHz): 7.58 (d, 1H, J = 10 Hz), 7.46–7.40 (m, 5H), 7.35–7.31 (m, 2H), 7.29–7.25 (m, 2H), 7.22 (s, 1H), 7.09 (d, 1H, J = 10 Hz), 7.02 (t, 2H), 3.31(s, 3H), 1.71(s, 6H). 13C NMR (DMSO-d6, 125 MHz): 28.66, 29.58, 108.23, 115.62, 121.61, 121.87, 126.58, 126.99, 127.54, 127.81, 128.05, 130.30, 131.53, 137.72, 139.35, 139.70, 144.08, 150.79, 165.97. Mass spec: found: M+ 354.1972; 354.1970 (calc); Δ = 0.6 p.p.m..

Refinement top

In the absence of significant anomalous scattering, the values of the Flack parameter were indeterminate. Accordingly, the Friedel-equivalent reflections were merged prior to the final refinements. Two reflections affected by the backstop were omitted from the refinements (using OMIT) and three others were deemed to be outliers. The methyl H atoms were constrained to an ideal geometry (C—H = 0.98 Å) with Uiso(H) = 1.5Ueq(C), but were allowed to rotate freely about the adjacent C—C bond. All other H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms with C—H distances of 1.00 (primary), 0.99 (methylene) or 0.95 (phenyl) Å with Uiso(H) = 1.2Ueq(C).

