Acta Crystallographica Section E: Crystallographic Communications

Acta Crystallogr E Crystallogr Commun. 71(Pt 3): 312-314

Crystal structure of the di-Mannich base 4,4′-dichloro-3,3′,5,5′-tetramethyl-2,2′-[imidazolidine-1,3-diylbis(methylene)]diphenol

Augusto Riveraa*, Luz Stella Nerioa, Michael Bolteb

a. Departamento de Química, Facultad de Ciencias, Universidad Nacional de Colombia, Sede Bogotá, Cra 30 No. 45-03, Bogotá, Colombia

b. Institut für Anorganische Chemie, Goethe-Universität, Max-von-Laue-Strasse 7, Frankfurt/Main D-60438, Germany

Correspondence e-mail: ariverau@unal.edu.co

© Rivera et al. 2015

DOI: 10.1107/S2056989015002212

Published online: 25 February 2015

Abstract

In the title compound, the imidizadoline ring adopts an envelope conformation and the nitrogen lone pairs are oriented in a syn disposition. The crystal packing is stabilized by C—H⋯O hydrogen-bonding interactions.

Abstract

The title compound, C₂₁H₂₆Cl₂N₂O₂, was prepared in a solvent-free microwave-assisted synthesis, and crystallizes in the orthorhombic space group Pna2₁. The imidazolidine ring adopts an envelope conformation and its mean plane is almost perpendicular to the two pendant aromatic rings [dihedral angles = 84.61 (9) and 86.54 (9)°]. The molecular structure shows the presence of two intramolecular O—H⋯N hydrogen bonds between the phenolic hydroxy groups and imidazolidine N atoms. The two 3-chloro-6-hydroxy-2,4-dimethylbenzyl groups are located in a cis orientation with respect to the imidazolidine fragment. As a result, the lone pairs of electrons on the N atoms are presumed to be disposed in a syn conformation. This is therefore the first example of an exception to the ‘rabbit-ears’ effect in such 2,2′-[imidazolidine-1,3-diylbis(methylene)]diphenol derivatives.

Chemical context  

As a continuation of our investigations of the Mannich reaction, we have synthesized a family of compounds of the type 2,2′-[imidazolidine-1,3-diylbis(methylene)]di(hydroxyaryl), from reactions between 1,3,6,8-tetrazatricyclo[4.4.1.13,8]dodecane (TATD) and phenols or naphthols (Rivera et al., 1993 ▸, 2005 ▸; Rivera & Quevedo, 2013 ▸). Such compounds are known to be valuable in homogeneous catalysis (Kober et al., 2012 ▸) and for the preparation of tetrahydrosalens (Rivera et al., 2004 ▸) and heterocalixarenes (Rivera & Quevedo, 2004 ▸). Mannich bases are also convenient models for studying the nature of hydrogen bonding and other weak non-covalent interactions, as they contain at least one phenolic or naphtholic hydroxy group as a proton donor, as well as an ortho-aminomethylgroup as a proton acceptor in the same molecule (Koll et al., 2006 ▸). Herein, as part of our systematic investigations of di-Mannich bases as convenient model systems for the study of intramolecular proton-transfer processes, we report the molecular and crystal structure of the title di-Mannich base, 4,4′-dichloro-3,3′,5,5′-tetramethyl-2,2′- [imidazolidine-1,3-diylbis(methylene)]diphenol (I).

In a previous report (Rivera & Quevedo, 2013 ▸), the title compound (I) was obtained under solvent-free conditions by heating a 1:4 mixture of TATD and 4-chloro-3,5-dimethylphenol in an oil bath with stirring at 423 K for 20 min. Drawbacks of this synthesis include the long reaction time and a requirement of considerable effort to optimize the reaction conditions and temperature control. We therefore subsequently explored this reaction under solvent-free, microwave-assisted conditions. The reaction was found to proceed smoothly under microwave irradiation in only 3 min at 403 K, in modest yield.

