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The title compound, C20H17N3, is a derivative of 1,3,5-triaryl-2-pyrazoline and can act as an N,N′-bidentate ligand. This mol­ecule features strong fluorescence that can be explained by an extended pyrid­yl–C=N—N–phenyl system. The three-dimensional structure is formed by means of an extended network of weak C—H...π hydrogen bonds supported by π–π inter­actions.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S010827011001841X/lg3030sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S010827011001841X/lg3030Isup2.hkl
Contains datablock I

CCDC reference: 782544

Comment top

1,3,5-Triaryl-2-pyrazolines present a wide range of interesting properties. They are used as whitening or brightening reagents (Wang et al., 2001; Dorlars et al., 1975) and as photosensitizers (Fushizaki & Sakikawa, 1971). Moreover, due to their fluorescence properties, these compounds have been utilized as fluorescence probes in some elaborate chemosensors (Bissell et al., 1993; de Silva et al., 1997). On the other hand, the fluorescent 3-(2-pyridyl) analogues of triarylpyrazolines themselves can serve as N,N'-type bidentate ligands for metal ions. Wang et al. (2001) reported that pyridylpyrazoline derivatives show specific fluorescent behaviour towards the Zn2+ ion among divalent transition metal ions, in particular the 5-(4-cyanophenyl) derivative. The stability constant in acetonitrile for the ZnL2 complex was determined as 3.4 × 1011 with a clear selectivity for other divalent ions such as copper(II) (Wang et al., 2001). Searching the Cambridge Structural Database (CSD, Version 5.31, February 2010 update; Allen, 2002), only two related structures were found with coordinates available: 1-(2-hydroxyethyl)-5-hydroxy-3-pyridin-2-yl-5-trifluoromethyl-4,5- dihydropyrazole (CSD refcode NIHDEO; Montoya et al., 2007) and 2,3-(6-phenyl-1,4-bis(2-pyridyl)-2,3,5-triazahepta-1,4-diene-1,3-diyl)C60fullerene carbon disulfide solvate (refcode NEPHAR; Miller et al., 2001). Here, a crystallographic study of the title ligand, (I), is presented.

Compound (I) shows an extended pyridyl–C3N2–N1–phenyl system, with atoms N2 and N32 present in an anti conformation (Fig. 1), as seen in 2,2'-bipyridyl. This conformation is probably forced by the repulsion between the two non-bonding electron pairs present on each N atom and by an intramolecular hydrogen-bond interaction between the N atom of the pyrazole ring and one H atom of the pyridine moiety, C36—H36···N2. Atom N2 is the acceptor of another intramolecular non-standard hydrogen bond (Steiner, 1996), C12—H12···N2. For details of intramolecular hydrogen-bond interactions for (I), see Table 1.

In order to achieve bidentate coordination to metal ions, an initial step from an s-trans to an s-cis conformation relative to the pyridyl-imino moiety should be achieved, similar to that in 2,2'-bipyridyl. The C3—C31 distance [1.4620 (18) Å] is slightly shorter than a single C—C bond but longer than a typical CC [Standard reference?]. In 2,2'-bipyridyl structures deposited in the CSD, this distance is 1.488 Å in BIPYRL04 (Kuhn et al., 2002) and 1.504 Å in BIPYRL (Merritt & Schroeder, 1956). A comparison with the two 3-pyridil-2-pyrazolines found in the CSD, with values of 1.471 Å in NEPHAR (cis; Miller et al., 2001) and 1.455 Å in NIHDEO (trans; Montoya et al., 2007), suggest that although all the values for pyrazolines are shorter than those for 2,2'-bipyridyl, a rotation along the C3—C31 bond is possible.

Although the five-membered pyrazoline ring cannot be planar, due to the presence of two sp3 C atoms, and additionally in (I) it is twisted on the C4—C5 bond, a comparison of deviations from the mean plane can be made. A correlation was found for these three structures: the longer the C3—C31 bond, the closer the atoms of the pyrazoline ring to the calculated mean plane: in (I) from 0.008 to 0.051 Å, for NEPHAR from 0.002 to 0.008 Å and for NIHDEO from 0.054 to 0.161 Å.

