Issue contents cross.png
Download PDF of article cross.png
Download CIF cross.png
3D view cross.png
Navigation cross.png
Highlighting cross.png
Dictionary of Crystallography reference
IUPAC Gold Book reference
more ...
Download citation cross.png
FormatBIBTeX
EndNote
RefMan
Refer
Medline
CIF
SGML
Plain Text
Text
cross.png
share
Previous article cross.png
Next article cross.png
Previous article cross.png
Issue contents cross.png
Download PDF of article cross.png
Download CIF cross.png
3D view cross.png
Navigation cross.png
Highlighting cross.png
Dictionary of Crystallography reference
IUPAC Gold Book reference
more ...
Download citation cross.png
FormatBIBTeX
EndNote
RefMan
Refer
Medline
CIF
SGML
Plain Text
Text
cross.png
share
Next article cross.png

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

Journal logoIUCrDATA
ISSN: 2414-3146
Volume 1| Part 3| March 2016| x160478
doi:10.1107/S2414314616004788

N,N,N′,N′,N′′,N′′-Hexa­methyl­guanidinium 1,1,3,3-tetra­cyano­prop-2-en-1-ide

Ioannis Tiritiris,a Ralf Kressa and Willi Kantlehnera*

aFakultät Chemie/Organische Chemie, Hochschule Aalen, Beethovenstrasse 1, D-73430 Aalen, Germany
*Correspondence e-mail: willi.kantlehner@hs-aalen.de

Edited by J. Simpson, University of Otago, New Zealand (Received 19 March 2016; accepted 21 March 2016; online 24 March 2016)

The asymmetric unit of the title salt, C7H18N3+·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.

CCDC reference: 1469774

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

Structure description

The reaction of phosgene with N,N,N′,N′-tetra­methyl­urea yields N,N,N′,N′-tetra­methyl­chloro­formamidinium chloride (Tiritiris & Kantlehner, 2008[Tiritiris, I. & Kantlehner, W. (2008). Z. Kristallogr. 223, 345-346.]), 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 anion exchange 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 asymmetric unit 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[link]).

[Figure 1]
Figure 1
The structure of the title compound, with displacement ellipsoids at the 50% probability level. All H atoms have been omitted for clarity (except for H9). Only the major orientation of the disordered cation is shown.

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[link]). 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 crystal structure analysis of known N,N,N′,N′,N′′,N′′-hexa­methyl­guanidinium salts [see, for example: tetra­phenyl­borate: Frey et al. (1998[Frey, W., Vettel, M., Edelmann, K. & Kantlehner, W. (1998). Z. Kristallogr. 213, 77-78.]); chloride: Oelkers & Sundermeyer (2011[Oelkers, B. & Sundermeyer, J. (2011). Green Chem. 13, 608-618.]); cyanate: Tiritiris & Kant­lehner (2015[Tiritiris, I. & Kantlehner, W. (2015). Acta Cryst. E71, o1076-o1077.])].

[Figure 2]
Figure 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.

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 crystal structure 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[Setifi, Z., Valkonen, A., Fernandes, M. A., Nummelin, S., Boughzala, H., Setifi, F. & Glidewell, C. (2015). Acta Cryst. E71, 509-515.]). Since no significant hydrogen bonding exists in the title compound, the crystal packing results from electrostatic inter­actions between the cations and anions (Fig. 3[link]).

[Figure 3]
Figure 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.

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 refinement details are summarized in Table 1[link]. The title compound crystallizes in the non-centrosymmetric space group P212121; however, in the absence of significant anomalous scattering effects, the determined Flack parameter x = −0.4 (10) (Parsons et al., 2013[Parsons, S., Flack, H. D. & Wagner, T. (2013). Acta Cryst. B69, 249-259.]) 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.

Table 1
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[Blessing, R. H. (1995). Acta Cryst. A51, 33-38.])
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 and SAINT (Bruker, 2008[Bruker (2008). APEXII and SAINT. 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 DIAMOND (Brandenburg & Putz, 2005[Brandenburg, K. & Putz, H. (2005). DIAMOND. Crystal Impact GbR, D-53002 Bonn, Germany.]).

Structural data

CCDC reference: 1469774

Crystal structure: contains datablocks I, global. DOI: 10.1107/S2414314616004788/sj4016sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2414314616004788/sj4016Isup2.hkl

checkCIF report


Synthesis and crystallization top

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.

