Hydrogen-bonded ribbons in ethyl (E)-3-[2-amino-4,6-bis­(dimethyl­amino)pyrimidin-5-yl]-2-cyano­acrylate and 2-[(2-amino-4,6-di-1-piperidylpyrimidin-5-yl)methyl­ene]malononitrile

The pyrimidine rings in ethyl (E)-3-[2-amino-4,6-bis­(dimethyl­amino)pyrimidin-5-yl]-2-cyano­acrylate, C₁₄H₂₀N₆O₂, (I), and 2-[(2-amino-4,6-di-1-piperidylpyrimidin-5-yl)methyl­ene]malononitrile, C₁₈H₂₃N₇, (II), which crystallizes with Z' = 2 in the space group, are both nonplanar with boat conformations. The mol­ecules of (I) are linked by a combination of N-H...N and N-H...O hydrogen bonds into chains of edge-fused R₂²(8) and R₄⁴(20) rings, while the two independent mol­ecules in (II) are linked by four N-H...N hydrogen bonds into chains of edge-fused R₂²(8) and R₂²(20) rings. This study illustrates both the readiness with which highly-substituted pyrimidine rings can be distorted from planarity and the significant differences between the supramolecular aggregation in two rather similar compounds.

S1. Comment

As part of a programme for the synthesis of new heterocyclic compounds with potential biological activity, we have investigated the functionalization at position C-5 in pyrimidines via modification of 4,6-dichloro-5-formylpyrimidines, using base-catalyzed condensation of the formyl group with an activated methylene reagent, followed by substitution at positions 4 and 6 using strongly nucleophilic amines. We report here the molecular and supramolecular structures of two examples, both prepared staring from 2-amino-4,6-dichloropyrimidine-5-carbaldehyde. Ethyl (E)-3-[2-amino-4,6-bis(dimethylamino)pyrimidin-5-yl]-2-cyanoacrylate, (I), was prepared from the starting pyrimidine by successive reaction with ethyl cyanoacetate to give the intermediate (III) (see scheme), followed by excess dimethylamine to give the product (I), while 2-[(2-amino-4,6-di-1-piperidylpyrimidin-5-yl)methylene]malononitrile, (II), was prepared by reaction of the same pyrimidine with malononitrile to form the intermediate (IV) followed by excess piperidine giving the product (II).

In each of compounds (I) (Fig. 1) and (II), which crystallizes with Z' = 2 in the P-1 space group (Fig. 2), the pyrimidine component is markedly nonplanar. The ring-puckering parameters (Cremer & Pople, 1975) (Table 1) are defined for the atom sequence N1—C2—N3—C4—C5—C6 in compound (I) and for Nx1—Cx2—Nx3—Cx4—Cx5—Cx6 (where x = 1 or 2 for the type 1 and type 2 molecules) in compound (II); these parameters show that the conformations of these rings are best described as boat conformations, for which the idealized values of the ring-puckering parameters are θ = 90° and ϕ = (60k)°, where k represent zero or an integer. We have previously observed such nonplanarity in a number of extensively substituted pyrimidine derivatives exhibiting boat (Quesada et al., 2004) or twist-boat (Melguizo et al., 2003; Quesada et al., 2002, 2003) conformations, and by comparison with less extensively substituted analogues, the distortions from planarity were ascribed to steric factors (Melguizo et al., 2003). The occurrence of nonplanar pyrimidine rings here in the presence of four substituents on each pyrimidine ring is certainly consistent with the earlier interpretation. The conformations of the three independent pyrimidine rings in compounds (I) and (II) are thus very similar and the molecules are all chiral: the ring-puckering parameters show that the two independent molecules selected as the asymmetric unit in compound (II) are of the same hand. The piperidine rings in compound (II) all adopt chair conformations. The bond distances are all within the normal ranges and there is no geometric evidence for any significant polarization of the molecular–electronic structures.

The molecules of compound (I) are linked into chains of edge-fused rings by two independent hydrogen bonds (Table 2). Amino atom N2 in the molecule at (x, y, z) acts as hydrogen-bond donor, via H2A and H2B, respectively, to ring atom N1 in the molecule at (2 - x, 1 - y, 1 - z) and carbonyl atom O55 in the molecule at (x, y, 1 + z). Propagation of these two hydrogen bonds by inversion and translation then generates a chain of edge-fused rings running parallel to the [001] direction, with R₂²(8) (Bernstein et al., 1995) rings centred at (1, 1/2, n + 1/2) (where n represents zero or an integer), and R₄⁴(20) rings centred at (1, 1/2, n) (where n represents zero or an integer) (Fig. 3). There are no direction-specific interactions between adjacent chains.

The supramolecular aggregation of compound (II) is dominated by four independent N—H···N hydrogen bonds (Table 3) which link the molecules into a chain of rings somewhat different from that in compound (I), while weaker C—H···N hydrogen bonds link these chains into sheets. The two independent molecules within the selected asymmetric unit are linked by the N—H···N hydrogen bonds involving H12A and H22A to form a dimeric unit which has approximate twofold rotational symmetry around (~0.25, y, ~0.5). These dimeric units are linked by two further N—H···N hydrogen bonds, involving H12B and H22B, into a chain of edge-fused rings running parallel to the [100] direction and containing alternating R₂²(8) and R₂²(20) rings (Fig. 4). Fairly weak C—H···N hydrogen bonds, all involving C atoms within the piperidine rings as the donors and nitrile N atoms as the acceptors, link the [100] chains into sheets parallel to (010): the C—H bonds involved are likely to be of low acidity so that the structural significance of these interactions may be marginal.

Related literature

For related literature, see: Bernstein et al. (1995); Cremer & Pople (1975); Melguizo et al. (2003); Quesada et al. (2002, 2003, 2004); Spek (2003).

S2. Experimental

For the synthesis of compound (I), a catalytic quantity of triethylamine (3 drops) together with calcium chloride (15 mg) were added to a solution of 2-amino-4,6-dichloropyrimidine-5-carbaldehyde (1.0 mmol) and ethyl 2-cyanoacetate (1.0 mmol) in ethanol (10 ml), and this mixture was stirred at ambient temperature for 2 h. The resulting precipitate was collected by filtration, washed with ethanol, dried and finally recrystallized from ethanol to give ethyl (E)-3-(2-amino-4,6-dichloropyrimidin-5-yl)-2-cyanoacrylate, (III), in 85% yield. For the synthesis of compound (II), a catalytic quantity of triethylamine (3 drops) together with calcium chloride (15 mg) were added to a solution of 2-amino-4,6-dichloropyrimidine-5-carbaldehyde (1.0 mmol) and malononitrile (1.0 mmol) in ethanol (10 ml) and this mixture was stirred at ambient temperature for 2 h. The resulting solid was collected by filtration, washed with ethanol, dried and finally recrystallized from ethanol to give 2-[(2-amino-4,6-dichloropyrimidin-5-yl)methylene]malononitrile, (IV), in 70% yield. For the conversion of (II) and (IV) to (I) and (II), respectively, the intermediate (III) or (IV) (0.4 mmol) was then added to a large excess of the appropriate amine (0.5 ml) in ethanol (10 ml) and heated under reflux for 1 h. On cooling to ambient temperature, the products (I) and (II) were precipitated as yellow crystalline solids, which were collected by filtration, washed with ethanol and dried at atmospheric pressure to give crystals suitable for single-crystal X-ray diffraction. For (I): yield 50% and m.p. 503–505 K; for (II), yield 70% and m.p. 467–468 K. HR–MS: found 337.2016; C₁₈H₂₃N₇ requires 337.2015.

S3. Refinement

Crystals of compounds (I) and (II) are triclinic; for each compound the space group P-1 was selected and confirmed by the subsequent structure analysis. All H atoms were located in difference maps and then treated as riding atoms with distances C—H = 0.95 (alkene), 0.98 (CH₃) or 0.99 Å (CH₂) and 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. For compound (I), the proportion of the reflections labelled `observed' was quite low, ca 49%, even at 120 K. Analysis of the refined structure of (II) using PLATON (Spek, 2003) showed that there were voids within the structure, centred at approximately (0, 0, 1/2) and accounting for some 13.6% of the total unit-cell volume. Several significant peaks corresponding to electron densities up to 2.02 e Å^-3 were located within the void space. However, these peaks could not be reconciled with any plausible molecular species, possibly because of disorder and/or mobility. Accordingly, the SQUEEZE option in PLATON was utilized; while this reduced R from 0.104 to 0.0646, the quality of the data set did not permit a meaningful evaluation of the electron population in the void.

Computing details

For both compounds, data collection: COLLECT (Hooft, 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. A molecule of compound (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. The two independent molecules of compound (II), showing the atom-labelling scheme for (a) a type 1 molecule and (b) a type 2 molecule. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 3. A stereoview of part of the crystal structure of compound (I), showing the formation of a hydrogen-bonded chain of edge fused R2^2(8) and R4^4(20) rings along [001]. For the sake of clarity, H atoms bonded to C atoms have all been omitted.
	Fig. 4. A stereoview of part of the crystal structure of compound (II), showing the formation of a hydrogen-bonded chain of edge fused R2^2(8) and R2^2(20) rings along [100]. For the sake of clarity, H atoms bonded to C atoms have all been omitted.

(I) ethyl (E)-3-[2-amino-4,6-bis(dimethylamino)pyrimidin-5-yl]-2-cyanoacrylate

Crystal data

C14H20N6O2	Z = 2
Mr = 304.36	F(000) = 324
Triclinic, P1	Dx = 1.331 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.5570 (15) Å	Cell parameters from 3468 reflections
b = 9.893 (2) Å	θ = 4.1–27.5°
c = 9.9739 (18) Å	µ = 0.09 mm^−1
α = 87.534 (13)°	T = 120 K
β = 77.251 (15)°	Block, colourless
γ = 67.431 (14)°	0.37 × 0.34 × 0.15 mm
V = 759.6 (3) Å^3

Data collection

Bruker–Nonius KappaCCD diffractometer	3468 independent reflections
Radiation source: Bruker–Nonius FR591 rotating anode	1715 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.085
Detector resolution: 9.091 pixels mm^-1	θmax = 27.5°, θmin = 4.1°
ϕ and ω scans	h = −11→11
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −12→12
Tmin = 0.971, Tmax = 0.986	l = −12→12
18938 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.069	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.236	H-atom parameters constrained
S = 1.03	w = 1/[σ^2(Fo^2) + (0.130P)^2 + 0.0863P] where P = (Fo^2 + 2Fc^2)/3
3468 reflections	(Δ/σ)max < 0.001
204 parameters	Δρmax = 0.44 e Å^−3
0 restraints	Δρmin = −0.37 e Å^−3

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

	x	y	z	Uiso*/Ueq
O55	0.5647 (3)	0.7337 (2)	−0.1477 (2)	0.0290 (6)
O56	0.3443 (3)	0.9501 (2)	−0.0864 (2)	0.0288 (6)
N1	0.8254 (3)	0.5391 (3)	0.3715 (2)	0.0235 (6)
N2	0.7796 (3)	0.6729 (3)	0.5677 (3)	0.0275 (7)
N3	0.5387 (3)	0.6968 (3)	0.4920 (2)	0.0245 (6)
N4	0.3022 (3)	0.7117 (3)	0.4087 (2)	0.0230 (6)
N6	0.8682 (3)	0.4237 (3)	0.1636 (2)	0.0241 (6)
N54	0.2080 (4)	1.0044 (3)	0.2559 (3)	0.0377 (8)
C2	0.7122 (4)	0.6373 (3)	0.4726 (3)	0.0241 (7)
C4	0.4739 (4)	0.6763 (3)	0.3874 (3)	0.0238 (7)
C5	0.5859 (4)	0.6154 (3)	0.2558 (3)	0.0233 (7)
C6	0.7613 (4)	0.5227 (3)	0.2651 (3)	0.0216 (7)
C41	0.2248 (4)	0.6563 (4)	0.3186 (3)	0.0283 (8)
C42	0.1864 (4)	0.8013 (4)	0.5305 (3)	0.0321 (8)
C51	0.5569 (4)	0.6707 (3)	0.1280 (3)	0.0219 (7)
C52	0.4365 (4)	0.7968 (3)	0.0886 (3)	0.0221 (7)
C53	0.3089 (4)	0.9116 (4)	0.1809 (3)	0.0256 (7)
C55	0.4578 (4)	0.8208 (3)	−0.0587 (3)	0.0227 (7)
C57	0.3524 (4)	0.9805 (4)	−0.2306 (3)	0.0297 (8)
C58	0.1876 (4)	1.1043 (4)	−0.2409 (3)	0.0350 (9)
C61	1.0537 (4)	0.3587 (4)	0.1554 (3)	0.0280 (8)
C62	0.8051 (4)	0.3512 (4)	0.0764 (3)	0.0291 (8)
H2A	0.8847	0.6190	0.5716	0.033*
H2B	0.7073	0.7204	0.6406	0.033*
H41A	0.3116	0.5652	0.2704	0.042*
H41B	0.1849	0.7293	0.2512	0.042*
H41C	0.1261	0.6372	0.3738	0.042*
H42A	0.2065	0.8920	0.5346	0.048*
H42B	0.2093	0.7469	0.6131	0.048*
H42C	0.0656	0.8253	0.5255	0.048*
H51	0.6365	0.6086	0.0523	0.026*
H57A	0.3656	0.8926	−0.2832	0.036*
H57B	0.4530	1.0074	−0.2689	0.036*
H58A	0.1746	1.1899	−0.1869	0.052*
H58B	0.0892	1.0754	−0.2052	0.052*
H58C	0.1907	1.1289	−0.3375	0.052*
H61A	1.0811	0.2714	0.2102	0.042*
H61B	1.0903	0.4298	0.1912	0.042*
H61C	1.1151	0.3309	0.0593	0.042*
H62A	0.6794	0.3806	0.1086	0.044*
H62B	0.8624	0.2448	0.0806	0.044*
H62C	0.8310	0.3795	−0.0188	0.044*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O55	0.0259 (12)	0.0319 (13)	0.0211 (12)	−0.0040 (10)	−0.0024 (10)	0.0013 (10)
O56	0.0296 (12)	0.0282 (13)	0.0224 (12)	−0.0054 (10)	−0.0047 (9)	0.0031 (10)
N1	0.0249 (14)	0.0253 (15)	0.0189 (14)	−0.0081 (12)	−0.0050 (11)	0.0005 (12)
N2	0.0272 (15)	0.0320 (16)	0.0214 (14)	−0.0082 (13)	−0.0064 (11)	−0.0033 (12)
N3	0.0255 (15)	0.0286 (15)	0.0187 (14)	−0.0093 (12)	−0.0056 (11)	0.0020 (12)
N4	0.0212 (14)	0.0275 (15)	0.0186 (13)	−0.0081 (12)	−0.0031 (11)	−0.0003 (11)
N6	0.0233 (14)	0.0251 (15)	0.0209 (14)	−0.0049 (12)	−0.0062 (11)	−0.0029 (12)
N54	0.0445 (18)	0.0276 (16)	0.0329 (17)	−0.0080 (14)	−0.0032 (14)	0.0030 (14)
C2	0.0283 (19)	0.0220 (17)	0.0194 (16)	−0.0083 (14)	−0.0036 (13)	0.0051 (13)
C4	0.0238 (17)	0.0225 (17)	0.0227 (17)	−0.0066 (14)	−0.0051 (13)	0.0014 (14)
C5	0.0235 (16)	0.0277 (18)	0.0190 (16)	−0.0107 (14)	−0.0029 (13)	−0.0015 (13)
C6	0.0261 (17)	0.0203 (17)	0.0188 (16)	−0.0104 (14)	−0.0041 (13)	0.0054 (13)
C41	0.0251 (17)	0.0304 (19)	0.0277 (18)	−0.0102 (15)	−0.0036 (14)	0.0016 (15)
C42	0.0285 (19)	0.0331 (19)	0.0255 (18)	−0.0056 (15)	0.0012 (14)	−0.0019 (15)
C51	0.0198 (16)	0.0244 (17)	0.0212 (16)	−0.0088 (14)	−0.0029 (12)	−0.0014 (14)
C52	0.0227 (17)	0.0237 (17)	0.0185 (16)	−0.0071 (14)	−0.0050 (12)	0.0010 (13)
C53	0.0294 (19)	0.0247 (18)	0.0223 (17)	−0.0097 (15)	−0.0069 (14)	0.0060 (15)
C55	0.0179 (16)	0.0247 (18)	0.0259 (18)	−0.0083 (14)	−0.0057 (14)	0.0024 (15)
C57	0.0331 (19)	0.035 (2)	0.0212 (17)	−0.0116 (16)	−0.0111 (14)	0.0077 (15)
C58	0.041 (2)	0.032 (2)	0.0305 (19)	−0.0089 (17)	−0.0162 (16)	0.0092 (16)
C61	0.0225 (17)	0.0329 (19)	0.0256 (18)	−0.0068 (15)	−0.0062 (14)	0.0016 (15)
C62	0.0315 (19)	0.0297 (19)	0.0265 (18)	−0.0118 (16)	−0.0058 (14)	−0.0042 (15)

Geometric parameters (Å, º)

O55—C55	1.212 (3)	C41—H41B	0.98
O56—C55	1.338 (4)	C41—H41C	0.98
O56—C57	1.449 (3)	C42—H42A	0.98
N1—C6	1.340 (4)	C42—H42B	0.98
N1—C2	1.353 (4)	C42—H42C	0.98
N2—C2	1.335 (4)	C51—C52	1.387 (4)
N2—H2A	0.8601	C51—H51	0.95
N2—H2B	0.86	C52—C53	1.423 (4)
N3—C4	1.340 (4)	C52—C55	1.460 (4)
N3—C2	1.342 (4)	C57—C58	1.492 (4)
N4—C4	1.342 (4)	C57—H57A	0.99
N4—C41	1.459 (4)	C57—H57B	0.99
N4—C42	1.460 (4)	C58—H58A	0.98
N6—C6	1.345 (4)	C58—H58B	0.98
N6—C61	1.451 (4)	C58—H58C	0.98
N6—C62	1.456 (4)	C61—H61A	0.98
N54—C53	1.146 (4)	C61—H61B	0.98
C4—C5	1.440 (4)	C61—H61C	0.98
C5—C51	1.400 (4)	C62—H62A	0.98
C5—C6	1.449 (4)	C62—H62B	0.98
C41—H41A	0.98	C62—H62C	0.98
C55—O56—C57	116.3 (2)	H42B—C42—H42C	109.5
C6—N1—C2	115.8 (3)	C52—C51—C5	133.6 (3)
C2—N2—H2A	118.2	C52—C51—H51	113.2
C2—N2—H2B	116.5	C5—C51—H51	113.2
H2A—N2—H2B	119.7	C51—C52—C53	124.7 (3)
C4—N3—C2	115.8 (3)	C51—C52—C55	116.9 (3)
C4—N4—C41	122.5 (3)	C53—C52—C55	117.9 (3)
C4—N4—C42	119.9 (3)	N54—C53—C52	178.9 (3)
C41—N4—C42	117.4 (3)	O55—C55—O56	122.8 (3)
C6—N6—C61	120.9 (3)	O55—C55—C52	124.5 (3)
C6—N6—C62	122.5 (3)	O56—C55—C52	112.7 (3)
C61—N6—C62	115.1 (3)	O56—C57—C58	107.7 (2)
N2—C2—N3	116.4 (3)	O56—C57—H57A	110.2
N2—C2—N1	116.5 (3)	C58—C57—H57A	110.2
N3—C2—N1	127.1 (3)	O56—C57—H57B	110.2
N3—C4—N4	118.5 (3)	C58—C57—H57B	110.2
N3—C4—C5	121.0 (3)	H57A—C57—H57B	108.5
N4—C4—C5	120.6 (3)	C57—C58—H58A	109.5
C51—C5—C4	125.4 (3)	C57—C58—H58B	109.5
C51—C5—C6	118.4 (3)	H58A—C58—H58B	109.5
C4—C5—C6	113.1 (3)	C57—C58—H58C	109.5
N1—C6—N6	117.8 (3)	H58A—C58—H58C	109.5
N1—C6—C5	120.8 (3)	H58B—C58—H58C	109.5
N6—C6—C5	121.2 (3)	N6—C61—H61A	109.5
N4—C41—H41A	109.5	N6—C61—H61B	109.5
N4—C41—H41B	109.5	H61A—C61—H61B	109.5
H41A—C41—H41B	109.5	N6—C61—H61C	109.5
N4—C41—H41C	109.5	H61A—C61—H61C	109.5
H41A—C41—H41C	109.5	H61B—C61—H61C	109.5
H41B—C41—H41C	109.5	N6—C62—H62A	109.5
N4—C42—H42A	109.5	N6—C62—H62B	109.5
N4—C42—H42B	109.5	H62A—C62—H62B	109.5
H42A—C42—H42B	109.5	N6—C62—H62C	109.5
N4—C42—H42C	109.5	H62A—C62—H62C	109.5
H42A—C42—H42C	109.5	H62B—C62—H62C	109.5
C4—N3—C2—N2	171.5 (3)	C61—N6—C6—C5	163.9 (3)
C4—N3—C2—N1	−12.5 (4)	C62—N6—C6—C5	−30.4 (4)
C6—N1—C2—N2	−169.3 (3)	C51—C5—C6—N1	137.2 (3)
C6—N1—C2—N3	14.7 (5)	C4—C5—C6—N1	−24.0 (4)
C2—N3—C4—N4	169.2 (3)	C51—C5—C6—N6	−38.8 (4)
C2—N3—C4—C5	−9.7 (4)	C4—C5—C6—N6	160.1 (3)
C41—N4—C4—N3	−161.8 (3)	C4—C5—C51—C52	7.9 (6)
C42—N4—C4—N3	14.2 (4)	C6—C5—C51—C52	−150.8 (3)
C41—N4—C4—C5	17.2 (4)	C5—C51—C52—C53	3.5 (6)
C42—N4—C4—C5	−166.9 (3)	C5—C51—C52—C55	175.3 (3)
N3—C4—C5—C51	−133.3 (3)	C57—O56—C55—O55	1.5 (4)
N4—C4—C5—C51	47.8 (5)	C57—O56—C55—C52	−177.9 (2)
N3—C4—C5—C6	26.3 (4)	C51—C52—C55—O55	5.5 (5)
N4—C4—C5—C6	−152.6 (3)	C53—C52—C55—O55	177.9 (3)
C2—N1—C6—N6	−178.5 (3)	C51—C52—C55—O56	−175.2 (3)
C2—N1—C6—C5	5.4 (4)	C53—C52—C55—O56	−2.8 (4)
C61—N6—C6—N1	−12.2 (4)	C55—O56—C57—C58	163.4 (3)
C62—N6—C6—N1	153.5 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···N1^i	0.86	2.55	3.398 (4)	170
N2—H2B···O55^ii	0.86	2.17	2.966 (3)	153

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

(II) 2-[(2-amino-4,6-di-1-piperidylpyrimidin-5-yl)methylene]malononitrile

Crystal data

C18H23N7	Z = 4
Mr = 337.43	F(000) = 720
Triclinic, P1	Dx = 1.152 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.6960 (8) Å	Cell parameters from 8590 reflections
b = 14.752 (3) Å	θ = 3.9–27.5°
c = 15.418 (3) Å	µ = 0.07 mm^−1
α = 116.332 (13)°	T = 120 K
β = 96.794 (10)°	Block, colourless
γ = 93.587 (9)°	0.62 × 0.38 × 0.32 mm
V = 1946.1 (6) Å^3

Data collection

Bruker–Nonius KappaCCD diffractometer	8590 independent reflections
Radiation source: Bruker–Nonius FR591 rotating anode	4805 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.049
Detector resolution: 9.091 pixels mm^-1	θmax = 27.5°, θmin = 3.9°
ϕ and ω scans	h = −12→12
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −18→19
Tmin = 0.962, Tmax = 0.977	l = −19→20
38120 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.065	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.206	H-atom parameters constrained
S = 1.10	w = 1/[σ^2(Fo^2) + (0.0985P)^2 + 0.7388P] where P = (Fo^2 + 2Fc^2)/3
8590 reflections	(Δ/σ)max < 0.001
451 parameters	Δρmax = 0.31 e Å^−3
0 restraints	Δρmin = −0.29 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
N11	0.1453 (2)	0.27967 (16)	0.62366 (14)	0.0216 (5)
N12	0.0453 (2)	0.23885 (17)	0.46741 (15)	0.0287 (5)
H12A	0.1140	0.2060	0.4455	0.034*
H12B	−0.0200	0.2403	0.4253	0.034*
N13	−0.0488 (2)	0.36072 (16)	0.58977 (15)	0.0242 (5)
N14	−0.1297 (2)	0.48813 (16)	0.71721 (15)	0.0221 (5)
N16	0.2347 (2)	0.30988 (16)	0.78053 (15)	0.0227 (5)
N154	−0.3884 (2)	0.39981 (19)	0.76521 (18)	0.0347 (6)
N156	−0.2001 (2)	0.35445 (19)	1.01184 (18)	0.0331 (6)
C12	0.0443 (3)	0.29356 (19)	0.56345 (18)	0.0220 (6)
C14	−0.0543 (3)	0.40955 (19)	0.68562 (18)	0.0205 (6)
C15	0.0191 (3)	0.37801 (19)	0.75365 (18)	0.0210 (6)
C16	0.1364 (3)	0.32394 (18)	0.71857 (19)	0.0205 (6)
C142	−0.2310 (3)	0.5034 (2)	0.64776 (19)	0.0261 (6)
H42A	−0.3234	0.5088	0.6697	0.031*
H42B	−0.2416	0.4438	0.5823	0.031*
C143	−0.1838 (3)	0.5991 (2)	0.6402 (2)	0.0318 (7)
H43A	−0.2576	0.6109	0.5975	0.038*
H43B	−0.0980	0.5901	0.6099	0.038*
C144	−0.1544 (3)	0.6910 (2)	0.7406 (2)	0.0303 (7)
H44A	−0.2434	0.7068	0.7664	0.036*
H44B	−0.1137	0.7509	0.7348	0.036*
C145	−0.0536 (3)	0.6708 (2)	0.8114 (2)	0.0286 (6)
H45A	−0.0435	0.7291	0.8777	0.034*
H45B	0.0396	0.6657	0.7907	0.034*
C146	−0.1027 (3)	0.57302 (19)	0.81622 (18)	0.0243 (6)
H46A	−0.0298	0.5591	0.8578	0.029*
H46B	−0.1892	0.5809	0.8457	0.029*
C151	−0.0341 (3)	0.37128 (18)	0.83164 (18)	0.0222 (6)
H151	0.0324	0.3562	0.8722	0.027*
C152	−0.1645 (3)	0.38224 (19)	0.86154 (18)	0.0218 (6)
C153	−0.2859 (3)	0.3934 (2)	0.8081 (2)	0.0256 (6)
C155	−0.1853 (3)	0.3664 (2)	0.9440 (2)	0.0241 (6)
C162	0.3265 (3)	0.2314 (2)	0.7419 (2)	0.0262 (6)
H62A	0.4131	0.2610	0.7306	0.031*
H62B	0.2789	0.1757	0.6783	0.031*
C163	0.3637 (3)	0.1892 (2)	0.8143 (2)	0.0308 (7)
H63A	0.2782	0.1521	0.8188	0.037*
H63B	0.4317	0.1400	0.7899	0.037*
C164	0.4260 (3)	0.2730 (2)	0.9156 (2)	0.0347 (7)
H64A	0.5170	0.3053	0.9129	0.042*
H64B	0.4430	0.2434	0.9617	0.042*
C165	0.3266 (3)	0.3536 (2)	0.9525 (2)	0.0318 (7)
H65A	0.2391	0.3232	0.9618	0.038*
H65B	0.3709	0.4104	1.0164	0.038*
C166	0.2936 (3)	0.3933 (2)	0.87794 (19)	0.0245 (6)
H66A	0.2258	0.4432	0.9001	0.029*
H66B	0.3804	0.4290	0.8734	0.029*
N21	0.3141 (2)	0.16895 (16)	0.39431 (15)	0.0225 (5)
N22	0.4239 (2)	0.27580 (18)	0.54959 (15)	0.0311 (6)
H22A	0.3508	0.2593	0.5687	0.037*
H22B	0.4893	0.3223	0.5907	0.037*
N23	0.5226 (2)	0.28412 (16)	0.42548 (15)	0.0232 (5)
N24	0.6120 (2)	0.29151 (16)	0.29581 (15)	0.0226 (5)
N26	0.2154 (2)	0.04855 (15)	0.23860 (15)	0.0222 (5)
N254	0.8560 (3)	0.16240 (19)	0.26326 (19)	0.0358 (6)
N256	0.6582 (2)	−0.10128 (18)	0.00068 (17)	0.0320 (6)
C22	0.4228 (3)	0.24072 (19)	0.45319 (19)	0.0230 (6)
C24	0.5270 (3)	0.24128 (19)	0.32853 (18)	0.0220 (6)
C25	0.4441 (3)	0.14492 (19)	0.26252 (18)	0.0211 (6)
C26	0.3216 (3)	0.12164 (19)	0.29805 (18)	0.0216 (6)
C242	0.7198 (3)	0.3752 (2)	0.36422 (19)	0.0261 (6)
H42C	0.8119	0.3615	0.3428	0.031*
H42D	0.7259	0.3793	0.4304	0.031*
C243	0.6859 (3)	0.4760 (2)	0.3687 (2)	0.0292 (7)
H43C	0.5988	0.4934	0.3966	0.035*
H43D	0.7627	0.5307	0.4119	0.035*
C244	0.6675 (3)	0.4692 (2)	0.26692 (19)	0.0275 (6)
H44C	0.7589	0.4626	0.2435	0.033*
H44D	0.6355	0.5328	0.2699	0.033*
C245	0.5616 (3)	0.3784 (2)	0.19463 (19)	0.0259 (6)
H45C	0.4669	0.3914	0.2112	0.031*
H45D	0.5615	0.3714	0.1277	0.031*
C246	0.5930 (3)	0.2788 (2)	0.19524 (18)	0.0235 (6)
H46C	0.5147	0.2243	0.1545	0.028*
H46D	0.6791	0.2583	0.1668	0.028*
C251	0.4928 (3)	0.06654 (19)	0.18434 (18)	0.0214 (6)
H251	0.4222	0.0121	0.1417	0.026*
C252	0.6244 (3)	0.05412 (19)	0.15815 (18)	0.0222 (6)
C253	0.7509 (3)	0.1163 (2)	0.2168 (2)	0.0259 (6)
C255	0.6434 (3)	−0.0320 (2)	0.0711 (2)	0.0236 (6)
C262	0.1141 (3)	0.0053 (2)	0.2785 (2)	0.0279 (6)
H62C	0.0285	0.0394	0.2836	0.033*
H62D	0.1551	0.0167	0.3451	0.033*
C263	0.0769 (3)	−0.1088 (2)	0.2110 (2)	0.0315 (7)
H63C	0.1609	−0.1433	0.2122	0.038*
H63D	0.0043	−0.1371	0.2356	0.038*
C264	0.0231 (3)	−0.1309 (2)	0.1060 (2)	0.0346 (7)
H64C	−0.0670	−0.1035	0.1032	0.042*
H64D	0.0065	−0.2056	0.0637	0.042*
C265	0.1303 (3)	−0.0819 (2)	0.0682 (2)	0.0306 (7)
H65C	0.2167	−0.1150	0.0635	0.037*
H65D	0.0911	−0.0915	0.0019	0.037*
C266	0.1647 (3)	0.0317 (2)	0.13820 (18)	0.0258 (6)
H66C	0.2373	0.0625	0.1157	0.031*
H66D	0.0799	0.0656	0.1378	0.031*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N11	0.0211 (12)	0.0243 (12)	0.0157 (11)	0.0017 (9)	0.0020 (9)	0.0061 (9)
N12	0.0270 (13)	0.0345 (13)	0.0184 (12)	0.0095 (10)	0.0018 (10)	0.0064 (10)
N13	0.0239 (12)	0.0265 (12)	0.0204 (12)	0.0062 (10)	0.0044 (9)	0.0085 (10)
N14	0.0236 (12)	0.0216 (11)	0.0187 (11)	0.0039 (9)	0.0022 (9)	0.0074 (9)
N16	0.0222 (12)	0.0241 (12)	0.0201 (12)	0.0043 (9)	0.0030 (9)	0.0086 (10)
N154	0.0226 (13)	0.0415 (15)	0.0419 (15)	−0.0035 (11)	−0.0007 (12)	0.0232 (13)
N156	0.0243 (13)	0.0448 (15)	0.0312 (14)	0.0049 (11)	0.0056 (11)	0.0178 (12)
C12	0.0204 (14)	0.0201 (13)	0.0226 (14)	−0.0004 (11)	0.0027 (11)	0.0078 (11)
C14	0.0175 (13)	0.0192 (13)	0.0205 (14)	−0.0020 (10)	0.0017 (11)	0.0062 (11)
C15	0.0221 (14)	0.0212 (13)	0.0165 (13)	0.0015 (11)	0.0007 (11)	0.0064 (11)
C16	0.0183 (13)	0.0179 (13)	0.0247 (14)	−0.0014 (10)	0.0010 (11)	0.0103 (11)
C142	0.0230 (14)	0.0320 (15)	0.0196 (14)	0.0086 (12)	−0.0001 (11)	0.0087 (12)
C143	0.0319 (16)	0.0380 (17)	0.0336 (16)	0.0134 (13)	0.0071 (13)	0.0219 (14)
C144	0.0273 (15)	0.0284 (15)	0.0377 (17)	0.0033 (12)	0.0039 (13)	0.0176 (14)
C145	0.0302 (16)	0.0213 (14)	0.0305 (16)	0.0001 (12)	0.0028 (12)	0.0095 (12)
C146	0.0250 (14)	0.0235 (14)	0.0204 (14)	0.0040 (11)	0.0018 (11)	0.0069 (12)
C151	0.0260 (14)	0.0191 (13)	0.0173 (13)	−0.0001 (11)	−0.0013 (11)	0.0062 (11)
C152	0.0187 (14)	0.0242 (14)	0.0215 (14)	0.0023 (11)	0.0029 (11)	0.0097 (11)
C153	0.0260 (15)	0.0237 (14)	0.0254 (15)	0.0000 (12)	0.0049 (12)	0.0097 (12)
C155	0.0174 (14)	0.0292 (15)	0.0245 (15)	0.0026 (11)	0.0039 (11)	0.0111 (12)
C162	0.0245 (15)	0.0276 (15)	0.0291 (15)	0.0086 (12)	0.0081 (12)	0.0137 (13)
C163	0.0276 (16)	0.0331 (16)	0.0370 (17)	0.0053 (13)	0.0040 (13)	0.0208 (14)
C164	0.0344 (17)	0.0414 (17)	0.0357 (17)	0.0016 (14)	−0.0016 (14)	0.0265 (15)
C165	0.0310 (16)	0.0409 (17)	0.0216 (15)	−0.0035 (13)	−0.0024 (12)	0.0151 (13)
C166	0.0205 (14)	0.0251 (14)	0.0254 (15)	0.0007 (11)	0.0006 (11)	0.0103 (12)
N21	0.0215 (12)	0.0246 (12)	0.0193 (12)	0.0012 (9)	0.0040 (9)	0.0081 (10)
N22	0.0268 (13)	0.0397 (14)	0.0192 (12)	−0.0077 (11)	0.0022 (10)	0.0086 (11)
N23	0.0231 (12)	0.0232 (11)	0.0194 (12)	−0.0009 (9)	0.0029 (9)	0.0068 (10)
N24	0.0241 (12)	0.0245 (12)	0.0172 (11)	−0.0042 (9)	−0.0009 (9)	0.0097 (10)
N26	0.0203 (11)	0.0215 (11)	0.0223 (12)	−0.0034 (9)	0.0028 (9)	0.0087 (10)
N254	0.0291 (14)	0.0367 (14)	0.0402 (15)	0.0059 (12)	−0.0005 (12)	0.0176 (12)
N256	0.0337 (14)	0.0319 (14)	0.0289 (14)	0.0054 (11)	0.0080 (11)	0.0116 (12)
C22	0.0244 (14)	0.0223 (14)	0.0220 (14)	0.0049 (11)	0.0057 (11)	0.0093 (12)
C24	0.0204 (14)	0.0249 (14)	0.0211 (14)	0.0020 (11)	0.0021 (11)	0.0113 (12)
C25	0.0211 (14)	0.0231 (13)	0.0173 (13)	0.0009 (11)	0.0010 (11)	0.0085 (11)
C26	0.0245 (14)	0.0206 (13)	0.0208 (14)	0.0034 (11)	0.0034 (11)	0.0105 (11)
C242	0.0216 (14)	0.0305 (15)	0.0213 (14)	−0.0064 (12)	−0.0038 (11)	0.0105 (12)
C243	0.0275 (15)	0.0254 (15)	0.0261 (15)	−0.0066 (12)	0.0013 (12)	0.0060 (12)
C244	0.0269 (15)	0.0225 (14)	0.0326 (16)	0.0001 (12)	0.0045 (12)	0.0125 (12)
C245	0.0273 (15)	0.0276 (15)	0.0221 (14)	0.0024 (12)	0.0023 (12)	0.0111 (12)
C246	0.0254 (14)	0.0247 (14)	0.0181 (14)	−0.0015 (11)	0.0013 (11)	0.0088 (11)
C251	0.0226 (14)	0.0230 (14)	0.0180 (13)	−0.0031 (11)	−0.0022 (11)	0.0107 (11)
C252	0.0252 (15)	0.0241 (14)	0.0184 (14)	0.0020 (11)	0.0035 (11)	0.0106 (12)
C253	0.0230 (15)	0.0277 (15)	0.0264 (15)	0.0075 (12)	0.0034 (12)	0.0115 (12)
C255	0.0222 (14)	0.0267 (15)	0.0233 (15)	0.0033 (12)	0.0034 (12)	0.0126 (13)
C262	0.0267 (15)	0.0255 (14)	0.0296 (16)	0.0000 (12)	0.0078 (12)	0.0105 (12)
C263	0.0355 (17)	0.0237 (14)	0.0333 (16)	−0.0015 (12)	0.0089 (13)	0.0111 (13)
C264	0.0285 (16)	0.0249 (15)	0.0396 (18)	−0.0042 (12)	0.0021 (13)	0.0068 (13)
C265	0.0300 (16)	0.0310 (15)	0.0203 (14)	−0.0017 (12)	−0.0002 (12)	0.0043 (12)
C266	0.0243 (14)	0.0268 (15)	0.0220 (14)	0.0011 (12)	−0.0006 (12)	0.0084 (12)

Geometric parameters (Å, º)

N11—C16	1.328 (3)	N21—C26	1.345 (3)
N11—C12	1.357 (3)	N21—C22	1.356 (3)
N12—C12	1.337 (3)	N22—C22	1.338 (3)
N12—H12A	0.8600	N22—H22A	0.8600
N12—H12B	0.8601	N22—H22B	0.8600
N13—C14	1.336 (3)	N23—C22	1.339 (3)
N13—C12	1.342 (3)	N23—C24	1.348 (3)
N14—C14	1.343 (3)	N24—C24	1.355 (3)
N14—C146	1.461 (3)	N24—C246	1.464 (3)
N14—C142	1.468 (3)	N24—C242	1.467 (3)
N16—C16	1.360 (3)	N26—C26	1.351 (3)
N16—C162	1.460 (3)	N26—C266	1.471 (3)
N16—C166	1.472 (3)	N26—C262	1.471 (3)
N154—C153	1.160 (3)	N254—C253	1.150 (3)
N156—C155	1.158 (3)	N256—C255	1.147 (3)
C14—C15	1.456 (4)	C24—C25	1.443 (4)
C15—C151	1.403 (4)	C25—C251	1.407 (4)
C15—C16	1.448 (4)	C25—C26	1.449 (4)
C142—C143	1.514 (4)	C242—C243	1.516 (4)
C142—H42A	0.9900	C242—H42C	0.9900
C142—H42B	0.9900	C242—H42D	0.9900
C143—C144	1.517 (4)	C243—C244	1.515 (4)
C143—H43A	0.9900	C243—H43C	0.9900
C143—H43B	0.9900	C243—H43D	0.9900
C144—C145	1.520 (4)	C244—C245	1.525 (4)
C144—H44A	0.9900	C244—H44C	0.9900
C144—H44B	0.9900	C244—H44D	0.9900
C145—C146	1.526 (4)	C245—C246	1.523 (4)
C145—H45A	0.9900	C245—H45C	0.9900
C145—H45B	0.9900	C245—H45D	0.9900
C146—H46A	0.9900	C246—H46C	0.9900
C146—H46B	0.9900	C246—H46D	0.9900
C151—C152	1.391 (4)	C251—C252	1.382 (4)
C151—H151	0.9500	C251—H251	0.9500
C152—C153	1.417 (4)	C252—C253	1.423 (4)
C152—C155	1.425 (4)	C252—C255	1.423 (4)
C162—C163	1.522 (4)	C262—C263	1.526 (4)
C162—H62A	0.9900	C262—H62C	0.9900
C162—H62B	0.9900	C262—H62D	0.9900
C163—C164	1.518 (4)	C263—C264	1.519 (4)
C163—H63A	0.9900	C263—H63C	0.9900
C163—H63B	0.9900	C263—H63D	0.9900
C164—C165	1.529 (4)	C264—C265	1.539 (4)
C164—H64A	0.9900	C264—H64C	0.9900
C164—H64B	0.9900	C264—H64D	0.9900
C165—C166	1.517 (4)	C265—C266	1.524 (4)
C165—H65A	0.9900	C265—H65C	0.9900
C165—H65B	0.9900	C265—H65D	0.9900
C166—H66A	0.9900	C266—H66C	0.9900
C166—H66B	0.9900	C266—H66D	0.9900
C16—N11—C12	116.4 (2)	C26—N21—C22	116.5 (2)
C12—N12—H12A	122.0	C22—N22—H22A	118.2
C12—N12—H12B	120.1	C22—N22—H22B	119.8
H12A—N12—H12B	117.7	H22A—N22—H22B	120.9
C14—N13—C12	116.0 (2)	C22—N23—C24	116.0 (2)
C14—N14—C146	124.2 (2)	C24—N24—C246	124.3 (2)
C14—N14—C142	120.7 (2)	C24—N24—C242	120.9 (2)
C146—N14—C142	114.3 (2)	C246—N24—C242	114.2 (2)
C16—N16—C162	120.3 (2)	C26—N26—C266	122.3 (2)
C16—N16—C166	121.3 (2)	C26—N26—C262	121.3 (2)
C162—N16—C166	113.6 (2)	C266—N26—C262	113.4 (2)
N12—C12—N13	117.1 (2)	N22—C22—N23	117.2 (2)
N12—C12—N11	115.5 (2)	N22—C22—N21	115.5 (2)
N13—C12—N11	127.2 (2)	N23—C22—N21	127.2 (2)
N13—C14—N14	118.1 (2)	N23—C24—N24	117.7 (2)
N13—C14—C15	120.8 (2)	N23—C24—C25	120.7 (2)
N14—C14—C15	121.1 (2)	N24—C24—C25	121.6 (2)
C151—C15—C16	118.5 (2)	C251—C25—C24	124.0 (2)
C151—C15—C14	125.5 (2)	C251—C25—C26	119.5 (2)
C16—C15—C14	113.6 (2)	C24—C25—C26	114.4 (2)
N11—C16—N16	117.8 (2)	N21—C26—N26	117.2 (2)
N11—C16—C15	121.0 (2)	N21—C26—C25	120.2 (2)
N16—C16—C15	121.0 (2)	N26—C26—C25	122.4 (2)
N14—C142—C143	111.1 (2)	N24—C242—C243	110.9 (2)
N14—C142—H42A	109.4	N24—C242—H42C	109.5
C143—C142—H42A	109.4	C243—C242—H42C	109.5
N14—C142—H42B	109.4	N24—C242—H42D	109.5
C143—C142—H42B	109.4	C243—C242—H42D	109.5
H42A—C142—H42B	108.0	H42C—C242—H42D	108.1
C142—C143—C144	110.9 (2)	C244—C243—C242	110.2 (2)
C142—C143—H43A	109.5	C244—C243—H43C	109.6
C144—C143—H43A	109.5	C242—C243—H43C	109.6
C142—C143—H43B	109.5	C244—C243—H43D	109.6
C144—C143—H43B	109.5	C242—C243—H43D	109.6
H43A—C143—H43B	108.0	H43C—C243—H43D	108.1
C143—C144—C145	110.8 (2)	C243—C244—C245	111.5 (2)
C143—C144—H44A	109.5	C243—C244—H44C	109.3
C145—C144—H44A	109.5	C245—C244—H44C	109.3
C143—C144—H44B	109.5	C243—C244—H44D	109.3
C145—C144—H44B	109.5	C245—C244—H44D	109.3
H44A—C144—H44B	108.1	H44C—C244—H44D	108.0
C144—C145—C146	112.5 (2)	C246—C245—C244	112.7 (2)
C144—C145—H45A	109.1	C246—C245—H45C	109.0
C146—C145—H45A	109.1	C244—C245—H45C	109.0
C144—C145—H45B	109.1	C246—C245—H45D	109.0
C146—C145—H45B	109.1	C244—C245—H45D	109.0
H45A—C145—H45B	107.8	H45C—C245—H45D	107.8
N14—C146—C145	109.3 (2)	N24—C246—C245	110.0 (2)
N14—C146—H46A	109.8	N24—C246—H46C	109.7
C145—C146—H46A	109.8	C245—C246—H46C	109.7
N14—C146—H46B	109.8	N24—C246—H46D	109.7
C145—C146—H46B	109.8	C245—C246—H46D	109.7
H46A—C146—H46B	108.3	H46C—C246—H46D	108.2
C152—C151—C15	132.9 (2)	C252—C251—C25	131.9 (2)
C152—C151—H151	113.5	C252—C251—H251	114.1
C15—C151—H151	113.5	C25—C251—H251	114.1
C151—C152—C153	124.9 (2)	C251—C252—C253	125.1 (2)