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top
[Figure 1] Fig. 1. Reaction scheme showing the synthetic procedure for obtaining the title compound.
[Figure 2] Fig. 2. Molecular structure of the asymmetric unit (Farrugia, 1997); displacement ellipsoids are shown at the 50% probability level. H atoms not shown for clarity.
[Figure 3] Fig. 3. Partial packing diagram of the unit cell showing key interactions (see text and Table 1) [Macrae et al., 2008]. Only significant H atoms are shown as balls for clarity. Symmetry (i) x - 1/2, 2 - y, z (ii) 1/2 - x, 1 - y, z (iii) x, y - 1, z (iv) 1 - x, 1 - y, 1/2 + z (v) x - 1/2, 1 - y, z. Ring centres shown as red balls are Cg1 (C19–C24), Cg2 (C4–C9) and Cg3 (C13–C18).
2-{[(Biphenyl-2-yl)diazenyl]methylidene}-1,3,3-trimethylindoline top
Crystal data top
C24H23N3F(000) = 752
Mr = 353.45Dx = 1.225 Mg m3
Orthorhombic, Pca21Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2acCell parameters from 9914 reflections
a = 14.2968 (17) Åθ = 2.5–27.3°
b = 8.2407 (10) ŵ = 0.07 mm1
c = 16.2671 (17) ÅT = 116 K
V = 1916.5 (4) Å3Needle, red
Z = 40.70 × 0.20 × 0.10 mm
Data collection top
Bruker APEXII CCD
diffractometer
1783 independent reflections
Graphite monochromator1764 reflections with I > 2σ(I)
Detector resolution: 8.333 pixels mm-1Rint = 0.041
ϕ and ω scansθmax = 25.2°, θmin = 2.5°
Absorption correction: multi-scan
[Blessing (1995) and SADABS (Bruker, 2005)]
h = 1717
Tmin = 0.640, Tmax = 0.746k = 99
34258 measured reflectionsl = 1919
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)] = 0.037Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.086H-atom parameters constrained
S = 1.23 w = 1/[σ2(Fo2) + (0.0282P)2 + 0.7948P]
where P = (Fo2 + 2Fc2)/3
1783 reflections(Δ/σ)max < 0.001
247 parametersΔρmax = 0.19 e Å3
1 restraintΔρmin = 0.16 e Å3
Crystal data top
C24H23N3V = 1916.5 (4) Å3
Mr = 353.45Z = 4
Orthorhombic, Pca21Mo Kα radiation
a = 14.2968 (17) ŵ = 0.07 mm1
b = 8.2407 (10) ÅT = 116 K
c = 16.2671 (17) Å0.70 × 0.20 × 0.10 mm
Data collection top
Bruker APEXII CCD
diffractometer
1783 independent reflections
Absorption correction: multi-scan
[Blessing (1995) and SADABS (Bruker, 2005)]
1764 reflections with I > 2σ(I)
Tmin = 0.640, Tmax = 0.746Rint = 0.041
34258 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0371 restraint
wR(F2) = 0.086H-atom parameters constrained
S = 1.23Δρmax = 0.19 e Å3
1783 reflectionsΔρmin = 0.16 e Å3
247 parameters
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
N10.78152 (16)1.0321 (3)0.45002 (13)0.0248 (5)
N20.64108 (16)0.6649 (3)0.43989 (14)0.0238 (5)
N30.58268 (16)0.6112 (3)0.38682 (14)0.0261 (5)
C10.7761 (2)1.1095 (4)0.36962 (19)0.0333 (7)
H1A0.71641.16690.36450.050*
H1B0.78061.02670.32660.050*
H1C0.82771.18690.36370.050*
C20.73892 (18)0.8894 (3)0.47008 (16)0.0216 (6)
C30.76949 (18)0.8406 (3)0.55730 (17)0.0235 (6)
C40.83106 (18)0.9831 (3)0.58035 (17)0.0250 (6)
C50.8798 (2)1.0170 (4)0.6516 (2)0.0376 (7)
H50.87860.94330.69650.045*
C60.9309 (2)1.1616 (4)0.6568 (2)0.0444 (9)
H60.96451.18630.70560.053*
C70.9329 (2)1.2686 (4)0.5914 (2)0.0421 (8)
H70.96791.36630.59620.050*
C80.8851 (2)1.2369 (4)0.5189 (2)0.0349 (7)
H80.88661.31010.47380.042*
C90.83496 (19)1.0929 (3)0.51568 (18)0.0258 (6)
C100.6853 (2)0.8259 (4)0.61544 (18)0.0321 (7)
H10A0.65040.92830.61570.048*
H10B0.70730.80190.67120.048*
H10C0.64430.73810.59650.048*
C110.8248 (2)0.6797 (3)0.55651 (19)0.0276 (6)
H11A0.84790.65630.61200.041*
