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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 67| Part 12| December 2011| Page o3169
https://doi.org/10.1107/S1600536811045351

N1,N4-Diethynyl-N1,N4-di­phenyl­benzene-1,4-di­amine

Hideyuki Tabataa and Tsunehisa Okunoa*

aDepartment of Material Science and Chemistry, Wakayama University, Sakaedani, Wakayama 640-8510, Japan
*Correspondence e-mail: okuno@center.wakayama-u.ac.jp

(Received 30 September 2011; accepted 28 October 2011; online 5 November 2011)

The title compound, C22H16N2, is the first example of an ynamine with H atoms bonded to the terminal C atoms. The environment around each N atom is almost planar. The distances of the N atoms from a least squares plane fitted through each N atom and the surrounding three C atoms, are 0.087 (3) and 0.041 (4) Å. The dihedral angles between these two planes and the central phenyl­ene ring are 23.34 (14) and 34.57 (14)°. The two acetyl­ene groups have an anti conformation, keeping a conjugation through the central benzene ring. The freely refined lengths of Csp—H are 1.00 (5) and 0.93 (4) Å, consistent with those of reported acetyl­enes. The H atoms bound to terminal C atoms have short contacts with the neighboring acetyl­enic C and N atoms. The closest contacts are an H⋯N distance of 2.67 (5) Å and an H⋯C distance of 2.74 (5) Å.

Related literature

For the related structures of ynamine compounds where a diphenyl­amino group is connected to a diacetyl­ene in the terminal position, see: Galli et al. (1988[Galli, R., Neuenschwander, M. & Engel, P. (1988). Helv. Chim. Acta, 71, 1914-1923.], 1989[Galli, R., Neuenschwander, M. & Engel, P. (1989). Helv. Chim. Acta, 72, 1324-1336.]). For the related structures of a diacetyl­ene compound having 9-carbazolyl groups at both ends, see: Mayerle & Flandera (1978[Mayerle, J. J. & Flandera, M. A. (1978). Acta Cryst. B34, 1374-1376.]). For the related structures of ynamine compounds incorporating a phenothia­zine-10-yl group, see: Okuno et al. (2006[Okuno, T., Ikeda, S., Kubo, N. & Sandman, D. J. (2006). Mol. Cryst. Liq. Cryst. Sci. Technol. Sect. A, 456, 35-44.]). For our work on the preparation and the structure of the related ynamine mol­ecule incoporating a part of the title compound, see: Tabata et al. (2011[Tabata, H., Tokoyama, H., Yamakado, H. & Okuno, T. (2011). J. Mater. Chem. doi:10.1039/C1JM13896K.]).

[Scheme 1]

Experimental

Crystal data

  • C22H16N2

  • Mr = 308.38

  • Monoclinic, P 21

  • a = 9.228 (3) Å

  • b = 7.752 (2) Å

  • c = 11.359 (4) Å

  • β = 100.880 (4)°

  • V = 798.0 (5) Å3

  • Z = 2

  • Mo Kα radiation

  • μ = 0.08 mm−1

  • T = 93 K

  • 0.25 × 0.12 × 0.08 mm
Data collection

  • Rigaku Saturn724 diffractometer

  • Absorption correction: numerical (NUMABS; Rigaku, 1999[Rigaku (1999). NUMABS. Rigaku Corporation, Tokyo, Japan.]) Tmin = 0.984, Tmax = 0.994

  • 6457 measured reflections

  • 1942 independent reflections

  • 1627 reflections with F2 > 2σ(F2)

  • Rint = 0.040
Refinement

  • R[F2 > 2σ(F2)] = 0.043

  • wR(F2) = 0.093

  • S = 1.03

  • 1939 reflections

  • 282 parameters

  • 1 restraint

  • All H-atom parameters refined

  • Δρmax = 0.32 e Å−3

  • Δρmin = −0.32 e Å−3

Table 1
The CH⋯π interactions of Csp—H with the acetylenic carbon and the nitrogen atoms (Å, °)

D—H⋯A D—H H⋯A D⋯A D—H⋯A
C20—H1⋯N1i 1.00 (5) 2.67 (5) 3.540 (5) 145 (4)
C22—H2⋯C20ii 0.93 (4) 2.74 (5) 3.478 (6) 137 (4)
Symmetry codes: (i) [-x+1, y+{\script{1\over 2}}, -z]; (ii) x, y, z+1.

