(2,4-Di­chloro­phen­yl)(3-hy­droxy­piperidin-1-yl)methanone: crystal structure and Hirshfeld analysis

Mohamooda Sumaya, U.; Reuben Jonathan, D.; Era, D.T.; Gomathi, S.; Usha, G.

doi:10.1107/S2414314617008136

organic compounds

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ISSN: 2414-3146

Volume 2| Part 6| June 2017| x170813

https://doi.org/10.1107/S2414314617008136

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(2,4-Dichlorophenyl)(3-hydroxypiperidin-1-yl)methanone: crystal structure and Hirshfeld analysis

U. Mohamooda Sumaya,^a D. Reuben Jonathan,^b Dravida Thendral Era,^c S. Gomathi ^d and G. Usha ^c ^*

^aDepartment of Physics, Bharathi Women's College, Chennai-108, Tamilnadu, India, ^bDepartment of Chemistry, Madras Christian College, Chennai-59, Tamilnadu, India, ^cPG and Research Department of Physics, Queen Mary's College, Chennai-4, Tamilnadu, India, and ^dPG Department of Physics, Bhaktavatsalam Memorial College for Women, Chennai-80, Tamilnadu, India
^*Correspondence e-mail: guqmc@yahoo.com

Edited by H. Stoeckli-Evans, University of Neuchâtel, Switzerland (Received 24 April 2017; accepted 1 June 2017; online 8 June 2017)

In the title compound, C₁₂H₁₃Cl₂NO₂, the piperidine ring adopts a chair conformation. The dihedral angle between the mean plane of the piperidine ring and the benzene ring is 58.5 (3)°. In the crystal, molecules are linked by O—H⋯O hydrogen bonds, forming chains propagating along the b-axis direction. The chains are linked by C—H⋯O hydrogen bonds, forming undulating sheets parallel to the ab plane. The C atoms of the hydroxypiperidine ring are disordered over two sets of sites with refined occupancies of 0.545 (7) and 0.455 (7). The intermolecular interactions in the crystal structure were quantified using Hirshfeld surface analysis.

Keywords: crystal structure; piperidine; Hirshfeld surface; two-dimensional fingerprint plot; hydrogen bonding.

CCDC reference: 1500603

Structure description

Piperidine derivatives exhibit a wide range of biological activities, such as antimicrobial, anti-inflammatory, antiviral, antimalarial and general anesthetics (Aridoss et al., 2009 ). The piperidine scaffold has played an important role in numerous pharmaceutical drugs (Das & Brahmachari, 2013 ). The substitution of hydroxyl, methoxy, nitro and alkyl group on the piperidine ring has been found to produce good antioxidant activities (Ravindernath & Reddy, 2017 ). Piperidines have also been found to have blood cholesterol-lowering activities (Parthiban et al., 2009 ). Compounds containing a piperidine moiety are used clinically to prevent post-operative vomiting, to speed up gastric emptying before anaesthesia, to facilitate radiological investigations and to correct a variety of disturbances of gastrointestinal functions (Sampath et al., 2004 ). Biologically active alkaloids of substituted piperidines have been targeted for their total or partial synthesis (Ramalingan et al., 2004 ).

The molecular structure of the title compound is illustrated in Fig. 1. The minor component of the piperidine ring has atoms labels N1/C1–C5. The bond lengths and bond angles are in normal ranges and in good agreement with the values reported for (4-chlorophenyl) 4-hydroxypiperidin-1-yl) methanone (4-chlorophenyl)-(piperidin-1-yl)methanone (0.75/0.25) (Revathi et al., 2015 ). The dihedral angle between the benzene ring (C7–C12) and the piperidine ring (N1′/C1′–C5′) mean plane is 58.5 (3)°. The torsion angle O1—C6—N1′—C5′ [12.1 (7)°], indicates that the keto group is in a +syn-periplanar (+sp) orientation with the hydroxypiperidine ring. The piperidine ring (N1′/C1′–C5′) adopts a chair conformation [puckering parameters: Q = 0.530 (9) Å, θ = 177.5 (10)° and φ = 351 (24) °].

