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Journal logoCRYSTALLOGRAPHIC
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ISSN: 2056-9890
Volume 70| Part 11| November 2014| Pages 344-347
doi:10.1107/S1600536814022016

Isotypic crystal structures of 1-benzyl-4-(4-bromo­phen­yl)-2-imino-1,2,5,6,7,8,9,10-octa­hydro­cyclo­octa­[b]pyridine-3-carbo­nitrile and 1-benzyl-4-(4-fluoro­phen­yl)-2-imino-1,2,5,6,7,8,9,10-octa­hydro­cyclo­octa­[b]pyridine-3-carbo­nitrile

R. A. Nagalakshmi,a J. Suresh,a S. Maharani,b R. Ranjith Kumarb and P. L. Nilantha Lakshmanc*

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 W. T. A. Harrison, University of Aberdeen, Scotland (Received 12 September 2014; accepted 6 October 2014; online 18 October 2014)

The mol­ecules of the two isotypic title compounds, C25H24BrN3, (I), and C25H24FN3, (II), comprise a 2-imino­pyridine ring fused with a cyclo­octane ring. In (I), the cyclo­octane ring adopts a twisted chair–chair conformation, while in (II), this ring adopts a twisted boat–chair conformation. The dihedral angles between the planes of the pyridine ring and the bromo­benzene and phenyl rings are 80.14 (12) and 71.72 (13)°, respectively, in (I). The equivalent angles in (II) are 75.25 (8) and 68.34 (9)°, respectively. In both crystals, inversion dimers linked by pairs of C—H⋯N inter­actions generate R22(14) loops, which are further connected by weak C—H⋯π inter­actions, generating (110) sheets.

CCDC references: 1027782; 1027783

1. Chemical context

The pyridine skeleton is of great importance to chemists as well as to biologists as it is found in a large variety of naturally occurring compounds and also in clinically useful mol­ecules having diverse biological activities. Its derivatives are known to possess anti­microbial (Jo et al., 2004[Jo, Y. W., Im, W. B., Rhee, J. K., Shim, M. J., Kim, W. B. & Choi, E. C. (2004). Bioorg. Med. Chem. 12, 5909-5915.]) and anti­viral (Mavel et al., 2002[Mavel, S., Renou, J., Galtier, C., Allouchi, H., Snoeck, R., Andrei, G., De Clercq, E., Balzarini, J. & Gueiffier, A. (2002). Bioorg. Med. Chem. 10, 941-946.]) activities. The heterocyclic 1,4-di­hydro­pyridine ring is a common feature in compounds with various pharmacological activities such as anti­microbial (Hooper et al., 1982[Hooper, D. C., Wolfson, J. S., McHugh, G. L., Winters, M. B. & Swartz, M. N. (1982). Antimicrob. Agents Chemother. 22, 662-671.]) and anti­thrombotic (Sunkel et al., 1990[Sunkel, C. E., de Casa-Juana, M. F., Santos, L., Gómez, M. M., Villarroya, M., González-Morales, M. A., Priego, J. G. & Ortega, M. P. (1990). J. Med. Chem. 33, 3205-3210.]) activities. The chemistry of imines in particular is of special inter­est in the literature due to their numerous practical applications (Echevarria et al., 1999[Echevarria, A., Nascimento, M. G., d, G., Gerônimo, V., Miller, J. & Giesbrecht, A. (1999). J. Braz. Chem. Soc. 10, 60-64.]). Imines have attracted much attention because of their wide variety of applications in the electronics and photonics fields (Wang et al., 2001[Wang, X., Shen, Y., Pan, Y. & Liang, Y. (2001). Langmuir, 17, 3162-3167.]). Imines and their complexes have a variety of applications in the biological, clinical and analytical fields (Singh et al., 1975[Singh, P., Goel, R. L. & Singh, B. P. J. (1975). Indian Chem, 52, 958-959Yoeong.]; Patel et al., 1999[Patel, P. R., Thaker, B. T. & Zele, S. (1999). Indian J. Chem. Sect. A, 38, 563-566.]). Our inter­est in the preparation of pharmacologically active 2-imino pyridines led us to synthesise the title compounds and we have undertaken the X-ray crystal structure determination of these compounds in order to establish their conformations.

2. Structural commentary

The structures of compounds (I)[link] and (II)[link] are shown in Figs. 1[link] and 2, respectively[link]. The cyclo­octane ring adopts a twisted chair–chair conformation in compound (I)[link] and twisted boat–chair conformation (Wiberg, 2003[Wiberg, K. B. (2003). J. Org. Chem. 68, 9322-9329.]) in compound (II)[link].

[Scheme 1]
[Figure 1]
Figure 1
The mol­ecular structure of (I)[link], showing 50% probability displacement ellipsoids.
[Figure 2]
Figure 2
The mol­ecular structure of (II)[link], showing 50% probability displacement ellipsoids.

In both compounds, the imino group is nearly coplanar with the pyridine ring, as indicated by the N1=C1—N3—C5 torsion angle [178.8 (2) for compound (I)[link] and 179.05 (13)° for compound (II)]. Steric hindrances rotate the phenyl (C13–C18) and aromatic (C31–C36) rings out of the plane of the central pyridine ring by 71.72 (13) and 80.14 (12)°, respectively, in compound (I)[link], and by 68.34 (9) and 75.25 (8)°, respectively, in compound (II)[link]. Opening up of the N3—C5—C4 angle [121.54 (19)° for compound (I)[link] and 121.29 (13)° for compound (II)] and considerable shortening of the C5—N3 [1.376 (3) Å for compound (I)[link] and 1.3777 (18) Å for compound (II)] bond distance may directly be attributed to the bulky substituents at the ortho position C5. The endocyclic angles of the pyridine ring cover the range 114.29 (18)–123.02 (2)° and 118.86 (13)–123.11 (12)° for compounds (I)[link] and (II)[link] respectively. The C1—N3—C5 angle [122.93 (2) for compound (I)[link] and 123.11 (12)° for compound (II)] is expanded as in pyridine itself [123.9 (3)°; Jin et al., 2005[Jin, Z.-M., Shun, N., Lü, Y.-P., Hu, M.-L. & Shen, L. (2005). Acta Cryst. C61, m43-m45.]].

3. Supramol­ecular features

In the crystals, pairs of C—H⋯N inter­actions form R22(14) ring motifs (Bernstein et al., 1995[Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555-1573.]), and the resulting dimers are further connected through weak C—H⋯π inter­actions involving the phenyl ring as acceptor (Tables 1[link] and 2[link], Figs. 3[link], 4[link]). In each case, the resulting supra­molecular structure is a layer propagating parallel to the (110) plane.

Table 1
Hydrogen-bond geometry (Å, °) for (I)[link]

Cg1 is the centroid of the C13–C18 phenyl ring.
D—H⋯A D—H H⋯A D⋯A D—H⋯A
C32—H32⋯N1i 0.93 2.56 3.421 (3) 154
C11—H11A⋯Cg1ii 0.97 2.97 3.648 (3) 128
Symmetry codes: (i) -x, -y, -z; (ii) -x+1, -y+1, -z.

Table 2
Hydrogen-bond geometry (Å, °) for (II)[link]

Cg1 is the centroid of the C13–C18 phenyl ring.
D—H⋯A D—H H⋯A D⋯A D—H⋯A
C32—H32⋯N1i 0.93 2.53 3.421 (2) 160
C11—H11A⋯Cg1ii 0.97 2.93 3.484 (2) 118
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) -x, -y+1, -z+1.
[Figure 3]
Figure 3
Partial packing diagram of the title compound (I)[link]. Dashed lines represent inter­molecular hydrogen bonds and C—H⋯π contacts. For clarity, H atoms not involved in hydrogen bonding have been omitted.
[Figure 4]
Figure 4
Partial packing diagram of the title compound (II)[link]. Dashed lines represent inter­molecular hydrogen bonds and C—H⋯π contacts. For clarity, H atoms not involved in hydrogen bonding have been omitted.