Data collection: CrystalClear (Rigaku, 2008[Rigaku (2008). CrystalClear. Rigaku Corporation, Tokyo, Japan.]); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SIR92 (Altomare et al., 1994[Altomare, A., Cascarano, G., Giacovazzo, C., Guagliardi, A., Burla, M. C., Polidori, G. & Camalli, M. (1994). J. Appl. Cryst. 27, 435.]); 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.]); software used to prepare material for publication: CrystalStructure (Rigaku, 2010[Rigaku (2010). CrystalStructure. Rigaku Corporation, Tokyo, Japan.]).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536811045351/nk2117sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536811045351/nk2117Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536811045351/nk2117Isup3.cml

checkCIF report


Comment top

Ynamines, where amino groups are connected to acetylene groups, are known to be unstable because of their high reactivity. Therefore, reports of crystal structures are limited to rather stable ynamines (Galli et al., 1988; Galli et al., 1989; Mayerle & Flandera, 1978; Okuno et al., 2006;) which carry some substituents, except for H atoms, on all C– and N-terminals. When H atoms are connected to C– or N-terminals, the stability of ynamines decreases drastically. In the course of our research in ynamine compounds to develop a conjugated linker, (Tabata et al., 2011) we have succeeded in preparation and characterization of the title compound. It is the first example of ynamines with H atoms in the C-terminals.

In the molecular structure, (Fig. 1) the geometric parameters are consistent with those of other reported ynamines. (Table 1) The bond lengths of Csp—H are 1.00 (5) Å and 0.93 (4) Å, where a marked difference is not recognized compared with those of other acetylenic compounds. The structures around the nitrogen atoms, plane (N1/C1/C7/C19) and plane (N2/C4/C13/C21), are almost planar, where the distances of the nitrogen atoms from the least squares planes are 0.087 (3) Å and 0.041 (4) Å, respectively. The dihedral angles of the plane (N1/C1/C7/C19) with the phenylene (C1/C2/C3/C4/C5/C6) and the phenyl rings (C7/C8/C9/C10/C11/C12) are 23.34 (14)° and 48.74 (15)°, respectively. The dihedral angles of the plane (N2/C4/C13/C21) with the phenylene (C1/C2/C3/C4/C5/C6) and the phenyl rings (C13/C14/C15/C16/C17/C18) are 34.57 (14)° and 29.28 (14)°, respectively. The two acetylene groups have an anti conformation, keeping a conjugation through the phenylene ring.

The H-atoms bound to C-terminals have short contacts with the neighboring acetylenic carbon and nitrogen atoms, giving Csp—H···π interactions. (Fig. 2, Table 2) The C20—H1 bond points to the C2(-x + 1, y + 1/2, -z) atom, where the closest contact is C20—H1···N1(-x + 1, y + 1/2, -z) of 2.67 (5) Å, indicating the interaction with the lone pair of N1. The H2 atom interacts with p-orbitals of an adjacent acetylenic carbon atom. The C22—H2 bond directs to the N1(x, y, z + 1) atom, with close contact C22—H2···C20(x, y, z + 1) of 2.74 (5) Å.

Related literature top

For the related structures of ynamine compounds where a diphenylamino group is connected to diacetylene terminal, see: Galli et al. (1988, 1989). For the related structures of a diacetylene compound having 9-carbazolyl groups in both ends, see: Mayerle & Flandera (1978). For the related structures of ynamine compounds incorporating a phenothiazine-10-yl group, see: Okuno et al. (2006). For our work on the preparation and the structure of the related ynamine molecule incoporating a part of the title compound, see: Tabata et al. (2011).

