The methanol hemisolvate of amiloride hydrochloride

In the asymmetric unit of N-(3,5-di­amino-6-chloro­pyrazin-2-yl­carbonyl)-N-(di­amino­methyl­ene)­ammonium chloride methanol hemisolvate, C₆H₉ClN₇O⁺·Cl^-·0.5CH₄O, there are two crystallographically different amiloride mol­ecules. Crystallographically identical amiloride mol­ecules are stacked one above the other, alternately rotated by 180°. These stacks are arranged parallel to each other, forming layer A. The least-squares plane of the non-H atoms of the other mol­ecules lying in layer B is tilted against the corresponding plane of the mol­ecules in layer A by an angle of 79.89 (3)°. The methanol mol­ecules and Cl^- anions are located between these layers, although the methanol mol­ecules are closer to layer A.

S1. Comment

Amiloride hydrochloride, a pyrazinecarboxamide derivate of guanidine, is a potassium-sparing diuretic. Selective binding to the mucosal membrane of distal tubular cells causes reduced potassium and hydrogen secretion and induces mild natriuresis. The area of application for amiloride is congestive heart failure and hypertension. It is often used in combination with thiazide and loop diuretics to prevent hypokalemia and metabolic alkalosis, the characteristic side effects of thiazide and loop diuretics (Laragh, 1982). In the 1960 s, the first patents were registered on the dihydrate, the form in which amiloride is used in drug preparations (Mazzo, 1986). It has been reported that amiloride dihydrate exists in two polymorphic forms (Jozwiakowski et al., 1993). The crystal structures thereof are unknown, probably because the polymorphs are difficult to grow as single crystals. Amiloride crystallizes better in the presence of methanol, whereby two moles of amiloride accommodate one mole of methanol in the crystal, and it is the structure of this, (I), which is described in the present paper. \sch

A perspective view of the molecules of (I) and the atom-labelling scheme is shown in Fig. 1, and Table 1 gives some selected geometric parameters. The least-squares plane through the 11 non-H atoms making up the ring system and a part of the side chain (C11, C12, N12, C13, C14, N11, C15, O11, N13, N14 and Cl11) indicates that this part of the molecule is planar. The r.m.s. deviation of the atoms is 0.0290 Å, with a maximum deviation of 0.0556 (8) Å for Cl11 lying on one side of the plane, and a maximum deviation of 0.0291 (14) Å for C14 lying on the other side. Furthermore, the least-squares plane through the four atoms of the guanidine group (N15, C16, N16 and N17) shows that they also lie in a plane, with an r.m.s deviation of 0.0000 Å. The angle between these two planes is 5.66 (9)°; therefore, the whole molecule is almost planar.

For the second amiloride molecule, the least-square planes through the 11 non-H atoms involved in the pyrazine ring and the carbonyl group of the side chain (C21, C22, N22, C23, C24, N21, C25, O21, N23, N24 and Cl21), and the four atoms from the guanidine side chain (N25, C26, N26 and N27), indicate planarity as well. The r.m.s. deviation for the former is 0.0670 Å, with a maximum deviation of 0.1219 (17) Å for N24 lying on one side, and a maximum deviation of 0.1215 (15) Å for N23 lying on the other side of the plane. For the latter, the r.m.s. deviation is 0.0014 Å. The pyrazine ring and the guanidine group form an angle of 11.63 (7)°. Therefore, this molecule may also be regarded as planar.

The planarity of the two molecules is manifested through intramolecular hydrogen bonds between the carbonyl O atom and the H atoms of two amino groups, one belonging to the guanidine system and the other to the pyrazine ring, all taking part in stabilization effects. In addition, there is a hydrogen bond between N11 of the pyrazine ring and H15 of the protonated amide group, and between N21 and H25 (Table 2).

The two amiloride molecules are connected by a hydrogen bond between the carbonyl O atom and atom H262 of the amino group. The amiloride molecules are protonated on N15 and N25, respectively. The bond distances shown in Table 1, involving C15, N15, C16, N16 and N17 for the first molecule, and C25, N25, C26, N27 and N26 for the second molecule, indicate that the positive charge is delocalized over all the atoms of the guanidine group.

