Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270101009118/ob1039sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270101009118/ob1039Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270101009118/ob1039IIsup3.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270101009118/ob1039IIIsup4.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270101009118/ob1039IVsup5.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270101009118/ob1039Vsup6.hkl |
CCDC references: 173365; 173366; 173367; 173368; 173369
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%.
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.
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.
C7H7N2+·C7H4NO4− | Dx = 1.439 Mg m−3 |
Mr = 285.26 | Melting point = 419–420 K |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
a = 12.522 (2) Å | Cell parameters from 8583 reflections |
b = 10.7827 (12) Å | θ = 2.5–27.5° |
c = 4.8838 (6) Å | µ = 0.11 mm−1 |
β = 93.230 (4)° | T = 297 K |
V = 658.35 (15) Å3 | Plate, colourless |
Z = 2 | 0.45 × 0.25 × 0.05 mm |
F(000) = 296 |
Rigaku R-AXIS Rapid diffractometer | 1152 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.046 |
Graphite monochromator | θmax = 27.5°, θmin = 2.5° |
Detector resolution: 10 pixels mm-1 | h = −16→16 |
oscillation scans | k = −13→13 |
10657 measured reflections | l = −6→6 |
1568 independent reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.048 | H-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 reflections | Δρmax = 0.15 e Å−3 |
192 parameters | Δρmin = −0.15 e Å−3 |
1 restraint | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.037 (7) |
C7H7N2+·C7H4NO4− | V = 658.35 (15) Å3 |
Mr = 285.26 | Z = 2 |
Monoclinic, P21 | Mo Kα radiation |
a = 12.522 (2) Å | µ = 0.11 mm−1 |
b = 10.7827 (12) Å | T = 297 K |
c = 4.8838 (6) Å | 0.45 × 0.25 × 0.05 mm |
β = 93.230 (4)° |
Rigaku R-AXIS Rapid diffractometer | 1152 reflections with I > 2σ(I) |
10657 measured reflections | Rint = 0.046 |
1568 independent reflections |
R[F2 > 2σ(F2)] = 0.048 | 1 restraint |
wR(F2) = 0.113 | H-atom parameters constrained |
S = 1.10 | Δρmax = 0.15 e Å−3 |
1568 reflections | Δρmin = −0.15 e Å−3 |
192 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
O1A | 0.3606 (2) | 0.3570 (3) | −0.1288 (6) | 0.0725 (8) | |
O2A | 0.3619 (3) | 0.1590 (3) | −0.0046 (5) | 0.0761 (9) | |
O3A | 0.1224 (3) | 0.4859 (3) | −0.8987 (7) | 0.0871 (11) | |
O4A | −0.0058 (3) | 0.3683 (4) | −1.0444 (7) | 0.1007 (12) | |
N1A | 0.0727 (3) | 0.3897 (4) | −0.8953 (6) | 0.0633 (9) | |
C1A | 0.2299 (3) | 0.2248 (3) | −0.3382 (6) | 0.0450 (8) | |
C2A | 0.1962 (3) | 0.3170 (3) | −0.5220 (6) | 0.0461 (8) | |
H2A | 0.2314 | 0.3929 | −0.5254 | 0.055* | |
C3A | 0.1091 (3) | 0.2925 (3) | −0.6995 (6) | 0.0466 (8) | |
C4A | 0.0546 (3) | 0.1808 (4) | −0.7036 (7) | 0.0564 (9) | |
H4A | −0.0036 | 0.1668 | −0.8266 | 0.068* | |
C5A | 0.0895 (3) | 0.0912 (4) | −0.5196 (8) | 0.0633 (10) | |
H5A | 0.0544 | 0.0152 | −0.5171 | 0.059 (11)* | |
C6A | 0.1762 (3) | 0.1130 (3) | −0.3383 (7) | 0.0551 (9) | |
H6A | 0.1986 | 0.0514 | −0.2146 | 0.066* | |
C7A | 0.3249 (3) | 0.2469 (4) | −0.1411 (7) | 0.0530 (9) | |
N1B | 0.5852 (3) | 0.4925 (3) | 0.6017 (6) | 0.0578 (8) | |
H1B | 0.5999 | 0.5461 | 0.7287 | 0.069* | |
C2B | 0.5002 (3) | 0.4946 (4) | 0.4273 (7) | 0.0603 (10) | |
H2B | 0.4472 | 0.5550 | 0.4248 | 0.072* | |
N3B | 0.5011 (2) | 0.3997 (3) | 0.2581 (6) | 0.0564 (8) | |
H3B | 0.4536 | 0.3832 | 0.1291 | 0.068* | |
C4B | 0.6339 (3) | 0.2245 (4) | 0.2128 (8) | 0.0639 (11) | |
H4B | 0.5985 | 0.1847 | 0.0650 | 0.077* | |
C5B | 0.7301 (4) | 0.1796 (5) | 0.3288 (10) | 0.0778 (13) | |
H5B | 0.7603 | 0.1085 | 0.2582 | 0.093* | |
C6B | 0.7814 (4) | 0.2406 (5) | 0.5506 (10) | 0.0778 (13) | |
H6B | 0.8454 | 0.2083 | 0.6251 | 0.093* | |
C7B | 0.7419 (3) | 0.3460 (5) | 0.6641 (8) | 0.0693 (12) | |
H7B | 0.7773 | 0.3857 | 0.8120 | 0.083* | |
C7aB | 0.6463 (3) | 0.3899 (4) | 0.5460 (7) | 0.0529 (8) | |
C3aB | 0.5927 (3) | 0.3310 (4) | 0.3258 (6) | 0.0497 (8) |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1A | 0.0734 (18) | 0.0693 (19) | 0.0706 (16) | −0.0097 (15) | −0.0331 (14) | 0.0061 (14) |
O2A | 0.092 (2) | 0.0696 (19) | 0.0627 (14) | 0.0149 (18) | −0.0284 (14) | 0.0128 (16) |
O3A | 0.093 (2) | 0.072 (2) | 0.093 (2) | −0.002 (2) | −0.0257 (19) | 0.027 (2) |
O4A | 0.086 (2) | 0.109 (3) | 0.101 (2) | 0.007 (2) | −0.0559 (18) | 0.014 (2) |
N1A | 0.0614 (19) | 0.073 (2) | 0.0534 (16) | 0.017 (2) | −0.0101 (14) | 0.0072 (19) |
C1A | 0.0484 (18) | 0.0468 (19) | 0.0391 (15) | 0.0037 (15) | −0.0034 (14) | −0.0029 (15) |
C2A | 0.0452 (18) | 0.0427 (18) | 0.0493 (16) | 0.0001 (16) | −0.0053 (14) | 0.0001 (16) |
C3A | 0.0428 (17) | 0.054 (2) | 0.0421 (15) | 0.0050 (16) | −0.0014 (13) | 0.0001 (15) |
C4A | 0.0452 (18) | 0.071 (3) | 0.0517 (18) | −0.006 (2) | −0.0063 (14) | −0.0102 (19) |
C5A | 0.067 (3) | 0.054 (2) | 0.068 (2) | −0.018 (2) | 0.0002 (19) | −0.004 (2) |
C6A | 0.070 (2) | 0.045 (2) | 0.0496 (18) | 0.004 (2) | −0.0002 (16) | 0.0047 (17) |
C7A | 0.054 (2) | 0.063 (2) | 0.0405 (16) | 0.007 (2) | −0.0054 (15) | 0.0010 (18) |
N1B | 0.064 (2) | 0.0590 (19) | 0.0494 (15) | −0.0101 (17) | −0.0049 (14) | −0.0057 (15) |
C2B | 0.063 (2) | 0.060 (2) | 0.057 (2) | −0.003 (2) | −0.0039 (19) | −0.004 (2) |
N3B | 0.0520 (16) | 0.065 (2) | 0.0514 (14) | −0.0079 (16) | −0.0099 (12) | −0.0040 (15) |
C4B | 0.071 (3) | 0.059 (2) | 0.062 (2) | −0.004 (2) | 0.0091 (19) | −0.007 (2) |
C5B | 0.082 (3) | 0.067 (3) | 0.088 (3) | 0.016 (3) | 0.031 (2) | 0.010 (3) |
C6B | 0.059 (2) | 0.089 (4) | 0.084 (3) | 0.005 (3) | −0.004 (2) | 0.019 (3) |