Figure 1
The molecular structure of the title compound, with the atom labelling and displacement ellipsoids drawn at the 30% probability level. The minor component of the piperidine ring has atoms labels N1/C1–C5 and dashed bonds.

In the crystal, molecules are linked by O—H⋯O hydrogen bonds, forming chains propagating along the b-axis direction (Table 1 and Fig. 2). The chains are linked via C—H⋯O hydrogen bonds, forming undulating sheets parallel to the ab plane (Table 1 and Fig. 2).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2A⋯O1ⁱ	0.82	2.04	2.735 (3)	142
C11—H11⋯O2ⁱⁱ	0.93	2.48	3.404 (4)	173
C4′—H4′1⋯O1ⁱⁱⁱ	0.97	2.57	3.456 (12)	152
Symmetry codes: (i) x, y-1, z; (ii) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, z]$ ; (iii) $[-x+1, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Figure 2
The crystal packing of the title compound, viewed along the a axis. The dashed lines indicate the hydrogen bonds (see Table 1

). For clarity, only the H atoms involved in these interactions have been included.

The Hirshfeld analysis (Crystal Explorer; Wolff et al., 2012 ) of the short contacts in the crystal can be summarized with finger print plots mapped over d_norm, electrostatic potential, shape index and curvedness. The electrostatic potentials were calculated using TONTO (Spackman & Jayatilaka, 2009 ) integrated within Crystal Explorer. The electrostatic potentials were mapped on Hirshfeld surfaces using the STO-3 G basis.

The strong O—H⋯O and C—H⋯O interactions are visualized as bright-red spots between the respective donor and acceptor atoms on the Hirshfeld surfaces mapped over d_norm (Fig. 3a) with neighbouring molecules connected by O2—H2A⋯O1 and C11—H11⋯O2 hydrogen bonds. This observation is revealed in the Hirshfeld surfaces mapped over the electrostatic potential (Fig. 3b) showing the negative potential around the oxygen atoms (light-red clouds) and the positive potential around hydrogen atoms (light-blue clouds). Fingerprint plots (Fig. 4a–f) for the Hirshfeld surfaces of the compound are shown with characteristic pseudo-symmetry wings in the upper left and lower right sides of d_e and d_i diagonal axes that represent the overall two-dimensional fingerprint plot and those delineated into H⋯H, H⋯Cl/Cl⋯H, H⋯O/O⋯H, H⋯C/C⋯H and C⋯C contacts.

Figure 3
(a) d_norm mapped on Hirshfeld surface for visualizing the intermolecular contacts of the title compound. (b) Hirshfeld surfaces mapped over the electrostatic potential. Dotted lines represent hydrogen bonds.

Figure 4
Two-dimensional fingerprint plots of the title compound showing the percentage contributions of individual types of interactions: (a) all intermolecular interactions, (b) H⋯H contacts, (c) H⋯Cl/Cl⋯H contacts and (d) O⋯H/H⋯O contacts and (e) H⋯C/C⋯H contacts. The outline of the full fingerprint is shown in gray. d_i (x axis) and d_e (y axis) are the closest internal and external distance from a given point on the Hirshfeld surface. Surfaces to the right highlight the relevant surface patches associated with the specific contacts with d_norm mapped.

The fingerprint plot of H⋯H contacts, which represent the largest contribution to the Hirshfeld surfaces (38.4%), are shown as one distinct pattern with a minimum value of d_e = d_i ≃1.4 Å (Fig. 4b). The H⋯Cl/Cl⋯H interactions appear as the next largest region of the fingerprint plot, highly concentrated at the edges, having almost the same d_e + di≃ 2.8 Å (Fig. 4c), with overall Hirshfeld surfaces of 29.9%. The reciprocal H⋯O/O⋯H contacts consists of 17.2% of the total Hirshfeld surfaces with d_e + d_i ≃ 2.0 Å (Fig. 4d), exhibited by two symmetrical narrow pointed wings indicating the intermolecular hydrogen-bond interactions O2—H2A⋯O1 and C11—H11⋯O2 in the crystal packing. The H⋯C/C⋯H interaction on the fingerprint plot, which contributes 7.4% of the overall Hirshfeld surfaces, are indicated by d_e + d_i ≃ 3.0 Å (Fig. 4e). The C⋯C contacts, which are the measure of π–π stacking interactions, occupy 1.6% of the Hirshfeld surfaces and appear as a unique triangle at about d_e + d_i ≃ 3.8 Å (Fig. 4f). The existence of π–π interactions is also visualized as red and blue triangles on the shape-indexed surfaces (Fig. 5), and as flat regions on the Hirshfeld surfaces mapped over curvedness in Fig. 6.

