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Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 72| Part 3| March 2016| Pages 382-386
doi:10.1107/S205698901600267X

Crystal structures of three anhydrous salts of the Lewis base 1,8-di­aza­bi­cyclo­[5.4.0]undec-7-ene (DBU) with the ring-substituted benzoic acid analogues 4-amino­benzoic acid, 3,5-di­nitro­benzoic acid and 3,5-di­nitro­salicylic acid

CROSSMARK_Color_square_no_text.svg
Graham Smitha* and Daniel E. Lynchb

aScience and Engineering Faculty, Queensland University of Technology, GPO Box 2434, Brisbane, Queensland 4001, Australia, and bExilica Ltd, The Technocentre, Puma Way, Coventry CV1 2TT, England
*Correspondence e-mail: g.smith@qut.edu.au

Edited by S. Parkin, University of Kentucky, USA (Received 27 January 2016; accepted 15 February 2016; online 20 February 2016)

The anhydrous salts of the Lewis base 1,8-di­aza­bicyclo­[5.4.0]undec-7-ene (DBU) with 4-amino­benzoic acid [1-aza-8-azoniabi­cyclo­[5.4.0]undec-7-ene 4-amino­benzoate, C9H17N2+·C7H6NO2− (I)], 3,5-di­nitro­benzoic acid [1-aza-8-azoniabi­cyclo­[5.4.0]undec-7-ene 3,5-di­nitro­benzoate, C9H17N2+·C7H3N2O6−, (II)] and 3,5-di­nitro­salicylic acid (DNSA) [1-aza-8-azoniabi­cyclo­[5.4.0]undec-7-ene 2-hy­droxy-3,5-di­nitro­benzoate, C9H17N2+·C7H3N2O7−, (III)] have been determined and their hydrogen-bonded structures are described. In both (II) and (III), the DBU cations have a common disorder in three of the C atoms of the six-membered ring moieties [site-occupancy factors (SOF) = 0.735 (3)/0.265 (3) and 0.686 (4)/0.314 (4), respectively], while in (III), there is additional rotational disorder in the DNSA anion, giving two sites (SOF = 0.72/0.28, values fixed) for the phenol group. In the crystals of (I) and (III), the cation–anion pairs are linked through a primary N—H⋯Ocarbox­yl hydrogen bond [2.665 (2) and 2.869 (3) Å, respectively]. In (II), the ion pairs are linked through an asymmetric three-centre R12(4), N—H⋯O,O′ chelate association. In (I), structure extension is through amine N—H⋯Ocarbox­yl hydrogen bonds between the PABA anions, giving a three-dimensional structure. The crystal structures of (II) and (III) are very similar, the cation–anion pairs being associated only through weak C—H⋯O hydrogen bonds, giving in both overall two-dimensional layered structures lying parallel to (001). No π–π ring associations are present in any of the structures.

CCDC references: 1453494; 1453493; 1453492

1. Chemical context and database survey

The Lewis base 1,8-di­aza­bicyclo­[5.4.0]undec-7-ene (DBU) is an alkaloid isolated from the sponge Niphates digitalis (Regalado et al., 2010[Regalado, E. L., Mendiola, J., Laguna, A., Nogueiras, C. & Thomas, O. P. (2010). Nat. Prod. Commun. 5, 1187-1190.]) but is commonly synthesized. It finds use as a curing agent for ep­oxy resins, as a catalyst in organic syntheses, and as a counter-cation in metal complex chemistry, e.g. with the penta­bromo­(tri­phenyl­phosphane)platinum(IV) monoanion (Motevalli et al., 1989[Motevalli, M., Hursthouse, M. B., Kelly, P. F. & Woollins, J. D. (1989). Polyhedron, 8, 893-896.]). It has also found use in binding organic liquids (BOLs), which usually comprise a mixture of amidines or guanidine and alcohol, and are used to reversibly capture and release gases such as CO2, CS2, SO2 or COS (Shannon et al., 2015[Shannon, M. S., Irvin, A. C., Liu, H., Moon, J. D., Hindman, M. S., Turner, C. H. & Bara, J. E. (2015). Ind. Eng. Chem. Res. 54, 462-471.]; Pérez et al., 2004[Pérez, E. R., Santos, R. H. A., Gambardella, M. T. P., de Macedo, L. G. M., Rodrigues-Filho, U. P., Launay, J. & Franco, D. W. (2004). J. Org. Chem. 69, 8005-8011.]; Heldebrant et al., 2009[Heldebrant, D. J., Yonker, C. R., Jessop, P. G. & Phan, L. (2009). Chem. Eur. J. 15, 7619-7627.]). The structure of one of these formed from the absorption of CO2 is the bicarbonate (Pérez et al., 2004[Pérez, E. R., Santos, R. H. A., Gambardella, M. T. P., de Macedo, L. G. M., Rodrigues-Filho, U. P., Launay, J. & Franco, D. W. (2004). J. Org. Chem. 69, 8005-8011.]).

As a very strong base (pKa ca 14), protonation of the N8 group of the six-membered hetero-ring of DBU is readily achieved and results in the formation of salts with carb­oxy­lic acids and phenols. The Cambridge Structural Database (2015 version) (Groom & Allen, 2014[Groom, C. R. & Allen, F. H. (2014). Angew. Chem. Int. Ed. 53, 662-671.]) contains 35 examples of organic salts of DBU, among them the benzyl di­thio­carbonate (Heldebrant et al., 2009[Heldebrant, D. J., Yonker, C. R., Jessop, P. G. & Phan, L. (2009). Chem. Eur. J. 15, 7619-7627.]) and the phenolate from 2,6-di(tert-but­yl)-4-nitro­phenol (Lynch & McClenaghan, 2003[Lynch, D. E. & McClenaghan, I. (2003). Cryst. Eng. 6, 99-107.]). However, of the total there are surprisingly few carboxyl­ate salts, e.g. with Kemp's triacid (1,3,5-tri­methyl­cyclo­hexane-1,3,5-tri­carb­oxy­lic acid) (a monoanionic aceto­nitrile salt) (Huczyński et al., 2008[Huczyński, A., Ratajczak-Sitarz, M., Katrusiak, A. & Brzezinski, B. (2008). J. Mol. Struct. 889, 64-71.]) and the dianionic salt of the tetra­(3-carb­oxy­phen­yl)-substituted porphyrin (Lipstman & Goldberg, 2013[Lipstman, S. & Goldberg, I. (2013). Cryst. Growth Des. 13, 942-952.]).

No reported crystal structures of salts with simple substituted benzoic acids are found, so in order to examine the hydrogen-bonding in crystals of the DBU salts with some common ring-substituted benzoic acids, a number of these were prepared. Suitable crystals were obtained with 4-amino­benzoic acid (PABA), (3,5-di­nitro­benzoic acid (DNBA) and (3,5-di­nitro­salicylic acid (DNSA), giving the anhydrous salts, C9H17N2+ C7H6NO2− (I)[link], C9H17N2+ C7H3N2O6− (II)[link] and C9H17N2+ C7H3N2O7− (III)[link], respectively and their structures and hydrogen-bonding modes are reported herein.

[Scheme 1]

2. Structural commentary

The asymmetric units of (I)–(III) comprise a BDU cation (A) and a 4-amino­benzoate anion (B), (I)[link] (Fig. 1[link]), a 3,5-di­nitro­benzoate anion (B), (II)[link] (Fig. 2[link]), and a 3,5-di­nitro­salicylate anion (B), (III)[link] (Fig. 3[link]). The cation–anion pairs in (I)[link] and (III)[link] are linked through a primary N8A—H⋯Ocarbox­yl hydrogen bond [2.665 (2) and 2.871 (3) Å, respectively; Tables 1[link] and 3[link]]. In (II)[link], the ion pairs are linked through an asymmetric three-centre R12(4), N8A—H⋯O,O′ chelate association [2.777 (2), 3.117 (2) Å; Table 2[link]]. With (III)[link], the corresponding longer contact with the second carboxyl O12B atom is 3.222 (3) Å (Fig. 3[link]).

Table 1
Hydrogen-bond geometry (Å, °) for (I)[link]

D—H⋯A D—H H⋯A D⋯A D—H⋯A
N8A—H8A⋯O11B 0.89 (2) 1.78 (2) 2.665 (2) 170 (2)
N4B—H41B⋯O11Bi 0.89 (2) 2.05 (2) 2.939 (2) 176 (2)
N4B—H42B⋯O12Bii 0.92 (2) 1.98 (2) 2.891 (2) 176 (2)
Symmetry codes: (i) [x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]; (ii) [-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}].

Table 3
Hydrogen-bond geometry (Å, °) for (III)[link]

D—H⋯A D—H H⋯A D⋯A D—H⋯A
N8A—H8A⋯O11B 0.88 (2) 1.99 (2) 2.871 (3) 176 (2)
O2B—H2B⋯O12B 0.84 1.72 2.473 (3) 149
C10A—H11A⋯O32Bi 0.99 2.45 3.251 (5) 138
C2A—H21A⋯O31Bii 0.99 2.48 3.281 (3) 138
Symmetry codes: (i) [-x+{\script{3\over 2}}, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]; (ii) [-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{3\over 2}}].

Table 2
Hydrogen-bond geometry (Å, °) for (II)[link]

D—H⋯A D—H H⋯A D⋯A D—H⋯A
N8A—H8A⋯O11B 0.90 (2) 1.88 (2) 2.777 (2) 177 (2)
N8A—H8A⋯O12B 0.90 (2) 2.53 (2) 3.117 (2) 124 (1)
C10A—H11A⋯O32Bi 0.99 2.44 3.247 (3) 138
C2A—H21A⋯O31Bii 0.99 2.56 3.309 (2) 133
C6A—H62A⋯O11B 0.99 2.60 3.438 (2) 143
Symmetry codes: (i) [-x-{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]; (ii) [-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}].
[Figure 1]
Figure 1
The atom-numbering scheme and the mol­ecular conformation of the DBU cation (A) and the PABA anion (B) in (I)[link] with displacement ellipsoids drawn at the 40% probability level. The cation–anion hydrogen bond is shown as a dashed line.
[Figure 2]
Figure 2
The atom-numbering scheme and the mol­ecular conformation of the DBU cation (A) and the DNBA anion (B) in (II)[link] with displacement ellipsoids drawn at the 40% probability level. The bonds in the minor disordered section of the six-membered ring of the cation and the cation–anion hydrogen bonds are shown as dashed lines.
[Figure 3]
Figure 3
The atom-numbering scheme and the mol­ecular conformation of the DBU cation (A) and the DNSA anion (B) in (III)[link] with displacement ellipsoids drawn at the 40% probability level. The bonds in the minor disordered section of the six-membered ring of the cation are shown as dashed lines.

With the structures of (II)[link] and (III)[link], there is disorder in the six-membered ring system involving atoms C9A and C10A (with alternative minor occupancy sites C12A and C13A), giving similar site occupancy factors [SOF 0.735 (3)/0.265 (3) and 0.686 (4)/0.314 (4) for (II)[link] and (III)[link], respectively]. This feature is found in three other structures among the CSD set: the previously mentioned 2,6-di(tert-but­yl)-4-nitro­phenolate (SOF 0.60/0.40) (Lynch & McClenaghan, 2003[Lynch, D. E. & McClenaghan, I. (2003). Cryst. Eng. 6, 99-107.]); in the 8-bromo­guanosine 8-bromo­guanoside adduct salt (SOF = 0.63/0.37) (Saftić et al., 2012[Saftić, D., Žinić, B. & Višnjevac, A. (2012). Tetrahedron, 68, 1062-1070.]) and in the counter-cation of a bromo­carbyne Mo complex (SOF = 0.83/0.17) (Cordiner et al., 2008[Cordiner, R. L., Hill, A. F. & Wagler, J. (2008). Organometallics, 27, 4532-4540.]).

With the PABA anion in (I)[link], the carboxyl­ate group is essentially coplanar with the benzene ring [torsion angle C2B—C1B—C11B— O11B = 179.25 (15)°, a feature similar to those found in the parent acid (Gracin & Fischer, 2005[Gracin, S. & Fischer, A. (2005). Acta Cryst. E61, o1242-o1244.]) and its co-crystals, e.g. with 4-nitro­benzoic acid (Bowers et al., 2005[Bowers, J. R., Hopkins, G. W., Yap, G. P. A. & Wheeler, K. A. (2005). Cryst. Growth Des. 5, 727-736.]).

