N3,N6,2,5,7-Penta­phenyl-2,5,7-triaza­bicyclo­[2.2.1]heptane-3,6-diamine

Taheri, A.; Moosavi, S.M.

doi:10.1107/S1600536809024416

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 8| August 2009| Page o1724

doi:10.1107/S1600536809024416

Open

access

N³,N⁶,2,5,7-Pentaphenyl-2,5,7-triazabicyclo[2.2.1]heptane-3,6-diamine

Amir Taheri ^a ^* and Sayed Mojtaba Moosavi ^a

^aDepartment of Chemistry, Imam Hossein University, Tehran, Iran
^*Correspondence e-mail: amir.tahery1@gmail.com

(Received 8 June 2009; accepted 24 June 2009; online 1 July 2009)

In the title compound, C₃₄H₃₁N₅, the observed molecular geometry suggests that anomeric effects are present in terms of short C—N bond lengths and reduced pyramidality of the N atoms.

Related literature

For the synthesis of the title compound and the structure of another 2,5,7–triazabicyclo[2.2.1]heptan derivative, see: Taheri & Moosavi (2009 ). For its precursors, see: Kliegman & Barnes (1970 ); Taheri & Moosavi (2008 ). For general background to azanorbornanes, see Alphen, (1933 ); Alvaro et al. (2007 ); Archelas & Morin (1984 ); Nitravati & Sikhibhushan (1939 , 1941 ); Potts & Husain (1972 ); Potts et al. (1974 ); Neunhoeffer & Fruhauf (1969 , 1970 ); Stanforth et al. (2002 ). For the syntheses of polyazapolycyclic compounds, see: Nielsen et al. (1990 , 1992 , 1998 ). For the anomeric effect, see: Senderowitz et al. (1992 ); Reed & Schleyer (1988 ); Watson et al. (1990 ); Davies et al. (1992 ).

Experimental

Crystal data

C₃₄H₃₁N₅
M_r = 509.64
Orthorhombic, P 2₁ 2₁ 2₁
a = 9.7427 (4) Å
b = 16.4049 (7) Å
c = 17.0658 (7) Å
V = 2727.6 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 100 K
0.25 × 0.15 × 0.10 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2003 ) T_min = 0.981, T_max = 0.990
27681 measured reflections
3131 independent reflections
2816 reflections with I > 2σ(I)
R_int = 0.060

Refinement

R[F² > 2σ(F²)] = 0.031
wR(F²) = 0.072
S = 1.01
3131 reflections
352 parameters
H-atom parameters constrained
Δρ_max = 0.17 e Å⁻³
Δρ_min = −0.17 e Å⁻³

Data collection: APEX2 (Bruker, 2005 ); cell refinement: SAINT-Plus (Bruker, 2001 ); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809024416/rk2152sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809024416/rk2152Isup2.hkl

checkCIF report

Comment top

There are different kinds of polyazapolycyclic skeletons (Nielsen et al., 1990) constituted of saturated rings with multiple N atoms, that can be utilized for high–density and energetic compounds syntheses (Nielsen et al., 1992). In cage skeleton, 2,4,6,8,10,12–hexabenzyl–2,4,6,8,10,12–hexaazaisowurtzitane is precursor for 2,4,6,8,10,12–hexanitro–2,4,6,8,10,12–hexaazaisowurtzitane, which is highly energetic compound (Nielsen et al., 1998). In norbornane skeletons, azanorbornane or azabicyclo[2.2.1]heptane (Archelas & Morin, 1984) and diazanorbornane derivatives (Alvaro et al., 2007) have been synthesized and characterized so far, but triazanorbornane derivatives have seldom been reported (Nitravati & Sikhibhushan, 1939, 1941; Alphen, 1933). The syntheses and molecular structures of triazabicyclo[2.2.1]heptaneshave been presented in a few papers without using X–ray crystal structure analysis (Potts & Husain, 1972; Potts et al., 1974; Neunhoeffer & Fruhauf, 1969,1970; Stanforth et al., 2002).

As a part of our continuing efforts on the development of polyazapolycyclics, structural stability and synthesis of 2,5,7–triazabicyclo[2.2.1]heptan derivative (Taheri & Moosavi, 2009) via a catalytic reaction between aminoethane derivatives (Kliegman & Barnes, 1970; Taheri & Moosavi, 2008) and glyoxal were recently described another crystal system of the title compound without any solvent on the crystal packing in which geometric parameters for stability of the skeleton is scrutinized by study of anomeric interactions.

The molecular structure of I shown in Fig. 1 has racemic configuration, all S– and all R–configuration molecules and composed of a six–membered piperazine ring and an N atom bridging between the C1 and C4 situations, norbornane skeleton construction. Notwithstanding the presence of two NH groups, viz. N31 and N61, and five N atoms carrying lone–pair electrons potentially available for H–bond creation, there are not actually intra– or intermolecular N—H···N or C—H···N hydrogen bonds. As shown in the scheme, the skeleton has a good local twofold symmetry, namely through the N7 bridge and almost perpendicular to the least–squares plane of the piperazine ring. It is noteworthy that the symmetry involves not only the skeleton but also the peripheral phenyl groups, except for that attached to the bridging N7 atom.

