Ethyl 2-(7-oxo-3,5-diphenyl-1,4-diaze­pan-2-yl)acetate

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

doi:10.1107/S160053681200757X

organic compounds

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ISSN: 2056-9890

Volume 68| Part 4| April 2012| Page o1034

doi:10.1107/S160053681200757X

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Ethyl 2-(7-oxo-3,5-diphenyl-1,4-diazepan-2-yl)acetate

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 3 February 2012; accepted 20 February 2012; online 10 March 2012)

In the title compound, C₂₁H₂₄N₂O₃, the diazepane ring adopts a chair conformation. The central diazepane ring forms dihedral angles 67.80 (7) and 72.29 (5)° with the two benzene rings. The ethoxycarbonyl group is disordered over two conformations with site-occupancy factors of 0.643 (5) and 0.357 (5). In the crystal, inversion dimers linked by pairs of N—H⋯O hydrogen bonds generate R₂²(8) loops.

Related literature

For general background to biological activities of diazepane derivatives, see: Hirokawa et al. (1998 ). For a related structure, see: Ravichandran et al. (2009 ). For puckering parameters, see: Cremer & Pople (1975 ). For graph-set notation, see: Bernstein et al. (1995 ).

Experimental

Crystal data

C₂₁H₂₄N₂O₃
M_r = 352.42
Monoclinic, P 2₁ /c
a = 10.3721 (19) Å
b = 20.666 (4) Å
c = 9.1954 (18) Å
β = 104.365 (5)°
V = 1909.4 (6) Å³
Z = 4
Mo Kα radiation
μ = 0.08 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 = 0.976, T_max = 0.980
22045 measured reflections
5000 independent reflections
3284 reflections with I > 2σ(I)
R_int = 0.029

Refinement

R[F² > 2σ(F²)] = 0.054
wR(F²) = 0.163
S = 1.03
5000 reflections
259 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.31 e Å⁻³
Δρ_min = −0.26 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O1ⁱ	0.88 (2)	1.97 (2)	2.846 (2)	174 (1)
Symmetry code: (i) -x+1, -y, -z-1.

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/S160053681200757X/pv2512sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681200757X/pv2512Isup2.hkl

Supporting information file. DOI: 10.1107/S160053681200757X/pv2512Isup3.cml

checkCIF report

Comment top

The 1,4-diazepane derivatives are of considerable importance due to their wide spectrum of biological activities (Hirokawa et al., 1998).

In the title molecule (Fig. 1), the central diazepane ring (C7–C11/N1/N2) forms dihedral angles 67.80 (7) and 72.29 (5)° with the two benzene rings (C1–C6) and (C12–C17), respectively; the dihedral angle between the two benzene rings is 55.96 (7)°. The sum of the bond angles around the N1 atom (362.9°) of the diazepane ring is in sp² hybridization, whereas the other atom N2 (335.6°) is in sp³ hybridization.

The diazepane ring adopts a chair conformation with puckering parameters (Cremer & Pople, 1975) q₂ = 0.45 (3) Å, q₃ = 0.79 (2) Å, φ₂= 36.8 (2)° and φ₃= -157.5 (2)°. The title compound exhibits structural similarities with another closely related structure (Ravichandran et al., 2009).

The crystal packing is stabilized by N–H···O intermolecular interaction (Tab. 1 and Fig. 2) which results in a dimer which may be described as an R²₂(8) motif in the graphset notation (Bernstein et al., 1995).

The ethoxy carbonyl moiety is disordered with occupancy factors of 0.643 (5):0.357 (5).

Related literature top

For general background to biological activities of diazepane derivatives, see: Hirokawa et al. (1998). For a related structure, see: Ravichandran et al. (2009). For puckering parameters, see: Cremer & Pople (1975). For graph-set notation, see: Bernstein et al. (1995).

