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Five two-component molecular crystals, benzimidazolium 3-nitro­benzoate, C7H7N2+·C7H4NO4-, (I), benzimidazolium 4-nitro­benzoate, C7H7N2+·C7H4NO4-, (II), 1H-benzotriazole-3-nitro­benzoic acid (1/1), C6H5N3·C7H5NO4, (III), imidazol­ium 3-nitro­benzoate, C3H5N2+·C7H4NO4-, (IV), and imid­azolium 4-nitro­benzoate, C3H5N2+·C7H4NO4-, (V), were prepared with the aim of making chiral crystals. Only (I) crystallizes in a chiral space group. The mol­ecules of (I) and (II) are linked by hydrogen bonds to form 21 spiral chains. In (III), (IV) and (V), macrocyclic structures are formed from two acid and two base components, by an alternate arrangement of the acid and base moieties.

Supporting information

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Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270101009118/ob1039sup1.cif
Contains datablocks global, I, II, III, IV, V

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Structure factor file (CIF format) https://doi.org/10.1107/S0108270101009118/ob1039Isup2.hkl
Contains datablock I

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Structure factor file (CIF format) https://doi.org/10.1107/S0108270101009118/ob1039IIsup3.hkl
Contains datablock II

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Structure factor file (CIF format) https://doi.org/10.1107/S0108270101009118/ob1039IIIsup4.hkl
Contains datablock III

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Structure factor file (CIF format) https://doi.org/10.1107/S0108270101009118/ob1039IVsup5.hkl
Contains datablock IV

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Structure factor file (CIF format) https://doi.org/10.1107/S0108270101009118/ob1039Vsup6.hkl
Contains datablock V

CCDC references: 173365; 173366; 173367; 173368; 173369

Comment top

Chiral crystals composed of achiral molecules have attracted great scientific interest, because of the mystery of chiral generation as well as their various uses. Many studies aiming to form chiral crystals have been summarized in the literature (Green et al., 1979; Koshima & Matsuura, 1998a,b). It has been reported that mutually interacting bifunctional molecules tend to form chiral crystals by forming spiral structures. Alternatively, to obtain chiral crystals, the formation of two-component molecular crystals from organic acids and bases is one of the most promising methods (Koshima & Matsuura, 1998c; Koshima et al., 1996; Koshima et al., 1999). Chiral two-component molecular crystals are often obtained if one of the components crystallizes into a non-centrosymmetric space group in addition to the formation of the spiral structure. In this study, we have prepared chiral two-component molecular crystals using 3- and 4-nitrobenzoic acids, (1) and (2), and benzimidazole, (3), benzotriazole, (4), and imidazole, (5), as hydrogen-bonding bifunctional acid and amine components, respectively, and herein we report the structures of the resultant crystals, (I)-(V). Components (3) and (4) crystallize into the non-centrosymmetric space groups Pna21 and P21, respectively (Escande & Galigne, 1974; Escande et al., 1974). \sch

Among the five two-component molecular crystals described here, only (I) belongs to a chiral space group, P21. The H atom of the carboxyl group of (1) in (I) is transferred to atom N3B of (3) (Fig. 1), as indicated by the bond distances in the carboxyl and imidazole moieties, and by the IR spectra of (I). The molecules of (1) and (3) are arranged alternately and are linked by hydrogen bonds to form a 21 spiral structure (Fig. 2). Neighbouring spirals are connected by C—H···O hydrogen bonds along the a and c axes.

In (II), the H atom of the carboxyl group is also transferred to the basic N atom, N3B, of (4) (Fig. 3) and a 21 spiral structure is formed along b (Fig. 4). In contrast with (I), neighbouring spirals are mirror images of each other and are engaged and connected by a C—H···O hydrogen bond. Each spiral is also connected to a neighbouring spiral, related by a translation along the a axis, by a C—H···O contact.

The molecular structures of the components of (III) are shown in Fig. 5. Contrary to the other crystals reported here, the H atom of the carboxyl group of (1) is not transferred to atom N3B of (4), as is indicated by the asymmetric C—O and N—N bond distances in the carboxyl and triazole moieties, respectively, and by the IR spectra. The neutral molecular component is due to the lower basicity of (4) than of (3). PM3 calculations (Stewart, 2000) for (3) and (4) provided the difference between the net charges on the basic N atoms of (3) and (4): the Mulliken charges on atom N3B are -0.12 and -0.02 for (3) and (4), respectively. Query spelling. Units? The crystal structure of (III) is shown in Fig. 6. No spiral structure is found in the crystal, despite the similarity between the molecular structures of (3) and (4). Instead of the spiral structure, a macrocyclic ring is formed from two molecules of (1) and two of (4), around a centre of symmetry. This structure can be regarded as analogous to the well known centrosymmetric dimer structure of carboxylic acids. In the present case, (4) acts as a coupler of the carboxyl groups. The macrocyclic rings are planar to within 0.26 Å, and are stacked with an interplanar distance of 3.32 Å. The stacked rings are bridged by the nitro group of (1) from neighbouring macro rings, related by 21 symmetry through C—H···O contacts.

The molecular structures of (IV) and (V) are shown in Figs. 7 and 8, respectively. The H atoms of the carboxyl groups are transferred to the basic N atoms. The crystal structures of (IV) and (V) are shown in Figs. 9 and 10, respectively. No formation of spiral structures is observed in (IV) and (V). Although the positions of the substituents on the acid components are different, the packing motifs of these crystals are very similar. Each component is arranged alternately along the b axis. Centrosymmetric hydrogen-bonding dimer structures are formed, as in (III), and the dimers are linked by C—H···O hydrogen bonds to form dimer structures, in the same manner as those of the N—H···O hydrogen-bonding dimers. The reason why spiral structures are not formed in (IV) and (V) is considered to be due to the difference between the lengths of the longest molecular axes of each component. The importance of molecular lengths for the formation of spiral structures has been discussed for the diastereomeric salts of carboxylic acids and 1-arylethylamine and its derivatives (Kinbara et al., 1996).

Experimental top

Crystals of the five compounds were obtained from solutions of equimolar mixtures of the components in acetonitrile-methanol (4:1), methanol, acetonitrile, acetonitrile-methanol (8:1) and acetonitrile-ethanol (5:4) for (I), (II), (III), (IV) and (V), respectively. Co-crystals of (2) and (4) suitable for structure analysis were unfortunately not obtained, in spite of many attempts. IR spectra and elemental analyses were carried out with a Bio-Rad FTS 135 spectrometer and a Yanaco CHN CORDER MT-3 analyser, respectively. IR spectroscopic data for (I), cm-1: 3423 (br), 3136, 3067, 2962, 2896, 2831, 1615, 1525, 1345, 1067, 790, 753, 600; analysis: calculated for C14H11N3O4: C 58.94, H 3.89, N 14.73%; found: C 59.23, H 3.97, N 14.91%. IR spectroscopic data for (II), cm-1: 3447 (br), 3089, 2990, 1626, 1547, 1516, 1239, 1101, 1005, 800, 750, 721, 612, 517; analysis: calculated for C14H11N3O4: C 58.94, H 3.89, N 14.73%; found: C 59.21, H 3.77, N 14.70%. IR spectroscopic data for (III), cm-1: 3470 (br), 3213, 1881, 1698, 1616, 1529, 1445, 1351, 1310, 1269, 1220, 1147, 1021, 820, 718, 695; analysis: calculated for C13H10N4O4: C 54.55, H 3.52, N 19.58%; found: C 54.23, H 3.56, N 19.61%. IR spectroscopic data for (IV), cm-1: 3450 (br), 3160, 3099, 3031, 1593, 1564, 1523, 1376, 1069, 838, 816, 709, 635, 515; analysis: calculated for C10H9N3O4: C 51.06, H 3.86, N 17.87%; found: C 51.07, H 4.01, N 17.44%. IR spectroscopic data for (V), cm-1: 3450 (br), 3160, 3098, 3010, 1555, 1516, 1392, 1342, 763, 722, 513; analysis: calculated for C10H9N3O4: C 51.06, H 3.86, N 17.87%; found: C 51.20, H 3.99, N 17.85%.

Refinement top

In the data collection of (III), many overlapping Bragg spots were observed on the image plates. The rejection of such spots led to the low completeness of 0.90. A l l H atoms for compounds (I) to (V) were found on difference maps. The carboxylic H atom in (III) was refined freely, giving an O—H bond distance of 1.02 (4) Å and a C—O—H bond angle of 110 (2)°. The remaining H atoms of the five compounds were refined as riding, with C—H = 0.93 Å and N—H = 0.86 Å, and with Uiso = 1.2Ueq of the parent atom. In the refinement of (I), all reflections of Bijvoet pairs were merged, as well as equivalent reflections, because of small imaginary dispersion terms of the component atoms. Subsequently, the imaginary dispersion terms were set to zero.

