2-tert-Butyl­amino-4-chloro-6-ethyl­amino-1,3,5-triazine: a structure with Z' = 4 containing two different mol­ecular conformations and two independent chains of hydrogen-bonded R₂²(8) rings

The title compound (trivial name terbutyl­azine), C₉H₁₆ClN₅, (I), crystallizes with Z' = 4 in the space group Pca2₁, and equal numbers of mol­ecules adopt two different conformations for the ethyl­amine groups. The four independent mol­ecules form two approximately enantio­morphic pairs. Eight independent N-H...N hydrogen bonds link the mol­ecules into two independent chains of R₂²(8) rings, in which the arrangement of the alkyl­amine substituents in the independent mol­ecules precludes any further crystallographic symmetry. The significance of this study lies in its finding of two distinct mol­ecular conformations within the structure and two distinct ways in which the mol­ecules are organized into hydrogen-bonded chains, and in its comparison of the hydrogen-bonded structure of (I) with those of analogous 1,3,5-triazines and pyrimidines.

S1. Comment

The formation of hydrogen-bonded rings of R₂²(8) type (Bernstein et al., 1995) built from pairs of N—H···N hydrogen bonds is a very common motif in the structures of aminopyrimidines which readily leads to the formation of chains of these rings (Rodríguez et al., 2008). We have recently attempted a rationalization of the patterns of supramolecular aggregation in 4,6-disubstituted-2-aminopyrmidines in terms of the formation versus fragmentation of such chains (Rodríguez et al., 2008). The formation of continuous chains of R₂²(8) rings can, in fact, be disrupted either by steric factors associated with bulky substituents or by the presence of alternative hydrogen-bond acceptors, giving in some cases short-chain fragments containing only four molecules, and in other cases only isolated dimer units. A number of the examples considered in the earlier study contain one chlorine substituent and two amine substituents, usually different, on the pyrimidine ring. With this in mind, we have now extended our study to encompass a similarly substituted 1,3,5-triazine derivative, the title compound, (I) (Fig. 1), the structure of which we report here along with a comparative analysis of the related structures (II)–(IV) retrieved from the Cambridge Structural Database (CSD, Version?; Allen, 2002).

Compound (I) crystallizes with Z' = 4 in space group Pca2₁, and the selected asymmetric unit consists of two hydrogen-bonded aggregates (Table 1). Molecules 1 and 2, containing atoms N11 and N21, respectively, are linked by two N—H···N hydrogen bonds in which the ethylamine atoms N16 and N26 act as the donors, forming an R₂²(8) ring. We denote this aggregate dimer A (Fig. 1a). By contrast, in dimer B, formed by molecules 3 and 4 (containing atoms N31 and N41, respectively), the hydrogen-bond donors in the R₂²(8) ring are atoms N34 and N46, which are parts of a tert-butylamine and an ethylamine group, respectively (Fig. 1b). Hence in dimer A, the two independent tert-butylamine groups are trans to one another in the dimer, whereas in dimer B, the tert-butylamine group based on atom N44 is trans to the ethylamine group based on atom N36. Possibly the simplest way to envisage the relationship between dimers A and B is via a 180° rotation of molecule 3 about the line Cl3—C32···N35.

The different arrangements of the alkylamine substituents in the two dimers are sufficient to preclude the possibility of any additional crystallographic symmetry. In addition, the conformations of the ethylamine groups differ (Table 2), although those of the tert-butylamine groups are all fairly similar. The C—N—C—C torsion angles defining the orientation of the ethyl groups indicate that the conformations of molecules 1 and 4 are similar, although approximately enantiomorphic, as are those of molecules 2 and 3, which are also approximately enantiomorphic. In each of the independent molecules, the alkylamine substituents are oriented so that the bonds Nx4—Cx41 and Nx6—Cx61 (where x = 1–4) are all approximately parallel to the corresponding Cx2-Clx bonds (Table 2). It is interesting to note that the atoms Cx41 in the tert-butyl groups (x = 1–4) and the atoms Cx61 in the ethyl groups (x = 1-4) do not deviate greatly from the planes of the adjacent triazine rings, as shown by the key torsion angles (Table 2).

In addition to the hydrogen bonds within the two independent dimers, there are four further N—H···N hydrogen bonds which link these dimers into chains (Table 1). In the type A dimer, atoms N14 and N24 at (x, y, z) act as hydrogen-bond donors to, respectively, atoms N23 at (-1/2 + x, 1 - y, z) and N13 at (1/2 + x, 1 - y, z), so forming a C₂²(10)C₂²(10)[R₂²(8)][R₂²(8)] chain of rings consisting of type A dimers related by the c-glide plane at y = 1/2 (Fig. 2). The final two N—H···N hydrogen bonds, having atoms N31 and N43 as the acceptors, give rise to an entirely analogous chain of type B dimers related by the c-glide plane at y = 0 (Fig. 2). There are two chains of each type passing through each unit cell, but there are no direction-specific interactions between the chains. In particular, there are no C—H···π(triazine) hydrogen bonds and no π–π stacking interactions in the structure.

The structures of three related compounds, (II)–(IV) (see scheme), each bearing one chlorine substituent and two primary amine substituents on a single 1,3,5-triazine ring, are recorded in the CSD. The original reports on these structures all essentially presented proof of constitution, with no analysis or discussion of the supramolecular aggregation, and it is therefore of interest briefly to compare their structures with that of compound (I). In each case, the hydrocarbyl fragments in the alkylamine substituents are oriented with the N—C bonds approximately parallel to the C—Cl bond, as in compound (I). Hence the ring atom N5 is never available as a potential hydrogen-bond acceptor. In compound (II) (CSD refcode EQOMEC; Diaz-Ortiz et al., 2003), there are two intramolecular N—H···N hydrogen bonds forming S(6) rings, but there are no direction-specific interactions between the molecules.

