research communications\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 71| Part 2| February 2015| Pages 192-194

Crystal structure of 2-benzyl­amino-4-p-tolyl-6,7-di­hydro-5H-cyclo­penta­[b]pyridine-3-carbo­nitrile

aDepartment of Physics, The Madura College, Madurai 625 011, India, bDepartment of Organic Chemistry, School of Chemistry, Madurai Kamaraj University, Madurai 625 021, India, and cDepartment of Food Science and Technology, University of Ruhuna, Mapalana, Kamburupitiya 81100, Sri Lanka
*Correspondence e-mail: plakshmannilantha@ymail.com

Edited by H. Stoeckli-Evans, University of Neuchâtel, Switzerland (Received 11 January 2015; accepted 12 January 2015; online 21 January 2015)

The title compound, C23H21N3, comprises a 2-amino-3-cyano­pyridine ring fused with a cyclo­pentane ring. The later adopts an envelope conformation with the central methyl­ene C atom as the flap. The benzyl and and p-tolyl rings are inclined to one another by 56.18 (15)°, and to the pyridine ring by 81.87 (14) and 47.60 (11)°, respectively. In the crystal, mol­ecules are linked by pairs of N—H⋯Nnitrile hydrogen bonds, forming inversion dimers with an R22(12) ring motif. The dimers are linked by C—H⋯π and ππ inter­actions [centroid–centroid distance = 3.7211 (12) Å], forming a three-dimensional framework.

1. Chemical context

The pyridine nucleus is prevalent in numerous natural products and is extremely important in the chemistry of biological systems (Bringmann et al., 2004[Bringmann, G., Reichert, Y. & Kane, V. V. (2004). Tetrahedron, 60, 3539-3574.]). Many naturally occurring and synthetic compounds containing the pyridine scaffold possess inter­esting pharmacological properties (Temple et al., 1992[Temple, C., Rener, G. A. Jr, Waud, W. R. & Noker, P. E. E. (1992). J. Med. Chem. 35, 3686-3690.]). Among them, 2-amino-3-cyano­pyridines have been identified as IKK-β inhibitors (Murata et al., 2003[Murata, T., Shimada, M., Sakakibara, S., Yoshino, T., Kadono, H., Masuda, T., Shimazaki, M., Shintani, T., Fuchikami, K., Sakai, K., Inbe, H., Takeshita, K., Niki, T., Umeda, M., Bacon, K. B., Ziegelbauer, K. B. & Lowinger, T. B. (2003). Bioorg. Med. Chem. Lett. 13, 913-918.]). The above observations prompted us to synthesize the title compound, which contains a pyridine 3-carbo­nitrile group, and we report herein on its crystal structure.

[Scheme 1]

2. Structural commentary

The mol­ecular structure of the title compound is shown Fig. 1[link]. As expected, the pyridine ring (N1/C2–C6) is almost planar (r.m.s. deviation = 0.009 Å). The cyclo­pentane ring fused with the pyridine ring adopts an envelope conformation with atom C8 as the flap, deviating by 0.3505 (1)Å from the mean plane defined by atoms (C5/C6/C7/C9). In the CH2–NH2 chain, the C—N bond lengths [C2—N3 = 1.349 (3) and N3—C21 = 1.437 (3) Å] are comparable with those reported for a similar structure (Nagalakshmi et al., 2014[Nagalakshmi, R. A., Suresh, J., Maharani, S., Kumar, R. R. & Lakshman, P. L. N. (2014). Acta Cryst. E70, 441-443.]). The endocyclic angle at C5 is contracted to 118.73 (19)° while that at C6 is expanded to 126.2 (2)°, due to the fusion of the five- and six-membered rings. Steric hindrance rotates the benzyl ring (C22–C27) out of the plane of the central pyridine ring by 81.87 (14)°. This twist may be due to the non-bonded inter­actions between one of the ortho-H atoms of the benzene ring and atom H21B of the CH2–NH2 chain. The benzyl and and p-tolyl (C41–C46) rings are inclined to one another by 56.18 (15)°, while the p-tolyl ring is inclined to the pyridine ring by 47.60 (11)°.

