6-(1H-Indol-3-yl)-4-phenyl-2,2′-bi­pyridine-5-carbonitrile

Zhu, W.; Xiang, Y.; Zhu, S.

doi:10.1107/S1600536809016195

organic compounds

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ISSN: 2056-9890

Volume 65| Part 6| June 2009| Page o1187

doi:10.1107/S1600536809016195

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6-(1H-Indol-3-yl)-4-phenyl-2,2′-bipyridine-5-carbonitrile

Weijun Zhu,^a ^* Yan Xiang ^b and Songlei Zhu ^c

^aXuzhou College of Industrial Technology, Xuzhou 221140, People's Republic of China, ^bXuzhou Pharmaceutical College, Xuzhou 221116, People's Republic of China, and ^cXuzhou Medical College, Xuzhou 221002, People's Republic of China
^*Correspondence e-mail: songleizhu@126.com

(Received 29 April 2009; accepted 29 April 2009; online 7 May 2009)

In the molecule of the title compound, C₂₅H₁₆N₄, the pyridine rings are oriented at a dihedral angle of 0.92 (3)°, while the dihedral angle between the benzene ring and the adjacent pyridine ring is 56.51 (3)°. In the crystal structure, intermolecular N—H⋯N hydrogen bonds link the molecules into centrosymmetric dimers, forming R₂²(16) ring motifs. π–π contacts between the pyridine ring and the indole ring system and between the pyridine rings [centroid–centroid distances = 3.923 (2) and 3.724 (2) Å] may further stabilize the structure. Two weak C—H⋯π interactions are also present.

Related literature

For general background, see: da Silva et al. (2001 ); Joshi & Chand (1982 ); Namba et al. (2005 ). For a related structure, see: Zhu et al., (2008 ). For bond-length data, see: Allen et al. (1987 ). For ring-motifs, see: Bernstein et al. (1995 ).

Experimental

Crystal data

C₂₅H₁₆N₄
M_r = 372.42
Triclinic, $[P \overline 1]$
a = 9.7744 (16) Å
b = 9.7927 (11) Å
c = 11.233 (2) Å
α = 73.121 (13)°
β = 86.008 (16)°
γ = 63.853 (10)°
V = 921.5 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 291 K
0.55 × 0.35 × 0.30 mm

Data collection

Rigaku Mercury diffractometer
Absorption correction: multi-scan (ABSCOR; Jacobson, 1998 ) T_min = 0.966, T_max = 0.976
8987 measured reflections
3349 independent reflections
2614 reflections with I > 2/s(I)
R_int = 0.027

Refinement

R[F² > 2σ(F²)] = 0.054
wR(F²) = 0.126
S = 1.12
3349 reflections
263 parameters
H-atom parameters constrained
Δρ_max = 0.16 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H4⋯N3ⁱ	0.86	2.23	3.066 (2)	164
C12—H12⋯Cg5ⁱⁱ	0.93	2.84	3.649 (3)	146
C23—H23⋯Cg4ⁱⁱⁱ	0.93	2.91	3.711 (3)	145
Symmetry codes: (i) -x+1, -y, -z+1; (ii) -x, -y+2, -z+1; (iii) x, y, z-1. Cg4 and Cg5 are the centroids of the C11–C16 and C20–C25 rings, respectively.

Data collection: CrystalClear (Rigaku/MSC, 2001 ); cell refinement: CrystalClear; data reduction: CrystalStructure (Rigaku/MSC, 2004 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPII (Johnson, 1976 ) and PLATON (Spek, 2009 ); software used to prepare material for publication: SHELXL97 and PLATON.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809016195/hk2679sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809016195/hk2679Isup2.hkl

checkCIF report

Comment top

Indole nucleus is a well known heterocycle (da Silva et al., 2001). Compounds carrying the indole moiety exhibit antibacterial and fungicidal activities (Joshi & Chand, 1982). Moreover, the bipyridines and the related complexes have also found numerous applications in asymmetric catalysis, photoinduced electron transfer, and polymer and dendrimer science (Namba et al., 2005). As a part of our programme devoted to the preparation of functionalized indole derivatives, we synthesized a series of indole substituted heterocycles (Zhu et al., 2008). We report herein the crystal structure of the title compound.

