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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 71| Part 4| April 2015| Page o224
doi:10.1107/S2056989015003989

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

CROSSMARK_Color_square_no_text.svg
Qi Quo,a Liangru Yang,a* Pu Mao,a Yongmei Xiaoa and Jinwei Yuana

aCollege of Chemistry and Chemical engineering, Henan University of Technology, Zhengzhou 450001, People's Republic of China
*Correspondence e-mail: lryang@haut.edu.cn

Edited by C. Rizzoli, Universita degli Studi di Parma, Italy (Received 5 February 2015; accepted 26 February 2015; online 4 March 2015)

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.

CCDC reference: 1051286

Similar articles

1. Related literature

For background on the synthesis and properties of N-heterocyclic carbenes, see: Hopkinson et al. (2014[Hopkinson, M. N., Richter, C., Schedler, M. & Glorius, F. (2014). Nature, 510, 485-496.]); Mata et al. (2007[Mata, J. A., Poyatos, M. & Peris, E. (2007). Coord. Chem. Rev. 251, 841-859.]); Dunsford & Cavell (2014[Dunsford, J. J. & Cavell, K. J. (2014). Organometallics, 33, 2902-2905.]); Mao et al. (2012[Mao, P., Yang, L., Xiao, Y., Yuan, J., Liu, X. & Song, M. (2012). J. Organomet. Chem. 705, 39-43.]).

[Scheme 1]

2. Experimental

2.1. Crystal data

  • C19H24N3+·Br−·H2O

  • Mr = 392.34

  • Orthorhombic, P b c a

  • a = 15.5868 (5) Å

  • b = 14.6323 (4) Å

  • c = 17.0439 (6) Å

  • V = 3887.2 (2) Å3

  • Z = 8

  • Mo Kα radiation

  • μ = 2.13 mm−1

  • T = 291 K

  • 0.3 × 0.28 × 0.26 mm

2.2. Data collection

  • Agilent Xcalibur (Eos, Gemini) diffractometer

  • Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011[Agilent (2011). CrysAlis PRO. Agilent Technologies UK Ltd, Yarnton, England.]) Tmin = 0.910, Tmax = 1.000

  • 10196 measured reflections

  • 3969 independent reflections

  • 2522 reflections with I > 2σ(I)

  • Rint = 0.031

2.3. Refinement

  • R[F2 > 2σ(F2)] = 0.051

  • wR(F2) = 0.134

  • S = 1.03

  • 3969 reflections

  • 227 parameters

  • 1 restraint

  • H atoms treated by a mixture of independent and constrained refinement

  • Δρmax = 0.83 e Å−3

  • Δρmin = −0.81 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

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-{\script{1\over 2}}, -z+{\script{3\over 2}}].

Data collection: CrysAlis PRO (Agilent, 2011[Agilent (2011). CrysAlis PRO. Agilent Technologies UK Ltd, Yarnton, England.]); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: OLEX2 (Dolomanov et al., 2009[Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339-341.]); software used to prepare material for publication: OLEX2.

Supporting information

CCDC reference: 1051286

Crystal structure: contains datablocks I, global. DOI: 10.1107/S2056989015003989/rz5148sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2056989015003989/rz5148Isup2.hkl

Supporting information file. DOI: 10.1107/S2056989015003989/rz5148Isup3.cml

checkCIF report


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.

Refinement top

The water H atoms could be located in a difference Fourier map, but only one of them (H1B) could be refined freely. The second H atom (H1A) was refined using a rigid-body approximation, with O—H constrained to be 0.9 Å, and with Uiso(H) = 1.5 Ueq(O). All other H atoms were placed geometrically and refined as riding, with C—H = 0.93–0.97 Å, and with Uiso(H) = 1.2 Ueq(C).

Structure description 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.