C7B | 0.058 (2) | 0.087 (3) | 0.061 (2) | −0.012 (2) | −0.0115 (17) | 0.012 (2) |
C7aB | 0.0545 (19) | 0.058 (2) | 0.0454 (15) | −0.0095 (18) | −0.0004 (14) | 0.0002 (17) |
C3aB | 0.0455 (18) | 0.057 (2) | 0.0463 (15) | −0.0046 (17) | 0.0012 (13) | 0.0024 (17) |
O1A—C7A | 1.269 (5) | N1B—C7aB | 1.381 (5) |
O2A—C7A | 1.234 (5) | N1B—H1B | 0.8600 |
O3A—N1A | 1.210 (5) | N3B—C2B | 1.316 (5) |
O4A—N1A | 1.212 (4) | C2B—H2B | 0.9300 |
N1A—C3A | 1.474 (5) | N3B—C3aB | 1.390 (4) |
C1A—C6A | 1.380 (5) | N3B—H3B | 0.8600 |
C1A—C2A | 1.389 (4) | C4B—C3aB | 1.386 (6) |
C1A—C7A | 1.507 (5) | C4B—C5B | 1.389 (6) |
C2A—C3A | 1.380 (4) | C4B—H4B | 0.9300 |
C2A—H2A | 0.9300 | C5B—C6B | 1.393 (7) |
C3A—C4A | 1.385 (5) | C5B—H5B | 0.9300 |
C4A—C5A | 1.373 (5) | C6B—C7B | 1.368 (7) |
C4A—H4A | 0.9300 | C6B—H6B | 0.9300 |
C5A—C6A | 1.382 (5) | C7B—C7aB | 1.383 (5) |
C5A—H5A | 0.9300 | C7B—H7B | 0.9300 |
C6A—H6A | 0.9300 | C7aB—C3aB | 1.389 (5) |
N1B—C2B | 1.326 (5) | ||
O3A—N1A—O4A | 123.7 (4) | C7aB—N1B—H1B | 125.6 |
O3A—N1A—C3A | 118.6 (3) | N3B—C2B—N1B | 110.8 (4) |
O4A—N1A—C3A | 117.7 (4) | N3B—C2B—H2B | 124.6 |
C6A—C1A—C2A | 119.7 (3) | N1B—C2B—H2B | 124.6 |
C6A—C1A—C7A | 120.4 (3) | C2B—N3B—C3aB | 107.5 (3) |
C2A—C1A—C7A | 119.9 (3) | C2B—N3B—H3B | 126.2 |
C3A—C2A—C1A | 118.0 (3) | C3aB—N3B—H3B | 126.2 |
C3A—C2A—H2A | 121.0 | C3aB—C4B—C5B | 117.4 (4) |
C1A—C2A—H2A | 121.0 | C3aB—C4B—H4B | 121.3 |
C2A—C3A—C4A | 123.2 (3) | C5B—C4B—H4B | 121.3 |
C2A—C3A—N1A | 118.4 (3) | C4B—C5B—C6B | 120.2 (4) |
C4A—C3A—N1A | 118.4 (3) | C4B—C5B—H5B | 119.9 |
C5A—C4A—C3A | 117.7 (3) | C6B—C5B—H5B | 119.9 |
C5A—C4A—H4A | 121.2 | C7B—C6B—C5B | 123.1 (4) |
C3A—C4A—H4A | 121.2 | C7B—C6B—H6B | 118.4 |
C4A—C5A—C6A | 120.6 (4) | C5B—C6B—H6B | 118.4 |
C4A—C5A—H5A | 119.7 | C6B—C7B—C7aB | 116.0 (4) |
C6A—C5A—H5A | 119.7 | C6B—C7B—H7B | 122.0 |
C1A—C6A—C5A | 120.9 (3) | C7aB—C7B—H7B | 122.0 |
C1A—C6A—H6A | 119.6 | N1B—C7aB—C7B | 131.9 (4) |
C5A—C6A—H6A | 119.6 | N1B—C7aB—C3aB | 105.7 (3) |
O2A—C7A—O1A | 124.9 (3) | C7B—C7aB—C3aB | 122.4 (4) |
O2A—C7A—C1A | 118.8 (4) | C4B—C3aB—C7aB | 120.8 (3) |
O1A—C7A—C1A | 116.2 (3) | C4B—C3aB—N3B | 131.9 (3) |
C2B—N1B—C7aB | 108.7 (3) | C7aB—C3aB—N3B | 107.3 (3) |
C2B—N1B—H1B | 125.6 | ||
C6A—C1A—C2A—C3A | 0.1 (5) | C7aB—N1B—C2B—N3B | −0.1 (4) |
C7A—C1A—C2A—C3A | 179.8 (3) | N1B—C2B—N3B—C3aB | −0.1 (4) |
C1A—C2A—C3A—C4A | −0.4 (5) | C3aB—C4B—C5B—C6B | 0.2 (6) |
C1A—C2A—C3A—N1A | 180.0 (3) | C4B—C5B—C6B—C7B | −0.4 (7) |
O3A—N1A—C3A—C2A | 2.1 (5) | C5B—C6B—C7B—C7aB | 0.2 (6) |
O4A—N1A—C3A—C2A | −177.9 (4) | C2B—N1B—C7aB—C7B | 179.4 (4) |
O3A—N1A—C3A—C4A | −177.5 (4) | C2B—N1B—C7aB—C3aB | 0.3 (4) |
O4A—N1A—C3A—C4A | 2.5 (5) | C6B—C7B—C7aB—N1B | −178.7 (4) |
C2A—C3A—C4A—C5A | 0.5 (5) | C6B—C7B—C7aB—C3aB | 0.2 (6) |
N1A—C3A—C4A—C5A | −179.9 (3) | C5B—C4B—C3aB—C7aB | 0.2 (5) |
C3A—C4A—C5A—C6A | −0.1 (5) | C5B—C4B—C3aB—N3B | 179.0 (4) |
C2A—C1A—C6A—C5A | 0.2 (5) | N1B—C7aB—C3aB—C4B | 178.8 (3) |
C7A—C1A—C6A—C5A | −179.5 (3) | C7B—C7aB—C3aB—C4B | −0.4 (6) |
C4A—C5A—C6A—C1A | −0.2 (6) | N1B—C7aB—C3aB—N3B | −0.3 (4) |
C6A—C1A—C7A—O2A | 9.0 (5) | C7B—C7aB—C3aB—N3B | −179.5 (3) |
C2A—C1A—C7A—O2A | −170.7 (3) | C2B—N3B—C3aB—C4B | −178.7 (4) |
C6A—C1A—C7A—O1A | −170.9 (3) | C2B—N3B—C3aB—C7aB | 0.2 (4) |
C2A—C1A—C7A—O1A | 9.4 (5) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1B—H1B···O2Ai | 0.86 | 1.86 | 2.717 (4) | 177 |
N3B—H3B···O1A | 0.86 | 1.69 | 2.550 (3) | 178 |
C5B—H5B···O3Aii | 0.93 | 2.70 | 3.553 (6) | 153 |
C5A—H5A···O4Aiii | 0.93 | 2.71 | 3.340 (5) | 126 |
Symmetry codes: (i) −x+1, y+1/2, −z+1; (ii) −x+1, y−1/2, −z−1; (iii) −x, y−1/2, −z−2. |
C7H7N2+·C7H4NO4− | Dx = 1.429 Mg m−3 |
Mr = 285.26 | Melting point = 435–437 K |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 13.8524 (5) Å | Cell parameters from 22373 reflections |
b = 7.6666 (4) Å | θ = 3.0–30.0° |
c = 12.5193 (7) Å | µ = 0.11 mm−1 |
β = 94.1400 (17)° | T = 297 K |
V = 1326.09 (11) Å3 | Block, colourless |
Z = 4 | 0.60 × 0.38 × 0.33 mm |
F(000) = 592 |
Rigaku R-AXIS Rapid diffractometer | 2856 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.034 |
Graphite monochromator | θmax = 30.0°, θmin = 3.0° |
Detector resolution: 10 pixels mm-1 | h = −19→19 |
oscillation scans | k = −10→10 |
23459 measured reflections | l = −17→17 |
3869 independent reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.053 | H-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 reflections | Δρmax = 0.22 e Å−3 |
191 parameters | Δρmin = −0.19 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.017 (3) |
C7H7N2+·C7H4NO4− | V = 1326.09 (11) Å3 |
Mr = 285.26 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 13.8524 (5) Å | µ = 0.11 mm−1 |
b = 7.6666 (4) Å | T = 297 K |
c = 12.5193 (7) Å | 0.60 × 0.38 × 0.33 mm |
β = 94.1400 (17)° |
Rigaku R-AXIS Rapid diffractometer | 2856 reflections with I > 2σ(I) |
23459 measured reflections | Rint = 0.034 |
3869 independent reflections |
R[F2 > 2σ(F2)] = 0.053 | 0 restraints |
wR(F2) = 0.153 | H-atom parameters constrained |
S = 1.07 | Δρmax = 0.22 e Å−3 |
3869 reflections | Δρmin = −0.19 e Å−3 |
191 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
O1A | 0.27374 (8) | 0.28350 (18) | 0.35534 (9) | 0.0571 (3) | |
O2A | 0.34931 (7) | 0.09537 (17) | 0.46916 (9) | 0.0516 (3) | |
O3A | −0.12902 (9) | 0.2382 (3) | 0.64492 (13) | 0.0831 (5) | |
O4A | −0.05470 (11) | 0.0597 (3) | 0.75529 (13) | 0.0930 (6) | |
N1A | −0.05868 (10) | 0.1511 (2) | 0.67521 (12) | 0.0584 (4) | |
C1A | 0.18762 (9) | 0.17376 (19) | 0.49722 (11) | 0.0380 (3) | |
C2A | 0.10543 (10) | 0.2684 (2) | 0.46465 (13) | 0.0475 (4) | |
H2A | 0.1051 | 0.3376 | 0.4036 | 0.057* | |
C3A | 0.02391 (10) | 0.2609 (2) | 0.52211 (14) | 0.0501 (4) | |