Computing details top

Data collection: PROCESS-AUTO (Rigaku Corporation, 1998) for (I), (II); DIP3000 Control Programs (MacScience, 1992) for (III); MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1988) for (IV), (V). Cell refinement: PROCESS-AUTO for (I), (II); SCALEPACK (Otwinowski & Minor, 1997) for (III); MSC/AFC Diffractometer Control Software for (IV), (V). Data reduction: TEXSAN (Molecular Structure Corporation, 1993) for (I), (II), (IV), (V); DENZO/SCALEPACK (Otwinowski & Minor, 1997) for (III). For all compounds, program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1996); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. The molecular components of (I) showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
[Figure 2] Fig. 2. The crystal structure of (I) viewed along the c axis. N—H···O and C—H···O hydrogen bonds are indicated by broken and dotted lines, respectively.
[Figure 3] Fig. 3. The molecular components of (II) showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
[Figure 4] Fig. 4. The crystal structure of (II) viewed along the b axis. N—H···O and C—H···O hydrogen bonds are indicated by broken and dotted lines, respectively.
[Figure 5] Fig. 5. The molecular components of (III) showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
[Figure 6] Fig. 6. The crystal structure of (III) viewed along the b axis. N—H···O and C—H···O hydrogen bonds are indicated by broken and dotted lines, respectively.
[Figure 7] Fig. 7. The molecular components of (IV) showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
[Figure 8] Fig. 8. The molecular components of (V) showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
[Figure 9] Fig. 9. The crystal structure of (IV) viewed along the a axis. N—H···O and C—H···O hydrogen bonds are indicated by broken and dotted lines, respectively.
[Figure 10] Fig. 10. The crystal structure of (V) viewed along the c axis. N—H···O and C—H···O hydrogen bonds are indicated by broken and dotted lines, respectively.
(I) Benzimidazolium 3-nitrobenzoate top
Crystal data top
C7H7N2+·C7H4NO4Dx = 1.439 Mg m3
Mr = 285.26Melting point = 419–420 K
Monoclinic, P21Mo Kα radiation, λ = 0.71073 Å
a = 12.522 (2) ÅCell parameters from 8583 reflections
b = 10.7827 (12) Åθ = 2.5–27.5°
c = 4.8838 (6) ŵ = 0.11 mm1
β = 93.230 (4)°T = 297 K
V = 658.35 (15) Å3Plate, colourless
Z = 20.45 × 0.25 × 0.05 mm
F(000) = 296
Data collection top
Rigaku R-AXIS Rapid
diffractometer
1152 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.046
Graphite monochromatorθmax = 27.5°, θmin = 2.5°
Detector resolution: 10 pixels mm-1h = 1616
oscillation scansk = 1313
10657 measured reflectionsl = 66
1568 independent reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.048H-atom parameters constrained
wR(F2) = 0.113 w = 1/[σ2(Fo2) + (0.0456P)2 + 0.0577P]
where P = (Fo2 + 2Fc2)/3
S = 1.10(Δ/σ)max < 0.001
1568 reflectionsΔρmax = 0.15 e Å3
192 parametersΔρmin = 0.15 e Å3
1 restraintExtinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.037 (7)
Crystal data top
C7H7N2+·C7H4NO4V = 658.35 (15) Å3
Mr = 285.26Z = 2
Monoclinic, P21Mo Kα radiation
a = 12.522 (2) ŵ = 0.11 mm1
b = 10.7827 (12) ÅT = 297 K
c = 4.8838 (6) Å0.45 × 0.25 × 0.05 mm
β = 93.230 (4)°
Data collection top
Rigaku R-AXIS Rapid
diffractometer
1152 reflections with I > 2σ(I)
10657 measured reflectionsRint = 0.046
1568 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0481 restraint
wR(F2) = 0.113H-atom parameters constrained
S = 1.10Δρmax = 0.15 e Å3
1568 reflectionsΔρmin = 0.15 e Å3
192 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*/Ueq
O1A0.3606 (2)0.3570 (3)0.1288 (6)0.0725 (8)
O2A0.3619 (3)0.1590 (3)0.0046 (5)0.0761 (9)
O3A0.1224 (3)0.4859 (3)0.8987 (7)0.0871 (11)
O4A0.0058 (3)0.3683 (4)1.0444 (7)0.1007 (12)
N1A0.0727 (3)0.3897 (4)0.8953 (6)0.0633 (9)
C1A0.2299 (3)0.2248 (3)0.3382 (6)0.0450 (8)
C2A0.1962 (3)0.3170 (3)0.5220 (6)0.0461 (8)
H2A0.23140.39290.52540.055*
C3A0.1091 (3)0.2925 (3)0.6995 (6)0.0466 (8)
C4A0.0546 (3)0.1808 (4)0.7036 (7)0.0564 (9)
H4A0.00360.16680.82660.068*
C5A0.0895 (3)0.0912 (4)0.5196 (8)0.0633 (10)
H5A0.05440.01520.51710.059 (11)*
C6A0.1762 (3)0.1130 (3)0.3383 (7)0.0551 (9)
H6A0.19860.05140.21460.066*
C7A0.3249 (3)0.2469 (4)0.1411 (7)0.0530 (9)
N1B0.5852 (3)0.4925 (3)0.6017 (6)0.0578 (8)
H1B0.59990.54610.72870.069*
C2B0.5002 (3)0.4946 (4)0.4273 (7)0.0603 (10)
H2B0.44720.55500.42480.072*
N3B0.5011 (2)0.3997 (3)0.2581 (6)0.0564 (8)
H3B0.45360.38320.12910.068*
C4B0.6339 (3)0.2245 (4)0.2128 (8)0.0639 (11)
H4B0.59850.18470.06500.077*
C5B0.7301 (4)0.1796 (5)0.3288 (10)0.0778 (13)
H5B0.76030.10850.25820.093*
C6B0.7814 (4)0.2406 (5)0.5506 (10)0.0778 (13)
H6B0.84540.20830.62510.093*
C7B0.7419 (3)0.3460 (5)0.6641 (8)0.0693 (12)
H7B0.77730.38570.81200.083*
C7aB0.6463 (3)0.3899 (4)0.5460 (7)0.0529 (8)
C3aB0.5927 (3)0.3310 (4)0.3258 (6)0.0497 (8)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O1A0.0734 (18)0.0693 (19)0.0706 (16)0.0097 (15)0.0331 (14)0.0061 (14)
O2A0.092 (2)0.0696 (19)0.0627 (14)0.0149 (18)0.0284 (14)0.0128 (16)
O3A0.093 (2)0.072 (2)0.093 (2)0.002 (2)0.0257 (19)0.027 (2)
O4A0.086 (2)0.109 (3)0.101 (2)0.007 (2)0.0559 (18)0.014 (2)
N1A0.0614 (19)0.073 (2)0.0534 (16)0.017 (2)0.0101 (14)0.0072 (19)
C1A0.0484 (18)0.0468 (19)0.0391 (15)0.0037 (15)0.0034 (14)0.0029 (15)
C2A0.0452 (18)0.0427 (18)0.0493 (16)0.0001 (16)0.0053 (14)0.0001 (16)
C3A0.0428 (17)0.054 (2)0.0421 (15)0.0050 (16)0.0014 (13)0.0001 (15)
C4A0.0452 (18)0.071 (3)0.0517 (18)0.006 (2)0.0063 (14)0.0102 (19)
C5A0.067 (3)0.054 (2)0.068 (2)0.018 (2)0.0002 (19)0.004 (2)
C6A0.070 (2)0.045 (2)0.0496 (18)0.004 (2)0.0002 (16)0.0047 (17)
C7A0.054 (2)0.063 (2)0.0405 (16)0.007 (2)0.0054 (15)0.0010 (18)
N1B0.064 (2)0.0590 (19)0.0494 (15)0.0101 (17)0.0049 (14)0.0057 (15)
C2B0.063 (2)0.060 (2)0.057 (2)0.003 (2)0.0039 (19)0.004 (2)
