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

Journal logoIUCrDATA
ISSN: 2414-3146
Volume 1| Part 4| April 2016| x160619
doi:10.1107/S2414314616006192

1,2,3,3-Tetra­methyl-7-nitro-3,4-di­hydro­isoquinolinium tetra­fluoro­borate

Mouna Bouzid,a Chakib Hrizib and Majed Kammouna*

aLaboratoire de Chimie des Substances Naturelles, Université de Sfax, Faculté des Sciences, BP 1171, 3000 Sfax, Tunisia, and bLaboratoire des Sciences de Matériaux et de l'Environnement, Université de Sfax, Faculté des Sciences, BP 1171, 3000 Sfax, Tunisia
*Correspondence e-mail: majed_kammoun@yahoo.fr

Edited by R. F. Baggio, Comisión Nacional de Energía Atómica, Argentina (Received 28 March 2016; accepted 12 April 2016; online 19 April 2016)

The title salt, C13H17N2O2+·BF4−, was prepared by the methyl­ation of the imine with Meerwein salt in di­chloro­methane. The asymmetric unit comprises a 1,3,3-trimethyl-7-nitro-3,4-di­hydro­isoquinolinium cation and a tetra­fluoro­borate anion. The coordination around the boron atom in the tetra­fluoro­borate anion is tetra­hedral. The heterocyclic ring adopts a half-chair conformation. The crystal packing is governed by means of C—H⋯F contacts, which lead to the formation of a three-dimensional network.

CCDC reference: 1473672

3D view (loading...)
[Scheme 3D1]
Chemical scheme
[Scheme 1]

Structure description

The iminium function is an important functional group in organic synthesis (Bohé & Kammoun, 2002[Bohé, L. & Kammoun, M. (2002). Tetrahedron Lett. 43, 803-805.], 2004[Bohé, L. & Kammoun, M. (2004). Tetrahedron Lett. 45, 747-751.]). As a result of its enhanced electrophilic character, the iminium functional group usually reacts easily with a wide range of nucleophiles.

Peracid oxidation of an iminium salt (I+) leads to oxaziridinium (Ox+). Catalytic oxidation methods through the iminium salt have been described (Hanquet & Lusinchi, 1993[Hanquet, G. & Lusinchi, X. (1993). Tetrahedron Lett. 34, 5299-5302.]). Oxidation of the iminium salt with a peracid involves the nucleophilic properties in a two-step mechanism: nucleophilic attack by the iminium peracid leading to a gem-amino perester, followed by intra­molecular nucleophilic substitution; this reaction resembles that of the peracid oxidation of imines leading to oxaziridines (Ogata & Sawaki, 1973[Ogata, Y. & Sawaki, Y. (1973). J. Am. Chem. Soc. 95, 4687-4692.]). We report here the synthesis and the crystal structure determination of a new iminium salt, C13H17N2O2+·BF4−.

The asymmetric unit comprises a BF4− anion and a 1,2,3,3-tetra­methyl-7-nitro-3,4-di­hydro­isoquinolinium cation (Fig. 1[link]). The B atom in the isolated BF4− anion is coord­inated by four fluoride anions with B—F bond lengths in the range 1.281 (5)–1.387 (5) Å and a F—B—F angle range of 104.8 (3)–113.3 (4)°. The heterocyclic ring adopts a half-chair conformation (r.m.s. deviation = 0.189 Å). It subtends an angle of 15.49 (3)° with the aromatic ring.

[Figure 1]
Figure 1
The asymmetric unit of the title compound. Displacement ellipsoids are drawn at the 50% probability level.

In the crystal, the organic cations are linked to the BF4− anions through C—H⋯F contacts (Table 1[link] and Fig. 2[link]).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A D⋯A D—H⋯A
C14—H14C⋯F3i 0.96 2.38 3.012 (4) 124
C12—H12B⋯F2 0.96 2.48 3.329 (5) 148
C4—H4A⋯F4ii 0.97 2.46 3.419 (4) 168
Symmetry codes: (i) x+1, y, z; (ii) [-x+1, y-{\script{1\over 2}}, -z+{\script{3\over 2}}].
[Figure 2]
Figure 2
Detail of title compound showing the way (dashed lines) in which the [BF4]− anion inter­acts with neighbouring organic cations. Displacement ellipsoids are drawn at the 50% probability level for the B and F atoms.