Experimental top

Powdered ethyl 2-(4-oxo-2,6-diphenyl piperidin-3-yl)acetate hydrochloride (2 g) was dissolved in an ice cold conc. H₂SO₄ placed in a conical flask equipped with 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. The solution was then poured slowly on to crushed ice with vigorous stirring, and the pH was adjusted at approximately 8.0 using 4 N sodium hydroxide solution and extracted with chloroform. The combined organic layer was dried over sodium sulfate and evaporated to get the crude product. The crude product was purified by recrystallization from benzene and ethanol (1:1) to afford colourless prismatic crystals of the title compound suitable for X-ray crystallographic studies.

Structure description top

The 1,4-diazepane derivatives are of considerable importance due to their wide spectrum of biological activities (Hirokawa et al., 1998).

The ethoxy carbonyl moiety is disordered with occupancy factors of 0.643 (5):0.357 (5).

For general background to biological activities of diazepane derivatives, see: Hirokawa et al. (1998). For a related structure, see: Ravichandran et al. (2009). For puckering parameters, see: Cremer & Pople (1975). For graph-set notation, see: Bernstein et al. (1995).

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. The molecular structure of the title compound with the atom numbering scheme, displacement ellipsoids are drawn at 30% probability level. H–atoms are present as small spheres of arbitary radius. The minor fraction of the disordered ethoxy carbonyl moiety has been represented by broken bonds.
	Fig. 2. The crystal packing of the title compound viewed down the a axis, showing hydrogen bonds resulting in R²₂(8) graph-set ring motif. H–atoms not involved in hydrogen bonds have been excluded for clarity.

Ethyl 2-(7-oxo-3,5-diphenyl-1,4-diazepan-2-yl)acetate top

Crystal data top

C₂₁H₂₄N₂O₃	F(000) = 752
M_r = 352.42	D_x = 1.226 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 5000 reflections
a = 10.3721 (19) Å	θ = 2.0–28.8°
b = 20.666 (4) Å	µ = 0.08 mm⁻¹
c = 9.1954 (18) Å	T = 293 K
β = 104.365 (5)°	Block, colourless
V = 1909.4 (6) Å³	0.30 × 0.30 × 0.25 mm
Z = 4

Data collection top

Bruker Kappa APEXII CCD diffractometer	5000 independent reflections
Radiation source: fine-focus sealed tube	3284 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.029
ω and φ scan	θ_max = 28.8°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Bruker 2008)	h = −14→12
T_min = 0.976, T_max = 0.980	k = −27→27
22045 measured reflections	l = −12→12

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.054	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.163	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ²(F_o²) + (0.0669P)² + 0.6968P] where P = (F_o² + 2F_c²)/3
5000 reflections	(Δ/σ)_max < 0.001
259 parameters	Δρ_max = 0.31 e Å⁻³
0 restraints	Δρ_min = −0.26 e Å⁻³

Crystal data top

C₂₁H₂₄N₂O₃	V = 1909.4 (6) Å³
M_r = 352.42	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 10.3721 (19) Å	µ = 0.08 mm⁻¹
b = 20.666 (4) Å	T = 293 K
c = 9.1954 (18) Å	0.30 × 0.30 × 0.25 mm
β = 104.365 (5)°

