2-[2-(3-Chloro­phen­yl)hydrazinyl­idene]-1,3-diphenyl­propane-1,3-dione

Bustos, C.; Alvarez-Thon, L.; Cárcamo, J.-G.; Ibañez, A.; Sánchez, C.

doi:10.1107/S1600536811017909

organic compounds

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ISSN: 2056-9890

Volume 67| Part 6| June 2011| Pages o1450-o1451

doi:10.1107/S1600536811017909

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2-[2-(3-Chlorophenyl)hydrazinylidene]-1,3-diphenylpropane-1,3-dione

Carlos Bustos,^a Luis Alvarez-Thon,^b ^* Juan-Guillermo Cárcamo,^c Andrés Ibañez ^d and Christian Sánchez ^a

^aInstituto de Ciencias Químicas, Universidad Austral de Chile, Avda. Los Robles s/n, Campus Isla Teja, Casilla 567, Valdivia, Chile, ^bDepartamento de Ciencias Físicas, Universidad Andres Bello, Avda. República 220, Santiago de Chile, Chile, ^cInstituto de Ciencias Moleculares y Microbiología, Universidad Austral de Chile, Avda. Los Robles s/n, Campus Isla Teja, Casilla 567, Valdivia, Chile, and ^dLaboratorio de Cristalografía, Difracción de Rayos-X, Departamento de Física, Facultad de Ciencias Físicas y Matemáticas, Universidad de Chile, Av. Blanco Encalada 2008, Santiago, Chile
^*Correspondence e-mail: lalvarez@unab.cl

(Received 4 May 2011; accepted 11 May 2011; online 20 May 2011)

The molecular structure of the title compound, C₂₁H₁₅ClN₂O₂, features one strong intramolecular N—H⋯O resonance-assisted hydrogen bond (RAHB). In the crystal, molecules form inversion-related dimers via pairs of weak intermolecular N—H⋯O contacts. These dimers are further stabilized via three weak C—H⋯O contacts, developing the three-dimensional structure.

Related literature

For resonance-assisted hydrogen bonds, see: Bertolasi et al. (1993 , 1994a ,b ); Inabe (1991 ); Krygowski et al. (1997 ); Olivieri et al. (1989 ). For details of the synthesis, see: Bustos et al. (2007 , 2009 ); Yao (1964 ).

Experimental

Crystal data

C₂₁H₁₅ClN₂O₂
M_r = 362.80
Monoclinic, P 2₁ /n
a = 10.2970 (9) Å
b = 10.3526 (9) Å
c = 16.8926 (15) Å
β = 102.131 (1)°
V = 1760.6 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.24 mm⁻¹
T = 297 K
0.60 × 0.31 × 0.23 mm

Data collection

Bruker D8 Discover with SMART CCD area-detector diffractometer
11123 measured reflections
3573 independent reflections
2657 reflections with I > 2σ(I)
R_int = 0.042

Refinement

R[F² > 2σ(F²)] = 0.042
wR(F²) = 0.119
S = 0.98
3573 reflections
239 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.39 e Å⁻³
Δρ_min = −0.16 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O2	0.922 (17)	1.930 (18)	2.6205 (18)	130.1 (14)
C12—H12⋯N2	0.93	2.55	3.016 (2)	111
N1—H1⋯O1ⁱ	0.922 (17)	2.628 (17)	3.344 (3)	135.0 (13)
C6—H6⋯O1ⁱ	0.93	2.63	3.390 (2)	140
Symmetry code: (i) -x, -y, -z+2.

Data collection: SMART (Bruker, 2001 ); cell refinement: SAINT (Bruker, 2000 ); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL/PC (Sheldrick, 2008); software used to prepare material for publication: PLATON (Spek, 2009 ) and Mercury (Macrae et al., 2006 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811017909/pk2324sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811017909/pk2324Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811017909/pk2324Isup3.cml

checkCIF report

Comment top

In recent years, much attention has been devoted to structural studies on heterodienic systems forming strong intramolecular hydrogen bonds, N—H···O, assisted by resonance (RAHB) which, inter alia, could have potential technological applications as bistate molecular switches (Olivieri et al., 1989; Inabe, 1991; Bertolasi et al., 1993; Bertolasi et al., 1994a; Bertolasi et al., 1994b; Krygowski et al., 1997; Bustos et al., 2007). On the other hand, it is well known that the phenyl diazonium salts are capable of coupling with a series of β-diketones that may yield the N—H···O moiety (Yao, 1964; Bustos et al., 2007; Bustos et al., 2009). In this report we present the crystal and molecular structure of the title compound 2-(2-(3-chlorophenyl)hydrazono)-1,3-diphenylpropane-1,3-dione, of formula 3-Cl—C₆H₄—NHN=C(COC₆H₅)₂.