Experimental top

N1,N4-diethynyl-N1,N4-diphenyl-1,4- phenylenediamine

n-BuLi in n-hexane (15.5 ml, 24.6 mmol) was added dropwise to a solution of N1,N4-bis(trichloroethenyl)-N1, N4-diphenyl-1,4-phenylenediamine (2.00 g, 3.85 mmol) in dry THF (100 ml) at -78 °C under an argon atmosphere. After the solution was stirred for 1 h, methanol (1.3 ml) was added to the solution. It was allowed to warm to -10 °C and poured into water (50 ml). The water layer was extracted with ether (100 ml), and the combined organic layer was washed with saturated brine (20 ml), and dried over anhydrous sodium sulfate. After the solvent was evaporated, the residue was purified by GPC to give 0.60 g (yield 50%) of the title compound as a reddish brown powder. The single crystals with sufficient quality were obtained by slow evaporation from a solution of chloroform in a refrigerator.

Refinement top

Friedel pairs were merged because the molecule itself was achiral and because there were not any anomalous scattering effects. Four reflections whose 2θ angles were lower than 8° were not used for refinement because of the effect of a beam stop. The C-bound H atoms were obtained from a difference Fourier map and were refined isotropically with the restriction of Csp—H range between 0.95 (4) Å and 1.15 (4) Å.

Structure description top

Ynamines, where amino groups are connected to acetylene groups, are known to be unstable because of their high reactivity. Therefore, reports of crystal structures are limited to rather stable ynamines (Galli et al., 1988; Galli et al., 1989; Mayerle & Flandera, 1978; Okuno et al., 2006;) which carry some substituents, except for H atoms, on all C– and N-terminals. When H atoms are connected to C– or N-terminals, the stability of ynamines decreases drastically. In the course of our research in ynamine compounds to develop a conjugated linker, (Tabata et al., 2011) we have succeeded in preparation and characterization of the title compound. It is the first example of ynamines with H atoms in the C-terminals.

In the molecular structure, (Fig. 1) the geometric parameters are consistent with those of other reported ynamines. (Table 1) The bond lengths of Csp—H are 1.00 (5) Å and 0.93 (4) Å, where a marked difference is not recognized compared with those of other acetylenic compounds. The structures around the nitrogen atoms, plane (N1/C1/C7/C19) and plane (N2/C4/C13/C21), are almost planar, where the distances of the nitrogen atoms from the least squares planes are 0.087 (3) Å and 0.041 (4) Å, respectively. The dihedral angles of the plane (N1/C1/C7/C19) with the phenylene (C1/C2/C3/C4/C5/C6) and the phenyl rings (C7/C8/C9/C10/C11/C12) are 23.34 (14)° and 48.74 (15)°, respectively. The dihedral angles of the plane (N2/C4/C13/C21) with the phenylene (C1/C2/C3/C4/C5/C6) and the phenyl rings (C13/C14/C15/C16/C17/C18) are 34.57 (14)° and 29.28 (14)°, respectively. The two acetylene groups have an anti conformation, keeping a conjugation through the phenylene ring.

The H-atoms bound to C-terminals have short contacts with the neighboring acetylenic carbon and nitrogen atoms, giving Csp—H···π interactions. (Fig. 2, Table 2) The C20—H1 bond points to the C2(-x + 1, y + 1/2, -z) atom, where the closest contact is C20—H1···N1(-x + 1, y + 1/2, -z) of 2.67 (5) Å, indicating the interaction with the lone pair of N1. The H2 atom interacts with p-orbitals of an adjacent acetylenic carbon atom. The C22—H2 bond directs to the N1(x, y, z + 1) atom, with close contact C22—H2···C20(x, y, z + 1) of 2.74 (5) Å.

For the related structures of ynamine compounds where a diphenylamino group is connected to diacetylene terminal, see: Galli et al. (1988, 1989). For the related structures of a diacetylene compound having 9-carbazolyl groups in both ends, see: Mayerle & Flandera (1978). For the related structures of ynamine compounds incorporating a phenothiazine-10-yl group, see: Okuno et al. (2006). For our work on the preparation and the structure of the related ynamine molecule incoporating a part of the title compound, see: Tabata et al. (2011).

