(8-Dimethylamino-1-naphthyl)dimethylammonium 3-carboxy-1,4,5,-6,7,7-hexachlorobicyclo[2.2.1]hept-5-ene-2-carboxylate hydrate

The structure of the title compound, C₁₄H₁₉N₂⁺·C₉H₃Cl₆O₄⁻·H₂O, consists of singly ionized 1,4,5,6,7,7-hexachlorobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid anions and protonated 1,8-bis(dimethylamino)naphthalene cations. In the (8-dimethylamino-1-napthyl)dimethylammonium cat­ion, a strong disordered intramolecular hydrogen bond is formed with N...N = 2.589 (3) Å. The geometry and occupancy obtained in the final restrained refinement suggest that the disordered hydrogen bond may be asymmetric. Water mol­ecules link the anion dimers into infinite chains via hydrogen bonding.

S1. Comment

The term `proton sponges' describes a class of compounds which combine an unusually high basicity with a low nucleophilic character. Most of these compounds are diamines (Llamas-Saiz et al., 1994). The [N—H···N]⁺ hydrogen bonds play an important role in these proton sponges. In a complex of 1,8-bis(dimethylamino)naphthalene (DMAN) with a (slightly) acidic compound, DMAN will absorb a proton from the acidic compound and an intramolecular hydrogen bond will be formed. These hydrogen bonds can be symmetric or asymmetric. When the bridge is asymmetric this will be reflected in the other bond distances of the DMAN·H⁺ cation (Kanters, Schouten, Duisenberg et al., 1991). It is remarkable that the N—H distance in proton sponges is found to be well out of the range usually observed for N—H···N hydrogen bonds in other molecules (Kanters, Schouten, Kroon & Grech, 1991). For protonated proton sponges the N···N distances are in the range 2.553–2.654 Å (Llamas-Saiz et al., 1994; Kanters, Schouten, Duisenberg et al., 1991). The H atom seems to be located on a rather flat potential energy surface, the nature of which is influenced by the crystal field environment (Jeffrey, 1997). The subject of the present study, (I), is the monohydrated complex of DMAN with 1,4,5,6,7,7-hexachloro-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid (1:1), in which DMAN accepts one proton from the carboxylic acid molecule. \scheme

The asymmetric unit of (I) (Fig. 1, Table 1) consists of one DMAN·H⁺ cation, one singly deprotonated (3-carboxy-1,4,5,6,7,7-hexachlorobicyclo[2.2.1]hept-5-ene-2-carboxylate)^- anion and one water molecule.

The DMAN ring system in (I) is planar (σ_plane 0.007 Å) and N1 and N2 lie within 0.020 and 0.022 Å, respectively, of the least squares mean plane of the ring system. The disordered H atoms (H1N and H2N) are also in the plane of the ring system, being displaced by only 0.040 and -0.038 Å, respectively. The DMAN residues are ordered in π-stacked colums along the a axis and the perpendicular distances between two DMAN molecules alternate between 4.261 and 4.711 Å.

Among the three different residues several types of hydrogen bonds were observed. In the DMAN molecule there is a strong, somewhat bent, intramolecular [N—H···N]⁺ hydrogen bond with an N···N distance of 2.589 (3) Å. The hydrogen is disordered over two positions whose occupancies refined to 0.60 (5) for H1N and 0.40 (5) for H2N. The resulting difference in occupancy of 0.20 (10) suggests a possible asymmetric hydrogen bond, although the evidence is not conclusive.

The deprotonated acid moiety accepts a hydrogen bond from the still-protonated acid moiety of a symmetry-related molecule, thereby forming a dimer [unitary graph set R₂²(14)] over the inversion centre at (0,0,1/2) (Fig. 2). Protonated and deprotonated acid moieties can easily be distinguished on the basis of their C—O bond lengths (Table 1). Intermolecular O···O distances clearly indicate that the water molecules link these rings into infinite chains along [100] by donating hydrogen bonds to both carboxylate O atoms. The water links also form hydrogen-bonded ring systems with the anions [unitary graph set DD, binary graph set R₄⁴(12)]. There are also weak intermolecular C—H···A interactions present (Table 2).

S2. Experimental

Crystals of (I) were obtained from a 1:1 solution of DMAN and 1,4,5,6,7,7-hexachlorobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid (Aldrich) in a mixture of acetonitrile and water.