In the molecule of the title compound (Fig 1), the bond lengths (Allen et al., 1987) and angles are within normal ranges. The indole ring system A (N4/C18-C25) is planar with a maximum deviation of -0.021 (3) Å for atom C25. Rings B (N1/C1-C5), C (N2/C6-C10) and D (C11-C16) are, of course, planar, and they are oriented at dihedral angles of A/B = 23.01 (3), A/C = 23.61 (3), A/D = 74.90 (3), B/C = 0.92 (3), B/D = 56.51 (3) and C/D = 56.51 (3) °. So, rings B and C are nearly coplanar.

In the crystal structure, intermolecular N-H···N hydrogen bonds (Table 1) link the molecules into centrosymmetric dimers forming R₂²(16) ring motifs (Fig. 2) (Bernstein et al., 1995), in which they may be effective in the stabilization of the structure. The π–π contacts between the pyridine ring and the indole ring system and the pyridine rings, Cg1—Cg2ⁱ and Cg2—Cg3ⁱⁱ [symmetry codes: (i) -x, 2 - y, 1 - z, (ii) -x, 1 - y, 1 - z, where Cg1, Cg2 and Cg3 are centroids of the rings (N4/C18-C20/C25), B (N1/C1-C5) and C (N2/C6-C10), respectively] may further stabilize the structure, with centroid-centroid distances of 3.923 (2) and 3.724 (2) Å. There also exist two weak C—H···π interactions (Table 1).

Related literature top

For general background, see: da Silva et al. (2001); Joshi & Chand (1982); Namba et al. (2005). For a related structure, see: Zhu et al., (2008). For bond-length data, see: Allen et al. (1987). For ring-motifs, see: Bernstein et al. (1995). Cg4 and Cg5 are the centroids of the C11–C16 and C20–C25 rings, respectively.

Experimental top

The title compound was prepared by one-pot reaction of 3-cyanoacetyl indole (2 mmol), benzaldehyde (2 mmol) and 2-acetyl pyridine (2 mmol) in present of ammonium acetate in ethanol. After refluxing for 5 h, the reaction mixture was cooled and washed with small amount of cool ethanol. The crude product was filtered and single crystals of the title compound were obtained from ethanol solution by slow evaporation at room temperature (yield; 80%, m.p. 567-568 K). Spectroscopic analysis: IR (KBr, n, cm^-1): 3337, 3050, 2218, 1573, 1535, 1438, 1214, 1145, 850, 745, 703. ¹H NMR (400 MHz, DMSO-d₆): 11.89 (br s, 1H, NH), 8.78 (d, J = 4.4 Hz, 1H, ArH), 8.58 (d, J = 8.0 Hz, 1H, ArH), 8.41 (d, J = 5.2 Hz, 2H, ArH), 8.31 (s, 1H, ArH), 8.11 (m, 1H, ArH), 7.79-7.81 (m, 2H, ArH), 7.56-7.66 (m, 5H, ArH), 7.24-7.29 (m, 2H, ArH)

Computing details top

Data collection: CrystalClear (Rigaku/MSC, 2001); cell refinement: CrystalClear (Rigaku/MSC, 2001); data reduction: CrystalStructure (Rigaku/MSC, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPII (Johnson, 1976) and PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. A partial packing diagram of the title compound. Hydrogen bonds are shown as dashed lines.

