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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 o3254
https://doi.org/10.1107/S1600536811046356

N,N′-Bis(pyridin-2-yl)benzene-1,4-di­amine–quinoxaline (2/1)

Barbara Wichera and Maria Gdanieca*

aFaculty of Chemistry, Adam Mickiewicz University, 60-780 Poznań, Poland
*Correspondence e-mail: magdan@amu.edu.pl

(Received 28 October 2011; accepted 3 November 2011; online 9 November 2011)

The asymmetric unit of the title compound, 2C16H14N4·C8H6N2, consits of one mol­ecule of N,N′-bis­(pyridin-2-yl)benzene-1,4-diamine (PDAB) and one half-mol­ecule of quinoxaline (QX) that is located around an inversion centre and disordered over two overlapping positions. The PDAB mol­ecule adopts a non-planar conformation with an E configuration at the two partially double exo C N bonds of the 2-pyridyl­amine units. In the crystal, these self-complementary units are N—H⋯N hydrogen bonded via a cyclic R22(8) motif, creating tapes of PDAB mol­ecules extending along [010]. Inversion-related tapes are arranged into pairs through π–π stacking inter­actions between the benzene rings [centroid–centroid distance = 3.818 (1) Å] and the two symmetry-independent pyridine groups [centroid–centroid distance = 3.760 (1) Å]. The QX mol­ecules are enclosed in a cavity formed between six PDAB tapes.

Related literature

For the structures of polymorphic forms of N,N′-di(pyridin-2-yl)benzene-1,4-diamine and its co-crystal with phenazine, see: Bensemann et al. (2002[Bensemann, I., Gdaniec, M. & Połoński, T. (2002). New J. Chem. 26, 448-456.]); Wicher & Gdaniec (2011[Wicher, B. & Gdaniec, M. (2011). Acta Cryst. E67, o3095.]); Gdaniec et al. (2005[Gdaniec, M., Bensemann, I. & Połoński, T. (2005). CrystEngComm, 7, 433-438.]).

[Scheme 1]

Experimental

Crystal data

  • 2C16H14N4·C8H6N2

  • Mr = 654.77

  • Monoclinic, P 21 /n

  • a = 11.8285 (9) Å

  • b = 9.1223 (7) Å

  • c = 14.7952 (9) Å

  • β = 93.698 (5)°

  • V = 1593.1 (2) Å3

  • Z = 2

  • Mo Kα radiation

  • μ = 0.09 mm−1

  • T = 130 K

  • 0.50 × 0.30 × 0.25 mm
Data collection

  • Kuma KM-4-CCD κ-geometry diffractometer

  • 8116 measured reflections

  • 2897 independent reflections

  • 2082 reflections with I > 2σ(I)

  • Rint = 0.033
Refinement

  • R[F2 > 2σ(F2)] = 0.045

  • wR(F2) = 0.121

  • S = 0.97

  • 2897 reflections

  • 226 parameters

  • H-atom parameters constrained

  • Δρmax = 0.22 e Å−3

  • Δρmin = −0.28 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A D⋯A D—H⋯A
N14—H14N⋯N2i 0.90 2.12 2.9998 (17) 166
N7—H7N⋯N16ii 0.90 2.13 3.0173 (18) 167
Symmetry codes: (i) x, y-1, z; (ii) x, y+1, z.

Data collection: CrysAlis CCD (Oxford Diffraction, 2002[Oxford Diffraction (2002). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England.]); cell refinement: CrysAlis RED (Oxford Diffraction, 2002[Oxford Diffraction (2002). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England.]); data reduction: CrysAlis RED; 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 for Windows (Farrugia, 1997[Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.]) and Mercury (Macrae et al., 2006[Macrae, C. F., Edgington, P. R., McCabe, P., Pidcock, E., Shields, G. P., Taylor, R., Towler, M. & van de Streek, J. (2006). J. Appl. Cryst. 39, 453-457.]); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536811046356/rz2662sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536811046356/rz2662Isup2.hkl

