1,3-Bis[(6-methyl-2-pyrid­yl)meth­yl]imidazolium bromide

Kim, G.Y.; Park, S.-K.; Lee, D.-H.; Park, G.

doi:10.1107/S1600536809006710

organic compounds

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ISSN: 2056-9890

Volume 65| Part 3| March 2009| Page o637

doi:10.1107/S1600536809006710

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1,3-Bis[(6-methyl-2-pyridyl)methyl]imidazolium bromide

Ga Young Kim,^a Sang-Kyu Park,^a Dong-Heon Lee ^a ^* and Gyungse Park ^b ^*

^aDepartment of Chemistry, Chonbuk National University, Jeonju, Chonbuk 561-756, Republic of Korea, and ^bDepartment of Chemistry, Kunsan National University, Kusan, Chonbuk 573-701, Republic of Korea
^*Correspondence e-mail: dhl@chonbuk.ac.kr, parkg@kunsan.ac.kr

(Received 20 January 2009; accepted 24 February 2009; online 28 February 2009)

The title compound, C₁₇H₁₉N₄⁺·Br⁻, is built up from 1,3-bis[(6-methyl-2-pyridinyl)methyl]imidazolium cations and bromide anions. Each of two 6-methyl-2-pyridyl rings is rotated out of the imidazole plane, making dihedral angles of 79.90 (9) and 86.40 (9)°. The packing is consolidated by aromatic π–π interactions between the pyridine rings of neighbouring molecules [centroid–centroid distance = 3.554 (2) Å] and by weak C—H⋯N and C—H⋯Br hydrogen bonds.

Related literature

For the synthesis of N-heterocyclic carbenes, see: Arduengo et al. (1991 ); Enders et al. (1996 ); Frenzel et al. (1999 ); Gardiner et al. (1999 ); Herrmann et al. (1998 ); McGuinness et al. (1998 ); Öfele (1968 ); Wanzlick & Schonherr (1968); Wanzlick & Schönherr (1968 ); Zhang & Trudell (2000 ). For related structures, see: Weskamp et al. (1999a b ).

Experimental

Crystal data

C₁₇H₁₉N₄⁺·Br⁻
M_r = 359.27
Monoclinic, P 2₁ /c
a = 8.2951 (4) Å
b = 12.4992 (5) Å
c = 16.1786 (7) Å
β = 95.709 (1)°
V = 1669.11 (13) Å³
Z = 4
Mo Kα radiation
μ = 2.47 mm⁻¹
T = 173 K
0.40 × 0.25 × 0.15 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.439, T_max = 0.709
10482 measured reflections
3923 independent reflections
2861 reflections with I > 2σ(I)
R_int = 0.070

Refinement

R[F² > 2σ(F²)] = 0.037
wR(F²) = 0.094
S = 1.00
3923 reflections
201 parameters
H-atom parameters constrained
Δρ_max = 0.92 e Å⁻³
Δρ_min = −0.50 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C7—H7A⋯N4ⁱ	0.99	2.34	3.308 (4)	165
C7—H7B⋯Brⁱⁱ	0.99	2.79	3.660 (3)	147
C9—H9A⋯Br	0.95	2.91	3.695 (3)	141
C10—H10A⋯Brⁱ	0.95	2.68	3.521 (3)	148
C11—H11A⋯Br	0.99	2.93	3.801 (3)	147
C11—H11B⋯Brⁱ	0.99	2.89	3.690 (3)	138
Symmetry codes: (i) $[-x+1, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) $[-x, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Data collection: SMART (Bruker, 1997 ); cell refinement: SAINT (Bruker, 1997); 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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809006710/lx2088sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809006710/lx2088Isup2.hkl

checkCIF report

Comment top

Many intensive researches have been focused on the synthesis of N-heterocyclic carbenes (NHCs) ligands due to their potential applications in important organic syntheses, such as Pd–catalysed Heck– and Suzuki–coupling, Co–catalysed ethylene copolymerisation, Ru–catalysed olefin metathesis and Rh–catalyse hydrosilylation (Frenzel et al., 1999; Enders et al., 1996; Gardiner et al., 1999; McGuinness et al., 1998; Weskamp et al., 1999a,b); Zhang & Trudell, 2000). We have interested in the use of tridentate N-heterocyclic carbene ligands. Here we report the crystal structure of the title compound, 1,3-bis[(6-methyl-2-pyridinyl)methyl]imidazolium bromide (Fig. 1).

