Crystal structure of 2,6-bis-(2-hy-droxy-5-methyl-phen-yl)-4-phenyl-pyridinium bromide di-chloro-methane hemisolvate hemihydrate.

The asymmetric unit in the structure of the title compound, C25H22NO2 (+)·Br (-)·0.5CH2Cl2·0.5H2O, comprises two pseudosymmetry-related cations, two bromide anions, a di-chloro-methane molecule and a water mol-ecule of solvation. The two independent cations are conformationally similar with the comparative dihedral angles between the central pyridine ring and the three benzene substituent rings being 3.0 (2), 36.4 (1) and 24.2 (1)°, and 3.7 (2), 36.5 (1) and 24.8 (1)°, respectively. In the crystal, the cations, anions and water mol-ecules are linked through O-H⋯O and O-H⋯Br hydrogen bonds, forming an insular unit. Within the cations there are also intra-molecular N-H⋯O hydrogen bonds. Adjacent centrosymmetrically related aggregates are linked by π-π stacking inter-actions between the pyridine ring and a benzene ring in both cations [ring-centroid separations = 3.525 (3) and 3.668 (3) Å], forming chains extending across the ac diagonal. Voids between these chains are filled by dichloromethane molecules.

Related literature

For general background to the chemistry affording 2,6-bis-(2-hy­droxy­phen­yl)pyridines, see: Huang et al. (2012 ▸, 2013 ▸); Kire­enko et al. (2013 ▸); Klein et al. (2010 ▸); Li et al. (2000 ▸); Steinhauser et al. (2004 ▸); Zhang et al. (2006 ▸). For the closely related structure of the parent derivative compound, see: Silva et al. (1997 ▸).

Experimental

Crystal data

2C25H22NO2 +·2Br−·CH2Cl2·H2O

M = 999.63

Monoclinic,

a = 14.7890 (12) Å

b = 17.5387 (14) Å

c = 19.0163 (15) Å

β = 112.577 (1)°

V = 4554.4 (6) Å3

Z = 4

Mo Kα radiation

μ = 1.95 mm−1

T = 150 K

0.25 × 0.20 × 0.10 mm

Data collection

Bruker SMART APEXII diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2008 ▸) T min = 0.642, T max = 0.829

34435 measured reflections

8482 independent reflections

6350 reflections with I > 2σ(I)

R int = 0.050

Refinement

R[F 2 > 2σ(F 2)] = 0.051

wR(F 2) = 0.132

S = 1.06

8482 reflections

585 parameters

15 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.99 e Å−3

Δρmin = −0.92 e Å−3

Data collection: APEX2 (Bruker, 2008 ▸); cell refinement: SAINT (Bruker, 2008 ▸); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▸); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▸); molecular graphics: SHELXTL (Sheldrick, 2008 ▸); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989015021386/zs2352sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015021386/zs2352Isup2.hkl

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Supporting information file. DOI: 10.1107/S2056989015021386/zs2352Isup3.mol

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Supporting information file. DOI: 10.1107/S2056989015021386/zs2352Isup4.cml

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. DOI: 10.1107/S2056989015021386/zs2352fig1.tif

The asymmetric unit in the structure of the title compound, with displacement ellipsoids shown at the 50% probability level. Hydrogen bonds are shown as dashed lines.

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x y z . DOI: 10.1107/S2056989015021386/zs2352fig2.tif

The result of superposition of one independent cation with another shifted by an x + , y + , z operation.

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A x y z . DOI: 10.1107/S2056989015021386/zs2352fig3.tif

Insular hydrogen bonded aggregates in the structure. Hydrogen bonds are shown as dashed lines. Suffix A indicates the symmetry operator −x + 1, y − , −z + .

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. DOI: 10.1107/S2056989015021386/zs2352fig4.tif

Chains formed by π–π stacking inter­actions between aromatic ring systems in adjacent H-bonded frameworks.

CCDC reference: 1436252

Additional supporting information: crystallographic information; 3D view; checkCIF report

2C25H22NO2+·2Br−·CH2Cl2·H2O	F(000) = 2048
Mr = 999.63	Dx = 1.458 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 6112 reflections
a = 14.7890 (12) Å	θ = 2.2–23.3°
b = 17.5387 (14) Å	µ = 1.95 mm−1
c = 19.0163 (15) Å	T = 150 K
β = 112.577 (1)°	Prism, orange
V = 4554.4 (6) Å3	0.25 × 0.20 × 0.10 mm
Z = 4

Bruker SMART APEXII diffractometer	8482 independent reflections
Radiation source: fine-focus sealed tube	6350 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.050
ω scans	θmax = 25.5°, θmin = 1.5°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −17→17
Tmin = 0.642, Tmax = 0.829	k = −21→21
34435 measured reflections	l = −23→23

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.051	Hydrogen site location: mixed
wR(F2) = 0.132	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ2(Fo2) + (0.0499P)2 + 10.5059P] where P = (Fo2 + 2Fc2)/3
8482 reflections	(Δ/σ)max = 0.001
585 parameters	Δρmax = 0.99 e Å−3
15 restraints	Δρmin = −0.92 e Å−3