4. Database survey

Similar structures reported in the literature are 2-meth­oxy-4-(2-meth­oxy­phen­yl)-5,6,7,8,9,10-hexa­hydro­cyclo­octa­[b]pyr­idine-3-carbo­nitrile (Vishnupriya et al., 2014a[Vishnupriya, R., Suresh, J., Maharani, S., Kumar, R. R. & Lakshman, P. L. N. (2014a). Acta Cryst. E70, o656.]) and 4-(2-fluorophen­yl)-2-meth­oxy-5,6,7,8,9,10-hexa­hydro­cyclo­octa­[b]-pyridine-3-carbo­nitrile (Vishnupriya et al., 2014b[Vishnupriya, R., Suresh, J., Maharani, S., Kumar, R. R. & Lakshman, P. L. N. (2014b). Acta Cryst. E70, o872.]). The twisted conformation of the cyclo­octane ring of compound (I)[link] is similar to those found in the related structures. However, the C=NH functional group present in the title compound allows the formation of C—H⋯N hydrogen bonds, which are not present in the above-cited compounds. In the title compounds, the bond lengths in the central pyridine ring span the range 1.369–1.446 Å, which compare well with the range observed in the similar structures (1.314–1.400 Å), but these bonds are systematically longer in the title compounds, due to the substitution of the pyridine N atom by a benzyl group. The bond length of the nitrile group attached to pyridine ring [N2 ≡C38 = 1.137 (3) Å in compound (I)[link] and 1.1426 (19) Å in compound (II)] and the linearity of the cyano moiety [N2≡C38—C2 = 176.3 (3) for compound (I)[link] and 175.68 (17)° for compound (II)] have characteristic features that are observed in 3-cyano-2-pyridine derivatives (Hursthouse et al., 1992[Hursthouse, M. B., Karaulov, A. I., Ciechanowicz-Rutkowska, M., Kolasa, A. & Zankowska-Jasińska, W. (1992). Acta Cryst. C48, 1257-1260.]; Patel et al., 2002[Patel, U. H., Dave, C. G., Jotani, M. M. & Shah, H. C. (2002). Acta Cryst. C58, o191-o192.]).

5. Synthesis and crystallization

The two compounds were prepared in a similar manner using 4-fluoro aldehyde (1 mmol) for compound (I)[link] and 4-bromo aldehyde (1 mmol) for compound (II)[link]. A mixture of cyclo­octa­none (1mmol), respective aldehyde (1 mmol) and malono­nitrile (1 mmol) were taken in ethanol (10 mL) to which p-toluene­sulfonic acid (pTSA) (0.5 mmol) was added. The reaction mixture was heated under reflux for 2–3 h. After completion of the reaction (TLC), the reaction 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 petroleum ether/ethyl acetate mixture (97:3 v/v) as eluent to afford pure product. The product was recrystallized from ethyl acetate, affording colourless crystals of compounds (I)[link] and (II)[link] [m.p. 493 K; yield 91% for (I)[link] and m.p. 473 K; yield 65% for (II)].

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3[link]. C-bound H atoms were placed in calculated positions and allowed to ride on their carrier atoms, with C—H = 0.93 (aromatic CH) or 0.97 Å (methyl­ene CH2). Imine atom H1 was found in a difference map and refined with a distance restraint in both compounds of N—H = 0.86 (10) Å. Isotropic displacement parameters for H atoms were calculated as Uiso = 1.5Ueq(C) for CH3 groups and Uiso = 1.2Ueq(carrier atom) for all other H atoms. The DELU restraint was applied in compound (II)[link].

Table 3
Experimental details

  (I) (II)
Crystal data
Chemical formula C25H24BrN3 C25H24FN3
Mr 446.38 385.47
Crystal system, space group Triclinic, P[\overline{1}] Triclinic, P[\overline{1}]
Temperature (K) 293 293
a, b, c (Å) 10.2103 (3), 10.7643 (4), 11.6942 (4) 10.1370 (4), 10.2078 (3), 11.8238 (4)
α, β, γ (°) 101.074 (1), 106.726 (1), 115.058 (1) 109.688 (2), 100.309 (2), 111.420 (2)
V (Å3) 1039.46 (6) 1006.73 (6)
Z 2 2
Radiation type Mo Kα Mo Kα
μ (mm−1) 1.99 0.08
Crystal size (mm) 0.21 × 0.19 × 0.18 0.21 × 0.19 × 0.18
 
Data collection
Diffractometer Bruker Kappa APEXII Bruker Kappa APEXII
Absorption correction Multi-scan (SADABS; Bruker, 2004[Bruker (2004). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]) Multi-scan (SADABS; Bruker, 2004[Bruker (2004). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.])
Tmin, Tmax 0.967, 0.974 0.967, 0.974
No. of measured, independent and observed [I > 2σ(I)] reflections 25106, 4532, 3830 23254, 3752, 2876
Rint 0.027 0.022
(sin θ/λ)max (Å−1) 0.639 0.606
 
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.039, 0.107, 1.03 0.039, 0.109, 1.05
No. of reflections 4532 3752
No. of parameters 266 267
No. of restraints 2 2
H-atom treatment H atoms treated by a mixture of independent and constrained refinement H atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å−3) 0.93, −0.87 0.17, −0.14
Computer programs: APEX2 and SAINT (Bruker, 2004[Bruker (2004). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]), SHELXS97, SHELXL97 and SHELXL2014/6 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]) and PLATON (Spek, 2009[Spek, A. L. (2009). Acta Cryst. D65, 148-155.]).

Supporting information

CCDC references: 1027782; 1027783

Crystal structure: contains datablocks global, I, II. DOI: 10.1107/S1600536814022016/hb7284sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814022016/hb7284Isup2.hkl

Structure factors: contains datablock II. DOI: 10.1107/S1600536814022016/hb7284IIsup3.hkl

Supporting information file. DOI: 10.1107/S1600536814022016/hb7284Isup4.cml

Supporting information file. DOI: 10.1107/S1600536814022016/hb7284IIsup5.cml

checkCIF report


Chemical context top

The pyridine skeleton is of great importance to chemists as well as to biologists as it is found in a large variety of naturally occurring compounds and also in clinically useful molecules having diverse biological activities. Its derivatives are known to possess anti­microbial (Jo et al., 2004) and anti­viral (Mavel et al., 2002) activities. The heterocyclic 1,4-di­hydro­pyridine ring is a common feature in compounds with various pharmacological activities such as anti­microbial (Hooper et al., 1982) and anti­thrombotic (Sunkel et al., 1990) activities. The chemistry of imines in particular are of special inter­est in the literature due to their numerous practical applications (Echevarria et al., 1999). Imines have attracted much attention because of their wide variety of applications in the electronics and photonics fields (Wang et al., 2001). Imines and their complexes have a variety of applications in the biological, clinical and analytical fields (Singh et al., 1975; Patel et al., 1999). Our inter­est in the preparation of pharmacologically active 2-imino pyridines led us to the title compounds and we have undertaken the X-ray crystal structure determination of these compounds in order to establish their conformations.

Structural commentary top

The structures of compounds (I) and (II) are shown in Figs. 1 and 2. The cyclo­octane ring adopts a twisted chair–chair conformation in compound (I) and twisted boat–chair conformation (Wiberg, 2003) in compound (II). In both compounds, the imino group is nearly coplanar with the pyridine ring, as indicated by the N1═C1—N3—C5 torsion angle [178.8 (2) for compound (I) and 179.05 (13)° for compound (II)]. Steric hindrances rotate the phenyl (C13–C18) and aromatic (C31–C36) rings out of the plane of the central pyridine ring by 71.72 (13) and 80.14 (12)°, respectively, in compound (I), and by 68.34 (9) and 75.25 (8)°, respectively, in compound (II). Opening up of the N3—C5—C4 angle [121.54 (19)° for compound (I) and 121.29 (13)° for compound (II)] and considerable shortening of the C5—N3 [1.376 (3) Å for compound (I) and 1.3777 (18) Å for compound (II)] bond distance may directly be attributed to the bulky substituents at the ortho position C5. The endocyclic angles of the pyridine ring cover the range 114.29 (18)–123.02 (2) 116.53 (5)–124.09° and 118.86 (13)–123.11 (12)° for compounds (I) and (II) respectively. The C1—N3—C5 angle [122.93 (2) for compound (I) and 123.11 (12)° for compound (II)] is expanded in comparison with the parent pyridine [123.9 (3)°; Jin, Shun et al., 2005].