S3. Refinement

The carboxylic H atom was located in a difference Fourier synthesis and subsequently included as part of a rigid rotating group. The water H atoms were placed in hydrogen-bond-forming positions and their coordinates were refined freely. The amino H atoms were introduced at calculated positions and during refinement idealized tetrahedral geometry at the N carrier atom was enforced, with the N—H bond distance and the H atom occupancies allowed to refine. All other H atoms were introduced at calculated positions and refined riding on their carrier atoms.

Computing details

Data collection: CAD-4 Software (Enraf-Nonius, 1989); cell refinement: CAD-4 Software; data reduction: HELENA (Spek, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 1998); software used to prepare material for publication: SHELXL97 and PLATON.

Figures

	Fig. 1. The molecular view of (I) (PLATON; Spek, 1998) showing the cation, anion and water molecule, with the atom-numbering scheme. Displacement ellipsoids are plotted at the 30% probability level and H atoms are drawn as spheres of arbitrary radii.
	Fig. 2. A plot of an infinite chain of hydrogen bonds in (I). The DMAN moieties and the chlorine-substituted rings of the heptene moieties have been omitted for clarity.

(8-dimethylamino-1-naphthyl)dimethylammonium 3-carboxy-1,4,5,6,7,7-hexachloro-bicyclo[2.2.1]hept-5-ene-2-carboxylate hydrate (1:1:1)

Crystal data

C14H19N2^+C9H3Cl6O4^−·H2O	Z = 2
Mr = 621.17	F(000) = 636
Triclinic, P1	Dx = 1.508 Mg m^−3
a = 8.7122 (5) Å	Mo Kα radiation, λ = 0.71073 Å
b = 12.8097 (11) Å	Cell parameters from 25 reflections
c = 13.7023 (12) Å	θ = 12.7–19.3°
α = 113.200 (7)°	µ = 0.67 mm^−1
β = 91.680 (6)°	T = 295 K
γ = 101.350 (6)°	Block, colourless
V = 1368.32 (19) Å^3	0.6 × 0.6 × 0.3 mm

Data collection

Enraf-Nonius CAD4 diffractometer	4286 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.036
β-filter monochromator	θmax = 27.5°, θmin = 1.6°
ω/2θ scans	h = −11→11
Absorption correction: ψ-scan (PLATON; Spek, 1998)	k = −16→16
Tmin = 0.745, Tmax = 0.819	l = −17→17
13079 measured reflections	3 standard reflections every 60 min
6272 independent reflections	intensity decay: none

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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.107	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ^2(Fo^2) + (0.0421P)^2 + 0.5928P] where P = (Fo^2 + 2Fc^2)/3
6272 reflections	(Δ/σ)max = 0.001
335 parameters	Δρmax = 0.32 e Å^−3
0 restraints	Δρmin = −0.40 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.