There are two intermolecular N—H···N hydrogen bonds in compound (III) (CSD refcode UFAGUE; Wen et al., 2007), and the authors commented only that the hydrogen bonds form a zigzag chain along [001]. In fact, one of the hydrogen bonds links pairs of molecules related by inversion, forming the familiar R₂²(8) ring motif, while the other links pairs of molecules related by rotation about a twofold axis in space group C2/c, so forming a second, independent, R₂²(8) motif. The combination of these two motifs thus generates a chain of R₂²(8) rings along [001] (Fig. 3). Two chains of this type, related to one another by the c-centring operation, pass through each unit cell, but with no direction-specific interactions between adjacent chains.

The structure of compound (IV) (CSD refcode SILTEN; Dong & Huang, 2007) was described by the authors in terms of chains along [010], although three independent intermolecular N—H···N hydrogen bonds were recorded. Re-examination of this structure shows, in fact, that the molecules are linked into sheets. One of the hydrogen bonds links inversion-related pairs of molecules to form the usual R₂²(8) dimers, and these units are further linked by the other two hydrogen bonds to form sheets parallel to (101) containing three types of ring, of R₂²(6), R₂²(8) and R⁶₆(40) types (Fig. 4). The formation of the large R⁶₆(40) rings in compound (IV) is probably controlled and effectively templated by the pair of inversion-related –CMe₂CH₂CMe₃ substituents within it (Fig. 4).

As in the pyrimidine series discussed recently (Rodríguez et al., 2008), so too in the analogous 1,3,5-triazines, where alternative hydrogen-bond acceptors are absent and the steric requirements of the substituents are not extreme, chains of R₂²(8) rings are formed, as in compounds (I) and (III). However, where alternative hydrogen-bond acceptors are available, the chain of rings can readily be disrupted, as in (IV), where the R₂²(8) dimer unit which forms the basic building block for the sheet formation provides the sole trace of any chain of rings, and in compound (II), where the intramolecular hydrogen bonding effectively prevents any intermolecular hydrogen-bond formation

S2. Experimental

A sample of compound (I) was purchased from Riedel de Haën. Crystals suitable for single-crystal X-ray diffraction were obtained by slow evaporation of a solution in ethanol–water (1:1 v/v) (m.p. 449 K).

S3. Refinement

The systematic absences permitted Pca2₁ and Pcam (= Pbcm, No. 57) as possible space groups. Pca2₁ was selected, and confirmed by the subsequent structure analysis. Although the ADDSYM routine in PLATON (Spek, 2003) suggested possible inversion symmetry in space group Pbca, the molecular conformations and the pattern of the intermolecular hydrogen bonds both preclude any additional crystallographic symmetry.

All H atoms were located in difference maps and treated as riding atoms in geometrically idealized positions, with C—H = 0.98 (CH₃) or 0.99 Å (CH₂) or N—H = 0.86 Å, and with U_iso(H) = kU_eq(carrier), where k = 1.5 for the methyl groups and 1.2 for all other H atoms. The two maxima in the final difference map are located 1.46 Å from atom Cl3 (1.29 e Å^-3) and 1.43 Å from atom Cl2 (1.19 e Å^-3). The correct orientation of the structure with respect to the polar axis direction was established using the Flack parameter (Flack, 1983).

Computing details

Data collection: COLLECT (Nonius, 1999); cell refinement: DIRAX/LSQ (Duisenberg et al., 2000); data reduction: EVALCCD (Duisenberg et al., 2003); program(s) used to solve structure: SIR2004 (Burla et al., 2005); program(s) used to refine structure: OSCAIL (McArdle, 2003) and SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PRPKAPPA (Ferguson, 1999).

Figures

	Fig. 1. The independent molecular components in compound (I), showing the atom-labelling scheme and the two hydrogen-bonded dimers formed within the selected asymmetric unit. (a) Dimer A formed from molecules 1 and 2. (b) Dimer B formed from molecules 3 and 4. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii. Hydrogen bonds are indicated by dashed lines.
	Fig. 2. A setereoview of part of the crystal structure of (I), showing the formation of the two independent hydrogen-bonded chains of rings. For the sake of clarity, H atoms bonded to C atoms have all been omitted. Hydrogen bonds are indicated by dashed lines.
	Fig. 3. A stereoview of part of the crystal structure of (III) (CSD refcode UFAGUE; Wen et al., 2007), showing the formation of a hydrogen-bonded chain along [001] containing two independent R2^2(8) rings. The original atom coordinates have been used (Wen et al., 2007). For the sake of clarity, H atoms bonded to C atoms have all been omitted. Hydrogen bonds are indicated by dashed lines.
	Fig. 4. A stereoview of part of the crystal structure of (IV) (CSD refcode SILTEN; Dong & Huang, 2007), showing the formation of a hydrogen-bonded sheet parallel to (101) containing rings of R2^2(6), R2^2(8) and R^66(40) types. The original atom coordinates have been used (Dong & Huang, 2007). For the sake of clarity, H atoms bonded to C atoms have all been omitted. Hydrogen bonds are indicated by dashed lines.

2-(tert-Butylamino)-4-chloro-6-ethylamino-1,3,5-triazine

Crystal data

C9H16ClN5	F(000) = 1952
Mr = 229.72	Dx = 1.275 Mg m^−3
Orthorhombic, Pca21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2ac	Cell parameters from 10971 reflections
a = 23.557 (3) Å	θ = 3.3–27.5°
b = 9.9789 (15) Å	µ = 0.30 mm^−1
c = 20.3594 (17) Å	T = 120 K
V = 4785.9 (10) Å^3	Block, colourless
Z = 16	0.45 × 0.30 × 0.25 mm