6-(1H-Indol-3-yl)-4-phenyl-2,2'-bipyridine-5-carbonitrile top

Crystal data top

C₂₅H₁₆N₄	Z = 2
M_r = 372.42	F(000) = 388
Triclinic, P1	D_x = 1.342 Mg m⁻³
Hall symbol: -P 1	Melting point = 567–568 K
a = 9.7744 (16) Å	Mo Kα radiation, λ = 0.71070 Å
b = 9.7927 (11) Å	Cell parameters from 3008 reflections
c = 11.233 (2) Å	θ = 3.1–25.3°
α = 73.121 (13)°	µ = 0.08 mm⁻¹
β = 86.008 (16)°	T = 291 K
γ = 63.853 (10)°	Block, yellow
V = 921.5 (3) Å³	0.55 × 0.35 × 0.30 mm

Data collection top

Rigaku Mercury diffractometer	3349 independent reflections
Radiation source: fine-focus sealed tube	2614 reflections with I > 2/s(I)
Graphite monochromator	R_int = 0.027
Detector resolution: 7.31 pixels mm^-1	θ_max = 25.3°, θ_min = 3.1°
ω scans	h = −11→11
Absorption correction: multi-scan (ABSCOR; Jacobson, 1998)	k = −10→11
T_min = 0.966, T_max = 0.976	l = −13→13
8987 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.054	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.126	H-atom parameters constrained
S = 1.12	w = 1/[σ²(F_o²) + (0.0538P)² + 0.1499P] where P = (F_o² + 2F_c²)/3
3349 reflections	(Δ/σ)_max < 0.001
263 parameters	Δρ_max = 0.16 e Å⁻³
0 restraints	Δρ_min = −0.21 e Å⁻³

Crystal data top

C₂₅H₁₆N₄	γ = 63.853 (10)°
M_r = 372.42	V = 921.5 (3) Å³
Triclinic, P1	Z = 2
a = 9.7744 (16) Å	Mo Kα radiation
b = 9.7927 (11) Å	µ = 0.08 mm⁻¹
c = 11.233 (2) Å	T = 291 K
α = 73.121 (13)°	0.55 × 0.35 × 0.30 mm
β = 86.008 (16)°

Data collection top

Rigaku Mercury diffractometer	3349 independent reflections
Absorption correction: multi-scan (ABSCOR; Jacobson, 1998)	2614 reflections with I > 2/s(I)
T_min = 0.966, T_max = 0.976	R_int = 0.027
8987 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.054	0 restraints
wR(F²) = 0.126	H-atom parameters constrained
S = 1.12	Δρ_max = 0.16 e Å⁻³
3349 reflections	Δρ_min = −0.21 e Å⁻³
263 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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

