organic compounds
N,N,N′,N′,N′′,N′′-Hexamethylguanidinium 1,1,3,3-tetracyanoprop-2-en-1-ide
aFakultät Chemie/Organische Chemie, Hochschule Aalen, Beethovenstrasse 1, D-73430 Aalen, Germany
*Correspondence e-mail: willi.kantlehner@hs-aalen.de
The 7H18N3+·C7HN4−, comprises one cation and one anion. The N,N,N′,N′,N′′,N′′-hexamethylguanidinium ion shows orientational disorder and two sets of N- and C-atom positions were found, with an occupancy ratio of 0.535 (3):0.465 (3). The C—N bond lengths in the guanidinium ion range from 1.339 (16) to 1.35 (2) Å, indicating partial double-bond character pointing towards charge delocalization within the NCN planes. The negative charge in the 1,1,3,3-tetracyanoprop-2-en-1-ide ion is delocalized within the CCC planes with the C—C bonds ranging in length from 1.379 (3) to 1.427 (3) Å, also indicating partial double-bond character.
of the title salt, CCCDC reference: 1469774
Structure description
The reaction of phosgene with N,N,N′,N′-tetramethylurea yields N,N,N′,N′-tetramethylchloroformamidinium chloride (Tiritiris & Kantlehner, 2008), which can be transformed by a mixture of dimethylamine and triethylamine into a mixture of N,N,N′,N′,N′′,N′′-hexamethylguanidinium chloride and triethylamine hydrochloride. Treating the salt mixture with an aqueous sodium hydroxide solution leads, after work up, to the pure guanidinium chloride. A further was possible by reacting N,N,N′,N′,N′′,N′′-hexamethylguanidinium chloride with sodium 1,1,3,3-tetracyano-prop-2-en-1-ide in acetonitrile. According to the structure analysis, the contains one N,N,N′,N′,N′′,N′′-hexamethylguanidinium ion and one 1,1,3,3-tetracyano-prop-2-en-1-ide ion (Fig. 1).
The cation shows orientational disorder and two sets of N and C positions were found, with an occupancy ratio of 0.535 (3):0.465 (3) (Fig. 2). The C—N bond lengths in the guanidinium ion range from 1.339 (16) to 1.35 (2) Å, indicating partial double-bond character. The N—C—N angles range from 119 (2) to 121.0 (15)°, indicating a nearly ideal trigonal–planar surrounding of the carbon atom C1 by the nitrogen atoms. The positive charge is completely delocalized in the CN3 planes. The C—N bond lengths in the cation are in very good agreement with the data from the analysis of known N,N,N′,N′,N′′,N′′-hexamethylguanidinium salts [see, for example: tetraphenylborate: Frey et al. (1998); chloride: Oelkers & Sundermeyer (2011); cyanate: Tiritiris & Kantlehner (2015)].
The negative charge in the 1,1,3,3-tetracyano-prop-2-en-1-ide ion is delocalized within the CCC planes and the C—C bond distances also indicate partial double-bond character [d(C8—C9) = 1.386 (3) Å; d(C9—C10) = 1.379 (3) Å; d(C8—C11) = 1.421 (3) Å; d(C8—C12) = 1.425 (3) Å; d(C10—C13) = 1.426 (3) Å; d(C10—C14) = 1.427 (3) Å]. The C—N bond lengths are in the range 1.148 (3) to 1.153 (3) Å and are characteristic for a triple bond. The dihedral angle between the C11–C8–C12 and the C13–C10–C14 planes is 2.38 (1)°, indicating that the anion is nearly flat. A similar anionic arrangement was observed in the of the compound 2,2′-bipyridin-1-ium 1,1,3,3-tetracyano-2-ethoxyprop-2-en-1-ide, with the C—C bond lengths ranging from 1.3956 (16) to 1.4261 (17) Å and the C—N bond lengths in the range 1.1471 (17) to 1.1522 (16) Å (Setifi et al., 2015). Since no significant hydrogen bonding exists in the title compound, the crystal packing results from electrostatic interactions between the cations and anions (Fig. 3).
Synthesis and crystallization
The title compound was obtained by mixing an acetonitrile solution of N,N,N′,N′,N′′,N′′-hexamethylguanidinium chloride with sodium 1,1,3,3-tetracyano-prop-2-en-1-ide dissolved in acetonitrile and stirring it for 18 h at room temperature. The precipitated sodium chloride was removed by filtration. After removal of the acetonitrile, the colorless residue was crystallized from an ethanolic solution. After evaporation of the solvent at ambient temperature, colorless single crystals suitable for X-ray analysis emerged.
