Ethyl 7-oxo-3,5-diphenyl-1,4-diazepane-2-carboxyl­ate

Jagadeesan, G.; Sethusankar, K.; Selvakumar, P.; Thennarasu, S.; Mandal, A.B.

doi:10.1107/S1600536812017084

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 68| Part 5| May 2012| Pages o1525-o1526

doi:10.1107/S1600536812017084

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Ethyl 7-oxo-3,5-diphenyl-1,4-diazepane-2-carboxylate

G. Jagadeesan,^a K. Sethusankar,^b ^* P. Selvakumar,^c S. Thennarasu ^c and A. B. Mandal ^c

^aDepartment of Physics, Dr MGR Educational and Research Institute, Dr MGR University, Chennai 600 095, India, ^bDepartment of Physics, RKM Vivekananda College (Autonomous), Chennai 600 004, India, and ^cOrganic Chemistry Division, Central Leather Research Institute, Adyar, Chennai 600 020, India
^*Correspondence e-mail: ksethusankar@yahoo.co.in

(Received 21 March 2012; accepted 18 April 2012; online 25 April 2012)

The title compound, C₂₀H₂₂N₂O₃, crystallizes with two independent molecules in the asymmetric unit. In both molecules, the diazepane rings adopt chair conformations. The mean planes of the diazepane rings in the two molecules form dihedral angles of 71.6 (4)/40.3 (5) and 75.9 (5)/58.6 (7)° with the neighbouring benzene rings. The carbonyl-group O atoms deviate significantly from the diazepane rings, by 0.685 (14) and 0.498 (13) Å. The ethoxycarbonyl groups show conformational difference between two molecules, as reflected in the orientation of the carbonyl O atoms and the C—C—O—C torsion angle of −179.0 (2)° in one molecule and 73.2 (2)° in the other. In one molecule there is a short N—H⋯O contact that generates an S(5) ring motif. In the crystal, N—H⋯O interactions generate R₂²(8) graph-set motifs and C—H⋯O interactions generate R₂²(10) and R₂²(14) graph-set motifs. C—H⋯π interactions also occur.

Related literature

For the biological importance of diazepanes, see: Wlodarczyk et al. (2005 ); Gopalakrishnan et al. (2007 ). For a related structure, see: Kumar et al. (2009 ). For puckering parameters, see: Cremer & Pople (1975 ). For graph-set notation, see: Bernstein et al. (1995 ).

Experimental

Crystal data

C₂₀H₂₂N₂O₃
M_r = 338.40
Triclinic, $[P \overline 1]$
a = 9.5352 (3) Å
b = 14.8809 (4) Å
c = 15.0800 (4) Å
α = 61.650 (1)°
β = 82.153 (2)°
γ = 71.344 (2)°
V = 1783.86 (9) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 293 K
0.30 × 0.30 × 0.25 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ) T_min = 0.975, T_max = 0.979
39936 measured reflections
9437 independent reflections
6221 reflections with I > 2σ(I)
R_int = 0.032

Refinement

R[F² > 2σ(F²)] = 0.052
wR(F²) = 0.181
S = 1.15
9437 reflections
465 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.30 e Å⁻³
Δρ_min = −0.29 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 and Cg2 are the centroids of the C33–C38 and C26–C31 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯O2	0.85 (2)	2.45 (2)	2.776 (2)	104 (2)
N2—H2⋯O6ⁱ	0.85 (2)	2.26 (2)	3.091 (1)	170 (2)
N4—H4A⋯O3ⁱⁱ	0.85 (2)	2.14 (2)	2.983 (1)	169 (2)
C2—H2B⋯O2ⁱⁱⁱ	0.97	2.53	3.233 (2)	130
C39—H39A⋯O5^iv	0.97	2.48	3.355 (2)	150
C9—H9⋯Cg1^v	0.93	2.89	3.735 (3)	152
C16—H16⋯Cg2^vi	0.93	2.91	3.712 (1)	146
Symmetry codes: (i) x, y, z-1; (ii) x, y, z+1; (iii) -x+1, -y, -z; (iv) -x, -y+1, -z+2; (v) -x+1, -y, -z+1; (vi) x+1, y-1, z.

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812017084/pv2527sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812017084/pv2527Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812017084/pv2527Isup3.cml

checkCIF report

Comment top

The title compound belongs to an important class of heterocyclic compounds that have widespread applications from pharmaceuticals (Wlodarczyk et al., 2005) to biology (Gopalakrishnan et al., 2007).

