1-[(4-Chloro­benzoyl)­methyl]-4-(N,N-di­methyl­amino)­pyridinium bromide sesquihydrate and 1-[(4-bromo­benzoyl)­methyl]-4-(N,N-di­methyl­amino)­pyridinium bromide sesquihydrate

The title compounds, C₁₅H₁₆ClN₂O⁺·Br^-·1.5H₂O and C₁₅H₁₆BrN₂O⁺·Br^-·1.5H₂O, are isomorphous. The benzene ring is oriented nearly normal to the pyridine ring in both compounds. The molecular packing is mainly influenced by intermolecular O-H...O and O-H...Br interactions, as well as weak intramolecular C-H...O interactions. The H₂OBr^- units form an extended water-bromide chain, with a bridging water mol­ecule on a twofold axis.

S1. Comment

Aminopyridines are key intermediates for the synthesis of important pharmaceuticals and agrochemicals. 4-Dimethylaminopyridine (DMAP) is an excellent catalyst for a variety of synthetic transformations under mild conditions, such as alkylations, acylations, silylations, esterifications, polymerizations and rearrangements (Prabakaran et al., 2001, and references therein). As part of our interest in the identification of bioactive compounds, we report here the structure determination of two of the derivatives of DMAP, the title compounds, (I) and (II). Compound (II) is isostructural with (I).

Perspective views of DMAP moieties of molecules of (I) and (II), with the atomic numbering schemes, are shown in Figs. 1 and 2, respectively. The corresponding bond lengths and angles in (I) and (II) are essentially equivalent and are comparable to those in a related structure (Prabakaran et al., 2001). The dimethylamine N atom is almost coplanar with the plane of pyridine ring in both (I) and (II) [2.9 (3)° in (I) and 2.6 (4)° in (II)]. The angles between the least-squares planes of the pyridine and phenyl rings are 81.01 (11)° in (I) and 78.64 (13)° in (II).

An interesting feature of the pyridinium systems is that they have a substantial degree of quinoidal character, since the C2—C3 and C5—C6 bond lengths in (I) and (II) [1.334 (4) and 1.339 (5) Å, and 1.339 (5) and 1.342 (5) Å] are significantly shorter than those observed for C3—C4 and C4—C5 [1.406 (4) and 1.413 (4) Å, and 1.407 (5) and 1.412 (5) Å]. The C4—N2 bond lengths in (I) and (II) are the same within experimental error [1.326 (4) and 1.327 (4) Å] and are intermediate between the C—N single- and double-bond distances [1.458 (4) and 1.326 (4) Å in (I), and 1.462 (5) and 1.327 (4) Å in (II)], indicating a significant conjugation. The sum of the bond angles at atoms N1 and N2 [359.7 (3) and 360.0 (3)°, and 359.7 (3) and 359.9 (3)°] for (I) and (II) are almost 360°, and hence there is little evidence for the presence of an sp³ lone pair.

Even after the substitution of halide atoms at the para position, the general conformation of the molecule has not been affected in (I) and (II). In both compounds, the asymmetric units contain two water molecules each, with the O atom of one of the water molecules lying on a special position (O2W, 0.0, 0.06, 1/4) on the twofold axis. In addition to the hydrogen-bonded clusters in the form of quadrilaterals as reported in the structure (Prabakaran et al., 2001), we observe additional hydrogen bonds connecting two quadrilaterals through the water molecule in the special position, running along the c axis as an infinite continuous chain. The (H₂O,Br)₂ clusters in (I) and (II) are sandwiched between organic molecules by C—H···Br⁻ hydrogen bonds and are illustrated in Figs. 3 and 4, respectively. The hydrogen-bonding geometry is given in Tables 1 and 2 for (I) and (II), respectively.

S2. Experimental

To a solution of p-chloro phenacyl bromide (0.85 g, 4 mmol) in dry acetone, DMAP (0.5 g, 41 mmol) was added. The mixture was refluxed for 30 min. After cooling, the resulting solid product was filtered off and washed with dry acetone to give (I) (m.p. 472–474 K), which was dried in a vacuum and recrystallized from ethanol. Compound (II) was prepared in an identical fashion but with p-bromo phenacyl bromide (0.85 g, 4 mmol) in dry acetone as the starting material (m.p. 501–504 K). The resulting solid, (II), was dried in a vaccum and recrystallized from ethanol.