N3B0.0520 (16)0.065 (2)0.0514 (14)0.0079 (16)0.0099 (12)0.0040 (15)
C4B0.071 (3)0.059 (2)0.062 (2)0.004 (2)0.0091 (19)0.007 (2)
C5B0.082 (3)0.067 (3)0.088 (3)0.016 (3)0.031 (2)0.010 (3)
C6B0.059 (2)0.089 (4)0.084 (3)0.005 (3)0.004 (2)0.019 (3)
C7B0.058 (2)0.087 (3)0.061 (2)0.012 (2)0.0115 (17)0.012 (2)
C7aB0.0545 (19)0.058 (2)0.0454 (15)0.0095 (18)0.0004 (14)0.0002 (17)
C3aB0.0455 (18)0.057 (2)0.0463 (15)0.0046 (17)0.0012 (13)0.0024 (17)
Geometric parameters (Å, º) top
O1A—C7A1.269 (5)N1B—C7aB1.381 (5)
O2A—C7A1.234 (5)N1B—H1B0.8600
O3A—N1A1.210 (5)N3B—C2B1.316 (5)
O4A—N1A1.212 (4)C2B—H2B0.9300
N1A—C3A1.474 (5)N3B—C3aB1.390 (4)
C1A—C6A1.380 (5)N3B—H3B0.8600
C1A—C2A1.389 (4)C4B—C3aB1.386 (6)
C1A—C7A1.507 (5)C4B—C5B1.389 (6)
C2A—C3A1.380 (4)C4B—H4B0.9300
C2A—H2A0.9300C5B—C6B1.393 (7)
C3A—C4A1.385 (5)C5B—H5B0.9300
C4A—C5A1.373 (5)C6B—C7B1.368 (7)
C4A—H4A0.9300C6B—H6B0.9300
C5A—C6A1.382 (5)C7B—C7aB1.383 (5)
C5A—H5A0.9300C7B—H7B0.9300
C6A—H6A0.9300C7aB—C3aB1.389 (5)
N1B—C2B1.326 (5)
O3A—N1A—O4A123.7 (4)C7aB—N1B—H1B125.6
O3A—N1A—C3A118.6 (3)N3B—C2B—N1B110.8 (4)
O4A—N1A—C3A117.7 (4)N3B—C2B—H2B124.6
C6A—C1A—C2A119.7 (3)N1B—C2B—H2B124.6
C6A—C1A—C7A120.4 (3)C2B—N3B—C3aB107.5 (3)
C2A—C1A—C7A119.9 (3)C2B—N3B—H3B126.2
C3A—C2A—C1A118.0 (3)C3aB—N3B—H3B126.2
C3A—C2A—H2A121.0C3aB—C4B—C5B117.4 (4)
C1A—C2A—H2A121.0C3aB—C4B—H4B121.3
C2A—C3A—C4A123.2 (3)C5B—C4B—H4B121.3
C2A—C3A—N1A118.4 (3)C4B—C5B—C6B120.2 (4)
C4A—C3A—N1A118.4 (3)C4B—C5B—H5B119.9
C5A—C4A—C3A117.7 (3)C6B—C5B—H5B119.9
C5A—C4A—H4A121.2C7B—C6B—C5B123.1 (4)
C3A—C4A—H4A121.2C7B—C6B—H6B118.4
C4A—C5A—C6A120.6 (4)C5B—C6B—H6B118.4
C4A—C5A—H5A119.7C6B—C7B—C7aB116.0 (4)
C6A—C5A—H5A119.7C6B—C7B—H7B122.0
C1A—C6A—C5A120.9 (3)C7aB—C7B—H7B122.0
C1A—C6A—H6A119.6N1B—C7aB—C7B131.9 (4)
C5A—C6A—H6A119.6N1B—C7aB—C3aB105.7 (3)
O2A—C7A—O1A124.9 (3)C7B—C7aB—C3aB122.4 (4)
O2A—C7A—C1A118.8 (4)C4B—C3aB—C7aB120.8 (3)
O1A—C7A—C1A116.2 (3)C4B—C3aB—N3B131.9 (3)
C2B—N1B—C7aB108.7 (3)C7aB—C3aB—N3B107.3 (3)
C2B—N1B—H1B125.6
C6A—C1A—C2A—C3A0.1 (5)C7aB—N1B—C2B—N3B0.1 (4)
C7A—C1A—C2A—C3A179.8 (3)N1B—C2B—N3B—C3aB0.1 (4)
C1A—C2A—C3A—C4A0.4 (5)C3aB—C4B—C5B—C6B0.2 (6)
C1A—C2A—C3A—N1A180.0 (3)C4B—C5B—C6B—C7B0.4 (7)
O3A—N1A—C3A—C2A2.1 (5)C5B—C6B—C7B—C7aB0.2 (6)
O4A—N1A—C3A—C2A177.9 (4)C2B—N1B—C7aB—C7B179.4 (4)
O3A—N1A—C3A—C4A177.5 (4)C2B—N1B—C7aB—C3aB0.3 (4)
O4A—N1A—C3A—C4A2.5 (5)C6B—C7B—C7aB—N1B178.7 (4)
C2A—C3A—C4A—C5A0.5 (5)C6B—C7B—C7aB—C3aB0.2 (6)
N1A—C3A—C4A—C5A179.9 (3)C5B—C4B—C3aB—C7aB0.2 (5)
C3A—C4A—C5A—C6A0.1 (5)C5B—C4B—C3aB—N3B179.0 (4)
C2A—C1A—C6A—C5A0.2 (5)N1B—C7aB—C3aB—C4B178.8 (3)
C7A—C1A—C6A—C5A179.5 (3)C7B—C7aB—C3aB—C4B0.4 (6)
C4A—C5A—C6A—C1A0.2 (6)N1B—C7aB—C3aB—N3B0.3 (4)
C6A—C1A—C7A—O2A9.0 (5)C7B—C7aB—C3aB—N3B179.5 (3)
C2A—C1A—C7A—O2A170.7 (3)C2B—N3B—C3aB—C4B178.7 (4)
C6A—C1A—C7A—O1A170.9 (3)C2B—N3B—C3aB—C7aB0.2 (4)
C2A—C1A—C7A—O1A9.4 (5)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1B—H1B···O2Ai0.861.862.717 (4)177
N3B—H3B···O1A0.861.692.550 (3)178
C5B—H5B···O3Aii0.932.703.553 (6)153
C5A—H5A···O4Aiii0.932.713.340 (5)126
Symmetry codes: (i) x+1, y+1/2, z+1; (ii) x+1, y1/2, z1; (iii) x, y1/2, z2.
(II) Benzimidazolium 4-nitrobenzoate top
Crystal data top
C7H7N2+·C7H4NO4Dx = 1.429 Mg m3
Mr = 285.26Melting point = 435–437 K
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 13.8524 (5) ÅCell parameters from 22373 reflections
b = 7.6666 (4) Åθ = 3.0–30.0°
c = 12.5193 (7) ŵ = 0.11 mm1
β = 94.1400 (17)°T = 297 K
V = 1326.09 (11) Å3Block, colourless
Z = 40.60 × 0.38 × 0.33 mm
F(000) = 592
Data collection top
Rigaku R-AXIS Rapid
diffractometer
2856 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.034
Graphite monochromatorθmax = 30.0°, θmin = 3.0°
Detector resolution: 10 pixels mm-1h = 1919
oscillation scansk = 1010
23459 measured reflectionsl = 1717
3869 independent reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.053H-atom parameters constrained
wR(F2) = 0.153 w = 1/[σ2(Fo2) + (0.0675P)2 + 0.2721P]
where P = (Fo2 + 2Fc2)/3
S = 1.07(Δ/σ)max < 0.001
3869 reflectionsΔρmax = 0.22 e Å3
191 parametersΔρmin = 0.19 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.017 (3)
Crystal data top
C7H7N2+·C7H4NO4V = 1326.09 (11) Å3
Mr = 285.26Z = 4
Monoclinic, P21/cMo Kα radiation
a = 13.8524 (5) ŵ = 0.11 mm1
b = 7.6666 (4) ÅT = 297 K
c = 12.5193 (7) Å0.60 × 0.38 × 0.33 mm
β = 94.1400 (17)°
Data collection top
Rigaku R-AXIS Rapid
diffractometer
2856 reflections with I > 2σ(I)
23459 measured reflectionsRint = 0.034
3869 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0530 restraints
wR(F2) = 0.153H-atom parameters constrained
S = 1.07Δρmax = 0.22 e Å3
3869 reflectionsΔρmin = 0.19 e Å3
191 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*/Ueq
O1A0.27374 (8)0.28350 (18)0.35534 (9)0.0571 (3)
O2A0.34931 (7)0.09537 (17)0.46916 (9)0.0516 (3)
O3A0.12902 (9)0.2382 (3)0.64492 (13)0.0831 (5)
O4A0.05470 (11)0.0597 (3)0.75529 (13)0.0930 (6)
N1A0.05868 (10)0.1511 (2)0.67521 (12)0.0584 (4)
C1A0.18762 (9)0.17376 (19)0.49722 (11)0.0380 (3)
C2A0.10543 (10)0.2684 (2)0.46465 (13)0.0475 (4)
H2A0.10510.33760.40360.057*
C3A0.02391 (10)0.2609 (2)0.52211 (14)0.0501 (4)
H3A0.03160.32340.50030.060*
C4A0.02729 (10)0.1582 (2)0.61241 (12)0.0439 (3)
C5A0.10692 (11)0.0611 (2)0.64667 (13)0.0522 (4)
H5A0.10670.00770.70780.063*
C6A0.18778 (11)0.0686 (2)0.58728 (13)0.0487 (4)
H6A0.24230.00270.60810.058*
C7A0.27719 (9)0.1857 (2)0.43537 (11)0.0421 (3)
N1B0.55467 (9)0.46429 (19)0.18892 (10)0.0463 (3)
H1B0.58150.50010.13310.056*
C2B0.46107 (11)0.4322 (2)0.19447 (12)0.0458 (4)
H2B0.41420.44510.13800.055*
N3B0.44405 (9)0.37930 (19)0.29193 (10)0.0456 (3)
H3B0.38840.35210.31330.055*
C4B0.55510 (13)0.3278 (2)0.46050 (13)0.0520 (4)
H4B0.50810.29060.50480.062*
C5B0.65128 (14)0.3387 (3)0.49696 (15)0.0597 (5)
H5B0.66950.30760.56730.072*
C6B0.72176 (13)0.3953 (3)0.43094 (17)0.0633 (5)