Structural commentary  

In the title molecule (I), Fig. 1 ▸, the imidazolidine ring adopts an envelope conformation, with atom C1 at the flap. The molecular structure shows two intramolecular O—H⋯N hydrogen bonds (Table 1 ▸) with S(6) graph-set motifs between the hydroxy groups of the substituted phenol rings and the two imidazolidine N atoms. The benzyl groups are located in an unexpected 1,3-diequatorial syn arrangement on the heterocyclic ring with dihedral angles between the mean plane through the N1/C2/C3/N2 atoms of the imidazolidine ring and the C11–C16 and C21–C26 aromatic rings of 84.61 (9) and 88.54 (9)°, respectively. The non-bonding electron pairs on the imidazolidine N atoms that are involved in both intra- and intermolecular hydrogen-bonding interactions adopt an unusual syn arrangement. As such, this molecule defies the well known ‘rabbit-ears’ effect (Hutchins et al., 1968 ▸) in which N–CH₂–N systems adopt anti conformations to avoid repulsions between the nitrogen lone pairs. Although in the very similar structure of meso-4,4′-difluoro-2,2′-{[(3aR,7aS)-2,3,3a,4,5,6,7,7a-octahydro-1H-1,3-benzimidazole-1,3-diyl]bis(methylene)}diphenol (Rivera et al., 2013 ▸) the N-atom lone pairs are syn, molecule (I) is the first reported exception to the ‘rabbit-ears’ effect in compounds of the 2,2′-[imidazolidine-1,3-diylbis(methylene)]diphenol type (Rivera et al., 2011 ▸, 2012a ▸,b ▸,c ▸, 2013 ▸, 2014 ▸).

Supramolecular features  

With both hydroxy groups of (I) involved in intramolecular hydrogen bonds, the only directional interaction in the crystal is a C13—H13⋯O2i bond (Table 1 ▸ and Fig. 2 ▸), which links adjacent molecules in a head-to-tail fashion into zigzag chains, extending along the c-axis direction (Fig. 2 ▸).

Database survey  

A search in the Cambridge Structural Database (Groom & Allen 2014 ▸) revealed previous reports of six structures of related 2,2′-[imidazolidine-1,3-diylbis(methylene)]diphenol compounds (Rivera et al., 2011 ▸, 2012a ▸,b ▸,c ▸, 2013 ▸, 2014 ▸). Each of these also shows intramolecular O—H⋯N hydrogen bonds between the two imidazolidine N atoms and the hydroxy groups. In addition, the D⋯A distances in these compounds compare well with those observed in the title compound. As with (I), the imidazolidine ring in the p-tert-butylphenol derivative (Rivera et al., 2013 ▸), adopts an envelope conformation whereas, in the other five the ring adopts a twist conformation. Furthermore, unlike the title compound, the nitrogen lone pairs in all six of the related derivatives are oriented in an anti disposition.

Synthesis and crystallization  

A mixture of 1,3,6,8-tetrazatricyclo[4.4.1.13,8]dodecane (0.100 g, 0.6 mmol) and 4-chloro-3,5-dimethylphenol (0.375 g, 2.4 mmol) without any solvent was exposed to microwave irradiation in a CEM Discover reactor (with 250 W as the maximum power) for 3 min at a temperature of 403 K. Once cooled to room temperature, the reaction mixture was dissolved with CHCl₃ which was removed under reduced pressure to yield the crude product. This was further purified by column chromatography on silica gel using a mixture of benzene:ethyl acetate (80:20) as eluent (yield 21%, m.p. = 421–422 K). Single crystals in the form of needles shorter than 1 mm were obtained from a chloroform:ethanol (50:50) solution by slow evaporation of the solvent at room temperature over a period of one week.

Refinement  

Crystal data, data collection and structure refinement details are summarized in Table 2 ▸. All the H atoms were located in difference electron density maps. The hydroxy H atoms were freely refined. C-bound H atoms were fixed geometrically (C—H = 0.95 to 0.99 Å) and refined using a riding model, with U iso(H) set to 1.2U eq (1.5U eq for methyl groups) of the parent atoms. The methyl groups were allowed to rotate but not to tip.

Figure 1View larger versionFigure 1. The title molecule, showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. Hydrogen bonds are shown as dashed lines.

Figure 2View larger versionFigure 2. A perspective view along the a axis of the crystal packing of the title compound,. The C—H⋯O hydrogen bonds are shown as dashed lines.