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.

	x	y	z	Uiso*/Ueq
Br1	0.37349 (4)	0.71568 (2)	0.20516 (2)	0.03429 (13)
Br2	0.99858 (4)	1.19630 (3)	0.23428 (3)	0.04276 (15)
O1	0.2325 (2)	0.71111 (18)	0.30809 (18)	0.0353 (7)
H7	0.1742 (17)	0.711 (3)	0.295 (3)	0.053*
H8	0.253 (4)	0.719 (3)	0.276 (2)	0.053*
C1	0.2288 (7)	0.1114 (6)	0.2630 (6)	0.132 (4)
H1A	0.2072	0.0637	0.2334	0.159*
H1B	0.1698	0.1427	0.2546	0.159*
Cl1	0.28379 (17)	0.08839 (13)	0.35994 (17)	0.1249 (9)
Cl2	0.3025 (3)	0.15925 (15)	0.2295 (2)	0.1806 (16)
N1	0.3903 (2)	0.45926 (17)	0.38647 (17)	0.0214 (7)
H1	0.3658	0.5022	0.3628	0.026*
O11	0.3172 (2)	0.59130 (16)	0.38313 (16)	0.0282 (6)
H3	0.284 (3)	0.625 (2)	0.359 (3)	0.049 (16)*
O12	0.4366 (2)	0.55415 (17)	0.29039 (16)	0.0326 (7)
H4	0.418 (3)	0.5929 (18)	0.268 (2)	0.034 (14)*
C11	0.3174 (3)	0.5801 (2)	0.4537 (2)	0.0233 (8)
C12	0.2787 (3)	0.6347 (2)	0.4869 (2)	0.0288 (9)
H12	0.2498	0.6795	0.4592	0.035*
C13	0.2816 (3)	0.6247 (2)	0.5598 (2)	0.0306 (10)
H13	0.2542	0.6625	0.5815	0.037*
C14	0.3240 (3)	0.5603 (2)	0.6016 (2)	0.0281 (9)
C15	0.3605 (3)	0.5048 (2)	0.5675 (2)	0.0259 (9)
H15	0.3882	0.4599	0.5954	0.031*
C16	0.3582 (3)	0.5126 (2)	0.4933 (2)	0.0218 (8)
C17	0.3961 (3)	0.4507 (2)	0.4591 (2)	0.0217 (8)
C18	0.4351 (3)	0.3826 (2)	0.4955 (2)	0.0223 (8)
H18	0.4397	0.3743	0.5461	0.027*
C19	0.3313 (4)	0.5514 (3)	0.6828 (3)	0.0428 (12)
H19A	0.2658	0.5551	0.6841	0.064*
H19B	0.3732	0.5917	0.7145	0.064*
H19C	0.3597	0.5015	0.7025	0.064*
C21	0.4112 (3)	0.4948 (2)	0.2400 (2)	0.0276 (9)
C22	0.3957 (3)	0.5043 (3)	0.1632 (2)	0.0314 (10)
H22	0.4036	0.5531	0.1448	0.038*
C23	0.3689 (3)	0.4430 (3)	0.1142 (2)	0.0336 (10)
H23	0.3575	0.4506	0.0620	0.040*
C24	0.3583 (3)	0.3703 (3)	0.1392 (2)	0.0335 (10)
C25	0.3768 (3)	0.3605 (2)	0.2163 (2)	0.0293 (9)
H25	0.3717	0.3110	0.2345	0.035*
C26	0.4027 (3)	0.4217 (2)	0.2674 (2)	0.0256 (9)
C27	0.4198 (3)	0.4063 (2)	0.3481 (2)	0.0238 (8)
C28	0.4607 (3)	0.3400 (2)	0.3845 (2)	0.0251 (9)
H28	0.4844	0.3033	0.3590	0.030*
C29	0.3259 (4)	0.3031 (3)	0.0851 (3)	0.0436 (12)
H29A	0.3653	0.2582	0.1089	0.065*
H29B	0.3347	0.3152	0.0379	0.065*
H29C	0.2566	0.2923	0.0736	0.065*
C31	0.4678 (3)	0.3259 (2)	0.4590 (2)	0.0237 (8)
C32	0.5077 (3)	0.2525 (2)	0.4977 (2)	0.0255 (9)
C33	0.5463 (3)	0.2452 (2)	0.5764 (2)	0.0280 (9)
H33	0.5508	0.2891	0.6069	0.034*
C34	0.5781 (3)	0.1763 (2)	0.6115 (3)	0.0330 (10)