S3. Refinement

Since the compounds are isostructural, (II) was refined with the coordinates of the dimethylamine pyridinium moiety of (I). The positions of the Br atoms and water molecules were determined from a difference Fourier map. The methyl H atoms were constrained to an ideal geometry (C—H = 0.96 Å), with U_iso(H) values of 1.5 U_eq(C). All remaining H atoms were placed in idealized positions (C—H = 0.93–0.97 Å) and were constrained to ride on their parent non-H atoms, with U_iso(H) values of 1.2 U_eq(C).

Computing details

For both compounds, data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: WinGX (Farrugia, 1999) and PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 and PARST (Nardelli, 1995).

Figures

Fig. 1: A view of the DMAP moiety of molecule (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are represented by circles of arbitrary radii. For clarity, atom Br1 and the water molecules have been omitted. Fig. 2: A view of the DMAP moiety of molecule (II), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level and the H atoms are represented by circles of arbitrary radii. For clarity, atom Br1 and the water molecules have been omitted. Fig. 3: A crystal packing diagram for (I), showing the presence of hydrogen-bonded (H2O,Br)2 clusters. Fig.4: A crystal packing diagram for (II), showing the presence of hydrogen-bonded (H2O,Br)2 clusters.

(I) 1-[(4-Chlorobenzoyl)methyl]-4-(N,N-dimethylamino)pyridinium bromide sesquihydrate

Crystal data

C15H16ClN2O^+·Br^−·1.5H2O	F(000) = 1560
Mr = 382.68	Dx = 1.475 Mg m^−3
Monoclinic, C2/c	Melting point: 473 K K
Hall symbol: -C 2yc	Mo Kα radiation, λ = 0.71073 Å
a = 20.661 (9) Å	Cell parameters from 873 reflections
b = 9.795 (4) Å	θ = 2.2–28.9°
c = 17.249 (7) Å	µ = 2.55 mm^−1
β = 99.182 (12)°	T = 298 K
V = 3446 (2) Å^3	Block, colorless
Z = 8	0.30 × 0.30 × 0.20 mm

Data collection

Bruker Smart 1K CCD diffractometer	3632 independent reflections
Radiation source: fine-focus sealed tube	2396 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.041
ω scans	θmax = 27.1°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Siemens, 1996)	h = −25→25
Tmin = 0.515, Tmax = 0.630	k = 0→12
13764 measured reflections	l = 0→21

