Crystal structure of 3-mesityl-1-[(pyridin-2-yl)meth­yl]-3,4,5,6-tetra­hydro­pyrim­idin-1-ium bromide monohydrate

Quo, Q.; Yang, L.; Mao, P.; Xiao, Y.; Yuan, J.

doi:10.1107/S2056989015003989

Crystal structure of 3-mesityl-1-[(pyridin-2-yl)methyl]-3,4,5,6-tetrahydropyrimidin-1-ium bromide monohydrate

Q. Quo, L. Yang, P. Mao, Y. Xiao and J. Yuan

In the title hydrated salt, C₁₉H₂₄N₃⁺·Br⁻·H₂O, the values of the N—C bond lengths within the tetrahydropyrimidinium ring indicate delocalization of the N=C double bond. In the cation, the dihedral angle formed by the pyridine and benzene rings is 14.97 (12)°. In the crystal, ions and water molecules are linked by O—H

Br, O—H

N, C—H

Br and C—H

O hydrogen bonds into chains running parallel to the b axis.

Keywords: crystal structure; NHC precursor; tetrahydropyrimidinium; hydrogen bonding.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S2056989015003989/rz5148sup1.cif Contains datablocks I, global
	Structure factor file (CIF format) https://doi.org/10.1107/S2056989015003989/rz5148Isup2.hkl Contains datablock I
	Chemical Markup Language (CML) file https://doi.org/10.1107/S2056989015003989/rz5148Isup3.cml Supplementary material

CCDC reference: 1051286

checkCIF report

Key indicators

Single-crystal X-ray study
T = 291 K
Mean (C-C) = 0.006 Å
R factor = 0.051
wR factor = 0.134
Data-to-parameter ratio = 17.5

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT906_ALERT_3_C Large K value in the Analysis of Variance ......      2.599 Check
PLAT910_ALERT_3_C Missing # of FCF Reflection(s) Below Th(Min) ...          6 Report

Alert level G
PLAT002_ALERT_2_G Number of Distance or Angle Restraints on AtSite          2 Note
PLAT005_ALERT_5_G No _iucr_refine_instructions_details  in the CIF     Please Do !
PLAT007_ALERT_5_G Number of Unrefined Donor-H Atoms ..............          1 Report
PLAT860_ALERT_3_G Number of Least-Squares Restraints .............          1 Note

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   2 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   4 ALERT level G = General information/check it is not something unexpected

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   3 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion
   2 ALERT type 5 Informative message, check

Comment top

N-Heterocyclic carbenes (NHCs) have been widely used as ancillary ligands for the preparation of transition-metal based catalysts (Hopkinson et al., 2014). Chelating NHC metal complexes have attracted particular research interest due to their enhanced stability and modular variability (Mata et al., 2007). Most of the reported chelating NHC metal complexes contain NHC ligands based on imidazole-derived five-membered heterocyclic rings. Ring-expanded NHCs based on six-, seven-, or eight-membered heterocyclic rings possessing enhanced σ-donor ability and easy modular variability began to attract extensive attention in recent years (Dunsford & Cavell, 2014). It would be of interest to explore whether the introduction of ring expanded NHCs to a chelating framework will result in new chelating complexes displaying novel reactivity and enhanced catalytic activities. To the best of our knowledge, no report on chelating NHC metal complexes has been presented. Following our interest in the development of ring-expanded NHCs based on substituted 1,4,5,6-tetrahydropyrimidine and their metal complexes (Mao et al., 2012), and with the intention of synthesizing chelating ring-expanded NHC metal complexes, we synthesized the chelating NHC precursor, 3-methyl-1-(pyridin-2-ylmethyl)-3,4,5,6-tetrahydropyrimidin-1-ium bromide and determined the structure of its monohydrate derivative. Research on the synthesis of carbene-metal complexes containing this ligand is currently in progress.