H34	0.6042	0.1730	0.6655	0.040*
C35	0.5721 (3)	0.1118 (2)	0.5680 (3)	0.0365 (11)
H35	0.5939	0.0640	0.5920	0.044*
C36	0.5345 (4)	0.1173 (2)	0.4896 (3)	0.0394 (11)
H36	0.5302	0.0731	0.4597	0.047*
C37	0.5029 (3)	0.1869 (2)	0.4544 (3)	0.0344 (10)
H37	0.4778	0.1902	0.4004	0.041*
N2	0.8706 (2)	0.96667 (17)	0.38890 (17)	0.0207 (7)
H2	0.8481	1.0100	0.3653	0.025*
O21	0.8014 (2)	1.10189 (16)	0.38610 (16)	0.0292 (7)
H5	0.763 (3)	1.134 (2)	0.365 (2)	0.040 (15)*
O22	0.9207 (2)	1.05281 (16)	0.29143 (16)	0.0323 (7)
H6	0.934 (3)	1.0917 (18)	0.277 (3)	0.040 (14)*
C41	0.8155 (3)	1.0944 (2)	0.4612 (2)	0.0234 (8)
C42	0.7898 (3)	1.1537 (2)	0.4984 (2)	0.0309 (10)
H42	0.7609	1.1987	0.4712	0.037*
C43	0.8060 (3)	1.1474 (2)	0.5745 (2)	0.0314 (10)
H43	0.7870	1.1880	0.5990	0.038*
C44	0.8495 (3)	1.0829 (2)	0.6162 (2)	0.0284 (9)
C45	0.8743 (3)	1.0243 (2)	0.5782 (2)	0.0265 (9)
H45	0.9038	0.9798	0.6061	0.032*
C46	0.8581 (3)	1.0274 (2)	0.5005 (2)	0.0216 (8)
C47	0.8837 (3)	0.9611 (2)	0.4636 (2)	0.0208 (8)
C48	0.9198 (3)	0.8924 (2)	0.4998 (2)	0.0231 (8)
H48	0.9288	0.8861	0.5517	0.028*
C49	0.8700 (3)	1.0787 (3)	0.7002 (2)	0.0380 (11)
H49A	0.8921	1.0271	0.7189	0.057*
H49B	0.8101	1.0906	0.7085	0.057*
H49C	0.9212	1.1155	0.7277	0.057*
C51	0.8924 (3)	0.9936 (2)	0.2414 (2)	0.0273 (9)
C52	0.8854 (3)	1.0006 (3)	0.1662 (2)	0.0331 (10)
H52	0.9006	1.0477	0.1485	0.040*
C53	0.8561 (3)	0.9384 (3)	0.1179 (2)	0.0357 (11)
H53	0.8510	0.9438	0.0668	0.043*
C54	0.8339 (3)	0.8682 (3)	0.1414 (2)	0.0352 (11)
C55	0.8426 (3)	0.8619 (2)	0.2168 (2)	0.0271 (9)
H55	0.8277	0.8146	0.2341	0.033*
C56	0.8727 (3)	0.9230 (2)	0.2678 (2)	0.0246 (9)
C57	0.8900 (3)	0.9097 (2)	0.3485 (2)	0.0224 (8)
C58	0.9268 (3)	0.8424 (2)	0.3845 (2)	0.0220 (8)
H58	0.9415	0.8023	0.3571	0.026*
C59	0.8031 (4)	0.8003 (3)	0.0885 (3)	0.0470 (13)
H59A	0.8494	0.7584	0.1096	0.071*
H59B	0.8026	0.8146	0.0385	0.071*
H59C	0.7373	0.7840	0.0829	0.071*
C61	0.9431 (3)	0.8322 (2)	0.4614 (2)	0.0225 (8)
C62	0.9826 (3)	0.7596 (2)	0.5007 (2)	0.0256 (9)
C63	1.0329 (3)	0.7553 (2)	0.5791 (2)	0.0297 (9)
H63	1.0431	0.8005	0.6086	0.036*
C64	1.0682 (3)	0.6878 (3)	0.6149 (3)	0.0361 (10)
H64	1.1025	0.6865	0.6686	0.043*
C65	1.0540 (3)	0.6209 (3)	0.5729 (3)	0.0382 (11)
H65	1.0779	0.5738	0.5977	0.046*
C66	1.0051 (4)	0.6234 (3)	0.4947 (3)	0.0426 (12)
H66	0.9959	0.5780	0.4655	0.051*
C67	0.9694 (4)	0.6919 (2)	0.4589 (3)	0.0354 (10)
H67	0.9355	0.6931	0.4052	0.042*