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
[Figure 1] 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−·H2ODx = 1.341 Mg m−3
Mr = 392.34Mo Kα radiation, λ = 0.7107 Å
Orthorhombic, PbcaCell parameters from 1997 reflections
a = 15.5868 (5) Åθ = 3.5–23.8°
b = 14.6323 (4) ŵ = 2.13 mm−1
c = 17.0439 (6) ÅT = 291 K
V = 3887.2 (2) Å3Block, colourless
Z = 80.3 × 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 Source2522 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.031
Detector resolution: 16.2312 pixels mm-1θmax = 26.4°, θmin = 3.0°
ω scansh = −10→19
Absorption correction: multi-scan
(CrysAlis PRO; Agilent, 2011)		k = −17→18
Tmin = 0.910, Tmax = 1.000l = −12→21
10196 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.051Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.134H atoms treated by a mixture of independent and constrained refinement
S = 1.03 w = 1/[σ2(Fo2) + (0.053P)2 + 3.4187P]
where P = (Fo2 + 2Fc2)/3
3969 reflections(Δ/σ)max < 0.001
227 parametersΔρmax = 0.83 e Å−3
1 restraintΔρmin = −0.81 e Å−3
Crystal data top
C19H24N3+·Br−·H2OV = 3887.2 (2) Å3
Mr = 392.34Z = 8
Orthorhombic, PbcaMo Kα radiation
a = 15.5868 (5) ŵ = 2.13 mm−1
b = 14.6323 (4) ÅT = 291 K
c = 17.0439 (6) Å0.3 × 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)
Tmin = 0.910, Tmax = 1.000Rint = 0.031
10196 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0511 restraint
wR(F2) = 0.134H atoms treated by a mixture of independent and constrained refinement
S = 1.03Δρmax = 0.83 e Å−3
3969 reflectionsΔρmin = −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
xyzUiso*/Ueq
Br10.26231 (3)0.64141 (3)0.81482 (3)0.06536 (19)
O10.3743 (3)0.6154 (2)0.6526 (2)0.0809 (10)
H1A0.35140.62820.69650.121*
H1B0.400 (4)0.557 (2)0.655 (4)0.16 (3)*
N10.4370 (2)0.4358 (2)0.68596 (18)0.0522 (8)
N20.25056 (17)0.39948 (18)0.67358 (16)0.0366 (7)
N30.17792 (18)0.48218 (18)0.57935 (16)0.0388 (7)
C10.5213 (3)0.4180 (4)0.6729 (3)0.0662 (12)
H10.55300.45970.64370.079*
C20.5614 (3)0.3423 (4)0.7005 (3)0.0711 (14)
H20.61910.33250.68940.085*
C30.5176 (3)0.2814 (4)0.7439 (3)0.0701 (13)
H30.54450.22940.76340.084*
C40.4320 (2)0.2977 (3)0.7589 (2)0.0543 (10)
H40.40000.25660.78850.065*
C50.3947 (2)0.3756 (2)0.7295 (2)0.0402 (8)
C60.3017 (2)0.3970 (2)0.7458 (2)0.0398 (8)
H6A0.27830.35100.78080.048*
H6B0.29770.45570.77200.048*
C70.2405 (2)0.3121 (2)0.6312 (2)0.0515 (10)
H7A0.23290.26270.66860.062*
H7B0.29170.29970.60070.062*
C80.1647 (3)0.3168 (3)0.5782 (3)0.0603 (11)
H8A0.16510.26410.54370.072*
H8B0.11280.31410.60950.072*
C90.1631 (3)0.4013 (2)0.5297 (2)0.0590 (11)
H9A0.20720.39780.48970.071*
H9B0.10800.40670.50380.071*
C100.21877 (19)0.4758 (2)0.64654 (18)0.0331 (7)
H100.22540.52850.67650.040*
C110.1455 (2)0.5698 (2)0.55251 (19)0.0374 (8)
C120.0677 (2)0.6013 (3)0.5810 (2)0.0464 (9)
C130.0378 (2)0.6844 (3)0.5527 (2)0.0513 (10)
H13−0.01370.70730.57180.062*
C140.0822 (3)0.7342 (2)0.4968 (2)0.0479 (9)
C150.1587 (3)0.6994 (2)0.4690 (2)0.0495 (9)
H150.18870.73200.43100.059*