The anomeric effect in N—C—N systems investigated extensively (Senderowitz et al., 1992), occurred between a lone pair on N and an antiperiplanar σ* orbital of the adjacent C—N bond (n_N→σ*_C—N), negative hyperconjugation (Reed & Schleyer, 1988).

There are four dissimilar anomeric effects manifested by the bond distances and N–atom pyramidality on four N'—C—N" fragments or n_N'→σ*_C—N" systems. Within the N'—C—N" unit, the N'—C bond is shorter, than the C—N" bond. On the other hand, the pyramidality of N' (the sum of the three bond angles around N') is larger than that of N". These geometric parameters related to the anomeric effect are shown in Tabl. 1. Among them, the n_N5→σ*_C4—N7 system shows a distinguished anomeric interaction and the largest bond–length difference [0.029 (2)Å], which is comparable to that reported for an other crystal system (Taheri & Mossavi, 2009).

However, the pyramidality differences in the N'—C—N" units are not so indicative. The differences within the N2—C2—N7 and N7—C4—N5 systems are 16.14 (16) and 17.83 (15)°, respectively, and these are much larger, than those for the N31—C3—N2 and N61—C6—N5 groups, 2.95 and 0.21°, respectively. Furthermore, the calculated pyramidalities for atoms N31 and N61 are not accurate because they include H atoms, whose positions were determined from adifference Fourier synthesis. Thus, the anomeric effect on the pyramidality is not clear in this molecule. It could be that, the anomeric effect on the angle is buried among the steric effects caused by the crowding of the substituent groups, which would strongly affect the molecular structure.

Reflecting the local twofold symmetry, the corresponding N atoms in this symmetric skeleton (N2 and N5, N31 and N61) have nearly the same pyramidality. The pyramidality angle of N7 [330.71 (19)°] is rather small, and the attached phenyl group is inclined from the local twofold axis in the direction of atoms N2, C3 and N31. Corresponding to this inclination, the C72—C71—N7 angle [122.79 (17)°] is distorted from theideal value of 120°, which is attributable to the short contact between the voluminous phenyl ring and the skeleton. For example, the H76···H1 separation (atom C1 is the bridgehead) is only 2.281Å . The same distortion is seen in another norbornane derivative [122.5 (4)°; Watson et al., 1990] for the phenyl ring on the bridging N7 atom.

The angle at the bridging N atom, C1—N7—C4, is 94.11 (13)°. Although this bridge angle is comparable to those reported for norbornane and diazanorbornane (Davies et al., 1992), it still indicates the presence of ring strain.

Related literature top

For the synthesis of the title compound and the structure of another 2,5,7–triazabicyclo[2.2.1]heptan derivative, see: Taheri & Moosavi (2009). For its precursors, see: Kliegman & Barnes (1970); Taheri & Moosavi (2008). For general background to azanorbornanes, see Alphen, (1933); Alvaro et al. (2007); Archelas & Morin (1984); Nitravati & Sikhibhushan (1939, 1941); Potts & Husain (1972); Potts et al. (1974); Neunhoeffer & Fruhauf (1969, 1970); Stanforth et al. (2002). For the syntheses of polyazapolycyclic compounds, see: Nielsen et al. (1990, 1992, 1998). For the anomeric effect, see: Senderowitz et al. (1992); Reed & Schleyer (1988); Watson et al. (1990); Davies et al. (1992).

Experimental top

Aqueous glyoxal (40% v/v, 1.15 ml, 0.01 mol) was added dropwise to a stirred solution of 1,1',2,2'–tetrakis(phenylamino)ethane (3.94 g, 0.01 mol) in ethanol (50 ml). The solution temperature was kept at 273 K during the reaction. The mixture was put aside for 24 h at a temperature of 278–283 K. The resulting white precipitate was filtered off and washed with cold ethanol to give 2.53 g (55% yield) of I (m.p. 428 K).

¹H NMR (CDCl₃): ¹H 6.59–7.30 (m, 25H, CH_Ar), 5.69 (s, 2H, CH), 4.93 (d, 2H, J = 10 Hz, CH), 3.69 (d, 2H, J = 10 Hz, NH). Addition of D₂O to the NMR sample caused the NH signals to disappeared and the CH doublet quickly converted to a singlet.

¹³C NMR (CDCl₃): ¹³C 144.8, 144.2, 143.6,129.3, 129.7, 122.1, 119.4, 118.7, 117.4, 113.7, 113.2 (CH_Ar), 76.0 (CH), 72.4 (CH).

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus (Bruker, 2001); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of I, with the atom–numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are presented as a small spheres of arbitrary radius.