Atom C56 is involved in an intramolecular interaction with the π system of the pyrazoline ring. This interaction can be described as a Carom—H···π interaction (Desiraju & Steiner, 1999; Nishio et al., 1998; Janiak, 2000), with the C—H group pointing rather to the middle of the N1—N2 bond (Table 2).

There are also intermolecular Carom—H···π interactions in (I) (Table 2 and Fig. 2). Atom C54 of the phenyl ring attached to atom C5 interacts with the pyridyl ring, and atom C33 from the pyridyl ring interacts with the phenyl ring attached to atom C5. To complete the two-dimensional network, another C—H···π interaction is found in the structure of (I): a centrosymmetric dimer is formed by means of two interactions between the pyrazoline rings, with atom C5 as donor and with the phenyl ring bonded to N1 (see Fig. 2). By means of these interactions two-dimensional layers are present, staggered in the c direction. The contact distances and geometric characteristics of these interactions seem to be a good example of C—H···π interactions in organic compounds.

The centrosymmetric dimer is also reinforced by three ππ interactions between the two rings involved in the Carom—H···π interactions, namely the pyrazoline ring and the phenyl ring bonded to N1 (Table 3). The presence of these three interactions shows that the entire aromatic systems of these two rings are involved. Another ππ interaction exists between the pyrazoline and pyridine rings (Table 3).

The molecule of (I) is strongly fluorescent, probably due to the extended pyridyl–C3N2–N1–phenyl system already mentioned. In chloroform, this compound presents both excitation and emission bands in the visible part of the spectrum (λexc = 397 nm and λem = 464 nm), presented in Fig. 3. Moreover, these fluorescent properties are pH sensitive, disappearing in acidic conditions but not in the presence of a base.

In conclusion, the structure of (I) described here, its theoretically good capacity for binding to metal ions (Wang et al., 2001) and its fluorescent properties support the idea that 1,5-diphenyl-3-(2-pyridyl)-2-pyrazoline could in future be an interesting means of studying ZnII or other metal ions by means of fluorescent techniques.

Related literature top

For related literature, see: Allen (2002); Bissell et al. (1993); Desiraju & Steiner (1999); Dorlars et al. (1975); Fushizaki & Sakikawa (1971); Janiak (2000); Kuhn et al. (2002); Merritt & Schroeder (1956); Miller et al. (2001); Montoya et al. (2007); Nishio et al. (1998); Parthé & Gelato (1985); Silva et al. (1997); Steiner (1996); Wang et al. (2001).

Experimental top

1,5-Diphenyl-3-(2-pyridyl)-2-pyrazoline, (I), was obtained in a two-step synthesis, as indicated in Fig. 4.

3-Phenyl-1-(2-pyridyl)-2-propen-1-one was prepared as follows. Benzaldehyde (3.6 g, 34 mmol) and 2-acetylpyridine (2 g, 17 mmol) were added to a solution of KOH (0.8 g) in EtOH–H2O (50:50 v/v, 10 ml). The mixture was sealed and stirred for 4 h. At first, the solution showed a bright-yellow colour and, finally, two different phases were present, one of them with an oily aspect. This phase turned solid when the mixture was frozen in an ice bath. A yellow powder was obtained, filtered off and then washed with cold EtOH–H2O (50:50 v/v) (yield 63%). Analysis, found: C 78.78, H 5.22, N 6.53%; calculated for C14H11NO.0.25H2O: C 78.67, H 5.42, N 6.55%; 1H NMR (Frequency?, CDCl3, δ, p.p.m.): 8.75 (ddd, 1H, H2, J = 4.8, 1.8 and 0.9 Hz), 8.31 (d, 1H, H8, J = 16 Hz), 8.19 (ddd, 1H, H5, J = 7.8, 1.2 and 0.9 Hz), 7.94 (d, 1H, H9, J = 16 Hz), 7.88 (dd, 1H, H4, J = 7.8 and 1.8 Hz), 7.73 (m, 2H, H11), 7.49 (dd, 1H, H3, J = 4.8 and 1.2 Hz), 7.42 (m, 3H, H12 and H13); IR (Medium?, ν, cm-1): 422 (w), 486 (s), 565 (s), 617 (m), 667 (s), 688 (m), 754 (vs), 797 (w), 846 (w), 873 (m), 893 (w), 989 (vs), 1030 (vs), 1089 (m), 1146 (m), 1172 (m), 1215 (s), 1289 (s), 1334 (vs), 1446 (s), 1463 (w), 1492 (m), 1570 (vs), 1603 (vs), 1668 (vs), 3007 (m), 3050 (m).