C160.1922 (2)0.6172 (2)0.4960 (2)0.0417 (8)
C170.0167 (3)0.5487 (3)0.6414 (3)0.0767 (14)
H17A0.04480.55270.69140.115*
H17B0.01280.48580.62580.115*
H17C−0.03990.57420.64540.115*
C180.0496 (3)0.8260 (3)0.4680 (3)0.0712 (13)
H18A0.03450.86340.51220.107*
H18B0.00000.81700.43560.107*
H18C0.09370.85580.43820.107*
C190.2774 (3)0.5823 (3)0.4660 (2)0.0587 (11)
H19A0.26810.52940.43370.088*
H19B0.31330.56610.50960.088*
H19C0.30490.62910.43560.088*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br10.0891 (4)0.0542 (3)0.0528 (3)0.0202 (2)0.0064 (2)−0.0031 (2)
O10.092 (3)0.062 (2)0.089 (3)−0.0072 (19)0.012 (2)0.009 (2)
N10.0478 (18)0.0560 (19)0.0527 (19)−0.0023 (16)0.0061 (16)0.0012 (17)
N20.0404 (15)0.0322 (14)0.0371 (15)0.0037 (12)0.0002 (14)−0.0037 (13)
N30.0463 (16)0.0359 (15)0.0343 (15)−0.0024 (14)−0.0022 (13)−0.0015 (13)
C10.059 (3)0.084 (3)0.056 (3)−0.010 (3)0.012 (2)−0.005 (2)
C20.039 (2)0.108 (4)0.066 (3)0.008 (3)−0.006 (2)−0.013 (3)
C30.059 (3)0.086 (3)0.066 (3)0.027 (3)−0.019 (2)−0.001 (3)
C40.054 (2)0.060 (2)0.049 (2)0.012 (2)−0.0039 (19)0.007 (2)
C50.0402 (18)0.046 (2)0.0341 (18)0.0022 (17)−0.0031 (16)−0.0017 (16)
C60.0403 (19)0.0441 (19)0.0350 (17)0.0053 (16)−0.0008 (16)0.0034 (16)
C70.058 (2)0.036 (2)0.060 (2)0.0042 (18)−0.004 (2)−0.0077 (19)
C80.072 (3)0.041 (2)0.067 (3)−0.003 (2)−0.014 (2)−0.011 (2)
C90.080 (3)0.050 (2)0.047 (2)−0.008 (2)−0.016 (2)−0.0093 (19)
C100.0310 (17)0.0345 (17)0.0338 (17)−0.0030 (15)0.0041 (15)0.0003 (15)
C110.0417 (19)0.0375 (18)0.0331 (17)−0.0023 (16)−0.0048 (16)0.0020 (16)
C120.048 (2)0.049 (2)0.042 (2)−0.0007 (18)−0.0003 (18)0.0061 (18)
C130.048 (2)0.057 (2)0.050 (2)0.008 (2)−0.0052 (19)−0.001 (2)
C140.063 (2)0.042 (2)0.0390 (19)0.000 (2)−0.0183 (19)0.0036 (17)
C150.065 (3)0.047 (2)0.0355 (18)−0.012 (2)−0.0045 (19)0.0067 (18)
C160.050 (2)0.0429 (19)0.0322 (18)−0.0049 (18)−0.0001 (17)−0.0010 (16)
C170.063 (3)0.084 (3)0.083 (3)0.013 (3)0.027 (3)0.029 (3)
C180.093 (3)0.053 (2)0.068 (3)0.012 (2)−0.019 (3)0.009 (2)
C190.061 (2)0.063 (2)0.052 (2)−0.005 (2)0.015 (2)0.002 (2)
Geometric parameters (Å, º) top
O1—H1A0.8501C8—H8B0.9700
O1—H1B0.94 (2)C8—C91.486 (5)
N1—C11.357 (5)C9—H9A0.9700
N1—C51.327 (4)C9—H9B0.9700
N2—C61.467 (4)C10—H100.9300
N2—C71.477 (4)C11—C121.385 (5)
N2—C101.306 (4)C11—C161.392 (5)
N3—C91.473 (4)C12—C131.388 (5)
N3—C101.314 (4)C12—C171.512 (5)
N3—C111.453 (4)C13—H130.9300
C1—H10.9300C13—C141.384 (5)
C1—C21.356 (7)C14—C151.381 (5)
C2—H20.9300C14—C181.518 (5)
C2—C31.344 (6)C15—H150.9300
C3—H30.9300C15—C161.390 (5)
C3—C41.380 (6)C16—C191.512 (5)
C4—H40.9300C17—H17A0.9600
C4—C51.375 (5)C17—H17B0.9600
C5—C61.510 (5)C17—H17C0.9600
C6—H6A0.9700C18—H18A0.9600
C6—H6B0.9700C18—H18B0.9600
C7—H7A0.9700C18—H18C0.9600
C7—H7B0.9700C19—H19A0.9600
C7—C81.489 (5)C19—H19B0.9600
C8—H8A0.9700C19—H19C0.9600
H1A—O1—H1B109.5N3—C9—H9B109.6
C5—N1—C1116.4 (4)C8—C9—H9A109.6
C6—N2—C7116.5 (3)C8—C9—H9B109.6
C10—N2—C6121.5 (3)H9A—C9—H9B108.1
C10—N2—C7121.8 (3)N2—C10—N3123.5 (3)
C10—N3—C9121.3 (3)N2—C10—H10118.2
C10—N3—C11120.4 (3)N3—C10—H10118.2