The molecular structure of the title compound is shown in Figure 1. As expected, the values of the bond distances within the pyrimidinyl ring indicate delocalization of the N═C bond that extends from N2 to N3 through C10, resulting in the increased acidity of the proton on C10 and convenient formation of a carbene functionality. In the cation, the benzene and pyridine rings form a dihedral angle of 14.97 (12)°. In the crystal structure, ions and water molecules are linked by O—H···N, O—H···Br, C—H···Br and C—H···O hydrogen bonds (Table 1) forming chains parallel to the b axis.

Related literature top

For background on the synthesis and properties of N-heterocyclic carbenes, see: Hopkinson et al. (2014); Mata et al. (2007); Dunsford & Cavell (2014); Mao et al. (2012).

Experimental top

A methanol solution (30 ml) of N-mesitylpropane-1,3-diamine (15 mmol, 2.88 g) was added dropwise to a methanol solution (30 ml) of pyridine-2-formaldehyde (15 mmol, 1.61 g) and the mixture was stirred at room temperature for 5 h. Infrared detection showed the disappearance of the carbonyl group. The mixture was then put into an ice-bath, and NaBH₄ (120 mmol, 4.54 g) was added portion-wise for 1 h, before being warmed up to room temperature and then heated to 70 °C overnight. The solvent was evaporated and the residue was poured into a mixture of water (20 ml) and CH₂Cl₂ (20 ml). The resulting suspension liquid was filtered and the filtrate was extracted by CH₂Cl₂ (10 ml) for 3 times. The combined organic phase was evaporated and the residue obtained was dissolved in methanol (10 ml) for the following reaction directly. The solution was then treated with aqueous HCHO solution (36.5%, 15 mmol). The mixture was stirred at room temperature for 6 h before being evaporated. Purification of the residue by flash chromatography (silica, pentane/CH₂Cl₂/Et₃N = 8/1/0.05, v/v/v) afforded the pure hexahydropyrimidine.

Hexahydropyrimidine (5 mmol, 1.48 g) was dissolved in DME (20 ml). NBS (5 mmol, 0.89 g) was added portion-wise and the resulting mixture was stirred at room temperature for 3 h, during which time a white precipitate formed. The precipitate was filtered and washed with DME. Crystallization of the precipitate from CH₂Cl₂/diethyl ether (1:1 v/v) afforded the title product as colourless crystals.

Structure description top

For background on the synthesis and properties of N-heterocyclic carbenes, see: Hopkinson et al. (2014); Mata et al. (2007); Dunsford & Cavell (2014); Mao et al. (2012).

Computing details top

Data collection: CrysAlis PRO (Agilent, 2011); cell refinement: CrysAlis PRO (Agilent, 2011); data reduction: CrysAlis PRO (Agilent, 2011); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

Figures top

Fig. 1. The molecular structure of the title compound showing 50% probability displacement ellipsoids.

3-Mesityl-1-[(pyridin-2-yl)methyl]-3,4,5,6-tetrahydropyrimidin-1-ium bromide monohydrate top

Crystal data top

C₁₉H₂₄N₃⁺·Br⁻·H₂O	D_x = 1.341 Mg m⁻³
M_r = 392.34	Mo Kα radiation, λ = 0.7107 Å
Orthorhombic, Pbca	Cell parameters from 1997 reflections
a = 15.5868 (5) Å	θ = 3.5–23.8°
b = 14.6323 (4) Å	µ = 2.13 mm⁻¹
c = 17.0439 (6) Å	T = 291 K
V = 3887.2 (2) Å³	Block, colourless
Z = 8	0.3 × 0.28 × 0.26 mm
F(000) = 1632

Data collection top

Agilent Xcalibur (Eos, Gemini) diffractometer	3969 independent reflections
Radiation source: Enhance (Mo) X-ray Source	2522 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.031
Detector resolution: 16.2312 pixels mm^-1	θ_max = 26.4°, θ_min = 3.0°
ω scans	h = −10→19
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	k = −17→18
T_min = 0.910, T_max = 1.000	l = −12→21
10196 measured reflections