Computing details top

Data collection: CrystalClear (Rigaku, 2008); cell refinement: CrystalClear (Rigaku, 2008); data reduction: CrystalClear (Rigaku, 2008); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: CrystalStructure (Rigaku, 2010).

Figures top
[Figure 1] Fig. 1. The asymmetric unit of the title compound with atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres.
[Figure 2] Fig. 2. C–H···π interactions between H-atoms of the C-terminals and the acetylenic carbon and the nitrogen atoms. [Symmetry codes: (i) -x + 1, y + 1/2, -z; (ii) x, y, z + 1]
N1,N4-Diethynyl-N1,N4-diphenylbenzene- 1,4-diamine top
Crystal data top
C22H16N2F(000) = 324.00
Mr = 308.38Dx = 1.283 Mg m−3
Monoclinic, P21Mo Kα radiation, λ = 0.71075 Å
Hall symbol: P 2ybCell parameters from 2741 reflections
a = 9.228 (3) Åθ = 3.2–27.5°
b = 7.752 (2) ŵ = 0.08 mm−1
c = 11.359 (4) ÅT = 93 K
β = 100.880 (4)°Prism, colourless
V = 798.0 (5) Å30.25 × 0.12 × 0.08 mm
Z = 2
Data collection top
Rigaku Saturn724
diffractometer		1627 reflections with F2 > 2σ(F2)
Detector resolution: 28.445 pixels mm-1Rint = 0.040
ω scansθmax = 27.5°
Absorption correction: numerical
(NUMABS; Rigaku, 1999)		h = −11→11
Tmin = 0.984, Tmax = 0.994k = −10→10
6457 measured reflectionsl = −14→10
1942 independent reflections
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.043All H-atom parameters refined
wR(F2) = 0.093 w = 1/[σ2(Fo2) + (0.010P)2 + 0.5P]
where P = (Fo2 + 2Fc2)/3
S = 1.03(Δ/σ)max < 0.001
1939 reflectionsΔρmax = 0.32 e Å−3
282 parametersΔρmin = −0.32 e Å−3
1 restraintExtinction correction: SHELXL97 (Sheldrick, 2008)
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.116 (10)
Secondary atom site location: difference Fourier map
Crystal data top
C22H16N2V = 798.0 (5) Å3
Mr = 308.38Z = 2
Monoclinic, P21Mo Kα radiation
a = 9.228 (3) ŵ = 0.08 mm−1
b = 7.752 (2) ÅT = 93 K
c = 11.359 (4) Å0.25 × 0.12 × 0.08 mm
β = 100.880 (4)°
Data collection top
Rigaku Saturn724
diffractometer		1942 independent reflections
Absorption correction: numerical
(NUMABS; Rigaku, 1999)		1627 reflections with F2 > 2σ(F2)
Tmin = 0.984, Tmax = 0.994Rint = 0.040
6457 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0431 restraint
wR(F2) = 0.093All H-atom parameters refined
S = 1.03Δρmax = 0.32 e Å−3
1939 reflectionsΔρmin = −0.32 e Å−3
282 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
N10.3719 (3)0.3729 (3)0.1482 (2)0.0205 (6)
N20.7581 (3)0.3249 (4)0.5970 (2)0.0199 (6)
C10.4697 (3)0.3595 (4)0.2614 (3)0.0179 (7)
C20.4381 (3)0.2478 (4)0.3489 (3)0.0185 (7)
C30.5345 (3)0.2341 (4)0.4589 (3)0.0189 (7)
C40.6630 (3)0.3317 (4)0.4816 (3)0.0169 (7)