Figure 5
Hirshfeld surfaces mapped over the shape index of the title compound.

Figure 6
Hirshfeld surfaces mapped over the curvedness of the title compound.

Synthesis and crystallization

The title compound was synthesized following a published procedure (Revathi et al., (2015). In a 250 ml round-bottomed flask, 100 ml of ethyl methyl ketone was added to 3-hydroxy piperidine (0.02 mol) and stirred at room temperature. After 5 min, triethylamine (0.04 mol) was added and the mixture was stirred for 15 min. Then 2,4-dichloro benzoyl chloride (0.04 mol) was added and the reaction mixture was stirred at room temperature for 2 h. A white precipitate of triethyl ammonium chloride was formed, which was removed by filtration and the filtrate was evaporated to give the crude product. It was recrystallized twice from ethyl methyl ketone to give yellow block-like crystals of the title compound (yield: 80%).

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The C atoms of the hydroxypiperidine ring were refined as disordered, over two set of sites with refined occupancies of 0.545 (7) (N1′/C1′–C5′) and 0.455 (7) [N1/C1–C5]. Distance restraints SADI, RIGU and DFIX were used to restrain bond lengths to target values.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₂H₁₃Cl₂NO₂
M_r	274.13
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	298
a, b, c (Å)	13.9866 (6), 7.9972 (4), 23.122 (1)
V (Å³)	2586.3 (2)
Z	8
Radiation type	Mo Kα
μ (mm⁻¹)	0.49
Crystal size (mm)	0.35 × 0.25 × 0.20

Data collection
Diffractometer	Bruker Kappa APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2004 )
T_min, T_max	0.892, 0.945
No. of measured, independent and observed [I > 2σ(I)] reflections	34472, 2763, 1602
R_int	0.046
(sin θ/λ)_max (Å⁻¹)	0.635

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.048, 0.164, 1.05
No. of reflections	2763
No. of parameters	210
No. of restraints	99
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.37
Computer programs: APEX2, SAINT and XPREP (Bruker, 2004), SHELXS97 (Sheldrick, 2008 ), SHELXL2014 (Sheldrick, 2015 ), ORTEP-3 for Windows (Farrugia, 2012 ) and PLATON (Spek, 2009 ).

Structural data

CCDC reference: 1500603

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2414314617008136/su4151sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314617008136/su4151Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314617008136/su4151Isup3.cml

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: APEX2 and SAINT (Bruker, 2004); data reduction: SAINT and XPREP (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and PLATON (Spek, 2009); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015) and PLATON (Spek, 2009).

(2,4-Dichlorophenyl)(3-hydroxypiperidin-1-yl)methanone top

Crystal data top

C₁₂H₁₃Cl₂NO₂	D_x = 1.408 Mg m⁻³
M_r = 274.13	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbca	Cell parameters from 7296 reflections
a = 13.9866 (6) Å	θ = 2.3–22.7°
b = 7.9972 (4) Å	µ = 0.49 mm⁻¹
c = 23.122 (1) Å	T = 298 K
V = 2586.3 (2) Å³	Block, yellow
Z = 8	0.35 × 0.25 × 0.20 mm
F(000) = 1136

Data collection top

Bruker Kappa APEXII CCD diffractometer	1602 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.046
ω and φ scan	θ_max = 26.9°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −15→17
T_min = 0.892, T_max = 0.945	k = −10→10
34472 measured reflections	l = −25→29
2763 independent reflections