checkCIF report


Comment top

N,N'-Di(pyridin-2-yl)benzene-1,4-diamine (PDAB) is a very versatile supramolecular reagent. It has been shown that it can cocrystallize with the aromatic base, phenazine, forming cocrystals with the 1:4 molar ratio (Gdaniec et al., 2005). In this cocrystal the PDAB molecule is centrosymmetric and adopts a nearly planar conformation and a Z,Z form, i.e. the configuration at the partially double exo C≐ N bonds of its two 2-pyridylamine units is Z. The PDAB molecules are hydrogen bonded to phenazine molecules but, most importantly, their π-faces are directed to the edges of the phenazine molecules arranged via π-π stacking interactions into quartets. To check whether a similar packing motif will be observed for a compound containing the pyrazine fragment but a reduced π-system compared to phenazine, an attempt was made to cocrystallize PDAB with quinoxaline (QX). Cocrystallization was successful when PDAB was dissolved in molten QX (m.p. 301 K) and the solution was slowly evaporated at 331 K yielding the title molecular complex with 2:1 PDAB/QX ratio (Fig. 1). In contrast with the PDAB/phenazine cocrystal, in the title complex the PDAB molecule is nonplanar and adopts an E,E form that promotes formation of a cyclic R22(8) motif via N—H···N hydrogen bond between the self-complementary 2-pyridylamine units (Table 1). These cyclic motifs assemble PDAB molecules into tapes extending along [010]. The tapes related by inversion center are arranged into pairs through π-π stacking interactions between the benzene rings [centroid-centroid distance 3.818 (1) Å] and the two symmetry independent pyridine groups [centroid-centroid distance 3.760 (1) Å] (Fig. 2). Similar tape motifs have been observed in two of the three PDAB polymorphs (Bensemann et al., 2002; Wicher & Gdaniec, 2011), however these polymorphic structures were not stabilized by π-π stacking interactions between the tapes.

The QX molecule, that is not hydrogen bonded to PDAB, is enclosed in a centrosymmetric cavity formed between six PDAB tapes (Fig. 3). This leads to a disorder of the non-centrosymmetric QX molecule which in the cavity is located, with equal occupancies, in two alternative overlapping positions. Thus QX molecule in this crystal structure simulates the shape of a naphthalene molecule.

As there are no specific interactions between QX and PDAB molecules the driving force for the complex formation with PDAB is different in the two cocrystals with the aromatic heterobases containing the pyrazine ring.

Related literature top

For the structures of polymorphic forms of N,N'-di(pyridin-2-yl)benzene-1,4-diamine and its co-crystal with phenazine, see: Bensemann et al. (2002); Wicher & Gdaniec (2011); Gdaniec et al. (2005).

Experimental top

N,N'-Di(pyridin-2-yl)benzene-1,4-diamine (0.07 g, 0.27 mmol) was dissolved in an excess of the melted quinoxaline. The solution was heated at 331 K and after a few days colourless crystal suitable for X-ray analysis were obtained.

Refinement top

All H atoms were located in difference electron-density maps, however for further refinement their positions were determined geometrically with N—H and C—H bond lengths of 0.90 Å and 0.95 Å, respectively. All H atoms were refined in the riding-model approximation, with Uiso(H)=1.2Ueq(N,C).