The asymmetric unit of the title compound consists the C₁₇H₉N₄ cation and Br anion. Each of two 6–methylpyridine rings is rotated out of the imidazole plane, with dihedral angle of N1/C2–C6 of 79.90 (9)° and N4/C12–C16 of 86.40 (9)°, respectively. The crystal packing (Fig. 2) is stabilized by intermolecular aromatic π—π interactions between the pyridine rings of neighbouring molecules. The Cg—Cgⁱⁱⁱ distance of 3.554 (2) Å (Cg is the centroid of the N1/C2-C6 pyridine ring; symmetry code as in Fig. 2). The molecular packing is further stabilized by C—H···N interactions between the hydrogen of 7–methylene group and the N atom of pyridine ring of the neighbouring molecule, with a C7—H7A···N4ⁱ separation of 2.34 (1) Å (Table 1 and Fig. 2; symmetry code as in Fig. 2). Additionally, five different intermolecular C—H···Br hydrogen bonds in the structure are observed (Table 1 & Fig. 2).

Related literature top

For the synthesis of N-heterocyclic carbenes, see: Arduengo et al. (1991); Öfele (1968); Wanzlick & Schonherr (1968). For related structures, see: Weskamp et al. (1999a,b).

For related literature, see: Enders et al. (1996); Frenzel et al. (1999); Gardiner et al. (1999); Herrmann et al. (1998); McGuinness et al. (1998); Wanzlick & Schönherr (1968); Zhang & Trudell (2000).

Experimental top

Synthesis of H(MepyCH₂)Im (1a): A mixture of imidazole (0.36 g, 6.0 mmol), 2-bromomethyl-6-methylpyridine (1.11 g, 6.0 mmol) and triethylamine (1.82 g, 1.8 mmol) in toluene (50 mL) was refluxed at 383 K for 10 h. After cooling, saturated aqueous NaHCO₃ solution was added and extracted with CH₂Cl₂ (3 x 20 mL). The combined organic fractions were dried over Na₂SO₄, filtered, and concentrated under reduced pressure to afford a dark colored solid in 53.0 % yield. Spectroscopic analysis: ¹H NMR(CDCl₃, 400MHz) : δ 7.62 (s, 1H, CH), 7.54 (t, 1H, J = 10 Hz, CH), 7.12 (s, 1H, CH), 7.09 (d, 1H, J = 1 Hz, CH), 6.99 (s, 1H, CH), 6.70 (d, 1H, J = 0.6Hz, CH), 5.21(s, 2H, CH₂), 2.56 (s, 3H, CH₃). ¹³C NMR (CDCl₃, 100MHz): δ 157.8, 154.1, 137.5, 136.6, 123.2, 122.5, 121.4, 118.9, 52.3, 23.9.

Synthesis of [H(MepyCH₂)₂-Im]Br (1): A mixture of (1a), H(MepyCH₂)Im, (0.52 g, 3.0 mmol) and 2-bromomethyl-6-methylpyridine (0.56 g, 3.0 mmol) in toluene (50 mL) was refluxed at 383 K for 14 h. After cooling, the solvents were removed by high-vacuum rotary evaporation. The residue was washed with Et₂O (5 x100 mL), and dried under the reduced pressure to afford a brown solid in 89.0 % yield. Single crystlas suitable for X-ray crystallography were obtained by Et₂O diffusion into a MeOH solution of the compound. Spectroscopic analysis: ¹H NMR (CDCl₃, 400 MHz) : δ 10.52 (s, 1H, CH), 7.66 (s, 2H, CH), 7.62 (t, 2H, J = 7.8 Hz), 7.54 (d, 2H, J = 7 Hz, CH), 7.14 (d, 2H, J = 7 Hz, CH), 5.65 (s, 4H, CH₂), 2.50 (s, 6H, CH₃). ¹³C NMR (CDCl₃, 100 MHz): δ 158.8, 151.3, 137.9, 137.3, 123.7, 122.1, 121.0, 54.2, 24.4.