The molecular structure of the title compound exhibits one weak intramolecular hydrogen bond (C12–H12···N2) and one strong intramolecular hydrogen bond (N1–H1···O2) assisted by resonance (RAHB), see Fig. 1 and Table 2. The molecules form an inversion dimer via a pair of weak intermolecular contacts N1–H1···O1^# and C6–H6···O1^# hydrogen bonds [Symmetry code: (#) -x, -y, 2 - z], (see Fig. 2). These dimers are further stabilized via three weak contacts of the type shown in Fig. 3, to develop the three-dimensional structure.

Related literature top

For resonance-assisted hydrogen bonds, see: Bertolasi et al. (1993, 1994a,b); Inabe (1991); Krygowski et al. (1997); Olivieri et al. (1989). For details of the synthesis, see: Bustos et al. (2007, 2009); Yao (1964).

Experimental top

Chemicals: 1,3-diphenylpropane-1,3-dione, 3-chloroaniline and sodium nitrite were procured from Sigma-Aldrich, and sodium hydroxide, sodium acetate, solvents and hydrochloric acid from Merck. Chemicals were used without further purification.

Procedure: In a 500 ml beaker were dissolved 2.24 g (0.01 mole) of 1,3-diphenylpropane-1,3-dione in 100 ml of an ethanol solution containing 0.4 g (0.01 mole) of sodium hydroxide and 3.65 g of sodium acetate. The resulting β-diketonate solution was kept at -5°C and diluted with water to around 220 mL with vigorous stirring. In another beaker, a diazonium ion solution was prepared adding 1.06 ml (0.01 mole) of 3-chloroaniline (99%, density 1.215 g/ml) in 8 ml of hydrochloric acid (5 mol/L), cooling at -5 °C, and adding a saturated aqueous solution containing 0.69 g (0.01 mole) of sodium nitrite. This solution was then added dropwise, with vigorous stirring, into the β-diketonate solution. During the addition, a yellow solid precipitate was observed. This precipitate was filtered by suction and washed with an abundant quantity of water. Single crystals suitable for X-ray studies were obtained by recrystallization from a saturated solution of the compound in a 3:1 ethanol/acetone mixture.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL/PC (Sheldrick, 2008); software used to prepare material for publication: PLATON (Spek, 2009) and Mercury (Macrae et al., 2006).

Figures top

	Fig. 1. View of the title compound showing displacement ellipsoids for non-H atoms at the 50% probability level. The strong intramolecular hydrogen bond (N1-H1···O2) assisted by resonance (RAHB) is depicted by a dashed line.
	Fig. 2. View of the formation of an inversion dimer via two weak intermolecular contacts (dashed lines). [Symmetry code: (#) -x, -y, 2 - z].
	Fig. 3. The dimers are connected via three weak contacts (dashed lines) to develop the three-dimensional structure.

2-[2-(3-Chlorophenyl)hydrazinylidene]-1,3-diphenylpropane-1,3-dione top

Crystal data top

C₂₁H₁₅ClN₂O₂	F(000) = 752
M_r = 362.80	D_x = 1.369 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 999 reflections
a = 10.2970 (9) Å	θ = 2.3–26.3°
b = 10.3526 (9) Å	µ = 0.24 mm⁻¹
c = 16.8926 (15) Å	T = 297 K
β = 102.131 (1)°	Polyhedron, yellow
V = 1760.6 (3) Å³	0.60 × 0.31 × 0.23 mm
Z = 4

