Crystal structure of the co-crystalline adduct 1,3,6,8-tetra­aza­tri­cyclo­[4.4.1.1^3,8]dodecane (TATD)–4-chloro-3,5-di­methyl­phenol (1/1)

In the crystal of the title co-crystalline adduct, the 1,3,6,8-tetra­aza­tri­cyclo­[4.4.1.1^3,8]dodecane (TATD) and 4-chloro-3,5-di­methyl­phenol are linked by inter­molecular O—H⋯N hydrogen bonds and C—H⋯π inter­actions.

Abstract

In the crystal of the title co-crystalline adduct, C₈H₁₆N₄·C₈H₉ClO, (I), prepared by solid-state reaction, the mol­ecules are linked by inter­molecular O—H⋯N hydrogen bonds, forming a D motif. The aza­adamantane structure in (I) is slightly distorted, with N—CH₂—CH₂—N torsion angles of 10.4 (3) and −9.0 (3)°. These values differ slightly from the corresponding torsion angles in the free aminal cage (0.0°) and in related co-crystalline adducts, which are not far from a planar geometry and consistent with a D _2d mol­ecular symmetry in the tetra­aza­tri­cyclo structure. The structures also differ in that there is a slight elongation of the N—C bond lengths about the N atom that accepts the hydrogen bond in (I) compared with the other N—C bond lengths. In the crystal, the two mol­ecules are not only linked by a classical O—H⋯N hydrogen bond but are further connected by weak C—H⋯π inter­actions, forming a two-dimensional supra­molecular network parallel to the bc plane.

Chemical context  

In our continuing investigations on the reactivity of cyclic aminals of the adamantane type with phenols, we have found that 1,3,6,8-tetra­aza­tri­cyclo­[4.4.1.1^3,8]dodecane (TATD) shows an inter­esting reactivity with 4-chloro-3,5-di­methyl­phenol under different conditions. Reaction between TATD with 4-chloro-3,5-di­methyl­phenol in solution yields symmetrical bis-benzoxazines (Rivera et al., 2005 ▸), but under heating in an oil bath (Rivera & Quevedo, 2013 ▸) or microwave-assisted solvent-free conditions, symmetrical N,N’-disubstituted imidazolidines (Rivera, Nerio & Bolte, 2015 ▸) are obtained. Therefore, we became inter­ested in exploring the reactivity of TATD with phenols under solvent-free conditions at room temperature. In the course of our investigations, we obtained the mol­ecular salt 8,10,12-tri­aza-1-azonia­tetra­cyclo[8.3.1.1^8,12.0^2,7]penta­decane 4-nitro­phenolate 4-nitro­phenol by grinding (2R,7R)-1,8,10,12-tetra­aza­tetra­cyclo­[8.3.1.1^8,12.0^2,7]penta­decane with 4-nitro­phenol (Rivera, Uribe, Ríos-Motta et al., 2015 ▸) and the 1:2 adduct 1,3,6,8-tetra­aza­tri­cyclo[4.4.1.1^3,8]dodecane (TATD)-4-bromo­phenol (Rivera, Uribe, Rojas et al., 2015 ▸) by grinding at room temperature.

Herein, we describe the synthesis of the title co-crystalline adduct 1,3,6,8-tetra­aza­tri­cyclo­[4.4.1.1^3,8]dodecane (TATD)–4-chloro-3,5-di­methyl­phenol under solvent-free conditions by simply grinding together the components at room temperature.