The Cl3 ion is hydrogen bonded to two amiloride molecules and to the methanol molecule. The closest distance to the first amiloride molecule is 2.50 (2) Å, to the second 2.46 (2) Å and to the hydroxyl group of the methanol molecule 2.38 (4) Å. The Cl4 ion, however, forms hydrogen bonds only to the two amiloride molecules. The closest distance between the Cl4 ion and the first amiloride molecule is 2.23 (3) Å, and 2.44 (3) Å for the second (Table 2).

Fig. 2 shows the crystal packing in (I) along the b axis. The Cl^- ions and the methanol molecules lie between layers A and B, which are obtained by rotating amiloride molecules alternately by 180° and stacking one upon the other. The methanol molecules are not placed exactly between the two layers, but closer to layer A. The non-H atoms of the amiloride molecules in the least-squares plane B are tilted against the corresponding plane A by an angle of about 79.89 (3)°. There is an N—H···O intermolecular bond from the protonated atom N25 to the methanol molecule, and a similar but weaker interaction from atom N26 through H262 to the same methanol O atom.

S2. Experimental

Yellow needlelike crystals of (I) were obtained by dissolving amiloride hydrochloride (200 mg) in methanol (6 g). The warm solution was cooled down to room temperature. As soon as the first crystals appeared, the beaker was sealed.

Computing details

Data collection: CAD-4-PC Software (Enraf-Nonius, 1992); cell refinement: CAD-4-PC Software; data reduction: SHELXS97 (Sheldrick, 1997) and OSCAIL (McArdle, 2001, 1995); program(s) used to solve structure: SHELXS97 and OSCAIL; program(s) used to refine structure: SHELXL97 (Sheldrick, 1997) and OSCAIL; molecular graphics: ORTEPIII (Burnett & Johnson, 1996), ORTEP-3 (Farrugia, 2000, 1997), PLATON (Spek, 2001) and DIAMOND (Pennington, 1999).

Figures

	Fig. 1. The molecular structure of (I) with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. The numbering scheme was chosen in such a way that a 1 is in front of all numbers in the first amiloride molecule and a 2 for the second.
	Fig. 2. A packing diagram for (I) viewed along the b axis.

N-(3,5-diamino-6-chloropyrazin-2-ylcarbonyl)-N-(diaminomethylene)ammonium chloride methanol hemisolvate

Crystal data

C6H9ClN7O^+·Cl^−·0.5CH4O	F(000) = 1160
Mr = 282.12	Dx = 1.568 Mg m^−3
Monoclinic, P21/a	Mo Kα radiation, λ = 0.71069 Å
a = 18.044 (3) Å	Cell parameters from 25 reflections
b = 7.486 (3) Å	θ = 12–18°
c = 19.052 (5) Å	µ = 0.54 mm^−1
β = 111.764 (15)°	T = 293 K
V = 2390.1 (13) Å^3	Needle, yellow
Z = 8	0.6 × 0.3 × 0.3 mm

Data collection

Enraf-Nonius CAD-4 diffractometer	Rint = 0.015
Radiation source: fine-focus sealed tube	θmax = 27.0°, θmin = 1.2°
Graphite monochromator	h = −23→21
ω/2θ scans	k = 0→9
5461 measured reflections	l = 0→24
5201 independent reflections	2 standard reflections every 120 min
4093 reflections with I > 2σ(I)	intensity decay: none

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)] = 0.032	All H-atom parameters refined
wR(F^2) = 0.093	w = 1/[σ^2(Fo^2) + (0.0515P)^2 + 0.5534P] where P = (Fo^2 + 2Fc^2)/3
S = 1.11	(Δ/σ)max = 0.037
5201 reflections	Δρmax = 0.38 e Å^−3
396 parameters	Δρmin = −0.25 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0051 (6)