In the title structure there are two crystallographically independent molecules (1 and 2) in an asymmetric unit (Fig. 1 and Fig. 2, respectively). The central diazepane rings (C4/C5/C12/C19/C20/N1/N2) and (C24/C25/C32/C39/C40/N3/N4) in the molecule 1 and 2 form dihedral angles of 71.6 (4)°, 40.3 (5)° and 75.9 (5)°, 58.6 (7)° with the neighbouring benzene rings (C6–C11), (C13–C18) and (C26–C31), (C33–C38), respectively. The dihedral angles between the pairs of benzene rings (C6–C11), (C13–C18) and (C26–C31), (C33–C38) are 54.8 (7)° and 58.4 (6)°, respectively. The sum of the bond angles around the atoms N₂ (362°) and N₄ (359.8°) of the diazepane rings indicate sp² hybridization, whereas the other N atoms, [N₁ (328.6°) and N₃ (331.2°)] indicate sp³ hybridization.

The atoms O3 and O6 deviate by 0.685 (14) Å and 0.498 (13) Å from the least square plane of the diazepane rings (C4/C5/C12/C19/C20/N1/N2) and (C24/C25/C32/C39/C40/N3/N4), respectively. The ethyl carboxylate groups exhibit significant conformational difference between the two molecules as reflected by the orientation of the carbonyl O-atoms and the torsion angles of C1—C2—O1—C3 is -179.0 (2)° for molecule 1 and C21—C22—O4—C23 is 73.2 (2)° in molecule 2. The conformational differences in the two molecules of the asymmetric unit of the title compound are evident in Fig. 3.

The diazepane rings (C4/C5/C12/C19/C20/N1/N2) and (C24/C25/C32/C39/C40/N3/N4) adopt chair conformations with puckering parameters (Cremer & Pople, 1975) Q₂ = 0.382 (2) Å, Q₃ = 0.678 (2) Å, ϕ₂ = 180.4 (2)°, ϕ₃ = 359.71 (14)° and Q₂ = 0.333 (2) Å, Q₃ = 0.670 (2) Å, ϕ₂ = 182.9 (3)°, ϕ₃ = 2.44 (14)°, respectively. The title compound exhibits structural similarities with another reported structure (Kumar et al., 2009).

The crystal packing is stabilized by intramolecular N–H···O, intermolecular N–H···O, C–H···O and C–H···π interactions (Table 1). The N2–H2···O2, N2–H2···O6ⁱ, N2–H4A···O3ⁱⁱ, C2–H2B···O2ⁱⁱⁱ and C39–H39B···O5^iv hydrogen bonds generates S(5) ring motif, dimers R²₂(8), R²₂(10) and R²₂(14) graphset motifs, respectively (Bernstein, et al., 1995). The crystal packing is further stabilized by C9—H9···Cg1^v and C16—H16···Cg2^vi interactions where Cg1 is center of gravity of (C33–C38) ring and Cg2 is center of gravity of (C26–C31) ring (Fig. 4; symmetry codes are given in Table 1)

Related literature top

For the biological importance of diazepanes, see: Wlodarczyk et al. (2005); Gopalakrishnan et al. (2007). For a related structure, see: Kumar et al. (2009). For puckering parameters, see: Cremer & Pople (1975). For graph-set notation, see: Bernstein et al. (1995).

Experimental top

In a typical reaction, powdered ethyl 4-oxo-2,6-diphenyl piperidine- 3-carboxylate hydrochloride (2 g) was dissolved in an ice cold conc. H₂SO₄ (10 ml) in chloroform (5 ml) placed in a conical flask equipped with a magnetic stirrer. After the complete dissolution, the temperature of the solution was brought to 298 K. Sodium azide (600 mg) was added in portions over a period of 20 minutes with vigorous stirring. After the addition was over, the solution was poured slowly on to crushed ice with vigorous stirring, and the PH was adjusted to 8.0 using 4 N sodium hydroxide and extracted with chloroform. The combined organic layer was dried over sodium sulfate and evaporated to get the crude product which was purified by recrystallization from benzene and ethanol (1:1) to afford colourless prisms of the title compound.

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. Molecule 1 of the title compound. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. Molecule 2 of the title compound. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 3. Molecule 1(Black) and Molecule 2 (Red) of the title compound overlapping each other, H atoms are shown as spheres of arbitrary radius.
	Fig. 4. The crystal packing of the title compound viewed down the c axis, showing hydrogen bonds resulting in S(5) ring motif, dimers R²₂(8), R²₂(10) and R²₂(14) graphset motifs; H-atoms not involved in hydrogen bonds have been excluded for clarity.