Data collection top

Bruker D8 Discover with SMART CCD area-detector diffractometer	2657 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.042
Graphite monochromator	θ_max = 26.3°, θ_min = 2.3°
ϕ and ω scans	h = −12→12
11123 measured reflections	k = −12→12
3573 independent 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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.119	H atoms treated by a mixture of independent and constrained refinement
S = 0.98	w = 1/[σ²(F_o²) + (0.071P)²] where P = (F_o² + 2F_c²)/3
3573 reflections	(Δ/σ)_max = 0.001
239 parameters	Δρ_max = 0.39 e Å⁻³
0 restraints	Δρ_min = −0.16 e Å⁻³

Crystal data top

C₂₁H₁₅ClN₂O₂	V = 1760.6 (3) Å³
M_r = 362.80	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 10.2970 (9) Å	µ = 0.24 mm⁻¹
b = 10.3526 (9) Å	T = 297 K
c = 16.8926 (15) Å	0.60 × 0.31 × 0.23 mm
β = 102.131 (1)°

Data collection top

Bruker D8 Discover with SMART CCD area-detector diffractometer	2657 reflections with I > 2σ(I)
11123 measured reflections	R_int = 0.042
3573 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	0 restraints
wR(F²) = 0.119	H atoms treated by a mixture of independent and constrained refinement
S = 0.98	Δρ_max = 0.39 e Å⁻³
3573 reflections	Δρ_min = −0.16 e Å⁻³
239 parameters

Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement on F² for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The observed criterion of F² > σ(F²) is used only for calculating -R-factor-obs 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
Cl1	0.69570 (5)	0.13603 (5)	1.18232 (3)	0.0776 (2)
O1	−0.05070 (10)	0.25054 (10)	0.91373 (7)	0.0598 (4)
O2	0.03738 (11)	−0.12050 (10)	0.92207 (7)	0.0630 (4)
N1	0.25273 (13)	−0.04080 (12)	1.02183 (8)	0.0510 (4)
N2	0.22035 (12)	0.07588 (11)	0.99272 (7)	0.0463 (4)
C1	0.36632 (15)	−0.05568 (14)	1.08450 (9)	0.0459 (5)
C2	0.46505 (14)	0.03750 (14)	1.09893 (9)	0.0477 (5)
C3	0.57101 (15)	0.01951 (15)	1.16316 (9)	0.0516 (5)
C4	0.58144 (17)	−0.08754 (18)	1.21159 (10)	0.0636 (6)
C5	0.48391 (18)	−0.18002 (18)	1.19538 (11)	0.0696 (7)
C6	0.37597 (17)	−0.16608 (16)	1.13176 (11)	0.0616 (6)
C7	0.16409 (16)	0.33878 (14)	0.92641 (8)	0.0466 (5)
C8	0.11665 (19)	0.46296 (15)	0.93282 (9)	0.0594 (6)
C9	0.1988 (2)	0.56842 (17)	0.93377 (11)	0.0743 (8)
C10	0.3278 (2)	0.55061 (18)	0.92704 (13)	0.0810 (8)
C11	0.3759 (2)	0.42915 (18)	0.91881 (12)	0.0752 (7)
C12	0.29480 (17)	0.32324 (16)	0.91906 (10)	0.0584 (6)
C13	−0.05962 (15)	0.01258 (14)	0.81261 (9)	0.0489 (5)
C14	−0.17413 (16)	−0.06169 (16)	0.79092 (10)	0.0580 (6)
C15	−0.25909 (19)	−0.0430 (2)	0.71700 (12)	0.0768 (7)
C16	−0.2295 (2)	0.0471 (2)	0.66386 (12)	0.0840 (8)
C17	−0.1161 (2)	0.1191 (2)	0.68373 (11)	0.0787 (8)
C18	−0.02983 (18)	0.10304 (17)	0.75838 (10)	0.0632 (6)
C19	0.06905 (15)	0.23015 (14)	0.92398 (8)	0.0466 (5)
C20	0.11471 (14)	0.09339 (14)	0.93512 (9)	0.0457 (5)
C21	0.02976 (14)	−0.01183 (15)	0.89255 (9)	0.0482 (5)
H1	0.1934 (18)	−0.1079 (15)	1.0080 (10)	0.062 (5)*
H2	0.46010	0.11030	1.06620	0.0570*
H4	0.65340	−0.09750	1.25480	0.0760*
H5	0.49060	−0.25330	1.22780	0.0840*
H6	0.31090	−0.22970	1.12080	0.0740*
H8	0.02860	0.47520	0.93650	0.0710*
H9	0.16670	0.65130	0.93900	0.0890*
H10	0.38330	0.62170	0.92810	0.0970*
H11	0.46310	0.41810	0.91310	0.0900*
H12	0.32800	0.24070	0.91430	0.0700*
H14	−0.19350	−0.12410	0.82630	0.0700*
H15	−0.33650	−0.09150	0.70320	0.0920*
H16	−0.28700	0.05920	0.61400	0.1010*
H17	−0.09640	0.17930	0.64710	0.0940*
H18	0.04710	0.15240	0.77180	0.0760*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0598 (3)	0.0744 (3)	0.0886 (4)	−0.0128 (2)	−0.0070 (3)	−0.0046 (2)
O1	0.0440 (7)	0.0589 (7)	0.0723 (7)	0.0061 (5)	0.0030 (5)	0.0073 (5)
O2	0.0609 (7)	0.0489 (7)	0.0717 (8)	−0.0080 (5)	−0.0030 (6)	0.0076 (6)
N1	0.0465 (7)	0.0428 (7)	0.0574 (8)	0.0001 (6)	−0.0032 (6)	0.0035 (6)
N2	0.0444 (7)	0.0431 (7)	0.0488 (7)	0.0025 (5)	0.0041 (6)	0.0035 (5)
C1	0.0420 (8)	0.0442 (8)	0.0497 (8)	0.0059 (6)	0.0057 (6)	0.0021 (6)
C2	0.0480 (9)	0.0454 (8)	0.0476 (8)	0.0038 (7)	0.0055 (7)	0.0041 (7)
C3	0.0466 (9)	0.0535 (9)	0.0522 (9)	0.0017 (7)	0.0048 (7)	−0.0048 (7)
C4	0.0539 (10)	0.0756 (12)	0.0559 (10)	0.0080 (9)	−0.0007 (8)	0.0142 (9)
C5	0.0577 (11)	0.0677 (11)	0.0798 (12)	0.0069 (9)	0.0060 (9)	0.0309 (10)
C6	0.0514 (9)	0.0528 (9)	0.0769 (12)	0.0008 (8)	0.0049 (8)	0.0174 (8)
C7	0.0525 (9)	0.0449 (8)	0.0385 (8)	0.0011 (7)	0.0005 (6)	0.0010 (6)
C8	0.0708 (11)	0.0498 (9)	0.0534 (9)	0.0075 (8)	0.0036 (8)	−0.0013 (7)
C9	0.1002 (17)	0.0449 (10)	0.0701 (12)	0.0008 (10)	0.0002 (11)	−0.0019 (8)
C10	0.0874 (16)	0.0552 (12)	0.0907 (15)	−0.0228 (10)	−0.0031 (12)	0.0091 (10)
C11	0.0633 (12)	0.0671 (12)	0.0928 (14)	−0.0129 (9)	0.0112 (10)	0.0116 (10)
C12	0.0560 (10)	0.0485 (9)	0.0690 (11)	−0.0021 (8)	0.0095 (8)	0.0032 (8)
C13	0.0444 (8)	0.0509 (9)	0.0495 (9)	0.0012 (7)	0.0059 (7)	−0.0072 (7)
C14	0.0531 (10)	0.0561 (10)	0.0618 (10)	−0.0040 (7)	0.0051 (8)	−0.0151 (8)
C15	0.0591 (11)	0.0872 (14)	0.0755 (13)	−0.0045 (10)	−0.0051 (10)	−0.0279 (12)
C16	0.0810 (15)	0.1068 (17)	0.0526 (11)	0.0086 (13)	−0.0125 (10)	−0.0128 (11)
C17	0.0879 (15)	0.0923 (15)	0.0525 (11)	0.0040 (12)	0.0071 (10)	0.0058 (10)
C18	0.0635 (11)	0.0705 (11)	0.0536 (10)	−0.0049 (9)	0.0079 (8)	0.0025 (8)
C19	0.0468 (9)	0.0509 (9)	0.0390 (8)	0.0024 (7)	0.0020 (6)	0.0035 (6)
C20	0.0424 (8)	0.0456 (8)	0.0464 (8)	−0.0002 (6)	0.0029 (6)	0.0033 (6)
C21	0.0429 (9)	0.0468 (9)	0.0540 (9)	−0.0015 (7)	0.0081 (7)	0.0001 (7)