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.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq
Cl11	0.80571 (3)	0.11717 (6)	0.33691 (2)	0.04885 (14)
Cl4	0.72079 (3)	−0.38684 (6)	0.36882 (2)	0.04518 (13)
Cl21	0.73044 (3)	−0.29421 (11)	0.05042 (3)	0.0689 (2)
Cl3	0.87986 (2)	−0.48970 (6)	0.24122 (2)	0.04012 (12)
O3	1.06120 (10)	−0.1727 (3)	0.82549 (10)	0.0682 (5)
N26	0.39456 (12)	−0.3859 (3)	−0.22527 (10)	0.0541 (5)
N25	0.43944 (9)	−0.2890 (2)	−0.10341 (8)	0.0385 (3)
O11	0.96392 (8)	−0.18892 (17)	0.65728 (7)	0.0434 (3)
N12	0.96971 (7)	0.27777 (18)	0.53170 (7)	0.0302 (3)
N13	0.91875 (9)	0.4131 (2)	0.41567 (9)	0.0392 (3)
N11	0.87465 (7)	−0.01867 (18)	0.47164 (7)	0.0299 (3)
N14	1.01910 (10)	0.1470 (2)	0.64899 (8)	0.0422 (4)
O21	0.36913 (7)	−0.2099 (2)	−0.03020 (8)	0.0586 (4)
N15	0.87447 (8)	−0.31054 (19)	0.54849 (8)	0.0351 (3)
N22	0.58790 (9)	−0.1666 (2)	0.15864 (8)	0.0409 (3)
N21	0.57720 (8)	−0.2595 (2)	0.01374 (7)	0.0365 (3)
N16	0.80125 (9)	−0.5672 (2)	0.53167 (10)	0.0428 (4)
N23	0.72302 (11)	−0.2150 (3)	0.20206 (10)	0.0500 (4)
N17	0.89474 (11)	−0.5067 (2)	0.64888 (9)	0.0459 (4)
N27	0.30421 (10)	−0.3376 (3)	−0.16845 (12)	0.0555 (5)
N24	0.45286 (12)	−0.1186 (3)	0.11596 (12)	0.0591 (5)
H3W	1.076 (2)	−0.243 (5)	0.7995 (19)	0.106 (12)*
H3A	1.169 (2)	−0.117 (6)	0.886 (2)	0.125 (14)*
H3B	1.146 (3)	−0.016 (7)	0.818 (3)	0.157 (18)*
H3C	1.114 (3)	0.018 (9)	0.883 (3)	0.21 (3)*
H15	0.8510 (11)	−0.290 (3)	0.5004 (11)	0.036 (5)*
H131	0.8935 (12)	0.407 (3)	0.3700 (13)	0.041 (5)*
H141	1.0204 (15)	0.054 (4)	0.6781 (14)	0.063 (7)*
H142	1.0432 (15)	0.239 (4)	0.6659 (14)	0.059 (7)*
H132	0.9504 (12)	0.501 (3)	0.4338 (11)	0.040 (5)*
H25	0.4828 (14)	−0.289 (3)	−0.1021 (12)	0.045 (6)*
H262	0.4422 (15)	−0.386 (3)	−0.2245 (13)	0.054 (7)*
H161	0.7853 (14)	−0.666 (3)	0.5545 (13)	0.061 (6)*
H271	0.2725 (15)	−0.380 (3)	−0.2001 (15)	0.060 (7)*