Data collection top

Bruker Kappa APEXII CCD diffractometer	5000 independent reflections
Absorption correction: multi-scan (SADABS; Bruker 2008)	3284 reflections with I > 2σ(I)
T_min = 0.976, T_max = 0.980	R_int = 0.029
22045 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.054	0 restraints
wR(F²) = 0.163	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	Δρ_max = 0.31 e Å⁻³
5000 reflections	Δρ_min = −0.26 e Å⁻³
259 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	Occ. (<1)
O2	0.8227 (16)	0.0990 (16)	−0.341 (3)	0.085 (2)	0.643 (5)
O3	0.8931 (6)	0.0099 (2)	−0.1768 (7)	0.0628 (9)	0.643 (5)
C19	0.8114 (11)	0.0628 (7)	−0.2506 (9)	0.0465 (12)	0.643 (5)
C20	1.0024 (8)	−0.0023 (4)	−0.2420 (8)	0.125 (2)	0.643 (5)
H20A	1.0214	0.0374	−0.2889	0.150*	0.643 (5)
H20B	1.0798	−0.0120	−0.1611	0.150*	0.643 (5)
C21	0.9894 (6)	−0.0484 (3)	−0.3406 (8)	0.129 (2)	0.643 (5)
H21A	0.9694	−0.0882	−0.2971	0.193*	0.643 (5)
H21B	1.0709	−0.0531	−0.3713	0.193*	0.643 (5)
H21C	0.9184	−0.0379	−0.4262	0.193*	0.643 (5)
O2'	0.799 (3)	0.092 (3)	−0.348 (6)	0.085 (2)	0.357 (5)
O3'	0.8947 (13)	0.0289 (5)	−0.2026 (14)	0.0628 (9)	0.357 (5)
C19'	0.797 (2)	0.0621 (15)	−0.223 (2)	0.0465 (12)	0.357 (5)
C20'	0.9985 (16)	0.0226 (9)	−0.2859 (16)	0.125 (2)	0.357 (5)
H20C	0.9687	−0.0100	−0.3629	0.150*	0.357 (5)
H20D	1.0023	0.0633	−0.3372	0.150*	0.357 (5)
C21'	1.1038 (13)	0.0098 (6)	−0.2240 (14)	0.129 (2)	0.357 (5)
H21D	1.1322	0.0376	−0.1386	0.193*	0.357 (5)
H21E	1.1618	0.0152	−0.2899	0.193*	0.357 (5)
H21F	1.1067	−0.0344	−0.1911	0.193*	0.357 (5)
C1	0.0824 (2)	0.22542 (12)	−0.4319 (4)	0.0848 (9)
H1	0.0401	0.1854	−0.4424	0.102*
C2	0.0089 (3)	0.28135 (16)	−0.4741 (4)	0.1085 (12)
H2	−0.0825	0.2786	−0.5139	0.130*
C3	0.0703 (3)	0.34092 (13)	−0.4575 (3)	0.0856 (8)
H3	0.0205	0.3782	−0.4870	0.103*
C4	0.2037 (2)	0.34509 (10)	−0.3979 (2)	0.0626 (5)
H4	0.2452	0.3853	−0.3846	0.075*
C5	0.27777 (19)	0.28931 (9)	−0.3569 (2)	0.0471 (4)
H5	0.3691	0.2925	−0.3168	0.056*
C6	0.21829 (17)	0.22904 (9)	−0.37441 (19)	0.0440 (4)
C7	0.30111 (16)	0.16807 (8)	−0.33946 (18)	0.0408 (4)
H7	0.2434	0.1316	−0.3299	0.049*
C8	0.36452 (19)	0.15567 (9)	−0.47117 (18)	0.0458 (4)
H8A	0.2989	0.1650	−0.5640	0.055*
H8B	0.4376	0.1858	−0.4636	0.055*
C9	0.41619 (18)	0.08813 (9)	−0.48056 (19)	0.0449 (4)
C10	0.58017 (16)	0.10519 (8)	−0.23581 (17)	0.0376 (3)
H10	0.6102	0.1460	−0.2707	0.045*
C11	0.48458 (16)	0.12102 (8)	−0.13579 (17)	0.0373 (3)
H11	0.4271	0.0836	−0.1336	0.045*
C12	0.55952 (16)	0.13754 (8)	0.02285 (17)	0.0391 (4)
C13	0.62934 (19)	0.19509 (9)	0.0542 (2)	0.0488 (4)
H13	0.6259	0.2252	−0.0219	0.059*
C14	0.7041 (2)	0.20809 (11)	0.1978 (2)	0.0631 (6)
H14	0.7509	0.2468	0.2175	0.076*
C15	0.7099 (2)	0.16440 (12)	0.3115 (2)	0.0664 (6)
H15	0.7614	0.1732	0.4075	0.080*
