organic compounds
1,2,3,3-Tetramethyl-7-nitro-3,4-dihydroisoquinolinium tetrafluoroborate
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
The title salt, C13H17N2O2+·BF4−, was prepared by the methylation of the imine with Meerwein salt in dichloromethane. The 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.
Keywords: crystal structure; iminium salt; tetrafluoroborate.
CCDC reference: 1473672
Structure description
The iminium function is an important , 2004). As a result of its enhanced electrophilic character, the iminium usually reacts easily with a wide range of nucleophiles.
in organic synthesis (Bohé & Kammoun, 2002Peracid 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 leading to oxaziridines (Ogata & Sawaki, 1973). We report here the synthesis and the determination of a new iminium salt, C13H17N2O2+·BF4−.
The 4− 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)°. 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.
comprises a BFIn the crystal, the organic cations are linked to the BF4− anions through C—H⋯F contacts (Table 1 and Fig. 2).
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). 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 (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 solution afforded colourless crystals suitable for X-ray diffraction.
Refinement
Crystal data, data collection and structure .
details are summarized in Table 2Structural data
CCDC reference: 1473672
10.1107/S2414314616006192/bg4001sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S2414314616006192/bg4001Isup2.hkl
Supporting information file. DOI: 10.1107/S2414314616006192/bg4001Isup3.cml
The iminium function is an important
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
leading to oxaziridines (Ogata et al., 1973). We report here the synthesis and the 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).
The symmetric
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.
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
(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.Crystal data, data collection and structure
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
the could not be reliably determined and then the Friedel pairs were merged and any references to the were removed.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
(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.
Crystal data, data collection and structure
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.The iminium function is an important
in organic synthesis (Bohé & Kammoun, 2002, 2004). As synthetic building blocks, iminium salts represent activated, masked 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
leading to oxaziridines (Ogata & Sawaki, 1973). We report here the synthesis and the determination of a new iminium salt, C13H17N2O2+·BF4-.The
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).