See full table Table 1. Hydrogen-bond geometry (, )

See full table Table 2. Experimental details

Supplementary Material

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Acknowledgments

We acknowledge the Dirección de Investigaciones, Sede Bogotá (DIB) de la Universidad Nacional de Colombia, for financial support of this work. LSN acknowledges COLCIENCIAS for a fellowship.

supplementary crystallographic information

Crystal data

See full table

Data collection

See full table

Refinement

See full table

Special details

See full table

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

See full table

Atomic displacement parameters (Å²)

See full table

Geometric parameters (Å, º)

See full table

Hydrogen-bond geometry (Å, º)

See full table

Symmetry code: (i) −x+1, −y+1, z+1/2.

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References

Groom, C. R. & Allen, F. H. (2014). Angew. Chem. Int. Ed. 53, 662–671.

Hutchins, R. O., Kopp, L. D. & Eliel, E. L. (1968). J. Am. Chem. Soc. 90, 7174–7175.

Kober, E., Nerkowski, T., Janas, Z. & Jerzykiewicz, L. B. (2012). Dalton Trans. 41, 5188–5191.

Koll, A., Karpfen, A. & Wolschann, P. (2006). J. Mol. Struct. 790, 55–64.

Parsons, S., Flack, H. D. & Wagner, T. (2013). Acta Cryst. B69, 249–259.

Rivera, A., Gallo, G. I., Gayón, M. E. & Joseph-Nathan, P. (1993). Synth. Commun 23, 2921–2929.

Rivera, A., Nerio, L. S. & Bolte, M. (2013). Acta Cryst. E69, o1166.

Rivera, A., Nerio, L. S. & Bolte, M. (2014). Acta Cryst. E70, o243.

Rivera, A., Nerio, L. S., Ríos-Motta, J., Fejfarová, K. & Dušek, M. (2012a). Acta Cryst. E68, o170–o171.

Rivera, A., Nerio, L. S., Ríos-Motta, J., Kučeráková, M. & Dušek, M. (2012b). Acta Cryst. E68, o3043–o3044.

Rivera, A., Nerio, L. S., Ríos-Motta, J., Kučeraková, M. & Dušek, M. (2012c). Acta Cryst. E68, o3172.

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Rivera, A., Quevedo, R., Navarro, M. A. & Maldonado, M. (2004). Synth. Commun. 34, 2479–2485.

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Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8.

Stoe & Cie (2001). X-AREA and X-RED32. Stoe & Cie, Darmstadt, Germany.

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C₂₁H₂₆Cl₂N₂O₂ | Dx = 1.349 Mg m⁻³
Mr = 409.34 | Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pna2₁ | Cell parameters from 16491 reflections
a = 20.1594 (11) Å | θ = 2.1–25.9°
b = 17.8088 (12) Å | µ = 0.34 mm⁻¹
c = 5.6120 (3) Å | T = 173 K
V = 2014.8 (2) Å³ | Needle, colourless
Z = 4 | 0.22 × 0.11 × 0.09 mm
F(000) = 864 |

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Stoe IPDS II two-circle diffractometer | 3280 reflections with I > 2σ(I)
Radiation source: Genix 3D IµS microfocus X-ray source | Rint = 0.080
ω scans | θmax = 25.4°, θmin = 2.0°
Absorption correction: multi-scan (X-AREA; Stoe & Cie, 2001) | h = −24→24
Tmin = 0.891, Tmax = 0.946 | k = −21→21
17730 measured reflections | l = −6→6
3708 independent reflections |

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Refinement on F² | Hydrogen site location: mixed
Least-squares matrix: full | H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.035 | w = 1/[σ²(Fo²) + (0.0492P)²] where P = (Fo² + 2Fc²)/3
wR(F²) = 0.082 | (Δ/σ)max = 0.001
S = 1.00 | Δρmax = 0.16 e Å⁻³
3708 reflections | Δρmin = −0.20 e Å⁻³
256 parameters | Absolute structure: Flack x determined using 1338 quotients [(I⁺)-(I⁻)]/[(I⁺)+(I⁻)] (Parsons et al., 2013)
1 restraint | Absolute structure parameter: 0.00 (4)

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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.