[Figure 1]
Figure 1
The mol­ecular structure of the title compound, showing the atom labelling. Displacement ellipsoids are drawn at the 30% probability level.

3. Supra­molecular features

In the crystal, mol­ecules are linked via pairs of N—H⋯Nnitrile inter­actions, forming inversion dimers which enclose [R_{2}^{2}](12) ring motifs. The dimers are connected through weak C—H⋯π inter­actions involving the CN group as acceptor (Table 1[link] and Fig. 2[link]). They are further connected by slipped parallel ππ stacking inter­actions involving the pyridine rings of inversion-related mol­ecules [Cg1⋯Cg1i = 3.7211 (12), normal distance = 3.5991 (8), slippage = 0.945 Å; Cg1 is the centroid of the N1/C2–C6 ring; symmetry code: (i) −x + 1, −y, −z], resulting in the formation of a three-dimensional framework.

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the N1/C2–C6 pyridine ring.

D—H⋯A D—H H⋯A DA D—H⋯A
N3—H3⋯N2i 0.86 2.25 2.982 (3) 144
C47—H47ACg1ii 0.96 2.84 3.681 (4) 147
Symmetry codes: (i) -x, -y, -z; (ii) [x, -y-{\script{1\over 2}}, z-{\script{3\over 2}}].
[Figure 2]
Figure 2
A view along the c axis of the crystal packing of the title compound. Hydrogen bonds are shown as dashed lines (see Table 1[link] for details) and H atoms not involved in hydrogen bonding have been omitted for clarity.

4. Database survey

Similar structures reported in the literature include 2-[2-(4-chloro­phen­yl)-2-oxoeth­oxy]-6,7-di­hydro-5H-cyclo­penta­[b]pyridine-3-carbo­nitrile (Mazina et al., 2005[Mazina, O. S., Rybakov, V. B., Troyanov, S. I., Babaev, E. V. & Aslanov, L. A. (2005). Kristallografiya, 50, 68-78.]) and 2-benzylamino-4-(4-meth­oxy­phen­yl)-6,7,8,9-tetra­hydro-5H-cyclohepta[b]pyridine-3-carbo­nitrile (Nagalakshmi et al., 2014[Nagalakshmi, R. A., Suresh, J., Maharani, S., Kumar, R. R. & Lakshman, P. L. N. (2014). Acta Cryst. E70, 441-443.]). In the first compound, the fused cyclo­pentane ring has an envelope conformation with the central methyl­ene C atom as the flap, similar to the situation in the title compound.

5. Synthesis and crystallization

A mixture of cyclo­penta­none (1 mmol) 1, 4-methyl­benzaldehyde (1 mmol), malono­nitrile (1 mmol) and benzyl­amine were taken in ethanol (10 mL) to which p-toluene­sulfonic acid (p-TSA) (1 mmol) was added. The reaction mixture was heated under reflux for 2–3 h. The reaction progress was monitored by thin layer chromatography. After completion of the reaction, the mixture was poured into crushed ice and extracted with ethyl acetate. The excess solvent was removed under vacuum and the residue was subjected to column chromatography using a petroleum ether/ethyl acetate mixture (97:3 v/v) as eluent to obtain the pure product. The product was recrystallized from ethyl acetate, affording colourless crystals of the title compound (yield: 70%, m.p.: 434 K).

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2[link]. The NH and C-bound H atoms were placed in calculated positions and allowed to ride on their carrier atoms: N—H = 0.86 Å, C—H = 0.93–0.97 Å, with Uiso(H) = 1.5Ueq(C) for methyl H atoms and = 1.2Ueq(N,C) for other H atoms.