Ethyl 7-oxo-3,5-diphenyl-1,4-diazepane-2-carboxylate top

Crystal data top

C₂₀H₂₂N₂O₃	Z = 4
M_r = 338.40	F(000) = 720
Triclinic, P1	D_x = 1.260 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.5352 (3) Å	Cell parameters from 9437 reflections
b = 14.8809 (4) Å	θ = 1.5–29.1°
c = 15.0800 (4) Å	µ = 0.09 mm⁻¹
α = 61.650 (1)°	T = 293 K
β = 82.153 (2)°	Block, colourless
γ = 71.344 (2)°	0.30 × 0.30 × 0.25 mm
V = 1783.86 (9) Å³

Data collection top

Bruker Kappa APEXII CCD diffractometer	9437 independent reflections
Radiation source: fine-focus sealed tube	6221 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.032
ω and ϕ scan	θ_max = 29.1°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −12→12
T_min = 0.975, T_max = 0.979	k = −20→20
39936 measured reflections	l = −20→20

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.181	H atoms treated by a mixture of independent and constrained refinement
S = 1.15	w = 1/[σ²(F_o²) + (0.1P)²] where P = (F_o² + 2F_c²)/3
9437 reflections	(Δ/σ)_max = 0.001
465 parameters	Δρ_max = 0.30 e Å⁻³
0 restraints	Δρ_min = −0.29 e Å⁻³

Crystal data top

C₂₀H₂₂N₂O₃	γ = 71.344 (2)°
M_r = 338.40	V = 1783.86 (9) Å³
Triclinic, P1	Z = 4
a = 9.5352 (3) Å	Mo Kα radiation
b = 14.8809 (4) Å	µ = 0.09 mm⁻¹
c = 15.0800 (4) Å	T = 293 K
α = 61.650 (1)°	0.30 × 0.30 × 0.25 mm
β = 82.153 (2)°

Data collection top

Bruker Kappa APEXII CCD diffractometer	9437 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2008)	6221 reflections with I > 2σ(I)
T_min = 0.975, T_max = 0.979	R_int = 0.032
39936 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.052	0 restraints
wR(F²) = 0.181	H atoms treated by a mixture of independent and constrained refinement
S = 1.15	Δρ_max = 0.30 e Å⁻³
9437 reflections	Δρ_min = −0.29 e Å⁻³
465 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.