H162	0.7760 (13)	−0.538 (3)	0.4868 (13)	0.048 (6)*
H231	0.7214 (14)	−0.214 (3)	0.2456 (15)	0.063 (7)*
H261	0.3635 (17)	−0.420 (4)	−0.2671 (17)	0.077 (8)*
H272	0.2998 (16)	−0.317 (4)	−0.1253 (16)	0.073 (8)*
H242	0.4560 (13)	−0.092 (3)	0.1620 (14)	0.055 (6)*
H241	0.4099 (15)	−0.125 (3)	0.0808 (14)	0.054 (7)*
H232	0.7630 (16)	−0.267 (3)	0.1983 (14)	0.062 (7)*
H171	0.8772 (16)	−0.599 (4)	0.6682 (15)	0.075 (8)*
H172	0.9293 (16)	−0.443 (4)	0.6765 (14)	0.067 (8)*
C11	0.87169 (9)	0.1195 (2)	0.43056 (8)	0.0305 (3)
C12	0.92071 (8)	0.2739 (2)	0.45901 (8)	0.0288 (3)
C13	0.97158 (9)	0.1361 (2)	0.57585 (8)	0.0300 (3)
C14	0.92442 (9)	−0.0167 (2)	0.54512 (8)	0.0295 (3)
C15	0.92443 (9)	−0.1741 (2)	0.58954 (9)	0.0324 (3)
C16	0.85701 (9)	−0.4642 (2)	0.57762 (9)	0.0337 (3)
C21	0.64480 (10)	−0.2513 (3)	0.06868 (9)	0.0382 (4)
C22	0.65247 (10)	−0.2105 (2)	0.14475 (9)	0.0373 (4)
C23	0.51640 (10)	−0.1693 (2)	0.10072 (10)	0.0385 (4)
C24	0.51010 (9)	−0.2205 (2)	0.02725 (9)	0.0348 (3)
C25	0.43430 (10)	−0.2376 (3)	−0.03534 (10)	0.0395 (4)
C26	0.37755 (10)	−0.3384 (2)	−0.16748 (10)	0.0404 (4)
C3	1.1268 (2)	−0.0555 (5)	0.8505 (2)	0.0791 (8)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl11	0.0517 (3)	0.0495 (3)	0.0285 (2)	−0.0140 (2)	−0.00468 (18)	0.00484 (17)
Cl4	0.0516 (3)	0.0448 (2)	0.0334 (2)	0.00319 (19)	0.00907 (18)	−0.00620 (17)
Cl21	0.0303 (2)	0.1311 (6)	0.0445 (3)	0.0022 (3)	0.01282 (19)	−0.0140 (3)
Cl3	0.0388 (2)	0.0510 (3)	0.0298 (2)	−0.00381 (18)	0.01190 (16)	0.00247 (17)
O3	0.0496 (9)	0.0826 (12)	0.0678 (10)	0.0000 (8)	0.0165 (8)	−0.0249 (9)
N26	0.0508 (10)	0.0711 (12)	0.0330 (8)	−0.0134 (9)	0.0069 (7)	−0.0100 (8)
N25	0.0273 (7)	0.0527 (9)	0.0325 (7)	−0.0052 (6)	0.0075 (6)	−0.0039 (6)
O11	0.0515 (7)	0.0416 (7)	0.0297 (6)	0.0003 (6)	0.0063 (5)	0.0046 (5)
N12	0.0274 (6)	0.0335 (7)	0.0281 (6)	−0.0017 (5)	0.0084 (5)	−0.0002 (5)