N³,N⁶,2,5,7-pentaphenyl-2,5,7-triazabicyclo[2.2.1]heptane- 3,6-diamine top

Crystal data top

C₃₄H₃₁N₅	F(000) = 1080
M_r = 509.64	D_x = 1.241 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 4705 reflections
a = 9.7427 (4) Å	θ = 2.4–22.0°
b = 16.4049 (7) Å	µ = 0.08 mm⁻¹
c = 17.0658 (7) Å	T = 100 K
V = 2727.6 (2) Å³	Prism, colourless
Z = 4	0.25 × 0.15 × 0.10 mm

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	3131 independent reflections
Radiation source: Fine–focus sealed tube	2816 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.060
ϕ and ω scans	θ_max = 26.4°, θ_min = 1.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −12→12
T_min = 0.981, T_max = 0.990	k = −20→20
27681 measured reflections	l = −21→21

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: Full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.031	H-atom parameters constrained
wR(F²) = 0.072	w = 1/[σ²(F_o²) + (0.0373P)² + 0.373P] where P = (F_o² + 2F_c²)/3
S = 1.01	(Δ/σ)_max < 0.001
3131 reflections	Δρ_max = 0.17 e Å⁻³
352 parameters	Δρ_min = −0.17 e Å⁻³
0 restraints	Absolute structure: 2419 Friedel pairs were merged
Primary atom site location: structure-invariant direct methods

Crystal data top

C₃₄H₃₁N₅	V = 2727.6 (2) Å³
M_r = 509.64	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 9.7427 (4) Å	µ = 0.08 mm⁻¹
b = 16.4049 (7) Å	T = 100 K
c = 17.0658 (7) Å	0.25 × 0.15 × 0.10 mm

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	3131 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	2816 reflections with I > 2σ(I)
T_min = 0.981, T_max = 0.990	R_int = 0.060
27681 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.031	0 restraints
wR(F²) = 0.072	H-atom parameters constrained
S = 1.01	Δρ_max = 0.17 e Å⁻³
3131 reflections	Δρ_min = −0.17 e Å⁻³
352 parameters	Absolute structure: 2419 Friedel pairs were merged