C16	0.6394 (2)	0.10777 (12)	0.2830 (2)	0.0618 (6)
H16	0.6417	0.0784	0.3602	0.074*
C17	0.56480 (19)	0.09428 (10)	0.1392 (2)	0.0498 (4)
H17	0.5176	0.0556	0.1205	0.060*
C18	0.70240 (17)	0.06669 (9)	−0.15516 (18)	0.0441 (4)
H18A	0.6754	0.0232	−0.1361	0.053*
H18B	0.7415	0.0868	−0.0591	0.053*
N1	0.51362 (15)	0.06727 (7)	−0.36699 (16)	0.0446 (4)
H1A	0.547 (2)	0.0287 (11)	−0.377 (2)	0.054*
N2	0.40150 (15)	0.17695 (7)	−0.19801 (15)	0.0419 (3)
H2A	0.358 (2)	0.1892 (10)	−0.130 (2)	0.050*
O1	0.36881 (14)	0.05339 (7)	−0.58997 (15)	0.0643 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O2	0.050 (6)	0.142 (7)	0.066 (3)	0.000 (5)	0.023 (5)	0.029 (4)
O3	0.0556 (9)	0.074 (3)	0.064 (2)	0.031 (2)	0.0251 (14)	0.0246 (16)
C19	0.037 (3)	0.0839 (15)	0.023 (4)	0.004 (2)	0.0146 (19)	−0.003 (3)
C20	0.117 (3)	0.177 (7)	0.111 (5)	0.098 (4)	0.084 (4)	0.075 (4)
C21	0.136 (5)	0.134 (4)	0.149 (5)	0.038 (3)	0.098 (4)	0.013 (3)
O2'	0.050 (6)	0.142 (7)	0.066 (3)	0.000 (5)	0.023 (5)	0.029 (4)
O3'	0.0556 (9)	0.074 (3)	0.064 (2)	0.031 (2)	0.0251 (14)	0.0246 (16)
C19'	0.037 (3)	0.0839 (15)	0.023 (4)	0.004 (2)	0.0146 (19)	−0.003 (3)
C20'	0.117 (3)	0.177 (7)	0.111 (5)	0.098 (4)	0.084 (4)	0.075 (4)
C21'	0.136 (5)	0.134 (4)	0.149 (5)	0.038 (3)	0.098 (4)	0.013 (3)
C1	0.0471 (12)	0.0646 (14)	0.126 (2)	0.0075 (11)	−0.0103 (13)	−0.0144 (14)
C2	0.0544 (15)	0.093 (2)	0.151 (3)	0.0259 (14)	−0.0247 (17)	−0.018 (2)
C3	0.0797 (17)	0.0709 (16)	0.0892 (18)	0.0377 (14)	−0.0114 (14)	−0.0073 (13)
C4	0.0752 (14)	0.0485 (11)	0.0594 (12)	0.0135 (10)	0.0078 (10)	0.0012 (9)
C5	0.0473 (10)	0.0458 (9)	0.0454 (9)	0.0064 (8)	0.0065 (8)	−0.0004 (7)
C6	0.0406 (9)	0.0483 (9)	0.0396 (8)	0.0094 (7)	0.0032 (7)	−0.0037 (7)
C7	0.0396 (8)	0.0377 (8)	0.0422 (8)	0.0014 (7)	0.0047 (7)	−0.0014 (6)
C8	0.0521 (10)	0.0443 (9)	0.0354 (8)	0.0098 (8)	0.0002 (7)	−0.0033 (7)
C9	0.0450 (9)	0.0473 (9)	0.0390 (8)	0.0059 (8)	0.0038 (7)	−0.0091 (7)
C10	0.0399 (8)	0.0401 (8)	0.0303 (7)	0.0020 (7)	0.0040 (6)	−0.0026 (6)
C11	0.0390 (8)	0.0377 (8)	0.0335 (7)	0.0014 (6)	0.0059 (6)	0.0009 (6)
C12	0.0420 (9)	0.0437 (9)	0.0324 (7)	0.0070 (7)	0.0106 (6)	0.0003 (6)
C13	0.0576 (11)	0.0445 (9)	0.0417 (9)	0.0013 (8)	0.0073 (8)	−0.0023 (7)
C14	0.0690 (14)	0.0585 (12)	0.0541 (11)	0.0015 (10)	0.0008 (10)	−0.0151 (9)
C15	0.0723 (14)	0.0845 (16)	0.0354 (9)	0.0191 (12)	0.0005 (9)	−0.0094 (10)
C16	0.0681 (13)	0.0825 (15)	0.0356 (9)	0.0183 (12)	0.0142 (9)	0.0124 (9)
C17	0.0539 (11)	0.0547 (10)	0.0422 (9)	0.0037 (9)	0.0145 (8)	0.0081 (8)
C18	0.0403 (9)	0.0547 (10)	0.0340 (8)	0.0061 (8)	0.0033 (7)	−0.0011 (7)
N1	0.0464 (8)	0.0414 (8)	0.0398 (7)	0.0096 (6)	−0.0011 (6)	−0.0101 (6)
N2	0.0462 (8)	0.0440 (8)	0.0334 (7)	0.0106 (6)	0.0060 (6)	−0.0020 (6)
O1	0.0632 (9)	0.0623 (8)	0.0527 (8)	0.0199 (7)	−0.0136 (6)	−0.0251 (6)