H3A | −0.0316 | 0.3234 | 0.5003 | 0.060* | |
C4A | 0.02729 (10) | 0.1582 (2) | 0.61241 (12) | 0.0439 (3) | |
C5A | 0.10692 (11) | 0.0611 (2) | 0.64667 (13) | 0.0522 (4) | |
H5A | 0.1067 | −0.0077 | 0.7078 | 0.063* | |
C6A | 0.18778 (11) | 0.0686 (2) | 0.58728 (13) | 0.0487 (4) | |
H6A | 0.2423 | 0.0027 | 0.6081 | 0.058* | |
C7A | 0.27719 (9) | 0.1857 (2) | 0.43537 (11) | 0.0421 (3) | |
N1B | 0.55467 (9) | 0.46429 (19) | 0.18892 (10) | 0.0463 (3) | |
H1B | 0.5815 | 0.5001 | 0.1331 | 0.056* | |
C2B | 0.46107 (11) | 0.4322 (2) | 0.19447 (12) | 0.0458 (4) | |
H2B | 0.4142 | 0.4451 | 0.1380 | 0.055* | |
N3B | 0.44405 (9) | 0.37930 (19) | 0.29193 (10) | 0.0456 (3) | |
H3B | 0.3884 | 0.3521 | 0.3133 | 0.055* | |
C4B | 0.55510 (13) | 0.3278 (2) | 0.46050 (13) | 0.0520 (4) | |
H4B | 0.5081 | 0.2906 | 0.5048 | 0.062* | |
C5B | 0.65128 (14) | 0.3387 (3) | 0.49696 (15) | 0.0597 (5) | |
H5B | 0.6695 | 0.3076 | 0.5673 | 0.072* | |
C6B | 0.72176 (13) | 0.3953 (3) | 0.43094 (17) | 0.0633 (5) | |
H6B | 0.7858 | 0.4016 | 0.4586 | 0.076* | |
C7B | 0.69926 (11) | 0.4423 (3) | 0.32573 (16) | 0.0567 (4) | |
H7B | 0.7465 | 0.4800 | 0.2820 | 0.068* | |
C7aB | 0.60221 (10) | 0.4304 (2) | 0.28809 (12) | 0.0415 (3) | |
C3aB | 0.53164 (10) | 0.3751 (2) | 0.35423 (12) | 0.0403 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1A | 0.0380 (5) | 0.0857 (9) | 0.0490 (6) | −0.0013 (6) | 0.0140 (5) | 0.0177 (6) |
O2A | 0.0357 (5) | 0.0772 (8) | 0.0437 (6) | 0.0115 (5) | 0.0143 (4) | 0.0013 (5) |
O3A | 0.0408 (6) | 0.1263 (14) | 0.0853 (10) | 0.0152 (8) | 0.0258 (6) | 0.0015 (10) |
O4A | 0.0616 (9) | 0.1499 (17) | 0.0720 (9) | 0.0005 (10) | 0.0359 (7) | 0.0297 (10) |
N1A | 0.0376 (6) | 0.0861 (11) | 0.0536 (8) | −0.0065 (7) | 0.0184 (6) | −0.0085 (8) |
C1A | 0.0305 (6) | 0.0470 (7) | 0.0376 (7) | −0.0014 (5) | 0.0096 (5) | −0.0027 (6) |
C2A | 0.0359 (6) | 0.0595 (9) | 0.0483 (8) | 0.0037 (6) | 0.0108 (6) | 0.0112 (7) |
C3A | 0.0328 (6) | 0.0601 (10) | 0.0587 (9) | 0.0072 (6) | 0.0120 (6) | 0.0033 (8) |
C4A | 0.0327 (6) | 0.0570 (9) | 0.0439 (7) | −0.0055 (6) | 0.0152 (5) | −0.0079 (6) |
C5A | 0.0417 (7) | 0.0708 (11) | 0.0457 (8) | −0.0007 (7) | 0.0150 (6) | 0.0120 (8) |
C6A | 0.0354 (7) | 0.0628 (10) | 0.0494 (8) | 0.0059 (7) | 0.0122 (6) | 0.0098 (7) |
C7A | 0.0310 (6) | 0.0600 (9) | 0.0362 (7) | −0.0019 (6) | 0.0096 (5) | −0.0029 (6) |
N1B | 0.0394 (6) | 0.0614 (8) | 0.0397 (6) | −0.0060 (6) | 0.0133 (5) | 0.0019 (6) |
C2B | 0.0384 (7) | 0.0606 (9) | 0.0390 (7) | −0.0055 (7) | 0.0064 (6) | 0.0027 (7) |
N3B | 0.0340 (5) | 0.0623 (8) | 0.0416 (6) | −0.0039 (5) | 0.0103 (5) | 0.0065 (6) |
C4B | 0.0537 (9) | 0.0589 (9) | 0.0437 (8) | −0.0027 (7) | 0.0065 (7) | 0.0065 (7) |
C5B | 0.0623 (10) | 0.0610 (10) | 0.0536 (10) | −0.0002 (8) | −0.0101 (8) | 0.0062 (8) |
C6B | 0.0434 (8) | 0.0647 (11) | 0.0793 (13) | −0.0034 (8) | −0.0115 (8) | 0.0051 (10) |
C7B | 0.0358 (7) | 0.0650 (10) | 0.0698 (11) | −0.0060 (7) | 0.0069 (7) | 0.0026 (9) |
C7aB | 0.0367 (6) | 0.0448 (7) | 0.0438 (7) | −0.0009 (6) | 0.0096 (6) | −0.0015 (6) |
C3aB | 0.0360 (6) | 0.0450 (7) | 0.0406 (7) | −0.0014 (5) | 0.0072 (5) | 0.0000 (6) |
O1A—C7A | 1.2494 (19) | N1B—C7aB | 1.387 (2) |
O2A—C7A | 1.2632 (18) | N1B—H1B | 0.8600 |
O3A—N1A | 1.219 (2) | N3B—C2B | 1.3231 (19) |
O4A—N1A | 1.221 (2) | C2B—H2B | 0.9300 |
N1A—C4A | 1.4746 (17) | N3B—C3aB | 1.3947 (19) |
C1A—C6A | 1.386 (2) | N3B—H3B | 0.8600 |
C1A—C2A | 1.386 (2) | C4B—C5B | 1.379 (2) |
C1A—C7A | 1.5120 (17) | C4B—C3aB | 1.395 (2) |
C2A—C3A | 1.383 (2) | C4B—H4B | 0.9300 |
C2A—H2A | 0.9300 | C5B—C6B | 1.393 (3) |
C3A—C4A | 1.376 (2) | C5B—H5B | 0.9300 |
C3A—H3A | 0.9300 | C6B—C7B | 1.379 (3) |
C4A—C5A | 1.374 (2) | C6B—H6B | 0.9300 |
C5A—C6A | 1.3896 (19) | C7B—C7aB | 1.395 (2) |
C5A—H5A | 0.9300 | C7B—H7B | 0.9300 |
C6A—H6A | 0.9300 | C7aB—C3aB | 1.3922 (19) |
N1B—C2B | 1.3265 (18) | ||
O3A—N1A—O4A | 123.88 (14) | C7aB—N1B—H1B | 125.6 |
O3A—N1A—C4A | 118.16 (16) | N3B—C2B—N1B | 110.19 (14) |
O4A—N1A—C4A | 117.95 (15) | N3B—C2B—H2B | 124.9 |
C6A—C1A—C2A | 119.79 (12) | N1B—C2B—H2B | 124.9 |
C6A—C1A—C7A | 119.91 (13) | C2B—N3B—C3aB | 108.49 (12) |
C2A—C1A—C7A | 120.30 (13) | C2B—N3B—H3B | 125.8 |
C3A—C2A—C1A | 120.61 (14) | C3aB—N3B—H3B | 125.8 |
C3A—C2A—H2A | 119.7 | C5B—C4B—C3aB | 116.93 (15) |
C1A—C2A—H2A | 119.7 | C5B—C4B—H4B | 121.5 |
C4A—C3A—C2A | 118.08 (14) | C3aB—C4B—H4B | 121.5 |
C4A—C3A—H3A | 121.0 | C4B—C5B—C6B | 121.61 (17) |
C2A—C3A—H3A | 121.0 | C4B—C5B—H5B | 119.2 |
C5A—C4A—C3A | 123.07 (13) | C6B—C5B—H5B | 119.2 |
C5A—C4A—N1A | 118.34 (14) | C7B—C6B—C5B | 121.88 (16) |
C3A—C4A—N1A | 118.59 (14) | C7B—C6B—H6B | 119.1 |
C4A—C5A—C6A | 118.08 (15) | C5B—C6B—H6B | 119.1 |
C4A—C5A—H5A | 121.0 | C6B—C7B—C7aB | 116.84 (15) |
C6A—C5A—H5A | 121.0 | C6B—C7B—H7B | 121.6 |
C1A—C6A—C5A | 120.36 (14) | C7aB—C7B—H7B | 121.6 |
C1A—C6A—H6A | 119.8 | N1B—C7aB—C3aB | 106.32 (12) |
C5A—C6A—H6A | 119.8 | N1B—C7aB—C7B | 132.36 (14) |
O1A—C7A—O2A | 125.53 (12) | C3aB—C7aB—C7B | 121.32 (15) |
O1A—C7A—C1A | 117.49 (13) | C7aB—C3aB—C4B | 121.43 (14) |
O2A—C7A—C1A | 116.98 (13) | C7aB—C3aB—N3B | 106.27 (12) |
C2B—N1B—C7aB | 108.73 (12) | C4B—C3aB—N3B | 132.30 (13) |
C2B—N1B—H1B | 125.6 | ||
C6A—C1A—C2A—C3A | 0.9 (3) | C7aB—N1B—C2B—N3B | 0.10 (19) |
C7A—C1A—C2A—C3A | −178.65 (15) | N1B—C2B—N3B—C3aB | −0.39 (19) |
C1A—C2A—C3A—C4A | 0.5 (3) | C3aB—C4B—C5B—C6B | 0.4 (3) |
C2A—C3A—C4A—C5A | −1.2 (3) | C4B—C5B—C6B—C7B | −0.4 (3) |
C2A—C3A—C4A—N1A | 179.15 (15) | C5B—C6B—C7B—C7aB | 0.0 (3) |
O3A—N1A—C4A—C5A | 179.58 (17) | C2B—N1B—C7aB—C3aB | 0.22 (17) |
O4A—N1A—C4A—C5A | 0.5 (3) | C2B—N1B—C7aB—C7B | 179.98 (18) |