The carboxyl­ate groups of the DNBA and DNSA anions in both (II)[link] and (III)[link] are also essentially coplanar with the benzene rings: torsion angles C2B—C1B—C11B—O11B = −176.60 (16) and −179.4 (2)°, respectively. The 5- and 3-substituted nitro groups are also either in-plane or out-of-plane [torsion angles C4B—C5B—N5B— O52B = 179.61 (16)° in (II)[link] and −177.5 (2)° in (III)[link] and C2B—C3B—N3B—O32B = −166.31 (17)° in (II)[link] and −155.2 (2)° in (III)]. Also, in (III)[link], the phenolic substituent group (O2B) is disordered by rotation about the C1B⋯C4B ring vector giving a minor site-occupancy factor for the O21B—H21B group of 0.28 (SOF fixed in the final refinement cycles). This is similar to the disorder in three examples among the DNSA proton-transfer salts with Lewis bases, e.g. with nicotinamide (SOF = 0.76/0.24) (Koman et al., 2003[Koman, M., Martiška, L., Valigura, D. & Glowiak, T. (2003). Acta Cryst. E59, o441-o442.]), with 2,6-di­amino­pyridine (0.90/0.10) (Smith et al., 2003[Smith, G., Wermuth, U. D., Healy, P. C. & White, J. M. (2003). Aust. J. Chem. 56, 707-713.]) and with quinoline-2-carb­oxy­lic acid (0.51/0.49) (Smith et al., 2007[Smith, G., Wermuth, U. D., Healy, P. C. & White, J. M. (2007). Aust. J. Chem. 60, 264-277.]). In (III)[link], the usual short intra­molecular phenol O—H⋯Ocarbox­yl hydrogen bond is present (Table 3[link]).

3. Supra­molecular features

In the crystal of (I)[link], the N8A—H⋯O11B hydrogen-bonded cation–anion pairs are extended through inter­molecular N4B—H⋯ O11Bi and ⋯N12Bii hydrogen-bonding extensions (Table 1[link]), giving an overall three-dimensional network structure (Fig. 4[link]). The structure contains no inter-ring π–π inter­actions or C—H⋯O hydrogen bonds.

[Figure 4]
Figure 4
The three-dimensional hydrogen-bonded framework structure of (I)[link] viewed approximately along a. For symmetry codes, see Table 1[link].

The unit-cell parameters, space group (Table 4[link]), and the overall crystal packing of (II)[link] and (III)[link] are very similar (Figs. 5[link] and 6[link]). Although no classical hydrogen-bonding inter­actions are present between the primary cation–anion pairs, with both structures there are two minor cation C—H⋯O hydrogen-bonding extensions to nitro O-atom acceptors, C2A—H⋯O31Bii [3.309 (2) Å in (II)[link] and 3.281 (3) Å in (III)] and C10A—H⋯O32Bi [3.247 (3) Å in (II)[link] and 3.251 (5) Å in (III)] (Tables 2[link] and 3[link]). These give two-dimensional layered structures lying parallel to (001). There are no inter-ring π–π inter­actions in either (II)[link] or (III)[link].

Table 4
Experimental details

  (I) (II) (III)
Crystal data
Chemical formula C9H17N2+·C7H6NO2− C9H17N2+·C7H3N2O6− C9H17N2+·C7H3N2O7−
Mr 289.37 364.36 380.36
Crystal system, space group Orthorhombic, P212121 Monoclinic, P21/n Monoclinic, P21/n
Temperature (K) 200 200 200
a, b, c (Å) 8.0986 (4), 12.9213 (6), 13.7344 (7) 6.0197 (4), 19.6228 (13), 14.3866 (8) 6.1537 (3), 19.1541 (14), 14.5527 (11)
α, β, γ (°) 90, 90, 90 90, 98.078 (5), 90 90, 98.343 (6), 90
V (Å3) 1437.23 (12) 1682.53 (18) 1697.2 (2)
Z 4 4 4
Radiation type Mo Kα Mo Kα Mo Kα
μ (mm−1) 0.09 0.11 0.12
Crystal size (mm) 0.40 × 0.26 × 0.24 0.30 × 0.13 × 0.08 0.30 × 0.13 × 0.10
 
Data collection
Diffractometer Oxford Diffraction Gemini-S CCD-detector Oxford Diffraction Gemini-S CCD-detector Oxford Diffraction Gemini-S CCD-detector
Absorption correction Multi-scan (CrysAlis PRO; Agilent, 2014[Agilent (2014). CrysAlis PRO. Agilent Technologies Ltd, Yarnton, England.]) Multi-scan (CrysAlis PRO; Agilent, 2014[Agilent (2014). CrysAlis PRO. Agilent Technologies Ltd, Yarnton, England.]) Multi-scan (CrysAlis PRO; Agilent, 2014[Agilent (2014). CrysAlis PRO. Agilent Technologies Ltd, Yarnton, England.])
Tmin, Tmax 0.93, 0.99 0.90, 0.99 0.920, 0.990
No. of measured, independent and observed [I > 2σ(I)] reflections 7372, 3324, 2847 7082, 3311, 2561 7800, 3339, 2347
Rint 0.031 0.024 0.034
(sin θ/λ)max (Å−1) 0.687 0.617 0.617
 
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.044, 0.098, 1.07 0.045, 0.109, 1.02 0.058, 0.123, 1.03
No. of reflections 3324 3311 3339
No. of parameters 199 245 263
No. of restraints 3 3 3
H-atom treatment H atoms treated by a mixture of independent and constrained refinement H atoms treated by a mixture of independent and constrained refinement H atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å−3) 0.20, −0.25 0.18, −0.22 0.29, −0.29
Computer programs: CrysAlis PRO (Agilent, 2014[Agilent (2014). CrysAlis PRO. Agilent Technologies Ltd, Yarnton, England.]), SIR92 (Altomare et al., 1993[Altomare, A., Cascarano, G., Giacovazzo, C. & Guagliardi, A. (1993). J. Appl. Cryst. 26, 343-350.]), SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]) within WinGX (Farrugia, 2012[Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849-854.]) and PLATON (Spek, 2009[Spek, A. L. (2009). Acta Cryst. D65, 148-155.]).
[Figure 5]
Figure 5
The packing of the hydrogen-bonded cation-anion pairs in the unit cell of (II)[link], viewed along a. The minor-component disordered atoms and the non-associative H atoms have been omitted.
[Figure 6]
Figure 6
The packing of the hydrogen-bonded cation-anion pairs in the unit cell of (III)[link], viewed along a. The minor-component disordered atoms and the non-associative H atoms have been omitted.

4. Synthesis and crystallization

The title compounds (I)–(III) were prepared by first dissolving 100 mg of either PABA, DNBA, or DNSA in 5 mL of warm ethanol followed by the addition, with stirring, of 111 mg (I)[link], 72 mg (II)[link] or 67 mg (III)[link] of BDU, respectively. Slow evaporation at room temperature gave colourless needles of (I)[link], colourless prisms of (II)[link], and fine yellow needles of (III)[link], from which specimens were cleaved for the X-ray analyses.

5. Refinement details

Crystal data, data collection and structure refinement details are given in Table 4[link]. Hydrogen atoms were placed in calculated positions [C—Haromatic = 0.95 Å or C—Hmethyl­ene = 0.99 Å] and were allowed to ride in the refinements, with Uiso(H) = 1.2Ueq(C). The amine and aminium H-atoms were located in difference-Fourier analyses and were allowed to refine with distance restraints [N—H = 0.90 (2) Å] and with Uiso(H) = 1.2Ueq(N). Disorder involving atoms C9A and C10A of the six-membered ring systems of both (II)[link] and (III)[link] gave refined minor occupancy sites C12A and C13A, with site occupancy factors of 0.735 (3)/0.265 (3) and 0.686 (4)/0.314 (4), respectively. Also in (III)[link], the phenol group of the DNSA anion was found to be disordered with the minor occupancy site (O21B) having a SOF = 0.28, which was fixed in the final cycles of refinement. In the structure of (I)[link], although of no relevance in the achiral mol­ecule, the Flack parameter (Flack, 1983[Flack, H. D. (1983). Acta Cryst. A39, 876-881.]) was determined as −0.1 (13) for 1668 Friedel pairs, which serves to indicate the lack of any usable anomalous scattering signal, as expected for an all-light-atom structure determined with Mo Kα X-rays.

Supporting information

CCDC references: 1453494; 1453493; 1453492

Crystal structure: contains datablocks global, I, II, III. DOI: 10.1107/S205698901600267X/pk2574sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S205698901600267X/pk2574Isup2.hkl

Structure factors: contains datablock II. DOI: 10.1107/S205698901600267X/pk2574IIsup3.hkl

Structure factors: contains datablock III. DOI: 10.1107/S205698901600267X/pk2574IIIsup4.hkl

Supporting information file. DOI: 10.1107/S205698901600267X/pk2574Isup5.cml

Supporting information file. DOI: 10.1107/S205698901600267X/pk2574IIsup6.cml

Supporting information file. DOI: 10.1107/S205698901600267X/pk2574IIIsup7.cml

checkCIF report


Chemical context and database survey top

The Lewis base 1,8-di­aza­bicyclo­[5.4.0]undec-7-ene (DBU) is an alkaloid isolated from the sponge Niphates digitalis (Regalado et al., 2010) but is commonly synthesized. It finds use as a curing agent for ep­oxy resins, as a catalyst in organic syntheses, and as a counter-cation in metal complex chemistry, e.g. with the penta­bromo­(tri­phenyl­phosphane)platinum(IV) monoanion (Motevalli et al., 1989). It has also found use in binding organic liquids (BOLs), which usually comprise a mixture of amidines or guanidine and alcohol, and are used to reversibly capture and release gases such as CO2, CS2, SO2 or COS (Shannon et al., 2015; Pérez et al., 2004; Heldebrant et al., 2009). The structure of one of these formed from the absorption of CO2 is the bicarbonate (Pérez et al., 2004).

As a very strong base (pKa ca 14), protonation of the N8 group of the six-membered hetero-ring of DBU is readily achieved and results in the formation of salts with carb­oxy­lic acids and phenols. The Cambridge Structural Database (2015 version) (Groom & Allen, 2014) contains 35 examples of organic salts of DBU, among them the benzyl di­thio­carbonate (Heldebrant et al., 2009) and the phenolate from 2,6-di(tert-butyl)-4-nitro­phenol (Lynch & McClenaghan, 2003). However, of the total there are surprisingly few carboxyl­ate salts, e.g. with Kemp's triacid (1,3,5-tri­methyl­cyclo­hexane-1,3,5-tri­carb­oxy­lic acid) (a monoanionic aceto­nitrile salt) (Huczyński et al., 2008) and the dianionic salt of the tetra­(3-carb­oxy­phenyl)-substituted porphyrin (Lipstman & Goldberg, 2013).

No reported crystal structures of salts with simple substituted benzoic acids are found, so in order to examine the hydrogen-bonding in crystals of the DBU salts with some common ring-substituted benzoic acids, a number of these were prepared. Suitable crystals were obtained with 4-amino­benzoic acid (PABA), (3,5-di­nitro­benzoic acid (DNBA) and (3,5-di­nitro­salicylic acid (DNSA), giving the anhydrous salts, C9H17N2+ C7H6NO2- (I), C9H17N2+ C7H3N2O6- (II) and C9H17N2+ C7H3N2O7- (III), respectively and their structures and hydrogen-bonding modes are reported herein.

Structural commentary top

The asymmetric units of (I)–(III) comprise a BDU cation (A) and a 4-amino­benzoate anion (B), (I) (Fig. 1), a 3,5-di­nitro­benzoate anion (B), (II) (Fig. 2), and a 3,5-di­nitro­salicylate anion (B), (III) (Fig. 3). The cation–anion pairs in (I) and (III) are linked through a primary N8A—H···Ocarboxyl hydrogen bond [2.665 (2) and 2.871 (3) Å, respectively; Tables 1 and 3]. In (II), the ion pairs are linked through an asymmetric three-centre R12(4), N8A—H···O,O' chelate association [2.777 (2), 3.117 (2) Å; Table 2]. With (III), the corresponding longer contact with the second carboxyl O12B atom is 3.222 (3) Å (Fig. 3).