Data collection

Bruker–Nonius KappaCCD diffractometer	10971 independent reflections
Radiation source: Bruker–Nonius FR591 rotating anode	7899 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.070
Detector resolution: 9.091 pixels mm^-1	θmax = 27.5°, θmin = 3.3°
ϕ and ω scans	h = −30→30
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −12→12
Tmin = 0.878, Tmax = 0.929	l = −26→26
113172 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.058	H-atom parameters constrained
wR(F^2) = 0.160	w = 1/[σ^2(Fo^2) + (0.0812P)^2 + 2.8742P] where P = (Fo^2 + 2Fc^2)/3
S = 1.07	(Δ/σ)max < 0.001
10971 reflections	Δρmax = 1.29 e Å^−3
557 parameters	Δρmin = −0.51 e Å^−3
1 restraint	Absolute structure: Flack (1983), with 5308 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.11 (6)

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

	x	y	z	Uiso*/Ueq
Cl1	−0.05031 (4)	0.64981 (10)	0.48699 (5)	0.0358 (2)
N11	0.00061 (12)	0.4740 (3)	0.41404 (15)	0.0277 (7)
N13	−0.10032 (11)	0.4765 (3)	0.41180 (15)	0.0267 (7)
N14	−0.14760 (12)	0.3382 (3)	0.34038 (15)	0.0287 (7)
N15	−0.04928 (11)	0.3284 (3)	0.33930 (16)	0.0258 (6)
N16	0.04824 (12)	0.3257 (3)	0.34751 (17)	0.0335 (7)
C12	−0.05037 (14)	0.5170 (4)	0.43098 (17)	0.0248 (8)
C14	−0.09753 (14)	0.3791 (3)	0.36396 (17)	0.0241 (7)
C16	−0.00162 (15)	0.3762 (4)	0.36689 (18)	0.0272 (8)
C141	−0.15674 (14)	0.2352 (4)	0.28875 (19)	0.0302 (8)
C142	−0.13220 (18)	0.2824 (4)	0.22303 (19)	0.0387 (9)
C143	−0.22111 (15)	0.2240 (5)	0.2819 (2)	0.0436 (10)
C144	−0.1328 (2)	0.1021 (4)	0.3094 (2)	0.0450 (11)
C161	0.05353 (15)	0.2291 (4)	0.2937 (2)	0.0363 (9)
C162	0.05419 (18)	0.2943 (4)	0.2268 (2)	0.0416 (10)
Cl2	0.20096 (4)	0.45802 (11)	0.29409 (5)	0.0372 (2)
N21	0.15012 (12)	0.4715 (3)	0.40607 (15)	0.0305 (7)
N23	0.24921 (12)	0.5175 (3)	0.40518 (15)	0.0284 (7)
N24	0.29536 (13)	0.5521 (3)	0.50273 (15)	0.0312 (7)
N25	0.19863 (11)	0.5131 (3)	0.50725 (15)	0.0265 (7)
N26	0.10238 (13)	0.4763 (4)	0.50418 (16)	0.0340 (8)
C22	0.20006 (14)	0.4857 (4)	0.37836 (19)	0.0294 (8)
C24	0.24608 (15)	0.5267 (4)	0.47271 (18)	0.0275 (8)
C26	0.15159 (14)	0.4892 (4)	0.47267 (17)	0.0273 (8)
C241	0.30430 (15)	0.5603 (4)	0.5745 (2)	0.0336 (9)
C242	0.26709 (18)	0.6665 (5)	0.6060 (2)	0.0492 (12)
C243	0.36680 (18)	0.6059 (5)	0.5826 (2)	0.0499 (12)
C244	0.29599 (19)	0.4226 (5)	0.6051 (2)	0.0483 (11)
C261	0.09770 (17)	0.4792 (5)	0.5758 (2)	0.0403 (10)
C262	0.04083 (19)	0.4226 (7)	0.5973 (3)	0.0647 (16)
Cl3	0.20421 (4)	0.10657 (10)	0.26166 (5)	0.0350 (2)
N31	0.14988 (12)	0.0384 (3)	0.15567 (15)	0.0305 (7)
N33	0.24950 (13)	0.0780 (3)	0.14776 (14)	0.0282 (7)
N34	0.29366 (12)	0.0596 (3)	0.04806 (15)	0.0274 (7)
N35	0.19614 (11)	0.0238 (3)	0.05049 (16)	0.0279 (7)
N36	0.10038 (12)	−0.0094 (4)	0.06129 (16)	0.0324 (7)
C32	0.20065 (14)	0.0687 (4)	0.17806 (18)	0.0267 (8)
C34	0.24488 (14)	0.0518 (3)	0.08206 (17)	0.0249 (7)
C36	0.15025 (15)	0.0178 (4)	0.08937 (18)	0.0282 (8)
C341	0.30111 (15)	0.0505 (4)	−0.02360 (19)	0.0317 (8)
C342	0.2916 (2)	−0.0938 (5)	−0.0459 (2)	0.0508 (12)
C343	0.36254 (16)	0.0908 (5)	−0.0374 (2)	0.0406 (10)
C344	0.26147 (19)	0.1485 (5)	−0.0587 (2)	0.0462 (11)
C361	0.09328 (15)	−0.0342 (4)	−0.0084 (2)	0.0362 (9)
C362	0.03829 (18)	−0.0989 (5)	−0.0233 (2)	0.0508 (12)
Cl4	0.44337 (4)	−0.15046 (10)	0.06999 (5)	0.0343 (2)
N41	0.39824 (12)	0.0404 (3)	0.13945 (15)	0.0263 (7)
N43	0.49748 (13)	0.0024 (3)	0.15130 (15)	0.0272 (6)
N44	0.54781 (12)	0.1205 (3)	0.22732 (16)	0.0306 (7)
N45	0.45148 (11)	0.1674 (3)	0.21856 (16)	0.0263 (7)
N46	0.35604 (13)	0.2062 (3)	0.20114 (16)	0.0321 (7)