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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.107	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	w = 1/[σ^2(Fo^2) + (0.0481P)^2 + 2.1711P] where P = (Fo^2 + 2Fc^2)/3
3632 reflections	(Δ/σ)max = 0.001
209 parameters	Δρmax = 0.33 e Å^−3
0 restraints	Δρmin = −0.39 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
Br1	0.131559 (17)	0.98279 (3)	0.021558 (19)	0.07272 (16)
Cl	0.31073 (6)	−0.01537 (10)	0.95388 (7)	0.0953 (3)
O1	0.59470 (14)	0.0002 (2)	0.8178 (2)	0.1040 (10)
O2W	0.0000	0.0606 (4)	0.2500	0.0810 (10)
H20W	0.001 (2)	0.009 (3)	0.213 (2)	0.090 (14)*
O3W	−0.0001 (2)	0.0729 (4)	0.89115 (18)	0.1011 (10)
H30W	0.029 (3)	0.039 (5)	0.926 (3)	0.122 (19)*
H31W	−0.031 (2)	0.069 (5)	0.906 (2)	0.095 (18)*
N1	0.65648 (13)	0.2379 (2)	0.82093 (15)	0.0673 (7)
N2	0.80471 (13)	0.2265 (3)	0.68744 (16)	0.0703 (7)
C1	0.60112 (17)	0.2267 (3)	0.8635 (2)	0.0739 (9)
H1A	0.5693	0.2972	0.8454	0.089*
H1B	0.6162	0.2410	0.9190	0.089*
C2	0.71617 (18)	0.1839 (3)	0.84964 (19)	0.0741 (9)
H2	0.7229	0.1477	0.9001	0.089*
C3	0.76544 (17)	0.1808 (3)	0.80820 (19)	0.0704 (9)
H3	0.8056	0.1438	0.8305	0.084*
C4	0.75758 (15)	0.2326 (3)	0.73126 (17)	0.0609 (8)
C5	0.69583 (17)	0.2918 (3)	0.70361 (19)	0.0717 (9)
H5	0.6883	0.3319	0.6541	0.086*
C6	0.64808 (18)	0.2907 (3)	0.7477 (2)	0.0763 (9)
H6	0.6076	0.3279	0.7271	0.092*
C7	0.86799 (17)	0.1633 (4)	0.7141 (2)	0.0979 (13)
H7A	0.9008	0.2330	0.7259	0.147*
H7B	0.8793	0.1050	0.6735	0.147*
H7C	0.8658	0.1103	0.7604	0.147*
C8	0.79628 (19)	0.2818 (4)	0.6079 (2)	0.0886 (11)
H8A	0.7763	0.2140	0.5715	0.133*
H8B	0.8383	0.3065	0.5951	0.133*
H8C	0.7687	0.3610	0.6048	0.133*
C9	0.56883 (16)	0.0887 (3)	0.85139 (19)	0.0682 (8)
C10	0.50638 (16)	0.0652 (3)	0.88073 (17)	0.0617 (8)
C11	0.47681 (19)	−0.0616 (4)	0.8711 (2)	0.0882 (11)
H11	0.4977	−0.1314	0.8481	0.106*
C12	0.4181 (2)	−0.0874 (4)	0.8944 (2)	0.0903 (11)