Synthesis and crystallization

The title salt (1) was prepared by methyl­ation of the imine nitrate (2) (500 mg, 2.5 mmol) with Meerwein salt in di­chloro­methane (15 ml) (Fig. 3[link]). Imine (2) has been described by Kammoun et al. (2012[Kammoun, M., Ben Salem, R. & Damak, M. (2012). Synth. Commun. 42, 2181-2190.]), as obtained from the commercially available tertiary alcohol (4). The mixture was stirred at room temperature for 8 h. The concentrate was chromatographed on silica gel, with di­chloro­methane as eluent (yield 42%). m.p. 426 K.

[Figure 3]
Figure 3
Reaction scheme.

Spectroscopic analysis,1H NMR (300 MHz, CDCl3, p.p.m): 1.61 (s, 6H, 2Me 3); 3.13 (s, 3H, Me 1); 3.54 (s, 2H, CH2 4); 3.91 (s, N—Me); 7.83 (d, J = 8.1, 1H aromatic H); 8.62 (dd, J = 8.1, J = 2.1, 1H, aromatic H); 8.86 (d, J = 2.1, 1H, aromatic H). 13C NMR (75 MHz, CDCl3, p.p.m): 21.15; 24.07; 38.82; 39.94; 64.61; 148.56; 125.82; 130.85; 131.13; 129.49; 143.97; 177.33. SM (FAB): 233 (M+.-tetra­fluoro­borate); 217 (M+.−16); 187 (M+.−46). Recrystallization from ether/hexane solution afforded colourless crystals suitable for X-ray diffraction.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2[link].

Table 2
Experimental details

Crystal data
Chemical formula C13H17N2O2+·BF4−
Mr 320.09
Crystal system, space group Monoclinic, P21/c
Temperature (K) 296
a, b, c (Å) 7.7265 (2), 13.4792 (4), 14.5827 (3)
β (°) 96.073 (1)
V (Å3) 1510.22 (7)
Z 4
Radiation type Mo Kα
μ (mm−1) 0.13
Crystal size (mm) 0.37 × 0.33 × 0.22
 
Data collection
Diffractometer Bruker SMART CCD area-detector
Absorption correction Multi-scan (SADABS; Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.])
Tmin, Tmax 0.964, 0.983
No. of measured, independent and observed [I > 2σ(I)] reflections 6335, 2752, 1794
Rint 0.025
(sin θ/λ)max (Å−1) 0.602
 
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.068, 0.244, 1.05
No. of reflections 2770
No. of parameters 203
H-atom treatment H-atom parameters constrained
Δρmax, Δρmin (e Å−3) 0.78, −0.47
Computer programs: SMART and SAINT (Bruker, 1998[Bruker (1998). SAINT, SMART and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]), SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]), SHELXL2014 (Sheldrick, 2015[Sheldrick, G. M. (2015). Acta Cryst. C71, 3-8.]) and ORTEP-3 for Windows (Farrugia, 2012[Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849-854.]).

Structural data

CCDC reference: 1473672

Crystal structure: contains datablock I. DOI: 10.1107/S2414314616006192/bg4001sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2414314616006192/bg4001Isup2.hkl

Supporting information file. DOI: 10.1107/S2414314616006192/bg4001Isup3.cml

checkCIF report


Chemical context top

The iminium function is an important functional group in organic synthesis (Bohe et al., 2002; 2004). As a synthetic building blocks, iminium salts represent activated, masked carbonyl coumpunds. Due to its enhanced electrophilic character, the iminium function usually reacts easily with a wide range of nucleophiles.

Peracid oxidation of an iminium salt (I+) lead to oxaziridinium(Ox+). Also, catalytic oxidation methods through the iminium salt have been described in the literature (Hanquet et al., 1993). Oxidation of the iminium salt with a peracid involves the nucleophilic properties in a two-step mechanism: nucleophilic attack by the iminium peracid leading to a gem-amino perester, followed by intra­molecular nucleophilic substitution; this reaction resembles that of the peracid oxidation of imines leading to oxaziridines (Ogata et al., 1973). We report here the synthesis and the crystal structure determination of a new iminium salt C13H17N2O2(BF4) (1).