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| x | y | z | Uiso*/Ueq |
Cl1 | 0.71322 (3) | 0.87262 (4) | 0.49746 (17) | 0.04042 (19) |
Cl2 | 0.63887 (4) | 0.04441 (4) | 0.5199 (2) | 0.0535 (2) |
O1 | 0.55382 (11) | 0.60445 (11) | 0.6973 (4) | 0.0383 (5) |
H1 | 0.574 (2) | 0.565 (3) | 0.595 (9) | 0.074 (13)* |
O2 | 0.52557 (10) | 0.34212 (11) | 0.6988 (4) | 0.0368 (5) |
H2 | 0.5460 (19) | 0.3744 (19) | 0.611 (7) | 0.044 (10)* |
N1 | 0.62589 (11) | 0.52659 (13) | 0.4013 (5) | 0.0304 (5) |
N2 | 0.61125 (12) | 0.40126 (13) | 0.4025 (5) | 0.0308 (5) |
C1 | 0.60746 (16) | 0.46539 (14) | 0.2433 (5) | 0.0326 (6) |
H1A | 0.5620 | 0.4721 | 0.1797 | 0.039* |
H1B | 0.6390 | 0.4605 | 0.1090 | 0.039* |
C2 | 0.68434 (15) | 0.49812 (15) | 0.5313 (7) | 0.0394 (7) |
H2A | 0.6872 | 0.5204 | 0.6925 | 0.047* |
H2B | 0.7258 | 0.5092 | 0.4435 | 0.047* |
C3 | 0.67177 (14) | 0.41297 (15) | 0.5448 (6) | 0.0341 (7) |
H3A | 0.7096 | 0.3846 | 0.4768 | 0.041* |
H3B | 0.6649 | 0.3968 | 0.7118 | 0.041* |
C4 | 0.63685 (15) | 0.59859 (15) | 0.2782 (6) | 0.0337 (6) |
H4A | 0.6020 | 0.6056 | 0.1558 | 0.040* |
H4B | 0.6803 | 0.5971 | 0.1959 | 0.040* |
C5 | 0.60838 (15) | 0.32829 (16) | 0.2813 (6) | 0.0337 (6) |
H5A | 0.6508 | 0.3195 | 0.1969 | 0.040* |
H5B | 0.5725 | 0.3294 | 0.1608 | 0.040* |
C11 | 0.63568 (13) | 0.66441 (15) | 0.4475 (5) | 0.0290 (6) |
C12 | 0.59219 (13) | 0.66519 (15) | 0.6419 (6) | 0.0304 (6) |
C13 | 0.58553 (14) | 0.72820 (15) | 0.7842 (6) | 0.0332 (6) |
H13 | 0.5558 | 0.7269 | 0.9154 | 0.040* |
C14 | 0.62147 (14) | 0.79335 (15) | 0.7393 (6) | 0.0326 (7) |
C15 | 0.66605 (13) | 0.79115 (14) | 0.5501 (6) | 0.0308 (6) |
C16 | 0.67502 (13) | 0.72850 (15) | 0.4053 (5) | 0.0296 (6) |
C17 | 0.61244 (17) | 0.86156 (17) | 0.8953 (7) | 0.0429 (8) |
H17A | 0.5790 | 0.8509 | 1.0175 | 0.064* |
H17B | 0.5977 | 0.9040 | 0.7976 | 0.064* |
H17C | 0.6547 | 0.8741 | 0.9720 | 0.064* |
C18 | 0.72556 (15) | 0.72805 (16) | 0.2061 (6) | 0.0387 (7) |
H18A | 0.7530 | 0.7733 | 0.2163 | 0.058* |
H18B | 0.7026 | 0.7270 | 0.0522 | 0.058* |
H18C | 0.7538 | 0.6835 | 0.2208 | 0.058* |
C21 | 0.59596 (13) | 0.26437 (14) | 0.4523 (5) | 0.0299 (6) |
C22 | 0.55305 (14) | 0.27410 (15) | 0.6465 (6) | 0.0317 (6) |
C23 | 0.53458 (15) | 0.21404 (16) | 0.7892 (6) | 0.0351 (6) |
H23 | 0.5045 | 0.2221 | 0.9169 | 0.042* |
C24 | 0.55924 (16) | 0.14239 (16) | 0.7492 (6) | 0.0385 (7) |
C25 | 0.60474 (15) | 0.13394 (15) | 0.5636 (6) | 0.0359 (7) |
C26 | 0.62373 (14) | 0.19245 (16) | 0.4129 (6) | 0.0334 (7) |
C27 | 0.67213 (16) | 0.18022 (16) | 0.2127 (6) | 0.0405 (7) |
H27A | 0.6872 | 0.1279 | 0.2141 | 0.061* |
H27B | 0.7103 | 0.2137 | 0.2333 | 0.061* |
H27C | 0.6504 | 0.1911 | 0.0604 | 0.061* |
C28 | 0.5373 (2) | 0.07780 (19) | 0.9026 (7) | 0.0534 (9) |
H28A | 0.5161 | 0.0395 | 0.8029 | 0.080* |
H28B | 0.5056 | 0.0958 | 1.0220 | 0.080* |
H28C | 0.5759 | 0.0560 | 0.9829 | 0.080* |