H12	0.3991	−0.1735	0.8876	0.108*
C13	0.38734 (19)	0.0157 (3)	0.92811 (18)	0.0699 (9)
C14	0.41627 (19)	0.1403 (3)	0.9413 (2)	0.0812 (11)
H14	0.3958	0.2084	0.9662	0.097*
C15	0.47567 (18)	0.1654 (3)	0.91781 (18)	0.0727 (9)
H15	0.4953	0.2505	0.9270	0.087*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Br1	0.0799 (3)	0.0676 (2)	0.0650 (2)	−0.00015 (16)	−0.00562 (16)	−0.00631 (15)
Cl	0.1196 (8)	0.0848 (6)	0.0890 (7)	−0.0048 (5)	0.0398 (6)	0.0005 (5)
O1	0.0833 (18)	0.0803 (17)	0.148 (3)	0.0042 (13)	0.0169 (18)	−0.0512 (16)
O2W	0.085 (2)	0.067 (2)	0.089 (3)	0.000	0.008 (2)	0.000
O3W	0.099 (2)	0.138 (3)	0.0667 (18)	0.019 (2)	0.0135 (18)	0.0154 (17)
N1	0.0838 (19)	0.0570 (15)	0.0606 (16)	0.0093 (13)	0.0100 (14)	0.0001 (12)
N2	0.0754 (18)	0.0637 (16)	0.0705 (17)	0.0051 (13)	0.0076 (14)	0.0071 (13)
C1	0.094 (2)	0.0605 (19)	0.070 (2)	0.0048 (17)	0.0200 (18)	−0.0076 (16)
C2	0.090 (2)	0.075 (2)	0.0517 (18)	−0.0017 (19)	−0.0029 (18)	0.0114 (16)
C3	0.069 (2)	0.073 (2)	0.063 (2)	0.0018 (16)	−0.0071 (16)	0.0178 (16)
C4	0.072 (2)	0.0502 (16)	0.0569 (19)	0.0040 (15)	0.0000 (16)	0.0013 (13)
C5	0.085 (2)	0.072 (2)	0.0546 (18)	0.0184 (18)	0.0032 (17)	0.0130 (15)
C6	0.087 (2)	0.069 (2)	0.070 (2)	0.0262 (18)	0.0018 (19)	0.0091 (16)
C7	0.074 (2)	0.095 (3)	0.127 (4)	0.016 (2)	0.023 (2)	0.025 (3)
C8	0.103 (3)	0.097 (3)	0.068 (2)	0.000 (2)	0.020 (2)	0.009 (2)
C9	0.077 (2)	0.0560 (18)	0.066 (2)	0.0125 (16)	−0.0068 (16)	−0.0127 (15)
C10	0.074 (2)	0.0505 (16)	0.0558 (17)	0.0105 (15)	−0.0039 (15)	−0.0053 (13)
C11	0.075 (2)	0.063 (2)	0.124 (3)	0.0049 (18)	0.009 (2)	−0.033 (2)
C12	0.094 (3)	0.062 (2)	0.111 (3)	−0.001 (2)	0.006 (2)	−0.023 (2)
C13	0.095 (2)	0.065 (2)	0.0497 (17)	0.0084 (17)	0.0120 (16)	0.0042 (14)
C14	0.123 (3)	0.0524 (19)	0.076 (2)	0.0090 (19)	0.041 (2)	−0.0059 (16)
C15	0.106 (3)	0.0471 (17)	0.069 (2)	0.0014 (17)	0.0256 (19)	−0.0044 (15)