The title compound (Scheme 1, above) has been prepared from the corresponding di­hydro­isoquinoleine imine by using the Meerwein salt as a methyl­ating agent, following the steps in Scheme 2 (below). Imine (2) has been described by (Kammoun et al., 2012), as obtained from the commercially available tertiary alcohol (4).

Structural commentary top

The symmetric unit cell of the title compound C13H17N2O2(BF4) contains a BF4- anion and a 1,2,3,3-tetra­methyl-7-nitro-3,4-di­hydro­isoquinolinium cation (Fig. 1).

The B atom in the isolated [BF4]- anion is coordinated by four fluoride anions with B–F bond lengths in the range 1.282 (5) - 1.379 (5) A° and a F—B—F angles span of 105.0 (3)–113.1 (5)° (Ideal tetra­gedral: 109°).

The aromatic ring in the cation is planar (rms deviation from the best plane: 0.0067Å). The heterocyclic ring, in turn, adopts a half-chair, far from planar conformation as shown by the rms deviation of fitted atoms: 0.189Å. Both planes subtend an angle of 15.49 (3)°.

The organic cations are linked to a [BF4]- anion through relatively weak C—H···Fcontacts, the most relevant of which are presented in Table 2 and shown in Fig. 2.

Synthesis and crystallization top

The iminium salt (Scheme 1, above) was prepared by methyl­ation of the imine nitrated (2) (500 mg, 2.5 mmol) with Meerwein salt in di­chloro­methane (15 ml). The mixture was stirred at room temperature for 8 hours. The concentrate was chromatographed on silica gel, with di­chloro­methane as eluent (yield 42%). m.p. 426 K. Spectroscopic analysis,1H NMR (300 MHz, CDCl3, p.p.m): 1.61 (s,6H, 2Me 3); 3.13 (s, 3H, Me 1); 3.54 (s, 2H, CH2 4); 3.91 (s ,N—Me);7.83 (d, J= 8.1 ,1H aromatic H); 8.62 ( dd, J = 8.1, J = 2.1, 1H, aromatic H); 8.86 (d, J = 2.1, 1H, aromatic H). 13C NMR (75 MHz, CDCl3, p.p.m): 21.15; 24.07; 38.82 ; 39.94; 64.61; 148.56 ; 125.82; 130.85; 131.13; 129.49; 143.97; 177.33. S.M (FAB): 233 (M+.-tetra­fluoro­borate); 217 (M+.-16); 187 (M+.-46). Recrystallizations from ether/hexane afford colorless crystals suitable for x-ray diffraction.

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 1.

All H atoms attached to C atoms were fixed geometrically and treated as riding with C—H = 0.93 Å (C Aromatic), 0.97 Å (C methyl­ene) and 0.96 Å (C methyl) and with Uiso(H) = 1.2 Ueq (C aromatic and C methyl­ene and Uiso(H) = 1.5 Ueq (C aromatic).

The residual electron density is rather large, due to a disordered fraction of the BF4 anion, too small as to accept a sensible modelling.

In the absence of significant anomalous scattering, the absolute configuration could not be reliably determined and then the Friedel pairs were merged and any references to the Flack parameter were removed.

Related literature top

For properties of the iminium function see Bohe & Kammoun (2002, 2004). For catalytic oxidation methods through the iminium salt see Hanquet & Lusinchi (1993) For literature related to the synthesis of the title compound see Kammoun et al. (2012); Ogata & Sawaki (1973).

Experimental top

The title salt (1) was prepared by methylation of the imine nitrate (2) (500 mg, 2.5 mmol) with Meerwein salt in dichloromethane (15 ml) (Fig. 3). Imine (2) has been described by Kammoun et al. (2012), as obtained from the commercially available tertiary alcohol (4).The mixture was stirred at room temperature for 8 h. The concentrate was chromatographed on silica gel, with dichloromethane as eluent (yield 42%). m.p. 426 K.