N13	0.0404 (8)	0.0435 (9)	0.0273 (7)	−0.0124 (7)	0.0051 (6)	0.0038 (6)
N11	0.0272 (6)	0.0332 (7)	0.0277 (6)	−0.0009 (5)	0.0082 (5)	−0.0004 (5)
N14	0.0472 (9)	0.0406 (9)	0.0276 (7)	−0.0059 (7)	0.0008 (6)	−0.0002 (6)
O21	0.0295 (6)	0.0912 (12)	0.0547 (8)	0.0016 (7)	0.0151 (6)	−0.0123 (8)
N15	0.0387 (7)	0.0344 (7)	0.0296 (7)	−0.0009 (6)	0.0097 (6)	0.0054 (6)
N22	0.0457 (8)	0.0452 (8)	0.0313 (7)	0.0012 (7)	0.0136 (6)	−0.0043 (6)
N21	0.0310 (6)	0.0483 (8)	0.0298 (7)	−0.0014 (6)	0.0110 (5)	−0.0022 (6)
N16	0.0336 (7)	0.0448 (9)	0.0474 (9)	−0.0038 (6)	0.0122 (7)	0.0119 (7)
N23	0.0432 (9)	0.0682 (12)	0.0309 (8)	0.0011 (8)	0.0047 (7)	−0.0075 (8)
N17	0.0552 (10)	0.0412 (9)	0.0383 (8)	−0.0026 (8)	0.0139 (7)	0.0107 (7)
N27	0.0321 (8)	0.0727 (13)	0.0490 (10)	−0.0116 (8)	0.0001 (8)	−0.0033 (9)
N24	0.0471 (10)	0.0906 (15)	0.0453 (10)	0.0067 (9)	0.0239 (9)	−0.0144 (10)
C11	0.0271 (7)	0.0368 (8)	0.0243 (7)	−0.0022 (6)	0.0056 (6)	0.0001 (6)
C12	0.0259 (7)	0.0331 (8)	0.0279 (7)	−0.0012 (6)	0.0105 (6)	−0.0011 (6)
C13	0.0265 (7)	0.0354 (8)	0.0269 (7)	0.0031 (6)	0.0085 (6)	−0.0008 (6)
C14	0.0280 (7)	0.0326 (8)	0.0274 (7)	0.0003 (6)	0.0097 (6)	0.0007 (6)
C15	0.0331 (8)	0.0333 (8)	0.0307 (7)	0.0039 (6)	0.0117 (6)	0.0013 (6)
C16	0.0318 (8)	0.0347 (8)	0.0378 (8)	0.0048 (6)	0.0165 (7)	0.0052 (7)
C21	0.0304 (7)	0.0520 (10)	0.0314 (8)	−0.0010 (7)	0.0106 (6)	−0.0035 (7)
C22	0.0389 (9)	0.0387 (9)	0.0305 (8)	−0.0029 (7)	0.0084 (7)	−0.0027 (7)
C23	0.0398 (9)	0.0430 (9)	0.0356 (8)	−0.0003 (7)	0.0172 (7)	−0.0028 (7)
C24	0.0303 (7)	0.0424 (9)	0.0318 (8)	−0.0008 (7)	0.0116 (6)	−0.0023 (7)
C25	0.0326 (8)	0.0473 (10)	0.0384 (9)	−0.0018 (7)	0.0131 (7)	−0.0031 (7)
C26	0.0365 (8)	0.0408 (9)	0.0347 (8)	−0.0067 (7)	0.0027 (7)	0.0043 (7)
C3	0.0745 (18)	0.085 (2)	0.0758 (19)	−0.0178 (16)	0.0253 (16)	−0.0093 (17)