Structure description top

N,N'-Di(pyridin-2-yl)benzene-1,4-diamine (PDAB) is a very versatile supramolecular reagent. It has been shown that it can cocrystallize with the aromatic base, phenazine, forming cocrystals with the 1:4 molar ratio (Gdaniec et al., 2005). In this cocrystal the PDAB molecule is centrosymmetric and adopts a nearly planar conformation and a Z,Z form, i.e. the configuration at the partially double exo C≐ N bonds of its two 2-pyridylamine units is Z. The PDAB molecules are hydrogen bonded to phenazine molecules but, most importantly, their π-faces are directed to the edges of the phenazine molecules arranged via π-π stacking interactions into quartets. To check whether a similar packing motif will be observed for a compound containing the pyrazine fragment but a reduced π-system compared to phenazine, an attempt was made to cocrystallize PDAB with quinoxaline (QX). Cocrystallization was successful when PDAB was dissolved in molten QX (m.p. 301 K) and the solution was slowly evaporated at 331 K yielding the title molecular complex with 2:1 PDAB/QX ratio (Fig. 1). In contrast with the PDAB/phenazine cocrystal, in the title complex the PDAB molecule is nonplanar and adopts an E,E form that promotes formation of a cyclic R22(8) motif via N—H···N hydrogen bond between the self-complementary 2-pyridylamine units (Table 1). These cyclic motifs assemble PDAB molecules into tapes extending along [010]. The tapes related by inversion center are arranged into pairs through π-π stacking interactions between the benzene rings [centroid-centroid distance 3.818 (1) Å] and the two symmetry independent pyridine groups [centroid-centroid distance 3.760 (1) Å] (Fig. 2). Similar tape motifs have been observed in two of the three PDAB polymorphs (Bensemann et al., 2002; Wicher & Gdaniec, 2011), however these polymorphic structures were not stabilized by π-π stacking interactions between the tapes.

The QX molecule, that is not hydrogen bonded to PDAB, is enclosed in a centrosymmetric cavity formed between six PDAB tapes (Fig. 3). This leads to a disorder of the non-centrosymmetric QX molecule which in the cavity is located, with equal occupancies, in two alternative overlapping positions. Thus QX molecule in this crystal structure simulates the shape of a naphthalene molecule.

As there are no specific interactions between QX and PDAB molecules the driving force for the complex formation with PDAB is different in the two cocrystals with the aromatic heterobases containing the pyrazine ring.

For the structures of polymorphic forms of N,N'-di(pyridin-2-yl)benzene-1,4-diamine and its co-crystal with phenazine, see: Bensemann et al. (2002); Wicher & Gdaniec (2011); Gdaniec et al. (2005).