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| U ¹¹ | U ²² | U ³³ | U ¹² | U ¹³ | U ²³
Cl1 | 0.0421 (4) | 0.0336 (3) | 0.0456 (4) | −0.0080 (3) | 0.0053 (4) | −0.0003 (4)
Cl2 | 0.0674 (5) | 0.0306 (3) | 0.0625 (6) | 0.0073 (3) | −0.0007 (6) | 0.0026 (4)
O1 | 0.0401 (11) | 0.0349 (10) | 0.0400 (14) | −0.0082 (9) | 0.0115 (10) | 0.0021 (9)
O2 | 0.0379 (11) | 0.0373 (11) | 0.0353 (13) | 0.0040 (9) | 0.0028 (10) | 0.0014 (10)
N1 | 0.0329 (12) | 0.0293 (11) | 0.0289 (13) | −0.0008 (9) | −0.0042 (11) | 0.0015 (10)
N2 | 0.0352 (13) | 0.0284 (11) | 0.0287 (13) | 0.0008 (9) | −0.0056 (11) | 0.0000 (10)
C1 | 0.0389 (15) | 0.0314 (14) | 0.0276 (17) | −0.0011 (11) | −0.0055 (13) | 0.0012 (12)
C2 | 0.0415 (15) | 0.0360 (14) | 0.041 (2) | −0.0018 (12) | −0.0137 (17) | 0.0032 (15)
C3 | 0.0362 (15) | 0.0345 (13) | 0.0316 (18) | 0.0020 (11) | −0.0093 (13) | −0.0026 (13)
C4 | 0.0397 (16) | 0.0294 (14) | 0.0319 (17) | −0.0007 (11) | 0.0015 (14) | 0.0043 (12)
C5 | 0.0385 (15) | 0.0328 (14) | 0.0297 (17) | −0.0006 (12) | −0.0014 (13) | −0.0034 (13)
C11 | 0.0294 (14) | 0.0299 (13) | 0.0278 (18) | 0.0023 (10) | −0.0001 (12) | 0.0028 (11)
C12 | 0.0277 (14) | 0.0317 (13) | 0.0316 (17) | 0.0003 (11) | 0.0017 (12) | 0.0036 (12)
C13 | 0.0314 (14) | 0.0368 (14) | 0.0314 (17) | 0.0021 (12) | 0.0052 (13) | 0.0011 (12)
C14 | 0.0320 (14) | 0.0318 (14) | 0.0342 (19) | 0.0028 (10) | −0.0001 (13) | −0.0008 (13)
C15 | 0.0286 (13) | 0.0298 (13) | 0.0341 (18) | −0.0021 (10) | −0.0026 (12) | 0.0020 (12)
C16 | 0.0268 (13) | 0.0325 (14) | 0.0294 (16) | 0.0033 (11) | 0.0004 (12) | 0.0048 (11)
C17 | 0.0484 (18) | 0.0375 (16) | 0.043 (2) | 0.0007 (13) | 0.0080 (16) | −0.0055 (14)
C18 | 0.0394 (16) | 0.0375 (15) | 0.0392 (19) | −0.0023 (12) | 0.0099 (15) | −0.0007 (13)
C21 | 0.0295 (13) | 0.0308 (13) | 0.0294 (18) | −0.0022 (11) | −0.0035 (12) | −0.0018 (11)
C22 | 0.0309 (14) | 0.0345 (14) | 0.0297 (17) | 0.0005 (11) | −0.0053 (12) | −0.0020 (12)
C23 | 0.0337 (15) | 0.0418 (16) | 0.0297 (16) | −0.0032 (12) | 0.0003 (13) | 0.0006 (13)
C24 | 0.0450 (17) | 0.0352 (15) | 0.0352 (19) | −0.0093 (12) | −0.0069 (15) | 0.0043 (13)
C25 | 0.0403 (15) | 0.0295 (13) | 0.038 (2) | −0.0003 (11) | −0.0085 (13) | −0.0005 (12)
C26 | 0.0309 (14) | 0.0346 (15) | 0.0347 (17) | −0.0020 (11) | −0.0047 (13) | −0.0045 (12)
C27 | 0.0421 (17) | 0.0390 (16) | 0.040 (2) | 0.0014 (13) | 0.0049 (15) | −0.0065 (14)
C28 | 0.065 (2) | 0.0424 (18) | 0.053 (2) | −0.0127 (16) | 0.0006 (19) | 0.0101 (16)