C42	0.44672 (14)	−0.0195 (3)	0.12719 (17)	0.0247 (8)
C44	0.49731 (14)	0.0997 (4)	0.19920 (17)	0.0247 (7)
C46	0.40351 (15)	0.1377 (4)	0.18716 (17)	0.0270 (8)
C441	0.56040 (15)	0.2138 (4)	0.2830 (2)	0.0331 (8)
C442	0.54482 (16)	0.3560 (4)	0.2659 (2)	0.0369 (9)
C443	0.62398 (16)	0.2048 (5)	0.2932 (2)	0.0455 (10)
C444	0.52934 (19)	0.1671 (4)	0.3447 (2)	0.0407 (10)
C461	0.35350 (16)	0.3116 (4)	0.2506 (2)	0.0381 (10)
C462	0.34785 (19)	0.2585 (5)	0.3195 (2)	0.0435 (10)
H14	−0.1773	0.3823	0.3552	0.034*
H16	0.0787	0.3630	0.3646	0.040*
H14A	−0.0909	0.2906	0.2267	0.058*
H14B	−0.1485	0.3698	0.2116	0.058*
H14C	−0.1416	0.2172	0.1887	0.058*
H14D	−0.2366	0.3101	0.2673	0.065*
H14E	−0.2377	0.1998	0.3244	0.065*
H14F	−0.2303	0.1547	0.2495	0.065*
H14G	−0.1474	0.0785	0.3529	0.068*
H14H	−0.0913	0.1077	0.3109	0.068*
H14I	−0.1441	0.0333	0.2776	0.068*
H16A	0.0214	0.1653	0.2958	0.044*
H16B	0.0890	0.1773	0.2995	0.044*
H16C	0.0187	0.3436	0.2201	0.062*
H16D	0.0580	0.2252	0.1929	0.062*
H16E	0.0863	0.3564	0.2240	0.062*
H24	0.3250	0.5388	0.4773	0.037*
H26	0.0729	0.4761	0.4777	0.041*
H24A	0.2721	0.7518	0.5828	0.074*
H24B	0.2778	0.6774	0.6521	0.074*
H24G	0.2272	0.6389	0.6032	0.074*
H24D	0.3921	0.5372	0.5646	0.075*
H24E	0.3752	0.6189	0.6294	0.075*
H24F	0.3726	0.6904	0.5591	0.075*
H23G	0.2559	0.3972	0.6023	0.072*
H24H	0.3076	0.4251	0.6513	0.072*
H24I	0.3191	0.3567	0.5815	0.072*
H25A	0.1014	0.5726	0.5916	0.048*
H25B	0.1288	0.4257	0.5954	0.048*
H26A	0.0101	0.4774	0.5790	0.097*
H26B	0.0385	0.4235	0.6453	0.097*
H26F	0.0371	0.3303	0.5814	0.097*
H34	0.3237	0.0626	0.0738	0.033*
H36	0.0721	−0.0085	0.0895	0.039*
H34A	0.3185	−0.1529	−0.0234	0.076*
H34B	0.2975	−0.1000	−0.0935	0.076*
H34C	0.2527	−0.1210	−0.0353	0.076*
H34D	0.3686	0.1836	−0.0233	0.061*
H34E	0.3702	0.0832	−0.0846	0.061*
H34F	0.3882	0.0315	−0.0132	0.061*
H34G	0.2220	0.1203	−0.0523	0.069*
H34H	0.2703	0.1493	−0.1058	0.069*
H34I	0.2668	0.2386	−0.0406	0.069*
H36A	0.1245	−0.0925	−0.0240	0.043*
H36B	0.0957	0.0518	−0.0325	0.043*
H36C	0.0368	−0.1870	−0.0020	0.076*
H36D	0.0344	−0.1098	−0.0709	0.076*
H36E	0.0073	−0.0429	−0.0067	0.076*
H44	0.5739	0.0682	0.2100	0.037*
H46	0.3248	0.1658	0.1883	0.038*
H44A	0.5629	0.3810	0.2243	0.055*
H44B	0.5579	0.4162	0.3008	0.055*
H44C	0.5035	0.3633	0.2614	0.055*
H44D	0.6435	0.2365	0.2536	0.068*
H44E	0.6346	0.1115	0.3018	0.068*
H44F	0.6350	0.2606	0.3307	0.068*
H44G	0.5373	0.2291	0.3809	0.061*
H44H	0.5423	0.0770	0.3566	0.061*
H44I	0.4884	0.1652	0.3362	0.061*
H46A	0.3208	0.3706	0.2410	0.046*
H46B	0.3884	0.3666	0.2477	0.046*
H46D	0.3149	0.1987	0.3221	0.065*
H46E	0.3427	0.3335	0.3501	0.065*
H46F	0.3823	0.2088	0.3314	0.065*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0357 (5)	0.0395 (5)	0.0323 (5)	−0.0027 (4)	−0.0022 (4)	−0.0103 (4)
N11	0.0217 (14)	0.0361 (18)	0.0252 (16)	−0.0028 (13)	−0.0004 (12)	−0.0015 (13)
N13	0.0214 (15)	0.0349 (17)	0.0237 (16)	0.0026 (12)	−0.0010 (12)	−0.0045 (13)
N14	0.0179 (14)	0.0382 (17)	0.0299 (16)	−0.0011 (12)	0.0040 (12)	−0.0114 (14)
N15	0.0188 (14)	0.0310 (15)	0.0275 (17)	0.0010 (12)	0.0002 (12)	−0.0013 (13)
N16	0.0180 (14)	0.0446 (19)	0.0378 (19)	0.0008 (13)	0.0006 (13)	−0.0038 (15)
C12	0.0249 (18)	0.0318 (19)	0.0178 (18)	−0.0010 (15)	−0.0012 (14)	0.0022 (15)
C14	0.0229 (17)	0.0260 (17)	0.0233 (18)	0.0019 (14)	−0.0019 (14)	0.0023 (14)
C16	0.0223 (17)	0.0341 (19)	0.0251 (18)	−0.0003 (15)	0.0003 (14)	0.0022 (15)
C141	0.0271 (17)	0.037 (2)	0.0262 (18)	−0.0031 (15)	0.0020 (15)	−0.0078 (16)
C142	0.046 (2)	0.043 (2)	0.027 (2)	−0.0018 (18)	0.0029 (18)	−0.0073 (18)
C143	0.0281 (18)	0.057 (3)	0.046 (2)	−0.0121 (19)	−0.0013 (18)	−0.014 (2)
