Literature DB >> 21202549

(S)-1-(2-Ammonio-3-methyl-butyl)-1,2-dihydro-pyridin-2-iminium dibromide.

Yifeng Wang¹, Jixv Zhang, Hui Chen, Shuping Luo.

Abstract

In the title compound, C(10)H(19)N(3) (2+)·2Br(-), the plane of the three butyl C atoms nearest to the pyridine ring is almost perpendicular to the ring [dihedral angle = 84.80 (2)°]. The N atom of the ammonium group is displaced by 1.150 (8) Å from the plane of these three C atoms. The iminium N atom lies on the opposite side of this plane. The crystal structure is stabilized by hydrogen bonds between the N and Br atoms, as well as by inter-molecular C-H⋯Br inter-actions.

Entities: CellLine Chemical Disease Gene

Year: 2008 PMID： 21202549 PMCID： PMC2961482 DOI： 10.1107/S1600536808012154

Source DB: PubMed Journal: Acta Crystallogr Sect E Struct Rep Online ISSN： 1600-5368

Related literature

For the synthesis of (S)-1-bromo-3-methylbutan-2-amine hydrobromide, see: Xu et al. (2006 ▶). For related literature, see: Luo et al. (2006 ▶).

Experimental

Crystal data

C10H19N3 2+·2Br− M = 341.10 Monoclinic, a = 5.9311 (11) Å b = 12.456 (2) Å c = 9.6807 (18) Å β = 99.733 (3)° V = 704.9 (2) Å3 Z = 2 Mo Kα radiation μ = 5.73 mm−1 T = 293 (2) K 0.45 × 0.34 × 0.20 mm

Data collection

Bruker SMART APEX CCD diffractometer Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.381, T max = 1.000 (expected range = 0.119–0.313) 4117 measured reflections 2307 independent reflections 2054 reflections with I > 2σ(I) R int = 0.038

Refinement

R[F 2 > 2σ(F 2)] = 0.041 wR(F 2) = 0.092 S = 0.99 2307 reflections 147 parameters 3 restraints H atoms treated by a mixture of independent and constrained refinement Δρmax = 0.91 e Å−3 Δρmin = −0.71 e Å−3 Absolute structure: Flack (1983 ▶), 696 Friedel pairs Flack parameter: 0.06 (2) Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT-Plus (Bruker, 2000 ▶); data reduction: SAINT-Plus; 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 datablocks global, I. DOI: 10.1107/S1600536808012154/cs2071sup1.cif Structure factors: contains datablocks I. DOI: 10.1107/S1600536808012154/cs2071Isup2.hkl Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C₁₀H₁₉N₃²⁺·2Br^–	F₀₀₀ = 340
M_r = 341.10	D_x = 1.607 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation λ = 0.71073 Å
a = 5.9311 (11) Å	Cell parameters from 1818 reflections
b = 12.456 (2) Å	θ = 5.4–53.4º
c = 9.6807 (18) Å	µ = 5.73 mm⁻¹
β = 99.733 (3)º	T = 293 (2) K
V = 704.9 (2) Å³	Prismatic, colorless
Z = 2	0.45 × 0.34 × 0.20 mm

Bruker SMART APEX CCD diffractometer	2307 independent reflections
Radiation source: fine-focus sealed tube	2054 reflections with I > 2σ(I)
Monochromator: graphite	R_int = 0.038
T = 293(2) K	θ_max = 27.0º
φ and ω scans	θ_min = 2.1º
Absorption correction: multi-scan(SADABS; Sheldrick, 1996)	h = −7→7
T_min = 0.381, T_max = 1.000	k = −12→15
4117 measured reflections	l = −12→12

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.041	w = 1/[σ²(F_o²) + (0.0533P)²] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.092	(Δ/σ)_max < 0.001
S = 0.99	Δρ_max = 0.91 e Å⁻³
2307 reflections	Δρ_min = −0.71 e Å⁻³
147 parameters	Extinction correction: none
3 restraints	Absolute structure: Flack (1983), 696 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.06 (2)
Secondary atom site location: difference Fourier map