O3A—N1A—C4A—C3A | −0.7 (2) | C6B—C7B—C7aB—N1B | −179.22 (17) |
O4A—N1A—C4A—C3A | −179.87 (18) | C6B—C7B—C7aB—C3aB | 0.5 (3) |
C3A—C4A—C5A—C6A | 0.5 (3) | N1B—C7aB—C3aB—C4B | 179.24 (15) |
N1A—C4A—C5A—C6A | −179.88 (16) | C7B—C7aB—C3aB—C4B | −0.5 (2) |
C2A—C1A—C6A—C5A | −1.7 (3) | N1B—C7aB—C3aB—N3B | −0.44 (17) |
C7A—C1A—C6A—C5A | 177.90 (15) | C7B—C7aB—C3aB—N3B | 179.77 (15) |
C4A—C5A—C6A—C1A | 1.0 (3) | C5B—C4B—C3aB—C7aB | 0.1 (3) |
C6A—C1A—C7A—O1A | −179.36 (15) | C5B—C4B—C3aB—N3B | 179.69 (17) |
C2A—C1A—C7A—O1A | 0.2 (2) | C2B—N3B—C3aB—C7aB | 0.51 (18) |
C6A—C1A—C7A—O2A | 0.8 (2) | C2B—N3B—C3aB—C4B | −179.12 (18) |
C2A—C1A—C7A—O2A | −179.65 (15) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1B—H1B···O2Ai | 0.86 | 1.81 | 2.6600 (15) | 171 |
N3B—H3B···O1A | 0.86 | 1.79 | 2.6469 (15) | 177 |
C2B—H2B···O2Aii | 0.93 | 2.26 | 3.125 (2) | 155 |
C6B—H6B···O3Aiii | 0.93 | 2.83 | 3.478 (3) | 128 |
Symmetry codes: (i) −x+1, y+1/2, −z+1/2; (ii) x, −y+1/2, z−1/2; (iii) x+1, y, z. |
C6H5N3·C7H5NO4 | Dx = 1.451 Mg m−3 |
Mr = 286.25 | Melting point = 406.0–406.5 K |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 14.342 (3) Å | Cell parameters from 1254 reflections |
b = 5.218 (1) Å | θ = 1.6–27.5° |
c = 18.161 (4) Å | µ = 0.11 mm−1 |
β = 105.40 (1)° | T = 297 K |
V = 1310.3 (5) Å3 | Needle, colourless |
Z = 4 | 0.35 × 0.15 × 0.10 mm |
F(000) = 592 |
MacScience DIP3000 diffractometer | 1486 reflections with I > 2σ(I) |
Radiation source: fine-focus rotating anode | Rint = 0.030 |
Graphite monochromator | θmax = 26.5°, θmin = 1.6° |
Detector resolution: 10 pixels mm-1 | h = −18→18 |
Weissenberg scans | k = −6→6 |
12254 measured reflections | l = −22→18 |
2465 independent reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.072 | H 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 reflections | Δρmax = 0.28 e Å−3 |
194 parameters | Δρmin = −0.29 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.015 (2) |
C6H5N3·C7H5NO4 | V = 1310.3 (5) Å3 |
Mr = 286.25 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 14.342 (3) Å | µ = 0.11 mm−1 |
b = 5.218 (1) Å | T = 297 K |
c = 18.161 (4) Å | 0.35 × 0.15 × 0.10 mm |
β = 105.40 (1)° |
MacScience DIP3000 diffractometer | 1486 reflections with I > 2σ(I) |
12254 measured reflections | Rint = 0.030 |
2465 independent reflections |
R[F2 > 2σ(F2)] = 0.072 | 0 restraints |
wR(F2) = 0.184 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.08 | Δρmax = 0.28 e Å−3 |
2465 reflections | Δρmin = −0.29 e Å−3 |
194 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
O1A | 0.3557 (2) | 0.9910 (5) | 0.47011 (15) | 0.0699 (8) | |
O2A | 0.34841 (19) | 1.0822 (5) | 0.34783 (14) | 0.0600 (7) | |
H22A | 0.400 (3) | 0.943 (7) | 0.355 (2) | 0.072* | |
O3A | 0.1456 (3) | 1.4581 (7) | 0.59382 (19) | 0.0980 (12) | |
O4A | 0.0607 (3) | 1.7732 (8) | 0.53840 (19) | 0.1115 (13) | |
N1A | 0.1172 (3) | 1.5998 (8) | 0.5396 (2) | 0.0699 (10) | |
C1A | 0.2507 (2) | 1.3212 (6) | 0.40831 (19) | 0.0460 (8) | |
C2A | 0.2180 (3) | 1.3651 (7) | 0.4728 (2) | 0.0510 (9) | |
H2A | 0.2412 | 1.2676 | 0.5167 | 0.061* | |
C3A | 0.1509 (2) | 1.5541 (7) | 0.4706 (2) | 0.0492 (9) | |
C4A | 0.1142 (3) | 1.7018 (7) | 0.4073 (2) | 0.0587 (10) | |
H4A | 0.0686 | 1.8287 | 0.4072 | 0.070* | |
C5A | 0.1470 (3) | 1.6564 (8) | 0.3433 (2) | 0.0622 (11) | |
H5A | 0.1232 | 1.7542 | 0.2995 | 0.075* | |
C6A | 0.2145 (3) | 1.4679 (7) | 0.3437 (2) | 0.0538 (9) | |
H6A | 0.2358 | 1.4394 | 0.3003 | 0.065* | |
C7A | 0.3237 (3) | 1.1141 (7) | 0.4124 (2) | 0.0505 (9) | |
N1B | 0.5496 (2) | 0.3927 (6) | 0.42715 (16) | 0.0530 (8) | |
H1B | 0.5680 | 0.2917 | 0.4657 | 0.064* | |
N2B | 0.4876 (2) | 0.5872 (6) | 0.42285 (17) | 0.0588 (9) | |
N3B | 0.4754 (2) | 0.7019 (6) | 0.35674 (17) | 0.0556 (8) | |
C3aB | 0.5316 (2) | 0.5756 (6) | 0.31697 (19) | 0.0449 (8) | |
C4B | 0.5450 (3) | 0.6218 (7) | 0.2444 (2) | 0.0519 (9) | |
H4B | 0.5145 | 0.7570 | 0.2141 | 0.062* | |
C5B | 0.6055 (3) | 0.4577 (7) | 0.2204 (2) | 0.0565 (10) | |
H5B | 0.6158 | 0.4811 | 0.1724 | 0.068* | |
C6B | 0.6519 (3) | 0.2569 (8) | 0.2661 (2) | 0.0588 (10) | |
H6B | 0.6919 | 0.1496 | 0.2473 | 0.071* | |
C7B | 0.6411 (3) | 0.2105 (7) | 0.3375 (2) | 0.0564 (10) | |
H7B | 0.6729 | 0.0765 | 0.3677 | 0.068* | |
C7aB | 0.5796 (2) | 0.3764 (6) | 0.36203 (19) | 0.0444 (8) |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1A | 0.082 (2) | 0.0759 (18) | 0.0502 (17) | 0.0310 (16) | 0.0144 (15) | 0.0123 (15) |
O2A | 0.0659 (17) | 0.0650 (17) | 0.0498 (16) | 0.0190 (14) | 0.0166 (14) | 0.0044 (13) |
O3A | 0.120 (3) | 0.121 (3) | 0.065 (2) | 0.012 (2) | 0.046 (2) | 0.011 (2) |
O4A | 0.128 (3) | 0.129 (3) | 0.086 (3) | 0.054 (3) | 0.042 (2) | −0.013 (2) |
N1A | 0.069 (2) | 0.084 (3) | 0.059 (3) | 0.002 (2) | 0.022 (2) | −0.010 (2) |
C1A | 0.0468 (19) | 0.0473 (18) | 0.041 (2) | 0.0029 (15) | 0.0071 (17) | 0.0054 (16) |
C2A | 0.057 (2) | 0.053 (2) | 0.042 (2) | −0.0037 (18) | 0.0101 (18) | 0.0026 (17) |
C3A | 0.047 (2) | 0.054 (2) | 0.048 (2) | 0.0004 (17) | 0.0144 (17) | −0.0022 (18) |
C4A | 0.058 (2) | 0.056 (2) | 0.061 (3) | 0.0107 (19) | 0.014 (2) | 0.003 (2) |
C5A | 0.065 (2) | 0.067 (2) | 0.051 (2) | 0.013 (2) | 0.009 (2) | 0.015 (2) |
C6A | 0.055 (2) | 0.060 (2) | 0.047 (2) | 0.0096 (18) | 0.0133 (18) | 0.0049 (18) |
C7A | 0.052 (2) | 0.053 (2) | 0.043 (2) | 0.0046 (18) | 0.0081 (18) | −0.0014 (18) |
N1B | 0.0579 (18) | 0.0595 (18) | 0.0425 (18) | 0.0149 (16) | 0.0151 (15) | 0.0093 (15) |
N2B | 0.063 (2) | 0.065 (2) | 0.051 (2) | 0.0183 (17) | 0.0205 (17) | 0.0049 (16) |
N3B | 0.0628 (19) | 0.0596 (18) | 0.0466 (19) | 0.0141 (16) | 0.0181 (16) | 0.0037 (15) |
C3aB | 0.0443 (19) | 0.0489 (19) | 0.042 (2) | −0.0006 (16) | 0.0117 (16) | −0.0034 (16) |