H6B0.78580.40160.45860.076*
C7B0.69926 (11)0.4423 (3)0.32573 (16)0.0567 (4)
H7B0.74650.48000.28200.068*
C7aB0.60221 (10)0.4304 (2)0.28809 (12)0.0415 (3)
C3aB0.53164 (10)0.3751 (2)0.35423 (12)0.0403 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O1A0.0380 (5)0.0857 (9)0.0490 (6)0.0013 (6)0.0140 (5)0.0177 (6)
O2A0.0357 (5)0.0772 (8)0.0437 (6)0.0115 (5)0.0143 (4)0.0013 (5)
O3A0.0408 (6)0.1263 (14)0.0853 (10)0.0152 (8)0.0258 (6)0.0015 (10)
O4A0.0616 (9)0.1499 (17)0.0720 (9)0.0005 (10)0.0359 (7)0.0297 (10)
N1A0.0376 (6)0.0861 (11)0.0536 (8)0.0065 (7)0.0184 (6)0.0085 (8)
C1A0.0305 (6)0.0470 (7)0.0376 (7)0.0014 (5)0.0096 (5)0.0027 (6)
C2A0.0359 (6)0.0595 (9)0.0483 (8)0.0037 (6)0.0108 (6)0.0112 (7)
C3A0.0328 (6)0.0601 (10)0.0587 (9)0.0072 (6)0.0120 (6)0.0033 (8)
C4A0.0327 (6)0.0570 (9)0.0439 (7)0.0055 (6)0.0152 (5)0.0079 (6)
C5A0.0417 (7)0.0708 (11)0.0457 (8)0.0007 (7)0.0150 (6)0.0120 (8)
C6A0.0354 (7)0.0628 (10)0.0494 (8)0.0059 (7)0.0122 (6)0.0098 (7)
C7A0.0310 (6)0.0600 (9)0.0362 (7)0.0019 (6)0.0096 (5)0.0029 (6)
N1B0.0394 (6)0.0614 (8)0.0397 (6)0.0060 (6)0.0133 (5)0.0019 (6)
C2B0.0384 (7)0.0606 (9)0.0390 (7)0.0055 (7)0.0064 (6)0.0027 (7)
N3B0.0340 (5)0.0623 (8)0.0416 (6)0.0039 (5)0.0103 (5)0.0065 (6)
C4B0.0537 (9)0.0589 (9)0.0437 (8)0.0027 (7)0.0065 (7)0.0065 (7)
C5B0.0623 (10)0.0610 (10)0.0536 (10)0.0002 (8)0.0101 (8)0.0062 (8)
C6B0.0434 (8)0.0647 (11)0.0793 (13)0.0034 (8)0.0115 (8)0.0051 (10)
C7B0.0358 (7)0.0650 (10)0.0698 (11)0.0060 (7)0.0069 (7)0.0026 (9)
C7aB0.0367 (6)0.0448 (7)0.0438 (7)0.0009 (6)0.0096 (6)0.0015 (6)
C3aB0.0360 (6)0.0450 (7)0.0406 (7)0.0014 (5)0.0072 (5)0.0000 (6)
Geometric parameters (Å, º) top
O1A—C7A1.2494 (19)N1B—C7aB1.387 (2)
O2A—C7A1.2632 (18)N1B—H1B0.8600
O3A—N1A1.219 (2)N3B—C2B1.3231 (19)
O4A—N1A1.221 (2)C2B—H2B0.9300
N1A—C4A1.4746 (17)N3B—C3aB1.3947 (19)
C1A—C6A1.386 (2)N3B—H3B0.8600
C1A—C2A1.386 (2)C4B—C5B1.379 (2)
C1A—C7A1.5120 (17)C4B—C3aB1.395 (2)
C2A—C3A1.383 (2)C4B—H4B0.9300
C2A—H2A0.9300C5B—C6B1.393 (3)
C3A—C4A1.376 (2)C5B—H5B0.9300
C3A—H3A0.9300C6B—C7B1.379 (3)
C4A—C5A1.374 (2)C6B—H6B0.9300
C5A—C6A1.3896 (19)C7B—C7aB1.395 (2)
C5A—H5A0.9300C7B—H7B0.9300
C6A—H6A0.9300C7aB—C3aB1.3922 (19)
N1B—C2B1.3265 (18)
O3A—N1A—O4A123.88 (14)C7aB—N1B—H1B125.6
O3A—N1A—C4A118.16 (16)N3B—C2B—N1B110.19 (14)
O4A—N1A—C4A117.95 (15)N3B—C2B—H2B124.9
C6A—C1A—C2A119.79 (12)N1B—C2B—H2B124.9
C6A—C1A—C7A119.91 (13)C2B—N3B—C3aB108.49 (12)
C2A—C1A—C7A120.30 (13)C2B—N3B—H3B125.8
C3A—C2A—C1A120.61 (14)C3aB—N3B—H3B125.8
C3A—C2A—H2A119.7C5B—C4B—C3aB116.93 (15)
C1A—C2A—H2A119.7C5B—C4B—H4B121.5
C4A—C3A—C2A118.08 (14)C3aB—C4B—H4B121.5
C4A—C3A—H3A121.0C4B—C5B—C6B121.61 (17)
C2A—C3A—H3A121.0C4B—C5B—H5B119.2
C5A—C4A—C3A123.07 (13)C6B—C5B—H5B119.2
C5A—C4A—N1A118.34 (14)C7B—C6B—C5B121.88 (16)
C3A—C4A—N1A118.59 (14)C7B—C6B—H6B119.1
C4A—C5A—C6A118.08 (15)C5B—C6B—H6B119.1
C4A—C5A—H5A121.0C6B—C7B—C7aB116.84 (15)
C6A—C5A—H5A121.0C6B—C7B—H7B121.6
C1A—C6A—C5A120.36 (14)C7aB—C7B—H7B121.6
C1A—C6A—H6A119.8N1B—C7aB—C3aB106.32 (12)
C5A—C6A—H6A119.8N1B—C7aB—C7B132.36 (14)
O1A—C7A—O2A125.53 (12)C3aB—C7aB—C7B121.32 (15)
O1A—C7A—C1A117.49 (13)C7aB—C3aB—C4B121.43 (14)
O2A—C7A—C1A116.98 (13)C7aB—C3aB—N3B106.27 (12)
C2B—N1B—C7aB108.73 (12)C4B—C3aB—N3B132.30 (13)
C2B—N1B—H1B125.6
C6A—C1A—C2A—C3A0.9 (3)C7aB—N1B—C2B—N3B0.10 (19)
C7A—C1A—C2A—C3A178.65 (15)N1B—C2B—N3B—C3aB0.39 (19)
C1A—C2A—C3A—C4A0.5 (3)C3aB—C4B—C5B—C6B0.4 (3)
C2A—C3A—C4A—C5A1.2 (3)C4B—C5B—C6B—C7B0.4 (3)
C2A—C3A—C4A—N1A179.15 (15)C5B—C6B—C7B—C7aB0.0 (3)
O3A—N1A—C4A—C5A179.58 (17)C2B—N1B—C7aB—C3aB0.22 (17)
O4A—N1A—C4A—C5A0.5 (3)C2B—N1B—C7aB—C7B179.98 (18)
O3A—N1A—C4A—C3A0.7 (2)C6B—C7B—C7aB—N1B179.22 (17)
O4A—N1A—C4A—C3A179.87 (18)C6B—C7B—C7aB—C3aB0.5 (3)
C3A—C4A—C5A—C6A0.5 (3)N1B—C7aB—C3aB—C4B179.24 (15)
N1A—C4A—C5A—C6A179.88 (16)C7B—C7aB—C3aB—C4B0.5 (2)
C2A—C1A—C6A—C5A1.7 (3)N1B—C7aB—C3aB—N3B0.44 (17)
C7A—C1A—C6A—C5A177.90 (15)C7B—C7aB—C3aB—N3B179.77 (15)
C4A—C5A—C6A—C1A1.0 (3)C5B—C4B—C3aB—C7aB0.1 (3)
C6A—C1A—C7A—O1A179.36 (15)C5B—C4B—C3aB—N3B179.69 (17)
C2A—C1A—C7A—O1A0.2 (2)C2B—N3B—C3aB—C7aB0.51 (18)
C6A—C1A—C7A—O2A0.8 (2)C2B—N3B—C3aB—C4B179.12 (18)
C2A—C1A—C7A—O2A179.65 (15)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1B—H1B···O2Ai0.861.812.6600 (15)171
N3B—H3B···O1A0.861.792.6469 (15)177
C2B—H2B···O2Aii0.932.263.125 (2)155
C6B—H6B···O3Aiii0.932.833.478 (3)128
Symmetry codes: (i) x+1, y+1/2, z+1/2; (ii) x, y+1/2, z1/2; (iii) x+1, y, z.
(III) Benzotriazole 3-nitrobenzoic acid clathrate top
Crystal data top
C6H5N3·C7H5NO4Dx = 1.451 Mg m3
Mr = 286.25Melting point = 406.0–406.5 K
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
a = 14.342 (3) ÅCell parameters from 1254 reflections
b = 5.218 (1) Åθ = 1.6–27.5°
c = 18.161 (4) ŵ = 0.11 mm1
β = 105.40 (1)°T = 297 K
V = 1310.3 (5) Å3Needle, colourless
Z = 40.35 × 0.15 × 0.10 mm
F(000) = 592
Data collection top
MacScience DIP3000
diffractometer
1486 reflections with I > 2σ(I)
Radiation source: fine-focus rotating anodeRint = 0.030
Graphite monochromatorθmax = 26.5°, θmin = 1.6°
Detector resolution: 10 pixels mm-1h = 1818
Weissenberg scansk = 66
12254 measured reflectionsl = 2218
2465 independent reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.072H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.184 w = 1/[σ2(Fo2) + (0.0593P)2 + 1.2302P]
where P = (Fo2 + 2Fc2)/3
S = 1.08(Δ/σ)max < 0.001
2465 reflectionsΔρmax = 0.28 e Å3
194 parametersΔρmin = 0.29 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.015 (2)
Crystal data top
C6H5N3·C7H5NO4V = 1310.3 (5) Å3
Mr = 286.25Z = 4
Monoclinic, P21/nMo Kα radiation
a = 14.342 (3) ŵ = 0.11 mm1
b = 5.218 (1) ÅT = 297 K
c = 18.161 (4) Å0.35 × 0.15 × 0.10 mm
β = 105.40 (1)°
Data collection top
MacScience DIP3000
diffractometer
1486 reflections with I > 2σ(I)
12254 measured reflectionsRint = 0.030
2465 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0720 restraints