Table 2
Experimental details

Crystal data
Chemical formula C23H21N3
Mr 339.43
Crystal system, space group Monoclinic, P21/c
Temperature (K) 293
a, b, c (Å) 8.6826 (4), 17.7282 (9), 12.0400 (6)
β (°) 94.253 (2)
V3) 1848.18 (16)
Z 4
Radiation type Mo Kα
μ (mm−1) 0.07
Crystal size (mm) 0.21 × 0.19 × 0.18
 
Data collection
Diffractometer Bruker Kappa APEXII
Absorption correction Multi-scan (SADABS; Bruker, 2004[Bruker (2004). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.])
Tmin, Tmax 0.967, 0.974
No. of measured, independent and observed [I > 2σ(I)] reflections 29178, 3452, 2262
Rint 0.034
(sin θ/λ)max−1) 0.606
 
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.058, 0.192, 1.08
No. of reflections 3452
No. of parameters 237
No. of restraints 1
H-atom treatment H-atom parameters constrained
Δρmax, Δρmin (e Å−3) 0.29, −0.21
Computer programs: APEX2 and SAINT (Bruker, 2004[Bruker (2004). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]), SHELXS2013 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]), SHELXL2014 (Sheldrick, 2015[Sheldrick, G. M. (2015). Acta Cryst. C71, 3-8.]) and PLATON (Spek, 2009[Spek, A. L. (2009). Acta Cryst. D65, 148-155.]).

Supporting information


Chemical context top

The pyridine nucleus is prevalent in numerous natural products and is extremely important in the chemistry of biological systems (Bringmann et al., 2004). Many naturally occurring and synthetic compounds containing the pyridine scaffold possess inter­esting pharmacological properties (Temple et al., 1992). Among them, 2-amino-3-cyano­pyridines have been identified as IKK-β inhibitors (Murata et al., 2003). The above observations prompted us to synthesize the title compound, which contains a pyridine 3-carbo­nitrile group, and we report herein on its crystal structure.

Structural commentary top

The molecular structure of the title compound is shown Fig. 1. As expected, the pyridine ring (N1/C2–C6) is almost planar (r.m.s. deviation = 0.009 Å). The cyclo­pentane ring fused with the pyridine ring adopts an envelope conformation with atom C8 as the flap, deviating by 0.3505 (1)Å from the mean plane defined by atoms (C5/C6/C7/C9). In the CH2–NH2 chain, the C—N bond lengths [C2—N3 = 1.349 (3) and N3—C21 = 1.437 (3) Å] are comparable with those reported for a similar structure (Nagalakshmi et al., 2014). The endocyclic angle at C5 is contracted to 118.73 (19)° while that at C6 is expanded to 126.2 (2)°, due to the fusion of the five- and six-membered rings. Steric hindrance rotates the benzyl ring (C22–C27) out of the plane of the central pyridine ring by 81.87 (14)°. This twist may be due to the non-bonded inter­actions between one of the ortho-H atoms of the benzene ring and atom H21B of the CH2–NH2 chain. The benzyl and and p-tolyl (C41–C46) rings are inclined to one another by 56.18 (15)°, while the p-tolyl ring is inclined to the pyridine ring by 47.60 (11)°.

Supra­molecular features top

In the crystal, molecules are linked via pairs of N—H···Nnitrile inter­actions, forming inversion dimers which enclose R22(12) ring motifs. The dimers are connected through weak C—H···π inter­actions involving the CN group as acceptor (Table 1 and Fig. 2). They are further connected by slipped parallel ππ stacking inter­actions involving the pyridine rings of inversion-related molecules [Cg1···Cg1i = 3.7211 (12), normal distance = 3.5991 (8), slippage = 0.945 Å; Cg1 is the centroid of the N1/C2–C6 ring; symmetry code: (i) -x +1, -y, -z], resulting in the formation of a three-dimensional framework.