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)] = 0.048	H-atom parameters constrained
wR(F²) = 0.164	w = 1/[σ²(F_o²) + (0.0683P)² + 1.3359P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max < 0.001
2763 reflections	Δρ_max = 0.26 e Å⁻³
210 parameters	Δρ_min = −0.37 e Å⁻³
99 restraints	Extinction correction: SHELXL2014 (Sheldrick, 2015), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0031 (8)

Special details top

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

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
N1	0.5092 (5)	0.0739 (7)	0.6677 (3)	0.0590 (18)	0.455 (7)
C1	0.4668 (5)	−0.0842 (8)	0.6489 (3)	0.060 (2)	0.455 (7)
H1A	0.4179	−0.0624	0.6201	0.071*	0.455 (7)
H1B	0.4367	−0.1387	0.6817	0.071*	0.455 (7)
C2	0.5422 (6)	−0.1979 (9)	0.6237 (4)	0.0564 (19)	0.455 (7)
H2	0.5683	−0.1471	0.5885	0.068*	0.455 (7)
C3	0.6208 (9)	−0.2243 (19)	0.6662 (6)	0.067 (3)	0.455 (7)
H3A	0.6706	−0.2914	0.6485	0.081*	0.455 (7)
H3B	0.5963	−0.2856	0.6992	0.081*	0.455 (7)
C4	0.6630 (7)	−0.0618 (12)	0.6866 (5)	0.073 (2)	0.455 (7)
H4A	0.6956	−0.0077	0.6546	0.087*	0.455 (7)
H4B	0.7098	−0.0838	0.7166	0.087*	0.455 (7)
C5	0.5869 (6)	0.0530 (11)	0.7098 (4)	0.066 (2)	0.455 (7)
H5A	0.5614	0.0071	0.7454	0.079*	0.455 (7)
H5B	0.6149	0.1611	0.7185	0.079*	0.455 (7)
N1'	0.5416 (4)	0.0869 (6)	0.6416 (3)	0.0533 (13)	0.545 (7)
C1'	0.5157 (4)	−0.0624 (6)	0.6095 (2)	0.0505 (15)	0.545 (7)
H1'1	0.5635	−0.0836	0.5800	0.061*	0.545 (7)
H1'2	0.4548	−0.0445	0.5903	0.061*	0.545 (7)
C2'	0.5083 (5)	−0.2121 (7)	0.6488 (3)	0.0543 (16)	0.545 (7)
H2'	0.4530	−0.1992	0.6744	0.065*	0.545 (7)
C3'	0.5973 (8)	−0.2377 (16)	0.6844 (5)	0.072 (3)	0.545 (7)
H3'1	0.6500	−0.2688	0.6593	0.086*	0.545 (7)
H3'2	0.5871	−0.3277	0.7118	0.086*	0.545 (7)
C4'	0.6221 (8)	−0.0775 (10)	0.7167 (4)	0.087 (2)	0.545 (7)
H4'1	0.5736	−0.0565	0.7459	0.104*	0.545 (7)
H4'2	0.6827	−0.0922	0.7365	0.104*	0.545 (7)
C5'	0.6287 (5)	0.0717 (8)	0.6773 (4)	0.0698 (19)	0.545 (7)
H5'1	0.6370	0.1723	0.7002	0.084*	0.545 (7)
H5'2	0.6840	0.0600	0.6523	0.084*	0.545 (7)
Cl2	0.28658 (9)	0.11880 (14)	0.68040 (4)	0.0990 (4)
Cl1	0.17370 (7)	0.32088 (17)	0.47207 (5)	0.1185 (5)
O2	0.49103 (16)	−0.3471 (2)	0.60880 (9)	0.0738 (7)