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
O1	0.47991 (14)	−0.06939 (10)	0.20798 (8)	0.0525 (3)
O2	0.59115 (16)	0.04761 (10)	0.09211 (8)	0.0624 (4)
O3	0.49513 (15)	0.29409 (9)	0.22928 (9)	0.0569 (3)
N1	0.74551 (15)	−0.04002 (10)	0.39917 (9)	0.0407 (3)
H1	0.833 (2)	−0.0769 (15)	0.4161 (13)	0.049*
N2	0.53465 (15)	0.14336 (10)	0.21778 (9)	0.0409 (3)
H2	0.5204 (19)	0.1802 (14)	0.1547 (14)	0.049*
C1	0.3938 (4)	−0.1898 (2)	0.1853 (2)	0.1086 (10)
H1A	0.4398	−0.2441	0.2491	0.163*
H1B	0.3960	−0.2216	0.1425	0.163*
H1C	0.2930	−0.1564	0.1954	0.163*
C2	0.4739 (3)	−0.10988 (17)	0.13802 (15)	0.0668 (6)
H2A	0.5734	−0.1417	0.1220	0.080*
H2B	0.4237	−0.0519	0.0760	0.080*
C3	0.54711 (18)	0.00514 (12)	0.17573 (11)	0.0422 (4)
C4	0.56892 (16)	0.02807 (11)	0.25989 (10)	0.0365 (3)
H4	0.5006	0.0025	0.3144	0.044*
C5	0.73055 (17)	−0.03196 (11)	0.30013 (10)	0.0375 (3)
H5	0.7964	0.0074	0.2531	0.045*
C6	0.77658 (17)	−0.14315 (12)	0.31021 (11)	0.0416 (4)
C7	0.7214 (2)	−0.22217 (14)	0.38552 (13)	0.0564 (5)
H7	0.6597	−0.2083	0.4337	0.068*
C8	0.7573 (3)	−0.32131 (15)	0.38941 (15)	0.0744 (6)
H8	0.7205	−0.3741	0.4408	0.089*
C9	0.8465 (3)	−0.34294 (16)	0.31860 (17)	0.0778 (7)
H9	0.8687	−0.4097	0.3210	0.093*
C10	0.9023 (2)	−0.26639 (17)	0.24476 (16)	0.0714 (6)
H10	0.9636	−0.2811	0.1968	0.086*
C11	0.8689 (2)	−0.16731 (15)	0.24034 (13)	0.0552 (5)
H11	0.9088	−0.1159	0.1898	0.066*
C12	0.73176 (16)	0.05855 (11)	0.40290 (10)	0.0364 (3)
H12	0.7962	0.0961	0.3522	0.044*
C13	0.78172 (16)	0.03114 (12)	0.50683 (10)	0.0373 (3)
C14	0.79566 (18)	−0.06809 (13)	0.58854 (11)	0.0456 (4)
H14	0.7732	−0.1204	0.5809	0.055*
C15	0.8426 (2)	−0.09052 (15)	0.68171 (12)	0.0549 (5)
H15	0.8518	−0.1578	0.7360	0.066*
C16	0.8757 (2)	−0.01420 (16)	0.69434 (12)	0.0571 (5)
H16	0.9076	−0.0295	0.7569	0.069*
C17	0.8614 (2)	0.08413 (16)	0.61463 (13)	0.0594 (5)
H17	0.8825	0.1364	0.6231	0.071*
C18	0.8156 (2)	0.10706 (14)	0.52086 (12)	0.0516 (4)
H18	0.8075	0.1743	0.4668	0.062*
C19	0.57133 (17)	0.13165 (12)	0.38076 (10)	0.0397 (3)
H19A	0.5049	0.0881	0.4144	0.048*
H19B	0.5567	0.1803	0.4092	0.048*
C20	0.53007 (16)	0.19611 (12)	0.26997 (10)	0.0386 (3)
O4	0.31252 (12)	0.53774 (10)	1.14341 (8)	0.0493 (3)
O5	0.07097 (13)	0.55078 (10)	1.15916 (8)	0.0552 (3)
O6	0.46013 (13)	0.30348 (9)	0.99326 (8)	0.0525 (3)
N3	0.16447 (14)	0.63277 (10)	0.83956 (9)	0.0405 (3)
H3	0.1599 (19)	0.6944 (15)	0.7926 (14)	0.049*
N4	0.32947 (14)	0.43294 (10)	1.03308 (9)	0.0411 (3)
H4A	0.3836 (19)	0.3987 (14)	1.0864 (13)	0.049*
C21	0.2862 (3)	0.4781 (2)	1.32355 (16)	0.0918 (8)
H21A	0.3543	0.4117	1.3302	0.138*
H21B	0.1867	0.4742	1.3285	0.138*
H21C	0.3055	0.4917	1.3762	0.138*
C22	0.3050 (2)	0.56515 (18)	1.22498 (14)	0.0647 (5)
H22A	0.2227	0.6287	1.2121	0.078*
H22B	0.3952	0.5813	1.2267	0.078*
C23	0.18582 (17)	0.53656 (12)	1.11706 (11)	0.0395 (3)
C24	0.20218 (16)	0.52322 (11)	1.02292 (10)	0.0355 (3)
H24	0.1137	0.5073	1.0154	0.043*
C25	0.20763 (16)	0.63003 (11)	0.93032 (10)	0.0356 (3)
H25	0.3083	0.6362	0.9232	0.043*
C26	0.10097 (16)	0.72316 (11)	0.94280 (10)	0.0365 (3)
C27	0.15310 (19)	0.78986 (13)	0.96197 (11)	0.0451 (4)
H27	0.2544	0.7797	0.9635	0.054*
C28	0.0547 (2)	0.87075 (14)	0.97860 (13)	0.0557 (5)
H28	0.0902	0.9156	0.9903	0.067*
C29	−0.0951 (2)	0.88640 (14)	0.97817 (13)	0.0571 (5)
H29	−0.1602	0.9409	0.9904	0.069*
C30	−0.14881 (19)	0.82081 (14)	0.95948 (12)	0.0506 (4)
H30	−0.2501	0.8307	0.9591	0.061*
C31	−0.05059 (17)	0.74068 (12)	0.94139 (11)	0.0421 (4)
H31	−0.0869	0.6973	0.9279	0.050*
C32	0.26852 (17)	0.56031 (12)	0.80412 (10)	0.0378 (3)
H32	0.3678	0.5678	0.8009	0.045*
C33	0.21848 (18)	0.59202 (12)	0.69885 (10)	0.0417 (4)
C34	0.0713 (2)	0.63035 (13)	0.67137 (12)	0.0505 (4)
H34	−0.0005	0.6397	0.7171	0.061*
C35	0.0286 (2)	0.65530 (15)	0.57568 (14)	0.0651 (6)
H35	−0.0714	0.6814	0.5582	0.078*
C36	0.1311 (3)	0.64200 (16)	0.50766 (15)	0.0734 (6)
H36	0.1019	0.6588	0.4439	0.088*
C37	0.2760 (3)	0.6040 (2)	0.53387 (15)	0.0824 (7)
H37	0.3472	0.5945	0.4879	0.099*
C38	0.3196 (2)	0.57900 (18)	0.62977 (14)	0.0691 (6)