Supra­molecular features top

In the crystals, pairs of C—H···N inter­actions form R22(14) ring motifs (Bernstein et al., 1995), and the resulting dimers are further connected through weak C—H···π inter­actions involving the phenyl ring as acceptor (Tables 1 and 2, Figs. 3,4). In each case, the resulting supra­molecular structure is a layer propagating parallel to the (110) plane.

Database survey top

Similar structures reported in the literature are 2-meth­oxy- 4-(2-meth­oxy­phenyl) -5,6,7,8,9,10-hexa­hydro­cyclo­octa­[b]pyridine-3-carbo­nitrile (Vishnupriya et al., 2014a) and 4-(2-fluoro­phenyl)-2-meth­oxy-5,6,7,8,9,10-hexa­hydro­cyclo­octa­[b]- pyridine-3-carbo­nitrile (Vishnupriya et al., 2014b). In the structure reported here, the twisted conformation of the cyclo­octane ring of compound (I) are similar to those found in the related structures. However, the C═ NH functional group present in the title compound allows the formation of C—H···N hydrogen bonds, which are not present in the above-cited compounds. In the title compounds, the bond lengths in the central pyridine ring span the range 1.369 – 1.446 Å , which compare well with the range observed in the similar structures (1.314 – 1.400 Å ), but these bonds are systematically longer in the title compounds, due to the substitution of the pyridine N atom by a benzyl group. The bond length of the nitrile group attached to pyridine ring (N2 ≡C38 = 1.137 (3) Å in compound (I) and 1.1426 (19) Å in compound (II))and linearity of the cyano moiety (N2≡C38—C2 = 176.3 (3) ° for compound (I) and 175.68 (17) ° for compound (II)) have characteristic features that are observed in 3-cyano-2- pyridine derivatives (Hursthouse, et al. 1992, Patel et al., 2002).

Synthesis and crystallization top

The two compounds were prepared in a similar manner using 4-fluoro aldehyde (1 mmol) for compound (I) and 4-bromo aldehyde (1 mmol) for compound (II). A mixture of cyclo­octa­none (1mmol), respective aldehyde (1 mmol) and malono­nitrile (1 mmol) were taken in ethanol (10 mL) to which p-toluene­sulfonic acid (pTSA) (0.5 mmol) was added. The reaction mixture was heated under reflux for 2–3 h. After completion of the reaction (TLC), the reaction 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 petroleum ether/ ethyl acetate mixture (97:3 v/v) as eluent to afford pure product. The product was recrystallized from ethyl acetate, affording colourless crystals of compounds (I) and (II) [m.p. 493 K; yield 91% for compound (I) and m.p. 473 K; yield 65% for compound (II)].

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 3. C-bound H atoms were placed in calculated positions and allowed to ride on their carrier atoms, with C—H = 0.93 (aromatic CH) or 0.97 Å (methyl­ene CH2). Imine atom H1 was found in a difference map and refined with a distance restraint in the both compounds of N—H = 0.86 (10) Å. Isotropic displacement parameters for H atoms were calculated as Uiso = 1.5Ueq(C) for CH3 groups and Uiso = 1.2Ueq(carrier atom) for all other H atoms. The DELU restraint was applied in compound (II).

Related literature top

For related literature, see: Wang et al. (2001); Bernstein et al. (1995); Echevarria et al. (1999); Hooper et al. (1982); Hursthouse et al. (1992); Jin et al. (2005); Patel et al. (1999, 2002); Singh et al. (1975); Sunkel (1990); Mavel et al. (2002); Vishnupriya et al. (2014a, 2014b); Wiberg (2003); Jo et al. (2004).

Structure description top

The pyridine skeleton is of great importance to chemists as well as to biologists as it is found in a large variety of naturally occurring compounds and also in clinically useful molecules having diverse biological activities. Its derivatives are known to possess anti­microbial (Jo et al., 2004) and anti­viral (Mavel et al., 2002) activities. The heterocyclic 1,4-di­hydro­pyridine ring is a common feature in compounds with various pharmacological activities such as anti­microbial (Hooper et al., 1982) and anti­thrombotic (Sunkel et al., 1990) activities. The chemistry of imines in particular are of special inter­est in the literature due to their numerous practical applications (Echevarria et al., 1999). Imines have attracted much attention because of their wide variety of applications in the electronics and photonics fields (Wang et al., 2001). Imines and their complexes have a variety of applications in the biological, clinical and analytical fields (Singh et al., 1975; Patel et al., 1999). Our inter­est in the preparation of pharmacologically active 2-imino pyridines led us to the title compounds and we have undertaken the X-ray crystal structure determination of these compounds in order to establish their conformations.

The structures of compounds (I) and (II) are shown in Figs. 1 and 2. The cyclo­octane ring adopts a twisted chair–chair conformation in compound (I) and twisted boat–chair conformation (Wiberg, 2003) in compound (II). In both compounds, the imino group is nearly coplanar with the pyridine ring, as indicated by the N1═C1—N3—C5 torsion angle [178.8 (2) for compound (I) and 179.05 (13)° for compound (II)]. Steric hindrances rotate the phenyl (C13–C18) and aromatic (C31–C36) rings out of the plane of the central pyridine ring by 71.72 (13) and 80.14 (12)°, respectively, in compound (I), and by 68.34 (9) and 75.25 (8)°, respectively, in compound (II). Opening up of the N3—C5—C4 angle [121.54 (19)° for compound (I) and 121.29 (13)° for compound (II)] and considerable shortening of the C5—N3 [1.376 (3) Å for compound (I) and 1.3777 (18) Å for compound (II)] bond distance may directly be attributed to the bulky substituents at the ortho position C5. The endocyclic angles of the pyridine ring cover the range 114.29 (18)–123.02 (2) 116.53 (5)–124.09° and 118.86 (13)–123.11 (12)° for compounds (I) and (II) respectively. The C1—N3—C5 angle [122.93 (2) for compound (I) and 123.11 (12)° for compound (II)] is expanded in comparison with the parent pyridine [123.9 (3)°; Jin, Shun et al., 2005].

In the crystals, pairs of C—H···N inter­actions form R22(14) ring motifs (Bernstein et al., 1995), and the resulting dimers are further connected through weak C—H···π inter­actions involving the phenyl ring as acceptor (Tables 1 and 2, Figs. 3,4). In each case, the resulting supra­molecular structure is a layer propagating parallel to the (110) plane.

Similar structures reported in the literature are 2-meth­oxy- 4-(2-meth­oxy­phenyl) -5,6,7,8,9,10-hexa­hydro­cyclo­octa­[b]pyridine-3-carbo­nitrile (Vishnupriya et al., 2014a) and 4-(2-fluoro­phenyl)-2-meth­oxy-5,6,7,8,9,10-hexa­hydro­cyclo­octa­[b]- pyridine-3-carbo­nitrile (Vishnupriya et al., 2014b). In the structure reported here, the twisted conformation of the cyclo­octane ring of compound (I) are similar to those found in the related structures. However, the C═ NH functional group present in the title compound allows the formation of C—H···N hydrogen bonds, which are not present in the above-cited compounds. In the title compounds, the bond lengths in the central pyridine ring span the range 1.369 – 1.446 Å , which compare well with the range observed in the similar structures (1.314 – 1.400 Å ), but these bonds are systematically longer in the title compounds, due to the substitution of the pyridine N atom by a benzyl group. The bond length of the nitrile group attached to pyridine ring (N2 ≡C38 = 1.137 (3) Å in compound (I) and 1.1426 (19) Å in compound (II))and linearity of the cyano moiety (N2≡C38—C2 = 176.3 (3) ° for compound (I) and 175.68 (17) ° for compound (II)) have characteristic features that are observed in 3-cyano-2- pyridine derivatives (Hursthouse, et al. 1992, Patel et al., 2002).