With the structures of (II) and (III), there is disorder in the six-membered ring system involving atoms C9A and C10A (with alternative minor occupancy sites C12A and C13A), giving similar site occupancy factors [SOF 0.735 (3)/0.265 (3) and 0.686 (4)/0.314 (4) for (II) and (III), respectively]. This feature is found in three other structures among the CSD set: the previously mentioned 2,6-di(tert-butyl)-4-nitro­phenolate (SOF 0.60/0.40) (Lynch & McClenaghan, 2003); in the 8-bromo­guanosine 8-bromo­guanoside adduct salt (SOF = 0.63/0.37) (Saftić et al., 2012) and in the counter-cation of a bromo­carbyne Mo complex (SOF = 0.83/0.17) (Cordiner et al., 2008).

With the PABA anion in (I), the carboxyl­ate group is essentially coplanar with the benzene ring [torsion angle C2B—C1B—C11B— O11B = 179.25 (15)°, a feature similar to those found in the parent acid (Gracin & Fischer, 2005) and its co-crystals, e.g. with 4-nitro­benzoic acid (Bowers et al., 2005).

The carboxyl­ate groups of the DNBA and DNSA anions in both (II) and (III) are also essentially coplanar with the benzene rings: torsion angles C2B—C1B—C11B—O11B = -176.60 (16) and -179.4 (2)°, respectively. The 5- and 3-substituted nitro groups are also either in-plane or out-of-plane [torsion angles C4B—C5B—N5B— O52B = 179.61 (16)° in (II) and -177.5 (2)° in (III) and C2B—C3B—N3B—O32B = -166.31 (17)° in (II) and -155.2 (2)° in (III)]. Also, in (III), the phenolic substituent group (O2B) is disordered by rotation about the C1B···C4B ring vector giving a minor site-occupancy factor for the O21B—H21B group of 0.28 (SOF fixed in the final refinement cycles). This is similar to the disorder in three examples among the DNSA proton-transfer salts with Lewis bases, e.g. with nicotinamide (SOF = 0.76/0.24) (Koman et al., 2003), with 2,6-di­amino­pyridine (0.90/0.10) (Smith et al., 2003) and with quinoline-2-carb­oxy­lic acid (0.51/0.49) (Smith et al., 2007). In (III), the usual short intra­molecular phenol O—H···Ocarboxyl hydrogen bond is present (Table 3).

Supra­molecular features top

In the crystal of (I), the N8A—H···O11B hydrogen-bonded cation–anion pairs are extended through inter­molecular N4B—H··· O11Bi and ···N12Bii hydrogen-bonding extensions (Table 1), giving an overall three-dimensional network structure (Fig. 4). The structure contains no inter-ring π–π inter­actions or C—H···O hydrogen bonds.

The unit-cell parameters, space group (Table 4), and the overall crystal packing of (II) and (III) are very similar (Figs. 5 and 6). Although no classical hydrogen-bonding inter­actions are present between the primary cation–anion pairs, with both structures there are two minor cation C—H···O hydrogen-bonding extensions to nitro O-atom acceptors, C2A—H···O31Bii [3.309 (2) Å in (II) and 3.281 (3) Å in (III)] and C10A—H···O32Bi [3.247 (3) Å in (II) and 3.251 (5) Å in (III)] (Tables 2 and 3). These give two-dimensional layered structures lying parallel to (001). There are no inter-ring π–π inter­actions in either (II) or (III).

Synthesis and crystallization top

The title compounds (I)–(III) were prepared by first dissolving 100 mg of either PABA, DNBA, or DNSA in 5 mL of warm ethanol followed by the addition, with stirring, of 111 mg (I), 72 mg (II) or 67 mg (III) of BDU, respectively. Slow evaporation at room temperature gave colourless needles of (I), colourless prisms of (II), and fine yellow needles of (III), from which specimens were cleaved for the X-ray analyses.

Refinement details top

Crystal data, data collection and structure refinement details are given in Table 4. Hydrogen atoms were placed in calculated positions [C—Haromatic = 0.95 Å or C—Hmethyl­ene = 0.99 Å] and were allowed to ride in the refinements, with Uiso(H) = 1.2Ueq(C). The amine and aminium H-atoms were located in difference-Fourier analyses and were allowed to refine with distance restraints [N—H = 0.90 (2) Å] and with Uiso(H) = 1.2Ueq(N). Disorder involving atoms C9A and C10A of the six-membered ring systems of both (II) and (III) gave refined minor occupancy sites C12A and C13A, with site occupancy factors of 0.735 (3)/0.265 (3) and 0.686 (4)/0.314 (4), respectively. Also in (III), the phenol group of the DNSA anion was found to be disordered with the minor occupancy site (O21B) having a SOF = 0.28, which was fixed in the final cycles of refinement. In the structure of (I), although of no relevance in the achiral molecule, the Flack parameter (Flack, 1983) was determined as -0.1 (13) for 1668 Friedel pairs, which serves to indicate the lack of any usable anomalous scattering signal, as expected for an all-light-atom structure determined with Mo Kα X-rays.

Structure description top

The Lewis base 1,8-di­aza­bicyclo­[5.4.0]undec-7-ene (DBU) is an alkaloid isolated from the sponge Niphates digitalis (Regalado et al., 2010) but is commonly synthesized. It finds use as a curing agent for ep­oxy resins, as a catalyst in organic syntheses, and as a counter-cation in metal complex chemistry, e.g. with the penta­bromo­(tri­phenyl­phosphane)platinum(IV) monoanion (Motevalli et al., 1989). It has also found use in binding organic liquids (BOLs), which usually comprise a mixture of amidines or guanidine and alcohol, and are used to reversibly capture and release gases such as CO2, CS2, SO2 or COS (Shannon et al., 2015; Pérez et al., 2004; Heldebrant et al., 2009). The structure of one of these formed from the absorption of CO2 is the bicarbonate (Pérez et al., 2004).

As a very strong base (pKa ca 14), protonation of the N8 group of the six-membered hetero-ring of DBU is readily achieved and results in the formation of salts with carb­oxy­lic acids and phenols. The Cambridge Structural Database (2015 version) (Groom & Allen, 2014) contains 35 examples of organic salts of DBU, among them the benzyl di­thio­carbonate (Heldebrant et al., 2009) and the phenolate from 2,6-di(tert-butyl)-4-nitro­phenol (Lynch & McClenaghan, 2003). However, of the total there are surprisingly few carboxyl­ate salts, e.g. with Kemp's triacid (1,3,5-tri­methyl­cyclo­hexane-1,3,5-tri­carb­oxy­lic acid) (a monoanionic aceto­nitrile salt) (Huczyński et al., 2008) and the dianionic salt of the tetra­(3-carb­oxy­phenyl)-substituted porphyrin (Lipstman & Goldberg, 2013).

No reported crystal structures of salts with simple substituted benzoic acids are found, so in order to examine the hydrogen-bonding in crystals of the DBU salts with some common ring-substituted benzoic acids, a number of these were prepared. Suitable crystals were obtained with 4-amino­benzoic acid (PABA), (3,5-di­nitro­benzoic acid (DNBA) and (3,5-di­nitro­salicylic acid (DNSA), giving the anhydrous salts, C9H17N2+ C7H6NO2- (I), C9H17N2+ C7H3N2O6- (II) and C9H17N2+ C7H3N2O7- (III), respectively and their structures and hydrogen-bonding modes are reported herein.

The asymmetric units of (I)–(III) comprise a BDU cation (A) and a 4-amino­benzoate anion (B), (I) (Fig. 1), a 3,5-di­nitro­benzoate anion (B), (II) (Fig. 2), and a 3,5-di­nitro­salicylate anion (B), (III) (Fig. 3). The cation–anion pairs in (I) and (III) are linked through a primary N8A—H···Ocarboxyl hydrogen bond [2.665 (2) and 2.871 (3) Å, respectively; Tables 1 and 3]. In (II), the ion pairs are linked through an asymmetric three-centre R12(4), N8A—H···O,O' chelate association [2.777 (2), 3.117 (2) Å; Table 2]. With (III), the corresponding longer contact with the second carboxyl O12B atom is 3.222 (3) Å (Fig. 3).

With the structures of (II) and (III), there is disorder in the six-membered ring system involving atoms C9A and C10A (with alternative minor occupancy sites C12A and C13A), giving similar site occupancy factors [SOF 0.735 (3)/0.265 (3) and 0.686 (4)/0.314 (4) for (II) and (III), respectively]. This feature is found in three other structures among the CSD set: the previously mentioned 2,6-di(tert-butyl)-4-nitro­phenolate (SOF 0.60/0.40) (Lynch & McClenaghan, 2003); in the 8-bromo­guanosine 8-bromo­guanoside adduct salt (SOF = 0.63/0.37) (Saftić et al., 2012) and in the counter-cation of a bromo­carbyne Mo complex (SOF = 0.83/0.17) (Cordiner et al., 2008).

With the PABA anion in (I), the carboxyl­ate group is essentially coplanar with the benzene ring [torsion angle C2B—C1B—C11B— O11B = 179.25 (15)°, a feature similar to those found in the parent acid (Gracin & Fischer, 2005) and its co-crystals, e.g. with 4-nitro­benzoic acid (Bowers et al., 2005).

The carboxyl­ate groups of the DNBA and DNSA anions in both (II) and (III) are also essentially coplanar with the benzene rings: torsion angles C2B—C1B—C11B—O11B = -176.60 (16) and -179.4 (2)°, respectively. The 5- and 3-substituted nitro groups are also either in-plane or out-of-plane [torsion angles C4B—C5B—N5B— O52B = 179.61 (16)° in (II) and -177.5 (2)° in (III) and C2B—C3B—N3B—O32B = -166.31 (17)° in (II) and -155.2 (2)° in (III)]. Also, in (III), the phenolic substituent group (O2B) is disordered by rotation about the C1B···C4B ring vector giving a minor site-occupancy factor for the O21B—H21B group of 0.28 (SOF fixed in the final refinement cycles). This is similar to the disorder in three examples among the DNSA proton-transfer salts with Lewis bases, e.g. with nicotinamide (SOF = 0.76/0.24) (Koman et al., 2003), with 2,6-di­amino­pyridine (0.90/0.10) (Smith et al., 2003) and with quinoline-2-carb­oxy­lic acid (0.51/0.49) (Smith et al., 2007). In (III), the usual short intra­molecular phenol O—H···Ocarboxyl hydrogen bond is present (Table 3).

In the crystal of (I), the N8A—H···O11B hydrogen-bonded cation–anion pairs are extended through inter­molecular N4B—H··· O11Bi and ···N12Bii hydrogen-bonding extensions (Table 1), giving an overall three-dimensional network structure (Fig. 4). The structure contains no inter-ring π–π inter­actions or C—H···O hydrogen bonds.

The unit-cell parameters, space group (Table 4), and the overall crystal packing of (II) and (III) are very similar (Figs. 5 and 6). Although no classical hydrogen-bonding inter­actions are present between the primary cation–anion pairs, with both structures there are two minor cation C—H···O hydrogen-bonding extensions to nitro O-atom acceptors, C2A—H···O31Bii [3.309 (2) Å in (II) and 3.281 (3) Å in (III)] and C10A—H···O32Bi [3.247 (3) Å in (II) and 3.251 (5) Å in (III)] (Tables 2 and 3). These give two-dimensional layered structures lying parallel to (001). There are no inter-ring π–π inter­actions in either (II) or (III).

Synthesis and crystallization top

The title compounds (I)–(III) were prepared by first dissolving 100 mg of either PABA, DNBA, or DNSA in 5 mL of warm ethanol followed by the addition, with stirring, of 111 mg (I), 72 mg (II) or 67 mg (III) of BDU, respectively. Slow evaporation at room temperature gave colourless needles of (I), colourless prisms of (II), and fine yellow needles of (III), from which specimens were cleaved for the X-ray analyses.

