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

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[4.4.1.1^3,8]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 ▸).

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.

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) .

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 ▸).

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.

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[4.4.1.1^3,8]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.

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 ▸).

Supplementary Material

CCDC reference: 1046907

Additional supporting information: crystallographic information; 3D view; checkCIF report

supplementary crystallographic information

Crystal data

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

Data collection

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

Refinement

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)

Special details

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.

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

	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*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
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)

Geometric parameters (Å, º)

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)

Hydrogen-bond geometry (Å, º)

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

Symmetry code: (i) −x+1, −y+1, z+1/2.