	x	y	z	U_iso*/U_eq
N1	0.94201 (16)	0.20772 (17)	0.54741 (13)	0.0355 (4)
N2	1.20413 (18)	0.3774 (2)	0.44026 (14)	0.0455 (4)
N3	0.5855 (2)	0.1895 (2)	0.28547 (16)	0.0606 (5)
N4	0.64100 (17)	−0.04598 (18)	0.69177 (14)	0.0422 (4)
H4	0.5936	−0.1043	0.7025	0.051*
C1	1.01436 (19)	0.2799 (2)	0.46717 (16)	0.0347 (4)
C2	0.98275 (19)	0.3310 (2)	0.33960 (16)	0.0371 (4)
H2	1.0382	0.3776	0.2873	0.045*
C3	0.86846 (19)	0.3126 (2)	0.28960 (16)	0.0353 (4)
C4	0.79281 (19)	0.2362 (2)	0.37308 (16)	0.0348 (4)
C5	0.83308 (19)	0.1829 (2)	0.50305 (16)	0.0334 (4)
C6	1.13427 (19)	0.3032 (2)	0.52184 (16)	0.0354 (4)
C7	1.1727 (2)	0.2494 (2)	0.64913 (18)	0.0449 (5)
H7	1.1226	0.1981	0.7039	0.054*
C8	1.2862 (2)	0.2731 (3)	0.6929 (2)	0.0519 (5)
H8	1.3135	0.2383	0.7779	0.062*
C9	1.3586 (2)	0.3482 (2)	0.6104 (2)	0.0494 (5)
H9	1.4361	0.3648	0.6378	0.059*
C10	1.3136 (2)	0.3981 (3)	0.4861 (2)	0.0521 (5)
H10	1.3625	0.4497	0.4302	0.063*
C11	0.8284 (2)	0.3777 (2)	0.15322 (16)	0.0379 (4)
C12	0.9407 (2)	0.3356 (2)	0.07066 (17)	0.0445 (5)
H12	1.0400	0.2617	0.1010	0.053*
C13	0.9065 (3)	0.4026 (3)	−0.05660 (18)	0.0529 (6)
H13	0.9823	0.3725	−0.1114	0.063*
C14	0.7602 (3)	0.5140 (3)	−0.10229 (19)	0.0555 (6)
H14	0.7376	0.5599	−0.1878	0.067*
C15	0.6484 (3)	0.5570 (3)	−0.02151 (19)	0.0532 (6)
H15	0.5498	0.6323	−0.0525	0.064*
C16	0.6809 (2)	0.4891 (2)	0.10587 (18)	0.0460 (5)
H16	0.6039	0.5181	0.1600	0.055*
C17	0.6772 (2)	0.2108 (2)	0.32443 (17)	0.0423 (5)
C18	0.7603 (2)	0.1025 (2)	0.59690 (16)	0.0352 (4)
C19	0.6856 (2)	0.0176 (2)	0.58127 (17)	0.0385 (4)
H19	0.6682	0.0056	0.5054	0.046*
C20	0.6833 (2)	−0.0028 (2)	0.78422 (17)	0.0380 (4)
C21	0.6582 (2)	−0.0376 (2)	0.90989 (18)	0.0476 (5)
H21	0.6081	−0.1001	0.9444	0.057*
C22	0.7105 (3)	0.0240 (3)	0.98141 (19)	0.0568 (6)
H22	0.6957	0.0029	1.0663	0.068*
C23	0.7851 (3)	0.1175 (3)	0.92946 (19)	0.0601 (6)
H23	0.8188	0.1581	0.9803	0.072*
C24	0.8104 (2)	0.1515 (3)	0.80452 (18)	0.0507 (5)
H24	0.8605	0.2143	0.7711	0.061*
C25	0.7595 (2)	0.0901 (2)	0.72879 (16)	0.0366 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0353 (8)	0.0367 (9)	0.0374 (8)	−0.0191 (7)	0.0027 (7)	−0.0097 (7)
N2	0.0430 (9)	0.0583 (11)	0.0475 (9)	−0.0321 (8)	0.0058 (8)	−0.0173 (8)
N3	0.0675 (12)	0.0748 (13)	0.0507 (10)	−0.0502 (11)	−0.0130 (9)	0.0006 (9)
N4	0.0439 (9)	0.0449 (9)	0.0476 (9)	−0.0298 (8)	0.0052 (7)	−0.0109 (7)
C1	0.0320 (9)	0.0349 (10)	0.0378 (10)	−0.0153 (8)	0.0024 (8)	−0.0102 (8)
C2	0.0336 (9)	0.0415 (11)	0.0369 (10)	−0.0206 (8)	0.0024 (8)	−0.0058 (8)
C3	0.0354 (10)	0.0346 (10)	0.0355 (10)	−0.0159 (8)	0.0005 (8)	−0.0081 (8)
C4	0.0346 (9)	0.0346 (10)	0.0362 (10)	−0.0172 (8)	0.0001 (8)	−0.0082 (8)
C5	0.0329 (9)	0.0314 (9)	0.0385 (10)	−0.0157 (8)	0.0034 (8)	−0.0114 (8)
C6	0.0319 (9)	0.0355 (10)	0.0407 (10)	−0.0152 (8)	0.0036 (8)	−0.0134 (8)
C7	0.0452 (11)	0.0490 (12)	0.0415 (11)	−0.0237 (10)	−0.0025 (9)	−0.0083 (9)
C8	0.0514 (12)	0.0575 (13)	0.0492 (12)	−0.0256 (11)	−0.0101 (10)	−0.0131 (10)
C9	0.0334 (10)	0.0567 (13)	0.0663 (14)	−0.0199 (10)	−0.0016 (10)	−0.0281 (11)
C10	0.0458 (12)	0.0661 (14)	0.0611 (13)	−0.0364 (11)	0.0121 (10)	−0.0249 (11)
C11	0.0418 (10)	0.0419 (11)	0.0360 (10)	−0.0255 (9)	0.0003 (8)	−0.0080 (8)
C12	0.0459 (11)	0.0509 (12)	0.0399 (11)	−0.0266 (10)	0.0016 (9)	−0.0089 (9)
C13	0.0668 (14)	0.0664 (15)	0.0398 (11)	−0.0420 (13)	0.0114 (10)	−0.0171 (10)
C14	0.0770 (16)	0.0650 (15)	0.0357 (11)	−0.0472 (13)	−0.0048 (11)	−0.0026 (10)
C15	0.0566 (13)	0.0545 (13)	0.0463 (12)	−0.0306 (11)	−0.0118 (11)	0.0018 (10)
C16	0.0448 (11)	0.0539 (12)	0.0410 (10)	−0.0260 (10)	−0.0005 (9)	−0.0085 (9)
C17	0.0457 (11)	0.0469 (12)	0.0382 (10)	−0.0283 (10)	0.0001 (9)	−0.0042 (9)
C18	0.0334 (9)	0.0345 (10)	0.0388 (10)	−0.0164 (8)	0.0030 (8)	−0.0098 (8)
C19	0.0408 (10)	0.0398 (11)	0.0387 (10)	−0.0215 (9)	0.0030 (8)	−0.0109 (8)
C20	0.0339 (10)	0.0373 (10)	0.0436 (11)	−0.0174 (8)	0.0041 (8)	−0.0105 (8)
C21	0.0476 (12)	0.0545 (13)	0.0449 (11)	−0.0305 (10)	0.0111 (9)	−0.0091 (10)
C22	0.0709 (15)	0.0729 (15)	0.0377 (11)	−0.0436 (13)	0.0129 (10)	−0.0146 (11)
C23	0.0815 (16)	0.0805 (16)	0.0432 (12)	−0.0570 (14)	0.0122 (11)	−0.0205 (11)
C24	0.0656 (14)	0.0626 (13)	0.0424 (11)	−0.0457 (12)	0.0096 (10)	−0.0145 (10)
C25	0.0356 (10)	0.0374 (10)	0.0394 (10)	−0.0199 (8)	0.0033 (8)	−0.0091 (8)