C4B | 0.056 (2) | 0.054 (2) | 0.046 (2) | −0.0048 (18) | 0.0140 (18) | 0.0034 (18) |
C5B | 0.060 (2) | 0.065 (2) | 0.048 (2) | −0.008 (2) | 0.022 (2) | −0.0057 (19) |
C6B | 0.054 (2) | 0.067 (2) | 0.060 (3) | 0.003 (2) | 0.023 (2) | −0.007 (2) |
C7B | 0.055 (2) | 0.056 (2) | 0.060 (2) | 0.0140 (18) | 0.019 (2) | 0.0014 (19) |
C7aB | 0.0441 (18) | 0.0487 (19) | 0.039 (2) | −0.0017 (16) | 0.0079 (16) | 0.0003 (16) |
O1A—C7A | 1.211 (4) | C6A—H6A | 0.9300 |
O2A—C7A | 1.323 (4) | N1B—N2B | 1.338 (4) |
O2A—H22A | 1.02 (4) | N1B—C7aB | 1.365 (4) |
O3A—N1A | 1.213 (4) | N1B—H1B | 0.8600 |
O4A—N1A | 1.211 (4) | N2B—N3B | 1.311 (4) |
N1A—C3A | 1.476 (4) | N3B—C3aB | 1.384 (4) |
C1A—C6A | 1.381 (5) | C3aB—C7aB | 1.388 (5) |
C1A—C2A | 1.391 (5) | C3aB—C4B | 1.402 (4) |
C1A—C7A | 1.492 (5) | C4B—C5B | 1.370 (5) |
C2A—C3A | 1.371 (5) | C4B—H4B | 0.9300 |
C2A—H2A | 0.9300 | C5B—C6B | 1.391 (5) |
C3A—C4A | 1.369 (5) | C5B—H5B | 0.9300 |
C4A—C5A | 1.385 (5) | C6B—C7B | 1.368 (5) |
C4A—H4A | 0.9300 | C6B—H6B | 0.9300 |
C5A—C6A | 1.379 (5) | C7B—C7aB | 1.390 (4) |
C5A—H5A | 0.9300 | C7B—H7B | 0.9300 |
C7A—O2A—H22A | 110 (2) | O2A—C7A—C1A | 113.3 (3) |
O4A—N1A—O3A | 123.3 (4) | N2B—N1B—C7aB | 110.8 (3) |
O4A—N1A—C3A | 118.3 (4) | N2B—N1B—H1B | 124.6 |
O3A—N1A—C3A | 118.4 (4) | C7aB—N1B—H1B | 124.6 |
C6A—C1A—C2A | 119.2 (3) | N3B—N2B—N1B | 109.0 (3) |
C6A—C1A—C7A | 123.0 (3) | N2B—N3B—C3aB | 107.8 (3) |
C2A—C1A—C7A | 117.8 (3) | N3B—C3aB—C7aB | 108.4 (3) |
C3A—C2A—C1A | 119.1 (3) | N3B—C3aB—C4B | 130.8 (3) |
C3A—C2A—H2A | 120.5 | C7aB—C3aB—C4B | 120.8 (3) |
C1A—C2A—H2A | 120.5 | C5B—C4B—C3aB | 116.7 (3) |
C4A—C3A—C2A | 122.6 (3) | C5B—C4B—H4B | 121.7 |
C4A—C3A—N1A | 118.9 (3) | C3aB—C4B—H4B | 121.7 |
C2A—C3A—N1A | 118.5 (3) | C4B—C5B—C6B | 121.6 (3) |
C3A—C4A—C5A | 118.0 (3) | C4B—C5B—H5B | 119.2 |
C3A—C4A—H4A | 121.0 | C6B—C5B—H5B | 119.2 |
C5A—C4A—H4A | 121.0 | C7B—C6B—C5B | 122.9 (3) |
C6A—C5A—C4A | 120.8 (4) | C7B—C6B—H6B | 118.6 |
C6A—C5A—H5A | 119.6 | C5B—C6B—H6B | 118.6 |
C4A—C5A—H5A | 119.6 | C6B—C7B—C7aB | 115.7 (3) |
C5A—C6A—C1A | 120.4 (3) | C6B—C7B—H7B | 122.1 |
C5A—C6A—H6A | 119.8 | C7aB—C7B—H7B | 122.1 |
C1A—C6A—H6A | 119.8 | N1B—C7aB—C3aB | 104.0 (3) |
O1A—C7A—O2A | 124.8 (3) | N1B—C7aB—C7B | 133.6 (3) |
O1A—C7A—C1A | 121.8 (3) | C3aB—C7aB—C7B | 122.4 (3) |
C6A—C1A—C2A—C3A | −0.4 (5) | C7aB—N1B—N2B—N3B | −0.1 (4) |
C7A—C1A—C2A—C3A | −180.0 (3) | N1B—N2B—N3B—C3aB | 0.1 (4) |
C1A—C2A—C3A—C4A | 0.3 (5) | N2B—N3B—C3aB—C7aB | −0.1 (4) |
C1A—C2A—C3A—N1A | −179.6 (3) | N2B—N3B—C3aB—C4B | −179.5 (4) |
O4A—N1A—C3A—C4A | −2.6 (6) | N3B—C3aB—C4B—C5B | −179.2 (4) |
O3A—N1A—C3A—C4A | 175.6 (4) | C7aB—C3aB—C4B—C5B | 1.5 (5) |
O4A—N1A—C3A—C2A | 177.3 (4) | C3aB—C4B—C5B—C6B | −0.6 (5) |
O3A—N1A—C3A—C2A | −4.5 (5) | C4B—C5B—C6B—C7B | −0.5 (6) |
C2A—C3A—C4A—C5A | −0.1 (6) | C5B—C6B—C7B—C7aB | 0.5 (6) |
N1A—C3A—C4A—C5A | 179.8 (3) | N2B—N1B—C7aB—C3aB | 0.0 (4) |
C3A—C4A—C5A—C6A | 0.0 (6) | N2B—N1B—C7aB—C7B | −178.8 (4) |
C4A—C5A—C6A—C1A | −0.1 (6) | N3B—C3aB—C7aB—N1B | 0.1 (4) |
C2A—C1A—C6A—C5A | 0.3 (5) | C4B—C3aB—C7aB—N1B | 179.5 (3) |
C7A—C1A—C6A—C5A | 179.9 (3) | N3B—C3aB—C7aB—C7B | 179.1 (3) |
C6A—C1A—C7A—O1A | 178.6 (4) | C4B—C3aB—C7aB—C7B | −1.5 (5) |
C2A—C1A—C7A—O1A | −1.8 (5) | C6B—C7B—C7aB—N1B | 179.1 (4) |
C6A—C1A—C7A—O2A | −1.3 (5) | C6B—C7B—C7aB—C3aB | 0.4 (5) |
C2A—C1A—C7A—O2A | 178.3 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
O2A—H22A···N3B | 1.02 (4) | 1.65 (4) | 2.669 (4) | 173 (3) |
N1B—H1B···O1Ai | 0.86 | 2.01 | 2.826 (4) | 157 |
N1B—H1B···N2Bi | 0.86 | 2.45 | 2.913 (4) | 115 |
C5B—H5B···O4Aii | 0.93 | 2.68 | 3.490 (5) | 146 |
C6B—H6B···O3Aiii | 0.93 | 2.75 | 3.303 (5) | 119 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x+1/2, −y+5/2, z−1/2; (iii) x+1/2, −y+3/2, z−1/2. |
C3H5N2+·C7H4NO4− | Dx = 1.516 Mg m−3 |
Mr = 235.20 | Melting point = 436–438 K |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 5.826 (2) Å | Cell parameters from 25 reflections |
b = 23.411 (7) Å | θ = 10–15° |
c = 7.556 (2) Å | µ = 0.12 mm−1 |
β = 90.53 (3)° | T = 297 K |
V = 1030.5 (6) Å3 | Plate, colourless |
Z = 4 | 0.35 × 0.23 × 0.08 mm |
F(000) = 488 |
Rigaku AFC-5R diffractometer | Rint = 0.052 |
Radiation source: normal-focus rotating anode | θmax = 27.5°, θmin = 2.8° |
Graphite monochromator | h = −7→7 |
ω scans | k = 0→30 |
4708 measured reflections | l = −9→9 |
2361 independent reflections | 3 standard reflections every 100 reflections |
1081 reflections with I > 2σ(I) | intensity decay: 0.6% |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.044 | H-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 reflections | Δρmax = 0.17 e Å−3 |
155 parameters | Δρmin = −0.17 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0090 (17) |
C3H5N2+·C7H4NO4− | V = 1030.5 (6) Å3 |
Mr = 235.20 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 5.826 (2) Å | µ = 0.12 mm−1 |
b = 23.411 (7) Å | T = 297 K |
c = 7.556 (2) Å | 0.35 × 0.23 × 0.08 mm |
β = 90.53 (3)° |
Rigaku AFC-5R diffractometer | Rint = 0.052 |
4708 measured reflections | 3 standard reflections every 100 reflections |
2361 independent reflections | intensity decay: 0.6% |
1081 reflections with I > 2σ(I) |
R[F2 > 2σ(F2)] = 0.044 | 0 restraints |
wR(F2) = 0.131 | H-atom parameters constrained |
S = 0.98 | Δρmax = 0.17 e Å−3 |
2361 reflections | Δρmin = −0.17 e Å−3 |
155 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
O1A | 0.7697 (3) | 0.14776 (7) | 0.3964 (3) | 0.0579 (5) | |
O2A | 0.5254 (3) | 0.09743 (7) | 0.5603 (3) | 0.0588 (6) | |
O3A | 0.7467 (3) | 0.35449 (8) | 0.4398 (3) | 0.0719 (6) | |
O4A | 0.4471 (4) | 0.39762 (8) | 0.5377 (3) | 0.0834 (7) | |