Database survey top

Similar structures reported in the literature include 2-[2-(4-chloro­phenyl)-2-oxo­eth­oxy]-6,7-di­hydro-5H-cyclo­penta­[b]pyridine-3-carbo­nitrile (Mazina et al., 2005) and 2-benzyl­amino-4-(4-meth­oxy­phenyl)-6,7,8,9-tetra­hydro-5H-cyclo­hepta[b]pyridine-3-carbo­nitrile (Nagalakshmi et al., 2014). In the first compound, the fused cyclo­pentane ring has an envelope conformation with the central methyl­ene C atom as the flap, similar to the situation in the title compound.

Synthesis and crystallization top

A mixture of cyclo­penta­none (1 mmol) 1, 4-methyl­benzaldehyde (1 mmol), malono­nitrile (1 mmol) and benzyl­amine were taken in ethanol (10 mL) to which p-TSA (p-toluene­sulfonic acid) (1 mmol) was added. The reaction mixture was heated under reflux for 2–3 h. The reaction progress was monitored by thin layer chromatography. After completion of the reaction, the mixture was poured into crushed ice and extracted with ethyl acetate. The excess solvent was removed under vacuum and the residue was subjected to column chromatography using a petroleum ether/ethyl acetate mixture (97:3 v/v) as eluent to obtain the pure product. The product was recrystallized from ethyl acetate, affording colourless crystals of the title compound (yield: 70%, m.p.: 434 K).

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 2. The NH and C-bound H atoms were placed in calculated positions and allowed to ride on their carrier atoms: N—H = 0.86 Å, C—H = 0.93–0.97 Å, with Uiso(H) = 1.5Ueq(C) for methyl H atoms and = 1.2Ueq(N,C) for other H atoms.

Related literature top

For related literature, see: Temple et al. (1992); Murata et al. (2003); Bringmann et al. (2004).;.

For related structure, see: Nagalakshmi et al.,(2014).