Geometric parameters (Å, º) top

N1—C1	1.339 (2)	C11—C12	1.385 (3)
N1—C5	1.347 (2)	C11—C16	1.391 (3)
N2—C10	1.334 (2)	C12—C13	1.384 (3)
N2—C6	1.341 (2)	C12—H12	0.9300
N3—C17	1.144 (2)	C13—C14	1.378 (3)
N4—C19	1.354 (2)	C13—H13	0.9300
N4—C20	1.377 (2)	C14—C15	1.369 (3)
N4—H4	0.8600	C14—H14	0.9300
C1—C2	1.381 (2)	C15—C16	1.384 (3)
C1—C6	1.490 (2)	C15—H15	0.9300
C2—C3	1.385 (2)	C16—H16	0.9300
C2—H2	0.9300	C18—C19	1.375 (2)
C3—C4	1.404 (2)	C18—C25	1.451 (2)
C3—C11	1.484 (2)	C19—H19	0.9300
C4—C5	1.420 (2)	C20—C21	1.384 (3)
C4—C17	1.432 (2)	C20—C25	1.405 (2)
C5—C18	1.465 (2)	C21—C22	1.372 (3)
C6—C7	1.388 (2)	C21—H21	0.9300
C7—C8	1.377 (3)	C22—C23	1.389 (3)
C7—H7	0.9300	C22—H22	0.9300
C8—C9	1.368 (3)	C23—C24	1.376 (3)
C8—H8	0.9300	C23—H23	0.9300
C9—C10	1.371 (3)	C24—C25	1.398 (3)
C9—H9	0.9300	C24—H24	0.9300
C10—H10	0.9300