C144	0.051 (3)	0.038 (2)	0.046 (3)	−0.001 (2)	−0.012 (2)	−0.0014 (19)
C161	0.0227 (17)	0.031 (2)	0.055 (2)	0.0064 (15)	0.0029 (18)	−0.0076 (19)
C162	0.041 (2)	0.045 (2)	0.039 (2)	−0.0051 (18)	0.0034 (19)	−0.010 (2)
Cl2	0.0328 (5)	0.0528 (6)	0.0260 (4)	−0.0026 (4)	−0.0008 (4)	−0.0050 (4)
N21	0.0223 (15)	0.049 (2)	0.0206 (15)	−0.0004 (13)	−0.0007 (12)	−0.0007 (14)
N23	0.0215 (14)	0.0404 (17)	0.0232 (15)	−0.0029 (13)	−0.0013 (12)	0.0026 (13)
N24	0.0239 (15)	0.0449 (19)	0.0247 (16)	−0.0033 (14)	−0.0012 (12)	−0.0020 (14)
N25	0.0186 (15)	0.0383 (18)	0.0227 (16)	−0.0025 (13)	0.0006 (11)	−0.0001 (13)
N26	0.0177 (14)	0.055 (2)	0.0298 (17)	−0.0012 (14)	0.0037 (12)	−0.0008 (15)
C22	0.0246 (18)	0.038 (2)	0.0257 (19)	0.0000 (16)	−0.0002 (14)	0.0010 (16)
C24	0.0256 (18)	0.0304 (19)	0.0265 (19)	−0.0013 (15)	−0.0006 (15)	0.0040 (15)
C26	0.0245 (18)	0.0349 (19)	0.0225 (18)	−0.0041 (15)	−0.0006 (14)	0.0021 (15)
C241	0.0289 (19)	0.049 (2)	0.023 (2)	0.0021 (16)	−0.0025 (16)	−0.0043 (18)
C242	0.040 (2)	0.067 (3)	0.041 (3)	−0.001 (2)	−0.003 (2)	−0.017 (2)
C243	0.037 (2)	0.076 (3)	0.037 (3)	−0.005 (2)	−0.0120 (19)	−0.013 (2)
C244	0.050 (3)	0.064 (3)	0.031 (2)	−0.002 (2)	−0.010 (2)	0.006 (2)
C261	0.036 (2)	0.052 (3)	0.032 (2)	0.0033 (19)	0.0068 (18)	0.0084 (19)
C262	0.038 (2)	0.111 (5)	0.046 (3)	0.007 (3)	0.001 (2)	0.033 (3)
Cl3	0.0282 (4)	0.0505 (6)	0.0263 (4)	−0.0029 (4)	0.0030 (4)	−0.0083 (4)
N31	0.0213 (15)	0.0416 (19)	0.0286 (17)	−0.0003 (13)	0.0018 (12)	−0.0041 (14)
N33	0.0217 (14)	0.0377 (17)	0.0251 (16)	0.0005 (13)	0.0008 (12)	−0.0037 (13)
N34	0.0183 (14)	0.0417 (18)	0.0222 (15)	−0.0017 (12)	0.0006 (12)	−0.0002 (13)
N35	0.0198 (15)	0.0383 (18)	0.0256 (17)	−0.0024 (13)	−0.0007 (12)	−0.0013 (13)
N36	0.0200 (14)	0.054 (2)	0.0234 (16)	−0.0046 (14)	0.0009 (13)	−0.0045 (15)
C32	0.0238 (18)	0.0343 (19)	0.0219 (18)	0.0006 (15)	0.0005 (14)	0.0020 (15)
C34	0.0205 (16)	0.0311 (18)	0.0232 (19)	−0.0017 (14)	0.0009 (13)	−0.0021 (15)
C36	0.0241 (18)	0.034 (2)	0.027 (2)	0.0009 (15)	−0.0011 (14)	−0.0034 (15)
C341	0.0276 (19)	0.045 (2)	0.022 (2)	−0.0012 (16)	0.0038 (15)	−0.0007 (17)
C342	0.051 (3)	0.058 (3)	0.044 (3)	−0.009 (2)	0.011 (2)	−0.017 (2)
C343	0.027 (2)	0.063 (3)	0.032 (2)	−0.0015 (19)	0.0074 (16)	0.004 (2)
C344	0.039 (2)	0.071 (3)	0.028 (2)	0.006 (2)	0.0024 (18)	0.017 (2)
C361	0.0277 (19)	0.055 (3)	0.026 (2)	−0.0023 (18)	−0.0019 (16)	−0.0050 (18)
C362	0.035 (2)	0.072 (3)	0.045 (3)	−0.005 (2)	−0.002 (2)	−0.027 (2)
Cl4	0.0340 (5)	0.0370 (5)	0.0318 (5)	0.0006 (4)	0.0003 (4)	−0.0091 (4)
N41	0.0201 (14)	0.0350 (17)	0.0239 (16)	0.0015 (12)	0.0026 (12)	−0.0037 (13)
N43	0.0232 (15)	0.0342 (16)	0.0242 (15)	−0.0008 (13)	0.0005 (12)	0.0006 (13)
N44	0.0222 (15)	0.0390 (18)	0.0305 (18)	0.0003 (13)	−0.0014 (13)	−0.0102 (15)
N45	0.0212 (14)	0.0308 (16)	0.0267 (16)	−0.0027 (12)	0.0012 (12)	−0.0001 (13)
N46	0.0237 (15)	0.0335 (17)	0.0390 (18)	0.0009 (13)	0.0004 (13)	−0.0103 (14)
C42	0.0269 (19)	0.0290 (18)	0.0181 (18)	−0.0010 (14)	0.0029 (14)	−0.0002 (14)
C44	0.0231 (17)	0.0272 (18)	0.0238 (17)	−0.0007 (14)	0.0027 (14)	−0.0017 (15)
C46	0.0257 (18)	0.0330 (19)	0.0224 (18)	0.0001 (15)	0.0011 (14)	0.0027 (15)
C441	0.0291 (18)	0.038 (2)	0.032 (2)	−0.0026 (16)	−0.0049 (16)	−0.0058 (16)
C442	0.035 (2)	0.038 (2)	0.038 (2)	−0.0038 (16)	0.0019 (18)	−0.0037 (18)
C443	0.030 (2)	0.054 (3)	0.053 (3)	0.0035 (19)	−0.007 (2)	−0.015 (2)
C444	0.045 (2)	0.046 (2)	0.032 (2)	0.0005 (19)	−0.0012 (18)	−0.0016 (18)
C461	0.0269 (19)	0.039 (2)	0.048 (3)	0.0028 (17)	0.0025 (17)	−0.0104 (18)
C462	0.038 (2)	0.046 (2)	0.046 (2)	−0.0083 (19)	0.0110 (19)	−0.017 (2)