For related literature, see: Wang et al. (2001); Bernstein et al. (1995); Echevarria et al. (1999); Hooper et al. (1982); Hursthouse et al. (1992); Jin et al. (2005); Patel et al. (1999, 2002); Singh et al. (1975); Sunkel (1990); Mavel et al. (2002); Vishnupriya et al. (2014a, 2014b); Wiberg (2003); Jo et al. (2004).

Synthesis and crystallization top

The two compounds were prepared in a similar manner using 4-fluoro aldehyde (1 mmol) for compound (I) and 4-bromo aldehyde (1 mmol) for compound (II). A mixture of cyclo­octa­none (1mmol), respective aldehyde (1 mmol) and malono­nitrile (1 mmol) were taken in ethanol (10 mL) to which p-toluene­sulfonic acid (pTSA) (0.5 mmol) was added. The reaction mixture was heated under reflux for 2–3 h. After completion of the reaction (TLC), the reaction 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 petroleum ether/ ethyl acetate mixture (97:3 v/v) as eluent to afford pure product. The product was recrystallized from ethyl acetate, affording colourless crystals of compounds (I) and (II) [m.p. 493 K; yield 91% for compound (I) and m.p. 473 K; yield 65% for compound (II)].

Refinement details top

Crystal data, data collection and structure refinement details are summarized in Table 3. C-bound H atoms were placed in calculated positions and allowed to ride on their carrier atoms, with C—H = 0.93 (aromatic CH) or 0.97 Å (methyl­ene CH2). Imine atom H1 was found in a difference map and refined with a distance restraint in the both compounds of N—H = 0.86 (10) Å. Isotropic displacement parameters for H atoms were calculated as Uiso = 1.5Ueq(C) for CH3 groups and Uiso = 1.2Ueq(carrier atom) for all other H atoms. The DELU restraint was applied in compound (II).