Special details top

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

Refinement. Refinement of F² against ALL reflections. The weighted R–factor wR and goodness of fit S are based on F², conventional R–factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R–factors(gt) etc. and is not relevant to the choice of reflections for refinement. R–factors based on F² are statistically about twice as large as those based on F, and R–factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
C1	0.66064 (19)	0.61819 (11)	0.23890 (10)	0.0161 (4)
H1A	0.6227	0.6561	0.2793	0.019*
N2	0.70778 (16)	0.53934 (9)	0.26954 (8)	0.0163 (3)
C3	0.71251 (19)	0.48417 (10)	0.20155 (10)	0.0164 (4)
H3A	0.8095	0.4679	0.1904	0.020*
C4	0.65972 (18)	0.54197 (11)	0.13717 (10)	0.0159 (4)
H4A	0.6216	0.5137	0.0900	0.019*
N5	0.77088 (16)	0.60077 (9)	0.11985 (8)	0.0163 (3)
C6	0.77956 (19)	0.65473 (11)	0.18816 (10)	0.0164 (4)
H6A	0.8698	0.6478	0.2153	0.020*
N7	0.56002 (15)	0.58946 (9)	0.18081 (8)	0.0158 (3)
C21	0.80912 (18)	0.53697 (11)	0.32784 (10)	0.0165 (4)
C22	0.82474 (19)	0.60204 (11)	0.38008 (10)	0.0184 (4)
H22A	0.7685	0.6490	0.3746	0.022*
C23	0.9213 (2)	0.59879 (12)	0.43974 (11)	0.0228 (4)
H23A	0.9299	0.6433	0.4750	0.027*
C24	1.0055 (2)	0.53119 (13)	0.44833 (11)	0.0246 (4)
H24A	1.0723	0.5293	0.4889	0.030*
C25	0.9907 (2)	0.46637 (13)	0.39682 (11)	0.0240 (4)
H25A	1.0482	0.4199	0.4021	0.029*
C26	0.89300 (19)	0.46840 (12)	0.33759 (11)	0.0209 (4)
H26A	0.8830	0.4230	0.3035	0.025*
N31	0.62863 (16)	0.41223 (9)	0.21507 (9)	0.0181 (3)
H31N	0.5424	0.4272	0.2275	0.022*
C32	0.6379 (2)	0.34644 (11)	0.16289 (10)	0.0180 (4)
C33	0.7651 (2)	0.31662 (12)	0.13812 (12)	0.0266 (4)
H33A	0.8470	0.3432	0.1541	0.032*
C34	0.7723 (2)	0.24833 (13)	0.09027 (13)	0.0333 (5)
H34A	0.8595	0.2287	0.0739	0.040*
C35	0.6546 (2)	0.20845 (12)	0.06601 (13)	0.0316 (5)
H35A	0.6604	0.1617	0.0333	0.038*
C36	0.5284 (2)	0.23776 (12)	0.09010 (11)	0.0259 (5)
H36A	0.4469	0.2108	0.0739	0.031*
C37	0.5193 (2)	0.30628 (11)	0.13780 (10)	0.0207 (4)
H37A	0.4318	0.3259	0.1535	0.025*
C51	0.88738 (19)	0.57525 (11)	0.07785 (10)	0.0157 (4)
C52	0.8730 (2)	0.51490 (11)	0.02028 (11)	0.0204 (4)
H52A	0.7861	0.4902	0.0118	0.024*
C53	0.9849 (2)	0.49093 (12)	−0.02443 (11)	0.0236 (4)
H53A	0.9735	0.4505	−0.0637	0.028*
C54	1.1129 (2)	0.52537 (12)	−0.01237 (11)	0.0231 (4)
H54A	1.1898	0.5078	−0.0421	0.028*
C55	1.1272 (2)	0.58591 (12)	0.04381 (11)	0.0227 (4)
H55A	1.2143	0.6106	0.0517	0.027*
C56	1.0161 (2)	0.61088 (11)	0.08871 (11)	0.0194 (4)
H56A	1.0277	0.6524	0.1270	0.023*
N61	0.76301 (16)	0.73814 (9)	0.16149 (9)	0.0179 (3)
H61N	0.6972	0.7403	0.1234	0.021*
C62	0.76841 (19)	0.80551 (11)	0.21117 (10)	0.0173 (4)
C63	0.6967 (2)	0.87592 (11)	0.18892 (12)	0.0217 (4)
H63A	0.6411	0.8750	0.1432	0.026*
C64	0.7058 (2)	0.94660 (12)	0.23260 (13)	0.0286 (5)
H64A	0.6594	0.9944	0.2156	0.034*
C65	0.7825 (2)	0.94832 (13)	0.30131 (13)	0.0328 (5)
H65A	0.7871	0.9965	0.3320	0.039*
C66	0.8519 (2)	0.87877 (13)	0.32424 (13)	0.0302 (5)
H66A	0.9041	0.8796	0.3712	0.036*
C67	0.8468 (2)	0.80757 (12)	0.27986 (11)	0.0221 (4)
H67A	0.8963	0.7606	0.2961	0.027*
C71	0.48078 (18)	0.65048 (11)	0.14169 (11)	0.0168 (4)
C72	0.49051 (19)	0.66496 (11)	0.06118 (11)	0.0196 (4)
H72A	0.5510	0.6332	0.0299	0.024*
C73	0.4118 (2)	0.72570 (12)	0.02695 (12)	0.0236 (4)
H73A	0.4190	0.7353	−0.0278	0.028*
C74	0.3232 (2)	0.77245 (12)	0.07143 (13)	0.0276 (5)
H74A	0.2707	0.8146	0.0477	0.033*
C75	0.3116 (2)	0.75718 (12)	0.15116 (13)	0.0273 (5)
H75A	0.2506	0.7890	0.1820	0.033*
C76	0.3880 (2)	0.69600 (11)	0.18629 (11)	0.0216 (4)
H76A	0.3773	0.6850	0.2406	0.026*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0168 (9)	0.0159 (8)	0.0157 (8)	0.0015 (7)	−0.0011 (7)	−0.0009 (7)
N2	0.0196 (8)	0.0148 (7)	0.0146 (7)	0.0016 (6)	−0.0009 (6)	−0.0003 (6)
C3	0.0168 (9)	0.0161 (8)	0.0164 (8)	−0.0004 (7)	0.0015 (7)	−0.0008 (7)
C4	0.0150 (8)	0.0169 (9)	0.0157 (8)	−0.0011 (7)	−0.0001 (7)	−0.0002 (7)
N5	0.0177 (8)	0.0163 (7)	0.0149 (7)	−0.0015 (6)	0.0002 (6)	−0.0020 (6)
C6	0.0182 (9)	0.0159 (8)	0.0152 (8)	0.0003 (7)	−0.0011 (8)	0.0003 (7)
N7	0.0170 (7)	0.0174 (7)	0.0131 (7)	0.0011 (6)	−0.0001 (6)	−0.0009 (6)
C21	0.0157 (9)	0.0201 (9)	0.0137 (8)	−0.0013 (7)	0.0018 (7)	0.0031 (7)
C22	0.0199 (9)	0.0190 (9)	0.0163 (9)	−0.0019 (8)	0.0004 (7)	0.0023 (8)
C23	0.0219 (10)	0.0303 (11)	0.0163 (9)	−0.0072 (9)	0.0017 (8)	0.0017 (8)
C24	0.0162 (9)	0.0405 (11)	0.0172 (9)	−0.0028 (9)	−0.0010 (8)	0.0060 (9)
C25	0.0178 (9)	0.0317 (11)	0.0224 (9)	0.0038 (9)	0.0027 (8)	0.0079 (9)
C26	0.0217 (9)	0.0223 (10)	0.0187 (9)	0.0017 (8)	0.0026 (8)	0.0016 (8)
N31	0.0170 (8)	0.0155 (7)	0.0219 (8)	−0.0007 (7)	0.0038 (7)	−0.0006 (6)
C32	0.0237 (10)	0.0141 (8)	0.0163 (8)	−0.0017 (8)	0.0013 (8)	0.0035 (7)
C33	0.0218 (10)	0.0210 (9)	0.0370 (11)	−0.0018 (8)	0.0028 (9)	−0.0053 (9)
C34	0.0308 (11)	0.0253 (10)	0.0439 (13)	0.0029 (10)	0.0108 (11)	−0.0081 (10)
C35	0.0433 (13)	0.0203 (10)	0.0313 (11)	−0.0041 (10)	0.0087 (10)	−0.0062 (9)
C36	0.0334 (11)	0.0235 (10)	0.0209 (10)	−0.0091 (9)	−0.0009 (9)	−0.0001 (8)
C37	0.0240 (10)	0.0196 (9)	0.0186 (9)	−0.0029 (8)	0.0036 (8)	0.0035 (8)
C51	0.0172 (9)	0.0157 (8)	0.0143 (8)	0.0025 (7)	0.0014 (7)	0.0039 (7)
C52	0.0184 (9)	0.0218 (9)	0.0209 (9)	−0.0019 (8)	0.0011 (8)	−0.0005 (8)
C53	0.0257 (10)	0.0223 (10)	0.0229 (9)	0.0034 (8)	0.0028 (9)	−0.0045 (8)
C54	0.0200 (10)	0.0270 (10)	0.0224 (9)	0.0075 (9)	0.0053 (8)	0.0046 (8)
C55	0.0150 (9)	0.0261 (10)	0.0269 (10)	−0.0008 (8)	−0.0016 (8)	0.0070 (8)
C56	0.0211 (9)	0.0180 (9)	0.0189 (9)	−0.0010 (8)	−0.0029 (8)	0.0025 (8)
N61	0.0227 (8)	0.0167 (7)	0.0143 (7)	−0.0021 (7)	−0.0032 (7)	0.0000 (6)
C62	0.0169 (9)	0.0172 (9)	0.0177 (8)	−0.0048 (8)	0.0051 (7)	−0.0014 (7)
C63	0.0199 (10)	0.0218 (9)	0.0236 (10)	−0.0031 (8)	0.0045 (8)	0.0014 (8)
C64	0.0281 (11)	0.0193 (10)	0.0386 (12)	−0.0029 (9)	0.0112 (10)	−0.0005 (9)
C65	0.0328 (12)	0.0255 (11)	0.0401 (12)	−0.0085 (9)	0.0115 (11)	−0.0153 (10)
C66	0.0249 (11)	0.0385 (12)	0.0272 (10)	−0.0102 (10)	0.0017 (9)	−0.0116 (9)
C67	0.0189 (9)	0.0261 (10)	0.0213 (9)	−0.0031 (8)	−0.0005 (8)	−0.0029 (8)
C71	0.0153 (9)	0.0155 (9)	0.0196 (9)	−0.0025 (7)	−0.0031 (7)	−0.0001 (7)
C72	0.0161 (9)	0.0218 (9)	0.0210 (9)	−0.0036 (8)	−0.0015 (8)	0.0004 (8)
C73	0.0246 (10)	0.0251 (10)	0.0213 (10)	−0.0080 (8)	−0.0056 (9)	0.0051 (8)
C74	0.0291 (11)	0.0192 (10)	0.0346 (12)	0.0003 (9)	−0.0126 (10)	0.0030 (9)
C75	0.0272 (11)	0.0211 (10)	0.0335 (11)	0.0069 (8)	−0.0070 (9)	−0.0081 (9)
C76	0.0245 (10)	0.0219 (10)	0.0184 (9)	0.0015 (8)	−0.0033 (8)	−0.0018 (8)