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SMART (Bruker, 1997); data reduction: SAINT (Bruker, 1997); 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 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound, showing displacement ellipsoids drawn at the 50% probability level.
	Fig. 2. π—π, C—H···N and C—H···Br interactions (dotted lines) in the title compound. Cg denotes the ring centroids. [Symmetry code : (i) -x+1, y+1/2, -z+3/2; (ii) -x, y+1/2, -z+3/2; (iii) -x+1, -y, -z+1; (iv) -x+1, y-1/2, -z+3/2.]

1,3-Bis[(6-methyl-2-pyridyl)methyl]imidazolium bromide top

Crystal data top

C₁₇H₁₉N₄⁺·Br⁻	F(000) = 736
M_r = 359.27	D_x = 1.430 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3923 reflections
a = 8.2951 (4) Å	θ = 2.1–28.3°
b = 12.4992 (5) Å	µ = 2.47 mm⁻¹
c = 16.1786 (7) Å	T = 173 K
β = 95.709 (1)°	Block, yellow
V = 1669.11 (13) Å³	0.40 × 0.25 × 0.15 mm
Z = 4

Data collection top

Bruker SMART CCD area-detector diffractometer	3923 independent reflections
Radiation source: fine-focus sealed tube	2861 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.070
Detector resolution: 10.0 pixels mm^-1	θ_max = 28.3°, θ_min = 2.1°
ϕ and ω scans	h = −10→9
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −8→16
T_min = 0.439, T_max = 0.709	l = −21→20
10482 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)] = 0.037	Hydrogen site location: difference Fourier map
wR(F²) = 0.094	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.0442P)²] where P = (F_o² + 2F_c²)/3
3923 reflections	(Δ/σ)_max < 0.001
201 parameters	Δρ_max = 0.92 e Å⁻³
0 restraints	Δρ_min = −0.50 e Å⁻³

Crystal data top

C₁₇H₁₉N₄⁺·Br⁻	V = 1669.11 (13) Å³
M_r = 359.27	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.2951 (4) Å	µ = 2.47 mm⁻¹
b = 12.4992 (5) Å	T = 173 K
c = 16.1786 (7) Å	0.40 × 0.25 × 0.15 mm
β = 95.709 (1)°