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Cl1—C15 | 1.760 (3) | C13—C14 | 1.391 (4)
Cl2—C25 | 1.754 (3) | C13—H13 | 0.9500
O1—C12 | 1.366 (3) | C14—C15 | 1.392 (4)
O1—H1 | 0.99 (5) | C14—C17 | 1.508 (4)
O2—C22 | 1.364 (3) | C15—C16 | 1.392 (4)
O2—H2 | 0.86 (4) | C16—C18 | 1.513 (4)
N1—C1 | 1.453 (4) | C17—H17A | 0.9800
N1—C4 | 1.473 (4) | C17—H17B | 0.9800
N1—C2 | 1.476 (4) | C17—H17C | 0.9800
N2—C1 | 1.452 (3) | C18—H18A | 0.9800
N2—C5 | 1.468 (4) | C18—H18B | 0.9800
N2—C3 | 1.473 (4) | C18—H18C | 0.9800
C1—H1A | 0.9900 | C21—C22 | 1.402 (4)
C1—H1B | 0.9900 | C21—C26 | 1.415 (4)
C2—C3 | 1.539 (4) | C22—C23 | 1.387 (4)
C2—H2A | 0.9900 | C23—C24 | 1.388 (4)
C2—H2B | 0.9900 | C23—H23 | 0.9500
C3—H3A | 0.9900 | C24—C25 | 1.396 (5)
C3—H3B | 0.9900 | C24—C28 | 1.503 (4)
C4—C11 | 1.509 (4) | C25—C26 | 1.396 (4)
C4—H4A | 0.9900 | C26—C27 | 1.504 (5)
C4—H4B | 0.9900 | C27—H27A | 0.9800
C5—C21 | 1.510 (4) | C27—H27B | 0.9800
C5—H5A | 0.9900 | C27—H27C | 0.9800
C5—H5B | 0.9900 | C28—H28A | 0.9800
C11—C12 | 1.399 (4) | C28—H28B | 0.9800
C11—C16 | 1.410 (4) | C28—H28C | 0.9800
C12—C13 | 1.384 (4) |  |
C12—O1—H1 | 101 (3) | C15—C14—C17 | 122.9 (3)
C22—O2—H2 | 106 (2) | C14—C15—C16 | 123.5 (2)
C1—N1—C4 | 113.9 (2) | C14—C15—Cl1 | 117.0 (2)
C1—N1—C2 | 104.4 (2) | C16—C15—Cl1 | 119.5 (2)
C4—N1—C2 | 114.3 (2) | C15—C16—C11 | 118.5 (3)
C1—N2—C5 | 114.2 (2) | C15—C16—C18 | 121.5 (3)
C1—N2—C3 | 105.4 (2) | C11—C16—C18 | 119.9 (3)
C5—N2—C3 | 114.2 (2) | C14—C17—H17A | 109.5
N2—C1—N1 | 101.6 (2) | C14—C17—H17B | 109.5
N2—C1—H1A | 111.5 | H17A—C17—H17B | 109.5
N1—C1—H1A | 111.5 | C14—C17—H17C | 109.5
N2—C1—H1B | 111.5 | H17A—C17—H17C | 109.5
N1—C1—H1B | 111.5 | H17B—C17—H17C | 109.5
H1A—C1—H1B | 109.3 | C16—C18—H18A | 109.5
N1—C2—C3 | 103.4 (2) | C16—C18—H18B | 109.5
N1—C2—H2A | 111.1 | H18A—C18—H18B | 109.5
C3—C2—H2A | 111.1 | C16—C18—H18C | 109.5
N1—C2—H2B | 111.1 | H18A—C18—H18C | 109.5
C3—C2—H2B | 111.1 | H18B—C18—H18C | 109.5
H2A—C2—H2B | 109.1 | C22—C21—C26 | 118.5 (3)
N2—C3—C2 | 104.4 (2) | C22—C21—C5 | 120.2 (2)
N2—C3—H3A | 110.9 | C26—C21—C5 | 121.2 (3)
C2—C3—H3A | 110.9 | O2—C22—C23 | 116.8 (3)
N2—C3—H3B | 110.9 | O2—C22—C21 | 121.9 (3)
C2—C3—H3B | 110.9 | C23—C22—C21 | 121.3 (3)
H3A—C3—H3B | 108.9 | C22—C23—C24 | 121.3 (3)
N1—C4—C11 | 112.2 (3) | C22—C23—H23 | 119.4
N1—C4—H4A | 109.2 | C24—C23—H23 | 119.4
C11—C4—H4A | 109.2 | C23—C24—C25 | 117.1 (3)
N1—C4—H4B | 109.2 | C23—C24—C28 | 120.4 (3)