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS2013 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015) and PLATON (Spek, 2009).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound, showing the atom labelling. Displacement ellipsoids are drawn at the 30% probability level.
[Figure 2] Fig. 2. A view along the c axis of the crystal packing of the title compound. Hydrogen bonds are shown as dashed lines (see Table 1 for details) and H atoms not involved in hydrogen bonding have been omitted for clarity.
2-Benzylamino-4-p-tolyl-6,7-dihydro-5H-cyclopenta[b]pyridine-3-carbonitrile top
Crystal data top
C23H21N3F(000) = 720
Mr = 339.43Dx = 1.220 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 8.6826 (4) ÅCell parameters from 2000 reflections
b = 17.7282 (9) Åθ = 2–31°
c = 12.0400 (6) ŵ = 0.07 mm1
β = 94.253 (2)°T = 293 K
V = 1848.18 (16) Å3Block, colourless
Z = 40.21 × 0.19 × 0.18 mm
Data collection top
Bruker Kappa APEXII
diffractometer
2262 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.034
ω and ϕ scansθmax = 25.5°, θmin = 2.1°
Absorption correction: multi-scan
(SADABS; Bruker, 2004)
h = 109
Tmin = 0.967, Tmax = 0.974k = 2121
29178 measured reflectionsl = 1414
3452 independent reflections
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.058 w = 1/[σ2(Fo2) + (0.1007P)2 + 0.5115P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.192(Δ/σ)max < 0.001
S = 1.08Δρmax = 0.29 e Å3
3452 reflectionsΔρmin = 0.21 e Å3
237 parametersExtinction correction: SHELXL2014 (Sheldrick, 2015), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
1 restraintExtinction coefficient: 0.017 (4)
Crystal data top
C23H21N3V = 1848.18 (16) Å3
Mr = 339.43Z = 4
Monoclinic, P21/cMo Kα radiation
a = 8.6826 (4) ŵ = 0.07 mm1
b = 17.7282 (9) ÅT = 293 K
c = 12.0400 (6) Å0.21 × 0.19 × 0.18 mm
β = 94.253 (2)°
Data collection top
Bruker Kappa APEXII
diffractometer
3452 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2004)
2262 reflections with I > 2σ(I)
Tmin = 0.967, Tmax = 0.974Rint = 0.034
29178 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0581 restraint
wR(F2) = 0.192H-atom parameters constrained
S = 1.08Δρmax = 0.29 e Å3
3452 reflectionsΔρmin = 0.21 e Å3
237 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C20.3577 (2)0.01812 (12)0.13085 (17)0.0430 (5)
C30.3439 (2)0.05541 (12)0.08637 (17)0.0442 (5)
C40.4663 (2)0.10693 (12)0.09975 (17)0.0440 (5)
C50.5989 (2)0.08141 (13)0.15993 (17)0.0485 (6)
C60.6012 (2)0.00880 (13)0.20121 (18)0.0484 (6)
C70.7526 (3)0.00857 (16)0.2642 (2)0.0644 (7)
H7A0.74250.00860.34390.077*
H7B0.79220.05710.24240.077*
C80.8547 (3)0.05436 (17)0.2313 (2)0.0738 (8)
H8A0.91710.03800.17220.089*
H8B0.92310.07000.29450.089*
C90.7499 (3)0.11988 (16)0.1912 (2)0.0676 (7)
H9A0.73970.15650.25010.081*