Refinement details top

Crystal data, data collection and structure refinement details are given in Table 4. Hydrogen atoms were placed in calculated positions [C—Haromatic = 0.95 Å or C—Hmethyl­ene = 0.99 Å] and were allowed to ride in the refinements, with Uiso(H) = 1.2Ueq(C). The amine and aminium H-atoms were located in difference-Fourier analyses and were allowed to refine with distance restraints [N—H = 0.90 (2) Å] and with Uiso(H) = 1.2Ueq(N). Disorder involving atoms C9A and C10A of the six-membered ring systems of both (II) and (III) gave refined minor occupancy sites C12A and C13A, with site occupancy factors of 0.735 (3)/0.265 (3) and 0.686 (4)/0.314 (4), respectively. Also in (III), the phenol group of the DNSA anion was found to be disordered with the minor occupancy site (O21B) having a SOF = 0.28, which was fixed in the final cycles of refinement. In the structure of (I), although of no relevance in the achiral molecule, the Flack parameter (Flack, 1983) was determined as -0.1 (13) for 1668 Friedel pairs, which serves to indicate the lack of any usable anomalous scattering signal, as expected for an all-light-atom structure determined with Mo Kα X-rays.

Computing details top

For all compounds, data collection: CrysAlis PRO (Agilent, 2014); cell refinement: CrysAlis PRO (Agilent, 2014); data reduction: CrysAlis PRO (Agilent, 2014); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008) within WinGX (Farrugia, 2012); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: PLATON (Spek, 2009).

Figures top
[Figure 1] Fig. 1. The atom-numbering scheme and the molecular conformation of the DBU cation (A) and the PABA anion (B) in (I) with displacement ellipsoids drawn at the 40% probability level. The cation–anion hydrogen bond is shown as a dashed line.
[Figure 2] Fig. 2. The atom-numbering scheme and the molecular conformation of the DBU cation (A) and the DNBA anion (B) in (II) with displacement ellipsoids drawn at the 40% probability level. The bonds in the minor disordered section of the six-membered ring of the cation and the cation–anion hydrogen bonds are shown as dashed lines.
[Figure 3] Fig. 3. The atom-numbering scheme and the molecular conformation of the DBU cation (A) and the DNSA anion (B) in (III) with displacement ellipsoids drawn at the 40% probability level. The bonds in the minor disordered section of the six-membered ring of the cation are shown as dashed lines.
[Figure 4] Fig. 4. The three-dimensional hydrogen-bonded framework structure of (I) viewed approximately along a. For symmetry codes, see Table 1.
[Figure 5] Fig. 5. The packing of the hydrogen-bonded cation-anion pairs in the unit cell of (II), viewed along a. The minor-component disordered atoms and the non-associative H atoms have been omitted.
[Figure 6] Fig. 6. The packing of the hydrogen-bonded cation-anion pairs in the unit cell of (III), viewed along a. The minor-component disordered atoms and the non-associative H atoms have been omitted.
(I) 1-Aza-8-azoniabicyclo[5.4.0]undec-7-ene 4-aminobenzoate top
Crystal data top
C9H17N2+·C7H6NO2−F(000) = 624
Mr = 289.37Dx = 1.337 Mg m−3
Orthorhombic, P212121Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 2097 reflections
a = 8.0986 (4) Åθ = 3.5–28.4°
b = 12.9213 (6) ŵ = 0.09 mm−1
c = 13.7344 (7) ÅT = 200 K
V = 1437.23 (12) Å3Prism, colourless
Z = 40.40 × 0.26 × 0.24 mm
Data collection top
Oxford Diffraction Gemini-S CCD-detector
diffractometer		3324 independent reflections
Radiation source: Enhance (Mo) X-ray source2847 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.031
Detector resolution: 16.067 pixels mm-1θmax = 29.2°, θmin = 3.3°
ω scansh = −10→10
Absorption correction: multi-scan
(CrysAlis PRO; Agilent, 2014)		k = −16→15
Tmin = 0.93, Tmax = 0.99l = −17→18
7372 measured reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.044H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.098 w = 1/[σ2(Fo2) + (0.0438P)2 + 0.0476P]
where P = (Fo2 + 2Fc2)/3
S = 1.07(Δ/σ)max < 0.001
3324 reflectionsΔρmax = 0.20 e Å−3
199 parametersΔρmin = −0.25 e Å−3
3 restraintsAbsolute structure: Flack (1983), 1668 Friedel pairs
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: −0.1 (13)
Crystal data top
C9H17N2+·C7H6NO2−V = 1437.23 (12) Å3
Mr = 289.37Z = 4
Orthorhombic, P212121Mo Kα radiation
a = 8.0986 (4) ŵ = 0.09 mm−1
b = 12.9213 (6) ÅT = 200 K
c = 13.7344 (7) Å0.40 × 0.26 × 0.24 mm
Data collection top
Oxford Diffraction Gemini-S CCD-detector
diffractometer		3324 independent reflections
Absorption correction: multi-scan
(CrysAlis PRO; Agilent, 2014)		2847 reflections with I > 2σ(I)
Tmin = 0.93, Tmax = 0.99Rint = 0.031
7372 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.044H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.098Δρmax = 0.20 e Å−3
S = 1.07Δρmin = −0.25 e Å−3
3324 reflectionsAbsolute structure: Flack (1983), 1668 Friedel pairs
199 parametersAbsolute structure parameter: −0.1 (13)
3 restraints
Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell esds are taken into account in the estimation of distances, angles and torsion angles