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2002); cell refinement: CrysAlis RED (Oxford Diffraction, 2002); data reduction: CrysAlis RED (Oxford Diffraction, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. : Asymmetric unit of the title compound with displacement ellipsoids shown at the 50% probability level. The elipsoids representing positions occupied equally by C and N atoms are coloured in grey and blue. The unlabelled atoms of quinoxaline are related to the labelled one by the symmetry operation: 1 - x,1 - y,1 - z.
[Figure 2] Fig. 2. : π-π stacking interactions connecting hydrogen-bonded PDAB tapes into pairs. N—H···N hydrogen bonds are shown as dashed lines.
[Figure 3] Fig. 3. : Crystal packing diagram viewed along b illustrating arrangement of the hydrogen-bonded tapes of PDAB in the crystal and quinoxaline molecules enclosed in the cavity formed between the tapes.
N,N'-Bis(pyridin-2-yl)benzene-1,4-diamine–quinoxaline (2/1) top
Crystal data top
2C16H14N4·C8H6N2F(000) = 688
Mr = 654.77Dx = 1.365 Mg m−3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 2533 reflections
a = 11.8285 (9) Åθ = 4.1–25.0°
b = 9.1223 (7) ŵ = 0.09 mm−1
c = 14.7952 (9) ÅT = 130 K
β = 93.698 (5)°Prism, colourless
V = 1593.1 (2) Å30.50 × 0.30 × 0.25 mm
Z = 2
Data collection top
Kuma KM-4-CCD κ-geometry
diffractometer		2082 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.033
Graphite monochromatorθmax = 25.4°, θmin = 4.1°
ω scansh = −13→14
8116 measured reflectionsk = −10→9
2897 independent reflectionsl = −17→17
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)] = 0.045Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.121H-atom parameters constrained
S = 0.97 w = 1/[σ2(Fo2) + (0.0796P)2]
where P = (Fo2 + 2Fc2)/3
2897 reflections(Δ/σ)max < 0.001
226 parametersΔρmax = 0.22 e Å−3
0 restraintsΔρmin = −0.28 e Å−3
Crystal data top
2C16H14N4·C8H6N2V = 1593.1 (2) Å3
Mr = 654.77Z = 2
Monoclinic, P21/nMo Kα radiation
a = 11.8285 (9) ŵ = 0.09 mm−1
b = 9.1223 (7) ÅT = 130 K
c = 14.7952 (9) Å0.50 × 0.30 × 0.25 mm
β = 93.698 (5)°
Data collection top
Kuma KM-4-CCD κ-geometry
diffractometer		2082 reflections with I > 2σ(I)
8116 measured reflectionsRint = 0.033
2897 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0450 restraints
wR(F2) = 0.121H-atom parameters constrained
S = 0.97Δρmax = 0.22 e Å−3
2897 reflectionsΔρmin = −0.28 e Å−3
226 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*/UeqOcc. (<1)
N20.34420 (10)0.46004 (13)0.12792 (9)0.0251 (3)
N70.44563 (11)0.24793 (13)0.12278 (9)0.0291 (3)
H7N0.50370.30820.11260.035*
N140.55190 (10)−0.35168 (13)0.12548 (9)0.0295 (3)
H14N0.4941−0.41220.13590.035*
N160.65420 (10)−0.56243 (13)0.11839 (9)0.0260 (3)
C10.34338 (12)0.31287 (16)0.13482 (10)0.0232 (4)
C30.24879 (13)0.53106 (17)0.14294 (10)0.0282 (4)
H30.24920.63490.13820.034*
C40.15003 (13)0.46477 (18)0.16475 (11)0.0301 (4)
H40.08410.52050.17450.036*
C50.15028 (13)0.31317 (18)0.17200 (11)0.0292 (4)
H50.08390.26300.18760.035*
C60.24654 (13)0.23600 (17)0.15651 (10)0.0266 (4)
H60.24740.13210.16040.032*
C80.46942 (13)0.09666 (16)0.12475 (10)0.0243 (4)
C90.40085 (12)−0.00484 (17)0.07789 (10)0.0264 (4)
