organic compounds
(2S,7S)-10-Ethyl-1,8,10,12-tetraazatetracyclo[8.3.1.18,12.02,7]pentadecan-10-ium iodide
aUniversidad Nacional de Colombia, Sede Bogotá, Facultad de Ciencias, Departamento de Química, Cra 30 No.45-03, Bogotá, Código Postal 111321, Colombia, bUniversidad Nacional de Colombia, Sede Manizales, Colombia, cDepartment of Solid State Chemistry, Institute of Chemical Technology, Technická 5, 166 28 Prague, Czech Republic, and dInstitute of Physics ASCR, v.v.i., Na Slovance 2, 182 21 Praha 8, Czech Republic
*Correspondence e-mail: ariverau@unal.edu.co
The title chiral quaternary ammonium salt, C13H25N4+·I−, was synthesized through the Menschutkin reaction between the cage aminal (2S,7S)-1,8,10,12-tetraazatetracyclo[8.3.1.18,12.02,7]pentadecane and ethyl iodide. The quaternization occurred regioselectively on the nitrogen with major sp3 character. The consists of anions and cations separated by normal distances. Ions are not linked through C—H⋯I hydrogen bonds.
Related literature
For related structures, see: Becka et al. (1963); Rivera et al. (2011b,c); Rivera, Sadat-Bernal et al. (2012). For the synthesis of the precursor (2S,7S)-1,8,10,12-tetraazatetracyclo [8.3.1.18,12.02,7]pentadecane, see: Rivera, Quiroga et al. (2012). For the preparation of the title salt, see: Rivera et al. (2011a). For bond-length data, see: Allen et al. (1987). For the structural consequences of the see: Kakanejadifard & Farnia (1997); Rivera et al. (2011b). For synthetic applications of chiral quaternary ammonium salts, see: Lygo Andrews (2004); Park et al. (2004); Kim & Huh (2001).
Experimental
Crystal data
|
Data collection: CrysAlis PRO (Agilent, 2010); cell CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: Superflip (Palatinus & Chapuis, 2007); program(s) used to refine structure: JANA2006 (Petříček et al., 2006); molecular graphics: DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: JANA2006.
Supporting information
https://doi.org/10.1107/S1600536812040159/bh2451sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812040159/bh2451Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S1600536812040159/bh2451Isup3.cml
Preparation of 10-ethyl-(2S,7S)-1,8,10,12-tetraazatetracyclo [8.3.1.18,12.02,7] pentadecan-10-ium iodide
The title compound was synthesized according to the published procedure (Rivera et al., 2011a) by reacting (2S,7S)-1,8,10,12-tetraazatetracyclo[8.3.1.18,12.02,7]pentadecane and iodoethane. After work up a solid was obtained and then dissolved in water. After standing for several days at room temperature, crystals suitable for X-ray diffraction were obtained in 45% yield. Mp = 450–452 K.
All H atoms were discernible in difference Fourier maps and could be refined to reasonable geometry, but according to common practice H atoms bonded to C atoms were kept in ideal positions with C—H = 0.96 Å. Uiso(H) was set to 1.2Ueq(carrier atom). The
for chiral centers C1 and C7 was determined using the of the iodine site, by refining a (Flack, 1983) based on 1353 Friedel pairs.The aminal (2S,7S)-1,8,10,12-tetraazatetracyclo [8.3.1.18,12.02,7]pentadecane is interesting because it presents a chiral molecular structure, which contains two pairs of non equivalent nitrogen atoms. (Rivera, Quiroga et al., 2012). Employing the method described, (Rivera et al., 2011a) the title compound (I) was readily prepared from (2S,7S)-1,8,10,12-tetraazatetracyclo [8.3.1.18,12.02,7]pentadecane by alkylation with iodo ethane in dry acetonitrile, at room temperature. The chiral quaternary ammonium salts are used as asymmetric
(Lygo Andrews, 2004) and enantioselective reactions (Kim & Huh, 2001; Park et al., 2004).The molecular structure and atom-numbering scheme for (I) are shown in Fig 1.The compound (I) crystallizes in the orthorhombic P212121
The of title molecule, C13H25N4+.I-, contains 10-ethyl-(2S,7S)-1,8,10,12-tetraazatetracyclo- [8.3.1.18,12.02,7]pentadecan-10-ium cation and one iodide anion. The N-monoalkylation produces ions where one nitrogen atom carries a full positive charge resulting in a distortion of the bond lengths and angles in the heterocyclic ring, compared to the molecular structure in the solid state of hexamethylenetetramine (Becka et al., 1963). The C—N distances and bond angles (C—N—C and N—C—N) vary from 1.426 (3) to 1.575 (3) Å and from 104.97 (15) to 118.54 (16)°, respectively.Crystallographic data indicate the existence of an α (CNC) around N2 = 341.47°; N6 = 342.22°; N13 = 332.7°] as occurring in other aminal derived salts (Rivera et al., 2011b,c; Rivera, Sadat-Bernal et al., 2012).The geometry of the N—C—C—N moiety is close to the syn-periplanar conformation, evidenced by the N2—C1—C7—N6 torsion angle, 37.7 (2)°. The organization of the crystal packing for the title compound exhibits a network connecting ions through C—H···I and C—H···C short contacts (Fig. 2).