Data collection: SMART (Bruker, 1998); cell
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).Fig. 1. The asymmetric unit of the title compound. Displacement ellipsoids are drawn at the 50% probability level. | |
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. | |
Fig. 3. Reaction scheme. |
C13H17N2O2+·BF4− | F(000) = 664 |
Mr = 320.09 | Dx = 1.408 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 7.7265 (2) Å | Cell parameters from 1794 reflections |
b = 13.4792 (4) Å | θ = 2.9–22.6° |
c = 14.5827 (3) Å | µ = 0.13 mm−1 |
β = 96.073 (1)° | T = 296 K |
V = 1510.22 (7) Å3 | Prism, colourless |
Z = 4 | 0.37 × 0.33 × 0.22 mm |
Bruker SMART CCD area-detector diffractometer | 1794 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.025 |
φ and ω scans | θmax = 25.4°, θmin = 3.5° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2008) | h = −9→9 |
Tmin = 0.964, Tmax = 0.983 | k = −11→16 |
6335 measured reflections | l = −17→17 |
2752 independent reflections |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.068 | H-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 reflections | Δρmax = 0.78 e Å−3 |
203 parameters | Δρmin = −0.47 e Å−3 |
C13H17N2O2+·BF4− | V = 1510.22 (7) Å3 |
Mr = 320.09 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 7.7265 (2) Å | µ = 0.13 mm−1 |
b = 13.4792 (4) Å | T = 296 K |
c = 14.5827 (3) Å | 0.37 × 0.33 × 0.22 mm |
β = 96.073 (1)° |
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 = 0.983 | Rint = 0.025 |
6335 measured reflections |
R[F2 > 2σ(F2)] = 0.068 | 0 restraints |
wR(F2) = 0.244 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.78 e Å−3 |
2770 reflections | Δρmin = −0.47 e Å−3 |
203 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
B1 | 0.2682 (5) | 0.5714 (3) | 0.8190 (3) | 0.0555 (10) | |
F1 | 0.3487 (4) | 0.5895 (3) | 0.74005 (18) | 0.1084 (10) | |
F2 | 0.3127 (4) | 0.4785 (2) | 0.8479 (2) | 0.1080 (10) | |
F3 | 0.1023 (4) | 0.5791 (3) | 0.8052 (4) | 0.191 (2) | |
F4 | 0.3427 (5) | 0.6376 (2) | 0.88258 (18) | 0.1151 (11) | |
O1 | 0.8422 (5) | 0.6099 (3) | 0.37772 (18) | 0.0962 (11) | |
O2 | 0.9054 (5) | 0.7123 (3) | 0.4856 (2) | 0.1028 (12) | |
N1 | 0.8482 (4) | 0.6332 (3) | 0.4566 (2) | 0.0636 (8) | |
N2 | 0.7341 (3) | 0.48461 (19) | 0.83658 (15) | 0.0406 (6) | |
C1 | 0.7342 (3) | 0.5531 (2) | 0.77464 (18) | 0.0378 (7) | |
C3 | 0.7267 (4) | 0.3756 (2) | 0.8128 (2) | 0.0468 (8) | |
C4 | 0.6195 (4) | 0.3635 (2) | 0.7200 (2) | 0.0485 (8) | |
H4A | 0.6279 | 0.2953 | 0.6996 | 0.073* | |
H4B | 0.4983 | 0.3770 | 0.7270 | 0.073* | |
C5 | 0.6784 (4) | 0.4035 (3) | 0.5566 (2) | 0.0505 (8) | |
H5 | 0.6421 | 0.3402 | 0.5377 | 0.061* | |
C6 | 0.7323 (4) | 0.4693 (3) | 0.4932 (2) | 0.0536 (8) | |
H6 | 0.7312 | 0.4518 | 0.4315 | 0.064* | |
C7 | 0.7881 (4) | 0.5620 (3) | 0.52354 (19) | 0.0474 (8) | |
C8 | 0.7896 (4) | 0.5919 (2) | 0.6134 (2) | 0.0440 (7) | |
H8 | 0.8275 | 0.6550 | 0.6317 | 0.053* | |