	x	y	z	U_iso*/U_eq
Br1	1.02019 (11)	0.21057 (4)	0.84434 (6)	0.03666 (18)
Br2	0.61945 (10)	0.78903 (5)	0.54550 (7)	0.03742 (19)
N1	0.7631 (8)	0.4733 (4)	0.2958 (5)	0.0269 (11)
N2	0.4665 (11)	0.5923 (5)	0.3096 (7)	0.0398 (14)
N3	0.9054 (9)	0.3672 (4)	0.5746 (5)	0.0291 (11)
H3A	0.7799	0.3302	0.5406	0.044*
H3B	0.9481	0.3518	0.6651	0.044*
H3C	1.0172	0.3496	0.5280	0.044*
C1	0.5506 (11)	0.5110 (5)	0.2454 (6)	0.0295 (14)
C2	0.4223 (13)	0.4609 (6)	0.1291 (7)	0.0404 (17)
H2	0.2766	0.4863	0.0937	0.048*
C3	0.5050 (15)	0.3772 (7)	0.0677 (7)	0.052 (2)
H3	0.4149	0.3427	−0.0072	0.062*
C4	0.7331 (15)	0.3408 (7)	0.1176 (8)	0.052 (2)
H4	0.7975	0.2856	0.0725	0.062*
C5	0.8497 (13)	0.3880 (6)	0.2301 (7)	0.0378 (16)
H5	0.9953	0.3628	0.2661	0.045*
C6	0.9101 (11)	0.5224 (6)	0.4176 (7)	0.0314 (14)
H6A	0.8922	0.5998	0.4119	0.038*
H6B	1.0686	0.5060	0.4131	0.038*
C7	0.8569 (10)	0.4843 (5)	0.5581 (6)	0.0274 (13)
H7	0.6928	0.4945	0.5567	0.033*
C8	0.9855 (11)	0.5495 (6)	0.6818 (7)	0.0369 (16)
H8	0.9549	0.6256	0.6605	0.044*
C9	0.8975 (15)	0.5251 (8)	0.8154 (7)	0.057 (2)
H9A	0.9414	0.4535	0.8456	0.086*
H9B	0.7338	0.5309	0.7994	0.086*
H9C	0.9614	0.5753	0.8867	0.086*
C10	1.2447 (12)	0.5333 (8)	0.6994 (8)	0.057 (2)
H10A	1.3194	0.5787	0.7734	0.086*
H10B	1.2962	0.5514	0.6135	0.086*
H10C	1.2809	0.4596	0.7224	0.086*
H2A	0.355 (12)	0.623 (8)	0.260 (9)	0.09 (4)*
H2B	0.525 (13)	0.636 (6)	0.371 (7)	0.06 (3)*

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0508 (4)	0.0348 (4)	0.0231 (3)	−0.0033 (3)	0.0026 (3)	−0.0009 (3)
Br2	0.0309 (3)	0.0355 (4)	0.0448 (4)	0.0023 (3)	0.0033 (3)	−0.0065 (3)
N1	0.033 (3)	0.025 (3)	0.024 (3)	0.001 (2)	0.007 (2)	0.004 (2)
N2	0.040 (4)	0.035 (4)	0.041 (4)	0.006 (3)	−0.002 (3)	−0.003 (3)
N3	0.032 (3)	0.029 (3)	0.026 (3)	−0.004 (2)	0.004 (2)	0.003 (2)
C1	0.041 (4)	0.028 (4)	0.018 (3)	−0.001 (3)	0.002 (3)	0.006 (3)
C2	0.042 (4)	0.051 (5)	0.025 (3)	−0.004 (3)	−0.005 (3)	0.006 (3)
C3	0.074 (5)	0.054 (5)	0.025 (4)	−0.011 (4)	−0.002 (4)	−0.012 (4)
C4	0.077 (6)	0.049 (5)	0.032 (4)	0.006 (4)	0.014 (4)	−0.010 (3)
C5	0.051 (4)	0.038 (4)	0.026 (4)	0.009 (3)	0.012 (3)	0.003 (3)
C6	0.031 (3)	0.032 (4)	0.028 (3)	−0.003 (3)	−0.004 (3)	0.001 (3)
C7	0.021 (3)	0.030 (3)	0.029 (3)	0.001 (2)	−0.001 (2)	0.003 (3)
C8	0.046 (4)	0.030 (4)	0.031 (4)	0.002 (3)	−0.004 (3)	−0.006 (3)
C9	0.066 (5)	0.077 (6)	0.025 (4)	0.014 (5)	−0.003 (4)	−0.015 (4)
C10	0.035 (4)	0.088 (7)	0.043 (5)	−0.016 (4)	−0.008 (3)	−0.014 (5)

Br1—H3B	2.4578	C4—C5	1.325 (10)
Br2—H2B	2.55 (7)	C4—H4	0.9300
N1—C1	1.356 (8)	C5—H5	0.9300
N1—C5	1.380 (8)	C6—C7	1.523 (9)
N1—C6	1.476 (8)	C6—H6A	0.9700
N2—C1	1.329 (9)	C6—H6B	0.9700
N2—H2A	0.84 (8)	C7—C8	1.538 (9)
N2—H2B	0.84 (7)	C7—H7	0.9800
N3—C7	1.490 (8)	C8—C9	1.506 (11)
N3—H3A	0.8900	C8—C10	1.531 (10)
N3—H3B	0.8900	C8—H8	0.9800
N3—H3C	0.8900	C9—H9A	0.9600
C1—C2	1.396 (9)	C9—H9B	0.9600
C2—C3	1.334 (11)	C9—H9C	0.9600
C2—H2	0.9300	C10—H10A	0.9600
C3—C4	1.431 (11)	C10—H10B	0.9600
C3—H3	0.9300	C10—H10C	0.9600