Computing details top

For both compounds, data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004). Program(s) used to solve structure: SHELXL97 (Sheldrick, 2008) for (I); SHELXS97 (Sheldrick, 2008) for (II). For both compounds, program(s) used to refine structure: SHELXL2014/6 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL2014/6 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), showing 50% probability displacement ellipsoids.
[Figure 2] Fig. 2. The molecular structure of (II), showing 50% probability displacement ellipsoids.
[Figure 3] Fig. 3. Partial packing diagram of the title compound (I). Dashed lines represent intermolecular hydrogen bonds and C—H···π contacts. For clarity, H atoms not involved in hydrogen bonding have been omitted.
[Figure 4] Fig. 4. Partial packing diagram of the title compound (II). Dashed lines represent intermolecular hydrogen bonds and C—H···π contacts. For clarity, H atoms not involved in hydrogen bonding have been omitted.
(I) 1-Benzyl-4-(4-bromophenyl)-2-imino-1,2,5,6,7,8,9,10-octahydrocycloocta[b]pyridine-3-carbonitrile top
Crystal data top
C25H24BrN3Z = 2
Mr = 446.38F(000) = 460
Triclinic, P1Dx = 1.426 Mg m−3
a = 10.2103 (3) ÅMo Kα radiation, λ = 0.71073 Å
b = 10.7643 (4) ÅCell parameters from 2000 reflections
c = 11.6942 (4) Åθ = 3–21°
α = 101.074 (1)°µ = 1.99 mm−1
β = 106.726 (1)°T = 293 K
γ = 115.058 (1)°Block, colourless
V = 1039.46 (6) Å30.21 × 0.19 × 0.18 mm
Data collection top
Bruker Kappa APEXII
diffractometer		3830 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.027
φ and ω scansθmax = 27.0°, θmin = 2.2°
Absorption correction: multi-scan
(SADABS; Bruker, 2004)		h = −13→13
Tmin = 0.967, Tmax = 0.974k = −13→13
25106 measured reflectionsl = −14→14
4532 independent reflections
Refinement top
Refinement on F22 restraints
Least-squares matrix: fullHydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.039H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.107 w = 1/[σ2(Fo2) + (0.0495P)2 + 0.8341P]
where P = (Fo2 + 2Fc2)/3
S = 1.03(Δ/σ)max < 0.001
4532 reflectionsΔρmax = 0.93 e Å−3
266 parametersΔρmin = −0.87 e Å−3
Crystal data top
C25H24BrN3γ = 115.058 (1)°
Mr = 446.38V = 1039.46 (6) Å3
Triclinic, P1Z = 2
a = 10.2103 (3) ÅMo Kα radiation
b = 10.7643 (4) ŵ = 1.99 mm−1
c = 11.6942 (4) ÅT = 293 K
α = 101.074 (1)°0.21 × 0.19 × 0.18 mm
β = 106.726 (1)°
Data collection top
Bruker Kappa APEXII
diffractometer		4532 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2004)		3830 reflections with I > 2σ(I)
Tmin = 0.967, Tmax = 0.974Rint = 0.027
25106 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0392 restraints
wR(F2) = 0.107H atoms treated by a mixture of independent and constrained refinement
S = 1.03Δρmax = 0.93 e Å−3
4532 reflectionsΔρmin = −0.87 e Å−3
266 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
C10.0878 (3)0.0974 (2)−0.1085 (2)0.0341 (4)
C20.0659 (2)0.1930 (2)−0.0207 (2)0.0339 (4)
C30.1891 (3)0.3193 (2)0.0767 (2)0.0343 (4)
C40.3478 (3)0.3602 (2)0.0957 (2)0.0361 (5)
C50.3719 (3)0.2714 (2)0.0138 (2)0.0335 (4)
C60.5365 (3)0.3076 (3)0.0277 (2)0.0433 (5)
H6A0.60460.41370.06020.052*
H6B0.53210.2693−0.05630.052*
C70.6116 (3)0.2460 (4)0.1167 (3)0.0571 (7)
H7A0.53280.14450.09590.069*
H7B0.69830.24560.09840.069*
C80.6748 (4)0.3263 (4)0.2585 (3)0.0647 (8)
H8A0.73580.28860.30380.078*
H8B0.74750.42940.27830.078*
C90.5525 (4)0.3159 (4)0.3098 (3)0.0631 (7)
H9A0.58350.30320.39130.076*
H9B0.45170.22820.25140.076*
C100.5269 (3)0.4473 (4)0.3292 (3)0.0582 (7)
H10A0.44250.42580.35820.070*
H10B0.62300.53190.39720.070*
C110.4847 (3)0.4898 (3)0.2120 (2)0.0457 (6)
H11A0.45720.56480.23170.055*
H11B0.57700.53140.19290.055*
C120.2749 (3)0.0440 (3)−0.1662 (2)0.0404 (5)
H12A0.1839−0.0548−0.19940.048*
H12B0.36680.0427−0.11360.048*
C130.3020 (3)0.0841 (2)−0.2770 (2)0.0391 (5)
C140.4290 (3)0.0892 (3)−0.3004 (3)0.0565 (7)
H140.49990.0716−0.24570.068*
C150.4510 (4)0.1206 (4)−0.4053 (3)0.0710 (10)
H150.53690.1244−0.42050.085*
C160.3473 (4)0.1460 (4)−0.4863 (3)0.0700 (9)
H160.36170.1658−0.55710.084*
C170.2225 (4)0.1422 (3)−0.4632 (3)0.0583 (7)
H170.15220.1601−0.51810.070*
C180.1998 (3)0.1120 (3)−0.3591 (2)0.0444 (5)
H180.11470.1105−0.34400.053*
C310.1563 (3)0.4135 (2)0.1609 (2)0.0357 (5)
C320.1211 (3)0.3808 (3)0.2607 (2)0.0450 (5)
H320.11410.29620.27400.054*
C330.0962 (3)0.4725 (3)0.3411 (2)0.0468 (6)
H330.07390.45060.40890.056*
C340.1048 (3)0.5954 (2)0.3197 (2)0.0393 (5)
C350.1356 (3)0.6289 (3)0.2198 (3)0.0485 (6)
H350.13890.71190.20530.058*
C360.1620 (3)0.5377 (3)0.1406 (2)0.0463 (6)
H360.18380.56010.07280.056*
C38−0.0952 (3)0.1466 (3)−0.0413 (2)0.0385 (5)
N1−0.0211 (3)−0.0218 (2)−0.2039 (2)0.0465 (5)
N2−0.2259 (3)0.1036 (3)−0.0637 (2)0.0552 (6)
N30.2469 (2)0.14417 (19)−0.08436 (17)0.0335 (4)
Br10.07794 (4)0.72595 (3)0.43133 (3)0.06264 (13)
H1−0.1109 (16)−0.035 (3)−0.205 (3)0.056 (9)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0355 (11)0.0344 (10)0.0315 (10)0.0164 (9)0.0131 (9)0.0148 (9)
C20.0328 (10)0.0360 (11)0.0326 (10)0.0164 (9)0.0132 (9)0.0150 (9)
C30.0369 (11)0.0338 (10)0.0338 (11)0.0182 (9)0.0158 (9)0.0134 (9)
C40.0321 (11)0.0341 (11)0.0351 (11)0.0137 (9)0.0123 (9)0.0092 (9)
C50.0337 (10)0.0360 (11)0.0313 (10)0.0170 (9)0.0136 (9)0.0147 (9)
C60.0362 (12)0.0488 (13)0.0427 (12)0.0200 (10)0.0193 (10)0.0118 (10)
C70.0480 (15)0.0759 (19)0.0521 (15)0.0418 (15)0.0150 (12)0.0165 (14)
C80.0502 (16)0.083 (2)0.0582 (18)0.0363 (16)0.0152 (14)0.0260 (16)
C90.0573 (17)0.0820 (19)0.0501 (16)0.0335 (16)0.0207 (13)0.0317 (15)
C100.0444 (14)0.0706 (17)0.0350 (13)0.0202 (13)0.0104 (11)0.0020 (12)
C110.0350 (12)0.0391 (12)0.0448 (13)0.0130 (10)0.0120 (10)0.0008 (10)
C120.0451 (12)0.0382 (12)0.0383 (12)0.0252 (10)0.0148 (10)0.0092 (9)
C130.0386 (12)0.0360 (11)0.0335 (11)0.0168 (10)0.0132 (9)0.0022 (9)
C140.0437 (14)0.0648 (17)0.0473 (15)0.0264 (13)0.0162 (12)−0.0001 (13)
C150.0487 (16)0.077 (2)0.0569 (18)0.0142 (15)0.0312 (15)−0.0062 (15)
C160.0627 (19)0.072 (2)0.0415 (15)0.0080 (16)0.0276 (14)0.0068 (14)
C170.0597 (17)0.0588 (17)0.0408 (14)0.0189 (14)0.0188 (13)0.0175 (12)
C180.0421 (12)0.0481 (13)0.0387 (12)0.0202 (11)0.0176 (10)0.0124 (10)
C310.0320 (10)0.0362 (11)0.0357 (11)0.0165 (9)0.0131 (9)0.0103 (9)
C320.0579 (15)0.0379 (12)0.0519 (14)0.0270 (11)0.0314 (12)0.0218 (11)
C330.0585 (15)0.0462 (13)0.0466 (13)0.0277 (12)0.0317 (12)0.0204 (11)
C340.0354 (11)0.0359 (11)0.0423 (12)0.0184 (10)0.0147 (10)0.0071 (9)
C350.0604 (15)0.0455 (13)0.0546 (15)0.0347 (12)0.0264 (13)0.0253 (12)
C360.0595 (15)0.0517 (14)0.0451 (13)0.0348 (13)0.0281 (12)0.0263 (11)
C380.0378 (12)0.0416 (12)0.0357 (11)0.0194 (10)0.0147 (9)0.0161 (10)
N10.0399 (11)0.0401 (11)0.0406 (11)0.0132 (9)0.0104 (9)0.0041 (9)
N20.0392 (12)0.0662 (15)0.0572 (14)0.0244 (11)0.0198 (10)0.0227 (12)
N30.0369 (9)0.0332 (9)0.0295 (9)0.0181 (8)0.0131 (7)0.0105 (7)
Br10.0776 (2)0.05343 (18)0.0665 (2)0.04027 (16)0.03763 (17)0.01234 (14)
Geometric parameters (Å, º) top
C1—N11.286 (3)C12—N31.477 (3)
C1—N31.401 (3)C12—C131.504 (3)
C1—C21.444 (3)C12—H12A0.9700
C2—C31.364 (3)C12—H12B0.9700
C2—C381.430 (3)C13—C181.379 (4)
C3—C41.421 (3)C13—C141.382 (3)
C3—C311.485 (3)C14—C151.387 (5)
C4—C51.370 (3)C14—H140.9300
C4—C111.509 (3)C15—C161.363 (5)
C5—N31.376 (3)C15—H150.9300
C5—C61.505 (3)C16—C171.363 (5)
C6—C71.532 (4)C16—H160.9300