Refinement top

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: inferred from neighbouring sites
wR(F²) = 0.134	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ²(F_o²) + (0.053P)² + 3.4187P] where P = (F_o² + 2F_c²)/3
3969 reflections	(Δ/σ)_max < 0.001
227 parameters	Δρ_max = 0.83 e Å⁻³
1 restraint	Δρ_min = −0.81 e Å⁻³

Crystal data top

C₁₉H₂₄N₃⁺·Br⁻·H₂O	V = 3887.2 (2) Å³
M_r = 392.34	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 15.5868 (5) Å	µ = 2.13 mm⁻¹
b = 14.6323 (4) Å	T = 291 K
c = 17.0439 (6) Å	0.3 × 0.28 × 0.26 mm

Data collection top

Agilent Xcalibur (Eos, Gemini) diffractometer	3969 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	2522 reflections with I > 2σ(I)
T_min = 0.910, T_max = 1.000	R_int = 0.031
10196 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.051	1 restraint
wR(F²) = 0.134	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	Δρ_max = 0.83 e Å⁻³
3969 reflections	Δρ_min = −0.81 e Å⁻³
227 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
Br1	0.26231 (3)	0.64141 (3)	0.81482 (3)	0.06536 (19)
O1	0.3743 (3)	0.6154 (2)	0.6526 (2)	0.0809 (10)
H1A	0.3514	0.6282	0.6965	0.121*
H1B	0.400 (4)	0.557 (2)	0.655 (4)	0.16 (3)*
N1	0.4370 (2)	0.4358 (2)	0.68596 (18)	0.0522 (8)
N2	0.25056 (17)	0.39948 (18)	0.67358 (16)	0.0366 (7)
N3	0.17792 (18)	0.48218 (18)	0.57935 (16)	0.0388 (7)
C1	0.5213 (3)	0.4180 (4)	0.6729 (3)	0.0662 (12)
H1	0.5530	0.4597	0.6437	0.079*
C2	0.5614 (3)	0.3423 (4)	0.7005 (3)	0.0711 (14)
H2	0.6191	0.3325	0.6894	0.085*
C3	0.5176 (3)	0.2814 (4)	0.7439 (3)	0.0701 (13)
H3	0.5445	0.2294	0.7634	0.084*
C4	0.4320 (2)	0.2977 (3)	0.7589 (2)	0.0543 (10)
H4	0.4000	0.2566	0.7885	0.065*
C5	0.3947 (2)	0.3756 (2)	0.7295 (2)	0.0402 (8)
C6	0.3017 (2)	0.3970 (2)	0.7458 (2)	0.0398 (8)
H6A	0.2783	0.3510	0.7808	0.048*
H6B	0.2977	0.4557	0.7720	0.048*
C7	0.2405 (2)	0.3121 (2)	0.6312 (2)	0.0515 (10)
H7A	0.2329	0.2627	0.6686	0.062*
H7B	0.2917	0.2997	0.6007	0.062*
C8	0.1647 (3)	0.3168 (3)	0.5782 (3)	0.0603 (11)
H8A	0.1651	0.2641	0.5437	0.072*
H8B	0.1128	0.3141	0.6095	0.072*
C9	0.1631 (3)	0.4013 (2)	0.5297 (2)	0.0590 (11)
H9A	0.2072	0.3978	0.4897	0.071*
H9B	0.1080	0.4067	0.5038	0.071*
C10	0.21877 (19)	0.4758 (2)	0.64654 (18)	0.0331 (7)
H10	0.2254	0.5285	0.6765	0.040*
C11	0.1455 (2)	0.5698 (2)	0.55251 (19)	0.0374 (8)
C12	0.0677 (2)	0.6013 (3)	0.5810 (2)	0.0464 (9)
C13	0.0378 (2)	0.6844 (3)	0.5527 (2)	0.0513 (10)