Refinement
Crystal data, data collection and structure . The title compound crystallizes in the non-centrosymmetric P212121; however, in the absence of significant effects, the determined x = −0.4 (10) (Parsons et al., 2013) is essentially meaningless. The atoms C1–C7 and N1–N3 of the cation are disordered over two sets of sites (C1A/C1B–C7A/C7B and N1A/N1B–N3A/N3B) with refined occupancies of 0.535 (3):0.465 (3). The major and minor disordered components were each restrained to have similar geometries and the Uij components of the ADPs of the corresponding atoms were restrained to be similar if closer than 1.7 Å.
details are summarized in Table 1Structural data
CCDC reference: 1469774
10.1107/S2414314616004788/sj4016sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S2414314616004788/sj4016Isup2.hkl
The title compound was obtained by mixing an acetonitrile solution of N,N,N',N',N'',N''- hexamethylguanidinium chloride with sodium 1,1,3,3-tetracyano-prop-2-en-1-ide dissolved in acetonitrile and stirring it for 18 h at room temperature. The precipitated sodium chloride was removed by filtration. After removing of the acetonitrile, the colorless residue was crystallized from an ethanolic solution. After evaporation of the solvent at ambient temperature, colorless single crystals suitable for X-ray analysis emerged.
Crystal data, data collection and structure
details are summarized in Table 1. The title compound crystallizes in the non-centrosymmetric P212121; however, in the absence of significant effects, the determined x = −0.4 (10) (Parsons et al., 2013) is essentially meaningless. The atoms C1–C7 and N1–N3 of the cation are disordered over two sets of sites (C1A/C1B–C7A/C7B and N1A/N1B–N3A/N3B) with refined occupancies of 0.535 (3):0.465 (3). The major and minor disordered components were each restrained to have similar geometries and the Uij components of the ADPs of the corresponding atoms were restrained to be similar if closer than 1.7 Å.The title compound was obtained by mixing an acetonitrile solution of N,N,N',N',N'',N''-hexamethylguanidinium chloride with sodium 1,1,3,3-tetracyano-prop-2-en-1-ide dissolved in acetonitrile and stirring it for 18 h at room temperature. The precipitated sodium chloride was removed by filtration. After removal of the acetonitrile, the colorless residue was crystallized from an ethanolic solution. After evaporation of the solvent at ambient temperature, colorless single crystals suitable for X-ray analysis emerged.
Crystal data, data collection and structure
details are summarized in Table 1. The title compound crystallizes in the non-centrosymmetric P212121; however, in the absence of significant effects, the determined x = −0.4 (10) (Parsons et al., 2013) is essentially meaningless. The atoms C1–C7 and N1–N3 of the cation are disordered over two sets of sites (C1A/C1B–C7A/C7B and N1A/N1B–N3A/N3B) with refined occupancies of 0.535 (3):0.465 (3). The major and minor disordered components were each restrained to have similar geometries and the Uij components of the ADPs of the corresponding atoms were restrained to be similar if closer than 1.7 Å.The reaction of phosgene with N,N,N',N'-tetramethylurea yields N,N,N',N'-tetramethylchloroformamidinium chloride (Tiritiris & Kantlehner, 2008a), which can be transformed by a mixture of dimethylamine and triethylamine into a mixture of N,N,N',N',N'',N''-hexamethylguanidinium chloride and triethylamine hydrochloride. Treating the salt mixture with an aqueous sodium hydroxide solution leads, after work up, to the pure guanidinium chloride. A further