	U11	U22	U33	U12	U13	U23
Br1	0.0507 (3)	0.0241 (2)	0.0290 (2)	−0.00541 (19)	0.0163 (2)	0.00051 (17)
Br2	0.0458 (3)	0.0455 (3)	0.0442 (3)	−0.0152 (2)	0.0254 (2)	0.0000 (2)
O1	0.0412 (19)	0.0322 (16)	0.0332 (18)	0.0032 (15)	0.0150 (16)	0.0008 (14)
C1	0.114 (7)	0.103 (7)	0.193 (11)	0.038 (6)	0.073 (8)	0.032 (7)
Cl1	0.0854 (14)	0.0902 (15)	0.167 (2)	−0.0199 (12)	0.0125 (15)	0.0345 (15)
Cl2	0.288 (4)	0.0771 (16)	0.247 (4)	−0.066 (2)	0.181 (4)	−0.0282 (19)
N1	0.0251 (18)	0.0179 (16)	0.0216 (17)	−0.0018 (13)	0.0093 (14)	−0.0006 (13)
O11	0.0392 (18)	0.0219 (15)	0.0278 (16)	0.0056 (13)	0.0176 (14)	0.0026 (12)
O12	0.0473 (19)	0.0242 (16)	0.0258 (16)	0.0014 (14)	0.0135 (14)	0.0034 (13)
C11	0.022 (2)	0.022 (2)	0.027 (2)	−0.0053 (16)	0.0099 (17)	−0.0046 (16)
C12	0.032 (2)	0.023 (2)	0.036 (2)	0.0015 (18)	0.017 (2)	−0.0020 (18)
C13	0.032 (2)	0.027 (2)	0.038 (3)	−0.0015 (18)	0.019 (2)	−0.0086 (18)
C14	0.029 (2)	0.030 (2)	0.029 (2)	−0.0027 (18)	0.0157 (19)	−0.0062 (17)
C15	0.026 (2)	0.025 (2)	0.027 (2)	0.0001 (17)	0.0113 (18)	−0.0008 (16)
C16	0.019 (2)	0.0214 (19)	0.024 (2)	−0.0038 (16)	0.0080 (17)	−0.0052 (16)
C17	0.022 (2)	0.0212 (19)	0.022 (2)	−0.0054 (16)	0.0082 (17)	−0.0046 (15)
C18	0.022 (2)	0.023 (2)	0.021 (2)	−0.0008 (16)	0.0076 (17)	−0.0001 (16)
C19	0.055 (3)	0.048 (3)	0.034 (3)	0.007 (2)	0.026 (2)	−0.005 (2)
C21	0.026 (2)	0.030 (2)	0.027 (2)	0.0039 (18)	0.0117 (18)	−0.0022 (18)
C22	0.032 (2)	0.038 (2)	0.026 (2)	0.0091 (19)	0.0136 (19)	0.0063 (18)
C23	0.027 (2)	0.051 (3)	0.025 (2)	0.011 (2)	0.0121 (19)	0.002 (2)
C24	0.029 (2)	0.044 (3)	0.029 (2)	0.008 (2)	0.0126 (19)	−0.009 (2)
C25	0.029 (2)	0.030 (2)	0.031 (2)	0.0055 (18)	0.0134 (19)	−0.0038 (18)
C26	0.026 (2)	0.026 (2)	0.026 (2)	0.0024 (17)	0.0121 (18)	−0.0019 (17)
C27	0.023 (2)	0.023 (2)	0.026 (2)	−0.0031 (16)	0.0100 (17)	−0.0046 (16)
C28	0.026 (2)	0.024 (2)	0.027 (2)	−0.0011 (17)	0.0127 (18)	−0.0051 (16)
C29	0.041 (3)	0.055 (3)	0.036 (3)	0.002 (2)	0.017 (2)	−0.018 (2)
C31	0.022 (2)	0.0211 (19)	0.029 (2)	−0.0041 (16)	0.0111 (17)	−0.0034 (16)
C32	0.026 (2)	0.021 (2)	0.033 (2)	−0.0009 (17)	0.0153 (18)	−0.0013 (17)
C33	0.027 (2)	0.024 (2)	0.033 (2)	−0.0013 (17)	0.0114 (19)	−0.0016 (18)