Structural commentary  

The crystal structure of the title compound, (I), has confirmed the presence of a 1:1 co-crystalline adduct. A view of this adduct is shown in Fig. 1 ▸. The asymmetric unit of the title compound contains a 1,3,6,8-tetra­aza­tri­cyclo­[4.4.1.1^3,8]dodecane (TATD) and a 4-chloro-3,5-di­methyl­phenol mol­ecule linked via an O—H⋯N hydrogen bond, forming a D motif (Bernstein et al., 1995 ▸). As in the 1:2 adduct with 4-bromo­phenol (Rivera, Uribe, Rojas et al., 2015 ▸) and the 1:1 adduct with hydro­quinone (Rivera et al., 2007 ▸), the inter­molecular O—H⋯N hydrogen bond in (I) also leads to a stable supra­molecular structure, but comparison of the title compound with the above-mentioned related structures shows that the three adducts differ in the O⋯N hydrogen-bond distances [2.752 (2) Å in (I), 2.705 (5) Å in the 1:2 adduct and 2.767 (2) Å in the co-crystalline adduct with hydro­quinone], which is in agreement with the differences in the pKa values between the species involved in the hydrogen bond (Majerz et al., 1997 ▸): 4-chloro-3,5-di­methyl­phenol (pKa = 9.76); p-bromo­phenol (pKa = 9.37) and hydro­quinone (pKa = 9.85) (Lide, 2003 ▸).

Figure 1.

Perspective view of the title compound, with displacement ellipsoids drawn at the 50% probability level. The hydrogen bond is drawn as a dashed line.

To a first approximation, the geometric parameters of the title mol­ecule agree well with those reported for similar structures (Rivera et al., 2007 ▸; Rivera, Uribe, Rojas et al., 2015 ▸) and are within normal ranges (Allen et al., 1987 ▸), but compared to the free aminal cage structure (Rivera et al., 2014 ▸) which belongs to the D_2d point group, two small differences are noted. The aza­adamantane structure in (I) is slightly distorted, with N—CH_2—CH₂—N torsion angles of 10.4 (3)° (N1—C1—C2—N2) and −9.0 (3)° (N3—C7—C8—N4). These values differ slightly from the values of the corresponding torsion angles in the free aminal cage (0.0°; Rivera et al., 2014 ▸), and the related co-crystalline adducts [2.4 (7)° (Rivera, Uribe, Rojas et al., 2015 ▸) and −0.62° (Rivera et al., 2007 ▸)] which shows that each N—C—C—N group is not far from a planar geometry and consistent with a D_2d mol­ecular symmetry in the tetra­aza­tri­cyclo structure. Furthermore, the structures also differ in the slight elongation of the N1—C bond lengths of the nitro­gen atom that accepts the hydrogen bond, [1.470 (2) and 1.480 (2) Å], compared to the the other N—C bond lengths (Table 1 ▸).

Table 1. Selected geometric parameters (, ).

N1C1	1.470(2)	N3C7	1.455(2)
N1C5	1.470(2)	N3C4	1.458(2)
N1C3	1.480(2)	N4C5	1.444(2)
N2C2	1.449(3)	N4C6	1.456(2)
N2C6	1.454(3)	N4C8	1.457(3)
N2C4	1.462(2)	Cl1C14	1.7534(16)
N3C3	1.446(2)	O11C11	1.356(2)
N1C1C2N2	10.4(3)	N3C7C8N4	9.0(3)

Supra­molecular features  

The two different mol­ecules in (I) are connected by a classical O—H⋯N hydrogen bond. The crystal packing is further stabilized by weak inter­molecular C—H⋯π inter­actions, linking the mol­ecules into two-dimensional sheets in the bc plane (Table 2 ▸ and Fig. 2 ▸). Furthermore, there are short N⋯Cl contacts [N4⋯Cl1ⁱ 3.1680 (15) Å; symmetry operator: (i) x, −y, z − ] linking the mol­ecules into zigzag chains running along the c-axis direction (Fig. 3 ▸).

Table 2. Hydrogen-bond geometry (, ).

Cg8 is the centroid of the C11C16 ring.

DHA	DH	HA	D A	DHA
O11H11N1	0.85(4)	1.92(4)	2.752(2)	165(3)
C3H3A Cg8i	0.99	2.89	3.837(2)	160
C8H8A Cg8ii	0.99	2.88	3.814(2)	157

Symmetry codes: (i) ; (ii) .

Figure 2.

Packing diagram of the title compound. Only H atoms involved in hydrogen bonding are shown. Hydrogen bonds are drawn as dashed lines.

Figure 3.