C11—C4—H4B | 109.2 | C25—C24—C28 | 122.6 (3)
H4A—C4—H4B | 107.9 | C26—C25—C24 | 123.5 (3)
N2—C5—C21 | 112.3 (2) | C26—C25—Cl2 | 119.1 (2)
N2—C5—H5A | 109.1 | C24—C25—Cl2 | 117.4 (2)
C21—C5—H5A | 109.1 | C25—C26—C21 | 118.2 (3)
N2—C5—H5B | 109.1 | C25—C26—C27 | 121.5 (3)
C21—C5—H5B | 109.1 | C21—C26—C27 | 120.3 (3)
H5A—C5—H5B | 107.9 | C26—C27—H27A | 109.5
C12—C11—C16 | 118.4 (3) | C26—C27—H27B | 109.5
C12—C11—C4 | 120.6 (2) | H27A—C27—H27B | 109.5
C16—C11—C4 | 120.9 (3) | C26—C27—H27C | 109.5
O1—C12—C13 | 117.1 (3) | H27A—C27—H27C | 109.5
O1—C12—C11 | 121.6 (3) | H27B—C27—H27C | 109.5
C13—C12—C11 | 121.2 (3) | C24—C28—H28A | 109.5
C12—C13—C14 | 121.4 (3) | C24—C28—H28B | 109.5
C12—C13—H13 | 119.3 | H28A—C28—H28B | 109.5
C14—C13—H13 | 119.3 | C24—C28—H28C | 109.5
C13—C14—C15 | 116.8 (3) | H28A—C28—H28C | 109.5
C13—C14—C17 | 120.3 (3) | H28B—C28—H28C | 109.5
C5—N2—C1—N1 | −168.1 (2) | C14—C15—C16—C18 | −178.2 (3)
C3—N2—C1—N1 | −42.0 (3) | Cl1—C15—C16—C18 | 1.3 (4)
C4—N1—C1—N2 | 170.7 (2) | C12—C11—C16—C15 | −3.7 (4)
C2—N1—C1—N2 | 45.4 (3) | C4—C11—C16—C15 | 172.2 (3)
C1—N1—C2—C3 | −31.0 (3) | C12—C11—C16—C18 | 176.3 (3)
C4—N1—C2—C3 | −156.0 (2) | C4—C11—C16—C18 | −7.8 (4)
C1—N2—C3—C2 | 22.5 (3) | N2—C5—C21—C22 | 37.3 (4)
C5—N2—C3—C2 | 148.6 (3) | N2—C5—C21—C26 | −146.7 (3)
N1—C2—C3—N2 | 5.2 (3) | C26—C21—C22—O2 | 178.5 (3)
C1—N1—C4—C11 | 163.0 (2) | C5—C21—C22—O2 | −5.4 (4)
C2—N1—C4—C11 | −77.2 (3) | C26—C21—C22—C23 | −4.0 (4)
C1—N2—C5—C21 | −166.3 (2) | C5—C21—C22—C23 | 172.1 (3)
C3—N2—C5—C21 | 72.3 (3) | O2—C22—C23—C24 | 179.3 (3)
N1—C4—C11—C12 | −36.2 (4) | C21—C22—C23—C24 | 1.7 (5)
N1—C4—C11—C16 | 148.0 (2) | C22—C23—C24—C25 | 1.7 (4)
C16—C11—C12—O1 | −178.3 (3) | C22—C23—C24—C28 | −178.6 (3)
C4—C11—C12—O1 | 5.8 (4) | C23—C24—C25—C26 | −3.0 (5)
C16—C11—C12—C13 | 2.7 (4) | C28—C24—C25—C26 | 177.3 (3)
C4—C11—C12—C13 | −173.2 (3) | C23—C24—C25—Cl2 | 177.3 (2)
O1—C12—C13—C14 | −178.7 (3) | C28—C24—C25—Cl2 | −2.4 (4)
C11—C12—C13—C14 | 0.3 (5) | C24—C25—C26—C21 | 0.8 (5)
C12—C13—C14—C15 | −2.2 (4) | Cl2—C25—C26—C21 | −179.5 (2)
C12—C13—C14—C17 | 179.1 (3) | C24—C25—C26—C27 | −179.0 (3)
C13—C14—C15—C16 | 1.2 (4) | Cl2—C25—C26—C27 | 0.7 (4)
C17—C14—C15—C16 | 179.8 (3) | C22—C21—C26—C25 | 2.7 (4)
C13—C14—C15—Cl1 | −178.4 (2) | C5—C21—C26—C25 | −173.4 (3)
C17—C14—C15—Cl1 | 0.3 (4) | C22—C21—C26—C27 | −177.5 (3)
C14—C15—C16—C11 | 1.8 (4) | C5—C21—C26—C27 | 6.4 (4)
Cl1—C15—C16—C11 | −178.7 (2) |  |