Geometric parameters (Å, º) top

O2—C19	1.14 (3)	C6—C7	1.514 (2)
O3—C20	1.430 (8)	C7—N2	1.462 (2)
O3—C19	1.445 (15)	C7—C8	1.536 (2)
C19—C18	1.596 (7)	C7—H7	0.9800
C20—C21	1.298 (11)	C8—C9	1.505 (2)
C20—H20A	0.9700	C8—H8A	0.9700
C20—H20B	0.9700	C8—H8B	0.9700
C21—H21A	0.9600	C9—O1	1.234 (2)
C21—H21B	0.9600	C9—N1	1.332 (2)
C21—H21C	0.9600	C10—N1	1.460 (2)
O2'—C19'	1.30 (5)	C10—C18	1.524 (2)
O3'—C19'	1.20 (3)	C10—C11	1.545 (2)
O3'—C20'	1.474 (16)	C10—H10	0.9800
C19'—C18	1.294 (16)	C11—N2	1.470 (2)
C20'—C21'	1.130 (18)	C11—C12	1.512 (2)
C20'—H20C	0.9700	C11—H11	0.9800
C20'—H20D	0.9700	C12—C17	1.385 (2)
C21'—H21D	0.9600	C12—C13	1.385 (3)
C21'—H21E	0.9600	C13—C14	1.382 (3)
C21'—H21F	0.9600	C13—H13	0.9300
C1—C6	1.379 (3)	C14—C15	1.371 (3)
C1—C2	1.386 (4)	C14—H14	0.9300
C1—H1	0.9300	C15—C16	1.370 (3)
C2—C3	1.377 (4)	C15—H15	0.9300
C2—H2	0.9300	C16—C17	1.385 (3)
C3—C4	1.359 (3)	C16—H16	0.9300
C3—H3	0.9300	C17—H17	0.9300
C4—C5	1.385 (3)	C18—H18A	0.9700
C4—H4	0.9300	C18—H18B	0.9700
C5—C6	1.381 (3)	N1—H1A	0.88 (2)
C5—H5	0.9300	N2—H2A	0.89 (2)