H9B0.78920.14500.12750.081*
C210.2359 (3)0.14216 (13)0.1612 (2)0.0534 (6)
H21A0.34100.15840.18120.064*
H21B0.19210.17620.10420.064*
C220.1449 (3)0.14823 (13)0.2613 (2)0.0549 (6)
C230.0421 (3)0.20537 (17)0.2721 (3)0.0822 (9)
H230.02330.23990.21450.099*
C240.0354 (4)0.2124 (2)0.3698 (4)0.1126 (14)
H240.10480.25170.37760.135*
C250.0081 (5)0.1610 (3)0.4533 (4)0.1160 (14)
H250.05730.16610.51890.139*
C260.0889 (4)0.1031 (3)0.4417 (3)0.1090 (12)
H260.10410.06730.49790.131*
C270.1653 (3)0.0970 (2)0.3468 (3)0.0825 (9)
H270.23300.05690.33990.099*
C310.1989 (3)0.07613 (12)0.03276 (19)0.0491 (5)
C410.4499 (2)0.18393 (12)0.05337 (18)0.0463 (5)
C420.4905 (3)0.24647 (14)0.1181 (2)0.0582 (6)
H420.53390.23960.19040.070*
C430.4680 (3)0.31822 (14)0.0777 (2)0.0665 (7)
H430.49380.35910.12370.080*
C440.4076 (3)0.33109 (14)0.0303 (2)0.0607 (7)
C450.3693 (3)0.26900 (14)0.0952 (2)0.0579 (6)
H450.32900.27600.16820.069*
C460.3891 (3)0.19646 (13)0.05444 (19)0.0507 (6)
H460.36130.15560.10010.061*
C470.3824 (4)0.40937 (16)0.0747 (3)0.0918 (10)
H47A0.37380.40800.15460.138*
H47B0.46810.44070.04930.138*
H47C0.28900.42960.04850.138*
N10.4863 (2)0.04087 (10)0.19013 (15)0.0480 (5)
N20.0782 (2)0.08761 (13)0.0074 (2)0.0701 (6)
N30.2394 (2)0.06733 (10)0.11551 (16)0.0546 (5)
H30.15930.05270.07500.066*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C20.0386 (11)0.0454 (12)0.0450 (12)0.0015 (9)0.0021 (9)0.0008 (9)
C30.0394 (10)0.0474 (12)0.0457 (11)0.0040 (9)0.0021 (8)0.0005 (9)
C40.0408 (11)0.0484 (12)0.0429 (11)0.0043 (9)0.0029 (9)0.0027 (9)
C50.0390 (12)0.0574 (14)0.0487 (12)0.0073 (10)0.0004 (9)0.0039 (10)
C60.0396 (11)0.0586 (14)0.0466 (12)0.0012 (10)0.0000 (9)0.0032 (10)
C70.0475 (13)0.0766 (17)0.0669 (16)0.0002 (12)0.0104 (11)0.0000 (13)
C80.0439 (14)0.099 (2)0.0761 (18)0.0074 (14)0.0084 (12)0.0033 (15)
C90.0488 (14)0.0777 (18)0.0745 (17)0.0163 (13)0.0067 (12)0.0030 (13)
C210.0517 (13)0.0445 (13)0.0634 (14)0.0034 (10)0.0008 (11)0.0024 (10)
C220.0408 (12)0.0492 (13)0.0740 (15)0.0024 (10)0.0011 (11)0.0106 (12)
C230.0639 (17)0.0627 (18)0.121 (3)0.0079 (14)0.0139 (17)0.0197 (17)
C240.075 (2)0.098 (3)0.169 (4)0.008 (2)0.039 (3)0.050 (3)
C250.088 (3)0.158 (4)0.106 (3)0.013 (3)0.031 (2)0.036 (3)
C260.090 (2)0.155 (4)0.086 (2)0.005 (3)0.0237 (19)0.010 (2)
C270.0696 (18)0.099 (2)0.080 (2)0.0108 (16)0.0145 (15)0.0080 (17)
C310.0422 (11)0.0453 (12)0.0592 (13)0.0070 (9)0.0006 (9)0.0041 (10)
C410.0402 (11)0.0480 (13)0.0514 (12)0.0070 (10)0.0076 (9)0.0033 (10)
C420.0614 (15)0.0544 (15)0.0585 (14)0.0130 (12)0.0016 (11)0.0057 (11)
C430.0762 (17)0.0521 (15)0.0720 (17)0.0152 (13)0.0109 (14)0.0111 (12)
C440.0662 (16)0.0472 (14)0.0708 (16)0.0058 (12)0.0201 (13)0.0017 (11)
C450.0647 (15)0.0572 (15)0.0528 (13)0.0004 (12)0.0119 (11)0.0033 (11)