C50.6951 (3)0.4417 (4)0.3933 (3)0.0178 (7)
C60.5999 (3)0.4552 (4)0.2837 (3)0.0190 (7)
C70.2146 (3)0.3531 (4)0.1369 (3)0.0193 (7)
C80.1366 (4)0.2700 (4)0.0355 (3)0.0240 (8)
C9−0.0163 (4)0.2602 (5)0.0191 (3)0.0291 (9)
C10−0.0907 (4)0.3317 (5)0.1017 (3)0.0286 (9)
C11−0.0121 (4)0.4117 (4)0.2036 (3)0.0249 (8)
C120.1407 (3)0.4234 (4)0.2211 (3)0.0208 (7)
C130.9137 (3)0.3538 (4)0.6126 (3)0.0194 (7)
C140.9879 (3)0.4337 (4)0.7169 (3)0.0226 (8)
C151.1393 (4)0.4586 (4)0.7329 (3)0.0263 (8)
C161.2172 (4)0.4105 (4)0.6452 (3)0.0262 (8)
C171.1418 (3)0.3325 (4)0.5412 (3)0.0229 (8)
C180.9911 (3)0.3013 (4)0.5250 (3)0.0212 (7)
C190.4187 (3)0.4520 (4)0.0562 (3)0.0223 (7)
C200.4608 (4)0.5242 (4)−0.0232 (3)0.0266 (9)
C210.6955 (3)0.3114 (4)0.6945 (3)0.0208 (7)
C220.6419 (4)0.3023 (4)0.7811 (3)0.0258 (8)
H10.498 (5)0.586 (6)−0.089 (4)0.056 (13)*
H20.601 (4)0.299 (6)0.850 (3)0.039 (10)*
H30.352 (4)0.178 (5)0.330 (3)0.017 (8)*
H40.502 (4)0.162 (5)0.523 (3)0.024 (9)*
H50.785 (4)0.509 (5)0.404 (3)0.021 (8)*
H60.624 (4)0.529 (5)0.223 (3)0.033 (10)*
H70.194 (3)0.217 (4)−0.021 (3)0.014 (7)*
H8−0.064 (4)0.207 (5)−0.054 (3)0.025 (9)*
H9−0.218 (4)0.329 (6)0.084 (3)0.038 (10)*
H10−0.065 (4)0.464 (5)0.262 (3)0.028 (9)*
H110.191 (4)0.486 (5)0.294 (3)0.033 (10)*
H120.934 (4)0.468 (5)0.779 (3)0.028 (9)*
H131.195 (4)0.509 (5)0.811 (3)0.033 (10)*
H141.336 (4)0.424 (6)0.662 (3)0.038 (10)*
H151.196 (4)0.298 (5)0.478 (3)0.025 (8)*
H160.939 (4)0.242 (5)0.449 (3)0.028 (9)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0205 (12)0.0205 (12)0.0205 (12)−0.0003 (10)0.0036 (10)0.0013 (10)
N20.0194 (11)0.0194 (12)0.0194 (12)0.0000 (10)0.0000 (9)0.0000 (10)
C10.0179 (13)0.0179 (14)0.0179 (13)0.0027 (11)0.0034 (11)−0.0016 (11)
C20.0186 (14)0.0186 (14)0.0186 (14)−0.0024 (11)0.0039 (11)−0.0004 (11)
C30.0192 (14)0.0192 (13)0.0192 (14)0.0003 (11)0.0056 (11)0.0029 (11)
C40.0170 (13)0.0170 (13)0.0170 (13)0.0017 (11)0.0040 (10)−0.0007 (12)
C50.0179 (14)0.0179 (13)0.0179 (13)−0.0012 (12)0.0039 (11)−0.0003 (11)
C60.0194 (14)0.0194 (14)0.0194 (13)−0.0005 (12)0.0070 (11)0.0025 (12)
C70.0192 (14)0.0192 (14)0.0192 (14)−0.0002 (12)0.0031 (11)0.0032 (11)
C80.0238 (15)0.0238 (15)0.0238 (15)0.0005 (12)0.0027 (13)−0.0014 (12)
C90.0278 (16)0.0278 (17)0.0278 (17)−0.0046 (13)−0.0046 (14)0.0009 (13)
C100.0280 (17)0.0280 (16)0.0280 (17)−0.0030 (14)0.0005 (13)0.0080 (15)
C110.0254 (16)0.0254 (15)0.0254 (15)0.0012 (13)0.0088 (13)0.0054 (13)
C120.0207 (14)0.0207 (14)0.0207 (14)−0.0018 (12)0.0030 (12)0.0017 (12)
C130.0190 (14)0.0190 (14)0.0190 (14)−0.0004 (12)0.0009 (11)0.0029 (11)
C140.0225 (15)0.0225 (14)0.0225 (15)−0.0008 (13)0.0034 (12)−0.0011 (13)