C6—H6A0.9700C17—C181.374 (4)
C6—H6B0.9700C17—H170.9300
C7—C81.508 (4)C18—H180.9300
C7—H7A0.9700C31—C321.380 (3)
C7—H7B0.9700C31—C361.383 (3)
C8—C91.507 (4)C32—C331.385 (3)
C8—H8A0.9700C32—H320.9300
C8—H8B0.9700C33—C341.365 (3)
C9—C101.531 (5)C33—H330.9300
C9—H9A0.9700C34—C351.368 (4)
C9—H9B0.9700C34—Br11.892 (2)
C10—C111.529 (4)C35—C361.382 (4)
C10—H10A0.9700C35—H350.9300
C10—H10B0.9700C36—H360.9300
C11—H11A0.9700C38—N21.137 (3)
C11—H11B0.9700N1—H10.8600 (10)
N1—C1—N3118.5 (2)C10—C11—H11B109.1
N1—C1—C2127.2 (2)H11A—C11—H11B107.9
N3—C1—C2114.29 (18)N3—C12—C13114.51 (18)
C3—C2—C38121.2 (2)N3—C12—H12A108.6
C3—C2—C1123.2 (2)C13—C12—H12A108.6
C38—C2—C1115.60 (19)N3—C12—H12B108.6
C2—C3—C4119.6 (2)C13—C12—H12B108.6
C2—C3—C31119.77 (19)H12A—C12—H12B107.6
C4—C3—C31120.68 (19)C18—C13—C14118.6 (2)
C5—C4—C3118.5 (2)C18—C13—C12121.5 (2)
C5—C4—C11121.4 (2)C14—C13—C12119.9 (2)
C3—C4—C11119.8 (2)C13—C14—C15120.1 (3)
C4—C5—N3121.54 (19)C13—C14—H14120.0
C4—C5—C6121.5 (2)C15—C14—H14120.0
N3—C5—C6116.91 (19)C16—C15—C14120.3 (3)
C5—C6—C7114.3 (2)C16—C15—H15119.8
C5—C6—H6A108.7C14—C15—H15119.8
C7—C6—H6A108.7C17—C16—C15119.8 (3)
C5—C6—H6B108.7C17—C16—H16120.1
C7—C6—H6B108.7C15—C16—H16120.1
H6A—C6—H6B107.6C16—C17—C18120.4 (3)
C8—C7—C6116.4 (2)C16—C17—H17119.8
C8—C7—H7A108.2C18—C17—H17119.8
C6—C7—H7A108.2C17—C18—C13120.7 (3)
C8—C7—H7B108.2C17—C18—H18119.6
C6—C7—H7B108.2C13—C18—H18119.6
H7A—C7—H7B107.3C32—C31—C36118.7 (2)
C9—C8—C7116.1 (3)C32—C31—C3121.5 (2)
C9—C8—H8A108.3C36—C31—C3119.8 (2)
C7—C8—H8A108.3C31—C32—C33120.8 (2)
C9—C8—H8B108.3C31—C32—H32119.6
C7—C8—H8B108.3C33—C32—H32119.6
H8A—C8—H8B107.4C34—C33—C32119.1 (2)
C8—C9—C10115.9 (3)C34—C33—H33120.5
C8—C9—H9A108.3C32—C33—H33120.5
C10—C9—H9A108.3C33—C34—C35121.4 (2)
C8—C9—H9B108.3C33—C34—Br1120.00 (18)
C10—C9—H9B108.3C35—C34—Br1118.56 (18)
H9A—C9—H9B107.4C34—C35—C36119.2 (2)
C11—C10—C9116.2 (2)C34—C35—H35120.4
C11—C10—H10A108.2C36—C35—H35120.4
C9—C10—H10A108.2C35—C36—C31120.7 (2)
C11—C10—H10B108.2C35—C36—H36119.6
C9—C10—H10B108.2C31—C36—H36119.6
H10A—C10—H10B107.4N2—C38—C2176.3 (3)
C4—C11—C10112.3 (2)C1—N1—H1107.0 (19)
C4—C11—H11A109.1C5—N3—C1122.93 (18)
C10—C11—H11A109.1C5—N3—C12120.97 (18)
C4—C11—H11B109.1C1—N3—C12116.00 (18)
N1—C1—C2—C3−178.7 (2)C14—C15—C16—C170.8 (5)
N3—C1—C2—C30.8 (3)C15—C16—C17—C18−0.4 (5)
N1—C1—C2—C381.7 (3)C16—C17—C18—C13−0.5 (4)
N3—C1—C2—C38−178.73 (18)C14—C13—C18—C171.0 (4)
C38—C2—C3—C4178.7 (2)C12—C13—C18—C17−177.1 (2)
C1—C2—C3—C4−0.8 (3)C2—C3—C31—C3280.6 (3)
C38—C2—C3—C31−2.0 (3)C4—C3—C31—C32−100.0 (3)
C1—C2—C3—C31178.55 (19)C2—C3—C31—C36−99.9 (3)
C2—C3—C4—C50.8 (3)C4—C3—C31—C3679.4 (3)
C31—C3—C4—C5−178.6 (2)C36—C31—C32—C33−1.7 (4)
C2—C3—C4—C11−172.9 (2)C3—C31—C32—C33177.7 (2)
C31—C3—C4—C117.7 (3)C31—C32—C33—C340.9 (4)
C3—C4—C5—N3−0.7 (3)C32—C33—C34—C350.7 (4)
C11—C4—C5—N3172.8 (2)C32—C33—C34—Br1−178.0 (2)
C3—C4—C5—C6179.9 (2)C33—C34—C35—C36−1.4 (4)
C11—C4—C5—C6−6.5 (3)Br1—C34—C35—C36177.4 (2)
C4—C5—C6—C788.6 (3)C34—C35—C36—C310.5 (4)
N3—C5—C6—C7−90.8 (3)C32—C31—C36—C351.1 (4)
C5—C6—C7—C8−76.6 (3)C3—C31—C36—C35−178.4 (2)
C6—C7—C8—C968.4 (4)C4—C5—N3—C10.8 (3)
C7—C8—C9—C10−98.9 (3)C6—C5—N3—C1−179.84 (19)
C8—C9—C10—C1155.3 (3)C4—C5—N3—C12−175.6 (2)
C5—C4—C11—C10−88.0 (3)C6—C5—N3—C123.8 (3)
C3—C4—C11—C1085.5 (3)N1—C1—N3—C5178.8 (2)
C9—C10—C11—C451.2 (3)C2—C1—N3—C5−0.7 (3)
N3—C12—C13—C18−50.3 (3)N1—C1—N3—C12−4.7 (3)
N3—C12—C13—C14131.6 (2)C2—C1—N3—C12175.76 (18)
C18—C13—C14—C15−0.6 (4)C13—C12—N3—C5−85.2 (2)
C12—C13—C14—C15177.5 (3)C13—C12—N3—C198.2 (2)
C13—C14—C15—C16−0.3 (5)
Hydrogen-bond geometry (Å, º) top
Cg1 is the centroid of the C13–C18 phenyl ring.
D—H···AD—HH···AD···AD—H···A
C32—H32···N1i0.932.563.421 (3)154
C11—H11A···Cg1ii0.972.973.648 (3)128
Symmetry codes: (i) −x, −y, −z; (ii) −x+1, −y+1, −z.
(II) 1-Benzyl-4-(4-fluorophenyl)-2-imino-1,2,5,6,7,8,9,10-octahydrocycloocta[b]pyridine-3-carbonitrile top
Crystal data top
C25H24FN3Z = 2
Mr = 385.47F(000) = 408
Triclinic, P1Dx = 1.272 Mg m−3
a = 10.1370 (4) ÅMo Kα radiation, λ = 0.71073 Å
b = 10.2078 (3) ÅCell parameters from 2000 reflections
c = 11.8238 (4) Åθ = 2–31°
α = 109.688 (2)°µ = 0.08 mm−1
β = 100.309 (2)°T = 293 K
γ = 111.420 (2)°Block, colourless
V = 1006.73 (6) Å30.21 × 0.19 × 0.18 mm
Data collection top
Bruker Kappa APEXII
diffractometer		2876 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.022
φ and ω scansθmax = 25.5°, θmin = 2.3°
Absorption correction: multi-scan
(SADABS; Bruker, 2004)		h = −12→12
Tmin = 0.967, Tmax = 0.974k = −12→12
23254 measured reflectionsl = −14→14
3752 independent reflections
Refinement top
Refinement on F2Hydrogen site location: mixed
Least-squares matrix: fullH atoms treated by a mixture of independent and constrained refinement
R[F2 > 2σ(F2)] = 0.039 w = 1/[σ2(Fo2) + (0.0436P)2 + 0.3339P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.109(Δ/σ)max < 0.001
S = 1.05Δρmax = 0.17 e Å−3
3752 reflectionsΔρmin = −0.14 e Å−3
267 parametersExtinction correction: SHELXL2014/6 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
2 restraintsExtinction coefficient: 0.027 (3)
Crystal data top
C25H24FN3γ = 111.420 (2)°
Mr = 385.47V = 1006.73 (6) Å3
Triclinic, P1Z = 2
a = 10.1370 (4) ÅMo Kα radiation
b = 10.2078 (3) ŵ = 0.08 mm−1
c = 11.8238 (4) ÅT = 293 K
α = 109.688 (2)°0.21 × 0.19 × 0.18 mm
β = 100.309 (2)°
Data collection top
Bruker Kappa APEXII
diffractometer		3752 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2004)		2876 reflections with I > 2σ(I)
Tmin = 0.967, Tmax = 0.974Rint = 0.022
23254 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0392 restraints
wR(F2) = 0.109H atoms treated by a mixture of independent and constrained refinement
S = 1.05Δρmax = 0.17 e Å−3
3752 reflectionsΔρmin = −0.14 e Å−3
267 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
C10.38640 (16)0.41969 (17)0.59999 (13)0.0347 (3)
C20.28977 (16)0.44165 (16)0.50992 (13)0.0343 (3)
C30.16525 (16)0.32042 (16)0.40896 (13)0.0341 (3)
C40.12688 (16)0.16454 (17)0.39051 (13)0.0366 (3)
C50.21646 (16)0.13987 (16)0.47452 (13)0.0345 (3)
C60.18252 (19)−0.02211 (18)0.46013 (15)0.0442 (4)
H6A0.0738−0.08600.42680.053*
H6B0.2196−0.01590.54420.053*
C70.2506 (2)−0.1046 (2)0.37256 (17)0.0562 (5)
H7A0.3563−0.03230.39750.067*
H7B0.2469−0.19270.38870.067*
C80.1783 (2)−0.1646 (2)0.22930 (17)0.0583 (5)
H8A0.2219−0.22770.18570.070*
H8B0.0716−0.23280.20460.070*
C90.1946 (2)−0.0406 (2)0.18178 (17)0.0570 (5)
H9A0.28130.05700.24410.068*
H9B0.2155−0.07170.10260.068*
C100.0585 (2)−0.0109 (2)0.15827 (15)0.0564 (5)
H10A−0.0238−0.10360.08640.068*
H10B0.08300.07430.13370.068*
C110.00304 (18)0.02948 (18)0.27088 (15)0.0475 (4)
H11A−0.07770.05570.24880.057*
H11B−0.0377−0.06160.28720.057*
C120.44774 (17)0.23479 (19)0.65601 (14)0.0411 (4)
H12A0.54780.32190.68760.049*
H12B0.45170.14140.60270.049*
C130.41019 (17)0.21501 (18)0.76831 (14)0.0409 (4)
C140.4226 (2)0.0975 (2)0.79530 (17)0.0578 (5)
H140.44690.02740.74060.069*
C150.3991 (2)0.0836 (3)0.9035 (2)0.0756 (7)
H150.40710.00400.92080.091*
C160.3641 (3)0.1865 (3)0.98465 (19)0.0782 (7)
H160.35000.17801.05800.094*
C170.3499 (2)0.3013 (2)0.95823 (17)0.0694 (6)
H170.32510.37061.01330.083*
C180.3719 (2)0.31600 (19)0.85034 (16)0.0521 (4)
H180.36090.39440.83280.063*
C310.07281 (16)0.35321 (17)0.31963 (13)0.0371 (3)
C320.12480 (18)0.39428 (18)0.22997 (15)0.0435 (4)
H320.21860.40330.22700.052*