C1—N1—C5	119.8 (6)	C7—C6—H6A	108.8
C1—N1—C6	122.1 (5)	N1—C6—H6B	108.8
C5—N1—C6	118.2 (5)	C7—C6—H6B	108.8
C1—N2—H2A	114 (7)	H6A—C6—H6B	107.7
C1—N2—H2B	133 (6)	N3—C7—C6	109.6 (5)
H2A—N2—H2B	107 (9)	N3—C7—C8	111.9 (5)
C7—N3—H3A	109.5	C6—C7—C8	112.3 (6)
C7—N3—H3B	109.5	N3—C7—H7	107.6
H3A—N3—H3B	109.5	C6—C7—H7	107.6
C7—N3—H3C	109.5	C8—C7—H7	107.6
H3A—N3—H3C	109.5	C9—C8—C10	111.4 (6)
H3B—N3—H3C	109.5	C9—C8—C7	111.3 (6)
N2—C1—N1	119.7 (6)	C10—C8—C7	111.9 (6)
N2—C1—C2	121.4 (7)	C9—C8—H8	107.3
N1—C1—C2	118.8 (7)	C10—C8—H8	107.3
C3—C2—C1	121.2 (7)	C7—C8—H8	107.3
C3—C2—H2	119.4	C8—C9—H9A	109.5
C1—C2—H2	119.4	C8—C9—H9B	109.5
C2—C3—C4	119.7 (7)	H9A—C9—H9B	109.5
C2—C3—H3	120.2	C8—C9—H9C	109.5
C4—C3—H3	120.2	H9A—C9—H9C	109.5
C5—C4—C3	117.9 (7)	H9B—C9—H9C	109.5
C5—C4—H4	121.0	C8—C10—H10A	109.5
C3—C4—H4	121.0	C8—C10—H10B	109.5
C4—C5—N1	122.5 (7)	H10A—C10—H10B	109.5
C4—C5—H5	118.7	C8—C10—H10C	109.5
N1—C5—H5	118.7	H10A—C10—H10C	109.5
N1—C6—C7	113.7 (5)	H10B—C10—H10C	109.5
N1—C6—H6A	108.8

C5—N1—C1—N2	179.3 (6)	C6—N1—C5—C4	−178.0 (7)
C6—N1—C1—N2	−2.4 (9)	C1—N1—C6—C7	82.3 (7)
C5—N1—C1—C2	1.2 (8)	C5—N1—C6—C7	−99.4 (7)
C6—N1—C1—C2	179.5 (6)	N1—C6—C7—N3	64.0 (7)
N2—C1—C2—C3	−177.9 (7)	N1—C6—C7—C8	−170.9 (5)
N1—C1—C2—C3	0.2 (10)	N3—C7—C8—C9	−67.1 (7)
C1—C2—C3—C4	−2.8 (11)	C6—C7—C8—C9	169.2 (6)
C2—C3—C4—C5	4.2 (11)	N3—C7—C8—C10	58.3 (8)
C3—C4—C5—N1	−3.0 (11)	C6—C7—C8—C10	−65.5 (8)
C1—N1—C5—C4	0.3 (10)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2B···Br2	0.84 (7)	2.55 (7)	3.368 (7)	167 (8)
N2—H2A···Br1ⁱ	0.84 (8)	2.53 (8)	3.357 (6)	168 (10)
N3—H3C···Br2ⁱⁱ	0.89	2.50	3.369 (5)	166
N3—H3B···Br1	0.89	2.46	3.238 (5)	147
N3—H3A···Br2ⁱⁱⁱ	0.89	2.43	3.281 (5)	160
C3—H3···Br1^iv	0.93	3.02	3.892 (8)	157
C4—H4···Br1^v	0.93	2.91	3.748 (8)	150
C6—H6A···Br1^vi	0.97	2.96	3.528 (7)	119
C5—H5···Br2ⁱⁱ	0.93	2.83	3.721 (7)	162
C8—H8···Br2	0.98	2.93	3.793 (7)	147

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2B⋯Br2	0.84 (7)	2.55 (7)	3.368 (7)	167 (8)
N2—H2A⋯Br1ⁱ	0.84 (8)	2.53 (8)	3.357 (6)	168 (10)
N3—H3C⋯Br2ⁱⁱ	0.89	2.50	3.369 (5)	166
N3—H3B⋯Br1	0.89	2.46	3.238 (5)	147
N3—H3A⋯Br2ⁱⁱⁱ	0.89	2.43	3.281 (5)	160
C3—H3⋯Br1^iv	0.93	3.02	3.892 (8)	157
C4—H4⋯Br1^v	0.93	2.91	3.748 (8)	150
C6—H6A⋯Br1^vi	0.97	2.96	3.528 (7)	119
C5—H5⋯Br2ⁱⁱ	0.93	2.83	3.721 (7)	162
C8—H8⋯Br2	0.98	2.93	3.793 (7)	147

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) ; (vi) .

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