(Kakanejadifard & Farnia, 1997; Rivera et al., 2011b) in (I), manifest in the following facts: a lengthening of N4—C bond lengths [N4—C3, 1.575 (3) Å; N4—C5, 1.531 (3) Å; N4—C15, 1.529 (3) Å], and shortening of bond lengths N4C—N [C3—N2, 1.432 (3) Å; C5—N6, 1.426 (3) Å; C15—N13, 1.434 (3) Å] comparable with normal bond distances (Allen et al., 1987). Distortion of the C—N—C bond angles decreased the p character of non charged N atoms and reduces the N-pyramidality [For related structures, see: Becka et al. (1963); Rivera et al. (2011b,c); Rivera, Sadat-Bernal et al. (2012). For the synthesis of the precursor (2S,7S)-1,8,10,12-tetraazatetracyclo [8.3.1.18,12.02,7]pentadecane, see: Rivera, Quiroga et al. (2012). For the preparation of the title salt, see: Rivera et al. (2011a). For bond-length data, see: Allen et al. (1987). For the structural consequences of the
see: Kakanejadifard & Farnia (1997); Rivera et al. (2011b). For synthetic applications of chiral quaternary ammonium salts, see: Lygo Andrews (2004); Park et al. (2004); Kim & Huh (2001).Data collection: CrysAlis PRO (Agilent, 2010); cell
CrysAlis PRO (Agilent, 2010); data reduction: CrysAlis PRO (Agilent, 2010); program(s) used to solve structure: Superflip (Palatinus & Chapuis, 2007); program(s) used to refine structure: JANA2006 (Petříček et al., 2006); molecular graphics: DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: JANA2006 (Petříček et al., 2006).C13H25N4+·I− | Dx = 1.625 Mg m−3 |
Mr = 364.3 | Melting point: 450 K |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.7107 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 3457 reflections |
a = 10.2227 (5) Å | θ = 3.1–27.0° |
b = 12.0375 (6) Å | µ = 2.14 mm−1 |
c = 12.0941 (6) Å | T = 120 K |
V = 1488.25 (13) Å3 | Prism, colourless |
Z = 4 | 0.24 × 0.06 × 0.04 mm |
F(000) = 736 |
Agilent Xcalibur (Atlas, Gemini ultra) diffractometer | 3223 independent reflections |
Radiation source: Enhance (Mo) X-ray Source | 3093 reflections with I > 3σ(I) |
Graphite monochromator | Rint = 0.016 |
Detector resolution: 10.3784 pixels mm-1 | θmax = 27.1°, θmin = 3.1° |
ω scans | h = −13→9 |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010) | k = −14→15 |
Tmin = 0.746, Tmax = 1 | l = −10→15 |
5935 measured reflections |
Refinement on F2 | H-atom parameters constrained |
R[F > 3σ(F)] = 0.017 | Weighting scheme based on measured s.u.'s w = 1/(σ2(I) + 0.0004I2) |
wR(F) = 0.041 | (Δ/σ)max = 0.018 |