was possible by reacting N,N,N',N',N'',N''-hexamethylguanidinium chloride with sodium 1,1,3,3-tetracyano-prop-2-en-1-ide in acetonitrile. According to the structure analysis, the contains one N,N,N',N',N'',N''-hexamethylguanidinium ion and one 1,1,3,3-tetracyano-prop-2-en-1-ide ion (Fig. 1).The cation shows orientational disorder and two sets of N and C positions were found, with an occupancy ratio of 0.535 (3):0.465 (3) (Fig. 2). The C—N bond lengths in the guanidinium ion range from 1.339 (16) to 1.35 (2) Å, indicating partial double-bond character. The N—C—N angles range from 119 (2) to 121.0 (15)°, indicating a nearly ideal trigonal–planar surrounding of the carbon atom C1 by the nitrogen atoms. The positive charge is completely delocalized in the CN3 planes. The C—N bond lengths in the cation are in very good agreement with the data from the
analysis of known N,N,N',N',N'',N''-hexamethylguanidinium salts [see, for example: tetraphenylborate: Frey et al. (1998); chloride: Oelkers & Sundermeyer (2011); cyanate: Tiritiris & Kantlehner (2015b)].The negative charge in the 1,1,3,3-tetracyano-prop-2-en-1-ide ion is delocalized within the CCC planes and the C—C bond distances also indicate partial double-bond character [d(C8—C9) = 1.386 (3) Å; d(C9—C10) = 1.379 (3) Å; d(C8—C11) = 1.421 (3) Å; d(C8—C12) = 1.425 (3) Å; d(C10—C13) = 1.426 (3) Å; d(C10—C14) = 1.427 (3) Å]. The C—N bond lengths are in the range 1.148 (3) to 1.153 (3) Å and are characteristic for a triple bond. The dihedral angle between the C11–C8–C12 and the C13–C10–C14 planes is 2.38 (1)°, indicating that the anion is nearly flat. A similar anionic arrangement was observed in the
of the compound 2,2'-bipyridin-1-ium 1,1,3,3-tetracyano-2-ethoxyprop-2-en-1-ide, with the C—C bond lengths ranging from 1.3956 (16) to 1.4261 (17) Å and the C—N bond lengths in the range 1.1471 (17) to 1.1522 (16) Å (Setifi et al., 2015a). Since no significant hydrogen bonding exists in the title compound, the crystal packing results from electrostatic interactions between the cations and anions (Fig. 3).Data collection: APEX2 (Bruker, 2008); cell
SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015).Fig. 1. The structure of the title compound, with displacement ellipsoids at the 50% probability level. All H atoms have been omitted for clarity. Only the major orientation of the disordered cation is shown. | |
Fig. 2. The structure of the orientationally disordered N,N,N',N',N'',N''-hexamethylguanidinium ion. The C and N atoms are disordered between the dark (major orientation) and the opaque (minor orientation) positions. All H atoms have been omitted for clarity. | |