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 > 2sigma(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*/Ueq
N1A0.32105 (18)0.84571 (11)0.67893 (11)0.0229 (4)
N8A0.36282 (18)0.67732 (12)0.62864 (11)0.0241 (5)
C2A0.2390 (2)0.94651 (14)0.66676 (13)0.0256 (5)
C3A0.3174 (2)1.01454 (14)0.58999 (14)0.0291 (6)
C4A0.2728 (2)0.98456 (14)0.48576 (14)0.0288 (6)
C5A0.3145 (2)0.87339 (14)0.45932 (13)0.0271 (5)
C6A0.2207 (2)0.79201 (14)0.51882 (13)0.0262 (5)
C7A0.3028 (2)0.77086 (13)0.61456 (13)0.0209 (5)
C9A0.4591 (2)0.64922 (14)0.71447 (13)0.0262 (5)
C10A0.5429 (2)0.74497 (13)0.75333 (13)0.0280 (6)
C11A0.4170 (2)0.82988 (15)0.76868 (13)0.0302 (6)
O11B0.28719 (17)0.51621 (9)0.51597 (9)0.0320 (4)
O12B0.29529 (19)0.56473 (11)0.36120 (11)0.0428 (5)
N4B0.6170 (2)0.11141 (13)0.33808 (12)0.0296 (5)
C1B0.3958 (2)0.39741 (13)0.40190 (12)0.0206 (5)
C2B0.43611 (19)0.36990 (13)0.30648 (12)0.0212 (5)
C3B0.5089 (2)0.27615 (13)0.28504 (12)0.0220 (5)
C4B0.5475 (2)0.20495 (13)0.35867 (13)0.0220 (5)
C5B0.5100 (2)0.23325 (13)0.45489 (12)0.0243 (5)
C6B0.4347 (2)0.32664 (13)0.47496 (13)0.0227 (5)
C11B0.3204 (2)0.50006 (14)0.42672 (14)0.0238 (5)
H8A0.342 (2)0.6279 (14)0.5850 (13)0.0290*
H10A0.598100.728800.815800.0340*
H11A0.341800.810700.822600.0360*
H12A0.473900.894900.786700.0360*
H13A0.628100.768600.706600.0340*
H21A0.240800.983600.729800.0310*
H22A0.122000.934600.649200.0310*
H31A0.438901.011400.597400.0350*
H32A0.282901.087000.601400.0350*
H41A0.152900.995400.476200.0350*
H42A0.331701.031400.440500.0350*
H51A0.434500.862600.468700.0320*
H52A0.290000.862600.389400.0320*
H61A0.106600.816600.530600.0310*
H62A0.214100.726900.481000.0310*
H91A0.542800.596600.697000.0310*
H92A0.385700.619500.764900.0310*
H2B0.412900.416900.255100.0250*
H3B0.533200.259500.219200.0260*
H5B0.536800.187600.506700.0290*
H6B0.408700.343200.540600.0270*
H41B0.666 (2)0.0742 (16)0.3845 (13)0.0360*
H42B0.647 (2)0.0939 (16)0.2759 (12)0.0360*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N1A0.0263 (7)0.0220 (8)0.0205 (7)0.0030 (6)−0.0033 (6)−0.0022 (6)
N8A0.0294 (8)0.0197 (8)0.0233 (8)−0.0004 (6)−0.0008 (6)−0.0024 (7)
C2A0.0276 (9)0.0223 (9)0.0269 (10)0.0053 (7)−0.0018 (7)−0.0053 (8)
C3A0.0311 (10)0.0218 (9)0.0343 (11)−0.0005 (8)−0.0031 (8)−0.0024 (8)
C4A0.0314 (10)0.0263 (9)0.0287 (10)0.0011 (8)−0.0008 (8)0.0041 (8)
C5A0.0295 (9)0.0292 (10)0.0225 (9)0.0039 (8)−0.0010 (7)−0.0007 (8)
C6A0.0312 (9)0.0221 (9)0.0253 (9)−0.0010 (7)−0.0062 (8)−0.0035 (8)
C7A0.0202 (8)0.0203 (9)0.0223 (9)−0.0013 (7)0.0013 (7)−0.0012 (7)
C9A0.0268 (9)0.0251 (9)0.0267 (10)0.0030 (8)−0.0003 (7)0.0033 (8)
C10A0.0269 (9)0.0301 (10)0.0269 (10)0.0034 (8)−0.0065 (8)−0.0010 (8)
C11A0.0365 (11)0.0306 (10)0.0235 (9)0.0053 (8)−0.0094 (8)−0.0056 (8)
O11B0.0520 (8)0.0207 (7)0.0233 (7)−0.0025 (6)0.0074 (6)−0.0035 (5)
O12B0.0643 (9)0.0337 (8)0.0305 (8)0.0187 (7)0.0123 (7)0.0099 (7)
N4B0.0406 (9)0.0260 (9)0.0223 (9)0.0072 (7)0.0000 (7)−0.0008 (7)
C1B0.0194 (8)0.0215 (9)0.0209 (9)−0.0045 (6)−0.0004 (7)0.0005 (7)
C2B0.0225 (9)0.0237 (9)0.0174 (8)−0.0015 (7)−0.0013 (6)0.0033 (7)
C3B0.0240 (8)0.0241 (8)0.0179 (8)−0.0032 (7)0.0001 (7)0.0010 (7)
C4B0.0216 (8)0.0195 (9)0.0250 (9)−0.0025 (7)−0.0011 (7)−0.0019 (7)
C5B0.0322 (9)0.0221 (9)0.0185 (8)0.0004 (8)−0.0011 (7)0.0046 (7)
C6B0.0288 (9)0.0228 (9)0.0166 (8)−0.0043 (7)0.0018 (7)−0.0017 (7)
C11B0.0255 (9)0.0221 (9)0.0237 (9)−0.0043 (7)0.0028 (7)0.0001 (7)
Geometric parameters (Å, º) top
O11B—C11B1.272 (2)C4A—H41A0.9900
O12B—C11B1.245 (2)C5A—H52A0.9900
N1A—C11A1.471 (2)C5A—H51A0.9900
N1A—C7A1.319 (2)C6A—H61A0.9900
N1A—C2A1.472 (2)C6A—H62A0.9900
N8A—C7A1.317 (2)C9A—H91A0.9900
N8A—C9A1.459 (2)C9A—H92A0.9900
N8A—H8A0.892 (18)C10A—H10A0.9900
N4B—C4B1.363 (2)C10A—H13A0.9900
N4B—H41B0.892 (18)C11A—H12A0.9900
N4B—H42B0.916 (17)C11A—H11A0.9900
C2A—C3A1.513 (3)C1B—C11B1.499 (2)
C3A—C4A1.526 (3)C1B—C2B1.397 (2)
C4A—C5A1.520 (3)C1B—C6B1.394 (2)
C5A—C6A1.533 (2)C2B—C3B1.379 (2)
C6A—C7A1.499 (2)C3B—C4B1.402 (2)
C9A—C10A1.509 (2)C4B—C5B1.404 (2)
C10A—C11A1.513 (2)C5B—C6B1.380 (2)
C2A—H21A0.9900C2B—H2B0.9500
C2A—H22A0.9900C3B—H3B0.9500
C3A—H31A0.9900C5B—H5B0.9500
C3A—H32A0.9900C6B—H6B0.9500
C4A—H42A0.9900
C2A—N1A—C7A121.49 (15)C5A—C6A—H62A109.00
C2A—N1A—C11A117.17 (14)H61A—C6A—H62A108.00
C7A—N1A—C11A121.26 (15)C7A—C6A—H62A109.00
C7A—N8A—C9A122.97 (15)C7A—C6A—H61A109.00
C7A—N8A—H8A119.3 (11)C10A—C9A—H91A110.00
C9A—N8A—H8A117.8 (12)N8A—C9A—H92A110.00
C4B—N4B—H41B120.9 (13)N8A—C9A—H91A110.00
H41B—N4B—H42B114.5 (17)C10A—C9A—H92A110.00
C4B—N4B—H42B121.5 (13)H91A—C9A—H92A108.00
N1A—C2A—C3A113.83 (14)C9A—C10A—H10A110.00
C2A—C3A—C4A114.02 (15)H10A—C10A—H13A108.00
C3A—C4A—C5A114.29 (15)C9A—C10A—H13A110.00
C4A—C5A—C6A114.26 (14)C11A—C10A—H10A110.00
C5A—C6A—C7A111.90 (14)C11A—C10A—H13A110.00
N8A—C7A—C6A117.38 (15)N1A—C11A—H11A110.00
N1A—C7A—N8A122.23 (16)N1A—C11A—H12A110.00
N1A—C7A—C6A120.28 (15)C10A—C11A—H11A110.00
N8A—C9A—C10A108.79 (14)H11A—C11A—H12A108.00
C9A—C10A—C11A109.93 (14)C10A—C11A—H12A110.00
N1A—C11A—C10A109.88 (14)C6B—C1B—C11B120.58 (15)
C3A—C2A—H22A109.00C2B—C1B—C11B122.25 (15)
H21A—C2A—H22A108.00C2B—C1B—C6B117.12 (15)
N1A—C2A—H22A109.00C1B—C2B—C3B121.59 (15)
C3A—C2A—H21A109.00C2B—C3B—C4B121.17 (15)
N1A—C2A—H21A109.00N4B—C4B—C3B121.61 (16)
C2A—C3A—H31A109.00N4B—C4B—C5B121.03 (16)
C2A—C3A—H32A109.00C3B—C4B—C5B117.36 (15)
H31A—C3A—H32A108.00C4B—C5B—C6B120.75 (16)
C4A—C3A—H31A109.00C1B—C6B—C5B122.00 (16)
C4A—C3A—H32A109.00O11B—C11B—O12B123.50 (17)
C3A—C4A—H42A109.00O11B—C11B—C1B116.76 (16)
H41A—C4A—H42A108.00O12B—C11B—C1B119.74 (17)
C5A—C4A—H41A109.00C1B—C2B—H2B119.00
C5A—C4A—H42A109.00C3B—C2B—H2B119.00
C3A—C4A—H41A109.00C2B—C3B—H3B119.00
C6A—C5A—H52A109.00C4B—C3B—H3B119.00
H51A—C5A—H52A108.00C4B—C5B—H5B120.00
C4A—C5A—H52A109.00C6B—C5B—H5B120.00
C6A—C5A—H51A109.00C1B—C6B—H6B119.00
C4A—C5A—H51A109.00C5B—C6B—H6B119.00
C5A—C6A—H61A109.00
C7A—N1A—C2A—C3A−74.8 (2)N8A—C9A—C10A—C11A52.82 (18)
C11A—N1A—C2A—C3A108.53 (17)C9A—C10A—C11A—N1A−52.69 (19)
C2A—N1A—C7A—N8A−173.67 (15)C6B—C1B—C2B—C3B1.0 (2)
C2A—N1A—C7A—C6A10.2 (2)C11B—C1B—C2B—C3B178.48 (15)
C11A—N1A—C7A—N8A2.9 (3)C2B—C1B—C6B—C5B0.1 (2)
C11A—N1A—C7A—C6A−173.23 (15)C11B—C1B—C6B—C5B−177.44 (15)
C2A—N1A—C11A—C10A−157.91 (14)C2B—C1B—C11B—O11B179.25 (15)
C7A—N1A—C11A—C10A25.4 (2)C2B—C1B—C11B—O12B−1.6 (3)
C9A—N8A—C7A—N1A−2.2 (3)C6B—C1B—C11B—O11B−3.4 (2)
C9A—N8A—C7A—C6A174.06 (15)C6B—C1B—C11B—O12B175.83 (16)
C7A—N8A—C9A—C10A−26.7 (2)C1B—C2B—C3B—C4B−0.9 (2)
N1A—C2A—C3A—C4A77.87 (18)C2B—C3B—C4B—N4B178.92 (16)
C2A—C3A—C4A—C5A−56.71 (19)C2B—C3B—C4B—C5B−0.4 (2)
C3A—C4A—C5A—C6A62.97 (19)N4B—C4B—C5B—C6B−177.86 (16)
C4A—C5A—C6A—C7A−83.76 (18)C3B—C4B—C5B—C6B1.4 (2)
C5A—C6A—C7A—N1A60.9 (2)C4B—C5B—C6B—C1B−1.3 (3)
C5A—C6A—C7A—N8A−115.39 (17)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N8A—H8A···O11B0.89 (2)1.78 (2)2.665 (2)170 (2)
N4B—H41B···O11Bi0.89 (2)2.05 (2)2.939 (2)176 (2)
N4B—H42B···O12Bii0.92 (2)1.98 (2)2.891 (2)176 (2)
Symmetry codes: (i) x+1/2, −y+1/2, −z+1; (ii) −x+1, y−1/2, −z+1/2.
(II) Aza-8-azoniabicyclo[5.4.0]undec-7-ene 3,5-dinitrobenzoate top
Crystal data top
C9H17N2+·C7H3N2O6−F(000) = 768
Mr = 364.36Dx = 1.438 Mg m−3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 1784 reflections
a = 6.0197 (4) Åθ = 4.0–28.0°
b = 19.6228 (13) ŵ = 0.11 mm−1
c = 14.3866 (8) ÅT = 200 K
β = 98.078 (5)°Needle, colourless
V = 1682.53 (18) Å30.30 × 0.13 × 0.08 mm
Z = 4
Data collection top
Oxford Diffraction Gemini-S CCD-detector
diffractometer		3311 independent reflections
Radiation source: fine-focus sealed tube2561 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.024
Detector resolution: 16.077 pixels mm-1θmax = 26.0°, θmin = 3.4°
ω scansh = −7→7
Absorption correction: multi-scan
(CrysAlis PRO; Agilent, 2014)		k = −14→24
Tmin = 0.90, Tmax = 0.99l = −9→17
7082 measured reflections
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)] = 0.045Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.109H atoms treated by a mixture of independent and constrained refinement
S = 1.01 w = 1/[σ2(Fo2) + (0.0435P)2 + 0.5615P]
where P = (Fo2 + 2Fc2)/3
3311 reflections(Δ/σ)max < 0.001
245 parametersΔρmax = 0.18 e Å−3
3 restraintsΔρmin = −0.22 e Å−3
Crystal data top
C9H17N2+·C7H3N2O6−V = 1682.53 (18) Å3
Mr = 364.36Z = 4
Monoclinic, P21/nMo Kα radiation
a = 6.0197 (4) ŵ = 0.11 mm−1
b = 19.6228 (13) ÅT = 200 K
c = 14.3866 (8) Å0.30 × 0.13 × 0.08 mm
β = 98.078 (5)°
Data collection top
Oxford Diffraction Gemini-S CCD-detector
diffractometer		3311 independent reflections
Absorption correction: multi-scan
(CrysAlis PRO; Agilent, 2014)		2561 reflections with I > 2σ(I)
Tmin = 0.90, Tmax = 0.99Rint = 0.024
7082 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0453 restraints
wR(F2) = 0.109H atoms treated by a mixture of independent and constrained refinement
S = 1.01Δρmax = 0.18 e Å−3
3311 reflectionsΔρmin = −0.22 e Å−3
245 parameters
Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell esds are taken into account in the estimation of distances, angles and torsion angles