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 1. The title compound crystallizes in the non-centrosymmetric space group P212121; however, in the absence of significant anomalous scattering effects, the determined Flack parameter 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.

Experimental top

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 top

Crystal data, data collection and structure refinement details are summarized in Table 1. The title compound crystallizes in the non-centrosymmetric space group P212121; however, in the absence of significant anomalous scattering effects, the determined Flack parameter 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.

Structure description top

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 anion exchange 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 asymmetric unit 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 crystal structure 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 crystal structure 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).

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: 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).

Figures top
[Figure 1] 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.
[Figure 2] 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.
[Figure 3] 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.
N,N,N',N',N'',N''-hexamethylguanidinium 1,1,3,3-tetracyanoprop-2-en-1-ide top
Crystal data top
C7H18N3+·C7HN4−Dx = 1.153 Mg m−3
Mr = 285.36Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P212121Cell parameters from 12519 reflections
a = 7.7705 (5) Åθ = 1.9–26.4°
b = 9.8189 (6) ŵ = 0.08 mm−1
c = 21.5478 (14) ÅT = 100 K
V = 1644.05 (18) Å3Block, colorless
Z = 40.20 × 0.14 × 0.10 mm
F(000) = 608
Data collection top
Bruker Kappa APEXII DUO
diffractometer		3368 independent reflections
Radiation source: fine-focus sealed tube2709 reflections with I > 2σ(I)
Triumph monochromatorRint = 0.039
φ scans, and ω scansθmax = 26.4°, θmin = 1.9°
Absorption correction: multi-scan
(Blessing, 1995)		h = −9→9
Tmin = 0.720, Tmax = 0.745k = −12→11
12519 measured reflectionsl = −26→25
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.036Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.076H-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 parametersΔρmax = 0.11 e Å−3
171 restraintsΔρmin = −0.13 e Å−3
Crystal data top
C7H18N3+·C7HN4−V = 1644.05 (18) Å3
Mr = 285.36Z = 4
Orthorhombic, P212121Mo Kα radiation
a = 7.7705 (5) ŵ = 0.08 mm−1
b = 9.8189 (6) ÅT = 100 K
c = 21.5478 (14) Å0.20 × 0.14 × 0.10 mm
Data collection top
Bruker Kappa APEXII DUO
diffractometer		3368 independent reflections
Absorption correction: multi-scan
(Blessing, 1995)		2709 reflections with I > 2σ(I)
Tmin = 0.720, Tmax = 0.745Rint = 0.039
12519 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.036171 restraints
wR(F2) = 0.076H-atom parameters constrained