Data collection top

Bruker SMART CCD area-detector diffractometer	3923 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2861 reflections with I > 2σ(I)
T_min = 0.439, T_max = 0.709	R_int = 0.070
10482 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	0 restraints
wR(F²) = 0.094	H-atom parameters constrained
S = 1.00	Δρ_max = 0.92 e Å⁻³
3923 reflections	Δρ_min = −0.50 e Å⁻³
201 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
Br	0.25933 (3)	−0.13979 (2)	0.728857 (17)	0.02867 (10)
N1	0.2300 (3)	0.43039 (18)	0.55743 (13)	0.0278 (5)
N2	0.1795 (3)	0.32251 (18)	0.69967 (13)	0.0249 (5)
N3	0.3401 (3)	0.18620 (18)	0.70972 (12)	0.0251 (5)
N4	0.6655 (3)	0.02641 (18)	0.63640 (13)	0.0278 (5)
C1	0.3308 (4)	0.4122 (3)	0.42228 (19)	0.0461 (8)
H1A	0.4447	0.3965	0.4401	0.069*
H1B	0.3231	0.4511	0.3695	0.069*
H1C	0.2699	0.3451	0.4151	0.069*
C2	0.2610 (3)	0.4796 (2)	0.48712 (16)	0.0316 (6)
C3	0.2275 (4)	0.5877 (2)	0.47302 (19)	0.0372 (7)
H3A	0.2493	0.6205	0.4223	0.045*
C4	0.1625 (4)	0.6461 (2)	0.5333 (2)	0.0405 (7)
H4A	0.1389	0.7199	0.5249	0.049*
C5	0.1314 (3)	0.5967 (2)	0.60658 (19)	0.0343 (7)
H5A	0.0881	0.6358	0.6496	0.041*
C6	0.1653 (3)	0.4883 (2)	0.61548 (16)	0.0268 (6)
C7	0.1255 (3)	0.4340 (2)	0.69380 (17)	0.0283 (6)
H7A	0.1770	0.4740	0.7422	0.034*
H7B	0.0068	0.4363	0.6963	0.034*
C8	0.0851 (3)	0.2329 (2)	0.68219 (17)	0.0297 (6)
H8A	−0.0289	0.2316	0.6684	0.036*
C9	0.1843 (3)	0.1478 (2)	0.68830 (17)	0.0302 (6)
H9A	0.1538	0.0750	0.6796	0.036*
C10	0.3325 (3)	0.2922 (2)	0.71530 (15)	0.0257 (6)
H10A	0.4222	0.3386	0.7283	0.031*
C11	0.4884 (3)	0.1223 (2)	0.71751 (17)	0.0280 (6)
H11A	0.4651	0.0515	0.7411	0.034*
H11B	0.5704	0.1582	0.7567	0.034*
C12	0.5575 (3)	0.1063 (2)	0.63500 (16)	0.0251 (6)
C13	0.5148 (3)	0.1686 (2)	0.56543 (16)	0.0298 (6)
H13A	0.4382	0.2250	0.5667	0.036*
C14	0.5875 (3)	0.1459 (2)	0.49366 (18)	0.0330 (6)
H14A	0.5608	0.1865	0.4446	0.040*
C15	0.6987 (3)	0.0642 (2)	0.49443 (17)	0.0331 (7)
H15A	0.7500	0.0480	0.4460	0.040*
C16	0.7350 (3)	0.0057 (2)	0.56687 (17)	0.0305 (6)
C17	0.8531 (4)	−0.0873 (3)	0.5706 (2)	0.0445 (8)
H17A	0.9412	−0.0744	0.6144	0.067*
H17B	0.8980	−0.0943	0.5170	0.067*
H17C	0.7964	−0.1535	0.5826	0.067*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br	0.02798 (15)	0.02717 (15)	0.03144 (16)	0.00081 (11)	0.00575 (11)	0.00151 (12)
N1	0.0321 (12)	0.0264 (12)	0.0249 (11)	−0.0012 (10)	0.0022 (10)	−0.0001 (9)
N2	0.0292 (12)	0.0238 (11)	0.0223 (11)	−0.0008 (9)	0.0057 (9)	−0.0003 (9)
N3	0.0275 (12)	0.0278 (12)	0.0205 (11)	0.0002 (10)	0.0043 (9)	0.0004 (9)
N4	0.0261 (12)	0.0312 (13)	0.0260 (11)	−0.0004 (10)	0.0014 (9)	−0.0010 (10)
C1	0.063 (2)	0.051 (2)	0.0266 (15)	0.0014 (17)	0.0125 (15)	0.0030 (14)
C2	0.0321 (15)	0.0388 (16)	0.0234 (13)	−0.0044 (13)	−0.0005 (11)	0.0019 (12)
C3	0.0381 (17)	0.0395 (18)	0.0332 (16)	−0.0073 (14)	−0.0008 (13)	0.0111 (14)
C4	0.0411 (17)	0.0278 (16)	0.052 (2)	0.0000 (13)	0.0002 (15)	0.0080 (14)
C5	0.0347 (16)	0.0268 (15)	0.0415 (17)	−0.0018 (13)	0.0035 (13)	−0.0015 (13)
C6	0.0234 (13)	0.0292 (15)	0.0273 (13)	−0.0039 (11)	−0.0008 (11)	−0.0005 (11)
C7	0.0329 (15)	0.0234 (14)	0.0290 (14)	0.0036 (11)	0.0057 (12)	−0.0016 (11)
C8	0.0279 (14)	0.0296 (15)	0.0318 (15)	−0.0043 (12)	0.0039 (12)	−0.0017 (12)
C9	0.0315 (14)	0.0280 (15)	0.0315 (14)	−0.0038 (12)	0.0052 (12)	−0.0033 (12)
C10	0.0315 (14)	0.0246 (14)	0.0211 (13)	−0.0041 (11)	0.0035 (11)	−0.0027 (10)
C11	0.0304 (14)	0.0296 (15)	0.0241 (13)	0.0062 (11)	0.0034 (11)	0.0028 (11)
C12	0.0241 (13)	0.0259 (13)	0.0251 (13)	−0.0039 (11)	0.0021 (11)	−0.0023 (11)
C13	0.0367 (16)	0.0260 (14)	0.0271 (14)	0.0015 (12)	0.0045 (12)	0.0020 (11)
C14	0.0381 (16)	0.0355 (16)	0.0258 (14)	−0.0051 (13)	0.0048 (12)	0.0055 (12)
C15	0.0308 (15)	0.0418 (17)	0.0283 (14)	−0.0083 (13)	0.0116 (12)	−0.0060 (13)
C16	0.0252 (14)	0.0361 (16)	0.0303 (14)	−0.0014 (12)	0.0023 (11)	−0.0053 (12)
C17	0.0432 (18)	0.053 (2)	0.0372 (17)	0.0125 (16)	0.0055 (14)	−0.0081 (15)