H2A	0.5240	−0.4291	0.6164	0.111*
O1	0.52333 (18)	0.3567 (3)	0.66457 (10)	0.0819 (7)
C11	0.2423 (2)	0.2233 (4)	0.57471 (12)	0.0592 (7)
H11	0.1798	0.1935	0.5839	0.071*
C12	0.3156 (2)	0.2009 (3)	0.61377 (12)	0.0557 (7)
C8	0.4269 (2)	0.3131 (4)	0.54690 (12)	0.0578 (7)
H8	0.4889	0.3446	0.5375	0.069*
C7	0.40901 (18)	0.2434 (3)	0.60078 (12)	0.0516 (7)
C10	0.2645 (2)	0.2910 (4)	0.52185 (12)	0.0618 (8)
C6	0.4908 (2)	0.2295 (4)	0.64243 (13)	0.0647 (8)
C9	0.3554 (2)	0.3364 (4)	0.50740 (13)	0.0617 (8)
H9	0.3686	0.3824	0.4713	0.074*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.062 (4)	0.042 (2)	0.073 (4)	−0.002 (2)	−0.022 (3)	−0.002 (2)
C1	0.059 (3)	0.044 (3)	0.075 (4)	−0.003 (2)	−0.014 (3)	−0.002 (3)
C2	0.062 (4)	0.041 (4)	0.066 (4)	−0.002 (3)	−0.010 (3)	0.004 (3)
C3	0.062 (5)	0.060 (5)	0.080 (6)	0.009 (4)	−0.015 (4)	0.001 (4)
C4	0.069 (4)	0.066 (4)	0.084 (5)	0.004 (3)	−0.028 (4)	0.000 (4)
C5	0.068 (4)	0.058 (4)	0.072 (4)	−0.002 (3)	−0.024 (3)	0.000 (3)
N1'	0.058 (3)	0.041 (2)	0.061 (3)	−0.0049 (17)	−0.016 (2)	0.0019 (19)
C1'	0.055 (3)	0.040 (2)	0.057 (3)	−0.004 (2)	−0.012 (2)	0.0009 (19)
C2'	0.065 (4)	0.042 (3)	0.056 (3)	−0.007 (3)	−0.010 (2)	0.002 (2)
C3'	0.083 (5)	0.054 (3)	0.080 (6)	−0.010 (3)	−0.032 (4)	0.015 (4)
C4'	0.112 (6)	0.064 (4)	0.083 (4)	−0.017 (4)	−0.046 (4)	0.011 (3)
C5'	0.067 (3)	0.059 (4)	0.083 (4)	−0.008 (3)	−0.030 (3)	0.005 (3)
Cl2	0.1290 (9)	0.0990 (8)	0.0690 (6)	−0.0346 (6)	0.0016 (5)	0.0209 (5)
Cl1	0.0863 (7)	0.1429 (11)	0.1263 (9)	−0.0206 (6)	−0.0527 (6)	0.0448 (7)
O2	0.0858 (15)	0.0407 (11)	0.0950 (16)	0.0020 (10)	−0.0279 (12)	−0.0061 (10)
O1	0.1036 (18)	0.0439 (13)	0.0982 (16)	−0.0080 (11)	−0.0416 (14)	−0.0033 (11)
C11	0.0446 (14)	0.0559 (17)	0.0771 (18)	−0.0014 (13)	0.0041 (14)	0.0004 (15)
C12	0.0639 (18)	0.0435 (15)	0.0598 (16)	−0.0027 (13)	0.0022 (13)	0.0017 (12)
C8	0.0466 (15)	0.0568 (17)	0.0700 (18)	−0.0026 (13)	0.0047 (13)	−0.0064 (14)
C7	0.0511 (16)	0.0369 (14)	0.0668 (17)	0.0017 (12)	−0.0082 (12)	−0.0051 (12)
C10	0.0520 (17)	0.0607 (19)	0.0728 (18)	0.0015 (14)	−0.0097 (14)	0.0044 (15)
C6	0.0714 (19)	0.0430 (15)	0.0797 (19)	−0.0009 (13)	−0.0217 (15)	−0.0021 (14)
C9	0.0645 (18)	0.0639 (19)	0.0568 (16)	−0.0043 (15)	0.0013 (14)	0.0022 (14)