S = 1.02Δρmax = 0.11 e Å−3
3368 reflectionsΔρmin = −0.13 e Å−3
293 parameters
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
C1A0.473 (2)0.769 (4)0.1683 (15)0.018 (2)0.535 (3)
C2A0.727 (2)0.7960 (18)0.1024 (8)0.034 (4)0.535 (3)
H2A0.72490.88830.11970.051*0.535 (3)
H2B0.72640.80110.05700.051*0.535 (3)
H2C0.83150.74910.11630.051*0.535 (3)
C3A0.5426 (8)0.5938 (8)0.0903 (4)0.0299 (15)0.535 (3)
H3A0.45010.54370.11110.045*0.535 (3)
H3B0.64730.53810.08990.045*0.535 (3)
H3C0.50820.61430.04760.045*0.535 (3)
C4A0.201 (2)0.727 (2)0.2239 (7)0.028 (3)0.535 (3)
H4A0.12810.64560.22030.042*0.535 (3)
H4B0.12840.80740.22930.042*0.535 (3)
H4C0.27740.71700.25980.042*0.535 (3)
C5A0.209 (2)0.7339 (19)0.1085 (9)0.027 (3)0.535 (3)
H5A0.28790.75140.07390.041*0.535 (3)
H5B0.11730.80230.10840.041*0.535 (3)
H5C0.15880.64290.10400.041*0.535 (3)
C6A0.7115 (10)0.8155 (9)0.2409 (4)0.0289 (15)0.535 (3)
H6A0.75540.72910.22460.043*0.535 (3)
H6B0.70450.81050.28630.043*0.535 (3)
H6C0.78930.88950.22900.043*0.535 (3)
C7A0.446 (2)0.9560 (16)0.2432 (9)0.027 (3)0.535 (3)
H7A0.34470.97690.21790.040*0.535 (3)
H7B0.52141.03610.24490.040*0.535 (3)
H7C0.40980.93160.28530.040*0.535 (3)
N1A0.5760 (4)0.7210 (3)0.12360 (16)0.0251 (8)0.535 (3)
N2A0.3046 (3)0.7416 (3)0.16741 (14)0.0207 (8)0.535 (3)
N3A0.5401 (4)0.8415 (3)0.21540 (14)0.0222 (8)0.535 (3)
C1B0.465 (2)0.764 (5)0.1653 (18)0.020 (3)0.465 (3)
C2B0.7389 (14)0.7854 (11)0.2214 (4)0.031 (2)0.465 (3)
H2B10.66590.76180.25690.047*0.465 (3)
H2B20.78860.87600.22780.047*0.465 (3)
H2B30.83150.71830.21740.047*0.465 (3)
C3B0.735 (3)0.805 (2)0.1080 (9)0.035 (4)0.465 (3)
H3B10.65670.82220.07330.052*0.465 (3)
H3B20.80280.72270.09940.052*0.465 (3)
H3B30.81320.88270.11300.052*0.465 (3)
C4B0.411 (2)0.9432 (18)0.2423 (10)0.027 (3)0.465 (3)
H4B10.45910.92510.28350.040*0.465 (3)
H4B20.30640.99830.24650.040*0.465 (3)
H4B30.49550.99270.21720.040*0.465 (3)
C5B0.218 (3)0.743 (3)0.2362 (9)0.030 (3)0.465 (3)
H5B10.20960.65330.21680.045*0.465 (3)
H5B20.11370.79590.22670.045*0.465 (3)
H5B30.22840.73280.28130.045*0.465 (3)
C6B0.213 (2)0.729 (2)0.0983 (11)0.032 (4)0.465 (3)
H6B10.13530.65350.10910.048*0.465 (3)
H6B20.21270.74160.05320.048*0.465 (3)
H6B30.17370.81220.11860.048*0.465 (3)
C7B0.4713 (9)0.5843 (10)0.0862 (5)0.0338 (19)0.465 (3)
H7B10.58000.56140.10670.051*0.465 (3)
H7B20.49420.61190.04320.051*0.465 (3)
H7B30.39550.50450.08630.051*0.465 (3)
N1B0.6359 (4)0.7857 (4)0.16509 (19)0.0248 (10)0.465 (3)
N2B0.3689 (5)0.8151 (4)0.21212 (17)0.0214 (10)0.465 (3)
N3B0.3883 (4)0.6959 (3)0.11918 (17)0.0227 (10)0.465 (3)
N40.4223 (3)−0.0855 (2)−0.00048 (8)0.0491 (6)
N50.5394 (3)0.2260 (2)0.13383 (9)0.0584 (6)
N60.5537 (3)0.46050 (19)−0.16125 (9)0.0439 (5)
N70.4329 (3)0.03094 (18)−0.15091 (8)0.0419 (5)
C80.5027 (3)0.1647 (2)0.01848 (9)0.0269 (5)
C90.5256 (3)0.2613 (2)−0.02772 (9)0.0277 (5)
H90.55630.3494−0.01330.033*
C100.5110 (2)0.2500 (2)−0.09130 (9)0.0255 (5)