H38	0.4199	0.5529	0.6467	0.083*
C39	0.27301 (17)	0.44403 (11)	0.87378 (10)	0.0390 (3)
H39A	0.1720	0.4414	0.8905	0.047*
H39B	0.3131	0.4036	0.8365	0.047*
C40	0.36168 (16)	0.38832 (11)	0.97132 (11)	0.0378 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0665 (8)	0.0548 (7)	0.0509 (6)	−0.0214 (6)	−0.0054 (5)	−0.0318 (6)
O2	0.1019 (10)	0.0526 (8)	0.0345 (6)	−0.0243 (7)	−0.0070 (6)	−0.0182 (5)
O3	0.0821 (9)	0.0307 (6)	0.0520 (6)	−0.0023 (6)	−0.0264 (6)	−0.0162 (5)
N1	0.0499 (8)	0.0327 (7)	0.0367 (6)	0.0007 (6)	−0.0144 (5)	−0.0178 (5)
N2	0.0556 (8)	0.0297 (6)	0.0313 (6)	−0.0030 (6)	−0.0119 (5)	−0.0119 (5)
C1	0.164 (3)	0.109 (2)	0.107 (2)	−0.079 (2)	0.0090 (19)	−0.0683 (18)
C2	0.0872 (14)	0.0718 (13)	0.0651 (11)	−0.0244 (11)	−0.0112 (10)	−0.0460 (11)
C3	0.0520 (9)	0.0344 (8)	0.0383 (8)	−0.0021 (7)	−0.0133 (7)	−0.0182 (6)
C4	0.0466 (8)	0.0300 (7)	0.0321 (6)	−0.0068 (6)	−0.0058 (6)	−0.0148 (6)
C5	0.0448 (8)	0.0333 (8)	0.0322 (6)	−0.0049 (6)	−0.0059 (6)	−0.0158 (6)
C6	0.0503 (9)	0.0333 (8)	0.0366 (7)	0.0014 (7)	−0.0124 (6)	−0.0177 (6)
C7	0.0824 (13)	0.0420 (10)	0.0433 (8)	−0.0139 (9)	−0.0050 (8)	−0.0195 (8)
C8	0.1198 (19)	0.0369 (10)	0.0579 (11)	−0.0176 (11)	−0.0180 (12)	−0.0135 (9)
C9	0.1173 (19)	0.0424 (11)	0.0682 (13)	0.0069 (12)	−0.0304 (13)	−0.0318 (11)
C10	0.0825 (14)	0.0554 (13)	0.0681 (12)	0.0154 (11)	−0.0139 (11)	−0.0404 (11)
C11	0.0606 (11)	0.0472 (10)	0.0508 (9)	0.0030 (8)	−0.0065 (8)	−0.0270 (8)
C12	0.0437 (8)	0.0336 (8)	0.0296 (6)	−0.0073 (6)	−0.0062 (6)	−0.0133 (6)
C13	0.0389 (8)	0.0399 (8)	0.0318 (6)	−0.0070 (6)	−0.0048 (5)	−0.0169 (6)
C14	0.0535 (9)	0.0424 (9)	0.0381 (7)	−0.0110 (7)	−0.0083 (7)	−0.0159 (7)
C15	0.0673 (11)	0.0535 (11)	0.0351 (7)	−0.0152 (9)	−0.0103 (7)	−0.0121 (7)
C16	0.0647 (11)	0.0714 (12)	0.0373 (8)	−0.0169 (9)	−0.0089 (7)	−0.0259 (8)
C17	0.0796 (13)	0.0655 (12)	0.0489 (9)	−0.0297 (10)	−0.0047 (9)	−0.0319 (9)
C18	0.0729 (11)	0.0462 (10)	0.0401 (8)	−0.0219 (9)	−0.0068 (7)	−0.0185 (7)
C19	0.0473 (8)	0.0349 (8)	0.0345 (7)	−0.0031 (6)	−0.0063 (6)	−0.0178 (6)
C20	0.0433 (8)	0.0310 (8)	0.0377 (7)	−0.0040 (6)	−0.0089 (6)	−0.0147 (6)
O4	0.0457 (6)	0.0578 (7)	0.0484 (6)	−0.0068 (5)	−0.0069 (5)	−0.0307 (5)
O5	0.0463 (7)	0.0703 (9)	0.0469 (6)	−0.0138 (6)	0.0031 (5)	−0.0278 (6)
O6	0.0574 (7)	0.0369 (6)	0.0519 (6)	0.0084 (5)	−0.0180 (5)	−0.0208 (5)
N3	0.0532 (8)	0.0281 (6)	0.0330 (6)	−0.0011 (6)	−0.0095 (5)	−0.0127 (5)
N4	0.0457 (7)	0.0334 (7)	0.0376 (6)	0.0016 (5)	−0.0151 (5)	−0.0153 (5)
C21	0.0918 (17)	0.138 (2)	0.0565 (12)	−0.0486 (17)	−0.0013 (11)	−0.0430 (14)
C22	0.0572 (11)	0.0839 (15)	0.0658 (11)	−0.0121 (10)	−0.0084 (9)	−0.0473 (11)
C23	0.0407 (8)	0.0339 (8)	0.0371 (7)	−0.0056 (6)	−0.0057 (6)	−0.0125 (6)
C24	0.0371 (7)	0.0298 (7)	0.0365 (7)	−0.0056 (6)	−0.0067 (6)	−0.0135 (6)
C25	0.0392 (8)	0.0317 (7)	0.0345 (7)	−0.0078 (6)	−0.0035 (6)	−0.0147 (6)
C26	0.0438 (8)	0.0291 (7)	0.0308 (6)	−0.0078 (6)	−0.0028 (6)	−0.0102 (5)
C27	0.0544 (9)	0.0379 (9)	0.0448 (8)	−0.0139 (7)	−0.0019 (7)	−0.0195 (7)
C28	0.0743 (12)	0.0413 (10)	0.0583 (10)	−0.0139 (9)	−0.0057 (9)	−0.0283 (8)
C29	0.0729 (13)	0.0411 (10)	0.0493 (9)	0.0018 (9)	−0.0049 (8)	−0.0246 (8)
C30	0.0484 (9)	0.0466 (10)	0.0437 (8)	−0.0005 (8)	−0.0059 (7)	−0.0172 (7)
C31	0.0480 (9)	0.0337 (8)	0.0390 (7)	−0.0067 (7)	−0.0072 (6)	−0.0136 (6)
C32	0.0421 (8)	0.0361 (8)	0.0343 (7)	−0.0079 (6)	−0.0061 (6)	−0.0159 (6)
C33	0.0562 (9)	0.0323 (8)	0.0337 (7)	−0.0094 (7)	−0.0066 (6)	−0.0132 (6)
C34	0.0594 (10)	0.0439 (9)	0.0428 (8)	−0.0152 (8)	−0.0127 (7)	−0.0122 (7)
C35	0.0842 (14)	0.0527 (11)	0.0542 (10)	−0.0224 (10)	−0.0298 (10)	−0.0119 (9)
C36	0.1207 (19)	0.0562 (12)	0.0440 (9)	−0.0227 (12)	−0.0246 (11)	−0.0188 (9)
C37	0.1040 (18)	0.0973 (18)	0.0479 (10)	−0.0151 (14)	−0.0004 (11)	−0.0434 (11)
C38	0.0660 (12)	0.0847 (15)	0.0489 (10)	−0.0016 (10)	−0.0067 (9)	−0.0354 (10)
C39	0.0456 (8)	0.0322 (8)	0.0383 (7)	−0.0038 (6)	−0.0110 (6)	−0.0172 (6)
C40	0.0409 (8)	0.0299 (7)	0.0386 (7)	−0.0064 (6)	−0.0070 (6)	−0.0131 (6)