C330.0391 (2)0.4221 (2)0.14484 (16)0.0491 (4)
H330.07340.44840.08390.059*
C34−0.09671 (19)0.4101 (2)0.15238 (16)0.0494 (4)
C35−0.1521 (2)0.3707 (2)0.23943 (18)0.0586 (5)
H35−0.24540.36370.24240.070*
C36−0.06628 (19)0.3413 (2)0.32320 (17)0.0526 (4)
H36−0.10270.31330.38270.063*
C380.33469 (17)0.60054 (18)0.53208 (14)0.0395 (3)
N10.50412 (15)0.52710 (17)0.69710 (13)0.0485 (4)
N20.37721 (18)0.73047 (17)0.55698 (14)0.0572 (4)
N30.34211 (13)0.26298 (14)0.57514 (11)0.0346 (3)
F1−0.18123 (13)0.43791 (15)0.06937 (11)0.0758 (4)
H10.520 (2)0.6177 (14)0.7008 (19)0.065 (6)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0340 (7)0.0397 (8)0.0314 (7)0.0162 (6)0.0147 (6)0.0157 (6)
C20.0359 (7)0.0374 (7)0.0328 (7)0.0173 (6)0.0154 (6)0.0167 (6)
C30.0353 (7)0.0403 (8)0.0326 (7)0.0194 (6)0.0157 (6)0.0181 (6)
C40.0347 (8)0.0383 (8)0.0350 (8)0.0157 (6)0.0112 (6)0.0158 (6)
C50.0360 (7)0.0376 (8)0.0322 (7)0.0162 (6)0.0153 (6)0.0167 (6)
C60.0515 (9)0.0422 (8)0.0411 (8)0.0199 (7)0.0139 (7)0.0238 (7)
C70.0739 (12)0.0487 (10)0.0532 (10)0.0376 (9)0.0180 (9)0.0221 (8)
C80.0773 (13)0.0448 (9)0.0506 (10)0.0314 (9)0.0204 (9)0.0156 (8)
C90.0743 (12)0.0491 (10)0.0431 (9)0.0251 (9)0.0243 (9)0.0169 (8)
C100.0729 (12)0.0428 (9)0.0354 (9)0.0186 (9)0.0039 (8)0.0135 (7)
C110.0421 (9)0.0407 (8)0.0467 (9)0.0137 (7)0.0027 (7)0.0172 (7)
C120.0405 (8)0.0499 (9)0.0373 (8)0.0251 (7)0.0112 (6)0.0204 (7)
C130.0387 (8)0.0425 (8)0.0324 (7)0.0133 (7)0.0039 (6)0.0164 (7)
C140.0618 (11)0.0604 (11)0.0516 (10)0.0290 (9)0.0076 (9)0.0299 (9)
C150.0747 (14)0.0776 (14)0.0661 (13)0.0202 (12)0.0013 (11)0.0504 (12)
C160.0799 (15)0.0760 (15)0.0375 (10)−0.0012 (12)0.0042 (10)0.0284 (10)
C170.0788 (14)0.0539 (11)0.0429 (10)0.0053 (10)0.0240 (10)0.0117 (9)
C180.0616 (11)0.0412 (9)0.0427 (9)0.0140 (8)0.0192 (8)0.0164 (7)
C310.0391 (8)0.0378 (8)0.0346 (8)0.0190 (6)0.0110 (6)0.0156 (6)
C320.0418 (8)0.0477 (9)0.0451 (9)0.0207 (7)0.0159 (7)0.0246 (7)
C330.0565 (10)0.0548 (10)0.0469 (9)0.0266 (8)0.0200 (8)0.0319 (8)
C340.0564 (10)0.0532 (10)0.0450 (9)0.0318 (8)0.0102 (8)0.0250 (8)
C350.0529 (10)0.0847 (13)0.0617 (11)0.0458 (10)0.0251 (9)0.0396 (10)
C360.0530 (10)0.0756 (12)0.0524 (10)0.0389 (9)0.0266 (8)0.0389 (9)
C380.0427 (8)0.0410 (8)0.0368 (8)0.0197 (7)0.0155 (7)0.0178 (7)
N10.0435 (8)0.0441 (8)0.0426 (8)0.0135 (7)0.0039 (6)0.0149 (6)
N20.0693 (10)0.0438 (8)0.0571 (9)0.0241 (7)0.0215 (8)0.0230 (7)
N30.0360 (6)0.0407 (7)0.0299 (6)0.0189 (5)0.0114 (5)0.0168 (5)
F10.0799 (8)0.1045 (9)0.0715 (7)0.0590 (7)0.0180 (6)0.0556 (7)
Geometric parameters (Å, º) top
C1—N11.2847 (19)C12—N31.4790 (18)
C1—N31.3994 (18)C12—C131.501 (2)
C1—C21.446 (2)C12—H12A0.9700
C2—C31.369 (2)C12—H12B0.9700
C2—C381.428 (2)C13—C181.381 (2)
C3—C41.419 (2)C13—C141.382 (2)
C3—C311.4896 (19)C14—C151.385 (3)
C4—C51.3737 (19)C14—H140.9300
C4—C111.505 (2)C15—C161.366 (3)
C5—N31.3777 (18)C15—H150.9300
C5—C61.502 (2)C16—C171.358 (3)
C6—C71.533 (2)C16—H160.9300
C6—H6A0.9700C17—C181.381 (2)
C6—H6B0.9700C17—H170.9300
C7—C81.520 (2)C18—H180.9300
C7—H7A0.9700C31—C361.380 (2)
C7—H7B0.9700C31—C321.384 (2)
C8—C91.518 (2)C32—C331.382 (2)
C8—H8A0.9700C32—H320.9300
C8—H8B0.9700C33—C341.358 (2)
C9—C101.517 (3)C33—H330.9300
C9—H9A0.9700C34—F11.3570 (18)
C9—H9B0.9700C34—C351.363 (2)
C10—C111.525 (2)C35—C361.382 (2)
C10—H10A0.9700C35—H350.9300
C10—H10B0.9700C36—H360.9300
C11—H11A0.9700C38—N21.1426 (19)
C11—H11B0.9700N1—H10.864 (9)
N1—C1—N3118.86 (13)C10—C11—H11B109.2
N1—C1—C2126.92 (14)H11A—C11—H11B107.9
N3—C1—C2114.22 (12)N3—C12—C13115.71 (12)
C3—C2—C38121.57 (13)N3—C12—H12A108.4
C3—C2—C1123.31 (13)C13—C12—H12A108.4
C38—C2—C1115.11 (13)N3—C12—H12B108.4
C2—C3—C4119.20 (13)C13—C12—H12B108.4
C2—C3—C31119.87 (13)H12A—C12—H12B107.4
C4—C3—C31120.92 (13)C18—C13—C14118.55 (15)
C5—C4—C3118.86 (13)C18—C13—C12122.21 (14)
C5—C4—C11120.91 (13)C14—C13—C12119.14 (15)
C3—C4—C11119.70 (13)C13—C14—C15120.31 (19)
C4—C5—N3121.29 (13)C13—C14—H14119.8
C4—C5—C6121.54 (13)C15—C14—H14119.8
N3—C5—C6117.16 (12)C16—C15—C14120.2 (2)
C5—C6—C7115.02 (13)C16—C15—H15119.9
C5—C6—H6A108.5C14—C15—H15119.9
C7—C6—H6A108.5C17—C16—C15119.92 (19)
C5—C6—H6B108.5C17—C16—H16120.0
C7—C6—H6B108.5C15—C16—H16120.0
H6A—C6—H6B107.5C16—C17—C18120.6 (2)
C8—C7—C6117.39 (15)C16—C17—H17119.7
C8—C7—H7A108.0C18—C17—H17119.7
C6—C7—H7A108.0C17—C18—C13120.41 (18)
C8—C7—H7B108.0C17—C18—H18119.8
C6—C7—H7B108.0C13—C18—H18119.8
H7A—C7—H7B107.2C36—C31—C32118.80 (14)
C9—C8—C7116.07 (15)C36—C31—C3121.03 (13)
C9—C8—H8A108.3C32—C31—C3120.16 (13)
C7—C8—H8A108.3C33—C32—C31120.83 (15)
C9—C8—H8B108.3C33—C32—H32119.6
C7—C8—H8B108.3C31—C32—H32119.6
H8A—C8—H8B107.4C34—C33—C32118.37 (15)
C10—C9—C8115.10 (16)C34—C33—H33120.8
C10—C9—H9A108.5C32—C33—H33120.8
C8—C9—H9A108.5F1—C34—C33118.67 (15)
C10—C9—H9B108.5F1—C34—C35118.52 (16)
C8—C9—H9B108.5C33—C34—C35122.81 (15)
H9A—C9—H9B107.5C34—C35—C36118.38 (16)
C9—C10—C11115.73 (14)C34—C35—H35120.8
C9—C10—H10A108.3C36—C35—H35120.8
C11—C10—H10A108.3C31—C36—C35120.80 (16)
C9—C10—H10B108.3C31—C36—H36119.6
C11—C10—H10B108.3C35—C36—H36119.6
H10A—C10—H10B107.4N2—C38—C2175.68 (17)
C4—C11—C10112.25 (13)C1—N1—H1109.5 (13)
C4—C11—H11A109.2C5—N3—C1123.11 (12)
C10—C11—H11A109.2C5—N3—C12120.92 (12)
C4—C11—H11B109.2C1—N3—C12115.68 (12)
N1—C1—C2—C3−179.54 (14)C14—C15—C16—C171.1 (3)
N3—C1—C2—C30.16 (19)C15—C16—C17—C18−0.6 (3)
N1—C1—C2—C381.5 (2)C16—C17—C18—C13−0.6 (3)
N3—C1—C2—C38−178.81 (12)C14—C13—C18—C171.4 (3)
C38—C2—C3—C4179.19 (13)C12—C13—C18—C17−174.81 (16)
C1—C2—C3—C40.3 (2)C2—C3—C31—C36−105.63 (18)
C38—C2—C3—C31−0.3 (2)C4—C3—C31—C3674.87 (19)
C1—C2—C3—C31−179.22 (13)C2—C3—C31—C3275.25 (18)
C2—C3—C4—C5−0.2 (2)C4—C3—C31—C32−104.25 (17)
C31—C3—C4—C5179.26 (13)C36—C31—C32—C33−0.4 (2)
C2—C3—C4—C11−172.00 (13)C3—C31—C32—C33178.75 (14)
C31—C3—C4—C117.5 (2)C31—C32—C33—C340.8 (2)
C3—C4—C5—N3−0.3 (2)C32—C33—C34—F1179.75 (15)
C11—C4—C5—N3171.40 (13)C32—C33—C34—C35−0.6 (3)
C3—C4—C5—C6−179.76 (13)F1—C34—C35—C36179.53 (16)
C11—C4—C5—C6−8.1 (2)C33—C34—C35—C36−0.2 (3)
C4—C5—C6—C787.41 (18)C32—C31—C36—C35−0.4 (3)
N3—C5—C6—C7−92.12 (16)C3—C31—C36—C35−179.49 (16)
C5—C6—C7—C8−73.7 (2)C34—C35—C36—C310.6 (3)
C6—C7—C8—C967.0 (2)C4—C5—N3—C10.7 (2)
C7—C8—C9—C10−99.2 (2)C6—C5—N3—C1−179.73 (12)
C8—C9—C10—C1154.5 (2)C4—C5—N3—C12−172.79 (13)
C5—C4—C11—C10−89.02 (17)C6—C5—N3—C126.73 (19)
C3—C4—C11—C1082.57 (17)N1—C1—N3—C5179.05 (13)
C9—C10—C11—C453.53 (19)C2—C1—N3—C5−0.67 (18)
N3—C12—C13—C18−47.2 (2)N1—C1—N3—C12−7.09 (19)
N3—C12—C13—C14136.67 (15)C2—C1—N3—C12173.18 (11)
C18—C13—C14—C15−0.9 (3)C13—C12—N3—C5−88.06 (16)
C12—C13—C14—C15175.42 (16)C13—C12—N3—C197.94 (15)
C13—C14—C15—C16−0.3 (3)
Hydrogen-bond geometry (Å, º) top
Cg1 is the centroid of the C13–C18 phenyl ring.
D—H···AD—HH···AD···AD—H···A
C32—H32···N1i0.932.533.421 (2)160
C11—H11A···Cg1ii0.972.933.484 (2)118
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x, −y+1, −z+1.
Hydrogen-bond geometry (Å, º) for (I) top
Cg1 is the centroid of the C13–C18 phenyl ring.
D—H···AD—HH···AD···AD—H···A
C32—H32···N1i0.932.563.421 (3)154
C11—H11A···Cg1ii0.972.973.648 (3)128
Symmetry codes: (i) −x, −y, −z; (ii) −x+1, −y+1, −z.
Hydrogen-bond geometry (Å, º) for (II) top
Cg1 is the centroid of the C13–C18 phenyl ring.
D—H···AD—HH···AD···AD—H···A
C32—H32···N1i0.932.533.421 (2)160
C11—H11A···Cg1ii0.972.933.484 (2)118
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x, −y+1, −z+1.