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	Occ. (<1)
N1	0.4274 (2)	0.79225 (16)	0.10208 (15)	0.0416 (6)
N2	0.3389 (2)	0.69069 (19)	0.22781 (15)	0.0489 (6)
C1	0.2808 (2)	0.58622 (19)	0.03054 (17)	0.0410 (7)
C2	0.3558 (3)	0.68381 (19)	0.01113 (17)	0.0418 (7)
C3	0.3622 (3)	0.6769 (2)	−0.0903 (2)	0.0600 (9)
C4	0.2930 (4)	0.5742 (3)	−0.1786 (2)	0.0745 (11)
C5	0.2194 (4)	0.4800 (3)	−0.1635 (2)	0.0692 (10)
C6	0.2108 (3)	0.4811 (2)	−0.0604 (2)	0.0531 (8)
C7	0.1352 (3)	0.3826 (2)	−0.0453 (3)	0.0706 (10)
C8	0.1277 (4)	0.3843 (3)	0.0536 (4)	0.0848 (13)
C9	0.1965 (4)	0.4860 (3)	0.1432 (3)	0.0735 (11)
C10	0.2704 (3)	0.5844 (2)	0.1335 (2)	0.0483 (8)
C11	0.4641 (4)	0.6764 (3)	0.2937 (3)	0.0916 (16)
C12	0.2168 (4)	0.7392 (3)	0.2927 (2)	0.0748 (11)
C13	0.6013 (3)	0.8224 (3)	0.1056 (2)	0.0725 (10)
C14	0.3562 (4)	0.8902 (2)	0.1097 (2)	0.0670 (10)
Cl1	−0.23133 (10)	0.63941 (6)	0.45831 (6)	0.0730 (3)
Cl4	0.18774 (9)	0.87102 (6)	0.82435 (5)	0.0661 (2)
Cl5	−0.16978 (11)	0.88067 (7)	0.88994 (5)	0.0780 (3)
Cl6	−0.42978 (9)	0.73966 (9)	0.66334 (9)	0.0940 (4)
Cl7A	0.16982 (8)	0.71621 (6)	0.55167 (5)	0.0561 (2)
Cl7B	−0.03243 (9)	0.60440 (5)	0.65705 (6)	0.0644 (2)
O28A	−0.2680 (2)	0.96606 (18)	0.62968 (14)	0.0661 (7)
O28B	−0.20688 (19)	0.94016 (16)	0.46864 (13)	0.0551 (6)
O29A	0.0090 (2)	1.08385 (14)	0.83283 (13)	0.0542 (6)
O29B	0.0780 (2)	1.13227 (13)	0.70034 (13)	0.0494 (5)
C21	−0.1357 (2)	0.75166 (18)	0.57849 (16)	0.0399 (6)
C22	−0.0629 (2)	0.86740 (17)	0.56825 (15)	0.0343 (6)
C23	0.0568 (2)	0.93294 (17)	0.67242 (15)	0.0327 (5)
C24	0.0337 (2)	0.84618 (18)	0.72709 (15)	0.0373 (6)
C25	−0.1304 (3)	0.8324 (2)	0.76085 (17)	0.0452 (7)
C26	−0.2303 (3)	0.7774 (2)	0.6737 (2)	0.0480 (8)
C27	0.0094 (3)	0.72899 (18)	0.62807 (16)	0.0392 (6)
C28	−0.1906 (2)	0.93008 (18)	0.55544 (17)	0.0390 (6)
C29	0.0429 (2)	1.05569 (18)	0.74321 (17)	0.0396 (6)
O30	−0.5503 (3)	1.0333 (3)	0.64988 (18)	0.0855 (9)
H1N	0.4097 (13)	0.7805 (8)	0.156 (4)	0.0500*	0.60 (5)
H3	0.41350	0.74180	−0.10100	0.0720*
H4	0.29770	0.57090	−0.24750	0.0890*
H5	0.17290	0.41220	−0.22270	0.0830*
H7	0.08920	0.31460	−0.10450	0.0850*
H8	0.07690	0.31790	0.06210	0.1020*
H9	0.19150	0.48610	0.21090	0.0880*
H11A	0.50520	0.74890	0.35400	0.1380*
H11B	0.54740	0.65350	0.25140	0.1380*
H11C	0.42100	0.61740	0.31830	0.1380*
H12A	0.26610	0.80910	0.35360	0.1120*
H12B	0.16020	0.68310	0.31650	0.1120*
H12C	0.14500	0.75690	0.25020	0.1120*
H13A	0.64400	0.89410	0.16650	0.1090*
H13B	0.62810	0.83150	0.04140	0.1090*
H13C	0.64440	0.76120	0.11100	0.1090*
H14A	0.40750	0.95880	0.17120	0.1000*
H14B	0.24600	0.87100	0.11650	0.1000*
H14C	0.36880	0.90460	0.04640	0.1000*
H2N	0.388 (5)	0.748 (6)	0.202 (2)	0.0590*	0.40 (5)
H22	−0.00440	0.85010	0.50580	0.0410*
H23	0.16320	0.93840	0.65060	0.0390*
H29B	0.11700	1.10320	0.64500	0.0740*