Geometric parameters (Å, º) top

O1—C3	1.317 (2)	O4—C23	1.3300 (18)
O1—C2	1.4566 (19)	O4—C22	1.456 (2)
O2—C3	1.1976 (19)	O5—C23	1.1986 (19)
O3—C20	1.2283 (18)	O6—C40	1.2306 (17)
N1—C12	1.4578 (19)	N3—C25	1.4609 (17)
N1—C5	1.4637 (16)	N3—C32	1.467 (2)
N1—H1	0.83 (2)	N3—H3	0.84 (2)
N2—C20	1.3389 (19)	N4—C40	1.3347 (19)
N2—C4	1.4550 (18)	N4—C24	1.4538 (18)
N2—H2	0.85 (2)	N4—H4A	0.85 (2)
C1—C2	1.461 (3)	C21—C22	1.472 (3)
C1—H1A	0.9600	C21—H21A	0.9600
C1—H1B	0.9600	C21—H21B	0.9600
C1—H1C	0.9600	C21—H21C	0.9600
C2—H2A	0.9700	C22—H22A	0.9700
C2—H2B	0.9700	C22—H22B	0.9700
C3—C4	1.5163 (19)	C23—C24	1.506 (2)
C4—C5	1.5496 (19)	C24—C25	1.551 (2)
C4—H4	0.9800	C24—H24	0.9800
C5—C6	1.506 (2)	C25—C26	1.511 (2)
C5—H5	0.9800	C25—H25	0.9800
C6—C7	1.384 (2)	C26—C31	1.385 (2)
C6—C11	1.385 (2)	C26—C27	1.394 (2)
C7—C8	1.377 (3)	C27—C28	1.376 (2)
C7—H7	0.9300	C27—H27	0.9300
C8—C9	1.368 (3)	C28—C29	1.372 (3)
C8—H8	0.9300	C28—H28	0.9300
C9—C10	1.357 (3)	C29—C30	1.384 (3)
C9—H9	0.9300	C29—H29	0.9300
C10—C11	1.375 (3)	C30—C31	1.378 (2)
C10—H10	0.9300	C30—H30	0.9300
C11—H11	0.9300	C31—H31	0.9300
C12—C13	1.5239 (17)	C32—C33	1.5236 (18)
C12—C19	1.538 (2)	C32—C39	1.529 (2)
C12—H12	0.9800	C32—H32	0.9800
C13—C18	1.380 (2)	C33—C38	1.360 (3)
C13—C14	1.381 (2)	C33—C34	1.375 (2)
C14—C15	1.3845 (19)	C34—C35	1.393 (2)
C14—H14	0.9300	C34—H34	0.9300
C15—C16	1.370 (3)	C35—C36	1.357 (3)
C15—H15	0.9300	C35—H35	0.9300
C16—C17	1.361 (3)	C36—C37	1.350 (3)
C16—H16	0.9300	C36—H36	0.9300
C17—C18	1.386 (2)	C37—C38	1.399 (2)
C17—H17	0.9300	C37—H37	0.9300
C18—H18	0.9300	C38—H38	0.9300
C19—C20	1.5107 (18)	C39—C40	1.5162 (17)
C19—H19A	0.9700	C39—H39A	0.9700
C19—H19B	0.9700	C39—H39B	0.9700