C460.0516 (13)0.0492 (13)0.0517 (13)0.0041 (10)0.0064 (10)0.0045 (10)
C470.128 (3)0.0530 (17)0.098 (2)0.0051 (17)0.030 (2)0.0105 (15)
N10.0421 (10)0.0507 (11)0.0507 (10)0.0011 (8)0.0007 (8)0.0014 (8)
N20.0472 (12)0.0668 (15)0.0941 (17)0.0074 (10)0.0100 (11)0.0156 (12)
N30.0435 (10)0.0502 (11)0.0685 (12)0.0082 (9)0.0078 (9)0.0129 (9)
Geometric parameters (Å, º) top
C2—N11.342 (3)C23—C241.404 (5)
C2—N31.349 (3)C23—H230.9300
C2—C31.411 (3)C24—C251.365 (6)
C3—C41.401 (3)C24—H240.9300
C3—C311.420 (3)C25—C261.341 (6)
C4—C51.390 (3)C25—H250.9300
C4—C411.478 (3)C26—C271.368 (4)
C5—C61.380 (3)C26—H260.9300
C5—C91.501 (3)C27—H270.9300
C6—N11.330 (3)C31—N21.140 (3)
C6—C71.499 (3)C41—C461.382 (3)
C7—C81.496 (4)C41—C421.386 (3)
C7—H7A0.9700C42—C431.371 (4)
C7—H7B0.9700C42—H420.9300
C8—C91.531 (4)C43—C441.384 (4)
C8—H8A0.9700C43—H430.9300
C8—H8B0.9700C44—C451.376 (3)
C9—H9A0.9700C44—C471.497 (4)
C9—H9B0.9700C45—C461.382 (3)
C21—N31.437 (3)C45—H450.9300
C21—C221.494 (3)C46—H460.9300
C21—H21A0.9700C47—H47A0.9600
C21—H21B0.9700C47—H47B0.9600
C22—C231.363 (4)C47—H47C0.9600
C22—C271.374 (4)N3—H30.8600
N1—C2—N3118.24 (19)C22—C23—H23119.9
N1—C2—C3121.54 (18)C24—C23—H23119.9
N3—C2—C3120.22 (18)C25—C24—C23119.3 (3)
C4—C3—C2121.10 (19)C25—C24—H24120.3
C4—C3—C31121.52 (19)C23—C24—H24120.3
C2—C3—C31117.30 (18)C26—C25—C24120.7 (4)
C5—C4—C3116.08 (19)C26—C25—H25119.7
C5—C4—C41123.40 (19)C24—C25—H25119.7
C3—C4—C41120.50 (18)C25—C26—C27119.7 (4)
C6—C5—C4118.73 (19)C25—C26—H26120.2
C6—C5—C9110.2 (2)C27—C26—H26120.2
C4—C5—C9131.1 (2)C26—C27—C22122.0 (3)
N1—C6—C5126.2 (2)C26—C27—H27119.0
N1—C6—C7122.5 (2)C22—C27—H27119.0
C5—C6—C7111.3 (2)N2—C31—C3174.7 (2)
C8—C7—C6103.1 (2)C46—C41—C42117.6 (2)
C8—C7—H7A111.1C46—C41—C4121.51 (19)
C6—C7—H7A111.1C42—C41—C4120.9 (2)
C8—C7—H7B111.1C43—C42—C41121.3 (2)
C6—C7—H7B111.1C43—C42—H42119.4
H7A—C7—H7B109.1C41—C42—H42119.4
C7—C8—C9107.4 (2)C42—C43—C44121.4 (2)
C7—C8—H8A110.2C42—C43—H43119.3
C9—C8—H8A110.2C44—C43—H43119.3
C7—C8—H8B110.2C45—C44—C43117.4 (2)
C9—C8—H8B110.2C45—C44—C47121.1 (3)
H8A—C8—H8B108.5C43—C44—C47121.5 (2)
C5—C9—C8102.8 (2)C44—C45—C46121.6 (2)
C5—C9—H9A111.2C44—C45—H45119.2
C8—C9—H9A111.2C46—C45—H45119.2
C5—C9—H9B111.2C41—C46—C45120.8 (2)
C8—C9—H9B111.2C41—C46—H46119.6
H9A—C9—H9B109.1C45—C46—H46119.6
N3—C21—C22113.74 (19)C44—C47—H47A109.5
N3—C21—H21A108.8C44—C47—H47B109.5
C22—C21—H21A108.8H47A—C47—H47B109.5
N3—C21—H21B108.8C44—C47—H47C109.5
C22—C21—H21B108.8H47A—C47—H47C109.5
H21A—C21—H21B107.7H47B—C47—H47C109.5
C23—C22—C27117.9 (3)C6—N1—C2116.30 (19)
C23—C22—C21121.4 (3)C2—N3—C21125.59 (19)
C27—C22—C21120.7 (2)C2—N3—H3117.2
C22—C23—C24120.3 (3)C21—N3—H3117.2
N1—C2—C3—C41.9 (3)C23—C24—C25—C261.6 (6)
N3—C2—C3—C4178.91 (19)C24—C25—C26—C272.2 (6)
N1—C2—C3—C31174.95 (19)C25—C26—C27—C220.6 (6)