Fig. 3. Molecular packing of the title compound (view along ac). Both orientations of the disordered N,N,N',N',N'',N''-hexamethylguanidinium ion are shown. |
C7H18N3+·C7HN4− | Dx = 1.153 Mg m−3 |
Mr = 285.36 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, P212121 | Cell parameters from 12519 reflections |
a = 7.7705 (5) Å | θ = 1.9–26.4° |
b = 9.8189 (6) Å | µ = 0.08 mm−1 |
c = 21.5478 (14) Å | T = 100 K |
V = 1644.05 (18) Å3 | Block, colorless |
Z = 4 | 0.20 × 0.14 × 0.10 mm |
F(000) = 608 |
Bruker Kappa APEXII DUO diffractometer | 3368 independent reflections |
Radiation source: fine-focus sealed tube | 2709 reflections with I > 2σ(I) |
Triumph monochromator | Rint = 0.039 |
φ scans, and ω scans | θmax = 26.4°, θmin = 1.9° |
Absorption correction: multi-scan (Blessing, 1995) | h = −9→9 |
Tmin = 0.720, Tmax = 0.745 | k = −12→11 |
12519 measured reflections | l = −26→25 |
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)] = 0.036 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.076 | H-atom parameters constrained |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0318P)2 + 0.107P] where P = (Fo2 + 2Fc2)/3 |
3368 reflections | (Δ/σ)max < 0.001 |
293 parameters | Δρmax = 0.11 e Å−3 |
171 restraints | Δρmin = −0.13 e Å−3 |
C7H18N3+·C7HN4− | V = 1644.05 (18) Å3 |
Mr = 285.36 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 7.7705 (5) Å | µ = 0.08 mm−1 |
b = 9.8189 (6) Å | T = 100 K |
c = 21.5478 (14) Å | 0.20 × 0.14 × 0.10 mm |
Bruker Kappa APEXII DUO diffractometer | 3368 independent reflections |
Absorption correction: multi-scan (Blessing, 1995) | 2709 reflections with I > 2σ(I) |
Tmin = 0.720, Tmax = 0.745 | Rint = 0.039 |
12519 measured reflections |
R[F2 > 2σ(F2)] = 0.036 | 171 restraints |
wR(F2) = 0.076 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.11 e Å−3 |
3368 reflections | Δρmin = −0.13 e Å−3 |
293 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s 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 > σ(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. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
C1A | 0.473 (2) | 0.769 (4) | 0.1683 (15) | 0.018 (2) | 0.535 (3) |
C2A | 0.727 (2) | 0.7960 (18) | 0.1024 (8) | 0.034 (4) | 0.535 (3) |
H2A | 0.7249 | 0.8883 | 0.1197 | 0.051* | 0.535 (3) |
H2B | 0.7264 | 0.8011 | 0.0570 | 0.051* | 0.535 (3) |
H2C | 0.8315 | 0.7491 | 0.1163 | 0.051* | 0.535 (3) |
C3A | 0.5426 (8) | 0.5938 (8) | 0.0903 (4) | 0.0299 (15) | 0.535 (3) |
H3A | 0.4501 | 0.5437 | 0.1111 | 0.045* | 0.535 (3) |
H3B | 0.6473 | 0.5381 | 0.0899 | 0.045* | 0.535 (3) |
H3C | 0.5082 | 0.6143 | 0.0476 | 0.045* | 0.535 (3) |
C4A | 0.201 (2) | 0.727 (2) | 0.2239 (7) | 0.028 (3) | 0.535 (3) |
H4A | 0.1281 | 0.6456 | 0.2203 | 0.042* | 0.535 (3) |
H4B | 0.1284 | 0.8074 | 0.2293 | 0.042* | 0.535 (3) |
H4C | 0.2774 | 0.7170 | 0.2598 | 0.042* | 0.535 (3) |
C5A | 0.209 (2) | 0.7339 (19) | 0.1085 (9) | 0.027 (3) | 0.535 (3) |
H5A | 0.2879 | 0.7514 | 0.0739 | 0.041* | 0.535 (3) |
H5B | 0.1173 | 0.8023 | 0.1084 | 0.041* | 0.535 (3) |
H5C | 0.1588 | 0.6429 | 0.1040 | 0.041* | 0.535 (3) |
C6A | 0.7115 (10) | 0.8155 (9) | 0.2409 (4) | 0.0289 (15) | 0.535 (3) |