H90.33350.02690.04520.032*
C100.42953 (13)−0.15119 (16)0.07830 (10)0.0256 (4)
H100.3813−0.21950.04630.031*
C110.52812 (13)−0.20032 (16)0.12488 (10)0.0253 (4)
C120.59638 (13)−0.09904 (17)0.17195 (11)0.0272 (4)
H120.6637−0.13070.20470.033*
C130.56739 (13)0.04714 (17)0.17172 (10)0.0270 (4)
H130.61520.11520.20420.032*
C150.65386 (13)−0.41581 (16)0.11138 (10)0.0239 (4)
C170.75049 (13)−0.63284 (18)0.10303 (11)0.0302 (4)
H170.7507−0.73670.10740.036*
C180.84841 (14)−0.56538 (18)0.08156 (11)0.0310 (4)
H180.9149−0.62010.07190.037*
C190.84671 (13)−0.41393 (18)0.07442 (11)0.0303 (4)
H190.9129−0.36280.05940.036*
C200.75006 (13)−0.33812 (17)0.08900 (10)0.0276 (4)
H200.7482−0.23430.08400.033*
C210.42626 (15)0.38226 (19)0.36086 (12)0.0393 (5)
H210.38390.33100.31420.047*
C220.53039 (16)0.44592 (18)0.34188 (13)0.0410 (5)
H220.55700.43630.28290.049*
N230.59282 (13)0.51949 (17)0.40527 (11)0.0368 (4)0.50
C230.59282 (13)0.51949 (17)0.40527 (11)0.0368 (4)0.50
H230.66290.56290.39220.044*0.50
C240.55231 (12)0.53158 (16)0.49075 (11)0.0275 (4)
C250.61465 (13)0.60804 (16)0.55764 (11)0.0357 (4)0.50
H250.68460.65290.54570.043*0.50
N250.61465 (13)0.60804 (16)0.55764 (11)0.0357 (4)0.50
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N20.0240 (7)0.0225 (7)0.0290 (7)0.0005 (5)0.0025 (6)−0.0026 (5)
N70.0227 (7)0.0202 (7)0.0449 (9)−0.0022 (5)0.0067 (6)−0.0004 (6)
N140.0224 (7)0.0208 (7)0.0457 (9)−0.0006 (5)0.0056 (6)0.0047 (6)
N160.0248 (7)0.0229 (7)0.0301 (8)0.0004 (5)0.0011 (6)−0.0004 (6)
C10.0249 (8)0.0223 (8)0.0223 (8)−0.0012 (6)0.0010 (6)−0.0020 (6)
C30.0301 (9)0.0246 (8)0.0298 (9)0.0026 (7)0.0012 (7)−0.0040 (7)
C40.0243 (8)0.0339 (9)0.0323 (9)0.0032 (7)0.0030 (7)−0.0048 (7)
C50.0247 (8)0.0361 (9)0.0270 (9)−0.0044 (7)0.0026 (7)−0.0009 (7)
C60.0283 (9)0.0239 (8)0.0277 (9)−0.0022 (7)0.0019 (7)0.0000 (6)
C80.0238 (8)0.0212 (8)0.0284 (9)−0.0007 (6)0.0059 (7)0.0001 (6)
C90.0241 (8)0.0258 (8)0.0292 (9)0.0000 (7)0.0004 (7)0.0024 (7)
C100.0244 (8)0.0253 (8)0.0271 (9)−0.0034 (6)0.0010 (6)−0.0015 (6)
C110.0257 (8)0.0219 (8)0.0289 (9)0.0009 (6)0.0056 (7)0.0024 (6)
C120.0231 (8)0.0299 (9)0.0283 (9)0.0019 (7)0.0003 (7)0.0026 (7)
C130.0248 (8)0.0277 (9)0.0288 (9)−0.0034 (7)0.0034 (7)−0.0035 (7)
C150.0242 (8)0.0246 (8)0.0225 (8)0.0002 (6)−0.0007 (6)0.0002 (6)
C170.0298 (9)0.0267 (8)0.0336 (9)0.0037 (7)−0.0010 (7)−0.0037 (7)
C180.0259 (9)0.0337 (9)0.0334 (9)0.0028 (7)0.0011 (7)−0.0068 (7)
C190.0231 (9)0.0374 (10)0.0302 (9)−0.0054 (7)0.0012 (7)−0.0031 (7)
C200.0273 (9)0.0259 (8)0.0292 (9)−0.0028 (7)−0.0004 (7)0.0008 (7)
C210.0462 (11)0.0331 (10)0.0372 (11)−0.0056 (8)−0.0086 (9)0.0026 (8)
C220.0550 (12)0.0324 (10)0.0362 (10)0.0004 (9)0.0081 (9)0.0027 (8)
N230.0364 (9)0.0337 (9)0.0411 (10)−0.0045 (7)0.0092 (7)0.0025 (7)
C230.0364 (9)0.0337 (9)0.0411 (10)−0.0045 (7)0.0092 (7)0.0025 (7)
C240.0263 (8)0.0214 (8)0.0344 (9)0.0003 (6)−0.0005 (7)0.0021 (7)
C250.0314 (8)0.0331 (9)0.0417 (10)−0.0057 (7)−0.0055 (7)0.0031 (7)
N250.0314 (8)0.0331 (9)0.0417 (10)−0.0057 (7)−0.0055 (7)0.0031 (7)
Geometric parameters (Å, º) top
N2—C31.3324 (18)C11—C121.385 (2)
N2—C11.3465 (19)C12—C131.377 (2)
N7—C11.3686 (19)C12—H120.9500