C1—N1—C5	119.18 (15)	C13—C12—H12	119.7
C10—N2—C6	117.30 (17)	C11—C12—H12	119.7
C19—N4—C20	109.41 (15)	C14—C13—C12	120.1 (2)
C19—N4—H4	125.3	C14—C13—H13	119.9
C20—N4—H4	125.3	C12—C13—H13	119.9
N1—C1—C2	123.09 (15)	C15—C14—C13	119.85 (19)
N1—C1—C6	116.67 (15)	C15—C14—H14	120.1
C2—C1—C6	120.24 (16)	C13—C14—H14	120.1
C1—C2—C3	119.94 (16)	C14—C15—C16	120.5 (2)
C1—C2—H2	120.0	C14—C15—H15	119.8
C3—C2—H2	120.0	C16—C15—H15	119.8
C2—C3—C4	117.25 (16)	C15—C16—C11	120.2 (2)
C2—C3—C11	119.47 (16)	C15—C16—H16	119.9
C4—C3—C11	123.25 (15)	C11—C16—H16	119.9
C3—C4—C5	120.12 (15)	N3—C17—C4	179.5 (2)
C3—C4—C17	118.82 (15)	C19—C18—C25	105.64 (15)
C5—C4—C17	121.05 (16)	C19—C18—C5	128.12 (16)
N1—C5—C4	120.37 (15)	C25—C18—C5	126.18 (15)
N1—C5—C18	115.71 (15)	N4—C19—C18	110.50 (16)
C4—C5—C18	123.91 (15)	N4—C19—H19	124.7
N2—C6—C7	122.15 (16)	C18—C19—H19	124.7
N2—C6—C1	115.83 (15)	N4—C20—C21	129.29 (17)
C7—C6—C1	122.01 (16)	N4—C20—C25	107.56 (15)
C8—C7—C6	118.82 (18)	C21—C20—C25	123.15 (17)
C8—C7—H7	120.6	C22—C21—C20	117.15 (18)
C6—C7—H7	120.6	C22—C21—H21	121.4
C9—C8—C7	119.50 (19)	C20—C21—H21	121.4
C9—C8—H8	120.2	C21—C22—C23	121.23 (19)
C7—C8—H8	120.2	C21—C22—H22	119.4
C8—C9—C10	118.03 (18)	C23—C22—H22	119.4
C8—C9—H9	121.0	C24—C23—C22	121.5 (2)
C10—C9—H9	121.0	C24—C23—H23	119.2
N2—C10—C9	124.20 (19)	C22—C23—H23	119.2
N2—C10—H10	117.9	C23—C24—C25	118.88 (18)
C9—C10—H10	117.9	C23—C24—H24	120.6
C12—C11—C16	118.78 (17)	C25—C24—H24	120.6
C12—C11—C3	119.99 (16)	C24—C25—C20	118.06 (17)
C16—C11—C3	121.11 (17)	C24—C25—C18	135.01 (17)
C13—C12—C11	120.51 (19)	C20—C25—C18	106.88 (15)