C3—O1—C2	115.98 (14)	C23—O4—C22	116.14 (13)
C12—N1—C5	117.12 (11)	C25—N3—C32	116.90 (11)
C12—N1—H1	105.4 (12)	C25—N3—H3	106.1 (12)
C5—N1—H1	103.2 (12)	C32—N3—H3	104.6 (12)
C20—N2—C4	125.40 (12)	C40—N4—C24	125.62 (11)
C20—N2—H2	116.9 (12)	C40—N4—H4A	114.4 (12)
C4—N2—H2	117.7 (12)	C24—N4—H4A	119.4 (12)
C2—C1—H1A	109.5	C22—C21—H21A	109.5
C2—C1—H1B	109.5	C22—C21—H21B	109.5
H1A—C1—H1B	109.5	H21A—C21—H21B	109.5
C2—C1—H1C	109.5	C22—C21—H21C	109.5
H1A—C1—H1C	109.5	H21A—C21—H21C	109.5
H1B—C1—H1C	109.5	H21B—C21—H21C	109.5
O1—C2—C1	108.45 (18)	O4—C22—C21	112.10 (18)
O1—C2—H2A	110.0	O4—C22—H22A	109.2
C1—C2—H2A	110.0	C21—C22—H22A	109.2
O1—C2—H2B	110.0	O4—C22—H22B	109.2
C1—C2—H2B	110.0	C21—C22—H22B	109.2
H2A—C2—H2B	108.4	H22A—C22—H22B	107.9
O2—C3—O1	125.40 (14)	O5—C23—O4	124.41 (14)
O2—C3—C4	123.26 (15)	O5—C23—C24	124.07 (13)
O1—C3—C4	111.28 (13)	O4—C23—C24	111.37 (13)
N2—C4—C3	107.04 (11)	N4—C24—C23	110.14 (11)
N2—C4—C5	112.95 (12)	N4—C24—C25	113.96 (12)
C3—C4—C5	108.33 (12)	C23—C24—C25	109.29 (12)
N2—C4—H4	109.5	N4—C24—H24	107.7
C3—C4—H4	109.5	C23—C24—H24	107.7
C5—C4—H4	109.5	C25—C24—H24	107.7
N1—C5—C6	108.35 (11)	N3—C25—C26	108.37 (11)
N1—C5—C4	110.42 (12)	N3—C25—C24	109.46 (11)
C6—C5—C4	110.90 (12)	C26—C25—C24	110.26 (12)
N1—C5—H5	109.0	N3—C25—H25	109.6
C6—C5—H5	109.0	C26—C25—H25	109.6
C4—C5—H5	109.0	C24—C25—H25	109.6
C7—C6—C11	118.05 (16)	C31—C26—C27	118.31 (14)
C7—C6—C5	121.24 (15)	C31—C26—C25	120.95 (13)
C11—C6—C5	120.60 (15)	C27—C26—C25	120.63 (13)
C8—C7—C6	120.29 (19)	C28—C27—C26	119.95 (16)
C8—C7—H7	119.9	C28—C27—H27	120.0
C6—C7—H7	119.9	C26—C27—H27	120.0
C9—C8—C7	120.7 (2)	C29—C28—C27	121.13 (17)
C9—C8—H8	119.6	C29—C28—H28	119.4
C7—C8—H8	119.6	C27—C28—H28	119.4
C10—C9—C8	119.57 (19)	C28—C29—C30	119.71 (16)
C10—C9—H9	120.2	C28—C29—H29	120.1
C8—C9—H9	120.2	C30—C29—H29	120.1
C9—C10—C11	120.5 (2)	C31—C30—C29	119.30 (16)
C9—C10—H10	119.8	C31—C30—H30	120.4
C11—C10—H10	119.8	C29—C30—H30	120.4
C10—C11—C6	120.86 (19)	C30—C31—C26	121.60 (15)
C10—C11—H11	119.6	C30—C31—H31	119.2
C6—C11—H11	119.6	C26—C31—H31	119.2
N1—C12—C13	109.03 (11)	N3—C32—C33	108.08 (11)
N1—C12—C19	111.03 (12)	N3—C32—C39	111.54 (13)
C13—C12—C19	110.09 (11)	C33—C32—C39	109.35 (11)
N1—C12—H12	108.9	N3—C32—H32	109.3
C13—C12—H12	108.9	C33—C32—H32	109.3
C19—C12—H12	108.9	C39—C32—H32	109.3
C18—C13—C14	118.12 (13)	C38—C33—C34	117.67 (14)
C18—C13—C12	119.56 (13)	C38—C33—C32	120.40 (14)
C14—C13—C12	122.33 (13)	C34—C33—C32	121.88 (14)
C13—C14—C15	120.77 (15)	C33—C34—C35	120.62 (18)
C13—C14—H14	119.6	C33—C34—H34	119.7
C15—C14—H14	119.6	C35—C34—H34	119.7
C16—C15—C14	120.35 (16)	C36—C35—C34	120.89 (19)
C16—C15—H15	119.8	C36—C35—H35	119.6
C14—C15—H15	119.8	C34—C35—H35	119.6
C17—C16—C15	119.46 (15)	C37—C36—C35	119.06 (17)
C17—C16—H16	120.3	C37—C36—H36	120.5
C15—C16—H16	120.3	C35—C36—H36	120.5
C16—C17—C18	120.59 (16)	C36—C37—C38	120.3 (2)
C16—C17—H17	119.7	C36—C37—H37	119.8
C18—C17—H17	119.7	C38—C37—H37	119.8
C13—C18—C17	120.70 (15)	C33—C38—C37	121.42 (19)
C13—C18—H18	119.7	C33—C38—H38	119.3
C17—C18—H18	119.7	C37—C38—H38	119.3
C20—C19—C12	114.10 (12)	C40—C39—C32	116.77 (12)
C20—C19—H19A	108.7	C40—C39—H39A	108.1
C12—C19—H19A	108.7	C32—C39—H39A	108.1
C20—C19—H19B	108.7	C40—C39—H39B	108.1
C12—C19—H19B	108.7	C32—C39—H39B	108.1
H19A—C19—H19B	107.6	H39A—C39—H39B	107.3
O3—C20—N2	121.37 (13)	O6—C40—N4	120.90 (12)
O3—C20—C19	120.51 (13)	O6—C40—C39	120.65 (13)
N2—C20—C19	118.12 (13)	N4—C40—C39	118.44 (13)