C150.0253 (16)0.0253 (16)0.0253 (16)−0.0015 (13)−0.0031 (13)0.0007 (13)
C160.0256 (16)0.0256 (16)0.0256 (16)0.0004 (13)0.0000 (13)0.0055 (13)
C170.0232 (15)0.0232 (15)0.0232 (14)0.0068 (13)0.0068 (12)0.0067 (13)
C180.0208 (14)0.0208 (14)0.0208 (14)0.0021 (12)0.0005 (12)0.0015 (12)
C190.0221 (14)0.0221 (14)0.0221 (14)−0.0003 (12)0.0028 (11)−0.0043 (12)
C200.0267 (17)0.0267 (16)0.0267 (16)−0.0017 (13)0.0057 (13)0.0010 (13)
C210.0203 (14)0.0203 (14)0.0203 (14)0.0000 (12)0.0000 (11)0.0000 (12)
C220.0260 (15)0.0260 (16)0.0260 (15)−0.0004 (13)0.0067 (13)0.0003 (13)
Geometric parameters (Å, º) top
N1—C11.428 (4)C15—C161.385 (6)
N1—C71.441 (4)C16—C171.391 (5)
N1—C191.351 (5)C17—C181.389 (4)
N2—C41.434 (4)C19—C201.187 (5)
N2—C131.431 (4)C21—C221.184 (6)
N2—C211.346 (5)C2—H30.95 (4)
C1—C21.390 (5)C3—H41.01 (4)
C1—C61.394 (4)C5—H50.97 (4)
C2—C31.394 (5)C6—H60.95 (4)
C3—C41.389 (4)C8—H70.99 (4)
C4—C51.390 (5)C9—H80.96 (4)
C5—C61.386 (5)C10—H91.15 (4)
C7—C81.395 (5)C11—H100.98 (4)
C7—C121.387 (5)C12—H111.00 (4)
C8—C91.390 (6)C14—H120.97 (4)
C9—C101.379 (6)C15—H131.02 (4)
C10—C111.391 (5)C16—H141.08 (4)
C11—C121.389 (5)C17—H150.99 (4)
C13—C141.396 (5)C18—H161.02 (4)
C13—C181.391 (5)C20—H11.00 (5)
C14—C151.388 (5)C22—H20.93 (4)
C1—N1—C7121.8 (3)N1—C19—C20178.7 (4)
C1—N1—C19119.3 (3)N2—C21—C22178.7 (4)
C7—N1—C19116.3 (3)C1—C2—H3118 (2)
C4—N2—C13122.3 (3)C3—C2—H3122 (2)
C4—N2—C21118.1 (3)C2—C3—H4117.6 (19)
C13—N2—C21119.1 (3)C4—C3—H4121.9 (19)
N1—C1—C2120.4 (3)C4—C5—H5122 (2)
N1—C1—C6120.1 (3)C6—C5—H5117 (2)
C2—C1—C6119.4 (3)C1—C6—H6120 (2)
C1—C2—C3120.2 (3)C5—C6—H6120 (2)
C2—C3—C4120.2 (3)C7—C8—H7118.0 (16)
N2—C4—C3120.2 (3)C9—C8—H7122.8 (16)
N2—C4—C5120.3 (3)C8—C9—H8115 (3)
C3—C4—C5119.4 (3)C10—C9—H8124 (3)
C4—C5—C6120.6 (3)C9—C10—H9119.7 (19)
C1—C6—C5120.1 (3)C11—C10—H9120 (2)
N1—C7—C8118.5 (3)C10—C11—H10120 (2)
N1—C7—C12121.0 (3)C12—C11—H10120 (2)
C8—C7—C12120.4 (3)C7—C12—H11124 (3)
C7—C8—C9119.2 (4)C11—C12—H11117 (3)
C8—C9—C10120.7 (3)C13—C14—H12120 (2)
C9—C10—C11119.8 (4)C15—C14—H12120 (2)
C10—C11—C12120.3 (4)C14—C15—H13120 (3)
C7—C12—C11119.6 (3)C16—C15—H13119 (3)
N2—C13—C14119.6 (3)C15—C16—H14120 (2)
N2—C13—C18120.3 (3)C17—C16—H14121 (2)
C14—C13—C18120.1 (3)C16—C17—H15120 (2)
C13—C14—C15119.5 (3)C18—C17—H15119 (2)
C14—C15—C16121.0 (3)C13—C18—H16121 (3)
C15—C16—C17118.9 (4)C17—C18—H16120 (3)
C16—C17—C18121.1 (4)C19—C20—H1179 (3)
C13—C18—C17119.4 (3)C21—C22—H2178 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C20—H1···N1i1.00 (5)2.67 (5)3.540 (5)145 (4)
C22—H2···C20ii0.93 (4)2.74 (5)3.478 (6)137 (4)
Symmetry codes: (i) −x+1, y+1/2, −z; (ii) x, y, z+1.