H30A	−0.477 (5)	0.999 (4)	0.626 (3)	0.1280*
H30B	−0.598 (5)	1.031 (4)	0.591 (4)	0.1280*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0384 (10)	0.0447 (10)	0.0412 (9)	0.0095 (8)	0.0068 (8)	0.0168 (8)
N2	0.0506 (11)	0.0613 (12)	0.0426 (10)	0.0206 (10)	0.0084 (9)	0.0253 (10)
C1	0.0339 (11)	0.0434 (12)	0.0472 (12)	0.0174 (9)	0.0074 (9)	0.0158 (10)
C2	0.0390 (11)	0.0473 (12)	0.0393 (11)	0.0150 (10)	0.0058 (9)	0.0154 (10)
C3	0.0714 (17)	0.0641 (16)	0.0456 (13)	0.0140 (14)	0.0058 (12)	0.0241 (13)
C4	0.086 (2)	0.086 (2)	0.0417 (14)	0.0208 (18)	0.0025 (14)	0.0155 (15)
C5	0.0657 (18)	0.0665 (18)	0.0501 (15)	0.0193 (15)	−0.0038 (13)	−0.0037 (14)
C6	0.0428 (13)	0.0450 (13)	0.0615 (15)	0.0166 (11)	0.0035 (11)	0.0085 (11)
C7	0.0598 (17)	0.0410 (14)	0.098 (2)	0.0143 (12)	0.0067 (16)	0.0136 (15)
C8	0.078 (2)	0.0501 (18)	0.135 (3)	0.0122 (15)	0.024 (2)	0.047 (2)
C9	0.084 (2)	0.0682 (19)	0.088 (2)	0.0211 (16)	0.0251 (17)	0.0496 (18)
C10	0.0456 (13)	0.0502 (13)	0.0579 (14)	0.0200 (11)	0.0129 (11)	0.0263 (12)
C11	0.095 (3)	0.101 (3)	0.091 (2)	0.035 (2)	−0.022 (2)	0.048 (2)
C12	0.0742 (19)	0.084 (2)	0.0627 (17)	0.0235 (16)	0.0329 (15)	0.0220 (16)
C13	0.0395 (14)	0.088 (2)	0.0662 (17)	−0.0021 (13)	0.0091 (12)	0.0144 (16)
C14	0.090 (2)	0.0577 (16)	0.0616 (16)	0.0334 (15)	0.0111 (15)	0.0250 (14)
Cl1	0.0857 (5)	0.0499 (4)	0.0569 (4)	0.0013 (3)	−0.0256 (3)	0.0033 (3)
Cl4	0.0760 (5)	0.0680 (4)	0.0531 (3)	0.0212 (3)	−0.0222 (3)	0.0232 (3)
Cl5	0.1221 (7)	0.0764 (5)	0.0537 (4)	0.0381 (5)	0.0487 (4)	0.0356 (4)
Cl6	0.0401 (4)	0.1072 (7)	0.1358 (8)	0.0010 (4)	0.0211 (4)	0.0574 (6)
Cl7A	0.0608 (4)	0.0610 (4)	0.0588 (4)	0.0347 (3)	0.0239 (3)	0.0264 (3)
Cl7B	0.0899 (5)	0.0448 (3)	0.0716 (4)	0.0205 (3)	0.0135 (4)	0.0345 (3)
O28A	0.0642 (11)	0.0968 (14)	0.0612 (11)	0.0514 (11)	0.0229 (9)	0.0404 (11)
O28B	0.0498 (9)	0.0812 (12)	0.0546 (10)	0.0269 (9)	0.0064 (8)	0.0430 (9)
O29A	0.0626 (11)	0.0440 (9)	0.0473 (9)	0.0108 (8)	0.0140 (8)	0.0096 (7)
O29B	0.0538 (10)	0.0364 (8)	0.0601 (10)	0.0128 (7)	0.0106 (8)	0.0204 (8)
C21	0.0412 (11)	0.0362 (11)	0.0373 (10)	0.0049 (9)	−0.0034 (9)	0.0123 (9)
C22	0.0365 (10)	0.0402 (11)	0.0294 (9)	0.0128 (9)	0.0043 (8)	0.0156 (8)
C23	0.0295 (9)	0.0362 (10)	0.0343 (9)	0.0097 (8)	0.0036 (8)	0.0154 (8)
C24	0.0419 (11)	0.0399 (11)	0.0322 (10)	0.0130 (9)	−0.0007 (8)	0.0156 (9)
C25	0.0581 (14)	0.0481 (12)	0.0409 (11)	0.0199 (11)	0.0209 (10)	0.0255 (10)
C26	0.0391 (12)	0.0495 (13)	0.0618 (14)	0.0080 (10)	0.0137 (11)	0.0299 (12)
C27	0.0482 (12)	0.0366 (11)	0.0380 (10)	0.0149 (9)	0.0087 (9)	0.0180 (9)
C28	0.0332 (10)	0.0424 (11)	0.0442 (11)	0.0091 (9)	0.0011 (9)	0.0204 (10)
C29	0.0336 (10)	0.0372 (11)	0.0443 (12)	0.0064 (9)	0.0009 (9)	0.0138 (9)
O30	0.0640 (13)	0.140 (2)	0.0626 (12)	0.0559 (14)	0.0090 (10)	0.0364 (14)