wR(F2) = 0.184H atoms treated by a mixture of independent and constrained refinement
S = 1.08Δρmax = 0.28 e Å3
2465 reflectionsΔρmin = 0.29 e Å3
194 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*/Ueq
O1A0.3557 (2)0.9910 (5)0.47011 (15)0.0699 (8)
O2A0.34841 (19)1.0822 (5)0.34783 (14)0.0600 (7)
H22A0.400 (3)0.943 (7)0.355 (2)0.072*
O3A0.1456 (3)1.4581 (7)0.59382 (19)0.0980 (12)
O4A0.0607 (3)1.7732 (8)0.53840 (19)0.1115 (13)
N1A0.1172 (3)1.5998 (8)0.5396 (2)0.0699 (10)
C1A0.2507 (2)1.3212 (6)0.40831 (19)0.0460 (8)
C2A0.2180 (3)1.3651 (7)0.4728 (2)0.0510 (9)
H2A0.24121.26760.51670.061*
C3A0.1509 (2)1.5541 (7)0.4706 (2)0.0492 (9)
C4A0.1142 (3)1.7018 (7)0.4073 (2)0.0587 (10)
H4A0.06861.82870.40720.070*
C5A0.1470 (3)1.6564 (8)0.3433 (2)0.0622 (11)
H5A0.12321.75420.29950.075*
C6A0.2145 (3)1.4679 (7)0.3437 (2)0.0538 (9)
H6A0.23581.43940.30030.065*
C7A0.3237 (3)1.1141 (7)0.4124 (2)0.0505 (9)
N1B0.5496 (2)0.3927 (6)0.42715 (16)0.0530 (8)
H1B0.56800.29170.46570.064*
N2B0.4876 (2)0.5872 (6)0.42285 (17)0.0588 (9)
N3B0.4754 (2)0.7019 (6)0.35674 (17)0.0556 (8)
C3aB0.5316 (2)0.5756 (6)0.31697 (19)0.0449 (8)
C4B0.5450 (3)0.6218 (7)0.2444 (2)0.0519 (9)
H4B0.51450.75700.21410.062*
C5B0.6055 (3)0.4577 (7)0.2204 (2)0.0565 (10)
H5B0.61580.48110.17240.068*
C6B0.6519 (3)0.2569 (8)0.2661 (2)0.0588 (10)
H6B0.69190.14960.24730.071*
C7B0.6411 (3)0.2105 (7)0.3375 (2)0.0564 (10)
H7B0.67290.07650.36770.068*
C7aB0.5796 (2)0.3764 (6)0.36203 (19)0.0444 (8)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O1A0.082 (2)0.0759 (18)0.0502 (17)0.0310 (16)0.0144 (15)0.0123 (15)
O2A0.0659 (17)0.0650 (17)0.0498 (16)0.0190 (14)0.0166 (14)0.0044 (13)
O3A0.120 (3)0.121 (3)0.065 (2)0.012 (2)0.046 (2)0.011 (2)
O4A0.128 (3)0.129 (3)0.086 (3)0.054 (3)0.042 (2)0.013 (2)
N1A0.069 (2)0.084 (3)0.059 (3)0.002 (2)0.022 (2)0.010 (2)
C1A0.0468 (19)0.0473 (18)0.041 (2)0.0029 (15)0.0071 (17)0.0054 (16)
C2A0.057 (2)0.053 (2)0.042 (2)0.0037 (18)0.0101 (18)0.0026 (17)
C3A0.047 (2)0.054 (2)0.048 (2)0.0004 (17)0.0144 (17)0.0022 (18)
C4A0.058 (2)0.056 (2)0.061 (3)0.0107 (19)0.014 (2)0.003 (2)
C5A0.065 (2)0.067 (2)0.051 (2)0.013 (2)0.009 (2)0.015 (2)
C6A0.055 (2)0.060 (2)0.047 (2)0.0096 (18)0.0133 (18)0.0049 (18)
C7A0.052 (2)0.053 (2)0.043 (2)0.0046 (18)0.0081 (18)0.0014 (18)
N1B0.0579 (18)0.0595 (18)0.0425 (18)0.0149 (16)0.0151 (15)0.0093 (15)
N2B0.063 (2)0.065 (2)0.051 (2)0.0183 (17)0.0205 (17)0.0049 (16)
N3B0.0628 (19)0.0596 (18)0.0466 (19)0.0141 (16)0.0181 (16)0.0037 (15)
C3aB0.0443 (19)0.0489 (19)0.042 (2)0.0006 (16)0.0117 (16)0.0034 (16)
C4B0.056 (2)0.054 (2)0.046 (2)0.0048 (18)0.0140 (18)0.0034 (18)
C5B0.060 (2)0.065 (2)0.048 (2)0.008 (2)0.022 (2)0.0057 (19)
C6B0.054 (2)0.067 (2)0.060 (3)0.003 (2)0.023 (2)0.007 (2)
C7B0.055 (2)0.056 (2)0.060 (2)0.0140 (18)0.019 (2)0.0014 (19)
C7aB0.0441 (18)0.0487 (19)0.039 (2)0.0017 (16)0.0079 (16)0.0003 (16)
Geometric parameters (Å, º) top
O1A—C7A1.211 (4)C6A—H6A0.9300
O2A—C7A1.323 (4)N1B—N2B1.338 (4)
O2A—H22A1.02 (4)N1B—C7aB1.365 (4)
O3A—N1A1.213 (4)N1B—H1B0.8600
O4A—N1A1.211 (4)N2B—N3B1.311 (4)
N1A—C3A1.476 (4)N3B—C3aB1.384 (4)
C1A—C6A1.381 (5)C3aB—C7aB1.388 (5)
C1A—C2A1.391 (5)C3aB—C4B1.402 (4)
C1A—C7A1.492 (5)C4B—C5B1.370 (5)
C2A—C3A1.371 (5)C4B—H4B0.9300
C2A—H2A0.9300C5B—C6B1.391 (5)
C3A—C4A1.369 (5)C5B—H5B0.9300
C4A—C5A1.385 (5)C6B—C7B1.368 (5)
C4A—H4A0.9300C6B—H6B0.9300
C5A—C6A1.379 (5)C7B—C7aB1.390 (4)
C5A—H5A0.9300C7B—H7B0.9300
C7A—O2A—H22A110 (2)O2A—C7A—C1A113.3 (3)
O4A—N1A—O3A123.3 (4)N2B—N1B—C7aB110.8 (3)
O4A—N1A—C3A118.3 (4)N2B—N1B—H1B124.6
O3A—N1A—C3A118.4 (4)C7aB—N1B—H1B124.6
C6A—C1A—C2A119.2 (3)N3B—N2B—N1B109.0 (3)
C6A—C1A—C7A123.0 (3)N2B—N3B—C3aB107.8 (3)
C2A—C1A—C7A117.8 (3)N3B—C3aB—C7aB108.4 (3)
C3A—C2A—C1A119.1 (3)N3B—C3aB—C4B130.8 (3)
C3A—C2A—H2A120.5C7aB—C3aB—C4B120.8 (3)
C1A—C2A—H2A120.5C5B—C4B—C3aB116.7 (3)
C4A—C3A—C2A122.6 (3)C5B—C4B—H4B121.7
C4A—C3A—N1A118.9 (3)C3aB—C4B—H4B121.7
C2A—C3A—N1A118.5 (3)C4B—C5B—C6B121.6 (3)
C3A—C4A—C5A118.0 (3)C4B—C5B—H5B119.2
C3A—C4A—H4A121.0C6B—C5B—H5B119.2
C5A—C4A—H4A121.0C7B—C6B—C5B122.9 (3)
C6A—C5A—C4A120.8 (4)C7B—C6B—H6B118.6
C6A—C5A—H5A119.6C5B—C6B—H6B118.6
C4A—C5A—H5A119.6C6B—C7B—C7aB115.7 (3)
C5A—C6A—C1A120.4 (3)C6B—C7B—H7B122.1
C5A—C6A—H6A119.8C7aB—C7B—H7B122.1
C1A—C6A—H6A119.8N1B—C7aB—C3aB104.0 (3)
O1A—C7A—O2A124.8 (3)N1B—C7aB—C7B133.6 (3)
O1A—C7A—C1A121.8 (3)C3aB—C7aB—C7B122.4 (3)
C6A—C1A—C2A—C3A0.4 (5)C7aB—N1B—N2B—N3B0.1 (4)
C7A—C1A—C2A—C3A180.0 (3)N1B—N2B—N3B—C3aB0.1 (4)
C1A—C2A—C3A—C4A0.3 (5)N2B—N3B—C3aB—C7aB0.1 (4)
C1A—C2A—C3A—N1A179.6 (3)N2B—N3B—C3aB—C4B179.5 (4)
O4A—N1A—C3A—C4A2.6 (6)N3B—C3aB—C4B—C5B179.2 (4)
O3A—N1A—C3A—C4A175.6 (4)C7aB—C3aB—C4B—C5B1.5 (5)
O4A—N1A—C3A—C2A177.3 (4)C3aB—C4B—C5B—C6B0.6 (5)
O3A—N1A—C3A—C2A4.5 (5)C4B—C5B—C6B—C7B0.5 (6)
C2A—C3A—C4A—C5A0.1 (6)C5B—C6B—C7B—C7aB0.5 (6)
N1A—C3A—C4A—C5A179.8 (3)N2B—N1B—C7aB—C3aB0.0 (4)
C3A—C4A—C5A—C6A0.0 (6)N2B—N1B—C7aB—C7B178.8 (4)
C4A—C5A—C6A—C1A0.1 (6)N3B—C3aB—C7aB—N1B0.1 (4)
C2A—C1A—C6A—C5A0.3 (5)C4B—C3aB—C7aB—N1B179.5 (3)
C7A—C1A—C6A—C5A179.9 (3)N3B—C3aB—C7aB—C7B179.1 (3)
C6A—C1A—C7A—O1A178.6 (4)C4B—C3aB—C7aB—C7B1.5 (5)
C2A—C1A—C7A—O1A1.8 (5)C6B—C7B—C7aB—N1B179.1 (4)
C6A—C1A—C7A—O2A1.3 (5)C6B—C7B—C7aB—C3aB0.4 (5)
C2A—C1A—C7A—O2A178.3 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2A—H22A···N3B1.02 (4)1.65 (4)2.669 (4)173 (3)
N1B—H1B···O1Ai0.862.012.826 (4)157
N1B—H1B···N2Bi0.862.452.913 (4)115
C5B—H5B···O4Aii0.932.683.490 (5)146
C6B—H6B···O3Aiii0.932.753.303 (5)119
Symmetry codes: (i) x+1, y+1, z+1; (ii) x+1/2, y+5/2, z1/2; (iii) x+1/2, y+3/2, z1/2.
(IV) Imidazolium 3-nitrobenzoate top
Crystal data top
C3H5N2+·C7H4NO4Dx = 1.516 Mg m3
Mr = 235.20Melting point = 436–438 K
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 5.826 (2) ÅCell parameters from 25 reflections
b = 23.411 (7) Åθ = 10–15°
c = 7.556 (2) ŵ = 0.12 mm1