C9 | 0.7324 (3) | 0.5249 (2) | 0.67690 (18) | 0.0377 (7) | |
C10 | 0.6776 (3) | 0.4307 (2) | 0.64861 (19) | 0.0414 (7) | |
C11 | 0.9148 (4) | 0.3407 (3) | 0.8092 (3) | 0.0645 (10) | |
H11A | 0.9654 | 0.3758 | 0.7614 | 0.097* | |
H11B | 0.9157 | 0.2708 | 0.7967 | 0.097* | |
H11C | 0.9811 | 0.3536 | 0.8675 | 0.097* | |
C12 | 0.6383 (5) | 0.3166 (3) | 0.8838 (2) | 0.0675 (10) | |
H12A | 0.6206 | 0.2495 | 0.8628 | 0.101* | |
H12B | 0.5279 | 0.3463 | 0.8918 | 0.101* | |
H12C | 0.7105 | 0.3168 | 0.9415 | 0.101* | |
C13 | 0.7541 (5) | 0.5110 (3) | 0.9354 (2) | 0.0617 (10) | |
H13A | 0.8347 | 0.5651 | 0.9455 | 0.093* | |
H13B | 0.7975 | 0.4548 | 0.9711 | 0.093* | |
H13C | 0.6433 | 0.5304 | 0.9538 | 0.093* | |
C14 | 0.7380 (4) | 0.6597 (2) | 0.8001 (2) | 0.0508 (8) | |
H14A | 0.6595 | 0.6712 | 0.8458 | 0.076* | |
H14B | 0.7030 | 0.6990 | 0.7464 | 0.076* | |
H14C | 0.8538 | 0.6779 | 0.8246 | 0.076* |
U11 | U22 | U33 | U12 | U13 | U23 | |
B1 | 0.051 (2) | 0.057 (3) | 0.059 (2) | −0.0020 (18) | 0.0109 (16) | 0.0062 (19) |
F1 | 0.130 (2) | 0.128 (3) | 0.0682 (16) | −0.0274 (18) | 0.0188 (15) | 0.0026 (15) |
F2 | 0.130 (2) | 0.083 (2) | 0.112 (2) | 0.0264 (17) | 0.0151 (17) | 0.0179 (16) |
F3 | 0.0461 (15) | 0.166 (4) | 0.361 (7) | 0.0160 (17) | 0.017 (2) | 0.006 (4) |
F4 | 0.173 (3) | 0.104 (2) | 0.0725 (17) | −0.043 (2) | 0.0317 (17) | −0.0150 (15) |
O1 | 0.141 (3) | 0.107 (3) | 0.0437 (16) | −0.011 (2) | 0.0243 (16) | 0.0114 (15) |
O2 | 0.162 (3) | 0.085 (2) | 0.0617 (18) | −0.036 (2) | 0.0108 (18) | 0.0212 (17) |
N1 | 0.0783 (19) | 0.066 (2) | 0.0452 (17) | −0.0030 (17) | 0.0016 (13) | 0.0150 (15) |
N2 | 0.0372 (12) | 0.0493 (16) | 0.0356 (12) | 0.0008 (10) | 0.0055 (9) | −0.0009 (11) |
C1 | 0.0309 (12) | 0.0423 (17) | 0.0399 (15) | 0.0012 (11) | 0.0028 (10) | −0.0021 (13) |
C3 | 0.0507 (16) | 0.0419 (18) | 0.0484 (17) | 0.0017 (14) | 0.0082 (13) | 0.0065 (14) |
C4 | 0.0541 (17) | 0.0399 (17) | 0.0520 (18) | −0.0047 (14) | 0.0076 (13) | −0.0033 (14) |
C5 | 0.0611 (18) | 0.0451 (19) | 0.0448 (17) | −0.0004 (15) | 0.0032 (14) | −0.0102 (14) |
C6 | 0.0631 (19) | 0.062 (2) | 0.0354 (15) | 0.0081 (16) | 0.0028 (13) | −0.0053 (15) |
C7 | 0.0495 (16) | 0.056 (2) | 0.0364 (15) | 0.0045 (14) | 0.0049 (12) | 0.0081 (14) |
C8 | 0.0446 (15) | 0.0432 (18) | 0.0434 (16) | −0.0011 (13) | 0.0009 (12) | 0.0024 (13) |
C9 | 0.0379 (13) | 0.0397 (17) | 0.0352 (14) | 0.0042 (12) | 0.0028 (10) | −0.0004 (12) |
C10 | 0.0399 (14) | 0.0424 (18) | 0.0417 (15) | 0.0031 (12) | 0.0028 (11) | −0.0021 (13) |
C11 | 0.0592 (19) | 0.063 (2) | 0.071 (2) | 0.0185 (17) | 0.0071 (16) | 0.0095 (19) |
C12 | 0.087 (2) | 0.061 (2) | 0.057 (2) | −0.006 (2) | 0.0190 (18) | 0.0169 (18) |
C13 | 0.074 (2) | 0.074 (3) | 0.0367 (16) | −0.0028 (19) | 0.0026 (14) | −0.0035 (16) |
C14 | 0.0532 (17) | 0.048 (2) | 0.0516 (17) | −0.0037 (14) | 0.0090 (13) | −0.0123 (15) |
B1—F3 | 1.281 (5) | C5—H5 | 0.9300 |