C34	0.031 (2)	0.032 (2)	0.034 (2)	−0.0006 (19)	0.010 (2)	0.0037 (19)
C35	0.038 (3)	0.023 (2)	0.051 (3)	0.0031 (19)	0.021 (2)	0.008 (2)
C36	0.053 (3)	0.022 (2)	0.051 (3)	0.002 (2)	0.029 (3)	−0.003 (2)
C37	0.049 (3)	0.025 (2)	0.035 (2)	0.004 (2)	0.022 (2)	0.0009 (18)
N2	0.0253 (18)	0.0185 (16)	0.0202 (16)	0.0015 (13)	0.0110 (14)	0.0017 (13)
O21	0.0441 (19)	0.0212 (15)	0.0266 (16)	0.0079 (14)	0.0184 (14)	0.0019 (12)
O22	0.052 (2)	0.0236 (16)	0.0258 (16)	−0.0005 (14)	0.0197 (15)	0.0030 (12)
C41	0.025 (2)	0.023 (2)	0.024 (2)	−0.0036 (16)	0.0113 (17)	−0.0024 (16)
C42	0.038 (3)	0.022 (2)	0.037 (2)	0.0015 (18)	0.020 (2)	−0.0030 (18)
C43	0.036 (3)	0.030 (2)	0.034 (2)	−0.0006 (19)	0.020 (2)	−0.0113 (19)
C44	0.027 (2)	0.034 (2)	0.028 (2)	−0.0028 (18)	0.0146 (19)	−0.0075 (18)
C45	0.024 (2)	0.031 (2)	0.024 (2)	0.0012 (17)	0.0095 (18)	−0.0019 (17)
C46	0.018 (2)	0.024 (2)	0.025 (2)	−0.0040 (16)	0.0108 (16)	−0.0068 (16)
C47	0.019 (2)	0.0225 (19)	0.023 (2)	−0.0038 (15)	0.0109 (16)	−0.0039 (16)
C48	0.027 (2)	0.024 (2)	0.020 (2)	−0.0006 (17)	0.0118 (17)	0.0008 (16)
C49	0.042 (3)	0.047 (3)	0.028 (2)	0.006 (2)	0.017 (2)	−0.008 (2)
C51	0.028 (2)	0.034 (2)	0.021 (2)	0.0101 (18)	0.0090 (18)	0.0021 (17)
C52	0.031 (2)	0.046 (3)	0.025 (2)	0.012 (2)	0.0132 (19)	0.0081 (19)
C53	0.029 (2)	0.061 (3)	0.018 (2)	0.017 (2)	0.0095 (19)	0.002 (2)
C54	0.026 (2)	0.053 (3)	0.022 (2)	0.018 (2)	0.0037 (18)	−0.010 (2)
C55	0.023 (2)	0.032 (2)	0.024 (2)	0.0090 (17)	0.0070 (17)	−0.0031 (17)
C56	0.023 (2)	0.029 (2)	0.023 (2)	0.0071 (17)	0.0099 (17)	0.0015 (16)
C57	0.022 (2)	0.022 (2)	0.023 (2)	−0.0032 (16)	0.0088 (17)	−0.0069 (16)
C58	0.025 (2)	0.0194 (19)	0.024 (2)	0.0002 (16)	0.0122 (17)	−0.0030 (15)
C59	0.040 (3)	0.061 (3)	0.035 (3)	0.012 (2)	0.008 (2)	−0.020 (2)
C61	0.021 (2)	0.0215 (19)	0.027 (2)	−0.0035 (16)	0.0103 (17)	0.0003 (16)
C62	0.031 (2)	0.022 (2)	0.030 (2)	0.0006 (17)	0.0185 (19)	0.0021 (17)
C63	0.034 (2)	0.028 (2)	0.029 (2)	−0.0018 (19)	0.015 (2)	0.0016 (18)
C64	0.040 (3)	0.039 (3)	0.031 (2)	0.001 (2)	0.015 (2)	0.008 (2)
C65	0.042 (3)	0.027 (2)	0.052 (3)	0.006 (2)	0.024 (2)	0.014 (2)
C66	0.062 (3)	0.023 (2)	0.049 (3)	0.001 (2)	0.028 (3)	−0.003 (2)
C67	0.049 (3)	0.024 (2)	0.037 (3)	0.001 (2)	0.020 (2)	0.0022 (18)