Geometric parameters (Å, º) top

C1—N2	1.469 (2)	C36—C37	1.391 (3)
C1—N7	1.472 (2)	C36—H36A	0.9500
C1—C6	1.566 (2)	C37—H37A	0.9500
C1—H1A	1.0000	C51—C56	1.396 (3)
N2—C21	1.402 (2)	C51—C52	1.402 (3)
N2—C3	1.472 (2)	C52—C53	1.387 (3)
C3—N31	1.454 (2)	C52—H52A	0.9500
C3—C4	1.540 (2)	C53—C54	1.385 (3)
C3—H3A	1.0000	C53—H53A	0.9500
C4—N7	1.451 (2)	C54—C55	1.388 (3)
C4—N5	1.480 (2)	C54—H54A	0.9500
C4—H4A	1.0000	C55—C56	1.388 (3)
N5—C51	1.406 (2)	C55—H55A	0.9500
N5—C6	1.466 (2)	C56—H56A	0.9500
C6—N61	1.451 (2)	N61—C62	1.394 (2)
C6—H6A	1.0000	N61—H61N	0.9140
N7—C71	1.430 (2)	C62—C67	1.399 (3)
C21—C22	1.399 (2)	C62—C63	1.402 (3)
C21—C26	1.400 (3)	C63—C64	1.381 (3)
C22—C23	1.387 (3)	C63—H63A	0.9500
C22—H22A	0.9500	C64—C65	1.390 (3)
C23—C24	1.387 (3)	C64—H64A	0.9500
C23—H23A	0.9500	C65—C66	1.383 (3)
C24—C25	1.387 (3)	C65—H65A	0.9500
C24—H24A	0.9500	C66—C67	1.393 (3)
C25—C26	1.389 (3)	C66—H66A	0.9500
C25—H25A	0.9500	C67—H67A	0.9500
C26—H26A	0.9500	C71—C72	1.397 (2)
N31—C32	1.402 (2)	C71—C76	1.398 (3)
N31—H31N	0.9006	C72—C73	1.386 (3)
C32—C37	1.398 (3)	C72—H72A	0.9500
C32—C33	1.398 (3)	C73—C74	1.382 (3)
C33—C34	1.388 (3)	C73—H73A	0.9500
C33—H33A	0.9500	C74—C75	1.388 (3)
C34—C35	1.384 (3)	C74—H74A	0.9500
C34—H34A	0.9500	C75—C76	1.386 (3)
C35—C36	1.383 (3)	C75—H75A	0.9500
C35—H35A	0.9500	C76—H76A	0.9500