B1—F2 | 1.353 (5) | C6—C7 | 1.379 (5) |
B1—F4 | 1.369 (5) | C6—H6 | 0.9300 |
B1—F1 | 1.387 (5) | C7—C8 | 1.370 (4) |
O1—N1 | 1.189 (4) | C8—C9 | 1.397 (4) |
O2—N1 | 1.214 (4) | C8—H8 | 0.9300 |
N1—C7 | 1.477 (4) | C9—C10 | 1.388 (4) |
N2—C1 | 1.292 (4) | C11—H11A | 0.9600 |
N2—C13 | 1.476 (4) | C11—H11B | 0.9600 |
N2—C3 | 1.510 (4) | C11—H11C | 0.9600 |
C1—C9 | 1.474 (4) | C12—H12A | 0.9600 |
C1—C14 | 1.484 (4) | C12—H12B | 0.9600 |
C3—C4 | 1.519 (4) | C12—H12C | 0.9600 |
C3—C12 | 1.523 (4) | C13—H13A | 0.9600 |
C3—C11 | 1.534 (4) | C13—H13B | 0.9600 |
C4—C10 | 1.485 (4) | C13—H13C | 0.9600 |
C4—H4A | 0.9700 | C14—H14A | 0.9600 |
C4—H4B | 0.9700 | C14—H14B | 0.9600 |
C5—C6 | 1.378 (5) | C14—H14C | 0.9600 |
C5—C10 | 1.392 (4) | ||
F3—B1—F2 | 109.9 (4) | C6—C7—N1 | 119.0 (3) |
F3—B1—F4 | 113.3 (4) | C7—C8—C9 | 118.2 (3) |
F2—B1—F4 | 108.5 (3) | C7—C8—H8 | 120.9 |
F3—B1—F1 | 112.6 (4) | C9—C8—H8 | 120.9 |
F2—B1—F1 | 107.4 (3) | C10—C9—C8 | 120.1 (3) |
F4—B1—F1 | 104.8 (3) | C10—C9—C1 | 119.7 (3) |
O1—N1—O2 | 123.0 (3) | C8—C9—C1 | 120.2 (3) |
O1—N1—C7 | 119.0 (3) | C9—C10—C5 | 119.7 (3) |
O2—N1—C7 | 118.0 (3) | C9—C10—C4 | 117.1 (3) |
C1—N2—C13 | 120.1 (3) | C5—C10—C4 | 123.2 (3) |
C1—N2—C3 | 122.6 (2) | C3—C11—H11A | 109.5 |
C13—N2—C3 | 117.2 (3) | C3—C11—H11B | 109.5 |
N2—C1—C9 | 119.4 (3) | H11A—C11—H11B | 109.5 |
N2—C1—C14 | 121.2 (3) | C3—C11—H11C | 109.5 |
C9—C1—C14 | 119.4 (3) | H11A—C11—H11C | 109.5 |
N2—C3—C4 | 108.2 (2) | H11B—C11—H11C | 109.5 |
N2—C3—C12 | 111.1 (3) | C3—C12—H12A | 109.5 |
C4—C3—C12 | 107.9 (3) | C3—C12—H12B | 109.5 |
N2—C3—C11 | 107.1 (2) | H12A—C12—H12B | 109.5 |
C4—C3—C11 | 111.5 (3) | C3—C12—H12C | 109.5 |
C12—C3—C11 | 111.0 (3) | H12A—C12—H12C | 109.5 |
C10—C4—C3 | 112.5 (2) | H12B—C12—H12C | 109.5 |
C10—C4—H4A | 109.1 | N2—C13—H13A | 109.5 |
C3—C4—H4A | 109.1 | N2—C13—H13B | 109.5 |
C10—C4—H4B | 109.1 | H13A—C13—H13B | 109.5 |
C3—C4—H4B | 109.1 | N2—C13—H13C | 109.5 |
H4A—C4—H4B | 107.8 | H13A—C13—H13C | 109.5 |
C6—C5—C10 | 120.6 (3) | H13B—C13—H13C | 109.5 |
C6—C5—H5 | 119.7 | C1—C14—H14A | 109.5 |
C10—C5—H5 | 119.7 | C1—C14—H14B | 109.5 |
C5—C6—C7 | 118.4 (3) | H14A—C14—H14B | 109.5 |
C5—C6—H6 | 120.8 | C1—C14—H14C | 109.5 |
C7—C6—H6 | 120.8 | H14A—C14—H14C | 109.5 |
C8—C7—C6 | 122.9 (3) | H14B—C14—H14C | 109.5 |
C8—C7—N1 | 118.0 (3) |
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−1/2, −z+3/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
C14—H14C···F3i | 0.96 | 2.38 | 3.012 (4) | 123.6 |
C12—H12B···F2 | 0.96 | 2.48 | 3.329 (5) | 148.1 |
C4—H4A···F4ii | 0.97 | 2.46 | 3.419 (4) | 168.2 |
Symmetry codes: (i) x+1, y, z; (ii) −x+1, y−1/2, −z+3/2. |
Experimental details
Crystal data | |
Chemical 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) |
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 (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.
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