Geometric parameters (Å, º)

Cl—C13	1.738 (4)	C5—H5	0.9300
O1—C9	1.213 (4)	C6—H6	0.9300
O2W—H20W	0.82 (3)	C7—H7A	0.9600
O3W—H30W	0.84 (6)	C7—H7B	0.9600
O3W—H31W	0.73 (4)	C7—H7C	0.9600
N1—C6	1.350 (4)	C8—H8A	0.9600
N1—C2	1.361 (4)	C8—H8B	0.9600
N1—C1	1.458 (4)	C8—H8C	0.9600
N2—C4	1.326 (4)	C9—C10	1.477 (5)
N2—C7	1.453 (4)	C10—C15	1.380 (4)
N2—C8	1.459 (4)	C10—C11	1.383 (5)
C1—C9	1.508 (4)	C11—C12	1.362 (5)
C1—H1A	0.9700	C11—H11	0.9300
C1—H1B	0.9700	C12—C13	1.370 (5)
C2—C3	1.334 (4)	C12—H12	0.9300
C2—H2	0.9300	C13—C14	1.362 (5)
C3—C4	1.406 (4)	C14—C15	1.375 (5)
C3—H3	0.9300	C14—H14	0.9300
C4—C5	1.413 (4)	C15—H15	0.9300
C5—C6	1.339 (5)
H30W—O3W—H31W	107 (5)	N2—C7—H7C	109.5
C6—N1—C2	117.6 (3)	H7A—C7—H7C	109.5
C6—N1—C1	120.4 (3)	H7B—C7—H7C	109.5
C2—N1—C1	121.7 (3)	N2—C8—H8A	109.5
C4—N2—C7	123.0 (3)	N2—C8—H8B	109.5
C4—N2—C8	122.1 (3)	H8A—C8—H8B	109.5
C7—N2—C8	114.9 (3)	N2—C8—H8C	109.5
N1—C1—C9	111.3 (3)	H8A—C8—H8C	109.5
N1—C1—H1A	109.4	H8B—C8—H8C	109.5
C9—C1—H1A	109.4	O1—C9—C10	121.9 (3)
N1—C1—H1B	109.4	O1—C9—C1	119.2 (3)
C9—C1—H1B	109.4	C10—C9—C1	118.9 (3)
H1A—C1—H1B	108.0	C15—C10—C11	117.9 (3)
C3—C2—N1	122.6 (3)	C15—C10—C9	122.7 (3)
C3—C2—H2	118.7	C11—C10—C9	119.5 (3)
N1—C2—H2	118.7	C12—C11—C10	121.9 (3)
C2—C3—C4	121.0 (3)	C12—C11—H11	119.1
C2—C3—H3	119.5	C10—C11—H11	119.1
C4—C3—H3	119.5	C11—C12—C13	118.9 (3)
N2—C4—C3	122.5 (3)	C11—C12—H12	120.5
N2—C4—C5	122.1 (3)	C13—C12—H12	120.5
C3—C4—C5	115.4 (3)	C14—C13—C12	120.7 (4)
C6—C5—C4	120.8 (3)	C14—C13—Cl	120.5 (3)
C6—C5—H5	119.6	C12—C13—Cl	118.8 (3)
C4—C5—H5	119.6	C13—C14—C15	119.9 (3)
C5—C6—N1	122.6 (3)	C13—C14—H14	120.0
C5—C6—H6	118.7	C15—C14—H14	120.0
N1—C6—H6	118.7	C14—C15—C10	120.5 (3)
N2—C7—H7A	109.5	C14—C15—H15	119.7
N2—C7—H7B	109.5	C10—C15—H15	119.7
H7A—C7—H7B	109.5
C6—N1—C1—C9	93.1 (3)	N1—C1—C9—O1	8.3 (5)
C2—N1—C1—C9	−80.2 (4)	N1—C1—C9—C10	−171.5 (3)
C6—N1—C2—C3	−0.5 (5)	O1—C9—C10—C15	−178.8 (3)
C1—N1—C2—C3	173.0 (3)	C1—C9—C10—C15	1.0 (5)
N1—C2—C3—C4	−0.8 (5)	O1—C9—C10—C11	1.2 (5)
C7—N2—C4—C3	1.4 (5)	C1—C9—C10—C11	−179.0 (3)
C8—N2—C4—C3	−179.4 (3)	C15—C10—C11—C12	2.4 (6)
C7—N2—C4—C5	−178.6 (3)	C9—C10—C11—C12	−177.5 (3)
C8—N2—C4—C5	0.6 (5)	C10—C11—C12—C13	0.2 (6)
C2—C3—C4—N2	−177.4 (3)	C11—C12—C13—C14	−2.9 (6)
C2—C3—C4—C5	2.5 (5)	C11—C12—C13—Cl	177.2 (3)
N2—C4—C5—C6	176.8 (3)	C12—C13—C14—C15	2.7 (5)
C3—C4—C5—C6	−3.2 (5)	Cl—C13—C14—C15	−177.4 (3)
C4—C5—C6—N1	2.1 (5)	C13—C14—C15—C10	0.1 (5)
C2—N1—C6—C5	−0.2 (5)	C11—C10—C15—C14	−2.6 (5)
C1—N1—C6—C5	−173.8 (3)	C9—C10—C15—C14	177.4 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2W—H20W···O3W^i	0.82 (3)	1.96 (4)	2.764 (4)	166 (4)
O3W—H30W···Br1^ii	0.84 (6)	2.54 (6)	3.360 (4)	167 (4)
O3W—H31W···Br1^iii	0.73 (4)	2.63 (4)	3.353 (4)	168 (5)
C8—H8A···Cl^iv	0.96	2.87	3.707 (4)	147
C1—H1A···O2W^v	0.97	2.44	3.351 (4)	157
C6—H6···O2W^v	0.93	2.56	3.394 (4)	149