Geometric parameters (Å, º)

Cl1—C12	1.748 (4)	Cl3—C32	1.746 (4)
N11—C12	1.321 (4)	N31—C32	1.315 (4)
N11—C16	1.370 (5)	N31—C36	1.366 (5)
N13—C12	1.304 (4)	N33—C32	1.309 (4)
N13—C14	1.378 (5)	N33—C34	1.367 (5)
N14—C14	1.337 (4)	N34—C34	1.344 (4)
N14—C141	1.486 (5)	N34—C341	1.472 (5)
N14—H14	0.88	N34—H34	0.8801
N15—C14	1.342 (4)	N35—C36	1.341 (5)
N15—C16	1.343 (4)	N35—C34	1.345 (4)
N16—C16	1.338 (5)	N36—C36	1.334 (4)
N16—C161	1.465 (5)	N36—C361	1.450 (5)
N16—H16	0.88	N36—H36	0.88
C141—C144	1.503 (6)	C341—C342	1.526 (6)
C141—C143	1.527 (5)	C341—C343	1.528 (5)
C141—C142	1.532 (5)	C341—C344	1.530 (6)
C142—H14A	0.98	C342—H34A	0.98
C142—H14B	0.98	C342—H34B	0.98
C142—H14C	0.98	C342—H34C	0.98
C143—H14D	0.98	C343—H34D	0.98
C143—H14E	0.98	C343—H34E	0.98
C143—H14F	0.98	C343—H34F	0.98
C144—H14G	0.98	C344—H34G	0.98
C144—H14H	0.98	C344—H34H	0.98
C144—H14I	0.98	C344—H34I	0.98
C161—C162	1.509 (6)	C361—C362	1.479 (5)
C161—H16A	0.99	C361—H36A	0.99
C161—H16B	0.99	C361—H36B	0.99
C162—H16C	0.98	C362—H36C	0.98
C162—H16D	0.98	C362—H36D	0.98
C162—H16E	0.98	C362—H36E	0.98
Cl2—C22	1.738 (4)	Cl4—C42	1.752 (4)
N21—C22	1.312 (4)	N41—C42	1.313 (4)
N21—C26	1.368 (5)	N41—C46	1.379 (5)
N23—C22	1.319 (4)	N43—C42	1.311 (4)
N23—C24	1.380 (5)	N43—C44	1.376 (5)
N24—C24	1.336 (5)	N44—C44	1.336 (4)
N24—C241	1.479 (5)	N44—C441	1.497 (5)
N24—H24	0.88	N44—H44	0.8799
N25—C24	1.328 (5)	N45—C46	1.332 (5)
N25—C26	1.334 (4)	N45—C44	1.333 (4)
N26—C26	1.331 (4)	N46—C46	1.341 (5)
N26—C261	1.463 (5)	N46—C461	1.457 (5)
N26—H26	0.88	N46—H46	0.88
C241—C242	1.517 (6)	C441—C442	1.507 (6)
C241—C244	1.522 (7)	C441—C443	1.515 (5)
C241—C243	1.550 (5)	C441—C444	1.526 (6)
C242—H24A	0.98	C442—H44A	0.98
C242—H24B	0.98	C442—H44B	0.98
C242—H24G	0.98	C442—H44C	0.98
C243—H24D	0.98	C443—H44D	0.98
C243—H24E	0.98	C443—H44E	0.98
C243—H24F	0.98	C443—H44F	0.98
C244—H23G	0.98	C444—H44G	0.98
C244—H24H	0.98	C444—H44H	0.98
C244—H24I	0.98	C444—H44I	0.98
C261—C262	1.519 (6)	C461—C462	1.506 (6)
C261—H25A	0.99	C461—H46A	0.99
C261—H25B	0.99	C461—H46B	0.99
C262—H26A	0.98	C462—H46D	0.98
C262—H26B	0.98	C462—H46E	0.98
C262—H26F	0.98	C462—H46F	0.98
C12—N11—C16	112.3 (3)	C32—N31—C36	111.8 (3)
C12—N13—C14	112.8 (3)	C32—N33—C34	112.2 (3)
C14—N14—C141	126.4 (3)	C34—N34—C341	127.5 (3)
C14—N14—H14	115.3	C34—N34—H34	112.5
C141—N14—H14	118.2	C341—N34—H34	119.7
C14—N15—C16	114.7 (3)	C36—N35—C34	114.5 (3)
C16—N16—C161	122.9 (3)	C36—N36—C361	123.7 (3)
C16—N16—H16	116.1	C36—N36—H36	112.7
C161—N16—H16	120.3	C361—N36—H36	123.5
N13—C12—N11	129.9 (3)	N33—C32—N31	130.7 (3)
N13—C12—Cl1	115.5 (3)	N33—C32—Cl3	113.7 (3)
N11—C12—Cl1	114.6 (3)	N31—C32—Cl3	115.6 (3)
N14—C14—N15	119.9 (3)	N34—C34—N35	119.7 (3)
N14—C14—N13	115.3 (3)	N34—C34—N33	115.1 (3)
N15—C14—N13	124.8 (3)	N35—C34—N33	125.1 (3)
N16—C16—N15	118.5 (3)	N36—C36—N35	117.8 (3)
N16—C16—N11	116.2 (3)	N36—C36—N31	116.6 (3)
N15—C16—N11	125.3 (3)	N35—C36—N31	125.6 (3)
N14—C141—C144	111.1 (3)	N34—C341—C342	109.6 (3)
N14—C141—C143	105.1 (3)	N34—C341—C343	106.2 (3)
C144—C141—C143	109.5 (4)	C342—C341—C343	109.5 (3)
N14—C141—C142	110.5 (3)	N34—C341—C344	110.5 (3)
C144—C141—C142	112.0 (3)	C342—C341—C344	112.0 (4)