O1—H7	0.80 (2)	C36—C37	1.384 (6)
O1—H8	0.79 (2)	C36—H36	0.9500
C1—Cl2	1.681 (10)	C37—H37	0.9500
C1—Cl1	1.752 (10)	N2—C57	1.357 (5)
C1—H1A	0.9900	N2—C47	1.362 (5)
C1—H1B	0.9900	N2—H2	0.8800
N1—C27	1.352 (5)	O21—C41	1.369 (5)
N1—C17	1.359 (5)	O21—H5	0.79 (2)
N1—H1	0.8800	O22—C51	1.361 (5)
O11—C11	1.355 (5)	O22—H6	0.79 (2)
O11—H3	0.79 (2)	C41—C42	1.390 (5)
O12—C21	1.366 (5)	C41—C46	1.404 (5)
O12—H4	0.79 (2)	C42—C43	1.378 (6)
C11—C12	1.386 (5)	C42—H42	0.9500
C11—C16	1.409 (5)	C43—C44	1.389 (6)
C12—C13	1.381 (6)	C43—H43	0.9500
C12—H12	0.9500	C44—C45	1.385 (5)
C13—C14	1.386 (6)	C44—C49	1.508 (6)
C13—H13	0.9500	C45—C46	1.405 (5)
C14—C15	1.389 (5)	C45—H45	0.9500
C14—C19	1.514 (6)	C46—C47	1.481 (5)
C15—C16	1.405 (5)	C47—C48	1.388 (5)
C15—H15	0.9500	C48—C61	1.399 (5)
C16—C17	1.481 (5)	C48—H48	0.9500
C17—C18	1.390 (5)	C49—H49A	0.9800
C18—C31	1.400 (5)	C49—H49B	0.9800
C18—H18	0.9500	C49—H49C	0.9800
C19—H19A	0.9800	C51—C52	1.399 (6)
C19—H19B	0.9800	C51—C56	1.408 (6)
C19—H19C	0.9800	C52—C53	1.385 (6)
C21—C22	1.399 (6)	C52—H52	0.9500
C21—C26	1.407 (6)	C53—C54	1.392 (7)
C22—C23	1.377 (6)	C53—H53	0.9500
C22—H22	0.9500	C54—C55	1.392 (6)
C23—C24	1.390 (6)	C54—C59	1.512 (6)
C23—H23	0.9500	C55—C56	1.399 (6)
C24—C25	1.394 (6)	C55—H55	0.9500
C24—C29	1.516 (6)	C56—C57	1.474 (5)
C25—C26	1.399 (6)	C57—C58	1.368 (5)
C25—H25	0.9500	C58—C61	1.400 (5)
C26—C27	1.482 (5)	C58—H58	0.9500
C27—C28	1.370 (6)	C59—H59A	0.9800
C28—C31	1.403 (5)	C59—H59B	0.9800
C28—H28	0.9500	C59—H59C	0.9800
C29—H29A	0.9800	C61—C62	1.479 (5)
C29—H29B	0.9800	C62—C63	1.389 (6)
C29—H29C	0.9800	C62—C67	1.400 (6)
C31—C32	1.487 (5)	C63—C64	1.365 (6)
C32—C33	1.388 (6)	C63—H63	0.9500
C32—C37	1.401 (6)	C64—C65	1.389 (6)
C33—C34	1.372 (6)	C64—H64	0.9500
C33—H33	0.9500	C65—C66	1.382 (7)
C34—C35	1.385 (6)	C65—H65	0.9500
C34—H34	0.9500	C66—C67	1.381 (6)
C35—C36	1.379 (6)	C66—H66	0.9500
C35—H35	0.9500	C67—H67	0.9500
H7—O1—H8	116 (6)	C36—C37—C32	120.5 (4)
Cl2—C1—Cl1	114.0 (6)	C36—C37—H37	119.7
Cl2—C1—H1A	108.7	C32—C37—H37	119.7
Cl1—C1—H1A	108.7	C57—N2—C47	124.2 (3)
Cl2—C1—H1B	108.7	C57—N2—H2	117.9
Cl1—C1—H1B	108.7	C47—N2—H2	117.9
H1A—C1—H1B	107.6	C41—O21—H5	113 (4)
C27—N1—C17	124.4 (3)	C51—O22—H6	117 (4)
C27—N1—H1	117.8	O21—C41—C42	119.8 (4)
C17—N1—H1	117.8	O21—C41—C46	119.5 (3)
C11—O11—H3	116 (4)	C42—C41—C46	120.7 (4)
C21—O12—H4	110 (3)	C43—C42—C41	120.2 (4)
O11—C11—C12	120.5 (4)	C43—C42—H42	119.9
O11—C11—C16	119.2 (3)	C41—C42—H42	119.9
C12—C11—C16	120.4 (4)	C42—C43—C44	121.3 (4)
C13—C12—C11	120.7 (4)	C42—C43—H43	119.3
C13—C12—H12	119.7	C44—C43—H43	119.3
C11—C12—H12	119.7	C45—C44—C43	117.7 (4)
C12—C13—C14	120.8 (4)	C45—C44—C49	122.0 (4)
C12—C13—H13	119.6	C43—C44—C49	120.4 (4)
C14—C13—H13	119.6	C44—C45—C46	123.2 (4)
C13—C14—C15	118.3 (4)	C44—C45—H45	118.4
C13—C14—C19	120.6 (4)	C46—C45—H45	118.4
C15—C14—C19	121.1 (4)	C41—C46—C45	116.9 (3)
C14—C15—C16	122.6 (4)	C41—C46—C47	123.4 (3)
C14—C15—H15	118.7	C45—C46—C47	119.7 (3)
C16—C15—H15	118.7	N2—C47—C48	116.9 (3)
C15—C16—C11	117.2 (3)	N2—C47—C46	118.5 (3)
C15—C16—C17	120.2 (3)	C48—C47—C46	124.5 (3)
C11—C16—C17	122.6 (3)	C47—C48—C61	121.4 (3)