H11B0.87780.68910.51870.041*
H11C0.78370.59140.53840.041*
C120.67785 (19)0.8119 (3)0.41935 (17)0.0245 (6)
H120.66060.86120.36880.029*
C130.55193 (18)0.4505 (3)0.40219 (17)0.0240 (6)
C140.5934 (2)0.3493 (4)0.46096 (19)0.0312 (7)
H140.64030.39140.49640.037*
C150.5666 (2)0.1883 (3)0.46788 (19)0.0316 (7)
H150.59480.12100.50830.038*
C160.4991 (2)0.1253 (3)0.4164 (2)0.0323 (7)
H160.48330.01350.41910.039*
C170.4546 (2)0.2260 (3)0.36077 (18)0.0282 (6)
H170.40650.18260.32710.034*
C180.47830 (19)0.3887 (3)0.35274 (16)0.0245 (6)
C190.42423 (19)0.4918 (3)0.29410 (17)0.0247 (6)
C200.32655 (19)0.4815 (3)0.29415 (18)0.0280 (6)
H200.29620.41280.33270.034*
C210.2735 (2)0.5700 (4)0.23883 (19)0.0336 (7)
H210.20730.56090.23970.040*
C220.3156 (2)0.6708 (4)0.1826 (2)0.0371 (7)
H220.27890.73080.14460.045*
C230.4127 (2)0.6838 (4)0.18199 (19)0.0367 (8)
H230.44240.75410.14380.044*
C240.4663 (2)0.5949 (4)0.23681 (18)0.0304 (7)
H240.53250.60410.23540.036*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0280 (12)0.0215 (11)0.0248 (12)0.0027 (9)0.0003 (9)0.0034 (10)
N20.0218 (11)0.0250 (12)0.0247 (11)0.0029 (9)0.0005 (9)0.0013 (10)
N30.0282 (12)0.0252 (12)0.0248 (12)0.0016 (10)0.0049 (10)0.0008 (10)
C10.0377 (16)0.0289 (15)0.0334 (16)0.0005 (13)0.0023 (13)0.0120 (14)
C20.0218 (13)0.0214 (12)0.0216 (13)0.0049 (11)0.0021 (11)0.0014 (12)
C30.0247 (14)0.0243 (13)0.0215 (13)0.0042 (11)0.0006 (11)0.0012 (12)
C40.0201 (13)0.0302 (15)0.0249 (13)0.0072 (11)0.0024 (11)0.0055 (12)
C50.0318 (16)0.0471 (18)0.0339 (16)0.0055 (14)0.0057 (14)0.0054 (16)
C60.0334 (17)0.056 (2)0.0438 (19)0.0024 (15)0.0076 (15)0.0196 (18)
C70.0269 (16)0.0374 (18)0.062 (2)0.0023 (14)0.0000 (15)0.0175 (17)
C80.0273 (16)0.0272 (15)0.0502 (18)0.0014 (12)0.0067 (14)0.0066 (15)
C90.0210 (13)0.0241 (14)0.0324 (14)0.0034 (11)0.0036 (12)0.0065 (13)
C100.0287 (15)0.0413 (18)0.0264 (15)0.0042 (14)0.0048 (12)0.0063 (13)
C110.0279 (14)0.0273 (14)0.0276 (14)0.0031 (12)0.0016 (12)0.0065 (13)
C120.0285 (14)0.0228 (14)0.0220 (13)0.0030 (11)0.0004 (11)0.0031 (11)
C130.0248 (14)0.0238 (13)0.0234 (13)0.0049 (11)0.0057 (11)0.0019 (11)
C140.0301 (15)0.0330 (16)0.0305 (15)0.0051 (12)0.0007 (13)0.0011 (13)
C150.0336 (16)0.0267 (15)0.0345 (16)0.0106 (12)0.0096 (13)0.0099 (14)
C160.0336 (16)0.0243 (14)0.0391 (16)0.0006 (13)0.0152 (13)0.0016 (14)
C170.0255 (14)0.0287 (15)0.0304 (15)0.0037 (12)0.0087 (12)0.0015 (12)
C180.0254 (14)0.0269 (14)0.0211 (13)0.0014 (11)0.0088 (11)0.0003 (11)
C190.0286 (14)0.0238 (13)0.0217 (13)0.0018 (11)0.0002 (12)0.0067 (12)
C200.0288 (15)0.0272 (15)0.0282 (14)0.0041 (12)0.0000 (13)0.0076 (13)
C210.0303 (16)0.0348 (16)0.0356 (16)0.0009 (13)0.0067 (13)0.0118 (14)
C220.0432 (18)0.0377 (17)0.0304 (16)0.0063 (15)0.0137 (14)0.0030 (14)
C230.0448 (19)0.0423 (19)0.0230 (15)0.0037 (15)0.0044 (14)0.0070 (14)
C240.0287 (15)0.0367 (17)0.0258 (14)0.0031 (13)0.0032 (12)0.0005 (13)
Geometric parameters (Å, º) top
N1—C21.364 (3)C11—H11A0.9800
N1—C91.405 (4)C11—H11B0.9800
N1—C11.457 (4)C11—H11C0.9800
N2—N31.280 (3)C12—H120.9500
N2—C121.362 (4)C13—C141.400 (4)
N3—C131.418 (4)C13—C181.419 (4)
C1—H1A0.9800C14—C151.386 (4)
C1—H1B0.9800C14—H140.9500
C1—H1C0.9800C15—C161.379 (5)
C2—C121.361 (4)C15—H150.9500
C2—C31.538 (4)C16—C171.383 (4)
C3—C41.515 (4)C16—H160.9500
C3—C101.536 (4)C17—C181.389 (4)
C3—C111.544 (4)C17—H170.9500
C4—C51.381 (4)C18—C191.493 (4)
C4—C91.388 (4)C19—C241.397 (4)
C5—C61.401 (5)C19—C201.399 (4)
C5—H50.9500C20—C211.384 (4)
C6—C71.381 (5)C20—H200.9500