N2—C1—N7	99.56 (13)	C34—C35—H35A	120.5
N2—C1—C6	107.62 (14)	C35—C36—C37	120.77 (19)
N7—C1—C6	104.06 (13)	C35—C36—H36A	119.6
N2—C1—H1A	114.7	C37—C36—H36A	119.6
N7—C1—H1A	114.7	C36—C37—C32	120.52 (18)
C6—C1—H1A	114.7	C36—C37—H37A	119.7
C21—N2—C1	119.82 (15)	C32—C37—H37A	119.7
C21—N2—C3	121.33 (15)	C56—C51—C52	118.57 (17)
C1—N2—C3	105.70 (13)	C56—C51—N5	122.19 (16)
N31—C3—N2	110.87 (14)	C52—C51—N5	119.16 (16)
N31—C3—C4	115.18 (15)	C53—C52—C51	120.51 (18)
N2—C3—C4	99.98 (13)	C53—C52—H52A	119.7
N31—C3—H3A	110.1	C51—C52—H52A	119.7
N2—C3—H3A	110.1	C54—C53—C52	120.67 (18)
C4—C3—H3A	110.1	C54—C53—H53A	119.7
N7—C4—N5	104.03 (13)	C52—C53—H53A	119.7
N7—C4—C3	100.84 (13)	C53—C54—C55	119.03 (18)
N5—C4—C3	107.43 (14)	C53—C54—H54A	120.5
N7—C4—H4A	114.4	C55—C54—H54A	120.5
N5—C4—H4A	114.4	C54—C55—C56	120.97 (18)
C3—C4—H4A	114.4	C54—C55—H55A	119.5
C51—N5—C6	122.58 (15)	C56—C55—H55A	119.5
C51—N5—C4	119.89 (14)	C55—C56—C51	120.24 (17)
C6—N5—C4	106.07 (13)	C55—C56—H56A	119.9
N61—C6—N5	108.27 (13)	C51—C56—H56A	119.9
N61—C6—C1	116.89 (15)	C62—N61—C6	123.55 (14)
N5—C6—C1	99.55 (13)	C62—N61—H61N	115.4
N61—C6—H6A	110.5	C6—N61—H61N	109.8
N5—C6—H6A	110.5	N61—C62—C67	123.32 (17)
C1—C6—H6A	110.5	N61—C62—C63	118.01 (16)
C71—N7—C4	119.85 (14)	C67—C62—C63	118.60 (17)
C71—N7—C1	116.75 (14)	C64—C63—C62	120.89 (18)
C4—N7—C1	94.11 (13)	C64—C63—H63A	119.6
C22—C21—C26	118.28 (16)	C62—C63—H63A	119.6
C22—C21—N2	120.50 (16)	C63—C64—C65	120.44 (19)
C26—C21—N2	121.17 (16)	C63—C64—H64A	119.8
C23—C22—C21	120.80 (17)	C65—C64—H64A	119.8
C23—C22—H22A	119.6	C66—C65—C64	118.98 (19)
C21—C22—H22A	119.6	C66—C65—H65A	120.5
C24—C23—C22	120.62 (18)	C64—C65—H65A	120.5
C24—C23—H23A	119.7	C65—C66—C67	121.38 (19)
C22—C23—H23A	119.7	C65—C66—H66A	119.3
C23—C24—C25	118.97 (18)	C67—C66—H66A	119.3
C23—C24—H24A	120.5	C66—C67—C62	119.67 (19)
C25—C24—H24A	120.5	C66—C67—H67A	120.2
C24—C25—C26	120.94 (19)	C62—C67—H67A	120.2
C24—C25—H25A	119.5	C72—C71—C76	119.23 (17)
C26—C25—H25A	119.5	C72—C71—N7	122.79 (17)
C25—C26—C21	120.38 (18)	C76—C71—N7	117.96 (16)
C25—C26—H26A	119.8	C73—C72—C71	119.93 (18)
C21—C26—H26A	119.8	C73—C72—H72A	120.0
C32—N31—C3	119.19 (15)	C71—C72—H72A	120.0
C32—N31—H31N	114.8	C74—C73—C72	120.86 (18)
C3—N31—H31N	109.9	C74—C73—H73A	119.6
C37—C32—C33	118.39 (16)	C72—C73—H73A	119.6
C37—C32—N31	120.28 (17)	C73—C74—C75	119.27 (19)
C33—C32—N31	121.24 (17)	C73—C74—H74A	120.4
C34—C33—C32	120.37 (19)	C75—C74—H74A	120.4
C34—C33—H33A	119.8	C76—C75—C74	120.74 (19)
C32—C33—H33A	119.8	C76—C75—H75A	119.6
C35—C34—C33	121.0 (2)	C74—C75—H75A	119.6
C35—C34—H34A	119.5	C75—C76—C71	119.91 (18)
C33—C34—H34A	119.5	C75—C76—H76A	120.0
C36—C35—C34	118.93 (18)	C71—C76—H76A	120.0
C36—C35—H35A	120.5