1,5-Diphenyl-3-(2-pyridyl)-2-pyrazoline, (I), was prepared as follows. 3-Phenyl-1-(2-pyridyl)-2-propen-1-one from the previous step (0.56 g, 2.5 mmol) and phenylhydrazine (0.43 g, 4 mmol) were added to a solution of KOH (0.20 g) in EtOH (20 ml) and the mixture was refluxed for 24 h. The resulting brown solution was left for 1–2 d at room temperature and a brownish product appeared which was filtered off. The filtrate was allowed to evaporate slowly and both a microcrystalline yellow product and yellow crystals of (I), suitable for X-ray diffraction studies, were formed [yield of (I) 33%]. [Please check rephrasing.] Analysis, found: C 79.90, H 5.70, N 13.84%; calculated for C20H17N3: C 80.24, H 5.72, N 14.04%; 1H NMR (Frequency?, CDCl3, δ, p.p.m.): 8.53 (bd, 1H, H33, J = 4.7 Hz), 8.15 (bd, 1H, H36, J = 8.0 Hz), 7.70 (dt, 1H, H35, J = 7.7 and 1.7 Hz), 7.30 [bm, 10H, H(arom.)], 7.18 (dd, 1H, H34, J = 6.5 and 1.6 Hz), 5.36 (dd, 1H, H5, Jcis = 7.0 Hz, Jtrans = 12.7 Hz), 3.99 (dd, 1H, H4A, Jtrans = 12.7 Hz, Jgem = 17.9 Hz), 3.33 (dd, 1H, H4B, Jcis = 7.0 Hz, Jgem = 17.9 Hz); ESI–HRMS (m/z), found: 322.1320 (in ethanol); exact mass calculated for C20H17N3Na+: 322.1320; IR (Medium?, ν, cm-1): 435 (w), 503 (m), 539 (w), 571 (w), 618 (w), 698 (s), 746 (s), 763 (s), 787 (s), 872 (m), 892 (vw), 952 (w), 982 (m), 998 (m), 1026 (m), 1074 (m), 1136 (vs), 1174 (vw), 1233 (m), 1249 (m), 1269 (m), 1327 (vs), 1351 (vw), 1389 (vs), 1439 (m), 1467 (s), 1502 (vs), 1555 (vs), 1597 (s), 2923 (m), 3025 (m); UV–vis.: λmax = 374 nm (ε = 16681 M-1 cm-1) in EtOH.

Refinement top

Monoclinic cell parameters were chosen according to the `best choice' criterion for monoclinic structures (Parthé & Gelato, 1985). All H atoms were placed in geometrically calculated positions and refined using a riding model, with C—H = 0.93–0.98 Å, and with Uiso(H) = 1.2Ueq(C).