H6A | 0.7554 | 0.7291 | 0.2246 | 0.043* | 0.535 (3) |
H6B | 0.7045 | 0.8105 | 0.2863 | 0.043* | 0.535 (3) |
H6C | 0.7893 | 0.8895 | 0.2290 | 0.043* | 0.535 (3) |
C7A | 0.446 (2) | 0.9560 (16) | 0.2432 (9) | 0.027 (3) | 0.535 (3) |
H7A | 0.3447 | 0.9769 | 0.2179 | 0.040* | 0.535 (3) |
H7B | 0.5214 | 1.0361 | 0.2449 | 0.040* | 0.535 (3) |
H7C | 0.4098 | 0.9316 | 0.2853 | 0.040* | 0.535 (3) |
N1A | 0.5760 (4) | 0.7210 (3) | 0.12360 (16) | 0.0251 (8) | 0.535 (3) |
N2A | 0.3046 (3) | 0.7416 (3) | 0.16741 (14) | 0.0207 (8) | 0.535 (3) |
N3A | 0.5401 (4) | 0.8415 (3) | 0.21540 (14) | 0.0222 (8) | 0.535 (3) |
C1B | 0.465 (2) | 0.764 (5) | 0.1653 (18) | 0.020 (3) | 0.465 (3) |
C2B | 0.7389 (14) | 0.7854 (11) | 0.2214 (4) | 0.031 (2) | 0.465 (3) |
H2B1 | 0.6659 | 0.7618 | 0.2569 | 0.047* | 0.465 (3) |
H2B2 | 0.7886 | 0.8760 | 0.2278 | 0.047* | 0.465 (3) |
H2B3 | 0.8315 | 0.7183 | 0.2174 | 0.047* | 0.465 (3) |
C3B | 0.735 (3) | 0.805 (2) | 0.1080 (9) | 0.035 (4) | 0.465 (3) |
H3B1 | 0.6567 | 0.8222 | 0.0733 | 0.052* | 0.465 (3) |
H3B2 | 0.8028 | 0.7227 | 0.0994 | 0.052* | 0.465 (3) |
H3B3 | 0.8132 | 0.8827 | 0.1130 | 0.052* | 0.465 (3) |
C4B | 0.411 (2) | 0.9432 (18) | 0.2423 (10) | 0.027 (3) | 0.465 (3) |
H4B1 | 0.4591 | 0.9251 | 0.2835 | 0.040* | 0.465 (3) |
H4B2 | 0.3064 | 0.9983 | 0.2465 | 0.040* | 0.465 (3) |
H4B3 | 0.4955 | 0.9927 | 0.2172 | 0.040* | 0.465 (3) |
C5B | 0.218 (3) | 0.743 (3) | 0.2362 (9) | 0.030 (3) | 0.465 (3) |
H5B1 | 0.2096 | 0.6533 | 0.2168 | 0.045* | 0.465 (3) |
H5B2 | 0.1137 | 0.7959 | 0.2267 | 0.045* | 0.465 (3) |
H5B3 | 0.2284 | 0.7328 | 0.2813 | 0.045* | 0.465 (3) |
C6B | 0.213 (2) | 0.729 (2) | 0.0983 (11) | 0.032 (4) | 0.465 (3) |
H6B1 | 0.1353 | 0.6535 | 0.1091 | 0.048* | 0.465 (3) |
H6B2 | 0.2127 | 0.7416 | 0.0532 | 0.048* | 0.465 (3) |
H6B3 | 0.1737 | 0.8122 | 0.1186 | 0.048* | 0.465 (3) |
C7B | 0.4713 (9) | 0.5843 (10) | 0.0862 (5) | 0.0338 (19) | 0.465 (3) |
H7B1 | 0.5800 | 0.5614 | 0.1067 | 0.051* | 0.465 (3) |
H7B2 | 0.4942 | 0.6119 | 0.0432 | 0.051* | 0.465 (3) |
H7B3 | 0.3955 | 0.5045 | 0.0863 | 0.051* | 0.465 (3) |
N1B | 0.6359 (4) | 0.7857 (4) | 0.16509 (19) | 0.0248 (10) | 0.465 (3) |
N2B | 0.3689 (5) | 0.8151 (4) | 0.21212 (17) | 0.0214 (10) | 0.465 (3) |
N3B | 0.3883 (4) | 0.6959 (3) | 0.11918 (17) | 0.0227 (10) | 0.465 (3) |
N4 | 0.4223 (3) | −0.0855 (2) | −0.00048 (8) | 0.0491 (6) | |
N5 | 0.5394 (3) | 0.2260 (2) | 0.13383 (9) | 0.0584 (6) | |
N6 | 0.5537 (3) | 0.46050 (19) | −0.16125 (9) | 0.0439 (5) | |
N7 | 0.4329 (3) | 0.03094 (18) | −0.15091 (8) | 0.0419 (5) | |
C8 | 0.5027 (3) | 0.1647 (2) | 0.01848 (9) | 0.0269 (5) | |
C9 | 0.5256 (3) | 0.2613 (2) | −0.02772 (9) | 0.0277 (5) | |
H9 | 0.5563 | 0.3494 | −0.0133 | 0.033* | |
C10 | 0.5110 (2) | 0.2500 (2) | −0.09130 (9) | 0.0255 (5) | |
C11 | 0.4570 (3) | 0.0269 (2) | 0.00714 (9) | 0.0299 (5) | |
C12 | 0.5233 (3) | 0.1998 (2) | 0.08220 (11) | 0.0366 (6) | |
C13 | 0.5355 (3) | 0.3669 (2) | −0.12963 (9) | 0.0308 (5) | |
C14 | 0.4672 (3) | 0.1278 (2) | −0.12346 (9) | 0.0284 (5) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1A | 0.022 (4) | 0.013 (4) | 0.019 (4) | 0.002 (4) | −0.002 (4) | 0.002 (4) |