N7—C1—N2—C21	179.24 (14)	C3—N31—C32—C37	−137.18 (17)
C6—C1—N2—C21	71.05 (19)	C3—N31—C32—C33	46.4 (2)
N7—C1—N2—C3	37.63 (16)	C37—C32—C33—C34	−0.5 (3)
C6—C1—N2—C3	−70.55 (16)	N31—C32—C33—C34	176.03 (18)
C21—N2—C3—N31	95.41 (19)	C32—C33—C34—C35	0.1 (3)
C1—N2—C3—N31	−123.70 (15)	C33—C34—C35—C36	0.1 (3)
C21—N2—C3—C4	−142.62 (16)	C34—C35—C36—C37	0.1 (3)
C1—N2—C3—C4	−1.74 (17)	C35—C36—C37—C32	−0.6 (3)
N31—C3—C4—N7	83.41 (17)	C33—C32—C37—C36	0.7 (3)
N2—C3—C4—N7	−35.43 (16)	N31—C32—C37—C36	−175.83 (16)
N31—C3—C4—N5	−167.99 (14)	C6—N5—C51—C56	−12.2 (3)
N2—C3—C4—N5	73.16 (16)	C4—N5—C51—C56	−150.44 (16)
N7—C4—N5—C51	179.59 (14)	C6—N5—C51—C52	171.14 (15)
C3—C4—N5—C51	73.24 (19)	C4—N5—C51—C52	32.9 (2)
N7—C4—N5—C6	35.30 (16)	C56—C51—C52—C53	0.4 (3)
C3—C4—N5—C6	−71.05 (16)	N5—C51—C52—C53	177.24 (17)
C51—N5—C6—N61	93.00 (19)	C51—C52—C53—C54	0.8 (3)
C4—N5—C6—N61	−123.91 (15)	C52—C53—C54—C55	−1.7 (3)
C51—N5—C6—C1	−144.42 (16)	C53—C54—C55—C56	1.3 (3)
C4—N5—C6—C1	−1.33 (16)	C54—C55—C56—C51	−0.1 (3)
N2—C1—C6—N61	−171.17 (14)	C52—C51—C56—C55	−0.8 (3)
N7—C1—C6—N61	83.81 (17)	N5—C51—C56—C55	−177.50 (16)
N2—C1—C6—N5	72.62 (15)	N5—C6—N61—C62	−178.74 (16)
N7—C1—C6—N5	−32.40 (16)	C1—C6—N61—C62	70.0 (2)
N5—C4—N7—C71	70.92 (18)	C6—N61—C62—C67	29.8 (3)
C3—C4—N7—C71	−177.85 (14)	C6—N61—C62—C63	−153.34 (17)
N5—C4—N7—C1	−53.25 (15)	N61—C62—C63—C64	−175.32 (18)
C3—C4—N7—C1	57.98 (14)	C67—C62—C63—C64	1.7 (3)
N2—C1—N7—C71	174.81 (14)	C62—C63—C64—C65	−2.4 (3)
C6—C1—N7—C71	−74.18 (17)	C63—C64—C65—C66	1.4 (3)
N2—C1—N7—C4	−58.68 (14)	C64—C65—C66—C67	0.3 (3)
C6—C1—N7—C4	52.34 (15)	C65—C66—C67—C62	−1.0 (3)
C1—N2—C21—C22	27.5 (2)	N61—C62—C67—C66	176.84 (18)
C3—N2—C21—C22	163.02 (15)	C63—C62—C67—C66	0.0 (3)
C1—N2—C21—C26	−155.37 (17)	C4—N7—C71—C72	2.7 (2)
C3—N2—C21—C26	−19.8 (2)	C1—N7—C71—C72	115.13 (19)
C26—C21—C22—C23	0.3 (3)	C4—N7—C71—C76	−178.65 (16)
N2—C21—C22—C23	177.56 (16)	C1—N7—C71—C76	−66.2 (2)
C21—C22—C23—C24	0.7 (3)	C76—C71—C72—C73	2.1 (3)
C22—C23—C24—C25	−0.7 (3)	N7—C71—C72—C73	−179.29 (16)
C23—C24—C25—C26	−0.3 (3)	C71—C72—C73—C74	−0.1 (3)
C24—C25—C26—C21	1.3 (3)	C72—C73—C74—C75	−1.0 (3)
C22—C21—C26—C25	−1.3 (3)	C73—C74—C75—C76	0.2 (3)
N2—C21—C26—C25	−178.49 (16)	C74—C75—C76—C71	1.8 (3)
N2—C3—N31—C32	−169.47 (15)	C72—C71—C76—C75	−2.9 (3)
C4—C3—N31—C32	77.9 (2)	N7—C71—C76—C75	178.37 (17)

Experimental details

Crystal data
Chemical formula	C₃₄H₃₁N₅
M_r	509.64
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	100
a, b, c (Å)	9.7427 (4), 16.4049 (7), 17.0658 (7)
V (Å³)	2727.6 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.25 × 0.15 × 0.10

Data collection
Diffractometer	Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2003)
T_min, T_max	0.981, 0.990
No. of measured, independent and observed [I > 2σ(I)] reflections	27681, 3131, 2816
R_int	0.060
(sin θ/λ)_max (Å⁻¹)	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.031, 0.072, 1.01
No. of reflections	3131
No. of parameters	352
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.17, −0.17
Absolute structure	2419 Friedel pairs were merged

Computer programs: APEX2 (Bruker, 2005), SAINT-Plus (Bruker, 2001), SHELXTL (Sheldrick, 2008).