C110.4570 (3)0.0269 (2)0.00714 (9)0.0299 (5)
C120.5233 (3)0.1998 (2)0.08220 (11)0.0366 (6)
C130.5355 (3)0.3669 (2)−0.12963 (9)0.0308 (5)
C140.4672 (3)0.1278 (2)−0.12346 (9)0.0284 (5)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C1A0.022 (4)0.013 (4)0.019 (4)0.002 (4)−0.002 (4)0.002 (4)
C2A0.026 (6)0.029 (5)0.048 (7)−0.006 (4)0.010 (5)−0.004 (5)
C3A0.037 (4)0.023 (3)0.029 (3)0.003 (3)0.004 (4)−0.007 (2)
C4A0.028 (4)0.038 (6)0.019 (5)−0.003 (3)0.003 (3)0.003 (4)
C5A0.033 (5)0.025 (4)0.022 (5)−0.007 (4)−0.004 (3)−0.001 (3)
C6A0.023 (3)0.036 (4)0.028 (4)0.003 (3)−0.014 (3)−0.002 (3)
C7A0.027 (5)0.022 (4)0.032 (4)0.001 (3)−0.003 (4)−0.008 (3)
N1A0.0233 (17)0.0238 (16)0.0282 (18)0.0004 (13)0.0053 (14)−0.0020 (14)
N2A0.0192 (15)0.0254 (16)0.0176 (17)−0.0042 (13)0.0006 (13)0.0001 (14)
N3A0.0190 (16)0.0221 (15)0.0255 (17)0.0000 (13)−0.0064 (14)−0.0002 (13)
C1B0.025 (5)0.017 (5)0.019 (5)0.000 (4)0.001 (5)0.002 (4)
C2B0.030 (4)0.031 (5)0.034 (5)0.000 (3)−0.003 (3)−0.004 (3)
C3B0.024 (7)0.058 (10)0.021 (5)0.002 (5)0.008 (4)0.003 (5)
C4B0.042 (7)0.018 (4)0.020 (4)−0.004 (4)0.003 (5)−0.001 (3)
C5B0.027 (5)0.032 (6)0.031 (7)−0.003 (4)0.012 (6)0.002 (6)
C6B0.019 (5)0.046 (7)0.032 (7)0.002 (4)−0.010 (4)0.002 (5)
C7B0.038 (5)0.030 (3)0.033 (4)0.002 (4)0.000 (5)−0.009 (2)
N1B0.0181 (18)0.032 (2)0.025 (2)0.0000 (15)0.0009 (16)0.0008 (18)
N2B0.026 (2)0.0186 (19)0.019 (2)−0.0001 (15)0.0034 (16)−0.0007 (15)
N3B0.0215 (18)0.0236 (19)0.023 (2)0.0026 (15)0.0003 (16)−0.0021 (17)
N40.0887 (17)0.0356 (11)0.0229 (10)−0.0180 (12)−0.0009 (11)0.0039 (9)
N50.1007 (17)0.0476 (12)0.0270 (12)−0.0207 (14)−0.0035 (12)−0.0047 (9)
N60.0597 (13)0.0333 (10)0.0389 (11)−0.0060 (10)0.0021 (11)0.0079 (10)
N70.0726 (15)0.0281 (10)0.0248 (10)0.0068 (10)−0.0085 (10)0.0000 (9)
C80.0345 (12)0.0271 (10)0.0190 (10)−0.0037 (9)0.0001 (9)−0.0024 (8)
C90.0289 (11)0.0244 (10)0.0298 (11)−0.0020 (9)−0.0001 (9)−0.0030 (9)
C100.0300 (12)0.0220 (10)0.0245 (10)0.0011 (9)0.0018 (8)0.0018 (8)
C110.0395 (11)0.0352 (12)0.0150 (10)−0.0053 (11)−0.0001 (10)0.0032 (9)
C120.0519 (15)0.0290 (11)0.0290 (12)−0.0100 (11)0.0002 (11)−0.0009 (9)
C130.0357 (11)0.0287 (11)0.0281 (11)−0.0008 (10)0.0005 (10)−0.0007 (10)
C140.0385 (11)0.0270 (11)0.0198 (10)0.0080 (10)−0.0005 (10)0.0064 (9)
Geometric parameters (Å, º) top
C1A—N2A1.339 (17)C2B—H2B30.9800
C1A—N1A1.339 (16)C3B—N1B1.466 (16)
C1A—N3A1.34 (3)C3B—H3B10.9800
C2A—N1A1.459 (14)C3B—H3B20.9800
C2A—H2A0.9800C3B—H3B30.9800
C2A—H2B0.9800C4B—N2B1.453 (16)
C2A—H2C0.9800C4B—H4B10.9800
C3A—N1A1.464 (8)C4B—H4B20.9800
C3A—H3A0.9800C4B—H4B30.9800
C3A—H3B0.9800C5B—N2B1.466 (17)
C3A—H3C0.9800C5B—H5B10.9800
C4A—N2A1.466 (15)C5B—H5B20.9800
C4A—H4A0.9800C5B—H5B30.9800
C4A—H4B0.9800C6B—N3B1.470 (16)
C4A—H4C0.9800C6B—H6B10.9800
C5A—N2A1.472 (15)C6B—H6B20.9800
C5A—H5A0.9800C6B—H6B30.9800
C5A—H5B0.9800C7B—N3B1.457 (10)
C5A—H5C0.9800C7B—H7B10.9800
C6A—N3A1.464 (8)C7B—H7B20.9800
C6A—H6A0.9800C7B—H7B30.9800