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

(II) 1-[(4-Bromobenzoyl)methyl]-4-(N,N-dimethylamino)pyridinium bromide sesquihydrate

Crystal data

C15H16BrN2O^+·Br^−·1.5H2O	F(000) = 1704
Mr = 427.14	Dx = 1.622 Mg m^−3
Monoclinic, C2/c	Melting point: 512.5 K K
Hall symbol: -C 2yc	Mo Kα radiation, λ = 0.71073 Å
a = 20.403 (6) Å	Cell parameters from 873 reflections
b = 10.022 (3) Å	θ = 2.3–27.4°
c = 17.386 (4) Å	µ = 4.64 mm^−1
β = 100.182 (8)°	T = 298 K
V = 3499.0 (17) Å^3	Block, colourless
Z = 8	0.40 × 0.30 × 0.30 mm

Data collection

Bruker Smart 1K CCD diffractometer	3587 independent reflections
Radiation source: fine-focus sealed tube	2391 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.045
ω scans	θmax = 26.4°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Siemens, 1996)	h = −25→25
Tmin = 0.258, Tmax = 0.337	k = 0→12
20471 measured reflections	l = 0→21

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)] = 0.038	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.111	w = 1/[σ^2(Fo^2) + (0.0507P)^2 + 3.7037P] where P = (Fo^2 + 2Fc^2)/3
S = 1.02	(Δ/σ)max = 0.001
3587 reflections	Δρmax = 0.58 e Å^−3
210 parameters	Δρmin = −0.79 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: 0.00162 (14)

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
Br1	0.13308 (2)	0.98601 (4)	0.01869 (2)	0.07221 (18)
Br2	0.30172 (3)	−0.01585 (5)	0.94999 (3)	0.0875 (2)
O1	0.59599 (16)	0.0066 (3)	0.8152 (2)	0.1054 (12)
O2W	0.0000	0.0624 (5)	0.2500	0.0847 (12)
H20W	−0.006 (3)	0.016 (4)	0.289 (3)	0.097 (17)*
O3W	0.5039 (2)	0.4293 (5)	0.1104 (2)	0.1077 (13)
H30W	0.478 (3)	0.450 (5)	0.078 (3)	0.095 (18)*
H31W	0.539 (3)	0.448 (6)	0.089 (3)	0.15 (2)*
N1	0.65949 (16)	0.2382 (3)	0.82071 (17)	0.0689 (8)
N2	0.80759 (15)	0.2303 (3)	0.68656 (18)	0.0694 (8)
C1	0.6039 (2)	0.2262 (4)	0.8631 (2)	0.0744 (11)
H1A	0.5716	0.2958	0.8459	0.089*
H1B	0.6202	0.2384	0.9185	0.089*
C2	0.7200 (2)	0.1811 (4)	0.8474 (2)	0.0709 (10)
H2	0.7275	0.1428	0.8969	0.085*
C3	0.76901 (19)	0.1778 (4)	0.8054 (2)	0.0670 (9)
H3	0.8092	0.1371	0.8262	0.080*
C4	0.76062 (18)	0.2349 (3)	0.7304 (2)	0.0602 (9)
C5	0.6984 (2)	0.2964 (4)	0.7046 (2)	0.0719 (10)
H5	0.6904	0.3390	0.6563	0.086*
C6	0.6506 (2)	0.2946 (4)	0.7486 (2)	0.0766 (11)
H6	0.6097	0.3335	0.7290	0.092*
C7	0.8713 (2)	0.1639 (5)	0.7120 (3)	0.0934 (14)