Spectroscopic analysis,1H NMR (300 MHz, CDCl3, p.p.m): 1.61 (s, 6H, 2Me 3); 3.13 (s, 3H, Me 1); 3.54 (s, 2H, CH2 4); 3.91 (s, N—Me); 7.83 (d, J = 8.1, 1H aromatic H); 8.62 (dd, J = 8.1, J = 2.1, 1H, aromatic H); 8.86 (d, J = 2.1, 1H, aromatic H). 13C NMR (75 MHz, CDCl3, p.p.m): 21.15; 24.07; 38.82; 39.94; 64.61; 148.56; 125.82; 130.85; 131.13; 129.49; 143.97; 177.33. SM (FAB): 233 (M+.-tetrafluoroborate); 217 (M+.-16); 187 (M+.-46). Recrystallization from ether/hexane afforded colourless crystals suitable for X-ray diffraction.

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 2. The residual electron density is rather large, due to a disordered fraction of the BF4 anion, too small as to accept a sensible modelling.

Structure description top

The iminium function is an important functional group in organic synthesis (Bohé & Kammoun, 2002, 2004). As synthetic building blocks, iminium salts represent activated, masked carbonyl compounds. As a result of its enhanced electrophilic character, the iminium function usually reacts easily with a wide range of nucleophiles.

Peracid oxidation of an iminium salt (I+) leads to oxaziridinium (Ox+). Catalytic oxidation methods through the iminium salt have been described (Hanquet & Lusinchi, 1993). Oxidation of the iminium salt with a peracid involves the nucleophilic properties in a two-step mechanism: nucleophilic attack by the iminium peracid leading to a gem-amino perester, followed by intramolecular nucleophilic substitution; this reaction resembles that of the peracid oxidation of imines leading to oxaziridines (Ogata & Sawaki, 1973). We report here the synthesis and the crystal structure determination of a new iminium salt, C13H17N2O2+·BF4-.

The asymmetric unit comprises a BF4- anion and a 1,2,3,3-tetramethyl-7-nitro-3,4-dihydroisoquinolinium cation (Fig. 1). The B atom in the isolated BF4- anion is coordinated by four fluoride anions with B—F bond lengths in the range 1.281 (5) - 1.387 (5) Å and a F—B—F angle range of 104.8 (3)–113.3 (4)° (ideal tetrahedral angle = 109°). The heterocyclic ring adopts a half-chair conformation (r.m.s. deviation = 0.189 Å). It subtends an angle of 15.49 (3)° with the aromatic ring.

In the crystal, the organic cations are linked to the BF4- anions through relatively weak C—H···F contacts (Table 2 and Fig. 2).

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012).