C6A—H6B0.9800N4—C111.148 (3)
C6A—H6C0.9800N5—C121.149 (3)
C7A—N3A1.468 (15)N6—C131.153 (3)
C7A—H7A0.9800N7—C141.151 (3)
C7A—H7B0.9800C8—C91.386 (3)
C7A—H7C0.9800C8—C111.421 (3)
C1B—N1B1.349 (19)C8—C121.425 (3)
C1B—N2B1.35 (2)C9—C101.379 (3)
C1B—N3B1.34 (3)C9—H90.9500
C2B—N1B1.452 (11)C10—C131.426 (3)
C2B—H2B10.9800C10—C141.427 (3)
C2B—H2B20.9800
N2A—C1A—N1A120 (2)H2B1—C2B—H2B3109.5
N2A—C1A—N3A119.9 (12)H2B2—C2B—H2B3109.5
N1A—C1A—N3A120.1 (13)N1B—C3B—H3B1109.5
N1A—C2A—H2A109.4N1B—C3B—H3B2109.4
N1A—C2A—H2B109.4H3B1—C3B—H3B2109.5
H2A—C2A—H2B109.5N1B—C3B—H3B3109.5
N1A—C2A—H2C109.5H3B1—C3B—H3B3109.5
H2A—C2A—H2C109.5H3B2—C3B—H3B3109.5
H2B—C2A—H2C109.5N2B—C4B—H4B1109.4
N1A—C3A—H3A109.5N2B—C4B—H4B2109.5
N1A—C3A—H3B109.5H4B1—C4B—H4B2109.5
H3A—C3A—H3B109.5N2B—C4B—H4B3109.5
N1A—C3A—H3C109.5H4B1—C4B—H4B3109.5
H3A—C3A—H3C109.5H4B2—C4B—H4B3109.5
H3B—C3A—H3C109.5N2B—C5B—H5B1109.5
N2A—C4A—H4A109.5N2B—C5B—H5B2109.5
N2A—C4A—H4B109.5H5B1—C5B—H5B2109.5
H4A—C4A—H4B109.5N2B—C5B—H5B3109.5
N2A—C4A—H4C109.5H5B1—C5B—H5B3109.5
H4A—C4A—H4C109.5H5B2—C5B—H5B3109.5
H4B—C4A—H4C109.5N3B—C6B—H6B1109.5
N2A—C5A—H5A109.5N3B—C6B—H6B2109.5
N2A—C5A—H5B109.5H6B1—C6B—H6B2109.5
H5A—C5A—H5B109.5N3B—C6B—H6B3109.5
N2A—C5A—H5C109.5H6B1—C6B—H6B3109.5
H5A—C5A—H5C109.5H6B2—C6B—H6B3109.5
H5B—C5A—H5C109.5N3B—C7B—H7B1109.5
N3A—C6A—H6A109.5N3B—C7B—H7B2109.5
N3A—C6A—H6B109.5H7B1—C7B—H7B2109.5
H6A—C6A—H6B109.5N3B—C7B—H7B3109.5
N3A—C6A—H6C109.5H7B1—C7B—H7B3109.5
H6A—C6A—H6C109.5H7B2—C7B—H7B3109.5
H6B—C6A—H6C109.5C1B—N1B—C2B122.7 (18)
N3A—C7A—H7A109.4C1B—N1B—C3B123.0 (19)
N3A—C7A—H7B109.5C2B—N1B—C3B114.3 (10)
H7A—C7A—H7B109.5C1B—N2B—C4B122.2 (19)
N3A—C7A—H7C109.5C1B—N2B—C5B121.8 (19)
H7A—C7A—H7C109.5C4B—N2B—C5B116.0 (12)
H7B—C7A—H7C109.5C1B—N3B—C7B122.8 (15)
C1A—N1A—C3A123.4 (15)C1B—N3B—C6B122.0 (17)
C1A—N1A—C2A121.7 (17)C7B—N3B—C6B115.1 (10)
C3A—N1A—C2A114.8 (8)C9—C8—C11124.07 (18)
C1A—N2A—C5A121.1 (17)C9—C8—C12120.82 (18)
C1A—N2A—C4A123.0 (16)C11—C8—C12115.10 (18)
C5A—N2A—C4A115.7 (11)C10—C9—C8130.39 (19)
C1A—N3A—C6A123.0 (13)C10—C9—H9114.8
C1A—N3A—C7A121.4 (15)C8—C9—H9114.8
C6A—N3A—C7A115.6 (8)C9—C10—C13119.99 (18)
N1B—C1B—N2B119 (2)C9—C10—C14124.71 (18)
N1B—C1B—N3B121.0 (15)C13—C10—C14115.28 (17)
N2B—C1B—N3B119.8 (14)N4—C11—C8178.1 (2)
N1B—C2B—H2B1109.5N5—C12—C8178.9 (2)
N1B—C2B—H2B2109.5N6—C13—C10179.0 (2)
H2B1—C2B—H2B2109.5N7—C14—C10178.1 (2)
N1B—C2B—H2B3109.5
N2A—C1A—N1A—C3A−29 (5)N2B—C1B—N1B—C3B−146 (3)
N3A—C1A—N1A—C3A148 (3)N3B—C1B—N1B—C3B32 (6)
N2A—C1A—N1A—C2A148 (3)N1B—C1B—N2B—C4B33 (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—C5A146 (3)N3B—C1B—N2B—C5B36 (6)
N1A—C1A—N2A—C4A148 (3)N1B—C1B—N3B—C7B34 (6)
N3A—C1A—N2A—C4A−29 (5)N2B—C1B—N3B—C7B−148 (3)
N2A—C1A—N3A—C6A144 (3)N1B—C1B—N3B—C6B−146 (3)
N1A—C1A—N3A—C6A−33 (5)N2B—C1B—N3B—C6B31 (6)
N2A—C1A—N3A—C7A−38 (5)C11—C8—C9—C100.1 (4)
N1A—C1A—N3A—C7A144 (3)C12—C8—C9—C10−179.4 (2)
N2B—C1B—N1B—C2B38 (6)C8—C9—C10—C13177.8 (2)
N3B—C1B—N1B—C2B−144 (3)C8—C9—C10—C14−0.3 (4)