Geometric parameters (Å, º) top

N1—C6	1.398 (7)	C2'—C3'	1.507 (11)
N1—C1	1.462 (8)	C2'—H2'	0.9800
N1—C5	1.469 (8)	C3'—C4'	1.524 (13)
C1—C2	1.510 (10)	C3'—H3'1	0.9700
C1—H1A	0.9700	C3'—H3'2	0.9700
C1—H1B	0.9700	C4'—C5'	1.505 (12)
C2—O2	1.434 (8)	C4'—H4'1	0.9700
C2—C3	1.491 (13)	C4'—H4'2	0.9700
C2—H2	0.9800	C5'—H5'1	0.9700
C3—C4	1.503 (15)	C5'—H5'2	0.9700
C3—H3A	0.9700	Cl2—C12	1.723 (3)
C3—H3B	0.9700	Cl1—C10	1.731 (3)
C4—C5	1.504 (14)	O2—H2A	0.8200
C4—H4A	0.9700	O1—C6	1.226 (3)
C4—H4B	0.9700	C11—C10	1.372 (4)
C5—H5A	0.9700	C11—C12	1.378 (4)
C5—H5B	0.9700	C11—H11	0.9300
N1'—C6	1.344 (6)	C12—C7	1.383 (4)
N1'—C1'	1.452 (6)	C8—C9	1.367 (4)
N1'—C5'	1.476 (6)	C8—C7	1.387 (4)
C1'—C2'	1.506 (7)	C8—H8	0.9300
C1'—H1'1	0.9700	C7—C6	1.500 (4)
C1'—H1'2	0.9700	C10—C9	1.364 (4)
C2'—O2	1.442 (7)	C9—H9	0.9300

C6—N1—C1	124.8 (5)	O2—C2'—H2'	109.6
C6—N1—C5	121.0 (5)	C1'—C2'—H2'	109.6
C1—N1—C5	113.4 (6)	C3'—C2'—H2'	109.6
N1—C1—C2	110.6 (6)	C2'—C3'—C4'	110.0 (9)
N1—C1—H1A	109.5	C2'—C3'—H3'1	109.7
C2—C1—H1A	109.5	C4'—C3'—H3'1	109.7
N1—C1—H1B	109.5	C2'—C3'—H3'2	109.7
C2—C1—H1B	109.5	C4'—C3'—H3'2	109.7
H1A—C1—H1B	108.1	H3'1—C3'—H3'2	108.2
O2—C2—C3	114.1 (8)	C5'—C4'—C3'	112.5 (7)
O2—C2—C1	104.2 (6)	C5'—C4'—H4'1	109.1
C3—C2—C1	110.2 (8)	C3'—C4'—H4'1	109.1
O2—C2—H2	109.4	C5'—C4'—H4'2	109.1
C3—C2—H2	109.4	C3'—C4'—H4'2	109.1
C1—C2—H2	109.4	H4'1—C4'—H4'2	107.8
C2—C3—C4	111.9 (10)	N1'—C5'—C4'	110.7 (6)
C2—C3—H3A	109.2	N1'—C5'—H5'1	109.5
C4—C3—H3A	109.2	C4'—C5'—H5'1	109.5
C2—C3—H3B	109.2	N1'—C5'—H5'2	109.5
C4—C3—H3B	109.2	C4'—C5'—H5'2	109.5
H3A—C3—H3B	107.9	H5'1—C5'—H5'2	108.1
C3—C4—C5	111.2 (9)	C2—O2—H2A	109.5
C3—C4—H4A	109.4	C10—C11—C12	117.8 (3)
C5—C4—H4A	109.4	C10—C11—H11	121.1
C3—C4—H4B	109.4	C12—C11—H11	121.1
C5—C4—H4B	109.4	C11—C12—C7	121.9 (3)
H4A—C4—H4B	108.0	C11—C12—Cl2	117.4 (2)
N1—C5—C4	110.8 (7)	C7—C12—Cl2	120.7 (2)
N1—C5—H5A	109.5	C9—C8—C7	121.6 (3)
C4—C5—H5A	109.5	C9—C8—H8	119.2
N1—C5—H5B	109.5	C7—C8—H8	119.2
C4—C5—H5B	109.5	C12—C7—C8	117.6 (2)
H5A—C5—H5B	108.1	C12—C7—C6	124.3 (3)
C6—N1'—C1'	125.0 (4)	C8—C7—C6	118.0 (3)
C6—N1'—C5'	119.9 (5)	C9—C10—C11	122.3 (3)
C1'—N1'—C5'	115.1 (5)	C9—C10—Cl1	119.0 (2)
N1'—C1'—C2'	111.3 (4)	C11—C10—Cl1	118.7 (2)
N1'—C1'—H1'1	109.4	O1—C6—N1'	120.9 (3)
C2'—C1'—H1'1	109.4	O1—C6—N1	119.7 (3)
N1'—C1'—H1'2	109.4	O1—C6—C7	119.3 (3)
C2'—C1'—H1'2	109.4	N1'—C6—C7	117.2 (3)
H1'1—C1'—H1'2	108.0	N1—C6—C7	118.3 (3)
O2—C2'—C1'	102.8 (4)	C10—C9—C8	118.8 (3)
O2—C2'—C3'	112.8 (7)	C10—C9—H9	120.6
C1'—C2'—C3'	112.4 (6)	C8—C9—H9	120.6