Geometric parameters (Å, º) top

N1—C6	1.339 (3)	C6—C7	1.503 (4)
N1—C2	1.341 (3)	C7—H7A	0.9900
N2—C10	1.324 (3)	C7—H7B	0.9900
N2—C8	1.380 (3)	C8—C9	1.343 (4)
N2—C7	1.464 (3)	C8—H8A	0.9500
N3—C10	1.330 (3)	C9—H9A	0.9500
N3—C9	1.389 (3)	C10—H10A	0.9500
N3—C11	1.462 (3)	C11—C12	1.518 (4)
N4—C16	1.339 (3)	C11—H11A	0.9900
N4—C12	1.341 (3)	C11—H11B	0.9900
C1—C2	1.506 (4)	C12—C13	1.385 (4)
C1—H1A	0.9800	C13—C14	1.390 (4)
C1—H1B	0.9800	C13—H13A	0.9500
C1—H1C	0.9800	C14—C15	1.375 (4)
C2—C3	1.393 (4)	C14—H14A	0.9500
C3—C4	1.371 (5)	C15—C16	1.389 (4)
C3—H3A	0.9500	C15—H15A	0.9500
C4—C5	1.383 (4)	C16—C17	1.518 (4)
C4—H4A	0.9500	C17—H17A	0.9800
C5—C6	1.388 (4)	C17—H17B	0.9800
C5—H5A	0.9500	C17—H17C	0.9800

C6—N1—C2	118.1 (2)	C9—C8—H8A	126.4
C10—N2—C8	108.7 (2)	N2—C8—H8A	126.4
C10—N2—C7	124.5 (2)	C8—C9—N3	107.0 (2)
C8—N2—C7	126.5 (2)	C8—C9—H9A	126.5
C10—N3—C9	108.2 (2)	N3—C9—H9A	126.5
C10—N3—C11	125.7 (2)	N2—C10—N3	108.8 (2)
C9—N3—C11	125.9 (2)	N2—C10—H10A	125.6
C16—N4—C12	118.2 (2)	N3—C10—H10A	125.6
C2—C1—H1A	109.5	N3—C11—C12	112.6 (2)
C2—C1—H1B	109.5	N3—C11—H11A	109.1
H1A—C1—H1B	109.5	C12—C11—H11A	109.1
C2—C1—H1C	109.5	N3—C11—H11B	109.1
H1A—C1—H1C	109.5	C12—C11—H11B	109.1
H1B—C1—H1C	109.5	H11A—C11—H11B	107.8
N1—C2—C3	122.1 (3)	N4—C12—C13	123.3 (2)
N1—C2—C1	117.0 (3)	N4—C12—C11	113.2 (2)
C3—C2—C1	120.9 (3)	C13—C12—C11	123.5 (2)
C4—C3—C2	119.1 (3)	C12—C13—C14	117.8 (3)
C4—C3—H3A	120.5	C12—C13—H13A	121.1
C2—C3—H3A	120.5	C14—C13—H13A	121.1
C3—C4—C5	119.5 (3)	C15—C14—C13	119.4 (3)
C3—C4—H4A	120.3	C15—C14—H14A	120.3
C5—C4—H4A	120.3	C13—C14—H14A	120.3
C4—C5—C6	118.1 (3)	C14—C15—C16	119.2 (3)
C4—C5—H5A	120.9	C14—C15—H15A	120.4
C6—C5—H5A	120.9	C16—C15—H15A	120.4
N1—C6—C5	123.1 (3)	N4—C16—C15	122.1 (3)
N1—C6—C7	118.9 (2)	N4—C16—C17	116.4 (3)
C5—C6—C7	118.0 (2)	C15—C16—C17	121.4 (3)
N2—C7—C6	113.2 (2)	C16—C17—H17A	109.5
N2—C7—H7A	108.9	C16—C17—H17B	109.5
C6—C7—H7A	108.9	H17A—C17—H17B	109.5
N2—C7—H7B	108.9	C16—C17—H17C	109.5
C6—C7—H7B	108.9	H17A—C17—H17C	109.5
H7A—C7—H7B	107.8	H17B—C17—H17C	109.5
C9—C8—N2	107.3 (2)