C20—O3—C19	111.8 (4)	C7—C8—H8A	108.4
O2—C19—O3	132.9 (14)	C9—C8—H8B	108.4
O2—C19—C18	125.4 (17)	C7—C8—H8B	108.4
O3—C19—C18	101.1 (6)	H8A—C8—H8B	107.5
C21—C20—O3	117.8 (8)	O1—C9—N1	121.47 (16)
C21—C20—H20A	107.8	O1—C9—C8	120.70 (16)
O3—C20—H20A	107.8	N1—C9—C8	117.83 (15)
C21—C20—H20B	107.8	N1—C10—C18	106.70 (13)
O3—C20—H20B	107.8	N1—C10—C11	111.32 (13)
H20A—C20—H20B	107.2	C18—C10—C11	113.57 (13)
C19'—O3'—C20'	131.8 (12)	N1—C10—H10	108.4
O3'—C19'—C18	133 (2)	C18—C10—H10	108.4
O3'—C19'—O2'	102 (2)	C11—C10—H10	108.4
C18—C19'—O2'	124 (3)	N2—C11—C12	108.01 (13)
C21'—C20'—O3'	119.9 (12)	N2—C11—C10	109.60 (13)
C21'—C20'—H20C	107.4	C12—C11—C10	111.71 (13)
O3'—C20'—H20C	107.4	N2—C11—H11	109.2
C21'—C20'—H20D	107.4	C12—C11—H11	109.2
O3'—C20'—H20D	107.4	C10—C11—H11	109.2
H20C—C20'—H20D	106.9	C17—C12—C13	118.39 (16)
C20'—C21'—H21D	109.5	C17—C12—C11	120.79 (16)
C20'—C21'—H21E	109.5	C13—C12—C11	120.77 (15)
H21D—C21'—H21E	109.5	C14—C13—C12	120.41 (18)
C20'—C21'—H21F	109.5	C14—C13—H13	119.8
H21D—C21'—H21F	109.5	C12—C13—H13	119.8
H21E—C21'—H21F	109.5	C15—C14—C13	120.6 (2)
C6—C1—C2	120.1 (2)	C15—C14—H14	119.7
C6—C1—H1	120.0	C13—C14—H14	119.7
C2—C1—H1	120.0	C16—C15—C14	119.77 (19)
C3—C2—C1	120.5 (2)	C16—C15—H15	120.1
C3—C2—H2	119.8	C14—C15—H15	120.1
C1—C2—H2	119.8	C15—C16—C17	119.98 (19)
C4—C3—C2	119.9 (2)	C15—C16—H16	120.0
C4—C3—H3	120.1	C17—C16—H16	120.0
C2—C3—H3	120.1	C12—C17—C16	120.88 (19)
C3—C4—C5	119.8 (2)	C12—C17—H17	119.6
C3—C4—H4	120.1	C16—C17—H17	119.6
C5—C4—H4	120.1	C19'—C18—C10	116.5 (12)
C6—C5—C4	121.16 (18)	C10—C18—C19	112.1 (5)
C6—C5—H5	119.4	C19'—C18—H18A	107.9
C4—C5—H5	119.4	C10—C18—H18A	109.2
C1—C6—C5	118.56 (18)	C19—C18—H18A	109.2
C1—C6—C7	120.55 (18)	C19'—C18—H18B	105.9
C5—C6—C7	120.81 (15)	C10—C18—H18B	109.2
N2—C7—C6	109.00 (13)	C19—C18—H18B	109.2
N2—C7—C8	111.87 (14)	H18A—C18—H18B	107.9
C6—C7—C8	107.62 (14)	C9—N1—C10	125.81 (15)
N2—C7—H7	109.4	C9—N1—H1A	116.7 (13)
C6—C7—H7	109.4	C10—N1—H1A	117.1 (13)
C8—C7—H7	109.4	C7—N2—C11	117.82 (13)
C9—C8—C7	115.33 (15)	C7—N2—H2A	106.8 (13)
C9—C8—H8A	108.4	C11—N2—H2A	107.3 (13)