Geometric parameters (Å, º) top

Cl1—C3	1.7418 (17)	C13—C21	1.487 (2)
O1—C19	1.2269 (19)	C14—C15	1.380 (3)
O2—C21	1.2264 (19)	C15—C16	1.373 (3)
N1—N2	1.3203 (17)	C16—C17	1.366 (3)
N1—C1	1.411 (2)	C17—C18	1.392 (3)
N2—C20	1.3107 (19)	C19—C20	1.491 (2)
N1—H1	0.922 (17)	C20—C21	1.485 (2)
C1—C6	1.386 (2)	C2—H2	0.9300
C1—C2	1.385 (2)	C4—H4	0.9300
C2—C3	1.380 (2)	C5—H5	0.9300
C3—C4	1.368 (2)	C6—H6	0.9300
C4—C5	1.373 (3)	C8—H8	0.9300
C5—C6	1.382 (3)	C9—H9	0.9300
C7—C8	1.388 (2)	C10—H10	0.9300
C7—C19	1.486 (2)	C11—H11	0.9300
C7—C12	1.387 (2)	C12—H12	0.9300
C8—C9	1.379 (3)	C14—H14	0.9300
C9—C10	1.369 (3)	C15—H15	0.9300
C10—C11	1.369 (3)	C16—H16	0.9300
C11—C12	1.379 (3)	C17—H17	0.9300
C13—C14	1.391 (2)	C18—H18	0.9300
C13—C18	1.389 (2)

Cl1···C21ⁱ	3.5703 (16)	C21···Cl1ⁱ	3.5703 (16)
Cl1···H10ⁱⁱ	3.1300	C4···H12ⁱ	2.9600
O1···C13	2.9882 (18)	C5···H12ⁱ	3.0100
O1···C18	3.083 (2)	C8···H16^vii	3.0200
O1···O2ⁱⁱⁱ	3.0602 (16)	C8···H8^viii	2.9800
O1···C15^iv	3.386 (2)	C9···H4^ix	2.9800
O1···C6ⁱⁱⁱ	3.390 (2)	C10···H11ⁱⁱ	3.1000
O2···O1ⁱⁱⁱ	3.0602 (16)	C14···H5^x	2.9100
O2···N1	2.6205 (18)	C15···H6^x	3.0300
O2···N2	2.8570 (16)	C19···H18	2.6600
O2···C19ⁱⁱⁱ	3.2328 (18)	C20···H12	2.7600
O2···C20ⁱⁱⁱ	3.1526 (19)	C20···H18	2.7700
O1···H15^iv	2.6400	C21···H1	2.500 (17)
O1···H1ⁱⁱⁱ	2.628 (17)	H1···O2	1.930 (18)
O1···H6ⁱⁱⁱ	2.6300	H1···C21	2.500 (17)
O1···H8	2.4700	H1···H6	2.3900
O2···H1	1.930 (18)	H1···O1ⁱⁱⁱ	2.628 (17)
O2···H9^v	2.7000	H2···N2	2.5400
O2···H14	2.5800	H4···C9^vii	2.9800
N1···O2	2.6205 (18)	H5···C14^xi	2.9100
N2···O2	2.8570 (16)	H6···H1	2.3900
N2···C12	3.016 (2)	H6···O1ⁱⁱⁱ	2.6300
N2···H2	2.5400	H6···C15^xi	3.0300
N2···H12	2.5500	H8···O1	2.4700
C1···C14ⁱⁱⁱ	3.402 (2)	H8···C8^viii	2.9800
C6···C14ⁱⁱⁱ	3.567 (2)	H8···H8^viii	2.4000
C6···O1ⁱⁱⁱ	3.390 (2)	H9···O2^xii	2.7000
C10···C11ⁱⁱ	3.577 (3)	H10···Cl1ⁱⁱ	3.1300
C11···C10ⁱⁱ	3.577 (3)	H11···C10ⁱⁱ	3.1000
C12···N2	3.016 (2)	H12···N2	2.5500
C13···O1	2.9882 (18)	H12···C20	2.7600
C14···C1ⁱⁱⁱ	3.402 (2)	H12···C4ⁱ	2.9600
C14···C6ⁱⁱⁱ	3.567 (2)	H12···C5ⁱ	3.0100
C15···O1^vi	3.386 (2)	H14···O2	2.5800
C18···C19	3.065 (2)	H15···O1^vi	2.6400
C18···O1	3.083 (2)	H16···C8^ix	3.0200
C19···O2ⁱⁱⁱ	3.2328 (18)	H18···C19	2.6600
C19···C18	3.065 (2)	H18···C20	2.7700
C20···O2ⁱⁱⁱ	3.1526 (19)