C5—N1—C1—C2	0.0 (3)	C16—C11—C12—C13	−0.3 (3)
C5—N1—C1—C6	−179.68 (15)	C3—C11—C12—C13	−176.21 (17)
N1—C1—C2—C3	2.0 (3)	C11—C12—C13—C14	1.0 (3)
C6—C1—C2—C3	−178.34 (16)	C12—C13—C14—C15	−0.7 (3)
C1—C2—C3—C4	−2.2 (3)	C13—C14—C15—C16	−0.1 (3)
C1—C2—C3—C11	175.87 (17)	C14—C15—C16—C11	0.8 (3)
C2—C3—C4—C5	0.7 (3)	C12—C11—C16—C15	−0.5 (3)
C11—C3—C4—C5	−177.30 (16)	C3—C11—C16—C15	175.28 (17)
C2—C3—C4—C17	−178.14 (16)	N1—C5—C18—C19	−157.15 (17)
C11—C3—C4—C17	3.8 (3)	C4—C5—C18—C19	24.1 (3)
C1—N1—C5—C4	−1.6 (2)	N1—C5—C18—C25	19.5 (3)
C1—N1—C5—C18	179.67 (15)	C4—C5—C18—C25	−159.21 (17)
C3—C4—C5—N1	1.2 (3)	C20—N4—C19—C18	0.8 (2)
C17—C4—C5—N1	−179.95 (17)	C25—C18—C19—N4	−0.5 (2)
C3—C4—C5—C18	179.84 (16)	C5—C18—C19—N4	176.68 (17)
C17—C4—C5—C18	−1.3 (3)	C19—N4—C20—C21	178.41 (19)
C10—N2—C6—C7	0.0 (3)	C19—N4—C20—C25	−0.8 (2)
C10—N2—C6—C1	−179.08 (16)	N4—C20—C21—C22	−178.64 (19)
N1—C1—C6—N2	−179.21 (15)	C25—C20—C21—C22	0.5 (3)
C2—C1—C6—N2	1.1 (3)	C20—C21—C22—C23	0.1 (3)
N1—C1—C6—C7	1.7 (3)	C21—C22—C23—C24	−0.3 (4)
C2—C1—C6—C7	−178.01 (17)	C22—C23—C24—C25	0.0 (4)
N2—C6—C7—C8	0.0 (3)	C23—C24—C25—C20	0.6 (3)
C1—C6—C7—C8	179.07 (17)	C23—C24—C25—C18	177.8 (2)
C6—C7—C8—C9	−0.3 (3)	N4—C20—C25—C24	178.46 (16)
C7—C8—C9—C10	0.4 (3)	C21—C20—C25—C24	−0.8 (3)
C6—N2—C10—C9	0.2 (3)	N4—C20—C25—C18	0.5 (2)
C8—C9—C10—N2	−0.4 (3)	C21—C20—C25—C18	−178.79 (17)
C2—C3—C11—C12	54.4 (2)	C19—C18—C25—C24	−177.5 (2)
C4—C3—C11—C12	−127.63 (19)	C5—C18—C25—C24	5.3 (3)
C2—C3—C11—C16	−121.39 (19)	C19—C18—C25—C20	0.0 (2)
C4—C3—C11—C16	56.6 (3)	C5—C18—C25—C20	−177.27 (16)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4···N3ⁱ	0.86	2.23	3.066 (2)	164
C12—H12···Cg5ⁱⁱ	0.93	2.84	3.649 (3)	146
C23—H23···Cg4ⁱⁱⁱ	0.93	2.91	3.711 (3)	145

Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x, −y+2, −z+1; (iii) x, y, z−1.

Experimental details

Crystal data
Chemical formula	C₂₅H₁₆N₄
M_r	372.42
Crystal system, space group	Triclinic, P1
Temperature (K)	291
a, b, c (Å)	9.7744 (16), 9.7927 (11), 11.233 (2)
α, β, γ (°)	73.121 (13), 86.008 (16), 63.853 (10)
V (Å³)	921.5 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.55 × 0.35 × 0.30

Data collection
Diffractometer	Rigaku Mercury diffractometer
Absorption correction	Multi-scan (ABSCOR; Jacobson, 1998)
T_min, T_max	0.966, 0.976
No. of measured, independent and observed [I > 2/s(I)] reflections	8987, 3349, 2614
R_int	0.027
(sin θ/λ)_max (Å⁻¹)	0.602

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.054, 0.126, 1.12
No. of reflections	3349
No. of parameters	263
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.16, −0.21

Computer programs: CrystalClear (Rigaku/MSC, 2001), CrystalStructure (Rigaku/MSC, 2004), SHELXS97 (Sheldrick, 2008), ORTEPII (Johnson, 1976) and PLATON (Spek, 2009), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4···N3ⁱ	0.86	2.23	3.066 (2)	164
C12—H12···Cg5ⁱⁱ	0.93	2.84	3.649 (3)	146
C23—H23···Cg4ⁱⁱⁱ	0.93	2.91	3.711 (3)	145

Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x, −y+2, −z+1; (iii) x, y, z−1.

Acknowledgements

This work was sponsored by the `Qing Lan' Project of Jiangsu Province for Excellent Young Teachers of XuZhou College of Industrial Technology, and the Special Foundation of the President of Xuzhou Medical College.

References

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