Partial packing diagram of the title compound, viewed along the b axis. Only H atoms involved in hydrogen bonding are shown. Hydrogen bonds are drawn as dashed lines and the short Cl⋯N contacts are shown as dotted lines. Atoms with suffix A are generated by the symmetry operator (x, −y, z − ) and atoms with suffix B are generated by the symmetry operator (x, −y, z + ).

Database survey  

The geometric parameters of 4-chloro-3,5-di­methyl­phenol in (I) (Table 1 ▸) agree well with those of found in the crystal structure containing only this mol­ecule (Cox, 1995 ▸), which crystallized with two mol­ecules in the asymmetric unit [C—O = 1.387 (3) and 1.378 (3) Å; C—Cl = 1.752 (2) and 1.749 (2) Å; C—C_meth­yl = 1.502 (3), 1.500 (3), 1.514 (3) and 1.505 (3) Å]. For 1,3,6,8-tetra­aza­tri­cyclo­[4.4.1.1^3,8]dodecane, two comparable structures were retrieved from the CSD (Groom & Allen, 2014 ▸). A least-squares fit of the structure that contains only 1,3,6,8-tetra­aza­tri­cyclo­[4.4.1.1^3,8]dodecane (Rivera et al., 2014 ▸) gives an r.m.s. deviation of 0.048 Å with 1,3,6,8-tetra­aza­tri­cyclo­[4.4.1.1^3,8]dodecane of (I) and a least-squares fit of 1,3,6,8-tetra­aza­tri­cyclo­[4.4.1.1^3,8]dodecane co-crystallized with hydro­quinone (Rivera et al., 2007 ▸) gives an r.m.s. deviation of 0.051 Å with 1,3,6,8-tetra­aza­tri­cyclo­[4.4.1.1^3,8]dodecane of (I). Thus, it can be concluded that the conformational freedom of 1,3,6,8-tetra­aza­tri­cyclo­[4.4.1.1^3,8]dodecane is rather limited.

Synthesis and crystallization  

A mixture of 1,3,6,8-tetra­aza­tri­cyclo­[4.4.1.^3,8]dodecane (TATD) (168 mg, 1 mmol) and 4-chloro-3,5-di­methyl­phenol (157 mg, 1 mmol) was ground using a mortar and pestle, at room temperature for 15 min., as required to complete the reaction (TLC). The mixture was then dissolved in methanol. Crystals suitable for X-ray diffraction were obtained from a methanol solution upon slow evaporation of the solvent at room temperature.

Refinement  

Crystal data, data collection and structure refinement details are summarized in Table 3 ▸. All H atoms were located in difference electron-density maps. The hydroxyl H atom was refined freely, while C-bound H atoms were fixed geometrically (C—H = 0.95, 0.98 or 0.99 Å) and refined using a riding model, with U _iso(H) values set at 1.2U _eq (1.5 for methyl groups) of the parent atom. The methyl groups were allowed to rotate but not to tip.

Table 3. Experimental details.

Crystal data
Chemical formula	C8H16N4C8H9ClO
M r	324.85
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	173
a, b, c ()	25.6048(18), 7.5295(7), 18.2317(13)
()	111.080(5)
V (3)	3279.7(5)
Z	8
Radiation type	Mo K
(mm1)	0.24
Crystal size (mm)	0.27 0.26 0.22
Data collection
Diffractometer	Stoe IPDS II two-circle
Absorption correction	Multi-scan (X-RED32; Stoe Cie, 2001 ▸)
T min, T max	0.738, 1.000
No. of measured, independent and observed [I > 2(I)] reflections	14414, 3066, 2512
R int	0.083
(sin /)max (1)	0.608
Refinement
R[F 2 > 2(F 2)], wR(F 2), S	0.040, 0.107, 1.02
No. of reflections	3066
No. of parameters	205
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
max, min (e 3)	0.26, 0.25

Computer programs: X-AREA (Stoe Cie, 2001 ▸), SHELXS97 and XP in SHELXTL-Plus (Sheldrick, 2008 ▸) and SHELXL2014 (Sheldrick, 2015 ▸).