N2—N1—C1	118.94 (12)	C19—C20—C21	119.83 (13)
N1—N2—C20	120.55 (12)	N2—C20—C19	114.55 (13)
N2—N1—H1	119.5 (11)	C13—C21—C20	120.28 (13)
C1—N1—H1	120.6 (11)	O2—C21—C13	119.97 (14)
N1—C1—C2	121.18 (13)	O2—C21—C20	119.69 (13)
N1—C1—C6	118.03 (14)	C1—C2—H2	121.00
C2—C1—C6	120.79 (15)	C3—C2—H2	121.00
C1—C2—C3	118.30 (14)	C3—C4—H4	121.00
C2—C3—C4	121.95 (15)	C5—C4—H4	121.00
Cl1—C3—C4	119.19 (12)	C4—C5—H5	119.00
Cl1—C3—C2	118.86 (12)	C6—C5—H5	119.00
C3—C4—C5	118.91 (16)	C1—C6—H6	121.00
C4—C5—C6	121.16 (17)	C5—C6—H6	121.00
C1—C6—C5	118.87 (16)	C7—C8—H8	120.00
C12—C7—C19	123.77 (14)	C9—C8—H8	120.00
C8—C7—C12	118.60 (15)	C8—C9—H9	120.00
C8—C7—C19	117.57 (15)	C10—C9—H9	120.00
C7—C8—C9	120.61 (18)	C9—C10—H10	120.00
C8—C9—C10	119.72 (17)	C11—C10—H10	120.00
C9—C10—C11	120.67 (18)	C10—C11—H11	120.00
C10—C11—C12	119.85 (19)	C12—C11—H11	120.00
C7—C12—C11	120.52 (16)	C7—C12—H12	120.00
C14—C13—C21	118.29 (14)	C11—C12—H12	120.00
C14—C13—C18	119.45 (15)	C13—C14—H14	120.00
C18—C13—C21	122.22 (14)	C15—C14—H14	120.00
C13—C14—C15	120.15 (16)	C14—C15—H15	120.00
C14—C15—C16	120.11 (18)	C16—C15—H15	120.00
C15—C16—C17	120.38 (19)	C15—C16—H16	120.00
C16—C17—C18	120.48 (18)	C17—C16—H16	120.00
C13—C18—C17	119.41 (17)	C16—C17—H17	120.00
O1—C19—C20	117.52 (13)	C18—C17—H17	120.00
O1—C19—C7	120.69 (13)	C13—C18—H18	120.00
C7—C19—C20	121.79 (13)	C17—C18—H18	120.00
N2—C20—C21	124.79 (13)