C6—H60.9500C21—C221.375 (5)
C7—C81.389 (5)C21—H210.9500
C7—H70.9500C22—C231.392 (5)
C8—C91.388 (4)C22—H220.9500
C8—H80.9500C23—C241.385 (4)
C10—H10A0.9800C23—H230.9500
C10—H10B0.9800C24—H240.9500
C10—H10C0.9800
C2—N1—C9111.6 (2)C3—C11—H11B109.5
C2—N1—C1124.6 (2)H11A—C11—H11B109.5
C9—N1—C1123.7 (2)C3—C11—H11C109.5
N3—N2—C12113.2 (2)H11A—C11—H11C109.5
N2—N3—C13114.0 (2)H11B—C11—H11C109.5
N1—C1—H1A109.5C2—C12—N2121.1 (2)
N1—C1—H1B109.5C2—C12—H12119.5
H1A—C1—H1B109.5N2—C12—H12119.5
N1—C1—H1C109.5C14—C13—N3123.0 (3)
H1A—C1—H1C109.5C14—C13—C18119.2 (3)
H1B—C1—H1C109.5N3—C13—C18117.7 (2)
C12—C2—N1123.1 (2)C15—C14—C13120.6 (3)
C12—C2—C3128.3 (2)C15—C14—H14119.7
N1—C2—C3108.6 (2)C13—C14—H14119.7
C4—C3—C10111.4 (2)C16—C15—C14120.3 (3)
C4—C3—C2101.0 (2)C16—C15—H15119.8
C10—C3—C2111.5 (2)C14—C15—H15119.8
C4—C3—C11111.8 (2)C15—C16—C17119.6 (3)
C10—C3—C11109.8 (2)C15—C16—H16120.2
C2—C3—C11111.3 (2)C17—C16—H16120.2
C5—C4—C9119.0 (3)C16—C17—C18121.9 (3)
C5—C4—C3131.1 (3)C16—C17—H17119.0
C9—C4—C3109.9 (2)C18—C17—H17119.0
C4—C5—C6119.0 (3)C17—C18—C13118.3 (3)
C4—C5—H5120.5C17—C18—C19118.9 (3)
C6—C5—H5120.5C13—C18—C19122.8 (2)
C7—C6—C5120.5 (3)C24—C19—C20117.8 (3)
C7—C6—H6119.7C24—C19—C18123.3 (2)
C5—C6—H6119.7C20—C19—C18118.8 (3)
C6—C7—C8121.6 (3)C21—C20—C19120.9 (3)
C6—C7—H7119.2C21—C20—H20119.5
C8—C7—H7119.2C19—C20—H20119.5
C9—C8—C7116.6 (3)C22—C21—C20120.8 (3)
C9—C8—H8121.7C22—C21—H21119.6
C7—C8—H8121.7C20—C21—H21119.6
C8—C9—C4123.3 (3)C21—C22—C23119.2 (3)
C8—C9—N1127.9 (3)C21—C22—H22120.4
C4—C9—N1108.8 (2)C23—C22—H22120.4
C3—C10—H10A109.5C24—C23—C22120.4 (3)
C3—C10—H10B109.5C24—C23—H23119.8
H10A—C10—H10B109.5C22—C23—H23119.8
C3—C10—H10C109.5C23—C24—C19120.9 (3)
H10A—C10—H10C109.5C23—C24—H24119.6
H10B—C10—H10C109.5C19—C24—H24119.6
C3—C11—H11A109.5
C12—N2—N3—C13173.1 (2)C2—N1—C9—C42.7 (3)
C9—N1—C2—C12175.1 (2)C1—N1—C9—C4174.8 (2)
C1—N1—C2—C127.4 (4)N1—C2—C12—N2176.2 (2)
C9—N1—C2—C33.1 (3)C3—C2—C12—N26.1 (4)
C1—N1—C2—C3174.4 (2)N3—N2—C12—C2177.9 (2)
C12—C2—C3—C4175.8 (3)N2—N3—C13—C1410.7 (4)
N1—C2—C3—C42.2 (3)N2—N3—C13—C18172.1 (2)
C12—C2—C3—C1057.5 (4)N3—C13—C14—C15173.7 (3)
N1—C2—C3—C10120.6 (3)C18—C13—C14—C153.5 (4)
C12—C2—C3—C1165.5 (3)C13—C14—C15—C160.5 (4)
N1—C2—C3—C11116.5 (2)C14—C15—C16—C173.5 (4)
C10—C3—C4—C560.5 (4)C15—C16—C17—C182.5 (4)
C2—C3—C4—C5179.0 (3)C16—C17—C18—C131.5 (4)
C11—C3—C4—C562.7 (4)C16—C17—C18—C19177.2 (2)
C10—C3—C4—C9119.1 (2)C14—C13—C18—C174.4 (4)
C2—C3—C4—C90.6 (3)N3—C13—C18—C17172.9 (2)
C11—C3—C4—C9117.7 (3)C14—C13—C18—C19174.2 (3)
C9—C4—C5—C60.5 (4)N3—C13—C18—C198.5 (4)
C3—C4—C5—C6179.0 (3)C17—C18—C19—C24132.0 (3)
C4—C5—C6—C70.2 (5)C13—C18—C19—C2449.4 (4)
C5—C6—C7—C80.2 (5)C17—C18—C19—C2045.8 (4)
C6—C7—C8—C90.3 (4)C13—C18—C19—C20132.8 (3)
C7—C8—C9—C40.1 (4)C24—C19—C20—C210.4 (4)
C7—C8—C9—N1179.6 (3)C18—C19—C20—C21177.5 (3)
C5—C4—C9—C80.5 (4)C19—C20—C21—C220.2 (4)
C3—C4—C9—C8179.2 (2)C20—C21—C22—C230.3 (5)
C5—C4—C9—N1179.3 (2)C21—C22—C23—C240.7 (5)
C3—C4—C9—N11.1 (3)C22—C23—C24—C190.6 (5)
C2—N1—C9—C8177.6 (3)C20—C19—C24—C230.0 (4)
C1—N1—C9—C84.9 (4)C18—C19—C24—C23177.8 (3)
Hydrogen-bond geometry (Å, º) top
Cg1, Cg2 and Cg3 are the centroids of the C19–C24, C4–C9 and C13–C18 rings, respectively.
D—H···AD—HH···AD···AD—H···A
C1—H1C···Cg1i0.982.863.582 (3)131
C1—H1A···Cg1ii0.983.023.948 (3)160
C11—H11B···Cg3iii0.982.743.721 (3)179
C22—H22···Cg2iv0.952.763.645 (3)155
Symmetry codes: (i) x+1/2, y+2, z; (ii) x, y+1, z; (iii) x+1/2, y+1, z; (iv) x+1, y+2, z1/2.