Computing details top

Data collection: COLLECT (Nonius, 1998); cell refinement: DENZO and SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997); 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); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
[Figure 2] Fig. 2. The C—H···π interactions in (I), forming a two-dimensional layer in the ab plane. Two C5—H5···Cg2i interactions, depicted in light shading (yellow in the electronic version of the journal), form centrosymmetric dimers, and two of these dimers interact by means of two C33—H33···Cg4iii interactions, depicted in dark shading (red in the electronic version of the journal), intertwined by C54—H54···Cg3ii interactions, [depicted in mid-shading (Orange in the electronic version of the journal) ?]. [Symmetry codes: (i) 1 - x, -y, 1 - z; (ii) x, -1 + y, z; (iii) -x, -y, 1 - z; (iv) -x, -1 - y, 1 - z; (v) x, 1 + y, z; (vi) 1 - x, 1 - y, 1 - z.]
[Figure 3] Fig. 3. The fluorescent properties of (I).
[Figure 4] Fig. 4. The synthetic pathway of (I), with the numbering scheme used throughout this article.
1,5-diphenyl-3-(2-pyridyl)-2-pyrazoline top
Crystal data top
C20H17N3F(000) = 632
Mr = 299.37Dx = 1.233 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 3853 reflections
a = 13.2312 (3) Åθ = 2.0–27.5°
b = 10.4394 (2) ŵ = 0.07 mm1
c = 11.7282 (2) ÅT = 294 K
β = 95.518 (2)°Prismatic, yellow
V = 1612.46 (6) Å30.25 × 0.25 × 0.25 mm
Z = 4
Data collection top
Nonius Kappa CCD area-detector
diffractometer
3678 independent reflections
Radiation source: fine-focus sealed tube2543 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.023
ϕ and ω scansθmax = 27.5°, θmin = 3.1°
Absorption correction: multi-scan
[DENZO and SCALEPACK (Otwinowski & Minor, 1997)]
h = 1717
Tmin = 0.933, Tmax = 0.982k = 1213
6706 measured reflectionsl = 1515
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)] = 0.047Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.133H-atom parameters constrained
S = 1.04 w = 1/[σ2(Fo2) + (0.0675P)2 + 0.1753P]
where P = (Fo2 + 2Fc2)/3
3678 reflections(Δ/σ)max < 0.001
208 parametersΔρmax = 0.12 e Å3
0 restraintsΔρmin = 0.15 e Å3
Crystal data top
C20H17N3V = 1612.46 (6) Å3
Mr = 299.37Z = 4
Monoclinic, P21/cMo Kα radiation
a = 13.2312 (3) ŵ = 0.07 mm1
b = 10.4394 (2) ÅT = 294 K
c = 11.7282 (2) Å0.25 × 0.25 × 0.25 mm
β = 95.518 (2)°
Data collection top
Nonius Kappa CCD area-detector
diffractometer
3678 independent reflections
Absorption correction: multi-scan
[DENZO and SCALEPACK (Otwinowski & Minor, 1997)]
2543 reflections with I > 2σ(I)
Tmin = 0.933, Tmax = 0.982Rint = 0.023
6706 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0470 restraints
wR(F2) = 0.133H-atom parameters constrained
S = 1.04Δρmax = 0.12 e Å3
3678 reflectionsΔρmin = 0.15 e Å3
208 parameters
Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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
N10.34223 (8)0.03736 (12)0.39813 (11)0.0581 (4)
N20.28088 (8)0.05371 (10)0.34465 (10)0.0485 (3)
C30.20366 (10)0.07129 (13)0.40262 (12)0.0444 (3)
C40.20656 (11)0.00835 (14)0.50927 (13)0.0529 (4)