Supplementary Material

CCDC reference: 1403518

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

supplementary crystallographic information

Crystal data

C8H16N4·C8H9ClO	F(000) = 1392
Mr = 324.85	Dx = 1.316 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 25.6048 (18) Å	Cell parameters from 12525 reflections
b = 7.5295 (7) Å	θ = 3.4–25.8°
c = 18.2317 (13) Å	µ = 0.24 mm−1
β = 111.080 (5)°	T = 173 K
V = 3279.7 (5) Å3	Block, colourless
Z = 8	0.27 × 0.26 × 0.22 mm

Data collection

Stoe IPDS II two-circle diffractometer	2512 reflections with I > 2σ(I)
Radiation source: Genix 3D IµS microfocus X-ray source	Rint = 0.083
ω scans	θmax = 25.6°, θmin = 3.4°
Absorption correction: multi-scan (X-RED32; Stoe & Cie, 2001)	h = −30→30
Tmin = 0.738, Tmax = 1.000	k = −9→9
14414 measured reflections	l = −19→22
3066 independent reflections

Refinement

Refinement on F2	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.040	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.107	w = 1/[σ2(Fo2) + (0.0635P)2 + 0.5777P] where P = (Fo2 + 2Fc2)/3
S = 1.02	(Δ/σ)max < 0.001
3066 reflections	Δρmax = 0.26 e Å−3
205 parameters	Δρmin = −0.25 e Å−3