H13	−0.0137	0.7073	0.5718	0.062*
C14	0.0822 (3)	0.7342 (2)	0.4968 (2)	0.0479 (9)
C15	0.1587 (3)	0.6994 (2)	0.4690 (2)	0.0495 (9)
H15	0.1887	0.7320	0.4310	0.059*
C16	0.1922 (2)	0.6172 (2)	0.4960 (2)	0.0417 (8)
C17	0.0167 (3)	0.5487 (3)	0.6414 (3)	0.0767 (14)
H17A	0.0448	0.5527	0.6914	0.115*
H17B	0.0128	0.4858	0.6258	0.115*
H17C	−0.0399	0.5742	0.6454	0.115*
C18	0.0496 (3)	0.8260 (3)	0.4680 (3)	0.0712 (13)
H18A	0.0345	0.8634	0.5122	0.107*
H18B	0.0000	0.8170	0.4356	0.107*
H18C	0.0937	0.8558	0.4382	0.107*
C19	0.2774 (3)	0.5823 (3)	0.4660 (2)	0.0587 (11)
H19A	0.2681	0.5294	0.4337	0.088*
H19B	0.3133	0.5661	0.5096	0.088*
H19C	0.3049	0.6291	0.4356	0.088*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0891 (4)	0.0542 (3)	0.0528 (3)	0.0202 (2)	0.0064 (2)	−0.0031 (2)
O1	0.092 (3)	0.062 (2)	0.089 (3)	−0.0072 (19)	0.012 (2)	0.009 (2)
N1	0.0478 (18)	0.0560 (19)	0.0527 (19)	−0.0023 (16)	0.0061 (16)	0.0012 (17)
N2	0.0404 (15)	0.0322 (14)	0.0371 (15)	0.0037 (12)	0.0002 (14)	−0.0037 (13)
N3	0.0463 (16)	0.0359 (15)	0.0343 (15)	−0.0024 (14)	−0.0022 (13)	−0.0015 (13)
C1	0.059 (3)	0.084 (3)	0.056 (3)	−0.010 (3)	0.012 (2)	−0.005 (2)
C2	0.039 (2)	0.108 (4)	0.066 (3)	0.008 (3)	−0.006 (2)	−0.013 (3)
C3	0.059 (3)	0.086 (3)	0.066 (3)	0.027 (3)	−0.019 (2)	−0.001 (3)
C4	0.054 (2)	0.060 (2)	0.049 (2)	0.012 (2)	−0.0039 (19)	0.007 (2)
C5	0.0402 (18)	0.046 (2)	0.0341 (18)	0.0022 (17)	−0.0031 (16)	−0.0017 (16)
C6	0.0403 (19)	0.0441 (19)	0.0350 (17)	0.0053 (16)	−0.0008 (16)	0.0034 (16)
C7	0.058 (2)	0.036 (2)	0.060 (2)	0.0042 (18)	−0.004 (2)	−0.0077 (19)
C8	0.072 (3)	0.041 (2)	0.067 (3)	−0.003 (2)	−0.014 (2)	−0.011 (2)
C9	0.080 (3)	0.050 (2)	0.047 (2)	−0.008 (2)	−0.016 (2)	−0.0093 (19)
C10	0.0310 (17)	0.0345 (17)	0.0338 (17)	−0.0030 (15)	0.0041 (15)	0.0003 (15)
C11	0.0417 (19)	0.0375 (18)	0.0331 (17)	−0.0023 (16)	−0.0048 (16)	0.0020 (16)
C12	0.048 (2)	0.049 (2)	0.042 (2)	−0.0007 (18)	−0.0003 (18)	0.0061 (18)
C13	0.048 (2)	0.057 (2)	0.050 (2)	0.008 (2)	−0.0052 (19)	−0.001 (2)
C14	0.063 (2)	0.042 (2)	0.0390 (19)	0.000 (2)	−0.0183 (19)	0.0036 (17)
C15	0.065 (3)	0.047 (2)	0.0355 (18)	−0.012 (2)	−0.0045 (19)	0.0067 (18)
C16	0.050 (2)	0.0429 (19)	0.0322 (18)	−0.0049 (18)	−0.0001 (17)	−0.0010 (16)
C17	0.063 (3)	0.084 (3)	0.083 (3)	0.013 (3)	0.027 (3)	0.029 (3)
C18	0.093 (3)	0.053 (2)	0.068 (3)	0.012 (2)	−0.019 (3)	0.009 (2)
C19	0.061 (2)	0.063 (2)	0.052 (2)	−0.005 (2)	0.015 (2)	0.002 (2)