C11—N3—C9118.3 (3)C12—C11—N3119.2 (3)
N1—C1—H1118.4C12—C11—C16122.3 (3)
C2—C1—N1123.1 (4)C16—C11—N3118.4 (3)
C2—C1—H1118.4C11—C12—C13117.6 (3)
C1—C2—H2120.1C11—C12—C17122.0 (3)
C3—C2—C1119.8 (4)C13—C12—C17120.4 (3)
C3—C2—H2120.1C12—C13—H13118.9
C2—C3—H3120.7C14—C13—C12122.2 (4)
C2—C3—C4118.6 (4)C14—C13—H13118.9
C4—C3—H3120.7C13—C14—C18121.4 (4)
C3—C4—H4120.5C15—C14—C13118.2 (3)
C5—C4—C3119.0 (4)C15—C14—C18120.3 (4)
C5—C4—H4120.5C14—C15—H15119.0
N1—C5—C4123.0 (3)C14—C15—C16122.1 (3)
N1—C5—C6116.3 (3)C16—C15—H15119.0
C4—C5—C6120.7 (3)C11—C16—C19121.7 (3)
N2—C6—C5111.8 (3)C15—C16—C11117.6 (3)
N2—C6—H6A109.3C15—C16—C19120.8 (3)
N2—C6—H6B109.3C12—C17—H17A109.5
C5—C6—H6A109.3C12—C17—H17B109.5
C5—C6—H6B109.3C12—C17—H17C109.5
H6A—C6—H6B107.9H17A—C17—H17B109.5
N2—C7—H7A109.7H17A—C17—H17C109.5
N2—C7—H7B109.7H17B—C17—H17C109.5
N2—C7—C8109.9 (3)C14—C18—H18A109.5
H7A—C7—H7B108.2C14—C18—H18B109.5
C8—C7—H7A109.7C14—C18—H18C109.5
C8—C7—H7B109.7H18A—C18—H18B109.5
C7—C8—H8A109.0H18A—C18—H18C109.5
C7—C8—H8B109.0H18B—C18—H18C109.5
H8A—C8—H8B107.8C16—C19—H19A109.5
C9—C8—C7112.9 (3)C16—C19—H19B109.5
C9—C8—H8A109.0C16—C19—H19C109.5
C9—C8—H8B109.0H19A—C19—H19B109.5
N3—C9—C8110.3 (3)H19A—C19—H19C109.5
N3—C9—H9A109.6H19B—C19—H19C109.5
N1—C1—C2—C3−1.0 (7)C9—N3—C11—C1297.5 (4)
N1—C5—C6—N262.8 (4)C9—N3—C11—C16−79.5 (4)
N2—C7—C8—C948.0 (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—C172.1 (5)C10—N3—C9—C824.2 (5)
N3—C11—C16—C15177.8 (3)C10—N3—C11—C12−82.0 (4)
N3—C11—C16—C19−3.6 (5)C10—N3—C11—C16101.0 (4)
C1—N1—C5—C4−1.5 (5)C11—N3—C9—C8−155.3 (3)
C1—N1—C5—C6178.3 (3)C11—N3—C10—N2−179.0 (3)
C1—C2—C3—C40.4 (7)C11—C12—C13—C141.2 (5)
C2—C3—C4—C5−0.4 (6)C12—C11—C16—C150.9 (5)
C3—C4—C5—N11.0 (6)C12—C11—C16—C19179.5 (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—C21.5 (6)C13—C14—C15—C16−0.8 (5)
C6—N2—C7—C8159.8 (3)C14—C15—C16—C110.4 (5)
C6—N2—C10—N3175.0 (3)C14—C15—C16—C19−178.3 (3)
C7—N2—C6—C566.3 (4)C16—C11—C12—C13−1.6 (5)
C7—N2—C10—N3−2.1 (5)C16—C11—C12—C17179.0 (4)
C7—C8—C9—N3−48.7 (5)C17—C12—C13—C14−179.3 (4)
C9—N3—C10—N21.5 (5)C18—C14—C15—C16177.6 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1A···Br10.852.463.292 (4)168
O1—H1B···N10.94 (2)1.94 (3)2.861 (5)165 (7)
C6—H6B···Br10.972.873.815 (3)166
C3—H3···O1i0.932.543.442 (6)165
Symmetry code: (i) −x+1, y−1/2, −z+3/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1A···Br10.852.463.292 (4)167.8
O1—H1B···N10.94 (2)1.94 (3)2.861 (5)165 (7)
C6—H6B···Br10.972.873.815 (3)166
C3—H3···O1i0.932.543.442 (6)164.7
Symmetry code: (i) −x+1, y−1/2, −z+3/2.
 

Acknowledgements

The authors thank Ms Y. Zhu for technical assistance. This research was supported by the National Natural Science Foundation of P. R. China (No. 21172055) and the High-level Talents Foundation of Henan University of Technology (11CXRC10).

References

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ISSN: 2056-9890
Volume 71| Part 4| April 2015| Page o224
doi:10.1107/S2056989015003989
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