C143—C141—C142	108.5 (3)	C343—C341—C344	108.9 (3)
C141—C142—H14A	109.5	C341—C342—H34A	109.5
C141—C142—H14B	109.5	C341—C342—H34B	109.5
H14A—C142—H14B	109.5	H34A—C342—H34B	109.5
C141—C142—H14C	109.5	C341—C342—H34C	109.5
H14A—C142—H14C	109.5	H34A—C342—H34C	109.5
H14B—C142—H14C	109.5	H34B—C342—H34C	109.5
C141—C143—H14D	109.5	C341—C343—H34D	109.5
C141—C143—H14E	109.5	C341—C343—H34E	109.5
H14D—C143—H14E	109.5	H34D—C343—H34E	109.5
C141—C143—H14F	109.5	C341—C343—H34F	109.5
H14D—C143—H14F	109.5	H34D—C343—H34F	109.5
H14E—C143—H14F	109.5	H34E—C343—H34F	109.5
C141—C144—H14G	109.5	C341—C344—H34G	109.5
C141—C144—H14H	109.5	C341—C344—H34H	109.5
H14G—C144—H14H	109.5	H34G—C344—H34H	109.5
C141—C144—H14I	109.5	C341—C344—H34I	109.5
H14G—C144—H14I	109.5	H34G—C344—H34I	109.5
H14H—C144—H14I	109.5	H34H—C344—H34I	109.5
N16—C161—C162	113.1 (3)	N36—C361—C362	112.1 (3)
N16—C161—H16A	109.0	N36—C361—H36A	109.2
C162—C161—H16A	109.0	C362—C361—H36A	109.2
N16—C161—H16B	109.0	N36—C361—H36B	109.2
C162—C161—H16B	109.0	C362—C361—H36B	109.2
H16A—C161—H16B	107.8	H36A—C361—H36B	107.9
C161—C162—H16C	109.5	C361—C362—H36C	109.5
C161—C162—H16D	109.5	C361—C362—H36D	109.5
H16C—C162—H16D	109.5	H36C—C362—H36D	109.5
C161—C162—H16E	109.5	C361—C362—H36E	109.5
H16C—C162—H16E	109.5	H36C—C362—H36E	109.5
H16D—C162—H16E	109.5	H36D—C362—H36E	109.5
C22—N21—C26	112.9 (3)	C42—N41—C46	112.1 (3)
C22—N23—C24	112.4 (3)	C42—N43—C44	112.4 (3)
C24—N24—C241	125.9 (3)	C44—N44—C441	126.7 (3)
C24—N24—H24	113.1	C44—N44—H44	111.0
C241—N24—H24	118.4	C441—N44—H44	122.3
C24—N25—C26	116.0 (3)	C46—N45—C44	115.6 (3)
C26—N26—C261	123.0 (3)	C46—N46—C461	123.3 (3)
C26—N26—H26	113.2	C46—N46—H46	113.6
C261—N26—H26	123.5	C461—N46—H46	120.2
N21—C22—N23	129.4 (4)	N43—C42—N41	130.3 (3)
N21—C22—Cl2	114.7 (3)	N43—C42—Cl4	114.5 (3)
N23—C22—Cl2	115.9 (3)	N41—C42—Cl4	115.3 (3)
N25—C24—N24	120.6 (3)	N45—C44—N44	121.1 (3)
N25—C24—N23	124.5 (3)	N45—C44—N43	124.7 (3)
N24—C24—N23	115.0 (3)	N44—C44—N43	114.2 (3)
N26—C26—N25	119.1 (3)	N45—C46—N46	119.5 (3)
N26—C26—N21	116.3 (3)	N45—C46—N41	124.8 (3)
N25—C26—N21	124.6 (3)	N46—C46—N41	115.7 (3)
N24—C241—C242	111.9 (3)	N44—C441—C442	111.3 (3)
N24—C241—C244	109.7 (3)	N44—C441—C443	105.2 (3)
C242—C241—C244	112.5 (4)	C442—C441—C443	109.2 (3)
N24—C241—C243	104.9 (3)	N44—C441—C444	109.8 (3)
C242—C241—C243	107.4 (4)	C442—C441—C444	111.2 (3)
C244—C241—C243	110.1 (4)	C443—C441—C444	110.1 (4)
C241—C242—H24A	109.5	C441—C442—H44A	109.5
C241—C242—H24B	109.5	C441—C442—H44B	109.5
H24A—C242—H24B	109.5	H44A—C442—H44B	109.5
C241—C242—H24G	109.5	C441—C442—H44C	109.5
H24A—C242—H24G	109.5	H44A—C442—H44C	109.5
H24B—C242—H24G	109.5	H44B—C442—H44C	109.5
C241—C243—H24D	109.5	C441—C443—H44D	109.5
C241—C243—H24E	109.5	C441—C443—H44E	109.5
H24D—C243—H24E	109.5	H44D—C443—H44E	109.5
C241—C243—H24F	109.5	C441—C443—H44F	109.5
H24D—C243—H24F	109.5	H44D—C443—H44F	109.5
H24E—C243—H24F	109.5	H44E—C443—H44F	109.5
C241—C244—H23G	109.5	C441—C444—H44G	109.5
C241—C244—H24H	109.5	C441—C444—H44H	109.5
H23G—C244—H24H	109.5	H44G—C444—H44H	109.5
C241—C244—H24I	109.5	C441—C444—H44I	109.5