Hydrogen-bond geometry (Å, º) top

Cg1 and Cg2 are the centroids of the C33–C38 and C26–C31 rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O2	0.85 (2)	2.45 (2)	2.776 (2)	104
N2—H2···O6ⁱ	0.85 (2)	2.26 (2)	3.091 (1)	170
N4—H4A···O3ⁱⁱ	0.85 (2)	2.14 (2)	2.983 (1)	169
C2—H2B···O2ⁱⁱⁱ	0.97	2.53	3.233 (2)	130
C39—H39A···O5^iv	0.97	2.48	3.355 (2)	150
C9—H9···Cg1^v	0.93	2.89	3.735 (3)	152
C16—H16···Cg2^vi	0.93	2.91	3.712 (1)	146

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

Experimental details

Crystal data
Chemical formula	C₂₀H₂₂N₂O₃
M_r	338.40
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	9.5352 (3), 14.8809 (4), 15.0800 (4)
α, β, γ (°)	61.650 (1), 82.153 (2), 71.344 (2)
V (Å³)	1783.86 (9)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.30 × 0.30 × 0.25

Data collection
Diffractometer	Bruker Kappa APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2008)
T_min, T_max	0.975, 0.979
No. of measured, independent and observed [I > 2σ(I)] reflections	39936, 9437, 6221
R_int	0.032
(sin θ/λ)_max (Å⁻¹)	0.684

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.052, 0.181, 1.15
No. of reflections	9437
No. of parameters	465
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.30, −0.29

Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

Cg1 and Cg2 are the centroids of the C33–C38 and C26–C31 rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O2	0.85 (2)	2.45 (2)	2.776 (2)	104
N2—H2···O6ⁱ	0.85 (2)	2.26 (2)	3.091 (1)	170
N4—H4A···O3ⁱⁱ	0.85 (2)	2.14 (2)	2.983 (1)	169
C2—H2B···O2ⁱⁱⁱ	0.97	2.53	3.233 (2)	130
C39—H39A···O5^iv	0.97	2.48	3.355 (2)	150
C9—H9···Cg1^v	0.93	2.89	3.735 (3)	152
C16—H16···Cg2^vi	0.93	2.91	3.712 (1)	146

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

Acknowledgements

GJ and KS thank Dr Babu Varghese, SAIF, IIT, Chennai, India, for the X-ray intensity data collection and Dr V. Murugan, Head of the Department of Physics, RKM Vivekananda College, Chennai, India, for providing facilities in the department to carry out this work.

References

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Volume 68| Part 5| May 2012| Pages o1525-o1526

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