Experimental details

Crystal data
Chemical formulaC22H16N2
Mr308.38
Crystal system, space groupMonoclinic, P21
Temperature (K)93
a, b, c (Å)9.228 (3), 7.752 (2), 11.359 (4)
β (°) 100.880 (4)
V (Å3)798.0 (5)
Z2
Radiation typeMo Kα
µ (mm−1)0.08
Crystal size (mm)0.25 × 0.12 × 0.08
Data collection
DiffractometerRigaku Saturn724
Absorption correctionNumerical
(NUMABS; Rigaku, 1999)
Tmin, Tmax0.984, 0.994
No. of measured, independent and
observed [F2 > 2σ(F2)] reflections		6457, 1942, 1627
Rint0.040
(sin θ/λ)max (Å−1)0.650
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.043, 0.093, 1.03
No. of reflections1939
No. of parameters282
No. of restraints1
H-atom treatmentAll H-atom parameters refined
Δρmax, Δρmin (e Å−3)0.32, −0.32

Computer programs: CrystalClear (Rigaku, 2008), SIR92 (Altomare et al., 1994), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), CrystalStructure (Rigaku, 2010).

Selected geometric parameters (Å, º) top
N1—C11.428 (4)N2—C131.431 (4)
N1—C71.441 (4)N2—C211.346 (5)
N1—C191.351 (5)C19—C201.187 (5)
N2—C41.434 (4)C21—C221.184 (6)
C1—N1—C7121.8 (3)C4—N2—C21118.1 (3)
C1—N1—C19119.3 (3)C13—N2—C21119.1 (3)
C7—N1—C19116.3 (3)N1—C19—C20178.7 (4)
C4—N2—C13122.3 (3)N2—C21—C22178.7 (4)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C20—H1···N1i1.00 (5)2.67 (5)3.540 (5)145 (4)
C22—H2···C20ii0.93 (4)2.74 (5)3.478 (6)137 (4)
Symmetry codes: (i) −x+1, y+1/2, −z; (ii) x, y, z+1.
 

Acknowledgements

This work was supported by Research for Promoting Technological Seeds from the Japan Science and Technology Agency (JST).

References

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 First citationFarrugia, L. J. (1997). J. Appl. Cryst. 30, 565.  CrossRef IUCr Journals Google Scholar
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 First citationRigaku (1999). NUMABS. Rigaku Corporation, Tokyo, Japan.  Google Scholar
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ISSN: 2056-9890
Volume 67| Part 12| December 2011| Page o3169
https://doi.org/10.1107/S1600536811045351
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