Geometric parameters relating anomeric interactions in N'—C—N" fragments (Å, °) top

Parameters	n_N31 → σ*_C3—N2	n_N2 → σ*_C2—N7	n_N7 → σ*_C4—N5	n_N61 → σ*_C6—N5
N'—C	1.454 (2)	1.469 (2)	1.451 (2)	1.451 (2)
C—N''	1.472 (2)	1.472 (2)	1.480 (2)	1.466 (2)
N'—C—N''	110.87 (14)	99.56 (13)	104.03 (13)	108.27 (13)
Pyr N'^a,b	343.89	346.85 (25)	330.71 (19)	348.75
Pyr N''	346.85 (25)	330.71 (19)	348.54 (24)	348.54 (24)

Notes: (a) Pyr denotes the pyramidality of the N atoms, the sum of the three angles around the N atom. (b) s.u. values are estimated from the sum of s.u. values when they are available.

Acknowledgements

We thank the Chemistry Group of Imam Hossain University for their cooperation.

References

Alphen, J. V. (1933). Recl. Trav. Chim. Pays-Bas, 52, 47–53. Google Scholar
Alvaro, G., Fabio, R. D., Gualandi, A., Fiorell, C., Monari, D., Savoia, D. & Zoli, L. (2007). Tetrahedron, 63, 12446–12453. Web of Science CSD CrossRef CAS Google Scholar
Archelas, A. & Morin, C. (1984). Tetrahedron Lett. 25, 1277–1278. CrossRef CAS Web of Science Google Scholar
Bruker (2001). SAINT-Plus. Bruker AXS, Madison, Wisconsin, USA. Google Scholar
Bruker (2005). APEX2. Bruker AXS, Madison,Wisconsin, USA. Google Scholar
Davies, J. W., Durrant, M. L., Walker, M. P. & Malpass, J. R. (1992). Tetrahedron, 48, 4379–4398. CrossRef CAS Web of Science Google Scholar
Kliegman, J. M. & Barnes, R. K. (1970). J. Org. Chem. 35, 3140–3143. CrossRef CAS Web of Science Google Scholar
Neunhoeffer, V. H. & Fruhauf, H. W. (1969). Tetrahedron Lett. 37, 3151–3154. Google Scholar
Neunhoeffer, V. H. & Fruhauf, H. W. (1970). Tetrahedron Lett. 38, 3355–3356. CrossRef Google Scholar
Nielsen, A. T., Chafin, A. P., Christian, S. L., Moore, D. W., Nadler, M. P., Nissan, R. A. & Zoli, L. (1998). Tetrahedron, 54, 11793–11812. CrossRef CAS Google Scholar
Nielsen, A. T., Nissan, R. A., Cafin, A. P., Gilardi, R. D. & Gorge, C. F. (1992). J. Org. Chem. 57, 6756–6759. CSD CrossRef CAS Web of Science Google Scholar
Nielsen, A. T., Nissan, R. A., Vanderah, D. J., Coon, C. L., Gilardi, R. D., George, C. F. & &Anderson, J. F. (1990). J. Org. Chem. 55, 1459–1466. CSD CrossRef CAS Web of Science Google Scholar
Nitravati, D. D. & Sikhibhushan, D. (1939). Proc. Natl Acad. Sci. India, 9, 93–98. Google Scholar
Nitravati, D. D. & Sikhibhushan, D. (1941). Chem. Abstr. 35, 1033. Google Scholar
Potts, K. T., Baum, J., Houghton, E., Roy, D. N. & Singh, U. P. (1974). J. Org. Chem. 39, 3619–3626. CrossRef CAS Web of Science Google Scholar
Potts, K. T. & Husain, S. (1972). J. Org. Chem. 37, 2049–2050. CrossRef CAS Web of Science Google Scholar
Reed, A. E. & Schleyer, P. V. R. (1988). Inorg. Chem. 27, 3969–3987. CrossRef CAS Web of Science Google Scholar
Senderowitz, H., Aped, P. & Fuchs, B. (1992). Tetrahedron, 48, 1131–1144. CrossRef CAS Web of Science Google Scholar
Sheldrick, G. M. (2003). SADABS. Bruker AXS, Madison, Wisconsin, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Stanforth, S. P., Tarbit, B. & Watson, M. D. (2002). Tetrahedron Lett. 43, 6015–6017. Web of Science CrossRef CAS Google Scholar
Taheri, A. & Moosavi, S. M. (2008). Acta Cryst. E64, o2316. Web of Science CSD CrossRef IUCr Journals Google Scholar
Taheri, A. & Moosavi, S. M. (2009). Acta Cryst. C65, o115–o117. Web of Science CSD CrossRef IUCr Journals Google Scholar
Watson, W. H., Nagl, A., Marchand, A. P., Vidyasagar, V. & Goodin, D. B. (1990). Acta Cryst. C46, 1127–1129. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar