2-Amino­benzimidazolium O-ethyl malonate: eight independent N-H...O hydrogen bonds generate sheets

The title compound, C₇H₈N₃⁺·C₅H₇O₄^-, crystallizes with Z' = 2 in space group P2₁/c; eight independent N-H...O hydrogen bonds [H...O = 1.75-1.88 Å, N...O = 2.699 (2)-2.829 (2) Å and N-H...O = 147-179°] link the four inde­pendent ions into sheets.

S1. Comment

The title adduct, (I), was isolated as a direct intermediate in the synthesis of dihydropyrimido[1,2-a]benzimidazolones from a three-component reaction of 2-aminobenzimidazole with Meldrum's acid and arylaldehydes. In fact, compound (I) is formed without participation of the arylaldehyde component and results simply from the reaction between 2-aminobenzimidazole and Meldrum's acid. It can also be obtained directly by reaction of 2-aminobenzothiazole with malonic acid monoethyl ester (see reaction scheme below).

Compound (I) is a salt crystallizing with Z' = 2 in space group P2₁/c. The C—C and C—N distances in the two independent cations are very similar (Table 1) and both cations approximate to local C_2v (mm2) symmetry. The C—C distances in the cations span a rather narrow range, from 1.374 (3) to 1.400 (3) Å, consistent with classical aromatic delocalization. The C—N distances are indicative of guanidinium-type delocalization and this can be further explored in terms of the corresponding bond orders, calculated using the recent recalibration by Kotelevskii & Prezhdo (2001) of the original equation relating bond order to bond length (Gordy, 1947). If, for this purpose, the dimensions of the two cations are averaged together under assumed local C_2v symmetry, the averaged C—NH₂ bond has a bond order of 1.77, the averaged endocyclic guanidinium bond has a bond order of 1.63, while the C—N bond exocyclic to the aromatic ring has a bond order of only 1.37. These values indicate strong guanidinium delocalization, isoelectronic with carbonate, with only modest interaction between the aromatic 6π system and the guanidinium 6π system. A similar pattern of C—N distances was found in 2-aminobenzimidazolium nitrate, where there are four independent cations in the asymmetric unit (Bats et al., 1999). The bond distances within the two anions of (I) show no unusual values, but the conformations of the anions are different, particularly in respect of the O-ethyl groups, as demonstrated by the principal torsion angles (Table 1).

The four independent ions are linked by eight N—H···O hydrogen bonds (Table 2) into a two-dimensional structure of some complexity. With such a number of independent molecular components, there is considerable flexibility in the selection of the asymmetric unit. For simplicity of analysis and description of the supramolecular aggregation, it has been found convenient to specify the asymmetric unit in terms of the formation of two neutral ion-pair aggregates (Fig. 1), in each of which a cation is linked to an anion by means of two N—H···O hydrogen bonds, all four of which are nearly linear. Cation 1 (containing atom N11) and anion 1 (containing atom O31) form neutral aggregate 1 (Fig. 1a), while cation 2 (containing atom N21) and anion 2 (containing atom O41) form neutral aggregate 2 (Fig. 1 b). There are then four N—H···O hydrogen bonds which link these aggregates into sheets and it is convenient to consider the action of each of these in turn.

Amino atom N11 in the type 1 aggregate at (x, y, z) acts as hydrogen-bond donor, via H11B, to carboxylate atom O41 in the type 2 aggregate also at (x, y, z); N21 in aggregate 2 at (x, y, z) in turn acts as hydrogen-bond donor, via H21B, to carboxylate atom O31 in the type 1 aggregate at (−1 + x, y, z). Propagation of these two hydrogen bonds then generates by translation a C₄²(12)[R₂²(8)][R₂²(8)] chain of rings (Bernstein et al., 1995) running parallel to the [100] direction (Fig. 2).

There are two further N—H···O hydrogen bonds, one of which involves only the type 1 aggregates, while the other involves only type 2 aggregates. Atom N12 in the type 1 aggregate at (x, y, z) acts as hydrogen-bond donor to carboxylate atom O32 at (1 − x, −0.5 + y, 0.5 − z), so producing a C₂¹(6)[R₂²(8)] chain of rings running parallel to the [010] direction and generated by the 2₁ screw axis along (1/2, y, 1/4) (Fig. 3). In a similar way, atom N22 in the type 2 aggregate at (x, y, z) acts as hydrogen-bond donor to carboxylate atom O42 at (-x, 0.5 + y, 0.5 − z), so generating a second C₂¹(6)[R₂²(8)] chain of rings around the 2₁ axis along (0, y, 1/4) (Fig. 4). This last hydrogen bond is accompanied by, and possibly weakly augmented by, a long contact between H22 at (x, y, z) and O43 at (-x, 0.5 + y, 0.5 − z) [H···O = 2.50 Å, N···O = 3.150 (2) Å and N—H···O = 121°], although it is doubtful if this can be regarded as a hydrogen bond.

The combination of [100] and [010] chains generates a (001) sheet. Two such sheets, related to one another by inversion, pass through each unit cell in the domains −0.03 < z < 0.53 and 0.47 < z < 1.03, but there are no direction-specific interactions between adjacent sheets. The two-dimensional supramolecular structure of (I) may be contrasted with the ribbon-type structure formed by 2-aminobenzimidazolium nitrate (Bats et al., 1999).

S2. Experimental

A mixture of 2-aminobenzimidazole (0.20 g, 1.50 mmol), Meldrum's acid (0.22 g, 1.52 mmol) and ethanol (10 ml) was heated under reflux for 1 h. Compound (I) was formed as a white solid which was collected by filtration and washed with ethanol (84% yield; m.p. 430 K). Crystals suitable for single-crystal X-ray diffraction analysis were obtained by crystallization from ethanol. Compound (I) was also obtained by crystallization from an ethanol solution mixing equimolar amounts of 2-aminobenzimidazole and malonic acid monoethyl ester.

S3. Refinement

The space group P2₁/c was uniquely assigned from the systematic absences. All H atoms were located in difference maps. H atoms bonded to C atoms were subsequently treated as riding atoms, with C—H distances of 0.95 (aromatic), 0.98 (CH₃) and 0.99 Å (CH₂). H atoms bonded to N atoms were allowed to ride at the positions identified from the difference maps, giving N—H distances in the range 0.93–1.03 Å.

Computing details

Data collection: KappaCCD Server Software (Nonius, 1997); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 and PRPKAPPA (Ferguson, 1999).

Figures

	Fig. 1. The independent components of compound (I), showing the atom-labelling scheme. (a) The neutral aggregate of type 1 and (b) the neutral aggregate of type 2. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. Stereoview of part of the crystal structure of (I), showing the formation of a chain of rings along [100]. For the sake of clarity, H atoms bonded to C atoms have been omitted.
	Fig. 3. Part of the crystal structure of compound (I), showing the formation of a [010] chain of rings formed by the type 1 aggregates. For the sake of clarity, H atoms bonded to C atoms have been omitted. Atoms marked with an asterisk (*) or hash (#) are at the symmetry positions (1 − x, −0.5 + y, 0.5 − z) and (1 − x, 0.5 + y, 0.5 − z), respectively.
	Fig. 4. Part of the crystal structure of compound (I), showing the formation of a [010] chain of rings formed by the type 2 aggregates. For the sake of clarity, H atoms bonded to C atoms have been omitted, but the long H···O contact (see text) is shown. Atoms marked with an asterisk (*) or hash (#) are at the symmetry positions (-x, 0.5 + y, 0.5 − z) and (-x, −0.5 + y, 0.5 − z), respectively.

2-Aminobenzimidazolium O-ethyl malonate

Crystal data

C7H8N3^+·C5H7O4^−	F(000) = 1120
Mr = 265.27	Dx = 1.341 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 5983 reflections
a = 12.0121 (2) Å	θ = 3.2–27.5°
b = 10.5379 (2) Å	µ = 0.10 mm^−1
c = 20.8249 (6) Å	T = 120 K
β = 94.7550 (8)°	Plate, colourless
V = 2626.99 (10) Å^3	0.22 × 0.16 × 0.02 mm
Z = 8

Data collection

Nonius KappaCCD diffractometer	5983 independent reflections
Radiation source: rotating anode	4204 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.115
ϕ scans, and ω scans with κ offsets	θmax = 27.5°, θmin = 3.2°
Absorption correction: multi-scan (DENZO-SMN; Otwinowski & Minor, 1997)	h = −15→15
Tmin = 0.974, Tmax = 0.998	k = −13→13
33691 measured reflections	l = −27→27

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)] = 0.061	H-atom parameters constrained
wR(F^2) = 0.171	w = 1/[σ^2(Fo^2) + (0.0837P)^2 + 0.7506P] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max < 0.001
5983 reflections	Δρmax = 0.26 e Å^−3
346 parameters	Δρmin = −0.33 e Å^−3
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0125 (18)

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

	x	y	z	Uiso*/Ueq
O31	0.78600 (11)	0.49346 (15)	0.22748 (7)	0.0319 (4)
O32	0.61246 (11)	0.53116 (15)	0.18638 (7)	0.0330 (4)
O33	0.67315 (15)	0.59736 (18)	0.03519 (8)	0.0515 (5)
O34	0.60923 (11)	0.75745 (15)	0.09240 (7)	0.0328 (4)
O41	0.29905 (11)	0.30770 (15)	0.22946 (7)	0.0319 (4)
O42	0.13905 (11)	0.25111 (14)	0.17480 (7)	0.0320 (4)
O43	0.16559 (12)	−0.00016 (15)	0.11187 (7)	0.0364 (4)
O44	0.25514 (11)	0.11340 (15)	0.04023 (7)	0.0339 (4)
N11	0.52969 (14)	0.32618 (19)	0.25327 (9)	0.0356 (4)
N12	0.58623 (13)	0.15722 (18)	0.32393 (8)	0.0308 (4)
N17	0.71491 (13)	0.28910 (17)	0.29607 (8)	0.0287 (4)
N21	0.01040 (14)	0.42118 (18)	0.24330 (9)	0.0355 (4)
N22	0.04014 (14)	0.59319 (17)	0.31636 (8)	0.0316 (4)
N27	0.18761 (13)	0.49189 (17)	0.28741 (8)	0.0292 (4)
C11	0.60504 (16)	0.2604 (2)	0.28875 (10)	0.0285 (5)
C12A	0.68717 (16)	0.1179 (2)	0.35643 (9)	0.0288 (5)
C13	0.71161 (18)	0.0205 (2)	0.39919 (10)	0.0347 (5)
C14	0.82314 (19)	0.0074 (2)	0.42294 (11)	0.0401 (5)
C15	0.90515 (19)	0.0898 (2)	0.40439 (11)	0.0401 (6)
C16	0.87964 (17)	0.1895 (2)	0.36143 (10)	0.0339 (5)
C16A	0.76873 (16)	0.2019 (2)	0.33809 (10)	0.0294 (5)
C21	0.07527 (16)	0.4983 (2)	0.28013 (10)	0.0292 (5)
C22A	0.13293 (17)	0.6529 (2)	0.34778 (10)	0.0310 (5)
C23	0.1425 (2)	0.7536 (2)	0.39020 (11)	0.0398 (6)
C24	0.2500 (2)	0.7906 (2)	0.41207 (11)	0.0438 (6)
C25	0.3431 (2)	0.7281 (2)	0.39234 (11)	0.0432 (6)
C26	0.33395 (17)	0.6252 (2)	0.35070 (10)	0.0350 (5)
C26A	0.22677 (16)	0.5883 (2)	0.32895 (10)	0.0301 (5)
C31	0.76122 (17)	0.6398 (2)	0.14043 (10)	0.0344 (5)
C32	0.71624 (16)	0.5467 (2)	0.18829 (9)	0.0275 (4)
C33	0.67865 (17)	0.6610 (2)	0.08345 (10)	0.0332 (5)
C35	0.52230 (17)	0.7772 (2)	0.04049 (10)	0.0346 (5)
C36	0.45300 (19)	0.8888 (2)	0.05781 (11)	0.0415 (6)
C41	0.30760 (16)	0.1483 (2)	0.14985 (10)	0.0311 (5)
C42	0.24258 (15)	0.2426 (2)	0.18757 (9)	0.0266 (4)
C43	0.23435 (16)	0.0780 (2)	0.10011 (10)	0.0286 (5)
C45	0.18627 (19)	0.0540 (3)	−0.01227 (10)	0.0400 (6)
C46	0.0823 (2)	0.1300 (3)	−0.02830 (12)	0.0475 (6)
H11A	0.5558	0.4001	0.2313	0.043*
H11B	0.4543	0.3042	0.2473	0.043*
H12	0.5202	0.1118	0.3263	0.037*
H17	0.7428	0.3638	0.2784	0.034*
H21A	0.0458	0.3585	0.2182	0.043*
H21B	−0.0666	0.4565	0.2322	0.043*
H22	−0.0418	0.6207	0.3195	0.038*
H27	0.2264	0.4259	0.2675	0.035*
H13	0.6553	−0.0352	0.4120	0.042*
H14	0.8435	−0.0591	0.4524	0.048*
H15	0.9803	0.0779	0.4213	0.048*
H16	0.9355	0.2459	0.3488	0.041*
H23	0.0785	0.7957	0.4038	0.048*
H24	0.2601	0.8600	0.4411	0.053*
H25	0.4154	0.7568	0.4079	0.052*
H26	0.3979	0.5823	0.3378	0.042*
H31A	0.7782	0.7218	0.1623	0.041*
H31B	0.8316	0.6061	0.1255	0.041*
H35A	0.4749	0.7005	0.0348	0.042*
H35B	0.5563	0.7939	−0.0004	0.042*
H36A	0.4180	0.8703	0.0977	0.062*
H36B	0.3949	0.9050	0.0229	0.062*
H36C	0.5009	0.9638	0.0642	0.062*
H41A	0.3660	0.1943	0.1284	0.037*
H41B	0.3453	0.0865	0.1802	0.037*
H45A	0.1659	−0.0330	0.0004	0.048*
H45B	0.2291	0.0477	−0.0508	0.048*
H46A	0.0383	0.1329	0.0093	0.071*
H46B	0.0380	0.0904	−0.0645	0.071*
H46C	0.1026	0.2165	−0.0401	0.071*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O31	0.0217 (7)	0.0426 (9)	0.0310 (8)	0.0028 (6)	0.0000 (5)	0.0059 (7)
O32	0.0208 (7)	0.0407 (9)	0.0376 (8)	0.0029 (6)	0.0016 (6)	0.0039 (7)
O33	0.0653 (12)	0.0585 (12)	0.0303 (9)	0.0264 (9)	0.0022 (8)	−0.0048 (8)
O34	0.0292 (8)	0.0416 (9)	0.0274 (7)	0.0087 (6)	0.0017 (6)	0.0027 (6)
O41	0.0220 (7)	0.0390 (9)	0.0345 (8)	−0.0004 (6)	0.0000 (6)	−0.0066 (7)
O42	0.0187 (7)	0.0362 (9)	0.0404 (8)	0.0000 (6)	−0.0008 (6)	−0.0013 (7)
O43	0.0349 (8)	0.0389 (9)	0.0350 (8)	−0.0074 (7)	0.0000 (6)	0.0013 (7)
O44	0.0301 (8)	0.0455 (10)	0.0261 (7)	−0.0018 (6)	0.0022 (6)	−0.0002 (7)
N11	0.0205 (8)	0.0482 (12)	0.0379 (10)	−0.0036 (8)	0.0006 (7)	0.0033 (9)
N12	0.0230 (8)	0.0365 (11)	0.0334 (9)	−0.0072 (7)	0.0042 (7)	−0.0039 (8)
N17	0.0207 (8)	0.0348 (10)	0.0307 (9)	−0.0052 (7)	0.0019 (6)	−0.0010 (8)
N21	0.0230 (9)	0.0386 (11)	0.0445 (11)	0.0029 (8)	−0.0002 (7)	−0.0035 (9)
N22	0.0248 (9)	0.0348 (10)	0.0354 (10)	0.0037 (7)	0.0038 (7)	0.0016 (8)
N27	0.0215 (8)	0.0330 (10)	0.0330 (9)	0.0029 (7)	0.0023 (7)	0.0006 (8)
C11	0.0221 (10)	0.0361 (12)	0.0277 (10)	−0.0052 (8)	0.0048 (7)	−0.0063 (9)
C12A	0.0268 (10)	0.0340 (12)	0.0262 (10)	−0.0020 (8)	0.0061 (7)	−0.0062 (9)
C13	0.0323 (11)	0.0359 (13)	0.0364 (12)	−0.0048 (9)	0.0066 (9)	−0.0015 (10)
C14	0.0417 (13)	0.0401 (14)	0.0387 (13)	0.0047 (10)	0.0042 (9)	0.0056 (10)
C15	0.0307 (11)	0.0483 (15)	0.0410 (13)	0.0010 (10)	0.0015 (9)	0.0035 (11)
C16	0.0252 (10)	0.0406 (13)	0.0362 (12)	−0.0030 (9)	0.0036 (8)	0.0001 (10)
C16A	0.0289 (10)	0.0310 (12)	0.0286 (10)	−0.0022 (9)	0.0048 (8)	−0.0030 (9)
C21	0.0227 (10)	0.0324 (12)	0.0328 (11)	0.0028 (8)	0.0037 (8)	0.0055 (9)
C22A	0.0306 (11)	0.0332 (12)	0.0290 (10)	0.0008 (9)	0.0012 (8)	0.0064 (9)
C23	0.0474 (14)	0.0351 (13)	0.0372 (12)	0.0043 (10)	0.0051 (10)	0.0032 (10)
C24	0.0563 (15)	0.0384 (14)	0.0356 (12)	−0.0051 (11)	−0.0027 (10)	0.0008 (11)
C25	0.0437 (13)	0.0486 (16)	0.0362 (12)	−0.0122 (11)	−0.0039 (10)	0.0084 (11)
C26	0.0296 (11)	0.0444 (14)	0.0305 (11)	−0.0035 (9)	−0.0003 (8)	0.0069 (10)
C26A	0.0291 (10)	0.0332 (12)	0.0279 (10)	−0.0007 (9)	0.0024 (8)	0.0062 (9)
C31	0.0255 (11)	0.0440 (14)	0.0343 (11)	0.0042 (9)	0.0053 (8)	0.0070 (10)
C32	0.0227 (10)	0.0336 (12)	0.0261 (10)	0.0062 (8)	0.0025 (7)	−0.0009 (9)
C33	0.0316 (11)	0.0387 (13)	0.0300 (11)	0.0058 (9)	0.0068 (8)	0.0052 (10)
C35	0.0304 (11)	0.0460 (14)	0.0268 (10)	0.0053 (10)	−0.0009 (8)	0.0059 (10)
C36	0.0399 (12)	0.0497 (15)	0.0351 (12)	0.0123 (11)	0.0045 (9)	0.0098 (11)
C41	0.0225 (10)	0.0416 (13)	0.0289 (10)	0.0000 (9)	0.0013 (7)	−0.0009 (9)
C42	0.0228 (10)	0.0299 (11)	0.0271 (10)	−0.0014 (8)	0.0017 (7)	0.0039 (8)
C43	0.0253 (10)	0.0329 (12)	0.0273 (10)	0.0061 (9)	0.0003 (8)	0.0005 (9)
C45	0.0400 (12)	0.0525 (15)	0.0269 (11)	−0.0028 (11)	−0.0009 (9)	−0.0067 (10)
C46	0.0436 (14)	0.0527 (16)	0.0437 (14)	−0.0050 (11)	−0.0108 (10)	0.0075 (12)

Geometric parameters (Å, º)

O31—C32	1.253 (2)	C15—C16	1.397 (3)
O32—C32	1.255 (2)	C15—H15	0.95
O33—C33	1.205 (3)	C16—C16A	1.386 (3)
O34—C33	1.338 (3)	C16—H16	0.95
O34—C35	1.454 (2)	C22A—C23	1.380 (3)
O41—C42	1.262 (2)	C22A—C26A	1.400 (3)
O42—C42	1.253 (2)	C23—C24	1.390 (3)
O43—C43	1.206 (3)	C23—H23	0.95
O44—C43	1.345 (2)	C24—C25	1.389 (4)
O44—C45	1.457 (3)	C24—H24	0.95
C11—N11	1.317 (3)	C25—C26	1.387 (3)
C11—N12	1.341 (3)	C25—H25	0.95
C11—N17	1.350 (2)	C26—C26A	1.385 (3)
N12—C12A	1.401 (3)	C26—H26	0.95
N17—C16A	1.390 (3)	C31—C33	1.499 (3)
N11—H11A	0.9683	C31—C32	1.529 (3)
N11—H11B	0.9335	C31—H31A	0.99
N12—H12	0.9313	C31—H31B	0.99
N17—H17	0.9420	C35—C36	1.502 (3)
C21—N21	1.325 (3)	C35—H35A	0.99
C21—N22	1.342 (3)	C35—H35B	0.99
C21—N27	1.347 (3)	C36—H36A	0.98
N22—C22A	1.395 (3)	C36—H36B	0.98
N27—C26A	1.391 (3)	C36—H36C	0.98
N21—H21A	0.9638	C41—C43	1.498 (3)
N21—H21B	1.0060	C41—C42	1.522 (3)
N22—H22	1.0337	C41—H41A	0.99
N27—H27	0.9512	C41—H41B	0.99
C12A—C13	1.374 (3)	C45—C46	1.498 (3)
C12A—C16A	1.397 (3)	C45—H45A	0.99
C13—C14	1.396 (3)	C45—H45B	0.99
C13—H13	0.95	C46—H46A	0.98
C14—C15	1.391 (3)	C46—H46B	0.98
C14—H14	0.95	C46—H46C	0.98
C33—O34—C35	115.00 (16)	C24—C25—H25	119.0
C43—O44—C45	116.05 (17)	C26A—C26—C25	116.6 (2)
C11—N11—H11A	117.0	C26A—C26—H26	121.7
C11—N11—H11B	123.9	C25—C26—H26	121.7
H11A—N11—H11B	119.0	C26—C26A—N27	131.8 (2)
C11—N12—C12A	109.00 (16)	C26—C26A—C22A	121.3 (2)
C11—N12—H12	128.9	N27—C26A—C22A	106.90 (17)
C12A—N12—H12	122.0	C33—C31—C32	111.42 (17)
C11—N17—C16A	108.81 (17)	C33—C31—H31A	109.3
C11—N17—H17	121.2	C32—C31—H31A	109.3
C16A—N17—H17	129.5	C33—C31—H31B	109.3
C21—N21—H21A	118.0	C32—C31—H31B	109.3
C21—N21—H21B	113.1	H31A—C31—H31B	108.0
H21A—N21—H21B	124.5	O31—C32—O32	124.83 (19)
C21—N22—C22A	108.89 (17)	O31—C32—C31	117.30 (17)
C21—N22—H22	126.2	O32—C32—C31	117.85 (17)
C22A—N22—H22	124.9	O33—C33—O34	123.2 (2)
C21—N27—C26A	108.52 (17)	O33—C33—C31	124.4 (2)
C21—N27—H27	120.6	O34—C33—C31	112.47 (18)
C26A—N27—H27	130.8	O34—C35—C36	108.15 (18)
N11—C11—N12	126.45 (18)	O34—C35—H35A	110.1
N11—C11—N17	124.4 (2)	C36—C35—H35A	110.1
N12—C11—N17	109.10 (18)	O34—C35—H35B	110.1
C13—C12A—C16A	122.24 (19)	C36—C35—H35B	110.1
C13—C12A—N12	131.58 (18)	H35A—C35—H35B	108.4
C16A—C12A—N12	106.17 (18)	C35—C36—H36A	109.5
C12A—C13—C14	116.8 (2)	C35—C36—H36B	109.5
C12A—C13—H13	121.6	H36A—C36—H36B	109.5
C14—C13—H13	121.6	C35—C36—H36C	109.5
C15—C14—C13	121.4 (2)	H36A—C36—H36C	109.5
C15—C14—H14	119.3	H36B—C36—H36C	109.5
C13—C14—H14	119.3	C43—C41—C42	112.50 (16)
C14—C15—C16	121.6 (2)	C43—C41—H41A	109.1
C14—C15—H15	119.2	C42—C41—H41A	109.1
C16—C15—H15	119.2	C43—C41—H41B	109.1
C16A—C16—C15	116.7 (2)	C42—C41—H41B	109.1
C16A—C16—H16	121.7	H41A—C41—H41B	107.8
C15—C16—H16	121.7	O42—C42—O41	125.09 (19)
C16—C16A—N17	131.8 (2)	O42—C42—C41	118.66 (18)
C16—C16A—C12A	121.3 (2)	O41—C42—C41	116.24 (16)
N17—C16A—C12A	106.91 (17)	O43—C43—O44	124.12 (19)
N21—C21—N22	125.80 (18)	O43—C43—C41	124.76 (19)
N21—C21—N27	124.75 (19)	O44—C43—C41	111.12 (18)
N22—C21—N27	109.44 (18)	O44—C45—C46	110.4 (2)
C23—C22A—N22	131.9 (2)	O44—C45—H45A	109.6
C23—C22A—C26A	121.8 (2)	C46—C45—H45A	109.6
N22—C22A—C26A	106.24 (18)	O44—C45—H45B	109.6
C22A—C23—C24	116.8 (2)	C46—C45—H45B	109.6
C22A—C23—H23	121.6	H45A—C45—H45B	108.1
C24—C23—H23	121.6	C45—C46—H46A	109.5
C25—C24—C23	121.3 (2)	C45—C46—H46B	109.5
C25—C24—H24	119.3	H46A—C46—H46B	109.5
C23—C24—H24	119.3	C45—C46—H46C	109.5
C26—C25—C24	122.1 (2)	H46A—C46—H46C	109.5
C26—C25—H25	119.0	H46B—C46—H46C	109.5
C12A—N12—C11—N11	−177.9 (2)	C26A—C22A—C23—C24	1.8 (3)
C12A—N12—C11—N17	1.0 (2)	C22A—C23—C24—C25	−0.5 (3)
C16A—N17—C11—N11	178.29 (19)	C23—C24—C25—C26	−0.8 (4)
C16A—N17—C11—N12	−0.7 (2)	C24—C25—C26—C26A	0.7 (3)
C11—N12—C12A—C13	178.0 (2)	C25—C26—C26A—N27	179.5 (2)
C11—N12—C12A—C16A	−1.0 (2)	C25—C26—C26A—C22A	0.6 (3)
C16A—C12A—C13—C14	−1.2 (3)	C21—N27—C26A—C26	−178.0 (2)
N12—C12A—C13—C14	179.9 (2)	C21—N27—C26A—C22A	1.0 (2)
C12A—C13—C14—C15	0.4 (3)	C23—C22A—C26A—C26	−2.0 (3)
C13—C14—C15—C16	0.3 (4)	N22—C22A—C26A—C26	178.75 (19)
C14—C15—C16—C16A	−0.2 (3)	C23—C22A—C26A—N27	178.91 (19)
C15—C16—C16A—N17	179.3 (2)	N22—C22A—C26A—N27	−0.4 (2)
C15—C16—C16A—C12A	−0.6 (3)	O31—C32—C31—C33	160.1 (2)
C11—N17—C16A—C16	−179.8 (2)	C32—C31—C33—O34	89.9 (2)
C11—N17—C16A—C12A	0.1 (2)	C32—C31—C33—O33	−88.7 (3)
C13—C12A—C16A—C16	1.3 (3)	C31—C33—O34—C35	−176.0 (2)
N12—C12A—C16A—C16	−179.58 (19)	C33—O34—C35—C36	−179.5 (2)
C13—C12A—C16A—N17	−178.57 (19)	C33—C31—C32—O32	−21.3 (3)
N12—C12A—C16A—N17	0.5 (2)	C35—O34—C33—O33	2.7 (3)
C22A—N22—C21—N21	−179.7 (2)	O41—C42—C41—C43	−178.5 (2)
C22A—N22—C21—N27	1.1 (2)	C42—C41—C43—O44	110.5 (2)
C26A—N27—C21—N21	179.4 (2)	C42—C41—C43—O43	−69.5 (3)
C26A—N27—C21—N22	−1.3 (2)	C41—C43—O44—C45	−178.2 (2)
C21—N22—C22A—C23	−179.6 (2)	C43—O44—C45—C46	89.1 (2)
C21—N22—C22A—C26A	−0.4 (2)	C43—C41—C42—O42	0.9 (3)
N22—C22A—C23—C24	−179.1 (2)	C45—O44—C43—O43	1.8 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N11—H11A···O32	0.97	1.83	2.797 (2)	175
N11—H11B···O41	0.93	1.87	2.781 (2)	164
N12—H12···O32^i	0.93	1.81	2.724 (2)	168
N17—H17···O31	0.94	1.83	2.759 (2)	168
N21—H21A···O42	0.96	1.88	2.829 (2)	170
N21—H21B···O31^ii	1.01	1.81	2.794 (2)	166
N22—H22···O42^iii	1.03	1.81	2.739 (2)	147
N22—H22···O43^iii	1.03	2.50	3.150 (2)	121
N27—H27···O41	0.95	1.75	2.699 (2)	179

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