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D—H···A | D—H | H···A | D···A | D—H···A
O1—H1···N1 | 0.99 (5) | 1.66 (5) | 2.606 (3) | 158 (4)
O2—H2···N2 | 0.86 (4) | 1.83 (4) | 2.619 (3) | 152 (3)
C13—H13···O2i | 0.95 | 2.59 | 3.464 (4) | 152

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Figure 1.

The title molecule, showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. Hydrogen bonds are shown as dashed lines.

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Figure 2.

A perspective view along the a axis of the crystal packing of the title compound,. The C—H⋯O hydrogen bonds are shown as dashed lines.

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Table 1. Hydrogen-bond geometry (, )

DHA | DH | HA | D A | DHA
O1H1N1 | 0.99(5) | 1.66(5) | 2.606(3) | 158(4)
O2H2N2 | 0.86(4) | 1.83(4) | 2.619(3) | 152(3)
C13H13O2i | 0.95 | 2.59 | 3.464(4) | 152

Symmetry code: (i) .

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Table 2. Experimental details

Crystal data
Chemical formula | C₂₁H₂₆Cl₂N₂O₂
M r | 409.34
Crystal system, space group | Orthorhombic, P n a2₁
Temperature (K) | 173
a, b, c () | 20.1594(11), 17.8088(12), 5.6120(3)
V (³) | 2014.8(2)
Z | 4
Radiation type | Mo K
(mm¹) | 0.34
Crystal size (mm) | 0.22 0.11 0.09
Data collection
Diffractometer | Stoe IPDS II two circle
Absorption correction | Multi-scan (X-AREA; Stoe Cie, 2001 ▸)
T min, T max | 0.891, 0.946
No. of measured, independent and observed [I > 2(I)] reflections | 17730, 3708, 3280
R int | 0.080
(sin /)max (¹) | 0.604
Refinement
R[F ² > 2(F ²)], wR(F ²), S | 0.035, 0.082, 1.00
No. of reflections | 3708
No. of parameters | 256
No. of restraints | 1
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement
max, min (e ³) | 0.16, 0.20
Absolute structure | Flack x determined using 1338 quotients [(I ⁺)(I )]/[(I ⁺)+(I )] (Parsons et al., 2013 ▸)
Absolute structure parameter | 0.00(4)

Computer programs: X-AREA and X-RED32 (Stoe Cie, 2001 ▸), SHELXS87 and XP in SHELXTL-Plus (Sheldrick, 2008 ▸), SHELXL2014 (Sheldrick, 2015 ▸).

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