C1—N1—N2—C20	−179.27 (14)	C8—C9—C10—C11	0.5 (3)
N2—N1—C1—C2	−20.0 (2)	C9—C10—C11—C12	−1.4 (3)
N2—N1—C1—C6	159.53 (14)	C10—C11—C12—C7	0.9 (3)
N1—N2—C20—C19	163.92 (13)	C18—C13—C14—C15	−1.8 (2)
N1—N2—C20—C21	−5.6 (2)	C21—C13—C18—C17	178.47 (16)
N1—C1—C6—C5	−177.52 (15)	C14—C13—C21—O2	30.3 (2)
C2—C1—C6—C5	2.0 (2)	C14—C13—C21—C20	−152.55 (15)
N1—C1—C2—C3	177.48 (14)	C18—C13—C21—O2	−147.25 (16)
C6—C1—C2—C3	−2.1 (2)	C18—C13—C21—C20	29.9 (2)
C1—C2—C3—Cl1	−179.79 (12)	C21—C13—C14—C15	−179.39 (16)
C1—C2—C3—C4	0.8 (2)	C14—C13—C18—C17	0.9 (3)
Cl1—C3—C4—C5	−178.97 (14)	C13—C14—C15—C16	1.4 (3)
C2—C3—C4—C5	0.4 (3)	C14—C15—C16—C17	−0.2 (3)
C3—C4—C5—C6	−0.5 (3)	C15—C16—C17—C18	−0.7 (3)
C4—C5—C6—C1	−0.8 (3)	C16—C17—C18—C13	0.3 (3)
C19—C7—C8—C9	−178.70 (14)	O1—C19—C20—N2	−136.93 (14)
C8—C7—C12—C11	0.5 (2)	C7—C19—C20—C21	−147.85 (13)
C8—C7—C19—O1	12.4 (2)	O1—C19—C20—C21	33.1 (2)
C8—C7—C19—C20	−166.55 (13)	C7—C19—C20—N2	42.09 (19)
C19—C7—C12—C11	177.53 (15)	N2—C20—C21—O2	16.7 (2)
C12—C7—C8—C9	−1.5 (2)	N2—C20—C21—C13	−160.48 (14)
C12—C7—C19—C20	16.4 (2)	C19—C20—C21—O2	−152.33 (14)
C12—C7—C19—O1	−164.61 (14)	C19—C20—C21—C13	30.5 (2)
C7—C8—C9—C10	1.0 (3)

Symmetry codes: (i) −x+1, −y, −z+2; (ii) −x+1, −y+1, −z+2; (iii) −x, −y, −z+2; (iv) −x−1/2, y+1/2, −z+3/2; (v) x, y−1, z; (vi) −x−1/2, y−1/2, −z+3/2; (vii) x+1/2, −y+1/2, z+1/2; (viii) −x, −y+1, −z+2; (ix) x−1/2, −y+1/2, z−1/2; (x) x−1/2, −y−1/2, z−1/2; (xi) x+1/2, −y−1/2, z+1/2; (xii) x, y+1, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2	0.922 (17)	1.930 (18)	2.6205 (18)	130.1 (14)
C12—H12···N2	0.93	2.55	3.016 (2)	111
N1—H1···O1ⁱⁱⁱ	0.922 (17)	2.628 (17)	3.344 (3)	135.0 (13)
C6—H6···O1ⁱⁱⁱ	0.93	2.63	3.390 (2)	140

Symmetry code: (iii) −x, −y, −z+2.

Experimental details

Crystal data
Chemical formula	C₂₁H₁₅ClN₂O₂
M_r	362.80
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	297
a, b, c (Å)	10.2970 (9), 10.3526 (9), 16.8926 (15)
β (°)	102.131 (1)
V (Å³)	1760.6 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.24
Crystal size (mm)	0.60 × 0.31 × 0.23

Data collection
Diffractometer	Bruker D8 Discover with SMART CCD area-detector diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	11123, 3573, 2657
R_int	0.042
(sin θ/λ)_max (Å⁻¹)	0.624

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.119, 0.98
No. of reflections	3573
No. of parameters	239
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.39, −0.16

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XP in SHELXTL/PC (Sheldrick, 2008), PLATON (Spek, 2009) and Mercury (Macrae et al., 2006).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2	0.922 (17)	1.930 (18)	2.6205 (18)	130.1 (14)
C12—H12···N2	0.93	2.55	3.016 (2)	111
N1—H1···O1ⁱ	0.922 (17)	2.628 (17)	3.3435 (27)	135.0 (13)
C6—H6···O1ⁱ	0.93	2.63	3.390 (2)	140

Symmetry code: (i) −x, −y, −z+2.

Acknowledgements

The authors thank the FONDECYT (grant Nos. 11100446 and 1080269) and Universidad Andrés Bello (grant No. DI-06–10-R).

References

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