Experimental details

Crystal data
Chemical formulaC7H18N3+·C7HN4−
Mr285.36
Crystal system, space groupOrthorhombic, P212121
Temperature (K)100
a, b, c (Å)7.7705 (5), 9.8189 (6), 21.5478 (14)
V (Å3)1644.05 (18)
Z4
Radiation typeMo Kα
µ (mm−1)0.08
Crystal size (mm)0.20 × 0.14 × 0.10
Data collection
DiffractometerBruker Kappa APEXII DUO
Absorption correctionMulti-scan
(Blessing, 1995)
Tmin, Tmax0.720, 0.745
No. of measured, independent and
observed [I > 2σ(I)] reflections		12519, 3368, 2709
Rint0.039
(sin θ/λ)max (Å−1)0.625
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.036, 0.076, 1.02
No. of reflections3368
No. of parameters293
No. of restraints171
H-atom treatmentH-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

First citationBlessing, R. H. (1995). Acta Cryst. A51, 33–38.  CrossRef CAS Web of Science IUCr Journals Google Scholar
 First citationBrandenburg, K. & Putz, H. (2005). DIAMOND. Crystal Impact GbR, D-53002 Bonn, Germany.  Google Scholar
 First citationBruker (2008). APEXII and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
 First citationFrey, W., Vettel, M., Edelmann, K. & Kantlehner, W. (1998). Z. Kristallogr. 213, 77–78.  CAS Google Scholar
 First citationOelkers, B. & Sundermeyer, J. (2011). Green Chem. 13, 608–618.  Web of Science CSD CrossRef CAS Google Scholar
 First citationParsons, S., Flack, H. D. & Wagner, T. (2013). Acta Cryst. B69, 249–259.  Web of Science CrossRef CAS IUCr Journals Google Scholar
 First citationSetifi, 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
 First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
 First citationSheldrick, G. M. (2015). Acta Cryst. C71, 3–8.  Web of Science CrossRef IUCr Journals Google Scholar
 First citationTiritiris, I. & Kantlehner, W. (2008). Z. Kristallogr. 223, 345–346.  CAS Google Scholar
 First citationTiritiris, I. & Kantlehner, W. (2015). Acta Cryst. E71, o1076–o1077.  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.

Journal logoIUCrDATA
ISSN: 2414-3146
Volume 1| Part 3| March 2016| x160478
doi:10.1107/S2414314616004788
Follow IUCr Journals
Sign up for e-alerts
E-alerts
Follow IUCr on Twitter
Twitter
Follow us on facebook
Facebook
Sign up for RSS feeds
RSS