Geometric parameters (Å, º)

Cl1—C21	1.748 (2)	C6—C7	1.398 (4)
Cl4—C24	1.753 (2)	C7—C8	1.350 (6)
Cl5—C25	1.699 (2)	C7—H7	0.93
Cl6—C26	1.696 (3)	C8—H8	0.93
Cl7A—C27	1.765 (2)	C9—C8	1.398 (6)
Cl7B—C27	1.765 (2)	C9—H9	0.93
O28A—C28	1.223 (3)	C10—C9	1.356 (5)
O28B—C28	1.253 (2)	C11—H11A	0.96
O29A—C29	1.200 (3)	C11—H11B	0.96
O29B—C29	1.322 (3)	C11—H11C	0.96
O29B—H29B	0.82	C12—H12A	0.96
O30—H30A	0.85 (5)	C12—H12B	0.96
O30—H30B	0.88 (5)	C12—H12C	0.96
N1—C2	1.456 (3)	C13—H13A	0.96
N1—C13	1.482 (3)	C13—H13B	0.96
N1—C14	1.475 (4)	C13—H13C	0.96
N1—H1N	0.82 (4)	C14—H14A	0.96
N2—C10	1.459 (3)	C14—H14B	0.96
N2—C12	1.479 (4)	C14—H14C	0.96
N2—C11	1.480 (4)	C21—C26	1.523 (3)
N2—H2N	0.97 (7)	C21—C27	1.547 (3)
C1—C2	1.418 (4)	C22—C21	1.555 (3)
C1—C6	1.431 (3)	C22—C23	1.566 (3)
C1—C10	1.425 (3)	C22—C28	1.538 (3)
C2—C3	1.361 (3)	C22—H22	0.98
C3—C4	1.396 (4)	C23—C29	1.519 (3)
C3—H3	0.93	C23—H23	0.98
C4—H4	0.93	C24—C23	1.554 (3)
C5—C4	1.345 (5)	C24—C25	1.514 (3)
C5—H5	0.93	C24—C27	1.547 (3)
C6—C5	1.412 (4)	C25—C26	1.309 (3)
C29—O29B—H29B	109.5	H12B—C12—H12C	109.5
H30A—O30—H30B	102 (4)	N1—C13—H13A	109.5
C2—N1—C13	112.0 (2)	N1—C13—H13B	109.5
C2—N1—C14	113.28 (19)	N1—C13—H13C	109.5
C14—N1—C13	112.0 (2)	H13A—C13—H13B	109.5
C2—N1—H1N	106.3	H13A—C13—H13C	109.5
C13—N1—H1N	106.3	H13B—C13—H13C	109.5
C14—N1—H1N	106.3	N1—C14—H14A	109.5
C10—N2—C11	113.2 (2)	N1—C14—H14B	109.5
C10—N2—C12	111.9 (2)	N1—C14—H14C	109.5
C11—N2—C12	111.4 (2)	H14A—C14—H14B	109.5
C10—N2—H2N	106.6	H14A—C14—H14C	109.5
C11—N2—H2N	106.6	H14B—C14—H14C	109.5
C12—N2—H2N	106.6	Cl1—C21—C22	113.80 (14)
C2—C1—C6	117.4 (2)	Cl1—C21—C27	115.64 (16)
C2—C1—C10	125.1 (2)	Cl1—C21—C26	116.06 (16)
C6—C1—C10	117.4 (2)	C22—C21—C26	109.45 (18)
N1—C2—C1	118.75 (19)	C22—C21—C27	101.43 (16)
N1—C2—C3	120.2 (2)	C26—C21—C27	98.57 (17)
C1—C2—C3	121.0 (2)	C21—C22—C23	101.54 (16)
C2—C3—C4	121.2 (3)	C21—C22—C28	111.57 (16)
C2—C3—H3	119.4	C23—C22—C28	116.09 (17)
C4—C3—H3	119.4	C21—C22—H22	109.1
C3—C4—C5	119.6 (3)	C23—C22—H22	109.1
C3—C4—H4	120.2	C28—C22—H22	109.1
C5—C4—H4	120.2	C22—C23—C24	103.07 (17)