Geometric parameters (Å, º)

N11—C11	1.286 (2)	C21—C22	1.437 (2)
N11—C14	1.3544 (19)	N23—C22	1.335 (2)
Cl11—C11	1.7395 (16)	N23—H231	0.84 (3)
C11—C12	1.434 (2)	N23—H232	0.84 (3)
N13—C12	1.322 (2)	N22—C22	1.328 (2)
N13—H131	0.82 (2)	N22—C23	1.352 (2)
N13—H132	0.85 (2)	N24—C23	1.338 (2)
N12—C12	1.3388 (19)	N24—H241	0.82 (2)
N12—C13	1.346 (2)	N24—H242	0.88 (2)
N14—C13	1.341 (2)	C23—C24	1.415 (2)
N14—H141	0.88 (3)	C24—C25	1.449 (2)
N14—H142	0.81 (3)	O21—C25	1.233 (2)
C13—C14	1.416 (2)	N25—C25	1.388 (2)
C14—C15	1.451 (2)	N25—H25	0.77 (2)
O11—C15	1.226 (2)	N25—C26	1.365 (2)
N15—C15	1.394 (2)	N26—C26	1.298 (3)
N15—H15	0.87 (2)	N26—H261	0.83 (3)
N15—C16	1.364 (2)	N26—H262	0.85 (2)
N16—C16	1.311 (2)	N27—C26	1.316 (3)
N16—H161	0.96 (3)	N27—H271	0.73 (3)
N16—H162	0.84 (2)	N27—H272	0.87 (3)
N17—C16	1.313 (2)	O3—C3	1.407 (4)
N17—H171	0.90 (3)	O3—H3W	0.84 (4)
N17—H172	0.81 (3)	C3—H3A	0.93 (4)
N21—C21	1.281 (2)	C3—H3B	0.88 (5)
N21—C24	1.359 (2)	C3—H3C	0.92 (6)
Cl21—C21	1.7352 (17)
C11—N11—C14	118.85 (13)	N22—C22—N23	118.95 (16)
N11—C11—C12	122.51 (14)	N22—C22—C21	119.35 (15)
N11—C11—Cl11	118.33 (12)	N23—C22—C21	121.70 (17)
C12—C11—Cl11	119.16 (12)	C22—N23—H231	115.8 (17)
N13—C12—C11	121.97 (14)	C22—N23—H232	121.9 (17)
N13—C12—N12	118.90 (15)	H231—N23—H232	116 (2)
N12—C12—C11	119.13 (14)	C22—N22—C23	118.41 (14)
C12—N13—H131	119.7 (15)	N22—C23—C24	120.94 (15)
C12—N13—H132	119.6 (13)	N24—C23—N22	116.99 (16)
H131—N13—H132	120 (2)	N24—C23—C24	122.05 (17)
C12—N12—C13	118.89 (13)	C23—N24—H242	122.4 (15)
N12—C13—C14	120.39 (14)	C23—N24—H241	115.8 (17)
N14—C13—N12	117.36 (15)	H242—N24—H241	121 (2)
N14—C13—C14	122.25 (15)	C23—C24—C25	122.91 (15)
C13—N14—H141	117.5 (16)	N21—C24—C23	119.67 (14)
C13—N14—H142	120.3 (17)	N21—C24—C25	117.41 (14)
H141—N14—H142	122 (2)	O21—C25—C24	123.83 (16)
C13—C14—C15	123.00 (14)	O21—C25—N25	121.11 (16)
N11—C14—C13	120.16 (14)	N25—C25—C24	115.06 (15)
N11—C14—C15	116.81 (14)	C25—N25—H25	112.9 (16)
O11—C15—C14	124.18 (15)	C26—N25—C25	126.48 (16)
O11—C15—N15	121.78 (15)	C26—N25—H25	120.7 (16)
N15—C15—C14	114.04 (14)	N26—C26—N25	117.43 (17)
C15—N15—H15	114.9 (13)	N27—C26—N25	119.74 (18)
C16—N15—C15	126.04 (14)	N26—C26—N27	122.83 (18)
C16—N15—H15	118.9 (13)	C26—N26—H261	127.9 (19)
N16—C16—N15	117.39 (15)	C26—N26—H262	122.6 (16)
N17—C16—N15	121.07 (16)	H262—N26—H261	110 (2)
N16—C16—N17	121.54 (17)	C26—N27—H271	119 (2)
C16—N16—H161	116.0 (14)	C26—N27—H272	115.6 (18)
C16—N16—H162	121.5 (16)	H271—N27—H272	123 (3)
H161—N16—H162	122 (2)	C3—O3—H3W	100 (2)
C16—N17—H171	119.1 (18)	O3—C3—H3A	107 (3)
C16—N17—H172	120.6 (19)	O3—C3—H3B	119 (3)
H171—N17—H172	120 (3)	O3—C3—H3C	102 (4)
C21—N21—C24	118.70 (14)	H3A—C3—H3B	105 (4)
N21—C21—C22	122.74 (15)	H3A—C3—H3C	99 (4)
N21—C21—Cl21	118.45 (13)	H3B—C3—H3C	123 (5)
C22—C21—Cl21	118.80 (12)