C20—O3—C19—O2	−7 (3)	C10—C11—C12—C13	70.74 (19)
C20—O3—C19—C18	−178.8 (7)	C17—C12—C13—C14	1.1 (3)
C19—O3—C20—C21	−97.5 (9)	C11—C12—C13—C14	−176.07 (17)
C20'—O3'—C19'—C18	177 (2)	C12—C13—C14—C15	−0.3 (3)
C20'—O3'—C19'—O2'	3 (4)	C13—C14—C15—C16	−0.9 (3)
C19'—O3'—C20'—C21'	149 (2)	C14—C15—C16—C17	1.2 (3)
C6—C1—C2—C3	−0.7 (5)	C13—C12—C17—C16	−0.8 (3)
C1—C2—C3—C4	−0.7 (5)	C11—C12—C17—C16	176.38 (16)
C2—C3—C4—C5	1.3 (4)	C15—C16—C17—C12	−0.3 (3)
C3—C4—C5—C6	−0.5 (3)	O3'—C19'—C18—C10	−167 (2)
C2—C1—C6—C5	1.5 (4)	O2'—C19'—C18—C10	5 (4)
C2—C1—C6—C7	−175.1 (3)	O3'—C19'—C18—C19	−151 (26)
C4—C5—C6—C1	−0.9 (3)	O2'—C19'—C18—C19	21 (22)
C4—C5—C6—C7	175.72 (17)	N1—C10—C18—C19'	69.2 (14)
C1—C6—C7—N2	−139.3 (2)	C11—C10—C18—C19'	−167.8 (14)
C5—C6—C7—N2	44.1 (2)	N1—C10—C18—C19	67.8 (6)
C1—C6—C7—C8	99.2 (2)	C11—C10—C18—C19	−169.1 (6)
C5—C6—C7—C8	−77.4 (2)	O2—C19—C18—C19'	−140 (25)
N2—C7—C8—C9	77.82 (19)	O3—C19—C18—C19'	32 (23)
C6—C7—C8—C9	−162.47 (14)	O2—C19—C18—C10	24.1 (19)
C7—C8—C9—O1	117.5 (2)	O3—C19—C18—C10	−163.3 (5)
C7—C8—C9—N1	−62.1 (2)	O1—C9—N1—C10	177.30 (18)
N1—C10—C11—N2	−81.30 (16)	C8—C9—N1—C10	−3.1 (3)
C18—C10—C11—N2	158.24 (14)	C18—C10—N1—C9	−168.04 (17)
N1—C10—C11—C12	159.02 (13)	C11—C10—N1—C9	67.5 (2)
C18—C10—C11—C12	38.57 (19)	C6—C7—N2—C11	174.23 (14)
N2—C11—C12—C17	132.98 (17)	C8—C7—N2—C11	−66.87 (19)
C10—C11—C12—C17	−106.41 (18)	C12—C11—N2—C7	−168.61 (14)
N2—C11—C12—C13	−49.9 (2)	C10—C11—N2—C7	69.48 (18)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1ⁱ	0.88 (2)	1.97 (2)	2.846 (2)	174 (1)

Symmetry code: (i) −x+1, −y, −z−1.

Experimental details

Crystal data
Chemical formula	C₂₁H₂₄N₂O₃
M_r	352.42
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	10.3721 (19), 20.666 (4), 9.1954 (18)
β (°)	104.365 (5)
V (Å³)	1909.4 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.30 × 0.30 × 0.25

Data collection
Diffractometer	Bruker Kappa APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker 2008)
T_min, T_max	0.976, 0.980
No. of measured, independent and observed [I > 2σ(I)] reflections	22045, 5000, 3284
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.679

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.054, 0.163, 1.03
No. of reflections	5000
No. of parameters	259
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.31, −0.26

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

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1ⁱ	0.88 (2)	1.97 (2)	2.846 (2)	174 (1)

Symmetry code: (i) −x+1, −y, −z−1.

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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