C4—C5—C6	121.9 (3)	C22—C23—C29	116.08 (16)
C4—C5—H5	119.0	C24—C23—C29	114.84 (16)
C6—C5—H5	119.0	Cl4—C23—C24	114.96 (14)
C7—C6—C5	121.7 (3)	C22—C23—H23	107.5
C7—C6—C1	119.6 (3)	C24—C23—H23	107.5
C5—C6—C1	118.8 (3)	C29—C23—H23	107.5
C8—C7—C6	121.3 (3)	C23—C24—C27	100.42 (16)
C8—C7—H7	119.4	C22—C24—C25	109.87 (17)
C6—C7—H7	119.4	C25—C24—C27	98.95 (18)
C7—C8—C9	119.9 (4)	Cl4—C24—C25	115.68 (15)
C7—C8—H8	120.1	Cl4—C24—C27	114.88 (16)
C9—C8—H8	120.1	Cl5—C25—C24	124.33 (17)
C8—C9—C10	121.5 (4)	Cl5—C25—C26	128.2 (2)
C8—C9—H9	119.3	C24—C25—C26	107.5 (2)
C10—C9—H9	119.3	C21—C26—C25	107.8 (2)
N2—C10—C1	118.7 (2)	Cl6—C26—C21	124.20 (18)
N2—C10—C9	120.9 (3)	Cl6—C26—C25	128.0 (2)
C9—C10—C1	120.4 (3)	C21—C27—C24	92.18 (17)
N2—C11—H11A	109.5	Cl7A—C27—Cl7B	106.72 (14)
N2—C11—H11B	109.5	Cl7A—C27—C21	115.10 (15)
N2—C11—H11C	109.5	Cl7A—C27—C24	114.19 (17)
H11A—C11—H11B	109.5	Cl7B—C27—C21	114.07 (17)
H11A—C11—H11C	109.5	Cl7B—C27—C24	114.44 (15)
H11B—C11—H11C	109.5	O28A—C28—O28B	125.1 (2)
N2—C12—H12A	109.5	O28A—C28—C22	118.2 (2)
N2—C12—H12B	109.5	O28B—C28—C22	116.73 (18)
N2—C12—H12C	109.5	O29A—C29—O29B	121.5 (2)
H12A—C12—H12B	109.5	O29A—C29—C23	123.6 (2)
H12A—C12—H12C	109.5	O29B—C29—C23	114.81 (18)
C14—N1—C2—C3	62.0 (3)	C22—C21—C27—Cl7A	−58.82 (19)
C14—N1—C2—C1	−118.4 (2)	C22—C21—C27—Cl7B	177.32 (14)
C13—N1—C2—C3	−65.9 (3)	C22—C21—C27—C24	59.25 (17)
C13—N1—C2—C1	113.7 (3)	C26—C21—C27—Cl7A	−170.79 (17)
C11—N2—C10—C9	60.8 (4)	C26—C21—C27—Cl7B	65.4 (2)
C12—N2—C10—C9	−66.1 (4)	C26—C21—C27—C24	−52.7 (2)
C12—N2—C10—C1	113.1 (3)	C27—C21—C26—C25	35.1 (3)
C11—N2—C10—C1	−120.0 (3)	C27—C21—C26—Cl6	−145.1 (2)
C2—C1—C6—C7	−179.9 (2)	C21—C22—C23—C29	−127.00 (18)
C2—C1—C6—C5	−0.2 (4)	C28—C22—C23—C24	120.61 (18)
C10—C1—C2—C3	178.9 (2)	C21—C22—C28—O28A	64.6 (3)
C6—C1—C10—C9	0.0 (4)	C21—C22—C28—O28B	−115.4 (2)
C6—C1—C2—C3	−0.7 (4)	C28—C22—C23—C29	−5.8 (3)
C6—C1—C2—N1	179.7 (2)	C21—C22—C23—C24	−0.57 (17)
C6—C1—C10—N2	−179.2 (2)	C23—C22—C28—O28B	128.9 (2)
C10—C1—C2—N1	−0.7 (4)	C23—C22—C28—O28A	−51.1 (3)
C10—C1—C6—C7	0.5 (3)	C22—C23—C24—C25	−65.63 (19)