C151—C152—C155	118.5 (2)	C251—C252—C255	120.2 (2)
C153—C152—C155	116.0 (2)	C253—C252—C255	114.4 (2)
N154—C153—C152	177.2 (3)	N254—C253—C252	176.7 (3)
N156—C155—C152	178.9 (3)	N256—C255—C252	179.7 (3)
N16—C162—C163	109.8 (2)	N26—C262—C263	109.2 (2)
N16—C162—H62A	109.7	N26—C262—H62C	109.8
C163—C162—H62A	109.7	C263—C262—H62C	109.8
N16—C162—H62B	109.7	N26—C262—H62D	109.8
C163—C162—H62B	109.7	C263—C262—H62D	109.8
H62A—C162—H62B	108.2	H62C—C262—H62D	108.3
C164—C163—C162	111.8 (2)	C264—C263—C262	112.0 (2)
C164—C163—H63A	109.2	C264—C263—H63C	109.2
C162—C163—H63A	109.2	C262—C263—H63C	109.2
C164—C163—H63B	109.2	C264—C263—H63D	109.2
C162—C163—H63B	109.2	C262—C263—H63D	109.2
H63A—C163—H63B	107.9	H63C—C263—H63D	107.9
C163—C164—C165	110.3 (2)	C263—C264—C265	110.3 (2)
C163—C164—H64A	109.6	C263—C264—H64C	109.6
C165—C164—H64A	109.6	C265—C264—H64C	109.6
C163—C164—H64B	109.6	C263—C264—H64D	109.6
C165—C164—H64B	109.6	C265—C264—H64D	109.6
H64A—C164—H64B	108.1	H64C—C264—H64D	108.1
C166—C165—C164	109.1 (2)	C266—C265—C264	109.5 (2)
C166—C165—H65A	109.9	C266—C265—H65C	109.8
C164—C165—H65A	109.9	C264—C265—H65C	109.8
C166—C165—H65B	109.9	C266—C265—H65D	109.8
C164—C165—H65B	109.9	C264—C265—H65D	109.8
H65A—C165—H65B	108.3	H65C—C265—H65D	108.2
N16—C166—C165	111.3 (2)	N26—C266—C265	111.0 (2)
N16—C166—H66A	109.4	N26—C266—H66C	109.4
C165—C166—H66A	109.4	C265—C266—H66C	109.4
N16—C166—H66B	109.4	N26—C266—H66D	109.4
C165—C166—H66B	109.4	C265—C266—H66D	109.4
H66A—C166—H66B	108.0	H66C—C266—H66D	108.0
C14—N13—C12—N12	175.7 (2)	C24—N23—C22—N22	174.1 (2)
C14—N13—C12—N11	−9.5 (4)	C24—N23—C22—N21	−10.5 (4)
C16—N11—C12—N12	−172.4 (2)	C26—N21—C22—N22	−170.4 (2)
C16—N11—C12—N13	12.7 (4)	C26—N21—C22—N23	14.2 (4)
C12—N13—C14—N14	170.1 (2)	C22—N23—C24—N24	170.3 (2)
C12—N13—C14—C15	−10.1 (3)	C22—N23—C24—C25	−9.9 (3)
C146—N14—C14—N13	−153.5 (2)	C246—N24—C24—N23	−156.3 (2)
C142—N14—C14—N13	15.4 (4)	C242—N24—C24—N23	14.6 (3)
C146—N14—C14—C15	26.7 (4)	C246—N24—C24—C25	24.0 (4)
C142—N14—C14—C15	−164.4 (2)	C242—N24—C24—C25	−165.2 (2)
N13—C14—C15—C151	−138.2 (3)	N23—C24—C25—C251	−138.9 (3)
N14—C14—C15—C151	41.6 (4)	N24—C24—C25—C251	40.8 (4)
N13—C14—C15—C16	24.0 (3)	N23—C24—C25—C26	24.1 (3)
N14—C14—C15—C16	−156.2 (2)	N24—C24—C25—C26	−156.2 (2)
C12—N11—C16—N16	178.8 (2)	C22—N21—C26—N26	178.8 (2)
C12—N11—C16—C15	4.0 (3)	C22—N21—C26—C25	2.7 (3)
C162—N16—C16—N11	−13.3 (3)	C266—N26—C26—N21	144.9 (2)
C166—N16—C16—N11	140.7 (2)	C262—N26—C26—N21	−14.2 (3)
C162—N16—C16—C15	161.6 (2)	C266—N26—C26—C25	−39.1 (4)
C166—N16—C16—C15	−44.5 (3)	C262—N26—C26—C25	161.8 (2)
C151—C15—C16—N11	142.9 (2)	C251—C25—C26—N21	143.7 (2)
C14—C15—C16—N11	−20.6 (3)	C24—C25—C26—N21	−20.1 (3)
C151—C15—C16—N16	−31.7 (3)	C251—C25—C26—N26	−32.2 (4)
C14—C15—C16—N16	164.7 (2)	C24—C25—C26—N26	164.0 (2)
C14—N14—C142—C143	−112.4 (3)	C24—N24—C242—C243	−113.0 (3)
C146—N14—C142—C143	57.6 (3)	C246—N24—C242—C243	58.7 (3)
N14—C142—C143—C144	−54.2 (3)	N24—C242—C243—C244	−55.8 (3)
C142—C143—C144—C145	52.8 (3)	C242—C243—C244—C245	52.9 (3)
C143—C144—C145—C146	−53.3 (3)	C243—C244—C245—C246	−51.6 (3)
C14—N14—C146—C145	113.2 (3)	C24—N24—C246—C245	115.8 (3)
C142—N14—C146—C145	−56.3 (3)	C242—N24—C246—C245	−55.5 (3)
C144—C145—C146—N14	53.8 (3)	C244—C245—C246—N24	51.3 (3)
C16—C15—C151—C152	−155.2 (3)	C24—C25—C251—C252	8.9 (4)
C14—C15—C151—C152	6.2 (5)	C26—C25—C251—C252	−153.3 (3)
C15—C151—C152—C153	7.4 (5)	C25—C251—C252—C253	9.7 (5)
C15—C151—C152—C155	177.7 (3)	C25—C251—C252—C255	−176.9 (3)
C16—N16—C162—C163	−148.1 (2)	C26—N26—C262—C263	−141.8 (2)
C166—N16—C162—C163	56.0 (3)	C266—N26—C262—C263	57.4 (3)
N16—C162—C163—C164	−54.6 (3)	N26—C262—C263—C264	−55.4 (3)
C162—C163—C164—C165	55.5 (3)	C262—C263—C264—C265	55.3 (3)
C163—C164—C165—C166	−55.5 (3)	C263—C264—C265—C266	−54.6 (3)
C16—N16—C166—C165	146.1 (2)	C26—N26—C266—C265	140.3 (2)
C162—N16—C166—C165	−58.3 (3)	C262—N26—C266—C265	−59.1 (3)
C164—C165—C166—N16	56.4 (3)	C264—C265—C266—N26	56.1 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N12—H12A···N21	0.86	2.19	3.021 (3)	162
N12—H12B···N254^i	0.86	2.36	3.126 (3)	148
N22—H22A···N11	0.86	2.24	3.049 (3)	156
N22—H22B···N154^ii	0.86	2.51	3.235 (3)	143
C162—H62A···N154^ii	0.99	2.54	3.472 (4)	156
C164—H64B···N256^iii	0.99	2.58	3.412 (4)	142
C246—H46C···N256^iv	0.99	2.58	3.515 (4)	158
C266—H66C···N256^iv	0.99	2.42	3.345 (4)	156

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