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
N1	0.37029 (5)	0.56339 (18)	0.36779 (8)	0.0224 (3)
N2	0.30414 (6)	0.8359 (2)	0.26828 (9)	0.0297 (3)
N3	0.40890 (6)	0.84503 (19)	0.33226 (9)	0.0260 (3)
N4	0.35050 (6)	0.58696 (19)	0.22295 (9)	0.0299 (3)
C1	0.31697 (7)	0.6087 (2)	0.37648 (11)	0.0313 (4)
H1A	0.3246	0.6345	0.4326	0.038*
H1B	0.2924	0.5030	0.3623	0.038*
C2	0.28501 (8)	0.7651 (3)	0.32812 (14)	0.0438 (5)
H2A	0.2455	0.7287	0.3022	0.053*
H2B	0.2857	0.8627	0.3649	0.053*
C3	0.41163 (7)	0.7098 (2)	0.38985 (10)	0.0267 (4)
H3A	0.4084	0.7700	0.4363	0.032*
H3B	0.4494	0.6559	0.4068	0.032*
C4	0.35575 (8)	0.9394 (2)	0.29998 (12)	0.0333 (4)
H4A	0.3578	1.0180	0.2575	0.040*
H4B	0.3524	1.0170	0.3419	0.040*
C5	0.36300 (7)	0.4777 (2)	0.29227 (11)	0.0285 (4)
H5A	0.3977	0.4111	0.2989	0.034*
H5B	0.3325	0.3894	0.2818	0.034*
C6	0.30356 (8)	0.7083 (3)	0.20810 (12)	0.0376 (5)
H6A	0.2997	0.7761	0.1599	0.045*
H6B	0.2693	0.6355	0.1961	0.045*
C7	0.43347 (9)	0.7933 (3)	0.27484 (12)	0.0386 (5)
H7A	0.4705	0.7391	0.3032	0.046*
H7B	0.4399	0.9020	0.2487	0.046*
C8	0.39926 (10)	0.6640 (3)	0.21162 (13)	0.0430 (5)
H8A	0.3865	0.7265	0.1604	0.052*
H8B	0.4241	0.5661	0.2084	0.052*
Cl1	0.35337 (2)	−0.26689 (6)	0.61168 (3)	0.03412 (16)
O11	0.43692 (5)	0.32897 (19)	0.47753 (9)	0.0390 (4)
H11	0.4116 (15)	0.396 (5)	0.447 (2)	0.084 (10)*
C11	0.41519 (7)	0.1923 (2)	0.50578 (10)	0.0257 (4)
C12	0.45255 (7)	0.0659 (2)	0.55103 (10)	0.0261 (4)
H12	0.4913	0.0774	0.5597	0.031*
C13	0.43430 (7)	−0.0768 (2)	0.58371 (10)	0.0250 (4)
C14	0.37708 (7)	−0.0899 (2)	0.56943 (10)	0.0237 (3)
C15	0.33830 (7)	0.0318 (2)	0.52312 (10)	0.0229 (3)
C16	0.35825 (7)	0.1742 (2)	0.49162 (10)	0.0245 (4)
H16	0.3327	0.2597	0.4601	0.029*
C17	0.27635 (7)	0.0110 (2)	0.50600 (12)	0.0311 (4)
H17A	0.2638	−0.1047	0.4813	0.047*
H17B	0.2559	0.1057	0.4704	0.047*
H17C	0.2692	0.0185	0.5552	0.047*
C18	0.47576 (8)	−0.2148 (3)	0.63056 (13)	0.0388 (5)
H18A	0.4719	−0.2311	0.6817	0.058*
H18B	0.5139	−0.1753	0.6384	0.058*
H18C	0.4684	−0.3277	0.6019	0.058*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
N1	0.0202 (6)	0.0238 (7)	0.0228 (7)	−0.0040 (5)	0.0074 (5)	0.0018 (5)
N2	0.0289 (7)	0.0269 (7)	0.0311 (8)	0.0034 (6)	0.0080 (6)	0.0026 (6)
N3	0.0285 (7)	0.0250 (7)	0.0264 (8)	−0.0061 (6)	0.0122 (6)	−0.0009 (6)
N4	0.0394 (8)	0.0270 (7)	0.0227 (8)	−0.0012 (6)	0.0104 (6)	−0.0047 (6)
C1	0.0261 (8)	0.0386 (10)	0.0328 (10)	−0.0012 (7)	0.0152 (8)	0.0041 (8)
C2	0.0350 (10)	0.0483 (11)	0.0558 (14)	0.0129 (9)	0.0259 (10)	0.0134 (10)
C3	0.0243 (8)	0.0289 (8)	0.0233 (9)	−0.0075 (6)	0.0042 (7)	0.0006 (7)
C4	0.0402 (10)	0.0206 (8)	0.0367 (11)	0.0003 (7)	0.0108 (8)	0.0009 (7)
C5	0.0331 (9)	0.0206 (8)	0.0309 (10)	−0.0020 (6)	0.0106 (7)	−0.0034 (7)
C6	0.0410 (10)	0.0353 (10)	0.0247 (10)	0.0032 (8)	−0.0024 (8)	−0.0014 (8)
C7	0.0408 (10)	0.0466 (11)	0.0376 (11)	−0.0112 (8)	0.0252 (9)	−0.0016 (9)
C8	0.0609 (13)	0.0429 (11)	0.0379 (12)	−0.0081 (10)	0.0333 (11)	−0.0079 (9)
Cl1	0.0372 (2)	0.0318 (2)	0.0342 (3)	−0.00899 (18)	0.01382 (19)	0.00941 (18)
O11	0.0250 (6)	0.0406 (8)	0.0481 (9)	−0.0075 (6)	0.0090 (6)	0.0216 (7)
C11	0.0256 (8)	0.0271 (8)	0.0240 (9)	−0.0081 (7)	0.0084 (7)	0.0023 (7)
C12	0.0194 (7)	0.0308 (9)	0.0256 (9)	−0.0054 (6)	0.0049 (6)	0.0012 (7)
C13	0.0267 (8)	0.0260 (8)	0.0197 (8)	−0.0027 (6)	0.0051 (7)	0.0003 (6)
C14	0.0298 (8)	0.0231 (8)	0.0189 (8)	−0.0077 (6)	0.0096 (7)	−0.0009 (6)
C15	0.0251 (8)	0.0253 (8)	0.0201 (8)	−0.0051 (6)	0.0102 (6)	−0.0028 (6)
C16	0.0240 (8)	0.0256 (8)	0.0220 (8)	−0.0011 (6)	0.0062 (7)	0.0033 (7)
C17	0.0255 (9)	0.0332 (9)	0.0373 (11)	−0.0038 (7)	0.0145 (7)	0.0008 (8)
C18	0.0325 (9)	0.0385 (10)	0.0387 (11)	0.0028 (8)	0.0047 (8)	0.0122 (9)