S = 1.19 | Δρmax = 0.23 e Å−3 |
3223 reflections | Δρmin = −0.47 e Å−3 |
164 parameters | Absolute structure: Flack (1983), 1353 Friedel pairs |
0 restraints | Absolute structure parameter: 0.026 (15) |
0 constraints |
C13H25N4+·I− | V = 1488.25 (13) Å3 |
Mr = 364.3 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 10.2227 (5) Å | µ = 2.14 mm−1 |
b = 12.0375 (6) Å | T = 120 K |
c = 12.0941 (6) Å | 0.24 × 0.06 × 0.04 mm |
Agilent Xcalibur (Atlas, Gemini ultra) diffractometer | 3223 independent reflections |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010) | 3093 reflections with I > 3σ(I) |
Tmin = 0.746, Tmax = 1 | Rint = 0.016 |
5935 measured reflections |
R[F > 3σ(F)] = 0.017 | H-atom parameters constrained |
wR(F) = 0.041 | Δρmax = 0.23 e Å−3 |
S = 1.19 | Δρmin = −0.47 e Å−3 |
3223 reflections | Absolute structure: Flack (1983), 1353 Friedel pairs |
164 parameters | Absolute structure parameter: 0.026 (15) |
0 restraints |
x | y | z | Uiso*/Ueq | ||
I1 | 0.995575 (12) | 0.462386 (9) | 0.966324 (9) | 0.01806 (4) | |
C1 | 0.4852 (2) | 0.29285 (13) | 0.73421 (15) | 0.0153 (5) | |
N2 | 0.36266 (17) | 0.33495 (15) | 0.78149 (16) | 0.0157 (5) | |
C3 | 0.2959 (2) | 0.26756 (17) | 0.86111 (18) | 0.0170 (6) | |
N4 | 0.20151 (16) | 0.17701 (14) | 0.81134 (14) | 0.0141 (5) | |
C5 | 0.2742 (2) | 0.08504 (16) | 0.74916 (17) | 0.0146 (6) | |
N6 | 0.35735 (17) | 0.12860 (15) | 0.66504 (15) | 0.0148 (5) | |
C7 | 0.4840 (2) | 0.16841 (14) | 0.70831 (15) | 0.0142 (5) | |
C8 | 0.6008 (2) | 0.13825 (18) | 0.63737 (19) | 0.0198 (7) | |
C9 | 0.7262 (2) | 0.16905 (18) | 0.6984 (2) | 0.0213 (7) | |
C10 | 0.7278 (2) | 0.28974 (16) | 0.73715 (19) | 0.0212 (7) | |
C11 | 0.6056 (2) | 0.31806 (19) | 0.8036 (2) | 0.0180 (6) | |
C12 | 0.2718 (2) | 0.37477 (18) | 0.69715 (19) | 0.0211 (6) | |
N13 | 0.19918 (17) | 0.28513 (15) | 0.64344 (16) | 0.0194 (5) | |
C14 | 0.2834 (2) | 0.20109 (17) | 0.58957 (18) | 0.0191 (6) | |
C15 | 0.1162 (2) | 0.23336 (18) | 0.72399 (18) | 0.0186 (6) | |
C16 | 0.1232 (2) | 0.13179 (17) | 0.90618 (18) | 0.0203 (6) | |
C17 | 0.0267 (2) | 0.04169 (19) | 0.87726 (19) | 0.0289 (7) | |
H1c1 | 0.490912 | 0.333228 | 0.66593 | 0.0183* | |
H1c3 | 0.247872 | 0.314369 | 0.91096 | 0.0204* | |
H2c3 | 0.358654 | 0.232404 | 0.908641 | 0.0204* | |
H1c5 | 0.325356 | 0.042413 | 0.80047 | 0.0175* | |
H2c5 | 0.212023 | 0.035003 | 0.716646 | 0.0175* | |
H1c7 | 0.493127 | 0.128663 | 0.776687 | 0.017* | |