H4A0.14510.05860.51110.063*
H4B0.21580.04450.57750.063*
C50.30015 (10)0.09512 (13)0.49805 (12)0.0501 (4)
H50.34870.08630.56620.06*
C110.43520 (10)0.06816 (13)0.35834 (14)0.0533 (4)
C120.46797 (11)0.00528 (17)0.26441 (15)0.0641 (4)
H120.42920.06090.22970.077*
C130.55795 (12)0.0405 (2)0.22203 (17)0.0813 (6)
H130.57870.00140.15830.098*
C140.61662 (13)0.1359 (2)0.2727 (2)0.0886 (7)
H140.67590.1610.24220.106*
C150.58730 (13)0.19475 (17)0.3694 (2)0.0822 (6)
H150.62870.25720.40590.099*
C160.49648 (11)0.16209 (15)0.41331 (18)0.0680 (5)
H160.47720.20260.47840.082*
C310.12510 (9)0.16559 (12)0.36746 (11)0.0422 (3)
N320.06340 (9)0.19534 (12)0.44860 (10)0.0517 (3)
C330.00631 (11)0.28613 (15)0.42250 (13)0.0575 (4)
H330.04890.30830.47790.069*
C340.01898 (11)0.34874 (15)0.31903 (13)0.0558 (4)
H340.06780.41240.30570.067*
C350.04245 (11)0.31490 (15)0.23566 (13)0.0543 (4)
H350.0350.35430.16420.065*
C360.11497 (10)0.22199 (14)0.25974 (11)0.0484 (3)
H360.15690.19710.20440.058*
C510.27228 (9)0.23431 (13)0.47910 (11)0.0447 (3)
C520.28940 (11)0.32248 (14)0.56656 (13)0.0546 (4)
H520.32170.29690.63680.066*
C530.25902 (12)0.44834 (16)0.55088 (15)0.0651 (4)
H530.27030.50670.61070.078*
C540.21222 (12)0.48747 (16)0.44724 (16)0.0673 (5)
H540.1920.57230.43650.081*
C550.19531 (12)0.40064 (17)0.35932 (15)0.0651 (4)
H550.16350.42670.2890.078*
C560.22537 (11)0.27529 (15)0.37512 (12)0.0534 (4)
H560.2140.21730.3150.064*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0451 (7)0.0504 (7)0.0814 (9)0.0071 (5)0.0200 (6)0.0139 (6)
N20.0415 (6)0.0429 (6)0.0625 (7)0.0009 (5)0.0130 (5)0.0014 (5)
C30.0425 (7)0.0416 (7)0.0504 (8)0.0024 (5)0.0106 (6)0.0034 (6)
C40.0536 (8)0.0485 (8)0.0581 (9)0.0039 (6)0.0131 (6)0.0018 (7)
C50.0479 (7)0.0486 (8)0.0537 (8)0.0014 (6)0.0039 (6)0.0016 (6)
C110.0384 (7)0.0447 (8)0.0774 (10)0.0024 (6)0.0086 (6)0.0109 (7)
C120.0431 (8)0.0740 (11)0.0770 (11)0.0008 (7)0.0145 (7)0.0025 (9)
C130.0488 (9)0.1099 (16)0.0881 (13)0.0011 (10)0.0208 (9)0.0134 (11)
C140.0490 (10)0.0966 (15)0.1231 (19)0.0049 (10)0.0229 (10)0.0331 (14)
C150.0497 (9)0.0570 (10)0.1386 (19)0.0104 (8)0.0026 (10)0.0183 (11)
C160.0488 (9)0.0490 (9)0.1062 (14)0.0030 (7)0.0070 (8)0.0035 (9)
C310.0388 (6)0.0427 (7)0.0463 (8)0.0037 (5)0.0103 (5)0.0045 (6)
N320.0503 (7)0.0562 (7)0.0510 (7)0.0062 (5)0.0169 (5)0.0033 (6)
C330.0483 (8)0.0653 (10)0.0620 (10)0.0107 (7)0.0212 (7)0.0014 (8)
C340.0449 (7)0.0600 (9)0.0624 (10)0.0088 (6)0.0055 (6)0.0042 (7)
C350.0520 (8)0.0627 (9)0.0474 (8)0.0015 (7)0.0009 (6)0.0059 (7)
C360.0455 (7)0.0576 (8)0.0433 (8)0.0015 (6)0.0108 (6)0.0050 (6)
C510.0401 (7)0.0479 (8)0.0467 (8)0.0037 (6)0.0071 (5)0.0030 (6)
C520.0575 (8)0.0554 (9)0.0506 (8)0.0037 (7)0.0039 (6)0.0071 (7)
C530.0625 (9)0.0553 (10)0.0789 (12)0.0042 (7)0.0145 (8)0.0198 (9)
C540.0589 (9)0.0493 (9)0.0958 (14)0.0049 (7)0.0181 (9)0.0061 (9)
C550.0622 (9)0.0709 (11)0.0620 (10)0.0099 (8)0.0054 (7)0.0182 (9)
C560.0535 (8)0.0608 (9)0.0460 (8)0.0010 (7)0.0056 (6)0.0037 (7)
Geometric parameters (Å, º) top
N1—N21.3632 (16)C31—N321.3484 (16)
N1—C111.3945 (18)C31—C361.3885 (19)
N1—C51.4739 (18)N32—C331.3373 (18)