N7—C81.4083 (19)C13—H130.9500
N7—H7N0.9001C15—C201.398 (2)
N14—C151.3685 (19)C17—C181.367 (2)
N14—C111.4090 (19)C17—H170.9500
N14—H14N0.9000C18—C191.386 (2)
N16—C171.3397 (19)C18—H180.9500
N16—C151.3415 (19)C19—C201.365 (2)
C1—C61.398 (2)C19—H190.9500
C3—C41.372 (2)C20—H200.9500
C3—H30.9500C21—N25i1.331 (2)
C4—C51.387 (2)C21—C25i1.331 (2)
C4—H40.9500C21—C221.406 (3)
C5—C61.370 (2)C21—H210.9499
C5—H50.9500C22—N231.336 (2)
C6—H60.9500C22—H220.9500
C8—C91.387 (2)N23—C241.385 (2)
C8—C131.388 (2)N23—H230.9500
C9—C101.377 (2)C24—C251.384 (2)
C9—H90.9500C24—C24i1.408 (3)
C10—C111.390 (2)C25—C21i1.331 (2)
C10—H100.9500C25—H250.9499
C3—N2—C1117.51 (13)C11—C12—H12119.7
C1—N7—C8126.76 (13)C12—C13—C8121.08 (14)
C1—N7—H7N116.6C12—C13—H13119.5
C8—N7—H7N116.6C8—C13—H13119.5
C15—N14—C11126.54 (13)N16—C15—N14114.37 (13)
C15—N14—H14N116.8N16—C15—C20121.68 (14)
C11—N14—H14N116.7N14—C15—C20123.92 (14)
C17—N16—C15117.59 (14)N16—C17—C18124.47 (15)
N2—C1—N7114.27 (13)N16—C17—H17117.8
N2—C1—C6121.83 (14)C18—C17—H17117.8
N7—C1—C6123.84 (14)C17—C18—C19117.27 (15)
N2—C3—C4124.61 (15)C17—C18—H18121.4
N2—C3—H3117.7C19—C18—H18121.4
C4—C3—H3117.7C20—C19—C18120.08 (15)
C3—C4—C5117.38 (15)C20—C19—H19120.0
C3—C4—H4121.3C18—C19—H19120.0
C5—C4—H4121.3C19—C20—C15118.89 (15)
C6—C5—C4119.79 (15)C19—C20—H20120.6
C6—C5—H5120.1C15—C20—H20120.6
C4—C5—H5120.1N25i—C21—C22121.85 (16)
C5—C6—C1118.86 (15)C25i—C21—C22121.85 (16)
C5—C6—H6120.6N25i—C21—H21119.1
C1—C6—H6120.6C25i—C21—H21119.1
C9—C8—C13118.40 (14)C22—C21—H21119.1
C9—C8—N7122.29 (14)N23—C22—C21121.25 (17)
C13—C8—N7119.25 (13)N23—C22—H22119.3
C10—C9—C8120.60 (14)C21—C22—H22119.4
C10—C9—H9119.7C22—N23—C24118.20 (15)
C8—C9—H9119.7C22—N23—H23121.1
C9—C10—C11120.88 (14)C24—N23—H23120.7
C9—C10—H10119.6C25—C24—N23119.55 (14)
C11—C10—H10119.6C25—C24—C24i120.10 (19)
C12—C11—C10118.52 (14)N23—C24—C24i120.34 (18)
C12—C11—N14122.74 (14)C21i—C25—C24118.25 (15)
C10—C11—N14118.68 (13)C21i—C25—H25120.8
C13—C12—C11120.52 (14)C24—C25—H25120.9
C13—C12—H12119.7
C3—N2—C1—N7−177.03 (13)C11—C12—C13—C80.1 (2)
C3—N2—C1—C60.3 (2)C9—C8—C13—C120.1 (2)
C8—N7—C1—N2−178.90 (14)N7—C8—C13—C12−177.06 (14)
C8—N7—C1—C63.9 (2)C17—N16—C15—N14178.27 (13)
C1—N2—C3—C4−0.1 (2)C17—N16—C15—C20−0.1 (2)
N2—C3—C4—C50.3 (2)C11—N14—C15—N16178.07 (14)
C3—C4—C5—C6−0.7 (2)C11—N14—C15—C20−3.6 (2)
C4—C5—C6—C10.9 (2)C15—N16—C17—C180.6 (2)
N2—C1—C6—C5−0.7 (2)N16—C17—C18—C19−0.7 (2)
N7—C1—C6—C5176.37 (14)C17—C18—C19—C200.3 (2)
C1—N7—C8—C947.3 (2)C18—C19—C20—C150.2 (2)
C1—N7—C8—C13−135.63 (16)N16—C15—C20—C19−0.3 (2)
C13—C8—C9—C100.1 (2)N14—C15—C20—C19−178.51 (14)
N7—C8—C9—C10177.18 (14)N25i—C21—C22—N23−0.1 (3)
C8—C9—C10—C11−0.6 (2)C25i—C21—C22—N23−0.1 (3)
C9—C10—C11—C120.8 (2)C21—C22—N23—C240.0 (3)
C9—C10—C11—N14178.09 (14)C22—N23—C24—C25−179.52 (15)
C15—N14—C11—C12−48.1 (2)C22—N23—C24—C24i−0.4 (3)
C15—N14—C11—C10134.72 (16)N23—C24—C25—C21i−179.92 (15)
C10—C11—C12—C13−0.6 (2)C24i—C24—C25—C21i1.0 (3)
N14—C11—C12—C13−177.76 (14)
Symmetry code: (i) −x+1, −y+1, −z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N14—H14N···N2ii0.902.122.9998 (17)166
N7—H7N···N16iii0.902.133.0173 (18)167
Symmetry codes: (ii) x, y−1, z; (iii) x, y+1, z.