N1A | 0.5558 (4) | 0.35409 (9) | 0.5048 (3) | 0.0536 (6) | |
C1A | 0.4715 (4) | 0.19711 (9) | 0.5409 (3) | 0.0351 (5) | |
C2A | 0.5675 (4) | 0.24973 (9) | 0.5027 (3) | 0.0335 (5) | |
H2A | 0.7099 | 0.2519 | 0.4485 | 0.040* | |
C3A | 0.4500 (4) | 0.29888 (9) | 0.5457 (3) | 0.0391 (6) | |
C4A | 0.2364 (4) | 0.29772 (12) | 0.6247 (3) | 0.0481 (7) | |
H4A | 0.1596 | 0.3313 | 0.6529 | 0.058* | |
C5A | 0.1416 (4) | 0.24485 (12) | 0.6601 (3) | 0.0517 (7) | |
H5A | −0.0026 | 0.2427 | 0.7114 | 0.062* | |
C6A | 0.2573 (4) | 0.19546 (11) | 0.6205 (3) | 0.0446 (6) | |
H6A | 0.1914 | 0.1604 | 0.6473 | 0.054* | |
C7A | 0.5982 (4) | 0.14308 (10) | 0.4954 (3) | 0.0422 (6) | |
N1B | 1.1590 (3) | −0.02477 (8) | 0.2889 (3) | 0.0462 (5) | |
H1B | 1.2744 | −0.0470 | 0.3067 | 0.055* | |
C2B | 1.1449 (4) | 0.02922 (10) | 0.3415 (3) | 0.0463 (6) | |
H2B | 1.2574 | 0.0493 | 0.4037 | 0.056* | |
N3B | 0.9446 (4) | 0.04946 (8) | 0.2905 (3) | 0.0466 (6) | |
H3B | 0.8959 | 0.0836 | 0.3086 | 0.056* | |
C4B | 0.8267 (4) | 0.00735 (11) | 0.2042 (3) | 0.0481 (6) | |
H4B | 0.6799 | 0.0103 | 0.1556 | 0.058* | |
C5B | 0.9616 (4) | −0.03922 (11) | 0.2023 (3) | 0.0485 (6) | |
H5B | 0.9269 | −0.0744 | 0.1517 | 0.058* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1A | 0.0570 (11) | 0.0405 (10) | 0.0764 (14) | 0.0069 (9) | 0.0161 (10) | −0.0075 (9) |
O2A | 0.0568 (11) | 0.0348 (10) | 0.0848 (15) | −0.0028 (9) | −0.0091 (10) | 0.0135 (9) |
O3A | 0.0642 (13) | 0.0511 (12) | 0.1005 (17) | −0.0125 (10) | 0.0043 (12) | 0.0142 (11) |
O4A | 0.1005 (16) | 0.0359 (10) | 0.114 (2) | 0.0160 (11) | −0.0201 (14) | −0.0108 (11) |
N1A | 0.0623 (15) | 0.0346 (12) | 0.0635 (15) | 0.0047 (11) | −0.0183 (12) | −0.0013 (11) |
C1A | 0.0335 (12) | 0.0373 (12) | 0.0343 (13) | 0.0003 (10) | −0.0053 (10) | −0.0010 (11) |
C2A | 0.0295 (11) | 0.0376 (12) | 0.0332 (12) | 0.0019 (9) | −0.0006 (9) | −0.0012 (10) |
C3A | 0.0408 (14) | 0.0363 (13) | 0.0400 (14) | 0.0049 (11) | −0.0077 (10) | −0.0018 (11) |
C4A | 0.0433 (14) | 0.0574 (17) | 0.0434 (15) | 0.0155 (12) | −0.0081 (12) | −0.0102 (13) |
C5A | 0.0319 (13) | 0.085 (2) | 0.0387 (14) | 0.0046 (13) | 0.0021 (10) | 0.0001 (15) |
C6A | 0.0391 (13) | 0.0534 (15) | 0.0412 (15) | −0.0069 (11) | −0.0051 (11) | 0.0078 (12) |
C7A | 0.0429 (13) | 0.0345 (13) | 0.0490 (15) | −0.0018 (11) | −0.0123 (12) | −0.0011 (11) |
N1B | 0.0481 (12) | 0.0368 (11) | 0.0539 (13) | 0.0071 (9) | 0.0086 (10) | 0.0098 (10) |
C2B | 0.0535 (15) | 0.0410 (14) | 0.0444 (15) | −0.0046 (12) | 0.0046 (12) | 0.0066 (12) |
N3B | 0.0532 (12) | 0.0361 (12) | 0.0508 (14) | 0.0079 (10) | 0.0098 (10) | 0.0040 (10) |
C4B | 0.0461 (14) | 0.0514 (16) | 0.0469 (15) | 0.0018 (13) | 0.0011 (12) | 0.0019 (13) |
C5B | 0.0566 (16) | 0.0394 (14) | 0.0496 (16) | −0.0038 (12) | 0.0050 (12) | −0.0011 (12) |
O1A—C7A | 1.258 (3) | C5A—C6A | 1.373 (3) |
O2A—C7A | 1.252 (3) | C5A—H5A | 0.9300 |
O3A—N1A | 1.220 (3) | C6A—H6A | 0.9300 |
O4A—N1A | 1.227 (3) | N1B—C2B | 1.328 (3) |
N1A—C3A | 1.466 (3) | N1B—C5B | 1.361 (3) |
C1A—C2A | 1.384 (3) | N1B—H1B | 0.8600 |
C1A—C6A | 1.391 (3) | N3B—C2B | 1.314 (3) |
C1A—C7A | 1.506 (3) | C2B—H2B | 0.9300 |
C2A—C3A | 1.379 (3) | N3B—C4B | 1.364 (3) |
C2A—H2A | 0.9300 | N3B—H3B | 0.8600 |
C3A—C4A | 1.386 (3) | C4B—C5B | 1.344 (3) |
C4A—C5A | 1.382 (4) | C4B—H4B | 0.9300 |
C4A—H4A | 0.9300 | C5B—H5B | 0.9300 |
O3A—N1A—O4A | 123.3 (2) | C1A—C6A—H6A | 119.5 |
O3A—N1A—C3A | 118.6 (2) | O2A—C7A—O1A | 125.5 (2) |
O4A—N1A—C3A | 118.1 (2) | O2A—C7A—C1A | 117.3 (2) |
C2A—C1A—C6A | 118.7 (2) | O1A—C7A—C1A | 117.1 (2) |
C2A—C1A—C7A | 120.0 (2) | C2B—N1B—C5B | 109.0 (2) |
C6A—C1A—C7A | 121.3 (2) | C2B—N1B—H1B | 125.5 |
C3A—C2A—C1A | 119.4 (2) | C5B—N1B—H1B | 125.5 |
C3A—C2A—H2A | 120.3 | N3B—C2B—N1B | 108.2 (2) |
C1A—C2A—H2A | 120.3 | N3B—C2B—H2B | 125.9 |
C2A—C3A—C4A | 122.3 (2) | N1B—C2B—H2B | 125.9 |
C2A—C3A—N1A | 118.4 (2) | C2B—N3B—C4B | 108.8 (2) |
C4A—C3A—N1A | 119.3 (2) | C2B—N3B—H3B | 125.6 |
C5A—C4A—C3A | 117.6 (2) | C4B—N3B—H3B | 125.6 |
C5A—C4A—H4A | 121.2 | C5B—C4B—N3B | 107.4 (2) |
C3A—C4A—H4A | 121.2 | C5B—C4B—H4B | 126.3 |
C6A—C5A—C4A | 121.0 (2) | N3B—C4B—H4B | 126.3 |
C6A—C5A—H5A | 119.5 | C4B—C5B—N1B | 106.6 (2) |
C4A—C5A—H5A | 119.5 | C4B—C5B—H5B | 126.7 |
C5A—C6A—C1A | 121.0 (2) | N1B—C5B—H5B | 126.7 |
C5A—C6A—H6A | 119.5 | ||
C6A—C1A—C2A—C3A | 0.6 (3) | C2A—C1A—C6A—C5A | 0.3 (3) |
C7A—C1A—C2A—C3A | −179.7 (2) | C7A—C1A—C6A—C5A | −179.4 (2) |
C1A—C2A—C3A—C4A | −0.7 (3) | C2A—C1A—C7A—O2A | 167.4 (2) |
C1A—C2A—C3A—N1A | 179.7 (2) | C6A—C1A—C7A—O2A | −12.9 (3) |
O3A—N1A—C3A—C2A | −2.4 (3) | C2A—C1A—C7A—O1A | −12.0 (3) |
O4A—N1A—C3A—C2A | 177.5 (2) | C6A—C1A—C7A—O1A | 167.7 (2) |
O3A—N1A—C3A—C4A | 178.0 (2) | C5B—N1B—C2B—N3B | −0.1 (3) |
O4A—N1A—C3A—C4A | −2.1 (3) | N1B—C2B—N3B—C4B | 0.4 (3) |
C2A—C3A—C4A—C5A | 0.0 (3) | C2B—N3B—C4B—C5B | −0.6 (3) |
N1A—C3A—C4A—C5A | 179.6 (2) | N3B—C4B—C5B—N1B | 0.5 (3) |
C3A—C4A—C5A—C6A | 1.0 (3) | C2B—N1B—C5B—C4B | −0.2 (3) |
C4A—C5A—C6A—C1A | −1.1 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1B—H1B···O2Ai | 0.86 | 1.93 | 2.745 (3) | 157 |
N3B—H3B···O1A | 0.86 | 1.80 | 2.644 (3) | 166 |
C4B—H4B···O4Aii | 0.93 | 2.69 | 3.372 (3) | 130 |
C5B—H5B···O3Aiii | 0.93 | 2.62 | 3.204 (3) | 121 |
Symmetry codes: (i) −x+2, −y, −z+1; (ii) x, −y+1/2, z−1/2; (iii) −x+2, y−1/2, −z+1/2. |
C3H5N2+·C7H4NO4− | F(000) = 244 |
Mr = 235.20 | Dx = 1.531 Mg m−3 |
Triclinic, P1 | Melting point = 468–469 K |
a = 7.5395 (7) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 11.8374 (15) Å | Cell parameters from 25 reflections |
c = 5.9689 (12) Å | θ = 10–15° |
α = 100.145 (14)° | µ = 0.12 mm−1 |
β = 90.731 (13)° | T = 297 K |