Figures top
[Figure 1] Fig. 1. The asymmetric unit of the title compound. Displacement ellipsoids are drawn at the 50% probability level.
[Figure 2] Fig. 2. Detail of title compound showing the way (dashed lines) in which the [BF4]- anion interacts with neighbouring organic cations. Displacement ellipsoids are drawn at the 50% probability level.
[Figure 3] Fig. 3. Reaction scheme.
1,2,3,3-Tetramethyl-7-nitro-3,4-dihydroisoquinolinium tetrafluoroborate top
Crystal data top
C13H17N2O2+·BF4−F(000) = 664
Mr = 320.09Dx = 1.408 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 7.7265 (2) ÅCell parameters from 1794 reflections
b = 13.4792 (4) Åθ = 2.9–22.6°
c = 14.5827 (3) ŵ = 0.13 mm−1
β = 96.073 (1)°T = 296 K
V = 1510.22 (7) Å3Prism, colourless
Z = 40.37 × 0.33 × 0.22 mm
Data collection top
Bruker SMART CCD area-detector
diffractometer		1794 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.025
φ and ω scansθmax = 25.4°, θmin = 3.5°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2008)		h = −9→9
Tmin = 0.964, Tmax = 0.983k = −11→16
6335 measured reflectionsl = −17→17
2752 independent reflections
Refinement top
Refinement on F20 restraints
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.068H-atom parameters constrained
wR(F2) = 0.244 w = 1/[σ2(Fo2) + (0.1509P)2 + 0.3904P]
where P = (Fo2 + 2Fc2)/3
S = 1.05(Δ/σ)max < 0.001
2770 reflectionsΔρmax = 0.78 e Å−3
203 parametersΔρmin = −0.47 e Å−3
Crystal data top
C13H17N2O2+·BF4−V = 1510.22 (7) Å3
Mr = 320.09Z = 4
Monoclinic, P21/cMo Kα radiation
a = 7.7265 (2) ŵ = 0.13 mm−1
b = 13.4792 (4) ÅT = 296 K
c = 14.5827 (3) Å0.37 × 0.33 × 0.22 mm
β = 96.073 (1)°
Data collection top
Bruker SMART CCD area-detector
diffractometer		2752 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2008)		1794 reflections with I > 2σ(I)
Tmin = 0.964, Tmax = 0.983Rint = 0.025
6335 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0680 restraints
wR(F2) = 0.244H-atom parameters constrained
S = 1.05Δρmax = 0.78 e Å−3
2770 reflectionsΔρmin = −0.47 e Å−3
203 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
B10.2682 (5)0.5714 (3)0.8190 (3)0.0555 (10)
F10.3487 (4)0.5895 (3)0.74005 (18)0.1084 (10)
F20.3127 (4)0.4785 (2)0.8479 (2)0.1080 (10)
F30.1023 (4)0.5791 (3)0.8052 (4)0.191 (2)
F40.3427 (5)0.6376 (2)0.88258 (18)0.1151 (11)
O10.8422 (5)0.6099 (3)0.37772 (18)0.0962 (11)
O20.9054 (5)0.7123 (3)0.4856 (2)0.1028 (12)
N10.8482 (4)0.6332 (3)0.4566 (2)0.0636 (8)
N20.7341 (3)0.48461 (19)0.83658 (15)0.0406 (6)
C10.7342 (3)0.5531 (2)0.77464 (18)0.0378 (7)
C30.7267 (4)0.3756 (2)0.8128 (2)0.0468 (8)
C40.6195 (4)0.3635 (2)0.7200 (2)0.0485 (8)
H4A0.62790.29530.69960.073*
H4B0.49830.37700.72700.073*
C50.6784 (4)0.4035 (3)0.5566 (2)0.0505 (8)
H50.64210.34020.53770.061*
C60.7323 (4)0.4693 (3)0.4932 (2)0.0536 (8)
H60.73120.45180.43150.064*
C70.7881 (4)0.5620 (3)0.52354 (19)0.0474 (8)
C80.7896 (4)0.5919 (2)0.6134 (2)0.0440 (7)
H80.82750.65500.63170.053*
C90.7324 (3)0.5249 (2)0.67690 (18)0.0377 (7)
C100.6776 (3)0.4307 (2)0.64861 (19)0.0414 (7)
C110.9148 (4)0.3407 (3)0.8092 (3)0.0645 (10)
H11A0.96540.37580.76140.097*
H11B0.91570.27080.79670.097*
H11C0.98110.35360.86750.097*
C120.6383 (5)0.3166 (3)0.8838 (2)0.0675 (10)
H12A0.62060.24950.86280.101*
H12B0.52790.34630.89180.101*
H12C0.71050.31680.94150.101*
C130.7541 (5)0.5110 (3)0.9354 (2)0.0617 (10)
H13A0.83470.56510.94550.093*
H13B0.79750.45480.97110.093*
H13C0.64330.53040.95380.093*
C140.7380 (4)0.6597 (2)0.8001 (2)0.0508 (8)
H14A0.65950.67120.84580.076*
H14B0.70300.69900.74640.076*
H14C0.85380.67790.82460.076*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
B10.051 (2)0.057 (3)0.059 (2)−0.0020 (18)0.0109 (16)0.0062 (19)