H1c8 | 0.600074 | 0.059842 | 0.62289 | 0.0237* | |
H2c8 | 0.596557 | 0.178345 | 0.568841 | 0.0237* | |
H1c9 | 0.800126 | 0.155718 | 0.651276 | 0.0256* | |
H2c9 | 0.737333 | 0.120781 | 0.760916 | 0.0256* | |
H1c10 | 0.804004 | 0.302556 | 0.781695 | 0.0254* | |
H2c10 | 0.733483 | 0.338024 | 0.674158 | 0.0254* | |
H1c11 | 0.606624 | 0.395538 | 0.822422 | 0.0216* | |
H2c11 | 0.603662 | 0.274033 | 0.869799 | 0.0216* | |
H1c12 | 0.211459 | 0.426301 | 0.729818 | 0.0254* | |
H2c12 | 0.319 | 0.416333 | 0.642393 | 0.0254* | |
H1c14 | 0.23152 | 0.156343 | 0.540652 | 0.0229* | |
H2c14 | 0.342843 | 0.237356 | 0.539822 | 0.0229* | |
H1c15 | 0.062251 | 0.178719 | 0.688439 | 0.0224* | |
H2c15 | 0.062416 | 0.288707 | 0.7586 | 0.0224* | |
H1c16 | 0.078397 | 0.191556 | 0.9426 | 0.0243* | |
H2c16 | 0.181437 | 0.105459 | 0.962693 | 0.0243* | |
H1c17 | −0.019759 | 0.019483 | 0.942586 | 0.0346* | |
H2c17 | −0.034168 | 0.069235 | 0.823415 | 0.0346* | |
H3c17 | 0.072673 | −0.021042 | 0.847344 | 0.0346* |
U11 | U22 | U33 | U12 | U13 | U23 | |
I1 | 0.01928 (7) | 0.01921 (7) | 0.01568 (7) | 0.00180 (7) | 0.00111 (8) | 0.00244 (4) |
C1 | 0.0163 (11) | 0.0137 (9) | 0.0159 (8) | −0.0011 (8) | −0.0006 (11) | −0.0009 (7) |
N2 | 0.0173 (9) | 0.0108 (9) | 0.0188 (10) | 0.0020 (7) | 0.0016 (8) | 0.0008 (8) |
C3 | 0.0184 (10) | 0.0152 (10) | 0.0174 (10) | 0.0000 (8) | 0.0010 (9) | −0.0024 (8) |
N4 | 0.0139 (9) | 0.0150 (9) | 0.0133 (8) | −0.0001 (7) | 0.0012 (8) | 0.0007 (7) |
C5 | 0.0180 (10) | 0.0118 (10) | 0.0140 (10) | −0.0001 (8) | 0.0006 (9) | −0.0012 (8) |
N6 | 0.0158 (9) | 0.0147 (9) | 0.0138 (9) | −0.0025 (7) | −0.0021 (8) | 0.0006 (7) |
C7 | 0.0168 (11) | 0.0124 (8) | 0.0132 (8) | −0.0004 (9) | −0.0006 (10) | 0.0005 (7) |
C8 | 0.0216 (11) | 0.0155 (11) | 0.0222 (12) | −0.0011 (9) | 0.0048 (10) | −0.0031 (9) |
C9 | 0.0167 (11) | 0.0211 (12) | 0.0260 (12) | 0.0019 (9) | 0.0039 (10) | −0.0022 (10) |
C10 | 0.0165 (11) | 0.0212 (12) | 0.0257 (12) | −0.0032 (8) | −0.0022 (10) | −0.0010 (10) |
C11 | 0.0203 (11) | 0.0150 (11) | 0.0187 (11) | −0.0033 (9) | 0.0002 (10) | −0.0007 (9) |
C12 | 0.0218 (11) | 0.0143 (11) | 0.0274 (11) | 0.0025 (9) | 0.0003 (10) | 0.0061 (9) |
N13 | 0.0180 (9) | 0.0201 (9) | 0.0200 (9) | 0.0011 (7) | −0.0001 (8) | 0.0059 (7) |
C14 | 0.0218 (11) | 0.0234 (11) | 0.0121 (10) | −0.0023 (9) | −0.0013 (9) | 0.0027 (9) |
C15 | 0.0147 (11) | 0.0216 (11) | 0.0196 (11) | 0.0034 (8) | −0.0044 (9) | 0.0028 (9) |