γ = 102.998 (9)° | Plate, colourless |
V = 510.19 (13) Å3 | 0.43 × 0.20 × 0.10 mm |
Z = 2 |
Rigaku AFC-5R diffractometer | Rint = 0.033 |
Radiation source: normal-focus rotating anode | θmax = 30.0°, θmin = 2.8° |
Graphite monochromator | h = −10→10 |
ω/2θ scans | k = −16→16 |
6177 measured reflections | l = −8→8 |
2988 independent reflections | 3 standard reflections every 100 reflections |
1679 reflections with I > 2σ(I) | intensity decay: 0.0% |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.047 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.140 | H-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 parameters | Δρmax = 0.21 e Å−3 |
0 restraints | Δρmin = −0.28 e Å−3 |
C3H5N2+·C7H4NO4− | γ = 102.998 (9)° |
Mr = 235.20 | V = 510.19 (13) Å3 |
Triclinic, P1 | Z = 2 |
a = 7.5395 (7) Å | Mo Kα radiation |
b = 11.8374 (15) Å | µ = 0.12 mm−1 |
c = 5.9689 (12) Å | T = 297 K |
α = 100.145 (14)° | 0.43 × 0.20 × 0.10 mm |
β = 90.731 (13)° |
Rigaku AFC-5R diffractometer | Rint = 0.033 |
6177 measured reflections | 3 standard reflections every 100 reflections |
2988 independent reflections | intensity decay: 0.0% |
1679 reflections with I > 2σ(I) |
R[F2 > 2σ(F2)] = 0.047 | 0 restraints |
wR(F2) = 0.140 | H-atom parameters constrained |
S = 1.00 | Δρmax = 0.21 e Å−3 |
2988 reflections | Δρmin = −0.28 e Å−3 |
154 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
O1A | −0.00788 (19) | 0.30138 (10) | 0.3639 (2) | 0.0509 (4) | |
O2A | 0.12014 (19) | 0.19374 (10) | 0.0960 (2) | 0.0495 (3) | |
O3A | 0.4107 (2) | 0.79860 (11) | −0.0484 (3) | 0.0671 (5) | |
O4A | 0.4693 (2) | 0.68839 (13) | −0.3542 (3) | 0.0685 (5) | |
N1A | 0.4066 (2) | 0.70209 (13) | −0.1660 (3) | 0.0462 (4) | |
C1A | 0.1692 (2) | 0.39848 (13) | 0.0991 (2) | 0.0307 (3) | |
C2A | 0.1707 (2) | 0.51001 (13) | 0.2229 (3) | 0.0332 (3) | |
H2A | 0.1192 | 0.5175 | 0.3639 | 0.040* | |
C3A | 0.2489 (2) | 0.61011 (13) | 0.1366 (3) | 0.0354 (4) | |
H3A | 0.2523 | 0.6850 | 0.2192 | 0.043* | |
C4A | 0.3215 (2) | 0.59576 (13) | −0.0754 (3) | 0.0343 (4) | |
C5A | 0.3194 (2) | 0.48653 (14) | −0.2040 (3) | 0.0365 (4) | |
H5A | 0.3677 | 0.4795 | −0.3470 | 0.044* | |
C6A | 0.2434 (2) | 0.38781 (14) | −0.1141 (3) | 0.0348 (4) | |
H6A | 0.2417 | 0.3133 | −0.1970 | 0.042* | |
C7A | 0.0874 (2) | 0.28898 (13) | 0.1942 (3) | 0.0353 (4) | |
N1B | −0.2291 (2) | −0.05050 (12) | 0.6421 (3) | 0.0436 (4) | |
H1B | −0.2264 | −0.0941 | 0.7425 | 0.052* | |
C2B | −0.1381 (2) | 0.06099 (15) | 0.6599 (3) | 0.0425 (4) | |
H2B | −0.0604 | 0.1048 | 0.7824 | 0.051* | |
N3B | −0.17668 (19) | 0.09910 (12) | 0.4742 (2) | 0.0419 (4) | |
H3B | −0.1350 | 0.1688 | 0.4467 | 0.050* | |
C4B | −0.2939 (2) | 0.00914 (16) | 0.3330 (3) | 0.0455 (4) | |
H4B | −0.3418 | 0.0119 | 0.1902 | 0.055* | |
C5B | −0.3272 (2) | −0.08435 (15) | 0.4392 (3) | 0.0450 (4) | |
H5B | −0.4030 | −0.1580 | 0.3841 | 0.054* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1A | 0.0671 (9) | 0.0355 (6) | 0.0493 (8) | 0.0025 (6) | 0.0180 (6) | 0.0170 (6) |
O2A | 0.0738 (9) | 0.0296 (6) | 0.0475 (7) | 0.0122 (6) | 0.0044 (6) | 0.0133 (5) |
O3A | 0.0871 (11) | 0.0349 (7) | 0.0772 (11) | −0.0006 (7) | 0.0041 (9) | 0.0233 (7) |
O4A | 0.0788 (10) | 0.0675 (10) | 0.0553 (9) | −0.0091 (8) | 0.0109 (8) | 0.0342 (8) |
N1A | 0.0459 (9) | 0.0407 (8) | 0.0523 (9) | −0.0024 (7) | −0.0047 (7) | 0.0256 (7) |
C1A | 0.0311 (8) | 0.0295 (7) | 0.0326 (8) | 0.0052 (6) | 0.0001 (6) | 0.0111 (6) |
C2A | 0.0364 (8) | 0.0323 (8) | 0.0314 (8) | 0.0072 (6) | 0.0044 (6) | 0.0082 (6) |
C3A | 0.0397 (9) | 0.0276 (7) | 0.0388 (8) | 0.0067 (7) | −0.0004 (7) | 0.0075 (6) |
C4A | 0.0316 (8) | 0.0332 (8) | 0.0394 (9) | 0.0014 (6) | −0.0016 (6) | 0.0179 (7) |
C5A | 0.0375 (9) | 0.0414 (9) | 0.0323 (8) | 0.0083 (7) | 0.0049 (6) | 0.0124 (7) |
C6A | 0.0394 (9) | 0.0312 (8) | 0.0345 (8) | 0.0089 (7) | 0.0032 (7) | 0.0064 (6) |
C7A | 0.0429 (9) | 0.0276 (7) | 0.0341 (8) | 0.0026 (7) | −0.0024 (7) | 0.0099 (6) |
N1B | 0.0541 (9) | 0.0365 (7) | 0.0478 (9) | 0.0160 (7) | 0.0142 (7) | 0.0202 (6) |
C2B | 0.0454 (10) | 0.0386 (9) | 0.0454 (10) | 0.0125 (8) | 0.0070 (8) | 0.0089 (7) |
N3B | 0.0479 (9) | 0.0327 (7) | 0.0497 (9) | 0.0101 (6) | 0.0147 (7) | 0.0179 (6) |
C4B | 0.0473 (10) | 0.0462 (10) | 0.0458 (10) | 0.0122 (8) | 0.0067 (8) | 0.0142 (8) |
C5B | 0.0456 (10) | 0.0336 (8) | 0.0555 (11) | 0.0069 (8) | 0.0087 (8) | 0.0099 (8) |
O1A—C7A | 1.256 (2) | C5A—C6A | 1.382 (2) |
O2A—C7A | 1.2536 (19) | C5A—H5A | 0.9300 |
O3A—N1A | 1.225 (2) | C6A—H6A | 0.9300 |
O4A—N1A | 1.223 (2) | N1B—C2B | 1.329 (2) |
N1A—C4A | 1.4743 (19) | N1B—C5B | 1.359 (2) |
C1A—C2A | 1.392 (2) | N1B—H1B | 0.8600 |
C1A—C6A | 1.394 (2) | N3B—C2B | 1.321 (2) |
C1A—C7A | 1.514 (2) | C2B—H2B | 0.9300 |
C2A—C3A | 1.388 (2) | N3B—C4B | 1.366 (2) |
C2A—H2A | 0.9300 | N3B—H3B | 0.8600 |
C3A—C4A | 1.383 (2) | C4B—C5B | 1.347 (2) |
C3A—H3A | 0.9300 | C4B—H4B | 0.9300 |
C4A—C5A | 1.379 (2) | C5B—H5B | 0.9300 |
O4A—N1A—O3A | 123.97 (15) | C1A—C6A—H6A | 119.6 |
O4A—N1A—C4A | 117.85 (16) | O2A—C7A—O1A | 125.72 (14) |
O3A—N1A—C4A | 118.18 (15) | O2A—C7A—C1A | 117.10 (14) |
C2A—C1A—C6A | 119.63 (13) | O1A—C7A—C1A | 117.18 (14) |
C2A—C1A—C7A | 120.51 (14) | C2B—N1B—C5B | 108.84 (15) |
C6A—C1A—C7A | 119.86 (14) | C2B—N1B—H1B | 125.6 |
C3A—C2A—C1A | 120.22 (14) | C5B—N1B—H1B | 125.6 |
C3A—C2A—H2A | 119.9 | N3B—C2B—N1B | 108.39 (16) |
C1A—C2A—H2A | 119.9 | N3B—C2B—H2B | 125.8 |
C4A—C3A—C2A | 118.36 (14) | N1B—C2B—H2B | 125.8 |
C4A—C3A—H3A | 120.8 | C2B—N3B—C4B | 108.56 (15) |
C2A—C3A—H3A | 120.8 | C2B—N3B—H3B | 125.7 |
C5A—C4A—C3A | 122.84 (14) | C4B—N3B—H3B | 125.7 |
C5A—C4A—N1A | 118.76 (14) | C5B—C4B—N3B | 107.23 (16) |