F10.130 (2)0.128 (3)0.0682 (16)−0.0274 (18)0.0188 (15)0.0026 (15)
F20.130 (2)0.083 (2)0.112 (2)0.0264 (17)0.0151 (17)0.0179 (16)
F30.0461 (15)0.166 (4)0.361 (7)0.0160 (17)0.017 (2)0.006 (4)
F40.173 (3)0.104 (2)0.0725 (17)−0.043 (2)0.0317 (17)−0.0150 (15)
O10.141 (3)0.107 (3)0.0437 (16)−0.011 (2)0.0243 (16)0.0114 (15)
O20.162 (3)0.085 (2)0.0617 (18)−0.036 (2)0.0108 (18)0.0212 (17)
N10.0783 (19)0.066 (2)0.0452 (17)−0.0030 (17)0.0016 (13)0.0150 (15)
N20.0372 (12)0.0493 (16)0.0356 (12)0.0008 (10)0.0055 (9)−0.0009 (11)
C10.0309 (12)0.0423 (17)0.0399 (15)0.0012 (11)0.0028 (10)−0.0021 (13)
C30.0507 (16)0.0419 (18)0.0484 (17)0.0017 (14)0.0082 (13)0.0065 (14)
C40.0541 (17)0.0399 (17)0.0520 (18)−0.0047 (14)0.0076 (13)−0.0033 (14)
C50.0611 (18)0.0451 (19)0.0448 (17)−0.0004 (15)0.0032 (14)−0.0102 (14)
C60.0631 (19)0.062 (2)0.0354 (15)0.0081 (16)0.0028 (13)−0.0053 (15)
C70.0495 (16)0.056 (2)0.0364 (15)0.0045 (14)0.0049 (12)0.0081 (14)
C80.0446 (15)0.0432 (18)0.0434 (16)−0.0011 (13)0.0009 (12)0.0024 (13)
C90.0379 (13)0.0397 (17)0.0352 (14)0.0042 (12)0.0028 (10)−0.0004 (12)
C100.0399 (14)0.0424 (18)0.0417 (15)0.0031 (12)0.0028 (11)−0.0021 (13)
C110.0592 (19)0.063 (2)0.071 (2)0.0185 (17)0.0071 (16)0.0095 (19)
C120.087 (2)0.061 (2)0.057 (2)−0.006 (2)0.0190 (18)0.0169 (18)
C130.074 (2)0.074 (3)0.0367 (16)−0.0028 (19)0.0026 (14)−0.0035 (16)
C140.0532 (17)0.048 (2)0.0516 (17)−0.0037 (14)0.0090 (13)−0.0123 (15)
Geometric parameters (Å, º) top
B1—F31.281 (5)C5—H50.9300
B1—F21.353 (5)C6—C71.379 (5)
B1—F41.369 (5)C6—H60.9300
B1—F11.387 (5)C7—C81.370 (4)
O1—N11.189 (4)C8—C91.397 (4)
O2—N11.214 (4)C8—H80.9300
N1—C71.477 (4)C9—C101.388 (4)
N2—C11.292 (4)C11—H11A0.9600
N2—C131.476 (4)C11—H11B0.9600
N2—C31.510 (4)C11—H11C0.9600
C1—C91.474 (4)C12—H12A0.9600
C1—C141.484 (4)C12—H12B0.9600
C3—C41.519 (4)C12—H12C0.9600
C3—C121.523 (4)C13—H13A0.9600
C3—C111.534 (4)C13—H13B0.9600
C4—C101.485 (4)C13—H13C0.9600
C4—H4A0.9700C14—H14A0.9600
C4—H4B0.9700C14—H14B0.9600
C5—C61.378 (5)C14—H14C0.9600
C5—C101.392 (4)
F3—B1—F2109.9 (4)C6—C7—N1119.0 (3)
F3—B1—F4113.3 (4)C7—C8—C9118.2 (3)
F2—B1—F4108.5 (3)C7—C8—H8120.9
F3—B1—F1112.6 (4)C9—C8—H8120.9
F2—B1—F1107.4 (3)C10—C9—C8120.1 (3)
F4—B1—F1104.8 (3)C10—C9—C1119.7 (3)
O1—N1—O2123.0 (3)C8—C9—C1120.2 (3)
O1—N1—C7119.0 (3)C9—C10—C5119.7 (3)
O2—N1—C7118.0 (3)C9—C10—C4117.1 (3)
C1—N2—C13120.1 (3)C5—C10—C4123.2 (3)
C1—N2—C3122.6 (2)C3—C11—H11A109.5
C13—N2—C3117.2 (3)C3—C11—H11B109.5
N2—C1—C9119.4 (3)H11A—C11—H11B109.5
N2—C1—C14121.2 (3)C3—C11—H11C109.5
C9—C1—C14119.4 (3)H11A—C11—H11C109.5
N2—C3—C4108.2 (2)H11B—C11—H11C109.5
N2—C3—C12111.1 (3)C3—C12—H12A109.5
C4—C3—C12107.9 (3)C3—C12—H12B109.5
N2—C3—C11107.1 (2)H12A—C12—H12B109.5
C4—C3—C11111.5 (3)C3—C12—H12C109.5
C12—C3—C11111.0 (3)H12A—C12—H12C109.5
C10—C4—C3112.5 (2)H12B—C12—H12C109.5
C10—C4—H4A109.1N2—C13—H13A109.5
C3—C4—H4A109.1N2—C13—H13B109.5
C10—C4—H4B109.1H13A—C13—H13B109.5
C3—C4—H4B109.1N2—C13—H13C109.5
H4A—C4—H4B107.8H13A—C13—H13C109.5
C6—C5—C10120.6 (3)H13B—C13—H13C109.5
C6—C5—H5119.7C1—C14—H14A109.5
C10—C5—H5119.7C1—C14—H14B109.5
C5—C6—C7118.4 (3)H14A—C14—H14B109.5
C5—C6—H6120.8C1—C14—H14C109.5
C7—C6—H6120.8H14A—C14—H14C109.5
C8—C7—C6122.9 (3)H14B—C14—H14C109.5
C8—C7—N1118.0 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C14—H14C···F3i0.962.383.012 (4)124
C12—H12B···F20.962.483.329 (5)148
C4—H4A···F4ii0.972.463.419 (4)168
Symmetry codes: (i) x+1, y, z; (ii) −x+1, y−1/2, −z+3/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C14—H14C···F3i0.962.383.012 (4)123.6
C12—H12B···F20.962.483.329 (5)148.1
C4—H4A···F4ii0.972.463.419 (4)168.2
Symmetry codes: (i) x+1, y, z; (ii) −x+1, y−1/2, −z+3/2.