Geometric parameters (Å, º)

N1—C1	1.470 (2)	C7—C8	1.522 (3)
N1—C5	1.470 (2)	C7—H7A	0.9900
N1—C3	1.480 (2)	C7—H7B	0.9900
N2—C2	1.449 (3)	C8—H8A	0.9900
N2—C6	1.454 (3)	C8—H8B	0.9900
N2—C4	1.462 (2)	Cl1—C14	1.7534 (16)
N3—C3	1.446 (2)	O11—C11	1.356 (2)
N3—C7	1.455 (2)	O11—H11	0.85 (4)
N3—C4	1.458 (2)	C11—C12	1.391 (2)
N4—C5	1.444 (2)	C11—C16	1.393 (2)
N4—C6	1.456 (2)	C12—C13	1.388 (2)
N4—C8	1.457 (3)	C12—H12	0.9500
C1—C2	1.521 (3)	C13—C14	1.396 (2)
C1—H1A	0.9900	C13—C18	1.512 (2)
C1—H1B	0.9900	C14—C15	1.391 (2)
C2—H2A	0.9900	C15—C16	1.397 (2)
C2—H2B	0.9900	C15—C17	1.511 (2)
C3—H3A	0.9900	C16—H16	0.9500
C3—H3B	0.9900	C17—H17A	0.9800
C4—H4A	0.9900	C17—H17B	0.9800
C4—H4B	0.9900	C17—H17C	0.9800
C5—H5A	0.9900	C18—H18A	0.9800
C5—H5B	0.9900	C18—H18B	0.9800
C6—H6A	0.9900	C18—H18C	0.9800
C6—H6B	0.9900
C1—N1—C5	113.12 (13)	N4—C6—H6B	107.5
C1—N1—C3	113.50 (13)	H6A—C6—H6B	107.0
C5—N1—C3	114.75 (13)	N3—C7—C8	115.84 (15)
C2—N2—C6	114.25 (16)	N3—C7—H7A	108.3
C2—N2—C4	113.62 (17)	C8—C7—H7A	108.3
C6—N2—C4	114.37 (16)	N3—C7—H7B	108.3
C3—N3—C7	114.43 (15)	C8—C7—H7B	108.3
C3—N3—C4	115.49 (14)	H7A—C7—H7B	107.4
C7—N3—C4	114.98 (16)	N4—C8—C7	115.87 (15)
C5—N4—C6	115.37 (15)	N4—C8—H8A	108.3
C5—N4—C8	114.79 (15)	C7—C8—H8A	108.3
C6—N4—C8	114.58 (16)	N4—C8—H8B	108.3
N1—C1—C2	116.37 (15)	C7—C8—H8B	108.3
N1—C1—H1A	108.2	H8A—C8—H8B	107.4
C2—C1—H1A	108.2	C11—O11—H11	112 (2)
N1—C1—H1B	108.2	O11—C11—C12	117.13 (15)
C2—C1—H1B	108.2	O11—C11—C16	123.30 (16)
H1A—C1—H1B	107.3	C12—C11—C16	119.58 (15)
N2—C2—C1	117.66 (15)	C13—C12—C11	121.22 (15)
N2—C2—H2A	107.9	C13—C12—H12	119.4
C1—C2—H2A	107.9	C11—C12—H12	119.4
N2—C2—H2B	107.9	C12—C13—C14	117.86 (15)
C1—C2—H2B	107.9	C12—C13—C18	119.89 (15)
H2A—C2—H2B	107.2	C14—C13—C18	122.22 (15)
N3—C3—N1	118.95 (14)	C15—C14—C13	122.59 (15)
N3—C3—H3A	107.6	C15—C14—Cl1	118.87 (12)
N1—C3—H3A	107.6	C13—C14—Cl1	118.54 (13)
N3—C3—H3B	107.6	C14—C15—C16	117.92 (14)