C16 | 0.0206 (11) | 0.0254 (12) | 0.0148 (10) | −0.0005 (9) | 0.0045 (9) | 0.0005 (9) |
C17 | 0.0255 (12) | 0.0346 (12) | 0.0265 (11) | −0.0074 (11) | 0.0048 (10) | 0.0037 (9) |
C1—C7 | 1.530 (2) | C9—H2c9 | 0.96 |
C1—C11 | 1.521 (3) | C10—C9 | 1.527 (3) |
C1—H1c1 | 0.96 | C10—C11 | 1.524 (3) |
N2—C1 | 1.467 (3) | C10—H1c10 | 0.96 |
N2—C3 | 1.432 (3) | C10—H2c10 | 0.96 |
N2—C12 | 1.460 (3) | C11—H1c11 | 0.96 |
C3—H1c3 | 0.96 | C11—H2c11 | 0.96 |
C3—H2c3 | 0.96 | C12—H1c12 | 0.96 |
N4—C3 | 1.575 (3) | C12—H2c12 | 0.96 |
N4—C5 | 1.531 (3) | N13—C12 | 1.462 (3) |
N4—C15 | 1.529 (3) | N13—C14 | 1.480 (3) |
N4—C16 | 1.501 (3) | N13—C15 | 1.434 (3) |
C5—H1c5 | 0.96 | C14—H1c14 | 0.96 |
C5—H2c5 | 0.96 | C14—H2c14 | 0.96 |
N6—C5 | 1.426 (3) | C15—H1c15 | 0.96 |
N6—C7 | 1.476 (3) | C15—H2c15 | 0.96 |
N6—C14 | 1.472 (3) | C16—H1c16 | 0.96 |
C7—H1c7 | 0.96 | C16—H2c16 | 0.96 |
C8—C7 | 1.514 (3) | C17—C16 | 1.507 (3) |
C8—C9 | 1.526 (3) | C17—H1c17 | 0.96 |
C8—H1c8 | 0.96 | C17—H2c17 | 0.96 |
C8—H2c8 | 0.96 | C17—H3c17 | 0.96 |
C9—H1c9 | 0.96 | ||
N2—C1—C7 | 114.27 (17) | H1c9—C9—H2c9 | 105.87 |
N2—C1—C11 | 114.02 (16) | C9—C10—H1c10 | 109.47 |
N2—C1—H1c1 | 102.26 | C9—C10—H2c10 | 109.47 |
C7—C1—C11 | 108.35 (17) | C11—C10—C9 | 111.49 (18) |
C7—C1—H1c1 | 108.66 | C11—C10—H1c10 | 109.47 |
C11—C1—H1c1 | 108.95 | C11—C10—H2c10 | 109.47 |
C1—N2—C3 | 118.26 (16) | H1c10—C10—H2c10 | 107.37 |
C1—N2—C12 | 112.59 (17) | C1—C11—C10 | 109.11 (18) |
C12—N2—C3 | 110.62 (17) | C1—C11—H1c11 | 109.47 |
N2—C3—N4 | 115.28 (17) | C1—C11—H2c11 | 109.47 |
N2—C3—H1c3 | 109.47 | C10—C11—H1c11 | 109.47 |
N2—C3—H2c3 | 109.47 | C10—C11—H2c11 | 109.47 |
N4—C3—H1c3 | 109.47 | H1c11—C11—H2c11 | 109.83 |
N4—C3—H2c3 | 109.47 | N2—C12—N13 | 113.02 (17) |
H1c3—C3—H2c3 | 102.97 | N2—C12—H1c12 | 109.47 |
C3—N4—C5 | 113.01 (15) | N2—C12—H2c12 | 109.47 |
C3—N4—C15 | 107.85 (15) | N13—C12—H1c12 | 109.47 |
C3—N4—C16 | 106.58 (15) | N13—C12—H2c12 | 109.47 |
C5—N4—C15 | 104.97 (15) | H1c12—C12—H2c12 | 105.67 |
C16—N4—C5 | 111.84 (15) | C12—N13—C14 | 113.87 (17) |
C16—N4—C15 | 112.64 (15) | C12—N13—C15 | 108.62 (17) |
N4—C5—H1c5 | 109.47 | C14—N13—C15 | 110.25 (17) |
N4—C5—H2c5 | 109.47 | N6—C14—N13 | 115.54 (18) |
N6—C5—N4 | 111.96 (16) | N6—C14—H1c14 | 109.47 |
N6—C5—H1c5 | 109.47 | N6—C14—H2c14 | 109.47 |
N6—C5—H2c5 | 109.47 | N13—C14—H1c14 | 109.47 |
H1c5—C5—H2c5 | 106.87 | N13—C14—H2c14 | 109.47 |
C7—N6—C5 | 112.91 (16) | H1c14—C14—H2c14 | 102.63 |