Experimental details

(I)(II)
Crystal data
Chemical formulaC25H24BrN3C25H24FN3
Mr446.38385.47
Crystal system, space groupTriclinic, P1Triclinic, P1
Temperature (K)293293
a, b, c (Å)10.2103 (3), 10.7643 (4), 11.6942 (4)10.1370 (4), 10.2078 (3), 11.8238 (4)
α, β, γ (°)101.074 (1), 106.726 (1), 115.058 (1)109.688 (2), 100.309 (2), 111.420 (2)
V (Å3)1039.46 (6)1006.73 (6)
Z22
Radiation typeMo KαMo Kα
µ (mm−1)1.990.08
Crystal size (mm)0.21 × 0.19 × 0.180.21 × 0.19 × 0.18
Data collection
DiffractometerBruker Kappa APEXIIBruker Kappa APEXII
Absorption correctionMulti-scan
(SADABS; Bruker, 2004)		Multi-scan
(SADABS; Bruker, 2004)
Tmin, Tmax0.967, 0.9740.967, 0.974
No. of measured, independent and
observed [I > 2σ(I)] reflections		25106, 4532, 3830 23254, 3752, 2876
Rint0.0270.022
(sin θ/λ)max (Å−1)0.6390.606
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.039, 0.107, 1.03 0.039, 0.109, 1.05
No. of reflections45323752
No. of parameters266267
No. of restraints22
H-atom treatmentH atoms treated by a mixture of independent and constrained refinementH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å−3)0.93, −0.870.17, −0.14

Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SHELXL97 (Sheldrick, 2008), SHELXS97 (Sheldrick, 2008), SHELXL2014/6 (Sheldrick, 2008), 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 Major Research Project F. No. 42–242/2013 (SR).

References

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ISSN: 2056-9890
Volume 70| Part 11| November 2014| Pages 344-347
doi:10.1107/S1600536814022016
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