N1—C17—C18	116.9 (3)	C47—C48—H48	119.3
N1—C17—C16	118.5 (3)	C61—C48—H48	119.3
C18—C17—C16	124.5 (3)	C44—C49—H49A	109.5
C17—C18—C31	121.3 (4)	C44—C49—H49B	109.5
C17—C18—H18	119.3	H49A—C49—H49B	109.5
C31—C18—H18	119.3	C44—C49—H49C	109.5
C14—C19—H19A	109.5	H49A—C49—H49C	109.5
C14—C19—H19B	109.5	H49B—C49—H49C	109.5
H19A—C19—H19B	109.5	O22—C51—C52	121.9 (4)
C14—C19—H19C	109.5	O22—C51—C56	118.2 (3)
H19A—C19—H19C	109.5	C52—C51—C56	119.9 (4)
H19B—C19—H19C	109.5	C53—C52—C51	119.4 (4)
O12—C21—C22	122.1 (4)	C53—C52—H52	120.3
O12—C21—C26	118.4 (3)	C51—C52—H52	120.3
C22—C21—C26	119.5 (4)	C52—C53—C54	122.4 (4)
C23—C22—C21	120.2 (4)	C52—C53—H53	118.8
C23—C22—H22	119.9	C54—C53—H53	118.8
C21—C22—H22	119.9	C53—C54—C55	117.5 (4)
C22—C23—C24	121.7 (4)	C53—C54—C59	122.0 (4)
C22—C23—H23	119.1	C55—C54—C59	120.6 (5)
C24—C23—H23	119.1	C54—C55—C56	122.2 (4)
C23—C24—C25	118.0 (4)	C54—C55—H55	118.9
C23—C24—C29	122.0 (4)	C56—C55—H55	118.9
C25—C24—C29	120.0 (4)	C55—C56—C51	118.7 (4)
C24—C25—C26	121.8 (4)	C55—C56—C57	118.9 (4)
C24—C25—H25	119.1	C51—C56—C57	122.3 (4)
C26—C25—H25	119.1	N2—C57—C58	118.8 (3)
C25—C26—C21	118.7 (4)	N2—C57—C56	118.9 (3)
C25—C26—C27	118.3 (4)	C58—C57—C56	122.3 (3)
C21—C26—C27	123.0 (3)	C57—C58—C61	120.6 (3)
N1—C27—C28	118.8 (4)	C57—C58—H58	119.7
N1—C27—C26	118.2 (3)	C61—C58—H58	119.7
C28—C27—C26	122.9 (3)	C54—C59—H59A	109.5
C27—C28—C31	120.5 (4)	C54—C59—H59B	109.5
C27—C28—H28	119.8	H59A—C59—H59B	109.5
C31—C28—H28	119.8	C54—C59—H59C	109.5
C24—C29—H29A	109.5	H59A—C59—H59C	109.5
C24—C29—H29B	109.5	H59B—C59—H59C	109.5
H29A—C29—H29B	109.5	C48—C61—C58	118.1 (3)
C24—C29—H29C	109.5	C48—C61—C62	121.0 (3)
H29A—C29—H29C	109.5	C58—C61—C62	120.9 (3)
H29B—C29—H29C	109.5	C63—C62—C67	117.6 (4)
C18—C31—C28	118.0 (4)	C63—C62—C61	122.3 (4)
C18—C31—C32	121.1 (4)	C67—C62—C61	120.1 (4)
C28—C31—C32	120.9 (3)	C64—C63—C62	121.8 (4)
C33—C32—C37	117.7 (4)	C64—C63—H63	119.1
C33—C32—C31	122.3 (4)	C62—C63—H63	119.1
C37—C32—C31	119.9 (4)	C63—C64—C65	120.1 (4)
C34—C33—C32	121.9 (4)	C63—C64—H64	120.0
C34—C33—H33	119.1	C65—C64—H64	120.0
C32—C33—H33	119.1	C66—C65—C64	119.5 (4)
C33—C34—C35	119.8 (4)	C66—C65—H65	120.2
C33—C34—H34	120.1	C64—C65—H65	120.2
C35—C34—H34	120.1	C67—C66—C65	120.1 (4)
C36—C35—C34	119.7 (4)	C67—C66—H66	120.0
C36—C35—H35	120.2	C65—C66—H66	120.0
C34—C35—H35	120.2	C66—C67—C62	121.0 (4)
C35—C36—C37	120.4 (4)	C66—C67—H67	119.5
C35—C36—H36	119.8	C62—C67—H67	119.5
C37—C36—H36	119.8
O11—C11—C12—C13	−177.9 (4)	O21—C41—C42—C43	−178.3 (4)
C16—C11—C12—C13	1.6 (6)	C46—C41—C42—C43	0.1 (6)
C11—C12—C13—C14	0.5 (6)	C41—C42—C43—C44	1.1 (6)
C12—C13—C14—C15	−2.1 (6)	C42—C43—C44—C45	−1.4 (6)
C12—C13—C14—C19	177.1 (4)	C42—C43—C44—C49	177.6 (4)
C13—C14—C15—C16	1.6 (6)	C43—C44—C45—C46	0.4 (6)
C19—C14—C15—C16	−177.6 (4)	C49—C44—C45—C46	−178.6 (4)
C14—C15—C16—C11	0.5 (6)	O21—C41—C46—C45	177.5 (3)
C14—C15—C16—C17	−178.5 (4)	C42—C41—C46—C45	−1.0 (6)
O11—C11—C16—C15	177.4 (3)	O21—C41—C46—C47	−3.9 (6)
C12—C11—C16—C15	−2.1 (5)	C42—C41—C46—C47	177.6 (4)
O11—C11—C16—C17	−3.6 (5)	C44—C45—C46—C41	0.8 (6)
C12—C11—C16—C17	176.9 (4)	C44—C45—C46—C47	−178.0 (4)
C27—N1—C17—C18	0.0 (5)	C57—N2—C47—C48	0.3 (5)