H23G—C244—H24I	109.5	H44G—C444—H44I	109.5
H24H—C244—H24I	109.5	H44H—C444—H44I	109.5
N26—C261—C262	110.3 (4)	N46—C461—C462	113.2 (3)
N26—C261—H25A	109.6	N46—C461—H46A	108.9
C262—C261—H25A	109.6	C462—C461—H46A	108.9
N26—C261—H25B	109.6	N46—C461—H46B	108.9
C262—C261—H25B	109.6	C462—C461—H46B	108.9
H25A—C261—H25B	108.1	H46A—C461—H46B	107.7
C261—C262—H26A	109.5	C461—C462—H46D	109.5
C261—C262—H26B	109.5	C461—C462—H46E	109.5
H26A—C262—H26B	109.5	H46D—C462—H46E	109.5
C261—C262—H26F	109.5	C461—C462—H46F	109.5
H26A—C262—H26F	109.5	H46D—C462—H46F	109.5
H26B—C262—H26F	109.5	H46E—C462—H46F	109.5
C14—N13—C12—N11	−4.0 (6)	C34—N33—C32—N31	0.5 (6)
C14—N13—C12—Cl1	175.2 (2)	C34—N33—C32—Cl3	−178.1 (3)
C16—N11—C12—N13	3.3 (6)	C36—N31—C32—N33	−2.0 (6)
C16—N11—C12—Cl1	−175.9 (2)	C36—N31—C32—Cl3	176.5 (3)
C141—N14—C14—N15	2.0 (6)	C341—N34—C34—N35	5.0 (6)
C141—N14—C14—N13	179.9 (3)	C341—N34—C34—N33	−173.2 (3)
C16—N15—C14—N14	−179.7 (3)	C36—N35—C34—N34	179.6 (3)
C16—N15—C14—N13	2.6 (5)	C36—N35—C34—N33	−2.4 (5)
C12—N13—C14—N14	−177.1 (3)	C32—N33—C34—N34	−179.9 (3)
C12—N13—C14—N15	0.7 (5)	C32—N33—C34—N35	2.0 (5)
C161—N16—C16—N15	5.4 (6)	C361—N36—C36—N35	0.8 (6)
C161—N16—C16—N11	−174.6 (3)	C361—N36—C36—N31	−179.8 (4)
C14—N15—C16—N16	176.6 (3)	C34—N35—C36—N36	179.8 (3)
C14—N15—C16—N11	−3.4 (5)	C34—N35—C36—N31	0.5 (6)
C12—N11—C16—N16	−179.1 (3)	C32—N31—C36—N36	−177.9 (3)
C12—N11—C16—N15	0.9 (5)	C32—N31—C36—N35	1.4 (6)
C14—N14—C141—C144	60.1 (5)	C34—N34—C341—C342	−72.0 (5)
C14—N14—C141—C143	178.3 (4)	C34—N34—C341—C343	169.9 (4)
C14—N14—C141—C142	−64.8 (5)	C34—N34—C341—C344	51.9 (5)
C16—N16—C161—C162	82.5 (4)	C36—N36—C361—C362	163.5 (4)
C26—N21—C22—N23	−2.1 (6)	C44—N43—C42—N41	3.7 (5)
C26—N21—C22—Cl2	177.7 (3)	C44—N43—C42—Cl4	−175.8 (3)
C24—N23—C22—N21	5.0 (6)	C46—N41—C42—N43	−2.5 (5)
C24—N23—C22—Cl2	−174.8 (3)	C46—N41—C42—Cl4	177.0 (3)
C26—N25—C24—N24	179.3 (3)	C46—N45—C44—N44	−179.7 (3)
C26—N25—C24—N23	−0.1 (5)	C46—N45—C44—N43	−1.4 (5)
C241—N24—C24—N25	3.7 (6)	C441—N44—C44—N45	1.9 (6)
C241—N24—C24—N23	−176.8 (4)	C441—N44—C44—N43	−176.5 (3)
C22—N23—C24—N25	−3.7 (5)	C42—N43—C44—N45	−1.5 (5)
C22—N23—C24—N24	176.9 (3)	C42—N43—C44—N44	176.9 (3)
C261—N26—C26—N25	−3.8 (6)	C44—N45—C46—N46	−176.4 (3)
C261—N26—C26—N21	173.8 (4)	C44—N45—C46—N41	2.8 (5)
C24—N25—C26—N26	−179.1 (4)	C461—N46—C46—N45	−1.3 (6)
C24—N25—C26—N21	3.5 (6)	C461—N46—C46—N41	179.3 (3)
C22—N21—C26—N26	179.9 (3)	C42—N41—C46—N45	−1.1 (5)
C22—N21—C26—N25	−2.6 (5)	C42—N41—C46—N46	178.2 (3)
C24—N24—C241—C242	−58.3 (5)	C44—N44—C441—C442	−58.9 (5)
C24—N24—C241—C244	67.4 (5)	C44—N44—C441—C443	−176.9 (4)
C24—N24—C241—C243	−174.4 (4)	C44—N44—C441—C444	64.6 (5)
C26—N26—C261—C262	−163.5 (4)	C46—N46—C461—C462	−80.7 (5)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N14—H14···N23^i	0.88	2.24	3.118 (4)	173
N16—H16···N21	0.88	2.17	3.049 (4)	175
N24—H24···N13^ii	0.88	2.21	3.090 (4)	175
N26—H26···N11	0.88	2.14	3.019 (4)	179
N34—H34···N41	0.88	2.22	3.093 (4)	172
N36—H36···N43^iii	0.88	2.16	3.039 (4)	175
N44—H44···N31^iv	0.88	2.36	3.228 (4)	170
N46—H46···N33	0.88	2.14	3.020 (4)	174

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