C2A | 0.026 (6) | 0.029 (5) | 0.048 (7) | −0.006 (4) | 0.010 (5) | −0.004 (5) |
C3A | 0.037 (4) | 0.023 (3) | 0.029 (3) | 0.003 (3) | 0.004 (4) | −0.007 (2) |
C4A | 0.028 (4) | 0.038 (6) | 0.019 (5) | −0.003 (3) | 0.003 (3) | 0.003 (4) |
C5A | 0.033 (5) | 0.025 (4) | 0.022 (5) | −0.007 (4) | −0.004 (3) | −0.001 (3) |
C6A | 0.023 (3) | 0.036 (4) | 0.028 (4) | 0.003 (3) | −0.014 (3) | −0.002 (3) |
C7A | 0.027 (5) | 0.022 (4) | 0.032 (4) | 0.001 (3) | −0.003 (4) | −0.008 (3) |
N1A | 0.0233 (17) | 0.0238 (16) | 0.0282 (18) | 0.0004 (13) | 0.0053 (14) | −0.0020 (14) |
N2A | 0.0192 (15) | 0.0254 (16) | 0.0176 (17) | −0.0042 (13) | 0.0006 (13) | 0.0001 (14) |
N3A | 0.0190 (16) | 0.0221 (15) | 0.0255 (17) | 0.0000 (13) | −0.0064 (14) | −0.0002 (13) |
C1B | 0.025 (5) | 0.017 (5) | 0.019 (5) | 0.000 (4) | 0.001 (5) | 0.002 (4) |
C2B | 0.030 (4) | 0.031 (5) | 0.034 (5) | 0.000 (3) | −0.003 (3) | −0.004 (3) |
C3B | 0.024 (7) | 0.058 (10) | 0.021 (5) | 0.002 (5) | 0.008 (4) | 0.003 (5) |
C4B | 0.042 (7) | 0.018 (4) | 0.020 (4) | −0.004 (4) | 0.003 (5) | −0.001 (3) |
C5B | 0.027 (5) | 0.032 (6) | 0.031 (7) | −0.003 (4) | 0.012 (6) | 0.002 (6) |
C6B | 0.019 (5) | 0.046 (7) | 0.032 (7) | 0.002 (4) | −0.010 (4) | 0.002 (5) |
C7B | 0.038 (5) | 0.030 (3) | 0.033 (4) | 0.002 (4) | 0.000 (5) | −0.009 (2) |
N1B | 0.0181 (18) | 0.032 (2) | 0.025 (2) | 0.0000 (15) | 0.0009 (16) | 0.0008 (18) |
N2B | 0.026 (2) | 0.0186 (19) | 0.019 (2) | −0.0001 (15) | 0.0034 (16) | −0.0007 (15) |
N3B | 0.0215 (18) | 0.0236 (19) | 0.023 (2) | 0.0026 (15) | 0.0003 (16) | −0.0021 (17) |
N4 | 0.0887 (17) | 0.0356 (11) | 0.0229 (10) | −0.0180 (12) | −0.0009 (11) | 0.0039 (9) |
N5 | 0.1007 (17) | 0.0476 (12) | 0.0270 (12) | −0.0207 (14) | −0.0035 (12) | −0.0047 (9) |
N6 | 0.0597 (13) | 0.0333 (10) | 0.0389 (11) | −0.0060 (10) | 0.0021 (11) | 0.0079 (10) |
N7 | 0.0726 (15) | 0.0281 (10) | 0.0248 (10) | 0.0068 (10) | −0.0085 (10) | 0.0000 (9) |
C8 | 0.0345 (12) | 0.0271 (10) | 0.0190 (10) | −0.0037 (9) | 0.0001 (9) | −0.0024 (8) |
C9 | 0.0289 (11) | 0.0244 (10) | 0.0298 (11) | −0.0020 (9) | −0.0001 (9) | −0.0030 (9) |
C10 | 0.0300 (12) | 0.0220 (10) | 0.0245 (10) | 0.0011 (9) | 0.0018 (8) | 0.0018 (8) |
C11 | 0.0395 (11) | 0.0352 (12) | 0.0150 (10) | −0.0053 (11) | −0.0001 (10) | 0.0032 (9) |
C12 | 0.0519 (15) | 0.0290 (11) | 0.0290 (12) | −0.0100 (11) | 0.0002 (11) | −0.0009 (9) |
C13 | 0.0357 (11) | 0.0287 (11) | 0.0281 (11) | −0.0008 (10) | 0.0005 (10) | −0.0007 (10) |
C14 | 0.0385 (11) | 0.0270 (11) | 0.0198 (10) | 0.0080 (10) | −0.0005 (10) | 0.0064 (9) |
C1A—N2A | 1.339 (17) | C2B—H2B3 | 0.9800 |
C1A—N1A | 1.339 (16) | C3B—N1B | 1.466 (16) |
C1A—N3A | 1.34 (3) | C3B—H3B1 | 0.9800 |
C2A—N1A | 1.459 (14) | C3B—H3B2 | 0.9800 |
C2A—H2A | 0.9800 | C3B—H3B3 | 0.9800 |
C2A—H2B | 0.9800 | C4B—N2B | 1.453 (16) |
C2A—H2C | 0.9800 | C4B—H4B1 | 0.9800 |
C3A—N1A | 1.464 (8) | C4B—H4B2 | 0.9800 |
C3A—H3A | 0.9800 | C4B—H4B3 | 0.9800 |
C3A—H3B | 0.9800 | C5B—N2B | 1.466 (17) |
C3A—H3C | 0.9800 | C5B—H5B1 | 0.9800 |
C4A—N2A | 1.466 (15) | C5B—H5B2 | 0.9800 |
C4A—H4A | 0.9800 | C5B—H5B3 | 0.9800 |
C4A—H4B | 0.9800 | C6B—N3B | 1.470 (16) |