β = 90.53 (3)°T = 297 K
V = 1030.5 (6) Å3Plate, colourless
Z = 40.35 × 0.23 × 0.08 mm
F(000) = 488
Data collection top
Rigaku AFC-5R
diffractometer
Rint = 0.052
Radiation source: normal-focus rotating anodeθmax = 27.5°, θmin = 2.8°
Graphite monochromatorh = 77
ω scansk = 030
4708 measured reflectionsl = 99
2361 independent reflections3 standard reflections every 100 reflections
1081 reflections with I > 2σ(I) intensity decay: 0.6%
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.044H-atom parameters constrained
wR(F2) = 0.131 w = 1/[σ2(Fo2) + (0.0489P)2 + 0.0063P]
where P = (Fo2 + 2Fc2)/3
S = 0.98(Δ/σ)max < 0.001
2361 reflectionsΔρmax = 0.17 e Å3
155 parametersΔρmin = 0.17 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0090 (17)
Crystal data top
C3H5N2+·C7H4NO4V = 1030.5 (6) Å3
Mr = 235.20Z = 4
Monoclinic, P21/cMo Kα radiation
a = 5.826 (2) ŵ = 0.12 mm1
b = 23.411 (7) ÅT = 297 K
c = 7.556 (2) Å0.35 × 0.23 × 0.08 mm
β = 90.53 (3)°
Data collection top
Rigaku AFC-5R
diffractometer
Rint = 0.052
4708 measured reflections3 standard reflections every 100 reflections
2361 independent reflections intensity decay: 0.6%
1081 reflections with I > 2σ(I)
Refinement top
R[F2 > 2σ(F2)] = 0.0440 restraints
wR(F2) = 0.131H-atom parameters constrained
S = 0.98Δρmax = 0.17 e Å3
2361 reflectionsΔρmin = 0.17 e Å3
155 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*/Ueq
O1A0.7697 (3)0.14776 (7)0.3964 (3)0.0579 (5)
O2A0.5254 (3)0.09743 (7)0.5603 (3)0.0588 (6)
O3A0.7467 (3)0.35449 (8)0.4398 (3)0.0719 (6)
O4A0.4471 (4)0.39762 (8)0.5377 (3)0.0834 (7)
N1A0.5558 (4)0.35409 (9)0.5048 (3)0.0536 (6)
C1A0.4715 (4)0.19711 (9)0.5409 (3)0.0351 (5)
C2A0.5675 (4)0.24973 (9)0.5027 (3)0.0335 (5)
H2A0.70990.25190.44850.040*
C3A0.4500 (4)0.29888 (9)0.5457 (3)0.0391 (6)
C4A0.2364 (4)0.29772 (12)0.6247 (3)0.0481 (7)
H4A0.15960.33130.65290.058*
C5A0.1416 (4)0.24485 (12)0.6601 (3)0.0517 (7)
H5A0.00260.24270.71140.062*
C6A0.2573 (4)0.19546 (11)0.6205 (3)0.0446 (6)
H6A0.19140.16040.64730.054*
C7A0.5982 (4)0.14308 (10)0.4954 (3)0.0422 (6)
N1B1.1590 (3)0.02477 (8)0.2889 (3)0.0462 (5)
H1B1.27440.04700.30670.055*
C2B1.1449 (4)0.02922 (10)0.3415 (3)0.0463 (6)
H2B1.25740.04930.40370.056*
N3B0.9446 (4)0.04946 (8)0.2905 (3)0.0466 (6)
H3B0.89590.08360.30860.056*
C4B0.8267 (4)0.00735 (11)0.2042 (3)0.0481 (6)
H4B0.67990.01030.15560.058*
C5B0.9616 (4)0.03922 (11)0.2023 (3)0.0485 (6)
H5B0.92690.07440.15170.058*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O1A0.0570 (11)0.0405 (10)0.0764 (14)0.0069 (9)0.0161 (10)0.0075 (9)
O2A0.0568 (11)0.0348 (10)0.0848 (15)0.0028 (9)0.0091 (10)0.0135 (9)
O3A0.0642 (13)0.0511 (12)0.1005 (17)0.0125 (10)0.0043 (12)0.0142 (11)
O4A0.1005 (16)0.0359 (10)0.114 (2)0.0160 (11)0.0201 (14)0.0108 (11)
N1A0.0623 (15)0.0346 (12)0.0635 (15)0.0047 (11)0.0183 (12)0.0013 (11)
C1A0.0335 (12)0.0373 (12)0.0343 (13)0.0003 (10)0.0053 (10)0.0010 (11)
C2A0.0295 (11)0.0376 (12)0.0332 (12)0.0019 (9)0.0006 (9)0.0012 (10)
C3A0.0408 (14)0.0363 (13)0.0400 (14)0.0049 (11)0.0077 (10)0.0018 (11)
C4A0.0433 (14)0.0574 (17)0.0434 (15)0.0155 (12)0.0081 (12)0.0102 (13)
C5A0.0319 (13)0.085 (2)0.0387 (14)0.0046 (13)0.0021 (10)0.0001 (15)
C6A0.0391 (13)0.0534 (15)0.0412 (15)0.0069 (11)0.0051 (11)0.0078 (12)
C7A0.0429 (13)0.0345 (13)0.0490 (15)0.0018 (11)0.0123 (12)0.0011 (11)
N1B0.0481 (12)0.0368 (11)0.0539 (13)0.0071 (9)0.0086 (10)0.0098 (10)
C2B0.0535 (15)0.0410 (14)0.0444 (15)0.0046 (12)0.0046 (12)0.0066 (12)
N3B0.0532 (12)0.0361 (12)0.0508 (14)0.0079 (10)0.0098 (10)0.0040 (10)
C4B0.0461 (14)0.0514 (16)0.0469 (15)0.0018 (13)0.0011 (12)0.0019 (13)
C5B0.0566 (16)0.0394 (14)0.0496 (16)0.0038 (12)0.0050 (12)0.0011 (12)
Geometric parameters (Å, º) top
O1A—C7A1.258 (3)C5A—C6A1.373 (3)
O2A—C7A1.252 (3)C5A—H5A0.9300
O3A—N1A1.220 (3)C6A—H6A0.9300
O4A—N1A1.227 (3)N1B—C2B1.328 (3)
N1A—C3A1.466 (3)N1B—C5B1.361 (3)
C1A—C2A1.384 (3)N1B—H1B0.8600
C1A—C6A1.391 (3)N3B—C2B1.314 (3)
C1A—C7A1.506 (3)C2B—H2B0.9300
C2A—C3A1.379 (3)N3B—C4B1.364 (3)
C2A—H2A0.9300N3B—H3B0.8600
C3A—C4A1.386 (3)C4B—C5B1.344 (3)
C4A—C5A1.382 (4)C4B—H4B0.9300
C4A—H4A0.9300C5B—H5B0.9300
O3A—N1A—O4A123.3 (2)C1A—C6A—H6A119.5
O3A—N1A—C3A118.6 (2)O2A—C7A—O1A125.5 (2)
O4A—N1A—C3A118.1 (2)O2A—C7A—C1A117.3 (2)
C2A—C1A—C6A118.7 (2)O1A—C7A—C1A117.1 (2)
C2A—C1A—C7A120.0 (2)C2B—N1B—C5B109.0 (2)
C6A—C1A—C7A121.3 (2)C2B—N1B—H1B125.5
C3A—C2A—C1A119.4 (2)C5B—N1B—H1B125.5
C3A—C2A—H2A120.3N3B—C2B—N1B108.2 (2)
C1A—C2A—H2A120.3N3B—C2B—H2B125.9
C2A—C3A—C4A122.3 (2)N1B—C2B—H2B125.9
C2A—C3A—N1A118.4 (2)C2B—N3B—C4B108.8 (2)
C4A—C3A—N1A119.3 (2)C2B—N3B—H3B125.6
C5A—C4A—C3A117.6 (2)C4B—N3B—H3B125.6
C5A—C4A—H4A121.2C5B—C4B—N3B107.4 (2)
C3A—C4A—H4A121.2C5B—C4B—H4B126.3
C6A—C5A—C4A121.0 (2)N3B—C4B—H4B126.3
C6A—C5A—H5A119.5C4B—C5B—N1B106.6 (2)
C4A—C5A—H5A119.5C4B—C5B—H5B126.7
C5A—C6A—C1A121.0 (2)N1B—C5B—H5B126.7
C5A—C6A—H6A119.5
C6A—C1A—C2A—C3A0.6 (3)C2A—C1A—C6A—C5A0.3 (3)
C7A—C1A—C2A—C3A179.7 (2)C7A—C1A—C6A—C5A179.4 (2)
C1A—C2A—C3A—C4A0.7 (3)C2A—C1A—C7A—O2A167.4 (2)
C1A—C2A—C3A—N1A179.7 (2)C6A—C1A—C7A—O2A12.9 (3)
O3A—N1A—C3A—C2A2.4 (3)C2A—C1A—C7A—O1A12.0 (3)
O4A—N1A—C3A—C2A177.5 (2)C6A—C1A—C7A—O1A167.7 (2)
O3A—N1A—C3A—C4A178.0 (2)C5B—N1B—C2B—N3B0.1 (3)
O4A—N1A—C3A—C4A2.1 (3)N1B—C2B—N3B—C4B0.4 (3)
C2A—C3A—C4A—C5A0.0 (3)C2B—N3B—C4B—C5B0.6 (3)
N1A—C3A—C4A—C5A179.6 (2)N3B—C4B—C5B—N1B0.5 (3)
C3A—C4A—C5A—C6A1.0 (3)C2B—N1B—C5B—C4B0.2 (3)
C4A—C5A—C6A—C1A1.1 (4)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1B—H1B···O2Ai0.861.932.745 (3)157
N3B—H3B···O1A0.861.802.644 (3)166
C4B—H4B···O4Aii0.932.693.372 (3)130
C5B—H5B···O3Aiii0.932.623.204 (3)121
Symmetry codes: (i) x+2, y, z+1; (ii) x, y+1/2, z1/2; (iii) x+2, y1/2, z+1/2.
(V) Imidazolium 4-nitrobenzoate top
Crystal data top
C3H5N2+·C7H4NO4F(000) = 244
Mr = 235.20Dx = 1.531 Mg m3
Triclinic, P1Melting point = 468–469 K
a = 7.5395 (7) ÅMo Kα radiation, λ = 0.71073 Å