C2—C1—C10—N2	1.1 (3)	C22—C23—C24—C27	37.95 (18)
C10—C1—C6—C5	−179.9 (3)	C29—C23—C24—C25	61.6 (2)
C2—C1—C10—C9	−179.7 (3)	C29—C23—C24—C27	165.16 (17)
C1—C2—C3—C4	1.1 (4)	C29—C23—C24—Cl4	−70.97 (18)
N1—C2—C3—C4	−179.3 (3)	C22—C23—C24—Cl4	161.82 (13)
C2—C3—C4—C5	−0.4 (5)	C24—C23—C29—O29A	−3.6 (3)
C3—C4—C5—C6	−0.6 (5)	C24—C23—C29—O29B	173.55 (16)
C4—C5—C6—C1	0.9 (5)	C22—C23—C29—O29A	116.7 (2)
C4—C5—C6—C7	−179.5 (3)	C22—C23—C29—O29B	−66.2 (2)
C5—C6—C7—C8	179.9 (5)	C23—C24—C25—Cl5	−111.8 (2)
C1—C6—C7—C8	−0.4 (4)	Cl4—C24—C25—Cl5	20.4 (3)
C6—C7—C8—C9	0.0 (5)	Cl4—C24—C25—C26	−159.2 (2)
C7—C8—C9—C10	0.5 (5)	C27—C24—C25—C26	−35.9 (3)
C8—C9—C10—C1	−0.5 (5)	Cl4—C24—C27—Cl7A	−64.0 (2)
C8—C9—C10—N2	178.7 (3)	Cl4—C24—C27—Cl7B	59.4 (2)
C26—C21—C22—C23	66.35 (19)	Cl4—C24—C27—C21	177.12 (15)
Cl1—C21—C22—C23	−161.98 (13)	C23—C24—C27—Cl7A	59.89 (18)
Cl1—C21—C22—C28	73.74 (18)	C23—C24—C27—Cl7B	−176.71 (15)
C27—C21—C22—C28	−161.40 (16)	C23—C24—C27—C21	−58.96 (17)
Cl1—C21—C26—Cl6	−21.0 (3)	C25—C24—C27—Cl7A	172.15 (16)
Cl1—C21—C26—C25	159.2 (2)	C25—C24—C27—Cl7B	−64.4 (2)
C22—C21—C26—Cl6	109.5 (2)	C25—C24—C27—C21	53.30 (19)
C22—C21—C26—C25	−70.3 (3)	C23—C24—C25—C26	68.6 (3)
C26—C21—C22—C28	−57.9 (2)	C27—C24—C25—Cl5	143.7 (2)
C27—C21—C22—C23	−37.11 (17)	Cl5—C25—C26—Cl6	1.1 (4)
Cl1—C21—C27—Cl7A	64.8 (2)	C24—C25—C26—C21	0.5 (3)
Cl1—C21—C27—Cl7B	−59.06 (19)	Cl5—C25—C26—C21	−179.1 (2)
Cl1—C21—C27—C24	−177.13 (15)	C24—C25—C26—Cl6	−179.3 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···N2	0.82 (4)	1.82 (3)	2.589 (3)	154 (4)
N2—H2N···N1	0.97 (7)	1.70 (5)	2.589 (3)	152 (4)
O29B—H29B···O28B^i	0.82	1.70	2.520 (2)	173
O30—H30B···O28B^ii	0.89 (5)	2.02 (5)	2.783 (3)	143 (4)
O30—H30A···O28A	0.85 (5)	1.95 (5)	2.749 (3)	156 (4)
C9—H9···Cl7B^iii	0.93	2.78	3.599 (4)	148
C12—H12C···O29B^i	0.96	2.58	3.297 (4)	132
C13—H13A···O30^i	0.96	2.54	3.220 (3)	128
C14—H14B···O29A^i	0.96	2.46	3.348 (4)	155
C23—H23···Cl7A	0.98	2.64	2.994 (2)	102
C23—H23···O30^iv	0.98	2.55	3.480 (4)	157

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