Geometric parameters (Å, º) top

O1—H1A	0.8501	C8—H8B	0.9700
O1—H1B	0.94 (2)	C8—C9	1.486 (5)
N1—C1	1.357 (5)	C9—H9A	0.9700
N1—C5	1.327 (4)	C9—H9B	0.9700
N2—C6	1.467 (4)	C10—H10	0.9300
N2—C7	1.477 (4)	C11—C12	1.385 (5)
N2—C10	1.306 (4)	C11—C16	1.392 (5)
N3—C9	1.473 (4)	C12—C13	1.388 (5)
N3—C10	1.314 (4)	C12—C17	1.512 (5)
N3—C11	1.453 (4)	C13—H13	0.9300
C1—H1	0.9300	C13—C14	1.384 (5)
C1—C2	1.356 (7)	C14—C15	1.381 (5)
C2—H2	0.9300	C14—C18	1.518 (5)
C2—C3	1.344 (6)	C15—H15	0.9300
C3—H3	0.9300	C15—C16	1.390 (5)
C3—C4	1.380 (6)	C16—C19	1.512 (5)
C4—H4	0.9300	C17—H17A	0.9600
C4—C5	1.375 (5)	C17—H17B	0.9600
C5—C6	1.510 (5)	C17—H17C	0.9600
C6—H6A	0.9700	C18—H18A	0.9600
C6—H6B	0.9700	C18—H18B	0.9600
C7—H7A	0.9700	C18—H18C	0.9600
C7—H7B	0.9700	C19—H19A	0.9600
C7—C8	1.489 (5)	C19—H19B	0.9600
C8—H8A	0.9700	C19—H19C	0.9600

H1A—O1—H1B	109.5	N3—C9—H9B	109.6
C5—N1—C1	116.4 (4)	C8—C9—H9A	109.6
C6—N2—C7	116.5 (3)	C8—C9—H9B	109.6
C10—N2—C6	121.5 (3)	H9A—C9—H9B	108.1
C10—N2—C7	121.8 (3)	N2—C10—N3	123.5 (3)
C10—N3—C9	121.3 (3)	N2—C10—H10	118.2
C10—N3—C11	120.4 (3)	N3—C10—H10	118.2
C11—N3—C9	118.3 (3)	C12—C11—N3	119.2 (3)
N1—C1—H1	118.4	C12—C11—C16	122.3 (3)
C2—C1—N1	123.1 (4)	C16—C11—N3	118.4 (3)
C2—C1—H1	118.4	C11—C12—C13	117.6 (3)
C1—C2—H2	120.1	C11—C12—C17	122.0 (3)
C3—C2—C1	119.8 (4)	C13—C12—C17	120.4 (3)
C3—C2—H2	120.1	C12—C13—H13	118.9
C2—C3—H3	120.7	C14—C13—C12	122.2 (4)
C2—C3—C4	118.6 (4)	C14—C13—H13	118.9
C4—C3—H3	120.7	C13—C14—C18	121.4 (4)
C3—C4—H4	120.5	C15—C14—C13	118.2 (3)
C5—C4—C3	119.0 (4)	C15—C14—C18	120.3 (4)
C5—C4—H4	120.5	C14—C15—H15	119.0
N1—C5—C4	123.0 (3)	C14—C15—C16	122.1 (3)
N1—C5—C6	116.3 (3)	C16—C15—H15	119.0
C4—C5—C6	120.7 (3)	C11—C16—C19	121.7 (3)
N2—C6—C5	111.8 (3)	C15—C16—C11	117.6 (3)
N2—C6—H6A	109.3	C15—C16—C19	120.8 (3)
N2—C6—H6B	109.3	C12—C17—H17A	109.5
C5—C6—H6A	109.3	C12—C17—H17B	109.5
C5—C6—H6B	109.3	C12—C17—H17C	109.5
H6A—C6—H6B	107.9	H17A—C17—H17B	109.5
N2—C7—H7A	109.7	H17A—C17—H17C	109.5
N2—C7—H7B	109.7	H17B—C17—H17C	109.5
N2—C7—C8	109.9 (3)	C14—C18—H18A	109.5
H7A—C7—H7B	108.2	C14—C18—H18B	109.5
C8—C7—H7A	109.7	C14—C18—H18C	109.5
C8—C7—H7B	109.7	H18A—C18—H18B	109.5
C7—C8—H8A	109.0	H18A—C18—H18C	109.5
C7—C8—H8B	109.0	H18B—C18—H18C	109.5
H8A—C8—H8B	107.8	C16—C19—H19A	109.5
C9—C8—C7	112.9 (3)	C16—C19—H19B	109.5
C9—C8—H8A	109.0	C16—C19—H19C	109.5
C9—C8—H8B	109.0	H19A—C19—H19B	109.5
N3—C9—C8	110.3 (3)	H19A—C19—H19C	109.5
N3—C9—H9A	109.6	H19B—C19—H19C	109.5