Experimental details

Crystal data
Chemical formula2C16H14N4·C8H6N2
Mr654.77
Crystal system, space groupMonoclinic, P21/n
Temperature (K)130
a, b, c (Å)11.8285 (9), 9.1223 (7), 14.7952 (9)
β (°) 93.698 (5)
V (Å3)1593.1 (2)
Z2
Radiation typeMo Kα
µ (mm−1)0.09
Crystal size (mm)0.50 × 0.30 × 0.25
Data collection
DiffractometerKuma KM-4-CCD κ-geometry
Absorption correction–
No. of measured, independent and
observed [I > 2σ(I)] reflections		8116, 2897, 2082
Rint0.033
(sin θ/λ)max (Å−1)0.602
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.045, 0.121, 0.97
No. of reflections2897
No. of parameters226
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å−3)0.22, −0.28

Computer programs: CrysAlis CCD (Oxford Diffraction, 2002), CrysAlis RED (Oxford Diffraction, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997) and Mercury (Macrae et al., 2006).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N14—H14N···N2i0.902.122.9998 (17)166
N7—H7N···N16ii0.902.133.0173 (18)167
Symmetry codes: (i) x, y−1, z; (ii) x, y+1, z.
 

References

First citationBensemann, I., Gdaniec, M. & Połoński, T. (2002). New J. Chem. 26, 448–456.  Web of Science CSD CrossRef CAS Google Scholar
 First citationFarrugia, L. J. (1997). J. Appl. Cryst. 30, 565.  CrossRef IUCr Journals Google Scholar
 First citationGdaniec, M., Bensemann, I. & Połoński, T. (2005). CrystEngComm, 7, 433–438.  Web of Science CSD CrossRef CAS Google Scholar
 First citationMacrae, C. F., Edgington, P. R., McCabe, P., Pidcock, E., Shields, G. P., Taylor, R., Towler, M. & van de Streek, J. (2006). J. Appl. Cryst. 39, 453–457.  Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
 First citationOxford Diffraction (2002). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England.  Google Scholar
 First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
 First citationWicher, B. & Gdaniec, M. (2011). Acta Cryst. E67, o3095.  Web of Science CSD CrossRef IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

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ISSN: 2056-9890
Volume 67| Part 12| December 2011| Page o3254
https://doi.org/10.1107/S1600536811046356
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