C4A—H4C | 0.9800 | C6B—H6B1 | 0.9800 |
C5A—N2A | 1.472 (15) | C6B—H6B2 | 0.9800 |
C5A—H5A | 0.9800 | C6B—H6B3 | 0.9800 |
C5A—H5B | 0.9800 | C7B—N3B | 1.457 (10) |
C5A—H5C | 0.9800 | C7B—H7B1 | 0.9800 |
C6A—N3A | 1.464 (8) | C7B—H7B2 | 0.9800 |
C6A—H6A | 0.9800 | C7B—H7B3 | 0.9800 |
C6A—H6B | 0.9800 | N4—C11 | 1.148 (3) |
C6A—H6C | 0.9800 | N5—C12 | 1.149 (3) |
C7A—N3A | 1.468 (15) | N6—C13 | 1.153 (3) |
C7A—H7A | 0.9800 | N7—C14 | 1.151 (3) |
C7A—H7B | 0.9800 | C8—C9 | 1.386 (3) |
C7A—H7C | 0.9800 | C8—C11 | 1.421 (3) |
C1B—N1B | 1.349 (19) | C8—C12 | 1.425 (3) |
C1B—N2B | 1.35 (2) | C9—C10 | 1.379 (3) |
C1B—N3B | 1.34 (3) | C9—H9 | 0.9500 |
C2B—N1B | 1.452 (11) | C10—C13 | 1.426 (3) |
C2B—H2B1 | 0.9800 | C10—C14 | 1.427 (3) |
C2B—H2B2 | 0.9800 | ||
N2A—C1A—N1A | 120 (2) | H2B1—C2B—H2B3 | 109.5 |
N2A—C1A—N3A | 119.9 (12) | H2B2—C2B—H2B3 | 109.5 |
N1A—C1A—N3A | 120.1 (13) | N1B—C3B—H3B1 | 109.5 |
N1A—C2A—H2A | 109.4 | N1B—C3B—H3B2 | 109.4 |
N1A—C2A—H2B | 109.4 | H3B1—C3B—H3B2 | 109.5 |
H2A—C2A—H2B | 109.5 | N1B—C3B—H3B3 | 109.5 |
N1A—C2A—H2C | 109.5 | H3B1—C3B—H3B3 | 109.5 |
H2A—C2A—H2C | 109.5 | H3B2—C3B—H3B3 | 109.5 |
H2B—C2A—H2C | 109.5 | N2B—C4B—H4B1 | 109.4 |
N1A—C3A—H3A | 109.5 | N2B—C4B—H4B2 | 109.5 |
N1A—C3A—H3B | 109.5 | H4B1—C4B—H4B2 | 109.5 |
H3A—C3A—H3B | 109.5 | N2B—C4B—H4B3 | 109.5 |
N1A—C3A—H3C | 109.5 | H4B1—C4B—H4B3 | 109.5 |
H3A—C3A—H3C | 109.5 | H4B2—C4B—H4B3 | 109.5 |
H3B—C3A—H3C | 109.5 | N2B—C5B—H5B1 | 109.5 |
N2A—C4A—H4A | 109.5 | N2B—C5B—H5B2 | 109.5 |
N2A—C4A—H4B | 109.5 | H5B1—C5B—H5B2 | 109.5 |
H4A—C4A—H4B | 109.5 | N2B—C5B—H5B3 | 109.5 |
N2A—C4A—H4C | 109.5 | H5B1—C5B—H5B3 | 109.5 |
H4A—C4A—H4C | 109.5 | H5B2—C5B—H5B3 | 109.5 |
H4B—C4A—H4C | 109.5 | N3B—C6B—H6B1 | 109.5 |
N2A—C5A—H5A | 109.5 | N3B—C6B—H6B2 | 109.5 |
N2A—C5A—H5B | 109.5 | H6B1—C6B—H6B2 | 109.5 |
H5A—C5A—H5B | 109.5 | N3B—C6B—H6B3 | 109.5 |
N2A—C5A—H5C | 109.5 | H6B1—C6B—H6B3 | 109.5 |
H5A—C5A—H5C | 109.5 | H6B2—C6B—H6B3 | 109.5 |
H5B—C5A—H5C | 109.5 | N3B—C7B—H7B1 | 109.5 |
N3A—C6A—H6A | 109.5 | N3B—C7B—H7B2 | 109.5 |
N3A—C6A—H6B | 109.5 | H7B1—C7B—H7B2 | 109.5 |
H6A—C6A—H6B | 109.5 | N3B—C7B—H7B3 | 109.5 |
N3A—C6A—H6C | 109.5 | H7B1—C7B—H7B3 | 109.5 |
H6A—C6A—H6C | 109.5 | H7B2—C7B—H7B3 | 109.5 |
H6B—C6A—H6C | 109.5 | C1B—N1B—C2B | 122.7 (18) |
N3A—C7A—H7A | 109.4 | C1B—N1B—C3B | 123.0 (19) |
N3A—C7A—H7B | 109.5 | C2B—N1B—C3B | 114.3 (10) |
H7A—C7A—H7B | 109.5 | C1B—N2B—C4B | 122.2 (19) |
N3A—C7A—H7C | 109.5 | C1B—N2B—C5B | 121.8 (19) |
H7A—C7A—H7C | 109.5 | C4B—N2B—C5B | 116.0 (12) |
H7B—C7A—H7C | 109.5 | C1B—N3B—C7B | 122.8 (15) |
C1A—N1A—C3A | 123.4 (15) | C1B—N3B—C6B | 122.0 (17) |
C1A—N1A—C2A | 121.7 (17) | C7B—N3B—C6B | 115.1 (10) |
C3A—N1A—C2A | 114.8 (8) | C9—C8—C11 | 124.07 (18) |
C1A—N2A—C5A | 121.1 (17) | C9—C8—C12 | 120.82 (18) |
C1A—N2A—C4A | 123.0 (16) | C11—C8—C12 | 115.10 (18) |
C5A—N2A—C4A | 115.7 (11) | C10—C9—C8 | 130.39 (19) |
C1A—N3A—C6A | 123.0 (13) | C10—C9—H9 | 114.8 |
C1A—N3A—C7A | 121.4 (15) | C8—C9—H9 | 114.8 |
C6A—N3A—C7A | 115.6 (8) | C9—C10—C13 | 119.99 (18) |
N1B—C1B—N2B | 119 (2) | C9—C10—C14 | 124.71 (18) |
N1B—C1B—N3B | 121.0 (15) | C13—C10—C14 | 115.28 (17) |