C14—N11—C11—C12	1.8 (2)	C24—N21—C21—C22	2.9 (3)
C14—N11—C11—Cl11	−178.45 (11)	C24—N21—C21—Cl21	−177.99 (13)
C13—N12—C12—N13	179.89 (14)	C23—N22—C22—N23	−177.43 (18)
C13—N12—C12—C11	0.2 (2)	C23—N22—C22—C21	2.7 (3)
N11—C11—C12—N13	178.07 (15)	N21—C21—C22—N22	−5.0 (3)
Cl11—C11—C12—N13	−1.7 (2)	Cl21—C21—C22—N22	175.88 (14)
N11—C11—C12—N12	−2.2 (2)	N21—C21—C22—N23	175.19 (19)
Cl11—C11—C12—N12	177.98 (11)	Cl21—C21—C22—N23	−3.9 (3)
C12—N12—C13—N14	−177.61 (14)	C22—N22—C23—N24	−177.81 (18)
C12—N12—C13—C14	2.1 (2)	C22—N22—C23—C24	1.1 (3)
C11—N11—C14—C13	0.6 (2)	C21—N21—C24—C23	1.1 (3)
C11—N11—C14—C15	178.75 (14)	C21—N21—C24—C25	−177.67 (17)
N14—C13—C14—N11	177.10 (15)	N24—C23—C24—N21	175.65 (19)
N12—C13—C14—N11	−2.6 (2)	N22—C23—C24—N21	−3.2 (3)
N14—C13—C14—C15	−0.9 (2)	N24—C23—C24—C25	−5.7 (3)
N12—C13—C14—C15	179.37 (14)	N22—C23—C24—C25	175.50 (17)
C16—N15—C15—O11	6.8 (3)	C26—N25—C25—O21	−9.7 (3)
C16—N15—C15—C14	−172.82 (15)	C26—N25—C25—C24	170.18 (17)
N11—C14—C15—O11	−177.11 (15)	N21—C24—C25—O21	178.47 (18)
C13—C14—C15—O11	1.0 (3)	C23—C24—C25—O21	−0.2 (3)
N11—C14—C15—N15	2.5 (2)	N21—C24—C25—N25	−1.4 (2)
C13—C14—C15—N15	−179.39 (14)	C23—C24—C25—N25	179.91 (17)
C15—N15—C16—N16	171.84 (15)	C25—N25—C26—N26	−178.54 (19)
C15—N15—C16—N17	−8.2 (3)	C25—N25—C26—N27	1.0 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N13—H131···Cl11	0.82 (2)	2.62 (2)	3.0083 (18)	110.5 (17)
N13—H131···Cl3^i	0.82 (2)	2.50 (2)	3.2155 (18)	147.1 (18)
N13—H132···N12^ii	0.85 (2)	2.13 (2)	2.986 (2)	174.2 (19)
N14—H141···O11	0.88 (3)	2.05 (3)	2.731 (2)	133 (2)
N14—H142···Cl3^iii	0.82 (3)	2.60 (3)	3.384 (2)	162 (2)
N15—H15···N11	0.87 (2)	2.19 (2)	2.631 (2)	111.5 (15)
N15—H15···Cl4	0.87 (2)	2.823 (19)	3.5629 (18)	144.2 (16)
N16—H161···Cl4^iv	0.96 (3)	2.23 (3)	3.1684 (19)	165 (2)
N16—H162···Cl4	0.84 (2)	2.38 (2)	3.196 (2)	166 (2)
N17—H171···Cl4^iv	0.90 (3)	2.71 (3)	3.469 (2)	144 (2)
N17—H172···O11	0.81 (3)	2.08 (3)	2.664 (3)	130 (2)
N23—H231···Cl4	0.84 (3)	2.69 (3)	3.441 (2)	150 (2)
N23—H232···Cl3	0.84 (3)	2.57 (3)	3.350 (2)	153 (2)
N24—H241···O21	0.82 (2)	2.07 (2)	2.718 (3)	137 (2)
N24—H242···Cl3^v	0.88 (2)	2.46 (2)	3.2278 (19)	145.2 (19)
N25—H25···N21	0.77 (2)	2.24 (2)	2.664 (2)	114.9 (19)
N25—H25···O3^vi	0.77 (2)	2.33 (2)	2.992 (2)	144 (2)
N26—H261···Cl4^vii	0.83 (3)	2.44 (3)	3.238 (2)	161 (3)
N26—H262···O11^vi	0.85 (2)	2.49 (2)	2.994 (2)	118.7 (19)
N26—H262···O3^vi	0.85 (2)	2.05 (3)	2.831 (3)	152 (2)
N27—H271···Cl3^vii	0.73 (3)	2.74 (3)	3.3483 (19)	142 (2)
N27—H272···O21	0.87 (3)	1.95 (3)	2.633 (3)	134 (2)
O3—H3W···Cl3^viii	0.83 (4)	2.38 (4)	3.184 (2)	161 (3)

Symmetry codes: (i) x, y+1, z; (ii) −x+2, −y+1, −z+1; (iii) −x+2, −y, −z+1; (iv) −x+3/2, y−1/2, −z+1; (v) x−1/2, −y−1/2, z; (vi) x−1/2, −y−1/2, z−1; (vii) −x+1, −y−1, −z; (viii) −x+2, −y−1, −z+1.