b = 11.8374 (15) ÅCell parameters from 25 reflections
c = 5.9689 (12) Åθ = 10–15°
α = 100.145 (14)°µ = 0.12 mm1
β = 90.731 (13)°T = 297 K
γ = 102.998 (9)°Plate, colourless
V = 510.19 (13) Å30.43 × 0.20 × 0.10 mm
Z = 2
Data collection top
Rigaku AFC-5R
diffractometer
Rint = 0.033
Radiation source: normal-focus rotating anodeθmax = 30.0°, θmin = 2.8°
Graphite monochromatorh = 1010
ω/2θ scansk = 1616
6177 measured reflectionsl = 88
2988 independent reflections3 standard reflections every 100 reflections
1679 reflections with I > 2σ(I) intensity decay: 0.0%
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)] = 0.047Hydrogen site location: difference Fourier map
wR(F2) = 0.140H-atom parameters constrained
S = 1.00 w = 1/[σ2(Fo2) + (0.0644P)2 + 0.0303P]
where P = (Fo2 + 2Fc2)/3
2988 reflections(Δ/σ)max < 0.001
154 parametersΔρmax = 0.21 e Å3
0 restraintsΔρmin = 0.28 e Å3
Crystal data top
C3H5N2+·C7H4NO4γ = 102.998 (9)°
Mr = 235.20V = 510.19 (13) Å3
Triclinic, P1Z = 2
a = 7.5395 (7) ÅMo Kα radiation
b = 11.8374 (15) ŵ = 0.12 mm1
c = 5.9689 (12) ÅT = 297 K
α = 100.145 (14)°0.43 × 0.20 × 0.10 mm
β = 90.731 (13)°
Data collection top
Rigaku AFC-5R
diffractometer
Rint = 0.033
6177 measured reflections3 standard reflections every 100 reflections
2988 independent reflections intensity decay: 0.0%
1679 reflections with I > 2σ(I)
Refinement top
R[F2 > 2σ(F2)] = 0.0470 restraints
wR(F2) = 0.140H-atom parameters constrained
S = 1.00Δρmax = 0.21 e Å3
2988 reflectionsΔρmin = 0.28 e Å3
154 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*/Ueq
O1A0.00788 (19)0.30138 (10)0.3639 (2)0.0509 (4)
O2A0.12014 (19)0.19374 (10)0.0960 (2)0.0495 (3)
O3A0.4107 (2)0.79860 (11)0.0484 (3)0.0671 (5)
O4A0.4693 (2)0.68839 (13)0.3542 (3)0.0685 (5)
N1A0.4066 (2)0.70209 (13)0.1660 (3)0.0462 (4)
C1A0.1692 (2)0.39848 (13)0.0991 (2)0.0307 (3)
C2A0.1707 (2)0.51001 (13)0.2229 (3)0.0332 (3)
H2A0.11920.51750.36390.040*
C3A0.2489 (2)0.61011 (13)0.1366 (3)0.0354 (4)
H3A0.25230.68500.21920.043*
C4A0.3215 (2)0.59576 (13)0.0754 (3)0.0343 (4)
C5A0.3194 (2)0.48653 (14)0.2040 (3)0.0365 (4)
H5A0.36770.47950.34700.044*
C6A0.2434 (2)0.38781 (14)0.1141 (3)0.0348 (4)
H6A0.24170.31330.19700.042*
C7A0.0874 (2)0.28898 (13)0.1942 (3)0.0353 (4)
N1B0.2291 (2)0.05050 (12)0.6421 (3)0.0436 (4)
H1B0.22640.09410.74250.052*
C2B0.1381 (2)0.06099 (15)0.6599 (3)0.0425 (4)
H2B0.06040.10480.78240.051*
N3B0.17668 (19)0.09910 (12)0.4742 (2)0.0419 (4)
H3B0.13500.16880.44670.050*
C4B0.2939 (2)0.00914 (16)0.3330 (3)0.0455 (4)
H4B0.34180.01190.19020.055*
C5B0.3272 (2)0.08435 (15)0.4392 (3)0.0450 (4)
H5B0.40300.15800.38410.054*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O1A0.0671 (9)0.0355 (6)0.0493 (8)0.0025 (6)0.0180 (6)0.0170 (6)
O2A0.0738 (9)0.0296 (6)0.0475 (7)0.0122 (6)0.0044 (6)0.0133 (5)
O3A0.0871 (11)0.0349 (7)0.0772 (11)0.0006 (7)0.0041 (9)0.0233 (7)
O4A0.0788 (10)0.0675 (10)0.0553 (9)0.0091 (8)0.0109 (8)0.0342 (8)
N1A0.0459 (9)0.0407 (8)0.0523 (9)0.0024 (7)0.0047 (7)0.0256 (7)
C1A0.0311 (8)0.0295 (7)0.0326 (8)0.0052 (6)0.0001 (6)0.0111 (6)
C2A0.0364 (8)0.0323 (8)0.0314 (8)0.0072 (6)0.0044 (6)0.0082 (6)
C3A0.0397 (9)0.0276 (7)0.0388 (8)0.0067 (7)0.0004 (7)0.0075 (6)
C4A0.0316 (8)0.0332 (8)0.0394 (9)0.0014 (6)0.0016 (6)0.0179 (7)
C5A0.0375 (9)0.0414 (9)0.0323 (8)0.0083 (7)0.0049 (6)0.0124 (7)
C6A0.0394 (9)0.0312 (8)0.0345 (8)0.0089 (7)0.0032 (7)0.0064 (6)
C7A0.0429 (9)0.0276 (7)0.0341 (8)0.0026 (7)0.0024 (7)0.0099 (6)
N1B0.0541 (9)0.0365 (7)0.0478 (9)0.0160 (7)0.0142 (7)0.0202 (6)
C2B0.0454 (10)0.0386 (9)0.0454 (10)0.0125 (8)0.0070 (8)0.0089 (7)
N3B0.0479 (9)0.0327 (7)0.0497 (9)0.0101 (6)0.0147 (7)0.0179 (6)
C4B0.0473 (10)0.0462 (10)0.0458 (10)0.0122 (8)0.0067 (8)0.0142 (8)
C5B0.0456 (10)0.0336 (8)0.0555 (11)0.0069 (8)0.0087 (8)0.0099 (8)
Geometric parameters (Å, º) top
O1A—C7A1.256 (2)C5A—C6A1.382 (2)
O2A—C7A1.2536 (19)C5A—H5A0.9300
O3A—N1A1.225 (2)C6A—H6A0.9300
O4A—N1A1.223 (2)N1B—C2B1.329 (2)
N1A—C4A1.4743 (19)N1B—C5B1.359 (2)
C1A—C2A1.392 (2)N1B—H1B0.8600
C1A—C6A1.394 (2)N3B—C2B1.321 (2)
C1A—C7A1.514 (2)C2B—H2B0.9300
C2A—C3A1.388 (2)N3B—C4B1.366 (2)
C2A—H2A0.9300N3B—H3B0.8600
C3A—C4A1.383 (2)C4B—C5B1.347 (2)
C3A—H3A0.9300C4B—H4B0.9300
C4A—C5A1.379 (2)C5B—H5B0.9300
O4A—N1A—O3A123.97 (15)C1A—C6A—H6A119.6
O4A—N1A—C4A117.85 (16)O2A—C7A—O1A125.72 (14)
O3A—N1A—C4A118.18 (15)O2A—C7A—C1A117.10 (14)
C2A—C1A—C6A119.63 (13)O1A—C7A—C1A117.18 (14)
C2A—C1A—C7A120.51 (14)C2B—N1B—C5B108.84 (15)
C6A—C1A—C7A119.86 (14)C2B—N1B—H1B125.6
C3A—C2A—C1A120.22 (14)C5B—N1B—H1B125.6
C3A—C2A—H2A119.9N3B—C2B—N1B108.39 (16)
C1A—C2A—H2A119.9N3B—C2B—H2B125.8
C4A—C3A—C2A118.36 (14)N1B—C2B—H2B125.8
C4A—C3A—H3A120.8C2B—N3B—C4B108.56 (15)
C2A—C3A—H3A120.8C2B—N3B—H3B125.7
C5A—C4A—C3A122.84 (14)C4B—N3B—H3B125.7
C5A—C4A—N1A118.76 (14)C5B—C4B—N3B107.23 (16)
C3A—C4A—N1A118.40 (15)C5B—C4B—H4B126.4
C4A—C5A—C6A118.06 (15)N3B—C4B—H4B126.4
C4A—C5A—H5A121.0C4B—C5B—N1B106.97 (16)
C6A—C5A—H5A121.0C4B—C5B—H5B126.5
C5A—C6A—C1A120.87 (15)N1B—C5B—H5B126.5
C5A—C6A—H6A119.6
C6A—C1A—C2A—C3A1.3 (2)C2A—C1A—C6A—C5A0.4 (2)
C7A—C1A—C2A—C3A178.82 (14)C7A—C1A—C6A—C5A179.75 (15)
C1A—C2A—C3A—C4A1.1 (2)C2A—C1A—C7A—O2A167.08 (15)
C2A—C3A—C4A—C5A0.0 (2)C6A—C1A—C7A—O2A13.0 (2)
C2A—C3A—C4A—N1A179.26 (14)C2A—C1A—C7A—O1A13.2 (2)
O4A—N1A—C4A—C5A1.1 (2)C6A—C1A—C7A—O1A166.65 (15)
O3A—N1A—C4A—C5A178.61 (15)C5B—N1B—C2B—N3B0.36 (19)
O4A—N1A—C4A—C3A179.57 (16)N1B—C2B—N3B—C4B0.65 (19)
O3A—N1A—C4A—C3A0.7 (2)C2B—N3B—C4B—C5B0.7 (2)
C3A—C4A—C5A—C6A0.9 (2)N3B—C4B—C5B—N1B0.46 (19)
N1A—C4A—C5A—C6A178.35 (14)C2B—N1B—C5B—C4B0.1 (2)
C4A—C5A—C6A—C1A0.7 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N3B—H3B···O1A0.861.802.6442 (18)168
N1B—H1B···O2Ai0.861.942.7425 (19)155
C4B—H4B···O3Aii0.932.683.326 (2)127
C5B—H5B···O4Aiii0.932.633.236 (2)123
Symmetry codes: (i) x, y, z+1; (ii) x, y+1, z; (iii) x1, y1, z+1.