C6—N1—C2—C3	−0.3 (4)	C8—N2—C10—N3	−0.9 (3)
C6—N1—C2—C1	−178.9 (3)	C7—N2—C10—N3	−175.1 (2)
N1—C2—C3—C4	0.8 (4)	C9—N3—C10—N2	0.9 (3)
C1—C2—C3—C4	179.4 (3)	C11—N3—C10—N2	175.9 (2)
C2—C3—C4—C5	−0.1 (4)	C10—N3—C11—C12	−89.3 (3)
C3—C4—C5—C6	−1.1 (4)	C9—N3—C11—C12	84.9 (3)
C2—N1—C6—C5	−1.0 (4)	C16—N4—C12—C13	−0.2 (4)
C2—N1—C6—C7	178.4 (2)	C16—N4—C12—C11	−179.6 (2)
C4—C5—C6—N1	1.7 (4)	N3—C11—C12—N4	−163.2 (2)
C4—C5—C6—C7	−177.7 (3)	N3—C11—C12—C13	17.3 (4)
C10—N2—C7—C6	73.2 (3)	N4—C12—C13—C14	0.4 (4)
C8—N2—C7—C6	−100.0 (3)	C11—C12—C13—C14	179.8 (3)
N1—C6—C7—N2	5.8 (3)	C12—C13—C14—C15	−0.5 (4)
C5—C6—C7—N2	−174.8 (2)	C13—C14—C15—C16	0.4 (4)
C10—N2—C8—C9	0.5 (3)	C12—N4—C16—C15	0.1 (4)
C7—N2—C8—C9	174.6 (2)	C12—N4—C16—C17	−178.4 (2)
N2—C8—C9—N3	0.1 (3)	C14—C15—C16—N4	−0.2 (4)
C10—N3—C9—C8	−0.6 (3)	C14—C15—C16—C17	178.2 (3)
C11—N3—C9—C8	−175.6 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7A···N4ⁱ	0.99	2.34	3.308 (4)	165
C7—H7B···Brⁱⁱ	0.99	2.79	3.660 (3)	147
C9—H9A···Br	0.95	2.91	3.695 (3)	141
C10—H10A···Brⁱ	0.95	2.68	3.521 (3)	148
C11—H11A···Br	0.99	2.93	3.801 (3)	147
C11—H11B···Brⁱ	0.99	2.89	3.690 (3)	138

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

Experimental details

Crystal data
Chemical formula	C₁₇H₁₉N₄⁺·Br⁻
M_r	359.27
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	173
a, b, c (Å)	8.2951 (4), 12.4992 (5), 16.1786 (7)
β (°)	95.709 (1)
V (Å³)	1669.11 (13)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	2.47
Crystal size (mm)	0.40 × 0.25 × 0.15

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.439, 0.709
No. of measured, independent and observed [I > 2σ(I)] reflections	10482, 3923, 2861
R_int	0.070
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.094, 1.00
No. of reflections	3923
No. of parameters	201
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.92, −0.50

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7A···N4ⁱ	0.99	2.34	3.308 (4)	165.0
C7—H7B···Brⁱⁱ	0.99	2.79	3.660 (3)	147.3
C9—H9A···Br	0.95	2.91	3.695 (3)	140.7
C10—H10A···Brⁱ	0.95	2.68	3.521 (3)	148.2
C11—H11A···Br	0.99	2.93	3.801 (3)	146.8
C11—H11B···Brⁱ	0.99	2.89	3.690 (3)	138.3

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

References

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