N2B—C1B—N3B | 119.8 (14) | N4—C11—C8 | 178.1 (2) |
N1B—C2B—H2B1 | 109.5 | N5—C12—C8 | 178.9 (2) |
N1B—C2B—H2B2 | 109.5 | N6—C13—C10 | 179.0 (2) |
H2B1—C2B—H2B2 | 109.5 | N7—C14—C10 | 178.1 (2) |
N1B—C2B—H2B3 | 109.5 | ||
N2A—C1A—N1A—C3A | −29 (5) | N2B—C1B—N1B—C3B | −146 (3) |
N3A—C1A—N1A—C3A | 148 (3) | N3B—C1B—N1B—C3B | 32 (6) |
N2A—C1A—N1A—C2A | 148 (3) | N1B—C1B—N2B—C4B | 33 (6) |
N3A—C1A—N1A—C2A | −35 (5) | N3B—C1B—N2B—C4B | −145 (3) |
N1A—C1A—N2A—C5A | −36 (5) | N1B—C1B—N2B—C5B | −146 (3) |
N3A—C1A—N2A—C5A | 146 (3) | N3B—C1B—N2B—C5B | 36 (6) |
N1A—C1A—N2A—C4A | 148 (3) | N1B—C1B—N3B—C7B | 34 (6) |
N3A—C1A—N2A—C4A | −29 (5) | N2B—C1B—N3B—C7B | −148 (3) |
N2A—C1A—N3A—C6A | 144 (3) | N1B—C1B—N3B—C6B | −146 (3) |
N1A—C1A—N3A—C6A | −33 (5) | N2B—C1B—N3B—C6B | 31 (6) |
N2A—C1A—N3A—C7A | −38 (5) | C11—C8—C9—C10 | 0.1 (4) |
N1A—C1A—N3A—C7A | 144 (3) | C12—C8—C9—C10 | −179.4 (2) |
N2B—C1B—N1B—C2B | 38 (6) | C8—C9—C10—C13 | 177.8 (2) |
N3B—C1B—N1B—C2B | −144 (3) | C8—C9—C10—C14 | −0.3 (4) |
Experimental details
Crystal data | |
Chemical formula | C7H18N3+·C7HN4− |
Mr | 285.36 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 100 |
a, b, c (Å) | 7.7705 (5), 9.8189 (6), 21.5478 (14) |
V (Å3) | 1644.05 (18) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.08 |
Crystal size (mm) | 0.20 × 0.14 × 0.10 |
Data collection | |
Diffractometer | Bruker Kappa APEXII DUO |
Absorption correction | Multi-scan (Blessing, 1995) |
Tmin, Tmax | 0.720, 0.745 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 12519, 3368, 2709 |
Rint | 0.039 |
(sin θ/λ)max (Å−1) | 0.625 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.036, 0.076, 1.02 |
No. of reflections | 3368 |
No. of parameters | 293 |
No. of restraints | 171 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.11, −0.13 |
Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008), SHELXL2014 (Sheldrick, 2015), DIAMOND (Brandenburg & Putz, 2005).
Acknowledgements
The authors thank Dr W. Frey (Institut für Organische Chemie, Universität Stuttgart) for measuring the diffraction data.
References
Blessing, R. H. (1995). Acta Cryst. A51, 33–38. CrossRef CAS Web of Science IUCr Journals Google Scholar
Brandenburg, K. & Putz, H. (2005). DIAMOND. Crystal Impact GbR, D-53002 Bonn, Germany. Google Scholar
Bruker (2008). APEXII and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Frey, W., Vettel, M., Edelmann, K. & Kantlehner, W. (1998). Z. Kristallogr. 213, 77–78. CAS Google Scholar
Oelkers, B. & Sundermeyer, J. (2011). Green Chem. 13, 608–618. Web of Science CSD CrossRef CAS Google Scholar
Parsons, S., Flack, H. D. & Wagner, T. (2013). Acta Cryst. B69, 249–259. Web of Science CrossRef CAS IUCr Journals Google Scholar
Setifi, Z., Valkonen, A., Fernandes, M. A., Nummelin, S., Boughzala, H., Setifi, F. & Glidewell, C. (2015). Acta Cryst. E71, 509–515. CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Tiritiris, I. & Kantlehner, W. (2008). Z. Kristallogr. 223, 345–346. CAS Google Scholar
Tiritiris, I. & Kantlehner, W. (2015). Acta Cryst. E71, o1076–o1077. Web of Science CSD CrossRef IUCr Journals Google Scholar
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