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 > 2sigma(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)
O11B−0.0061 (2)0.68797 (7)0.41185 (9)0.0408 (4)
O12B−0.0380 (2)0.64765 (8)0.26602 (10)0.0556 (5)
O31B−0.5921 (3)0.46963 (8)0.17213 (10)0.0567 (5)
O32B−0.8865 (3)0.46500 (9)0.24178 (11)0.0703 (6)
O51B−0.8471 (2)0.55899 (8)0.55381 (10)0.0514 (5)
O52B−0.5787 (3)0.62813 (8)0.60351 (10)0.0576 (6)
N3B−0.6966 (3)0.48464 (8)0.23584 (11)0.0416 (5)
N5B−0.6770 (3)0.59011 (8)0.54409 (10)0.0363 (5)
C1B−0.2967 (3)0.60944 (8)0.36270 (11)0.0264 (5)
C2B−0.3972 (3)0.56537 (8)0.29419 (11)0.0288 (5)
C3B−0.5892 (3)0.53100 (8)0.30888 (11)0.0289 (5)
C4B−0.6880 (3)0.53844 (8)0.38905 (12)0.0293 (5)
C5B−0.5807 (3)0.58130 (8)0.45649 (11)0.0265 (5)
C6B−0.3873 (3)0.61637 (8)0.44556 (11)0.0269 (5)
C11B−0.0952 (3)0.65174 (9)0.34516 (13)0.0327 (5)
N1A0.6514 (2)0.81846 (7)0.36517 (9)0.0288 (4)
N8A0.3270 (3)0.75625 (8)0.33371 (10)0.0364 (5)
C2A0.8281 (3)0.85009 (9)0.43221 (13)0.0350 (6)
C3A0.7557 (3)0.91508 (9)0.47621 (13)0.0378 (6)
C4A0.6172 (3)0.90383 (10)0.55531 (13)0.0390 (6)
C5A0.4046 (3)0.86226 (10)0.52884 (13)0.0383 (6)
C6A0.4433 (3)0.78996 (9)0.49381 (11)0.0334 (5)
C7A0.4773 (3)0.78797 (8)0.39270 (11)0.0262 (5)
C9A0.3565 (6)0.74500 (17)0.2353 (2)0.0357 (10)0.735 (3)
C10A0.4681 (5)0.80757 (15)0.20241 (17)0.0364 (8)0.735 (3)
C11A0.6839 (3)0.82115 (10)0.26593 (12)0.0364 (6)
C13A0.3000 (16)0.7705 (5)0.2305 (8)0.0357 (10)0.265 (3)
C12A0.5368 (12)0.7669 (4)0.2074 (5)0.0364 (8)0.265 (3)
H2B−0.334700.558900.237800.0350*
H4B−0.822600.515300.397200.0350*
H6B−0.317000.645000.494300.0320*
H8A0.217 (3)0.7342 (9)0.3570 (12)0.0440*
H10A0.499200.800700.137300.0440*0.735 (3)
H21A0.958300.860300.399500.0420*
H22A0.878100.817000.482700.0420*
H31A0.667000.942800.426800.0450*
H32A0.891300.941600.500800.0450*
H41A0.575200.948800.578700.0470*
H42A0.712000.880500.607600.0470*
H51A0.305500.886900.479200.0460*
H52A0.324800.859000.584400.0460*
H61A0.576900.770300.532500.0400*
H62A0.312500.761200.502300.0400*
H91A0.209200.737600.196500.0430*0.735 (3)
H92A0.451200.704300.229900.0430*0.735 (3)
H11A0.366800.847300.202800.0440*0.735 (3)
H12A0.797100.786800.254100.0440*0.735 (3)
H13A0.741500.866700.251700.0440*0.735 (3)
H14A0.536700.775500.139600.0440*0.265 (3)
H15A0.599400.720900.222100.0440*0.265 (3)
H16A0.234300.816200.216200.0430*0.265 (3)
H17A0.203300.735900.194900.0430*0.265 (3)
H18A0.843900.812900.260600.0440*0.265 (3)
H19A0.643800.867100.240500.0440*0.265 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O11B0.0376 (7)0.0403 (8)0.0454 (7)−0.0139 (6)0.0090 (6)−0.0054 (6)
O12B0.0558 (9)0.0740 (11)0.0419 (8)−0.0258 (8)0.0238 (7)−0.0043 (7)
O31B0.0690 (10)0.0566 (10)0.0423 (8)0.0063 (8)0.0003 (7)−0.0213 (7)
O32B0.0733 (11)0.0811 (12)0.0539 (9)−0.0503 (10)−0.0006 (8)−0.0091 (9)
O51B0.0472 (8)0.0586 (9)0.0543 (8)−0.0128 (7)0.0276 (7)0.0036 (7)
O52B0.0663 (10)0.0729 (11)0.0380 (8)−0.0175 (8)0.0228 (7)−0.0229 (8)
N3B0.0534 (11)0.0353 (9)0.0329 (8)−0.0074 (8)−0.0055 (8)−0.0016 (7)
N5B0.0392 (9)0.0378 (9)0.0343 (8)−0.0006 (7)0.0132 (7)0.0021 (7)
C1B0.0250 (8)0.0242 (8)0.0298 (8)0.0011 (7)0.0034 (7)0.0032 (7)
C2B0.0342 (9)0.0280 (9)0.0251 (8)0.0037 (7)0.0070 (7)0.0017 (7)
C3B0.0338 (9)0.0244 (9)0.0268 (8)−0.0015 (7)−0.0021 (7)−0.0001 (7)
C4B0.0263 (8)0.0258 (9)0.0352 (9)−0.0016 (7)0.0021 (7)0.0055 (8)
C5B0.0284 (8)0.0259 (9)0.0264 (8)0.0035 (7)0.0078 (7)0.0013 (7)
C6B0.0275 (8)0.0247 (9)0.0279 (8)−0.0004 (7)0.0020 (7)−0.0018 (7)
C11B0.0297 (9)0.0309 (9)0.0382 (10)−0.0006 (8)0.0072 (8)0.0031 (8)
N1A0.0255 (7)0.0325 (8)0.0285 (7)−0.0044 (6)0.0039 (6)0.0020 (6)
N8A0.0358 (8)0.0484 (10)0.0250 (7)−0.0178 (7)0.0045 (6)−0.0008 (7)
C2A0.0236 (9)0.0388 (10)0.0410 (10)−0.0059 (8)−0.0007 (8)0.0001 (8)
C3A0.0347 (10)0.0330 (10)0.0434 (10)−0.0076 (8)−0.0020 (8)0.0000 (9)
C4A0.0405 (10)0.0399 (11)0.0343 (9)−0.0025 (8)−0.0032 (8)−0.0064 (9)
C5A0.0357 (10)0.0495 (12)0.0302 (9)−0.0046 (9)0.0062 (8)−0.0083 (8)
C6A0.0357 (10)0.0403 (10)0.0237 (8)−0.0113 (8)0.0024 (7)0.0050 (8)
C7A0.0254 (8)0.0250 (8)0.0272 (8)−0.0015 (7)0.0006 (7)0.0028 (7)
C9A0.0418 (19)0.041 (2)0.0236 (10)−0.0039 (14)0.0026 (12)−0.0018 (16)
C10A0.0443 (15)0.0390 (16)0.0263 (10)−0.0024 (12)0.0061 (10)0.0036 (12)
C11A0.0348 (10)0.0427 (11)0.0339 (9)−0.0043 (8)0.0126 (8)0.0047 (8)
C13A0.0418 (19)0.041 (2)0.0236 (10)−0.0039 (14)0.0026 (12)−0.0018 (16)
C12A0.0443 (15)0.0390 (16)0.0263 (10)−0.0024 (12)0.0061 (10)0.0036 (12)
Geometric parameters (Å, º) top
O11B—C11B1.253 (2)C5A—C6A1.534 (3)
O12B—C11B1.238 (2)C6A—C7A1.498 (2)
O31B—N3B1.218 (2)C9A—C10A1.507 (4)
O32B—N3B1.221 (3)C10A—C11A1.503 (3)
O51B—N5B1.217 (2)C12A—C13A1.510 (12)
O52B—N5B1.223 (2)C12A—C11A1.555 (8)
N3B—C3B1.469 (2)C2A—H21A0.9900
N5B—C5B1.470 (2)C2A—H22A0.9900
N1A—C2A1.469 (2)C3A—H31A0.9900
N1A—C7A1.315 (2)C3A—H32A0.9900
N1A—C11A1.469 (2)C4A—H41A0.9900
N8A—C13A1.497 (11)C4A—H42A0.9900
N8A—C9A1.468 (3)C5A—H51A0.9900
N8A—C7A1.308 (2)C5A—H52A0.9900
N8A—H8A0.895 (18)C6A—H61A0.9900
C1B—C11B1.520 (3)C6A—H62A0.9900
C1B—C2B1.385 (2)C9A—H91A0.9900
C1B—C6B1.386 (2)C9A—H92A0.9900
C2B—C3B1.380 (2)C10A—H10A0.9900
C3B—C4B1.378 (2)C10A—H11A0.9900
C4B—C5B1.375 (2)C11A—H12A0.9900
C5B—C6B1.380 (2)C11A—H13A0.9900
C2B—H2B0.9500C12A—H14A0.9900
C4B—H4B0.9500C12A—H15A0.9900
C6B—H6B0.9500C13A—H16A0.9900
C2A—C3A1.515 (3)C13A—H17A0.9900
C3A—C4A1.518 (3)C11A—H18A0.9900
C4A—C5A1.520 (3)C11A—H19A0.9900
O31B—N3B—O32B124.33 (17)C3A—C2A—H22A109.00
O31B—N3B—C3B117.77 (17)H21A—C2A—H22A108.00
O32B—N3B—C3B117.89 (16)C2A—C3A—H31A109.00
O51B—N5B—O52B123.92 (16)C2A—C3A—H32A109.00
O51B—N5B—C5B118.63 (15)C4A—C3A—H31A109.00
O52B—N5B—C5B117.44 (16)C4A—C3A—H32A109.00
C2A—N1A—C11A116.09 (13)H31A—C3A—H32A108.00
C7A—N1A—C11A121.98 (14)C3A—C4A—H41A109.00
C2A—N1A—C7A121.91 (14)C3A—C4A—H42A109.00
C7A—N8A—C9A122.1 (2)C5A—C4A—H41A108.00
C7A—N8A—C13A121.6 (4)C5A—C4A—H42A108.00
C13A—N8A—H8A118.6 (12)H41A—C4A—H42A108.00
C9A—N8A—H8A119.0 (11)C4A—C5A—H51A109.00
C7A—N8A—H8A117.9 (11)C4A—C5A—H52A109.00
C2B—C1B—C6B119.23 (16)C6A—C5A—H51A109.00
C2B—C1B—C11B120.13 (15)C6A—C5A—H52A109.00
C6B—C1B—C11B120.60 (15)H51A—C5A—H52A108.00
C1B—C2B—C3B119.19 (15)C5A—C6A—H61A109.00
N3B—C3B—C2B119.14 (15)C5A—C6A—H62A109.00
N3B—C3B—C4B117.78 (16)C7A—C6A—H61A109.00
C2B—C3B—C4B123.08 (15)C7A—C6A—H62A109.00
C3B—C4B—C5B116.13 (16)H61A—C6A—H62A108.00
C4B—C5B—C6B123.01 (16)N8A—C9A—H91A110.00
N5B—C5B—C4B118.32 (16)N8A—C9A—H92A110.00
N5B—C5B—C6B118.67 (14)C10A—C9A—H91A110.00
C1B—C6B—C5B119.30 (15)C10A—C9A—H92A110.00
O11B—C11B—C1B116.66 (16)H91A—C9A—H92A108.00
O11B—C11B—O12B126.65 (17)C9A—C10A—H10A110.00
O12B—C11B—C1B116.68 (16)C9A—C10A—H11A110.00
C3B—C2B—H2B120.00C11A—C10A—H10A110.00
C1B—C2B—H2B120.00C11A—C10A—H11A110.00
C3B—C4B—H4B122.00H10A—C10A—H11A108.00
C5B—C4B—H4B122.00N1A—C11A—H12A109.00
C5B—C6B—H6B120.00N1A—C11A—H13A109.00
C1B—C6B—H6B120.00C10A—C11A—H12A109.00
N1A—C2A—C3A113.94 (15)C10A—C11A—H13A109.00
C2A—C3A—C4A114.29 (15)H12A—C11A—H13A108.00
C3A—C4A—C5A114.95 (15)C13A—C12A—H14A110.00
C4A—C5A—C6A114.65 (15)C13A—C12A—H15A110.00
C5A—C6A—C7A113.01 (14)H14A—C12A—H15A108.00
N1A—C7A—N8A121.94 (15)N8A—C13A—H16A111.00
N1A—C7A—C6A120.27 (15)N8A—C13A—H17A111.00
N8A—C7A—C6A117.79 (16)C12A—C13A—H16A111.00
N8A—C9A—C10A107.5 (2)C12A—C13A—H17A111.00
C9A—C10A—C11A109.8 (2)H16A—C13A—H17A109.00
N1A—C11A—C10A111.27 (16)N1A—C11A—H18A109.00
N8A—C13A—C12A103.6 (7)N1A—C11A—H19A109.00
N1A—C2A—H21A109.00C12A—C11A—H18A109.00
N1A—C2A—H22A109.00C12A—C11A—H19A109.00
C3A—C2A—H21A109.00H18A—C11A—H19A108.00
O31B—N3B—C3B—C2B12.0 (2)C6B—C1B—C11B—O11B5.9 (2)
O31B—N3B—C3B—C4B−168.62 (16)C6B—C1B—C11B—O12B−173.03 (16)
O32B—N3B—C3B—C2B−166.31 (17)C11B—C1B—C2B—C3B−175.52 (15)
O32B—N3B—C3B—C4B13.1 (2)C2B—C1B—C6B—C5B−2.6 (2)
O51B—N5B—C5B—C4B0.3 (2)C11B—C1B—C6B—C5B174.94 (15)
O51B—N5B—C5B—C6B−179.75 (16)C1B—C2B—C3B—N3B179.56 (15)
O52B—N5B—C5B—C4B179.61 (16)C1B—C2B—C3B—C4B0.2 (3)
O52B—N5B—C5B—C6B−0.5 (2)C2B—C3B—C4B—C5B−1.7 (2)
C2A—N1A—C11A—C10A−162.56 (17)N3B—C3B—C4B—C5B178.91 (15)
C7A—N1A—C2A—C3A−71.6 (2)C3B—C4B—C5B—C6B1.1 (2)
C11A—N1A—C2A—C3A110.16 (17)C3B—C4B—C5B—N5B−178.96 (15)
C2A—N1A—C7A—N8A−175.79 (16)N5B—C5B—C6B—C1B−178.93 (15)
C2A—N1A—C7A—C6A5.5 (2)C4B—C5B—C6B—C1B1.0 (3)
C11A—N1A—C7A—N8A2.4 (3)N1A—C2A—C3A—C4A78.97 (19)
C11A—N1A—C7A—C6A−176.35 (15)C2A—C3A—C4A—C5A−57.1 (2)
C7A—N1A—C11A—C10A19.2 (2)C3A—C4A—C5A—C6A60.0 (2)
C9A—N8A—C7A—C6A−173.3 (2)C4A—C5A—C6A—C7A−81.00 (19)
C9A—N8A—C7A—N1A7.9 (3)C5A—C6A—C7A—N1A63.5 (2)
C7A—N8A—C9A—C10A−37.5 (3)C5A—C6A—C7A—N8A−115.29 (18)
C6B—C1B—C2B—C3B2.0 (2)N8A—C9A—C10A—C11A55.9 (3)
C2B—C1B—C11B—O11B−176.60 (16)C9A—C10A—C11A—N1A−48.3 (3)
C2B—C1B—C11B—O12B4.4 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N8A—H8A···O11B0.90 (2)1.88 (2)2.777 (2)177 (2)
N8A—H8A···O12B0.90 (2)2.53 (2)3.117 (2)124 (1)
C10A—H11A···O32Bi0.992.443.247 (3)138
C11A—H13A···O52Bii0.992.523.071 (2)115
C2A—H21A···O31Biii0.992.563.309 (2)133
C6A—H62A···O11B0.992.603.438 (2)143
C9A—H91A···O12B0.992.603.127 (4)114
Symmetry codes: (i) −x−1/2, y+1/2, −z+1/2; (ii) x+3/2, −y+3/2, z−1/2; (iii) −x+1/2, y+1/2, −z+1/2.
(III) 1-Aza-8-azoniabicyclo[5.4.0]undec-7-ene 2-hydroxy-3,5-dinitrobenzoate top
Crystal data top
C9H17N2+·C7H3N2O7−F(000) = 800
Mr = 380.36Dx = 1.489 Mg m−3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 1891 reflections
a = 6.1537 (3) Åθ = 3.5–26.6°
b = 19.1541 (14) ŵ = 0.12 mm−1
c = 14.5527 (11) ÅT = 200 K
β = 98.343 (6)°Needle, yellow
V = 1697.2 (2) Å30.30 × 0.13 × 0.10 mm
Z = 4
Data collection top
Oxford Diffraction Gemini-S CCD-detector
diffractometer		3339 independent reflections
Radiation source: Enhance (Mo) X-ray source2347 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.034
Detector resolution: 16.077 pixels mm-1θmax = 26.0°, θmin = 3.4°
ω scansh = −7→7
Absorption correction: multi-scan
(CrysAlis PRO; Agilent, 2014)		k = −23→23
Tmin = 0.920, Tmax = 0.990l = −17→17
7800 measured reflections
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)] = 0.058Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.123H atoms treated by a mixture of independent and constrained refinement
S = 1.03 w = 1/[σ2(Fo2) + (0.0374P)2 + 0.7569P]
where P = (Fo2 + 2Fc2)/3
3339 reflections(Δ/σ)max < 0.001
263 parametersΔρmax = 0.29 e Å−3
3 restraintsΔρmin = −0.29 e Å−3
Crystal data top
C9H17N2+·C7H3N2O7−V = 1697.2 (2) Å3
Mr = 380.36Z = 4
Monoclinic, P21/nMo Kα radiation
a = 6.1537 (3) ŵ = 0.12 mm−1
b = 19.1541 (14) ÅT = 200 K
c = 14.5527 (11) Å0.30 × 0.13 × 0.10 mm
β = 98.343 (6)°
Data collection top
Oxford Diffraction Gemini-S CCD-detector
diffractometer		3339 independent reflections
Absorption correction: multi-scan
(CrysAlis PRO; Agilent, 2014)		2347 reflections with I > 2σ(I)
Tmin = 0.920, Tmax = 0.990Rint = 0.034
7800 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0583 restraints
wR(F2) = 0.123H atoms treated by a mixture of independent and constrained refinement
S = 1.03Δρmax = 0.29 e Å−3
3339 reflectionsΔρmin = −0.29 e Å−3
263 parameters
Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell esds are taken into account in the estimation of distances, angles and torsion angles