C27—N1—C17—C16	−178.2 (3)	C57—N2—C47—C46	−179.0 (3)
C15—C16—C17—N1	178.3 (3)	C41—C46—C47—N2	3.8 (5)
C11—C16—C17—N1	−0.6 (5)	C45—C46—C47—N2	−177.6 (3)
C15—C16—C17—C18	0.2 (6)	C41—C46—C47—C48	−175.5 (4)
C11—C16—C17—C18	−178.7 (4)	C45—C46—C47—C48	3.1 (6)
N1—C17—C18—C31	0.6 (5)	N2—C47—C48—C61	1.1 (6)
C16—C17—C18—C31	178.7 (4)	C46—C47—C48—C61	−179.6 (4)
O12—C21—C22—C23	−179.2 (4)	O22—C51—C52—C53	−180.0 (4)
C26—C21—C22—C23	2.3 (6)	C56—C51—C52—C53	2.1 (6)
C21—C22—C23—C24	−1.2 (6)	C51—C52—C53—C54	−0.6 (6)
C22—C23—C24—C25	−0.8 (6)	C52—C53—C54—C55	−0.4 (6)
C22—C23—C24—C29	178.1 (4)	C52—C53—C54—C59	−179.3 (4)
C23—C24—C25—C26	1.8 (6)	C53—C54—C55—C56	−0.2 (6)
C29—C24—C25—C26	−177.2 (4)	C59—C54—C55—C56	178.7 (4)
C24—C25—C26—C21	−0.7 (6)	C54—C55—C56—C51	1.7 (6)
C24—C25—C26—C27	179.2 (4)	C54—C55—C56—C57	−173.7 (4)
O12—C21—C26—C25	−179.9 (4)	O22—C51—C56—C55	179.4 (3)
C22—C21—C26—C25	−1.4 (6)	C52—C51—C56—C55	−2.6 (6)
O12—C21—C26—C27	0.2 (6)	O22—C51—C56—C57	−5.4 (6)
C22—C21—C26—C27	178.8 (4)	C52—C51—C56—C57	172.7 (4)
C17—N1—C27—C28	−1.8 (6)	C47—N2—C57—C58	−1.2 (6)
C17—N1—C27—C26	175.9 (3)	C47—N2—C57—C56	−179.9 (3)
C25—C26—C27—N1	−142.9 (4)	C55—C56—C57—N2	−147.1 (4)
C21—C26—C27—N1	36.9 (6)	C51—C56—C57—N2	37.7 (5)
C25—C26—C27—C28	34.7 (6)	C55—C56—C57—C58	34.3 (6)
C21—C26—C27—C28	−145.4 (4)	C51—C56—C57—C58	−141.0 (4)
N1—C27—C28—C31	2.8 (6)	N2—C57—C58—C61	0.7 (6)
C26—C27—C28—C31	−174.8 (4)	C56—C57—C58—C61	179.4 (4)
C17—C18—C31—C28	0.4 (6)	C47—C48—C61—C58	−1.5 (6)
C17—C18—C31—C32	−178.8 (4)	C47—C48—C61—C62	179.3 (4)
C27—C28—C31—C18	−2.2 (6)	C57—C58—C61—C48	0.6 (6)
C27—C28—C31—C32	177.0 (4)	C57—C58—C61—C62	179.8 (4)
C18—C31—C32—C33	−22.9 (6)	C48—C61—C62—C63	−25.3 (6)
C28—C31—C32—C33	157.9 (4)	C58—C61—C62—C63	155.5 (4)
C18—C31—C32—C37	154.1 (4)	C48—C61—C62—C67	154.4 (4)
C28—C31—C32—C37	−25.0 (6)	C58—C61—C62—C67	−24.8 (6)
C37—C32—C33—C34	−0.7 (6)	C67—C62—C63—C64	−0.4 (6)
C31—C32—C33—C34	176.5 (4)	C61—C62—C63—C64	179.3 (4)
C32—C33—C34—C35	0.1 (6)	C62—C63—C64—C65	−0.1 (7)
C33—C34—C35—C36	0.2 (7)	C63—C64—C65—C66	0.7 (7)
C34—C35—C36—C37	0.1 (7)	C64—C65—C66—C67	−0.9 (7)
C35—C36—C37—C32	−0.8 (7)	C65—C66—C67—C62	0.4 (7)
C33—C32—C37—C36	1.0 (6)	C63—C62—C67—C66	0.2 (6)
C31—C32—C37—C36	−176.2 (4)	C61—C62—C67—C66	−179.5 (4)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O11	0.88	1.82	2.547 (4)	138
N2—H2···O21	0.88	1.85	2.575 (4)	138
O11—H3···O1	0.79 (2)	1.80 (3)	2.578 (4)	167 (5)
O12—H4···Br1	0.79 (2)	2.43 (2)	3.219 (3)	175 (5)
O21—H5···Br1i	0.79 (2)	2.41 (2)	3.200 (3)	170 (5)
O22—H6···Br2	0.79 (2)	2.35 (2)	3.131 (3)	170 (5)
O1—H7···Br2ii	0.80 (2)	2.41 (2)	3.206 (3)	173 (5)
O1—H8···Br1	0.79 (2)	2.61 (3)	3.365 (3)	159 (5)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O11	0.88	1.82	2.547 (4)	138
N2—H2⋯O21	0.88	1.85	2.575 (4)	138
O11—H3⋯O1	0.79 (2)	1.80 (3)	2.578 (4)	167 (5)
O12—H4⋯Br1	0.79 (2)	2.43 (2)	3.219 (3)	175 (5)
O21—H5⋯Br1i	0.79 (2)	2.41 (2)	3.200 (3)	170 (5)
O22—H6⋯Br2	0.79 (2)	2.35 (2)	3.131 (3)	170 (5)
O1—H7⋯Br2ii	0.80 (2)	2.41 (2)	3.206 (3)	173 (5)
O1—H8⋯Br1	0.79 (2)	2.61 (3)	3.365 (3)	159 (5)

Symmetry codes: (i) ; (ii) .