H7A	0.9044	0.2037	0.6864	0.140*
H7B	0.8670	0.0709	0.6988	0.140*
H7C	0.8843	0.1733	0.7675	0.140*
C8	0.7986 (2)	0.2906 (4)	0.6089 (2)	0.0864 (12)
H8A	0.7789	0.2266	0.5706	0.130*
H8B	0.8410	0.3180	0.5978	0.130*
H8C	0.7699	0.3669	0.6072	0.130*
C9	0.57064 (19)	0.0916 (4)	0.8496 (2)	0.0693 (10)
C10	0.50795 (19)	0.0681 (4)	0.8791 (2)	0.0636 (9)
C11	0.4776 (2)	−0.0563 (4)	0.8692 (3)	0.0913 (14)
H11	0.4985	−0.1245	0.8465	0.110*
C12	0.4185 (2)	−0.0817 (4)	0.8914 (3)	0.0895 (13)
H12	0.3994	−0.1661	0.8841	0.107*
C13	0.3873 (2)	0.0173 (4)	0.9243 (2)	0.0675 (10)
C14	0.4164 (2)	0.1402 (4)	0.9384 (2)	0.0807 (12)
H14	0.3955	0.2064	0.9627	0.097*
C15	0.4764 (2)	0.1647 (4)	0.9163 (2)	0.0737 (11)
H15	0.4964	0.2478	0.9265	0.088*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Br1	0.0722 (3)	0.0767 (3)	0.0633 (3)	−0.00071 (19)	−0.00033 (18)	−0.00665 (18)
Br2	0.1099 (4)	0.0803 (3)	0.0785 (3)	−0.0046 (2)	0.0336 (3)	−0.0022 (2)
O1	0.082 (2)	0.084 (2)	0.151 (3)	0.0041 (15)	0.024 (2)	−0.0548 (19)
O2W	0.077 (3)	0.071 (3)	0.103 (4)	0.000	0.007 (3)	0.000
O3W	0.093 (3)	0.165 (4)	0.065 (2)	0.017 (3)	0.015 (2)	0.022 (2)
N1	0.084 (2)	0.0597 (19)	0.0623 (19)	0.0081 (16)	0.0118 (16)	−0.0001 (15)
N2	0.074 (2)	0.066 (2)	0.0671 (19)	0.0045 (16)	0.0073 (16)	0.0070 (15)
C1	0.092 (3)	0.066 (2)	0.067 (2)	0.007 (2)	0.021 (2)	−0.0098 (19)
C2	0.084 (3)	0.067 (2)	0.055 (2)	0.004 (2)	−0.007 (2)	0.0071 (18)
C3	0.066 (2)	0.071 (2)	0.061 (2)	0.0062 (18)	0.0013 (18)	0.0110 (18)
C4	0.072 (2)	0.0498 (19)	0.055 (2)	0.0076 (17)	0.0019 (17)	0.0016 (15)
C5	0.085 (3)	0.071 (2)	0.058 (2)	0.020 (2)	0.007 (2)	0.0156 (18)
C6	0.088 (3)	0.067 (2)	0.072 (3)	0.026 (2)	0.006 (2)	0.011 (2)
C7	0.077 (3)	0.096 (3)	0.110 (3)	0.019 (2)	0.022 (2)	0.021 (3)
C8	0.104 (3)	0.087 (3)	0.069 (3)	−0.001 (2)	0.017 (2)	0.013 (2)
C9	0.073 (2)	0.065 (2)	0.064 (2)	0.012 (2)	−0.0055 (18)	−0.0126 (18)
C10	0.075 (2)	0.054 (2)	0.057 (2)	0.0116 (18)	−0.0026 (17)	−0.0045 (16)
C11	0.077 (3)	0.067 (3)	0.125 (4)	0.007 (2)	0.004 (3)	−0.035 (3)
C12	0.078 (3)	0.070 (3)	0.118 (4)	−0.001 (2)	0.010 (3)	−0.029 (3)
C13	0.088 (3)	0.065 (2)	0.0488 (18)	0.0106 (19)	0.0101 (17)	0.0014 (16)
C14	0.118 (4)	0.060 (2)	0.073 (3)	0.001 (2)	0.043 (2)	−0.0084 (19)
C15	0.105 (3)	0.050 (2)	0.069 (2)	−0.002 (2)	0.026 (2)	−0.0077 (18)