N2—C31.2935 (16)C33—C341.374 (2)
C3—C311.4620 (18)C33—H330.93
C3—C41.499 (2)C34—C351.376 (2)
C4—C51.5501 (19)C34—H340.93
C4—H4A0.97C35—C361.374 (2)
C4—H4B0.97C35—H350.93
C5—C511.510 (2)C36—H360.93
C5—H50.98C51—C521.3805 (19)
C11—C121.387 (2)C51—C561.382 (2)
C11—C161.391 (2)C52—C531.381 (2)
C12—C131.383 (2)C52—H520.93
C12—H120.93C53—C541.372 (2)
C13—C141.363 (3)C53—H530.93
C13—H130.93C54—C551.375 (2)
C14—C151.378 (3)C54—H540.93
C14—H140.93C55—C561.375 (2)
C15—C161.395 (2)C55—H550.93
C15—H150.93C56—H560.93
C16—H160.93
N2—N1—C11120.81 (12)C15—C16—H16120.5
N2—N1—C5113.42 (10)N32—C31—C36122.17 (12)
C11—N1—C5125.77 (12)N32—C31—C3114.73 (12)
C3—N2—N1108.82 (11)C36—C31—C3123.09 (12)
N2—C3—C31121.56 (12)C33—N32—C31116.92 (12)
N2—C3—C4113.68 (12)N32—C33—C34124.20 (13)
C31—C3—C4124.69 (11)N32—C33—H33117.9
C3—C4—C5102.11 (11)C34—C33—H33117.9
C3—C4—H4A111.3C33—C34—C35118.36 (14)
C5—C4—H4A111.3C33—C34—H34120.8
C3—C4—H4B111.3C35—C34—H34120.8
C5—C4—H4B111.3C36—C35—C34118.91 (14)
H4A—C4—H4B109.2C36—C35—H35120.5
N1—C5—C51112.46 (11)C34—C35—H35120.5
N1—C5—C4101.21 (11)C35—C36—C31119.38 (12)
C51—C5—C4112.89 (11)C35—C36—H36120.3
N1—C5—H5110C31—C36—H36120.3
C51—C5—H5110C52—C51—C56118.48 (14)
C4—C5—H5110C52—C51—C5120.79 (13)
C12—C11—C16119.28 (14)C56—C51—C5120.68 (13)
C12—C11—N1120.65 (14)C51—C52—C53120.70 (15)
C16—C11—N1120.07 (15)C51—C52—H52119.6
C13—C12—C11120.35 (17)C53—C52—H52119.6
C13—C12—H12119.8C54—C53—C52120.12 (15)
C11—C12—H12119.8C54—C53—H53119.9
C14—C13—C12120.73 (19)C52—C53—H53119.9
C14—C13—H13119.6C53—C54—C55119.67 (15)
C12—C13—H13119.6C53—C54—H54120.2
C13—C14—C15119.40 (17)C55—C54—H54120.2
C13—C14—H14120.3C54—C55—C56120.14 (15)
C15—C14—H14120.3C54—C55—H55119.9
C14—C15—C16121.04 (18)C56—C55—H55119.9
C14—C15—H15119.5C55—C56—C51120.87 (14)
C16—C15—H15119.5C55—C56—H56119.6
C11—C16—C15119.06 (18)C51—C56—H56119.6
C11—C16—H16120.5
C11—N1—N2—C3175.16 (13)N2—C3—C31—N32164.86 (12)
C5—N1—N2—C34.53 (16)C4—C3—C31—N3211.98 (19)
N1—N2—C3—C31178.81 (12)N2—C3—C31—C3614.3 (2)
N1—N2—C3—C41.65 (16)C4—C3—C31—C36168.86 (13)
N2—C3—C4—C56.54 (16)C36—C31—N32—C332.6 (2)
C31—C3—C4—C5176.41 (12)C3—C31—N32—C33176.60 (12)
N2—N1—C5—C51112.56 (13)C31—N32—C33—C340.7 (2)
C11—N1—C5—C5167.77 (18)N32—C33—C34—C351.2 (2)
N2—N1—C5—C48.18 (15)C33—C34—C35—C361.2 (2)
C11—N1—C5—C4171.50 (14)C34—C35—C36—C310.6 (2)
C3—C4—C5—N18.06 (14)N32—C31—C36—C352.6 (2)
C3—C4—C5—C51112.37 (13)C3—C31—C36—C35176.52 (12)
N2—N1—C11—C121.0 (2)N1—C5—C51—C52141.39 (13)
C5—N1—C11—C12178.66 (14)C4—C5—C51—C52104.85 (15)
N2—N1—C11—C16179.44 (13)N1—C5—C51—C5641.19 (17)
C5—N1—C11—C160.9 (2)C4—C5—C51—C5672.57 (16)
C16—C11—C12—C133.5 (2)C56—C51—C52—C530.9 (2)
N1—C11—C12—C13176.91 (15)C5—C51—C52—C53176.58 (13)
C11—C12—C13—C141.0 (3)C51—C52—C53—C540.7 (2)
C12—C13—C14—C152.1 (3)C52—C53—C54—C550.3 (2)
C13—C14—C15—C162.8 (3)C53—C54—C55—C560.2 (2)
C12—C11—C16—C152.9 (2)C54—C55—C56—C510.4 (2)
N1—C11—C16—C15177.56 (14)C52—C51—C56—C550.7 (2)
C14—C15—C16—C110.3 (3)C5—C51—C56—C55176.74 (13)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C12—H12···N20.932.492.800 (2)100
C36—H36···N20.932.672.911 (2)96