N3—C2—C3—C314.2 (3)C23—C22—C27—C261.6 (4)
C2—C3—C4—C50.8 (3)C21—C22—C27—C26176.9 (3)
C31—C3—C4—C5175.9 (2)C5—C4—C41—C46134.4 (2)
C2—C3—C4—C41179.58 (18)C3—C4—C41—C4646.9 (3)
C31—C3—C4—C412.9 (3)C5—C4—C41—C4247.7 (3)
C3—C4—C5—C60.1 (3)C3—C4—C41—C42131.0 (2)
C41—C4—C5—C6178.90 (19)C46—C41—C42—C431.5 (3)
C3—C4—C5—C9179.6 (2)C4—C41—C42—C43176.5 (2)
C41—C4—C5—C90.9 (4)C41—C42—C43—C441.7 (4)
C4—C5—C6—N10.6 (3)C42—C43—C44—C450.8 (4)
C9—C5—C6—N1179.2 (2)C42—C43—C44—C47179.8 (3)
C4—C5—C6—C7179.6 (2)C43—C44—C45—C460.4 (4)
C9—C5—C6—C70.2 (3)C47—C44—C45—C46178.7 (2)
N1—C6—C7—C8166.9 (2)C42—C41—C46—C450.4 (3)
C5—C6—C7—C814.1 (3)C4—C41—C46—C45177.59 (19)
C6—C7—C8—C922.1 (3)C44—C45—C46—C410.6 (4)
C6—C5—C9—C813.4 (3)C5—C6—N1—C21.6 (3)
C4—C5—C9—C8166.8 (2)C7—C6—N1—C2179.4 (2)
C7—C8—C9—C522.0 (3)N3—C2—N1—C6178.59 (19)
N3—C21—C22—C23134.3 (2)C3—C2—N1—C62.2 (3)
N3—C21—C22—C2747.2 (3)N1—C2—N3—C212.6 (3)
C27—C22—C23—C242.2 (4)C3—C2—N3—C21176.6 (2)
C21—C22—C23—C24176.3 (3)C22—C21—N3—C2101.2 (3)
C22—C23—C24—C250.7 (5)
Hydrogen-bond geometry (Å, º) top
Cg1 is the centroid of the N1/C2–C6 pyridine ring.
D—H···AD—HH···AD···AD—H···A
N3—H3···N2i0.862.252.982 (3)144
C47—H47A···Cg1ii0.962.843.681 (4)147
Symmetry codes: (i) x, y, z; (ii) x, y1/2, z3/2.
Hydrogen-bond geometry (Å, º) top
Cg1 is the centroid of the N1/C2–C6 pyridine ring.
D—H···AD—HH···AD···AD—H···A
N3—H3···N2i0.862.252.982 (3)144
C47—H47A···Cg1ii0.962.843.681 (4)147
Symmetry codes: (i) x, y, z; (ii) x, y1/2, z3/2.

Experimental details

Crystal data
Chemical formulaC23H21N3
Mr339.43
Crystal system, space groupMonoclinic, P21/c
Temperature (K)293
a, b, c (Å)8.6826 (4), 17.7282 (9), 12.0400 (6)
β (°) 94.253 (2)
V3)1848.18 (16)
Z4
Radiation typeMo Kα
µ (mm1)0.07
Crystal size (mm)0.21 × 0.19 × 0.18
Data collection
DiffractometerBruker Kappa APEXII
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2004)
Tmin, Tmax0.967, 0.974
No. of measured, independent and
observed [I > 2σ(I)] reflections
29178, 3452, 2262
Rint0.034
(sin θ/λ)max1)0.606
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.058, 0.192, 1.08
No. of reflections3452
No. of parameters237
No. of restraints1
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.29, 0.21

Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SHELXS2013 (Sheldrick, 2008), SHELXL2014 (Sheldrick, 2015) and PLATON (Spek, 2009).

 

Acknowledgements

JS and RAN thank the management of The Madura College (Autonomous), Madurai, for their encouragement and support. RRK thanks the University Grants Commission, New Delhi, for funds through a Major Research Project F. No. 42–242/2013 (SR).

References

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Volume 71| Part 2| February 2015| Pages 192-194
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