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 > 2sigma(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)
O2B0.8426 (4)0.56153 (13)0.78929 (15)0.0433 (8)0.720
O11B0.5084 (3)0.68879 (9)0.59293 (13)0.0433 (6)
O12B0.5450 (3)0.64525 (10)0.73596 (13)0.0522 (7)
O31B1.1116 (4)0.45700 (12)0.81707 (17)0.0819 (10)
O32B1.4080 (4)0.47261 (13)0.75765 (15)0.0761 (9)
O51B1.3286 (3)0.55867 (11)0.44585 (14)0.0594 (7)
O52B1.0707 (4)0.63206 (11)0.39870 (14)0.0670 (8)
N3B1.2118 (4)0.48306 (12)0.76028 (16)0.0467 (8)
N5B1.1654 (3)0.59169 (11)0.45698 (15)0.0407 (7)
C1B0.8002 (3)0.60950 (11)0.63899 (16)0.0268 (7)
C2B0.9062 (3)0.56600 (12)0.70947 (16)0.0297 (7)
C3B1.0956 (4)0.53052 (12)0.69146 (16)0.0310 (7)
C4B1.1816 (3)0.53943 (11)0.61041 (16)0.0308 (7)
C5B1.0735 (3)0.58226 (11)0.54278 (15)0.0276 (7)
C6B0.8810 (3)0.61671 (11)0.55531 (15)0.0263 (7)
C11B0.6029 (4)0.65080 (12)0.65595 (19)0.0346 (8)
O21B0.7762 (10)0.6571 (3)0.4915 (5)0.052 (3)0.280
N1A−0.1524 (3)0.82026 (10)0.63820 (13)0.0293 (6)
N8A0.1714 (3)0.76040 (11)0.67301 (14)0.0369 (7)
C2A−0.3262 (3)0.85087 (13)0.56984 (17)0.0357 (8)
C3A−0.2606 (4)0.91805 (13)0.52684 (18)0.0397 (8)
C4A−0.1188 (4)0.90797 (14)0.45044 (17)0.0409 (8)
C5A0.0934 (4)0.86814 (13)0.48033 (17)0.0393 (9)
C6A0.0612 (4)0.79368 (13)0.51409 (16)0.0340 (8)
C7A0.0226 (3)0.79083 (11)0.61294 (15)0.0265 (7)
C9A0.1399 (9)0.7478 (2)0.7696 (4)0.0366 (18)0.686 (4)
C10A0.0234 (6)0.8111 (2)0.8005 (3)0.0379 (11)0.686 (4)
C11A−0.1871 (4)0.82349 (13)0.73612 (16)0.0363 (8)
C13A0.189 (2)0.7738 (7)0.7752 (11)0.0366 (18)0.314 (4)
C12A−0.0464 (13)0.7704 (5)0.7958 (6)0.0379 (11)0.314 (4)
H4B1.313500.516500.601100.0370*
H6B0.802400.643800.507000.0320*0.720
H2B0.738700.589500.791900.0650*0.720
H21B0.660800.672000.509300.0770*0.280
H61B0.854600.561200.767700.0360*0.280
H8A0.280 (3)0.7394 (11)0.6508 (15)0.0320*
H10A−0.008900.803800.864500.0460*0.686 (4)
H21A−0.456700.859900.600600.0430*
H22A−0.369100.816400.519800.0430*
H31A−0.179400.947500.576300.0480*
H32A−0.395300.943600.500800.0480*
H41A−0.205700.882700.398200.0490*
H42A−0.082100.954400.427200.0490*
H51A0.183000.894400.530800.0470*
H52A0.177200.866100.427300.0470*
H61A−0.065700.772300.474400.0410*
H62A0.193100.765700.507200.0410*
H91A0.283500.741400.809200.0440*0.686 (4)
H92A0.050400.705400.773900.0440*0.686 (4)
H11A0.119500.852600.800700.0460*0.686 (4)
H12A−0.296400.787800.747600.0440*0.686 (4)
H13A−0.246500.869900.749100.0440*0.686 (4)
H14A−0.106100.722900.782300.0460*0.314 (4)
H15A−0.049500.780400.862300.0460*0.314 (4)
H16A0.253400.820400.791200.0440*0.314 (4)
H17A0.280800.737900.811000.0440*0.314 (4)
H18A−0.343900.814600.740100.0440*0.314 (4)
H19A−0.150900.871000.760600.0440*0.314 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O2B0.0472 (13)0.0563 (16)0.0297 (14)0.0095 (12)0.0168 (11)0.0083 (12)
O11B0.0356 (9)0.0369 (10)0.0579 (12)0.0124 (8)0.0087 (8)0.0063 (9)
O12B0.0492 (11)0.0640 (13)0.0484 (12)0.0080 (10)0.0245 (9)−0.0040 (10)
O31B0.0774 (15)0.0847 (18)0.0749 (17)−0.0226 (13)−0.0181 (12)0.0525 (14)
O32B0.0708 (15)0.0894 (18)0.0629 (15)0.0492 (13)−0.0082 (11)0.0045 (12)
O51B0.0542 (11)0.0636 (13)0.0680 (14)0.0066 (10)0.0346 (10)−0.0115 (11)
O52B0.0918 (15)0.0703 (15)0.0456 (13)0.0168 (13)0.0323 (11)0.0224 (11)
N3B0.0592 (15)0.0338 (13)0.0411 (14)0.0003 (11)−0.0127 (12)0.0001 (11)
N5B0.0464 (12)0.0388 (13)0.0405 (13)−0.0040 (10)0.0189 (10)−0.0056 (11)
C1B0.0259 (11)0.0216 (12)0.0323 (13)−0.0038 (9)0.0021 (9)−0.0035 (10)
C2B0.0341 (12)0.0270 (13)0.0280 (13)−0.0057 (10)0.0044 (10)−0.0019 (10)
C3B0.0361 (12)0.0241 (12)0.0300 (14)−0.0006 (10)−0.0049 (10)0.0015 (10)
C4B0.0256 (11)0.0245 (12)0.0406 (15)−0.0010 (10)−0.0006 (10)−0.0054 (11)
C5B0.0297 (11)0.0257 (12)0.0285 (13)−0.0056 (10)0.0077 (10)−0.0023 (10)
C6B0.0288 (11)0.0214 (12)0.0275 (13)−0.0017 (9)−0.0001 (9)0.0021 (10)
C11B0.0292 (12)0.0284 (13)0.0466 (16)−0.0028 (10)0.0068 (11)−0.0055 (12)
O21B0.043 (4)0.059 (5)0.053 (4)0.008 (3)0.009 (3)0.025 (4)
N1A0.0254 (9)0.0319 (11)0.0304 (11)0.0014 (8)0.0038 (8)−0.0007 (9)
N8A0.0333 (11)0.0476 (13)0.0299 (12)0.0157 (10)0.0051 (9)0.0034 (10)
C2A0.0254 (11)0.0378 (14)0.0427 (15)0.0059 (10)0.0006 (10)−0.0026 (12)
C3A0.0358 (13)0.0339 (14)0.0464 (16)0.0066 (11)−0.0044 (11)0.0003 (12)
C4A0.0442 (14)0.0384 (15)0.0365 (15)−0.0024 (12)−0.0061 (11)0.0074 (12)
C5A0.0370 (13)0.0508 (17)0.0308 (14)−0.0005 (12)0.0075 (10)0.0080 (12)
C6A0.0340 (12)0.0413 (15)0.0262 (13)0.0081 (11)0.0029 (10)−0.0052 (11)
C7A0.0270 (11)0.0226 (12)0.0291 (13)−0.0006 (9)0.0014 (9)−0.0035 (10)
C9A0.042 (3)0.037 (4)0.0292 (18)0.001 (2)0.000 (2)0.005 (3)
C10A0.047 (2)0.041 (2)0.0263 (17)−0.0052 (17)0.0070 (16)−0.0033 (19)
C11A0.0363 (13)0.0419 (15)0.0335 (14)−0.0014 (11)0.0150 (11)−0.0058 (12)
C13A0.042 (3)0.037 (4)0.0292 (18)0.001 (2)0.000 (2)0.005 (3)
C12A0.047 (2)0.041 (2)0.0263 (17)−0.0052 (17)0.0070 (16)−0.0033 (19)
Geometric parameters (Å, º) top
O2B—C2B1.281 (3)C3A—C4A1.522 (4)
O11B—C11B1.247 (3)C4A—C5A1.520 (4)
O12B—C11B1.271 (3)C5A—C6A1.531 (4)
O21B—C6B1.305 (7)C6A—C7A1.493 (3)
O31B—N3B1.208 (3)C9A—C10A1.510 (6)
O32B—N3B1.230 (4)C10A—C11A1.503 (5)
O51B—N5B1.217 (3)C12A—C13A1.523 (15)
O52B—N5B1.230 (3)C2A—H21A0.9900
O2B—H2B0.8400C2A—H22A0.9900
O21B—H21B0.8400C3A—H31A0.9900
N3B—C3B1.460 (3)C3A—H32A0.9900
N5B—C5B1.455 (3)C4A—H41A0.9900
N1A—C2A1.473 (3)C4A—H42A0.9900
N1A—C11A1.473 (3)C5A—H51A0.9900
N1A—C7A1.314 (3)C5A—H52A0.9900
N8A—C9A1.467 (6)C6A—H61A0.9900
N8A—C13A1.498 (16)C6A—H62A0.9900
N8A—C7A1.308 (3)C9A—H91A0.9900
N8A—H8A0.88 (2)C9A—H92A0.9900
C1B—C11B1.499 (3)C10A—H10A0.9900
C1B—C6B1.387 (3)C10A—H11A0.9900
C1B—C2B1.406 (3)C11A—H12A0.9900
C2B—C3B1.406 (3)C11A—H13A0.9900
C3B—C4B1.372 (3)C12A—H14A0.9900
C4B—C5B1.376 (3)C12A—H15A0.9900
C5B—C6B1.391 (3)C13A—H16A0.9900
C2B—H61B0.9500C13A—H17A0.9900
C4B—H4B0.9500C11A—H18A0.9900
C6B—H6B0.9500C11A—H19A0.9900
C2A—C3A1.511 (3)
C2B—O2B—H2B109.00C9A—C10A—C11A110.2 (3)
C6B—O21B—H21B110.00N1A—C11A—C10A111.3 (2)
O32B—N3B—C3B117.7 (2)N8A—C13A—C12A104.7 (9)
O31B—N3B—O32B123.7 (2)N1A—C2A—H21A109.00
O31B—N3B—C3B118.6 (2)N1A—C2A—H22A109.00
O52B—N5B—C5B117.7 (2)C3A—C2A—H21A109.00
O51B—N5B—C5B118.7 (2)C3A—C2A—H22A109.00
O51B—N5B—O52B123.5 (2)H21A—C2A—H22A108.00
C2A—N1A—C11A116.36 (18)C2A—C3A—H31A109.00
C7A—N1A—C11A121.90 (19)C2A—C3A—H32A109.00
C2A—N1A—C7A121.74 (19)C4A—C3A—H31A109.00
C7A—N8A—C13A122.0 (5)C4A—C3A—H32A109.00
C7A—N8A—C9A122.5 (3)H31A—C3A—H32A108.00
C9A—N8A—H8A119.3 (14)C3A—C4A—H41A109.00
C13A—N8A—H8A119.6 (15)C3A—C4A—H42A109.00
C7A—N8A—H8A117.0 (14)C5A—C4A—H41A109.00
C2B—C1B—C6B120.78 (18)C5A—C4A—H42A109.00
C2B—C1B—C11B119.6 (2)H41A—C4A—H42A108.00
C6B—C1B—C11B119.6 (2)C4A—C5A—H51A109.00
O2B—C2B—C1B122.0 (2)C4A—C5A—H52A109.00
C1B—C2B—C3B117.4 (2)C6A—C5A—H51A109.00
O2B—C2B—C3B120.5 (2)C6A—C5A—H52A109.00
N3B—C3B—C4B117.1 (2)H51A—C5A—H52A108.00
C2B—C3B—C4B122.3 (2)C5A—C6A—H61A109.00
N3B—C3B—C2B120.6 (2)C5A—C6A—H62A109.00
C3B—C4B—C5B118.84 (19)C7A—C6A—H61A109.00
C4B—C5B—C6B121.43 (19)C7A—C6A—H62A109.00
N5B—C5B—C4B118.69 (18)H61A—C6A—H62A108.00
N5B—C5B—C6B119.88 (19)N8A—C9A—H91A110.00
O21B—C6B—C1B118.7 (3)N8A—C9A—H92A110.00
O21B—C6B—C5B122.0 (3)C10A—C9A—H91A110.00
C1B—C6B—C5B119.23 (19)C10A—C9A—H92A110.00
O12B—C11B—C1B116.6 (2)H91A—C9A—H92A109.00
O11B—C11B—C1B119.3 (2)C9A—C10A—H10A110.00
O11B—C11B—O12B124.1 (2)C9A—C10A—H11A110.00
C3B—C2B—H61B121.00C11A—C10A—H10A110.00
C1B—C2B—H61B122.00C11A—C10A—H11A110.00
C5B—C4B—H4B121.00H10A—C10A—H11A108.00
C3B—C4B—H4B121.00N1A—C11A—H12A109.00
C1B—C6B—H6B120.00N1A—C11A—H13A109.00
C5B—C6B—H6B121.00C10A—C11A—H12A109.00
N1A—C2A—C3A114.04 (18)C10A—C11A—H13A109.00
C2A—C3A—C4A114.2 (2)H12A—C11A—H13A108.00
C3A—C4A—C5A114.5 (2)C13A—C12A—H15A110.00
C4A—C5A—C6A114.4 (2)H14A—C12A—H15A108.00
C5A—C6A—C7A112.9 (2)N8A—C13A—H16A111.00
N1A—C7A—N8A121.8 (2)N8A—C13A—H17A111.00
N1A—C7A—C6A120.35 (19)C12A—C13A—H16A111.00
N8A—C7A—C6A117.82 (19)C12A—C13A—H17A111.00
N8A—C9A—C10A106.7 (3)H16A—C13A—H17A109.00
O31B—N3B—C3B—C2B23.9 (3)C6B—C1B—C11B—O11B3.1 (3)
O31B—N3B—C3B—C4B−157.2 (2)C6B—C1B—C11B—O12B−175.8 (2)
O32B—N3B—C3B—C2B−155.2 (2)C2B—C1B—C11B—O11B−179.4 (2)
O32B—N3B—C3B—C4B23.8 (3)C2B—C1B—C11B—O12B1.8 (3)
O51B—N5B—C5B—C4B3.7 (3)C11B—C1B—C6B—C5B175.2 (2)
O51B—N5B—C5B—C6B−176.8 (2)O2B—C2B—C3B—N3B5.6 (4)
O52B—N5B—C5B—C4B−177.5 (2)O2B—C2B—C3B—C4B−173.3 (2)
O52B—N5B—C5B—C6B2.0 (3)C1B—C2B—C3B—N3B−178.5 (2)
C2A—N1A—C7A—N8A−176.4 (2)C1B—C2B—C3B—C4B2.7 (3)
C2A—N1A—C7A—C6A6.0 (3)C2B—C3B—C4B—C5B−2.9 (3)
C11A—N1A—C7A—N8A2.7 (3)N3B—C3B—C4B—C5B178.3 (2)
C11A—N1A—C7A—C6A−175.0 (2)C3B—C4B—C5B—C6B0.4 (3)
C2A—N1A—C11A—C10A−163.0 (2)C3B—C4B—C5B—N5B179.9 (2)
C7A—N1A—C2A—C3A−71.7 (3)N5B—C5B—C6B—C1B−177.36 (19)
C11A—N1A—C2A—C3A109.2 (2)C4B—C5B—C6B—C1B2.1 (3)
C7A—N1A—C11A—C10A17.9 (3)N1A—C2A—C3A—C4A78.8 (3)
C7A—N8A—C9A—C10A−38.8 (4)C2A—C3A—C4A—C5A−57.5 (3)
C9A—N8A—C7A—C6A−173.2 (3)C3A—C4A—C5A—C6A61.0 (3)
C9A—N8A—C7A—N1A9.1 (4)C4A—C5A—C6A—C7A−82.0 (3)
C6B—C1B—C2B—C3B0.0 (3)C5A—C6A—C7A—N1A63.3 (3)
C11B—C1B—C2B—O2B−1.6 (3)C5A—C6A—C7A—N8A−114.5 (2)
C11B—C1B—C2B—C3B−177.5 (2)N8A—C9A—C10A—C11A56.2 (4)
C2B—C1B—C6B—C5B−2.3 (3)C9A—C10A—C11A—N1A−47.7 (4)
C6B—C1B—C2B—O2B175.9 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N8A—H8A···O11B0.88 (2)1.99 (2)2.871 (3)176 (2)
O2B—H2B···O12B0.841.722.473 (3)149
C10A—H11A···O32Bi0.992.453.251 (5)138
C11A—H13A···O52Bii0.992.593.093 (3)111
C2A—H21A···O31Biii0.992.483.281 (3)138
Symmetry codes: (i) −x+3/2, y+1/2, −z+3/2; (ii) x−3/2, −y+3/2, z+1/2; (iii) −x+1/2, y+1/2, −z+3/2.
Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
N8A—H8A···O11B0.892 (18)1.783 (18)2.665 (2)169.7 (18)
N4B—H41B···O11Bi0.892 (18)2.049 (19)2.939 (2)176.2 (17)
N4B—H42B···O12Bii0.916 (17)1.976 (17)2.891 (2)176.2 (17)
Symmetry codes: (i) x+1/2, −y+1/2, −z+1; (ii) −x+1, y−1/2, −z+1/2.
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
N8A—H8A···O11B0.895 (18)1.883 (18)2.777 (2)177.2 (16)
N8A—H8A···O12B0.895 (18)2.528 (18)3.117 (2)124.0 (14)
C10A—H11A···O32Bi0.992.443.247 (3)138
C2A—H21A···O31Bii0.992.563.309 (2)133
C6A—H62A···O11B0.992.603.438 (2)143
Symmetry codes: (i) −x−1/2, y+1/2, −z+1/2; (ii) −x+1/2, y+1/2, −z+1/2.
Hydrogen-bond geometry (Å, º) for (III) top
D—H···AD—HH···AD···AD—H···A
N8A—H8A···O11B0.88 (2)1.99 (2)2.871 (3)176 (2)
O2B—H2B···O12B0.841.722.473 (3)149
C10A—H11A···O32Bi0.992.453.251 (5)138
C2A—H21A···O31Bii0.992.483.281 (3)138
Symmetry codes: (i) −x+3/2, y+1/2, −z+3/2; (ii) −x+1/2, y+1/2, −z+3/2.