Geometric parameters (Å, º)

Br2—C13	1.907 (4)	C5—H5	0.9300
O1—C9	1.209 (4)	C6—H6	0.9300
O2W—H20W	0.85 (4)	C7—H7A	0.9600
O3W—H30W	0.74 (5)	C7—H7B	0.9600
O3W—H31W	0.89 (6)	C7—H7C	0.9600
N1—C6	1.357 (5)	C8—H8A	0.9600
N1—C2	1.365 (4)	C8—H8B	0.9600
N1—C1	1.462 (5)	C8—H8C	0.9600
N2—C4	1.327 (4)	C9—C10	1.479 (5)
N2—C7	1.457 (5)	C10—C15	1.385 (5)
N2—C8	1.461 (5)	C10—C11	1.389 (6)
C1—C9	1.510 (5)	C11—C12	1.353 (6)
C1—H1A	0.9700	C11—H11	0.9300
C1—H1B	0.9700	C12—C13	1.359 (5)
C2—C3	1.339 (5)	C12—H12	0.9300
C2—H2	0.9300	C13—C14	1.370 (5)
C3—C4	1.407 (5)	C14—C15	1.369 (5)
C3—H3	0.9300	C14—H14	0.9300
C4—C5	1.412 (5)	C15—H15	0.9300
C5—C6	1.342 (5)
H30W—O3W—H31W	99 (5)	N2—C7—H7C	109.5
C6—N1—C2	117.0 (3)	H7A—C7—H7C	109.5
C6—N1—C1	120.7 (3)	H7B—C7—H7C	109.5
C2—N1—C1	122.0 (3)	N2—C8—H8A	109.5
C4—N2—C7	122.5 (3)	N2—C8—H8B	109.5
C4—N2—C8	122.1 (3)	H8A—C8—H8B	109.5
C7—N2—C8	115.4 (3)	N2—C8—H8C	109.5
N1—C1—C9	111.3 (3)	H8A—C8—H8C	109.5
N1—C1—H1A	109.4	H8B—C8—H8C	109.5
C9—C1—H1A	109.4	O1—C9—C10	122.1 (4)
N1—C1—H1B	109.4	O1—C9—C1	119.1 (4)
C9—C1—H1B	109.4	C10—C9—C1	118.8 (3)
H1A—C1—H1B	108.0	C15—C10—C11	116.9 (4)
C3—C2—N1	122.9 (3)	C15—C10—C9	123.5 (4)
C3—C2—H2	118.6	C11—C10—C9	119.6 (3)
N1—C2—H2	118.6	C12—C11—C10	122.3 (4)
C2—C3—C4	121.0 (3)	C12—C11—H11	118.9
C2—C3—H3	119.5	C10—C11—H11	118.9
C4—C3—H3	119.5	C11—C12—C13	119.3 (4)
N2—C4—C3	122.5 (3)	C11—C12—H12	120.3
N2—C4—C5	122.2 (3)	C13—C12—H12	120.3
C3—C4—C5	115.3 (3)	C12—C13—C14	120.8 (4)
C6—C5—C4	121.1 (3)	C12—C13—Br2	119.2 (3)
C6—C5—H5	119.5	C14—C13—Br2	120.0 (3)
C4—C5—H5	119.5	C15—C14—C13	119.5 (4)
C5—C6—N1	122.7 (4)	C15—C14—H14	120.3
C5—C6—H6	118.7	C13—C14—H14	120.3
N1—C6—H6	118.7	C14—C15—C10	121.2 (4)
N2—C7—H7A	109.5	C14—C15—H15	119.4
N2—C7—H7B	109.5	C10—C15—H15	119.4
H7A—C7—H7B	109.5
C6—N1—C1—C9	94.3 (4)	N1—C1—C9—O1	8.3 (5)
C2—N1—C1—C9	−78.4 (4)	N1—C1—C9—C10	−171.9 (3)
C6—N1—C2—C3	−0.8 (6)	O1—C9—C10—C15	−177.7 (4)
C1—N1—C2—C3	172.2 (4)	C1—C9—C10—C15	2.5 (5)
N1—C2—C3—C4	0.4 (6)	O1—C9—C10—C11	1.6 (6)
C7—N2—C4—C3	1.0 (6)	C1—C9—C10—C11	−178.2 (4)
C8—N2—C4—C3	−179.6 (4)	C15—C10—C11—C12	2.8 (6)
C7—N2—C4—C5	−178.3 (4)	C9—C10—C11—C12	−176.5 (4)
C8—N2—C4—C5	1.0 (6)	C10—C11—C12—C13	0.2 (7)
C2—C3—C4—N2	−178.2 (4)	C11—C12—C13—C14	−2.9 (7)
C2—C3—C4—C5	1.1 (5)	C11—C12—C13—Br2	176.4 (4)
N2—C4—C5—C6	177.0 (4)	C12—C13—C14—C15	2.4 (6)
C3—C4—C5—C6	−2.4 (6)	Br2—C13—C14—C15	−176.9 (3)
C4—C5—C6—N1	2.2 (7)	C13—C14—C15—C10	0.8 (6)
C2—N1—C6—C5	−0.5 (6)	C11—C10—C15—C14	−3.3 (6)
C1—N1—C6—C5	−173.6 (4)	C9—C10—C15—C14	176.0 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2W—H20W···O3W^i	0.85 (4)	1.95 (4)	2.784 (5)	167 (5)
O3W—H30W···Br1^ii	0.74 (5)	2.65 (5)	3.369 (4)	168 (5)
O3W—H31W···Br1^iii	0.89 (6)	2.48 (6)	3.360 (4)	174 (5)
C8—H8A···Br2^iv	0.96	2.92	3.732 (5)	143
C1—H1A···O2W^v	0.97	2.46	3.373 (5)	156
C6—H6···O2W^v	0.93	2.55	3.394 (5)	151

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