Experimental details

(I)(II)(III)(IV)
Crystal data
Chemical formulaC7H7N2+·C7H4NO4C7H7N2+·C7H4NO4C6H5N3·C7H5NO4C3H5N2+·C7H4NO4
Mr285.26285.26286.25235.20
Crystal system, space groupMonoclinic, P21Monoclinic, P21/cMonoclinic, P21/nMonoclinic, P21/c
Temperature (K)297297297297
a, b, c (Å)12.522 (2), 10.7827 (12), 4.8838 (6)13.8524 (5), 7.6666 (4), 12.5193 (7)14.342 (3), 5.218 (1), 18.161 (4)5.826 (2), 23.411 (7), 7.556 (2)
α, β, γ (°)90, 93.230 (4), 9090, 94.1400 (17), 9090, 105.40 (1), 9090, 90.53 (3), 90
V3)658.35 (15)1326.09 (11)1310.3 (5)1030.5 (6)
Z2444
Radiation typeMo KαMo KαMo KαMo Kα
µ (mm1)0.110.110.110.12
Crystal size (mm)0.45 × 0.25 × 0.050.60 × 0.38 × 0.330.35 × 0.15 × 0.100.35 × 0.23 × 0.08
Data collection
DiffractometerRigaku R-AXIS Rapid
diffractometer
Rigaku R-AXIS Rapid
diffractometer
MacScience DIP3000
diffractometer
Rigaku AFC-5R
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
10657, 1568, 1152 23459, 3869, 2856 12254, 2465, 1486 4708, 2361, 1081
Rint0.0460.0340.0300.052
(sin θ/λ)max1)0.6490.7040.6280.650
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.048, 0.113, 1.10 0.053, 0.153, 1.07 0.072, 0.184, 1.08 0.044, 0.131, 0.98
No. of reflections1568386924652361
No. of parameters192191194155
No. of restraints1000
H-atom treatmentH-atom parameters constrainedH-atom parameters constrainedH atoms treated by a mixture of independent and constrained refinementH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.15, 0.150.22, 0.190.28, 0.290.17, 0.17


(V)
Crystal data
Chemical formulaC3H5N2+·C7H4NO4
Mr235.20
Crystal system, space groupTriclinic, P1
Temperature (K)297
a, b, c (Å)7.5395 (7), 11.8374 (15), 5.9689 (12)
α, β, γ (°)100.145 (14), 90.731 (13), 102.998 (9)
V3)510.19 (13)
Z2
Radiation typeMo Kα
µ (mm1)0.12
Crystal size (mm)0.43 × 0.20 × 0.10
Data collection
DiffractometerRigaku AFC-5R
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
6177, 2988, 1679
Rint0.033
(sin θ/λ)max1)0.703
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.047, 0.140, 1.00
No. of reflections2988
No. of parameters154
No. of restraints0
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.21, 0.28

Computer programs: PROCESS-AUTO (Rigaku Corporation, 1998), DIP3000 Control Programs (MacScience, 1992), MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1988), PROCESS-AUTO, MSC/AFC Diffractometer Control Software, TEXSAN (Molecular Structure Corporation, 1993), DENZO/SCALEPACK (Otwinowski & Minor, 1997), SIR92 (Altomare et al., 1994), SHELXL97 (Sheldrick, 1997), ORTEPIII (Burnett & Johnson, 1996), SHELXL97.

Selected bond lengths (Å) for (I) top
O1A—C7A1.269 (5)N1B—C2B1.326 (5)
O2A—C7A1.234 (5)N3B—C2B1.316 (5)
Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
N1B—H1B···O2Ai0.861.862.717 (4)177
N3B—H3B···O1A0.861.692.550 (3)178
C5B—H5B···O3Aii0.932.703.553 (6)153
C5A—H5A···O4Aiii0.932.713.340 (5)126
Symmetry codes: (i) x+1, y+1/2, z+1; (ii) x+1, y1/2, z1; (iii) x, y1/2, z2.
Selected bond lengths (Å) for (II) top
O1A—C7A1.2494 (19)N1B—C2B1.3265 (18)
O2A—C7A1.2632 (18)N3B—C2B1.3231 (19)
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
N1B—H1B···O2Ai0.861.812.6600 (15)171
N3B—H3B···O1A0.861.792.6469 (15)177
C2B—H2B···O2Aii0.932.263.125 (2)155
C6B—H6B···O3Aiii0.932.833.478 (3)128
Symmetry codes: (i) x+1, y+1/2, z+1/2; (ii) x, y+1/2, z1/2; (iii) x+1, y, z.
Selected bond lengths (Å) for (III) top
O1A—C7A1.211 (4)N1B—N2B1.338 (4)
O2A—C7A1.323 (4)N2B—N3B1.311 (4)
Hydrogen-bond geometry (Å, º) for (III) top
D—H···AD—HH···AD···AD—H···A
O2A—H22A···N3B1.02 (4)1.65 (4)2.669 (4)173 (3)
N1B—H1B···O1Ai0.862.012.826 (4)157
C5B—H5B···O4Aii0.932.683.490 (5)146
C6B—H6B···O3Aiii0.932.753.303 (5)119
Symmetry codes: (i) x+1, y+1, z+1; (ii) x+1/2, y+5/2, z1/2; (iii) x+1/2, y+3/2, z1/2.
Selected bond lengths (Å) for (IV) top
O1A—C7A1.258 (3)N1B—C2B1.328 (3)
O2A—C7A1.252 (3)N3B—C2B1.314 (3)
Hydrogen-bond geometry (Å, º) for (IV) top
D—H···AD—HH···AD···AD—H···A
N1B—H1B···O2Ai0.861.932.745 (3)157
N3B—H3B···O1A0.861.802.644 (3)166
C4B—H4B···O4Aii0.932.693.372 (3)130
C5B—H5B···O3Aiii0.932.623.204 (3)121
Symmetry codes: (i) x+2, y, z+1; (ii) x, y+1/2, z1/2; (iii) x+2, y1/2, z+1/2.
Selected bond lengths (Å) for (V) top
O1A—C7A1.256 (2)N1B—C2B1.329 (2)
O2A—C7A1.2536 (19)N3B—C2B1.321 (2)
Hydrogen-bond geometry (Å, º) for (V) top
D—H···AD—HH···AD···AD—H···A
N3B—H3B···O1A0.861.802.6442 (18)168
N1B—H1B···O2Ai0.861.942.7425 (19)155
C4B—H4B···O3Aii0.932.683.326 (2)127
C5B—H5B···O4Aiii0.932.633.236 (2)123
Symmetry codes: (i) x, y, z+1; (ii) x, y+1, z; (iii) x1, y1, z+1.
 

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