C7—N6—C14 | 118.54 (16) | N4—C15—H1c15 | 109.47 |
C14—N6—C5 | 110.77 (16) | N4—C15—H2c15 | 109.47 |
C1—C7—H1c7 | 108.1 | N13—C15—N4 | 108.96 (17) |
N6—C7—C1 | 113.40 (17) | N13—C15—H1c15 | 109.47 |
N6—C7—C8 | 114.37 (16) | N13—C15—H2c15 | 109.47 |
N6—C7—H1c7 | 103.22 | H1c15—C15—H2c15 | 109.98 |
C8—C7—C1 | 110.15 (17) | N4—C16—C17 | 115.63 (18) |
C8—C7—H1c7 | 106.98 | N4—C16—H1c16 | 109.47 |
C7—C8—C9 | 109.28 (18) | N4—C16—H2c16 | 109.47 |
C7—C8—H1c8 | 109.47 | C17—C16—H1c16 | 109.47 |
C7—C8—H2c8 | 109.47 | C17—C16—H2c16 | 109.47 |
C9—C8—H1c8 | 109.47 | H1c16—C16—H2c16 | 102.52 |
C9—C8—H2c8 | 109.47 | C16—C17—H1c17 | 109.47 |
H1c8—C8—H2c8 | 109.66 | C16—C17—H2c17 | 109.47 |
C8—C9—C10 | 112.85 (18) | C16—C17—H3c17 | 109.47 |
C8—C9—H1c9 | 109.47 | H1c17—C17—H2c17 | 109.47 |
C8—C9—H2c9 | 109.47 | H1c17—C17—H3c17 | 109.47 |
C10—C9—H1c9 | 109.47 | H2c17—C17—H3c17 | 109.47 |
C10—C9—H2c9 | 109.47 |
Experimental details
Crystal data | |
Chemical formula | C13H25N4+·I− |
Mr | 364.3 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 120 |
a, b, c (Å) | 10.2227 (5), 12.0375 (6), 12.0941 (6) |
V (Å3) | 1488.25 (13) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 2.14 |
Crystal size (mm) | 0.24 × 0.06 × 0.04 |
Data collection | |
Diffractometer | Agilent Xcalibur (Atlas, Gemini ultra) |
Absorption correction | Multi-scan (CrysAlis PRO; Agilent, 2010) |
Tmin, Tmax | 0.746, 1 |
No. of measured, independent and observed [I > 3σ(I)] reflections | 5935, 3223, 3093 |
Rint | 0.016 |
(sin θ/λ)max (Å−1) | 0.641 |
Refinement | |
R[F > 3σ(F)], wR(F), S | 0.017, 0.041, 1.19 |
No. of reflections | 3223 |
No. of parameters | 164 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.23, −0.47 |
Absolute structure | Flack (1983), 1353 Friedel pairs |
Absolute structure parameter | 0.026 (15) |
Computer programs: CrysAlis PRO (Agilent, 2010), Superflip (Palatinus & Chapuis, 2007), JANA2006 (Petříček et al., 2006), DIAMOND (Brandenburg & Putz, 2005), JANA2006 (Petříček et al., 2006).
Footnotes
‡Other affiliation: Institute of Physics ASCR, v.v.i., Na Slovance 2, 182 21 Praha 8, Czech Republic.
Acknowledgements
We acknowledge the Dirección de Investigaciones, Sede Bogotá (DIB) y Sede Manizales (DIMA) de la Universidad Nacional de Colombia, for financial support of this work, as well as the Institutional research plan No. AVOZ10100521 of the Institute of Physics and the Praemium Academiae project of the Academy of Sciences of the Czech Republic (ASCR).