Experimental details

Crystal data
Chemical formulaC20H17N3
Mr299.37
Crystal system, space groupMonoclinic, P21/c
Temperature (K)294
a, b, c (Å)13.2312 (3), 10.4394 (2), 11.7282 (2)
β (°) 95.518 (2)
V3)1612.46 (6)
Z4
Radiation typeMo Kα
µ (mm1)0.07
Crystal size (mm)0.25 × 0.25 × 0.25
Data collection
DiffractometerNonius Kappa CCD area-detector
diffractometer
Absorption correctionMulti-scan
[DENZO and SCALEPACK (Otwinowski & Minor, 1997)]
Tmin, Tmax0.933, 0.982
No. of measured, independent and
observed [I > 2σ(I)] reflections
6706, 3678, 2543
Rint0.023
(sin θ/λ)max1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.047, 0.133, 1.04
No. of reflections3678
No. of parameters208
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.12, 0.15

Computer programs: COLLECT (Nonius, 1998), DENZO and SCALEPACK (Otwinowski & Minor, 1997), SHELXS97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C12—H12···N20.932.492.800 (2)100
C36—H36···N20.932.672.911 (2)96
C—H···π interactions in (I) (Å, °) top
D—H···CgD—HH···CgD—H···CgD—H···Cg
C56—H56···Cg10.932.672.9535 (17)98
C5—H5···Cg2i0.982.833.6326 (16)140
C54—H54···Cg3ii0.932.733.5548 (18)149
C33—H33···Cg4iii0.932.773.6018 (16)149
Symmetry codes: (i) -x+1, -y, -z+1; (ii) x, -1+y, z; (iii) -x, -y, -z+1. Cg1, Cg2, Cg3 and Cg4 are the centroids of the N1/N2/C3–C5, C11–C16, C31/N32/C33–C36 and C51–C56 rings, respectively.
Main ππ interactions in (I) (Å, °) top
CgI···CgJCg···CgαβγCgI-PerpCgJ-PerpSlippage
Cg1···Cg2i3.9840 (10)3.47 (8)27.4927.483.5347 (6)3.5341 (7)
Cg2···Cg1i3.9841 (10)3.47 (8)27.4827.493.5342 (7)3.5347 (6)
Cg2···Cg2i4.9030 (11)044.8044.803.4789 (8)3.4788 (8)3.455
Cg3···Cg1iii5.8443 (8)14.66 (7)50.1264.782.4907 (6)3.7469 (6)
Symmetry codes: (i) -x+1, -y, -z+1; (iii) -x, -y, -z+1. Cg1, Cg2 and Cg3 are the centroids of the N1/N2/C3–C5, C11–C16 and C31/N32/C33–C36, rings, respectively. As in PLATON (Spek, 2009), α is the dihedral angle between planes I and J, β is the angle between the CgI\rightrarrow CgJ vector and the normal to the plane I, γ is the angle between the CgI\rightrarrow CgJ vector and the normal to the plane J, CgI-Perp is the perpendicular distance of CgI from ring J, CgJ-Perp is the perpendicular distance of CgJ from ring I, and Slippage is the distance between CgI and the perpendicular projection of CgJ on ring I.
 

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