Experimental details

Crystal data
Chemical formulaC13H17N2O2+·BF4−
Mr320.09
Crystal system, space groupMonoclinic, P21/c
Temperature (K)296
a, b, c (Å)7.7265 (2), 13.4792 (4), 14.5827 (3)
β (°) 96.073 (1)
V (Å3)1510.22 (7)
Z4
Radiation typeMo Kα
µ (mm−1)0.13
Crystal size (mm)0.37 × 0.33 × 0.22
Data collection
DiffractometerBruker SMART CCD area-detector
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2008)
Tmin, Tmax0.964, 0.983
No. of measured, independent and
observed [I > 2σ(I)] reflections		6335, 2752, 1794
Rint0.025
(sin θ/λ)max (Å−1)0.602
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.068, 0.244, 1.05
No. of reflections2770
No. of parameters203
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å−3)0.78, −0.47

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SHELXS97 (Sheldrick, 2008), SHELXL2014 (Sheldrick, 2015), ORTEP-3 for Windows (Farrugia, 2012).

 

Acknowledgements

This research was supported by the Ministry of High Education and Scientific Research, Tunisia.

References

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 First citationBohé, L. & Kammoun, M. (2004). Tetrahedron Lett. 45, 747–751.  Google Scholar
 First citationBruker (1998). SAINT, SMART and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
 First citationFarrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854.  Web of Science CrossRef CAS IUCr Journals Google Scholar
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 First citationOgata, Y. & Sawaki, Y. (1973). J. Am. Chem. Soc. 95, 4687–4692.  CrossRef CAS Google Scholar
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 First citationSheldrick, G. M. (2015). Acta Cryst. C71, 3–8.  Web of Science CrossRef IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

Journal logoIUCrDATA
ISSN: 2414-3146
Volume 1| Part 4| April 2016| x160619
doi:10.1107/S2414314616006192
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