Experimental details

(I)(II)(III)
Crystal data
Chemical formulaC9H17N2+·C7H6NO2−C9H17N2+·C7H3N2O6−C9H17N2+·C7H3N2O7−
Mr289.37364.36380.36
Crystal system, space groupOrthorhombic, P212121Monoclinic, P21/nMonoclinic, P21/n
Temperature (K)200200200
a, b, c (Å)8.0986 (4), 12.9213 (6), 13.7344 (7)6.0197 (4), 19.6228 (13), 14.3866 (8)6.1537 (3), 19.1541 (14), 14.5527 (11)
α, β, γ (°)90, 90, 9090, 98.078 (5), 9090, 98.343 (6), 90
V (Å3)1437.23 (12)1682.53 (18)1697.2 (2)
Z444
Radiation typeMo KαMo KαMo Kα
µ (mm−1)0.090.110.12
Crystal size (mm)0.40 × 0.26 × 0.240.30 × 0.13 × 0.080.30 × 0.13 × 0.10
Data collection
DiffractometerOxford Diffraction Gemini-S CCD-detectorOxford Diffraction Gemini-S CCD-detectorOxford Diffraction Gemini-S CCD-detector
Absorption correctionMulti-scan
(CrysAlis PRO; Agilent, 2014)		Multi-scan
(CrysAlis PRO; Agilent, 2014)		Multi-scan
(CrysAlis PRO; Agilent, 2014)
Tmin, Tmax0.93, 0.990.90, 0.990.920, 0.990
No. of measured, independent and
observed [I > 2σ(I)] reflections		7372, 3324, 2847 7082, 3311, 2561 7800, 3339, 2347
Rint0.0310.0240.034
(sin θ/λ)max (Å−1)0.6870.6170.617
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.044, 0.098, 1.07 0.045, 0.109, 1.01 0.058, 0.123, 1.03
No. of reflections332433113339
No. of parameters199245263
No. of restraints333
H-atom treatmentH atoms treated by a mixture of independent and constrained refinementH atoms treated by a mixture of independent and constrained refinementH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å−3)0.20, −0.250.18, −0.220.29, −0.29
Absolute structureFlack (1983), 1668 Friedel pairs??
Absolute structure parameter−0.1 (13)??

Computer programs: CrysAlis PRO (Agilent, 2014), SIR92 (Altomare et al., 1993), SHELXL97 (Sheldrick, 2008) within WinGX (Farrugia, 2012), PLATON (Spek, 2009).

 

Acknowledgements

GS acknowledges financial support from the Science and Engineering Faculty, Queensland University of Technology.

References

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ISSN: 2056-9890
Volume 72| Part 3| March 2016| Pages 382-386
doi:10.1107/S205698901600267X
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