N1—C1—C2—C3	−1.0 (7)	C9—N3—C11—C12	97.5 (4)
N1—C5—C6—N2	62.8 (4)	C9—N3—C11—C16	−79.5 (4)
N2—C7—C8—C9	48.0 (5)	C10—N2—C6—C5	−110.9 (3)
N3—C11—C12—C13	−178.5 (3)	C10—N2—C7—C8	−23.0 (5)
N3—C11—C12—C17	2.1 (5)	C10—N3—C9—C8	24.2 (5)
N3—C11—C16—C15	177.8 (3)	C10—N3—C11—C12	−82.0 (4)
N3—C11—C16—C19	−3.6 (5)	C10—N3—C11—C16	101.0 (4)
C1—N1—C5—C4	−1.5 (5)	C11—N3—C9—C8	−155.3 (3)
C1—N1—C5—C6	178.3 (3)	C11—N3—C10—N2	−179.0 (3)
C1—C2—C3—C4	0.4 (7)	C11—C12—C13—C14	1.2 (5)
C2—C3—C4—C5	−0.4 (6)	C12—C11—C16—C15	0.9 (5)
C3—C4—C5—N1	1.0 (6)	C12—C11—C16—C19	179.5 (3)
C3—C4—C5—C6	−178.8 (4)	C12—C13—C14—C15	−0.1 (5)
C4—C5—C6—N2	−117.3 (4)	C12—C13—C14—C18	−178.4 (4)
C5—N1—C1—C2	1.5 (6)	C13—C14—C15—C16	−0.8 (5)
C6—N2—C7—C8	159.8 (3)	C14—C15—C16—C11	0.4 (5)
C6—N2—C10—N3	175.0 (3)	C14—C15—C16—C19	−178.3 (3)
C7—N2—C6—C5	66.3 (4)	C16—C11—C12—C13	−1.6 (5)
C7—N2—C10—N3	−2.1 (5)	C16—C11—C12—C17	179.0 (4)
C7—C8—C9—N3	−48.7 (5)	C17—C12—C13—C14	−179.3 (4)
C9—N3—C10—N2	1.5 (5)	C18—C14—C15—C16	177.6 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···Br1	0.85	2.46	3.292 (4)	168
O1—H1B···N1	0.94 (2)	1.94 (3)	2.861 (5)	165 (7)
C6—H6B···Br1	0.97	2.87	3.815 (3)	166
C3—H3···O1ⁱ	0.93	2.54	3.442 (6)	165

Symmetry code: (i) −x+1, y−1/2, −z+3/2.