Experimental details

Crystal data
Chemical formulaC24H23N3
Mr353.45
Crystal system, space groupOrthorhombic, Pca21
Temperature (K)116
a, b, c (Å)14.2968 (17), 8.2407 (10), 16.2671 (17)
V3)1916.5 (4)
Z4
Radiation typeMo Kα
µ (mm1)0.07
Crystal size (mm)0.70 × 0.20 × 0.10
Data collection
DiffractometerBruker APEXII CCD
diffractometer
Absorption correctionMulti-scan
[Blessing (1995) and SADABS (Bruker, 2005)]
Tmin, Tmax0.640, 0.746
No. of measured, independent and
observed [I > 2σ(I)] reflections
34258, 1783, 1764
Rint0.041
(sin θ/λ)max1)0.599
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.037, 0.086, 1.23
No. of reflections1783
No. of parameters247
No. of restraints1
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.19, 0.16

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SAINT, SHELXS97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and Mercury (Macrae et al., 2008), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top
Cg1, Cg2 and Cg3 are the centroids of the C19–C24, C4–C9 and C13–C18 rings, respectively.
D—H···AD—HH···AD···AD—H···A
C1—H1C···Cg1i0.982.863.582 (3)131
C1—H1A···Cg1ii0.983.023.948 (3)160
C11—H11B···Cg3iii0.982.743.721 (3)179
C22—H22···Cg2iv0.952.763.645 (3)155
Symmetry codes: (i) x+1/2, y+2, z; (ii) x, y+1, z; (iii) x+1/2, y+1, z; (iv) x+1, y+2, z1/2.
 

Acknowledgements

We thank Dr J. Wikaira of the University of Canterbury, New Zealand, for her assistance with the data collection.

References

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