C3A—C4A—N1A | 118.40 (15) | C5B—C4B—H4B | 126.4 |
C4A—C5A—C6A | 118.06 (15) | N3B—C4B—H4B | 126.4 |
C4A—C5A—H5A | 121.0 | C4B—C5B—N1B | 106.97 (16) |
C6A—C5A—H5A | 121.0 | C4B—C5B—H5B | 126.5 |
C5A—C6A—C1A | 120.87 (15) | N1B—C5B—H5B | 126.5 |
C5A—C6A—H6A | 119.6 | ||
C6A—C1A—C2A—C3A | −1.3 (2) | C2A—C1A—C6A—C5A | 0.4 (2) |
C7A—C1A—C2A—C3A | 178.82 (14) | C7A—C1A—C6A—C5A | −179.75 (15) |
C1A—C2A—C3A—C4A | 1.1 (2) | C2A—C1A—C7A—O2A | −167.08 (15) |
C2A—C3A—C4A—C5A | 0.0 (2) | C6A—C1A—C7A—O2A | 13.0 (2) |
C2A—C3A—C4A—N1A | −179.26 (14) | C2A—C1A—C7A—O1A | 13.2 (2) |
O4A—N1A—C4A—C5A | 1.1 (2) | C6A—C1A—C7A—O1A | −166.65 (15) |
O3A—N1A—C4A—C5A | −178.61 (15) | C5B—N1B—C2B—N3B | 0.36 (19) |
O4A—N1A—C4A—C3A | −179.57 (16) | N1B—C2B—N3B—C4B | −0.65 (19) |
O3A—N1A—C4A—C3A | 0.7 (2) | C2B—N3B—C4B—C5B | 0.7 (2) |
C3A—C4A—C5A—C6A | −0.9 (2) | N3B—C4B—C5B—N1B | −0.46 (19) |
N1A—C4A—C5A—C6A | 178.35 (14) | C2B—N1B—C5B—C4B | 0.1 (2) |
C4A—C5A—C6A—C1A | 0.7 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
N3B—H3B···O1A | 0.86 | 1.80 | 2.6442 (18) | 168 |
N1B—H1B···O2Ai | 0.86 | 1.94 | 2.7425 (19) | 155 |
C4B—H4B···O3Aii | 0.93 | 2.68 | 3.326 (2) | 127 |
C5B—H5B···O4Aiii | 0.93 | 2.63 | 3.236 (2) | 123 |
Symmetry codes: (i) −x, −y, −z+1; (ii) −x, −y+1, −z; (iii) x−1, y−1, z+1. |
Experimental details
(I) | (II) | (III) | (IV) | |
Crystal data | ||||
Chemical formula | C7H7N2+·C7H4NO4− | C7H7N2+·C7H4NO4− | C6H5N3·C7H5NO4 | C3H5N2+·C7H4NO4− |
Mr | 285.26 | 285.26 | 286.25 | 235.20 |
Crystal system, space group | Monoclinic, P21 | Monoclinic, P21/c | Monoclinic, P21/n | Monoclinic, P21/c |
Temperature (K) | 297 | 297 | 297 | 297 |
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), 90 | 90, 94.1400 (17), 90 | 90, 105.40 (1), 90 | 90, 90.53 (3), 90 |
V (Å3) | 658.35 (15) | 1326.09 (11) | 1310.3 (5) | 1030.5 (6) |
Z | 2 | 4 | 4 | 4 |
Radiation type | Mo Kα | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.11 | 0.11 | 0.11 | 0.12 |
Crystal size (mm) | 0.45 × 0.25 × 0.05 | 0.60 × 0.38 × 0.33 | 0.35 × 0.15 × 0.10 | 0.35 × 0.23 × 0.08 |
Data collection | ||||
Diffractometer | Rigaku 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 |
Rint | 0.046 | 0.034 | 0.030 | 0.052 |
(sin θ/λ)max (Å−1) | 0.649 | 0.704 | 0.628 | 0.650 |
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 reflections | 1568 | 3869 | 2465 | 2361 |
No. of parameters | 192 | 191 | 194 | 155 |
No. of restraints | 1 | 0 | 0 | 0 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained | H atoms treated by a mixture of independent and constrained refinement | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.15, −0.15 | 0.22, −0.19 | 0.28, −0.29 | 0.17, −0.17 |
(V) | |
Crystal data | |
Chemical formula | C3H5N2+·C7H4NO4− |
Mr | 235.20 |
Crystal system, space group | Triclinic, 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) |
V (Å3) | 510.19 (13) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.12 |
Crystal size (mm) | 0.43 × 0.20 × 0.10 |
Data collection | |
Diffractometer | Rigaku AFC-5R diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6177, 2988, 1679 |
Rint | 0.033 |
(sin θ/λ)max (Å−1) | 0.703 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.047, 0.140, 1.00 |
No. of reflections | 2988 |
No. of parameters | 154 |
No. of restraints | 0 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 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.
O1A—C7A | 1.269 (5) | N1B—C2B | 1.326 (5) |
O2A—C7A | 1.234 (5) | N3B—C2B | 1.316 (5) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1B—H1B···O2Ai | 0.86 | 1.86 | 2.717 (4) | 177 |
N3B—H3B···O1A | 0.86 | 1.69 | 2.550 (3) | 178 |
C5B—H5B···O3Aii | 0.93 | 2.70 | 3.553 (6) | 153 |
C5A—H5A···O4Aiii | 0.93 | 2.71 | 3.340 (5) | 126 |
Symmetry codes: (i) −x+1, y+1/2, −z+1; (ii) −x+1, y−1/2, −z−1; (iii) −x, y−1/2, −z−2. |
O1A—C7A | 1.2494 (19) | N1B—C2B | 1.3265 (18) |
O2A—C7A | 1.2632 (18) | N3B—C2B | 1.3231 (19) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1B—H1B···O2Ai | 0.86 | 1.81 | 2.6600 (15) | 171 |
N3B—H3B···O1A | 0.86 | 1.79 | 2.6469 (15) | 177 |
C2B—H2B···O2Aii | 0.93 | 2.26 | 3.125 (2) | 155 |
C6B—H6B···O3Aiii | 0.93 | 2.83 | 3.478 (3) | 128 |
Symmetry codes: (i) −x+1, y+1/2, −z+1/2; (ii) x, −y+1/2, z−1/2; (iii) x+1, y, z. |
O1A—C7A | 1.211 (4) | N1B—N2B | 1.338 (4) |
O2A—C7A | 1.323 (4) | N2B—N3B | 1.311 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
O2A—H22A···N3B | 1.02 (4) | 1.65 (4) | 2.669 (4) | 173 (3) |
N1B—H1B···O1Ai | 0.86 | 2.01 | 2.826 (4) | 157 |
C5B—H5B···O4Aii | 0.93 | 2.68 | 3.490 (5) | 146 |
C6B—H6B···O3Aiii | 0.93 | 2.75 | 3.303 (5) | 119 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x+1/2, −y+5/2, z−1/2; (iii) x+1/2, −y+3/2, z−1/2. |
O1A—C7A | 1.258 (3) | N1B—C2B | 1.328 (3) |
O2A—C7A | 1.252 (3) | N3B—C2B | 1.314 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1B—H1B···O2Ai | 0.86 | 1.93 | 2.745 (3) | 157 |
N3B—H3B···O1A | 0.86 | 1.80 | 2.644 (3) | 166 |
C4B—H4B···O4Aii | 0.93 | 2.69 | 3.372 (3) | 130 |
C5B—H5B···O3Aiii | 0.93 | 2.62 | 3.204 (3) | 121 |
Symmetry codes: (i) −x+2, −y, −z+1; (ii) x, −y+1/2, z−1/2; (iii) −x+2, y−1/2, −z+1/2. |
O1A—C7A | 1.256 (2) | N1B—C2B | 1.329 (2) |
O2A—C7A | 1.2536 (19) | N3B—C2B | 1.321 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
N3B—H3B···O1A | 0.86 | 1.80 | 2.6442 (18) | 168 |
N1B—H1B···O2Ai | 0.86 | 1.94 | 2.7425 (19) | 155 |
C4B—H4B···O3Aii | 0.93 | 2.68 | 3.326 (2) | 127 |
C5B—H5B···O4Aiii | 0.93 | 2.63 | 3.236 (2) | 123 |
Symmetry codes: (i) −x, −y, −z+1; (ii) −x, −y+1, −z; (iii) x−1, y−1, z+1. |
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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).