C6—N1—C1—C2	113.1 (9)	C11—C12—C7—C6	177.0 (3)
C5—N1—C1—C2	−56.9 (9)	Cl2—C12—C7—C6	−2.5 (4)
N1—C1—C2—O2	178.6 (5)	C9—C8—C7—C12	−1.2 (4)
N1—C1—C2—C3	55.8 (10)	C9—C8—C7—C6	−177.3 (3)
O2—C2—C3—C4	−172.0 (8)	C12—C11—C10—C9	−0.3 (5)
C1—C2—C3—C4	−55.2 (11)	C12—C11—C10—Cl1	−179.8 (2)
C2—C3—C4—C5	54.0 (13)	C1'—N1'—C6—O1	−170.7 (4)
C6—N1—C5—C4	−115.2 (10)	C5'—N1'—C6—O1	12.1 (7)
C1—N1—C5—C4	55.3 (10)	C1'—N1'—C6—C7	−8.9 (7)
C3—C4—C5—N1	−52.7 (12)	C5'—N1'—C6—C7	173.9 (5)
C6—N1'—C1'—C2'	−123.6 (7)	C1—N1—C6—O1	173.5 (6)
C5'—N1'—C1'—C2'	53.8 (7)	C5—N1—C6—O1	−17.2 (9)
N1'—C1'—C2'—O2	−175.0 (4)	C1—N1—C6—C7	12.0 (9)
N1'—C1'—C2'—C3'	−53.6 (9)	C5—N1—C6—C7	−178.6 (5)
O2—C2'—C3'—C4'	168.9 (6)	C12—C7—C6—O1	−105.1 (4)
C1'—C2'—C3'—C4'	53.4 (10)	C8—C7—C6—O1	70.7 (4)
C2'—C3'—C4'—C5'	−53.3 (12)	C12—C7—C6—N1'	92.8 (5)
C6—N1'—C5'—C4'	124.2 (9)	C8—C7—C6—N1'	−91.4 (4)
C1'—N1'—C5'—C4'	−53.3 (9)	C12—C7—C6—N1	56.4 (6)
C3'—C4'—C5'—N1'	52.4 (12)	C8—C7—C6—N1	−127.8 (5)
C10—C11—C12—C7	−0.5 (4)	C11—C10—C9—C8	0.2 (5)
C10—C11—C12—Cl2	179.0 (2)	Cl1—C10—C9—C8	179.8 (2)
C11—C12—C7—C8	1.2 (4)	C7—C8—C9—C10	0.5 (4)
Cl2—C12—C7—C8	−178.3 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2A···O1ⁱ	0.82	2.04	2.735 (3)	142
C11—H11···O2ⁱⁱ	0.93	2.48	3.404 (4)	173
C4′—H4′1···O1ⁱⁱⁱ	0.97	2.57	3.456 (12)	152

Symmetry codes: (i) x, y−1, z; (ii) −x+1/2, y+1/2, z; (iii) −x+1, y−1/2, −z+3/2.

Acknowledgements

The authors thank the Central Instrumentation Facility (DST–FIST), Queen Mary's College, Chennai-4, for computing facilities and SAIF, IIT, Madras, for the X-ray data collection facility.

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