References
Agilent (2010). CrysAlis PRO. Agilent Technologies, Yarnton, England. Google Scholar
Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CSD CrossRef Web of Science Google Scholar
Becka, L. N. & Cruickshank, D. W. J. (1963). Proc. R. Soc. London Ser. A, 273, 435–455. CSD CrossRef CAS Web of Science Google Scholar
Brandenburg, K. & Putz, H. (2005). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Kakanejadifard, A. & Farnia, S. M. F. (1997). Tetrahedron, 53, 2551–2556. CSD CrossRef CAS Web of Science Google Scholar
Kim, D. Y. & Huh, S. C. (2001). Tetrahedron, 57, 8933–8938. Web of Science CrossRef CAS Google Scholar
Lygo, B. & Andrews, B. I. (2004). Acc. Chem. Res. 37, 518–525. Web of Science CrossRef PubMed CAS Google Scholar
Palatinus, L. & Chapuis, G. (2007). J. Appl. Cryst. 40, 786–790. Web of Science CrossRef CAS IUCr Journals Google Scholar
Park, E. J., Kim, M. H. & Kim, D. Y. (2004). J. Org. Chem. 69, 6897–6899. Web of Science CrossRef PubMed CAS Google Scholar
Petříček, V., Dusěk, M. & Palatinus, L. (2006). JANA2006. Institute of Physics, Praha, Czech Republic. Google Scholar
Rivera, A., Quiroga, D., Jiménez-Cruz, L., Fejfarová, K. & Dušek, M. (2012). Tetrahedron Lett. 53, 345–348. Web of Science CSD CrossRef CAS Google Scholar
Rivera, A., Sadat-Bernal, J., Ríos-Motta, J., Dušek, M. & Fejfarová, K. (2011b). J. Chem. Crystallogr. 41, 591–595. Web of Science CSD CrossRef CAS Google Scholar
Rivera, A., Sadat-Bernal, J., Ríos-Motta, J., Dušek, M. & Palatinus, L. (2011a). Chem. Cent. J. 5, article number 55. Web of Science CSD CrossRef Google Scholar
Rivera, A., Sadat-Bernal, J., Ríos-Motta, J., Fejfarová, K. & Dušek, M. (2011c). Acta Cryst. E67, o2629. Web of Science CSD CrossRef IUCr Journals Google Scholar
Rivera, A., Sadat-Bernal, J., Ríos-Motta, J., Fejfarová, K. & Dušek, M. (2012). Acta Cryst. E68, o17. Web of Science CSD 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.
The aminal (2S,7S)-1,8,10,12-tetraazatetracyclo [8.3.1.18,12.02,7]pentadecane is interesting because it presents a chiral molecular structure, which contains two pairs of non equivalent nitrogen atoms. (Rivera, Quiroga et al., 2012). Employing the method described, (Rivera et al., 2011a) the title compound (I) was readily prepared from (2S,7S)-1,8,10,12-tetraazatetracyclo [8.3.1.18,12.02,7]pentadecane by alkylation with iodo ethane in dry acetonitrile, at room temperature. The chiral quaternary ammonium salts are used as asymmetric phase-transfer catalysis (Lygo Andrews, 2004) and enantioselective reactions (Kim & Huh, 2001; Park et al., 2004).The molecular structure and atom-numbering scheme for (I) are shown in Fig 1.
The compound (I) crystallizes in the orthorhombic P212121 chiral space group. The asymmetric unit of title molecule, C13H25N4+.I-, contains 10-ethyl-(2S,7S)-1,8,10,12-tetraazatetracyclo- [8.3.1.18,12.02,7]pentadecan-10-ium cation and one iodide anion. The N-monoalkylation produces ions where one nitrogen atom carries a full positive charge resulting in a distortion of the bond lengths and angles in the heterocyclic ring, compared to the molecular structure in the solid state of hexamethylenetetramine (Becka et al., 1963). The C—N distances and bond angles (C—N—C and N—C—N) vary from 1.426 (3) to 1.575 (3) Å and from 104.97 (15) to 118.54 (16)°, respectively.
Crystallographic data indicate the existence of an anomeric effect (Kakanejadifard & Farnia, 1997; Rivera et al., 2011b) in (I), manifest in the following facts: a lengthening of N4—C bond lengths [N4—C3, 1.575 (3) Å; N4—C5, 1.531 (3) Å; N4—C15, 1.529 (3) Å], and shortening of bond lengths N4C—N [C3—N2, 1.432 (3) Å; C5—N6, 1.426 (3) Å; C15—N13, 1.434 (3) Å] comparable with normal bond distances (Allen et al., 1987). Distortion of the C—N—C bond angles decreased the p character of non charged N atoms and reduces the N-pyramidality [α (CNC) around N2 = 341.47°; N6 = 342.22°; N13 = 332.7°] as occurring in other aminal derived salts (Rivera et al., 2011b,c; Rivera, Sadat-Bernal et al., 2012).The geometry of the N—C—C—N moiety is close to the syn-periplanar conformation, evidenced by the N2—C1—C7—N6 torsion angle, 37.7 (2)°. The organization of the crystal packing for the title compound exhibits a network connecting ions through C—H···I and C—H···C short contacts (Fig. 2).