N1—C3—H3B	107.6	C14—C15—C17	121.63 (15)
H3A—C3—H3B	107.0	C16—C15—C17	120.45 (15)
N3—C4—N2	118.66 (14)	C11—C16—C15	120.81 (15)
N3—C4—H4A	107.6	C11—C16—H16	119.6
N2—C4—H4A	107.6	C15—C16—H16	119.6
N3—C4—H4B	107.6	C15—C17—H17A	109.5
N2—C4—H4B	107.6	C15—C17—H17B	109.5
H4A—C4—H4B	107.1	H17A—C17—H17B	109.5
N4—C5—N1	118.91 (13)	C15—C17—H17C	109.5
N4—C5—H5A	107.6	H17A—C17—H17C	109.5
N1—C5—H5A	107.6	H17B—C17—H17C	109.5
N4—C5—H5B	107.6	C13—C18—H18A	109.5
N1—C5—H5B	107.6	C13—C18—H18B	109.5
H5A—C5—H5B	107.0	H18A—C18—H18B	109.5
N2—C6—N4	119.39 (15)	C13—C18—H18C	109.5
N2—C6—H6A	107.5	H18A—C18—H18C	109.5
N4—C6—H6A	107.5	H18B—C18—H18C	109.5
N2—C6—H6B	107.5
C5—N1—C1—C2	−73.2 (2)	C3—N3—C7—C8	74.7 (2)
C3—N1—C1—C2	59.8 (2)	C4—N3—C7—C8	−62.5 (2)
C6—N2—C2—C1	59.7 (2)	C5—N4—C8—C7	−63.3 (2)
C4—N2—C2—C1	−74.0 (2)	C6—N4—C8—C7	73.6 (2)
N1—C1—C2—N2	10.4 (3)	N3—C7—C8—N4	−9.0 (3)
C7—N3—C3—N1	−79.67 (19)	O11—C11—C12—C13	178.74 (17)
C4—N3—C3—N1	57.2 (2)	C16—C11—C12—C13	−1.2 (3)
C1—N1—C3—N3	−84.10 (19)	C11—C12—C13—C14	0.3 (3)
C5—N1—C3—N3	48.1 (2)	C11—C12—C13—C18	178.17 (17)
C3—N3—C4—N2	−51.5 (2)	C12—C13—C14—C15	1.1 (3)
C7—N3—C4—N2	85.2 (2)	C18—C13—C14—C15	−176.72 (17)
C2—N2—C4—N3	78.8 (2)	C12—C13—C14—Cl1	−178.85 (13)
C6—N2—C4—N3	−54.8 (2)	C18—C13—C14—Cl1	3.3 (2)
C6—N4—C5—N1	−51.7 (2)	C13—C14—C15—C16	−1.5 (2)
C8—N4—C5—N1	84.85 (19)	Cl1—C14—C15—C16	178.46 (13)
C1—N1—C5—N4	79.28 (19)	C13—C14—C15—C17	177.67 (16)
C3—N1—C5—N4	−53.1 (2)	Cl1—C14—C15—C17	−2.4 (2)
C2—N2—C6—N4	−83.3 (2)	O11—C11—C16—C15	−179.15 (17)
C4—N2—C6—N4	50.0 (2)	C12—C11—C16—C15	0.8 (3)
C5—N4—C6—N2	56.6 (2)	C14—C15—C16—C11	0.5 (3)
C8—N4—C6—N2	−80.1 (2)	C17—C15—C16—C11	−178.67 (17)

Hydrogen-bond geometry (Å, º)

Cg8 is the centroid of the C11–C16 ring.

D—H···A	D—H	H···A	D···A	D—H···A
O11—H11···N1	0.85 (4)	1.92 (4)	2.752 (2)	165 (3)
C3—H3A···Cg8i	0.99	2.89	3.837 (2)	160
C8—H8A···Cg8ii	0.99	2.88	3.814 (2)	157

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