Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807050945/bv2074sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807050945/bv2074Isup2.hkl |
CCDC reference: 667413
Key indicators
- Single-crystal X-ray study
- T = 150 K
- Mean (C-C) = 0.002 Å
- R factor = 0.031
- wR factor = 0.087
- Data-to-parameter ratio = 9.2
checkCIF/PLATON results
No syntax errors found
Alert level B PLAT430_ALERT_2_B Short Inter D...A Contact O2 .. O5 .. 2.80 Ang.
Alert level G REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is correct. If it is not, please give the correct count in the _publ_section_exptl_refinement section of the submitted CIF. From the CIF: _diffrn_reflns_theta_max 28.37 From the CIF: _reflns_number_total 2951 Count of symmetry unique reflns 2993 Completeness (_total/calc) 98.60% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 0 Fraction of Friedel pairs measured 0.000 Are heavy atom types Z>Si present no
0 ALERT level A = In general: serious problem 1 ALERT level B = Potentially serious problem 0 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 1 ALERT type 2 Indicator that the structure model may be wrong or deficient 0 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
For related literature on mononitro-substituted Tröger's base analogues, see: Webb & Wilcox (1990); Pardo et al., (1996). For dinitro-substituted Tröger's base analogues, see: Mederski et al. (2003); Li et al. (2005); Bhuiyan et al. (2007).
For related literature, see: Faroughi et al. (2006); Jensen & Wärnmark (2001); Kostyanovsky et al. (2003); Lenev et al. (2006); Mederski et al. (2003); Sergeyev et al. (2005); Solano et al. (2005); Sucholeiki et al. (1988).
Synthetic details will be reported elsewhere. Crystals of (I) were obtained by slow evaporation of a dichloromethane solution.
For over 100 years since the first synthesis of Tröger's base it was believed that analogues bearing electron-withdrawing groups could not be prepared in good yields, if at all. This belief was dispelled with the first synthesis of dihalogenated analogues (Jensen & Wärnmark, 2001), tetrabromo (Faroughi et al., 2006) and dinitro analogues (Mederski et al., 2003; Li et al., 2005; Bhuiyan et al., 2007). Compound (I) is the first example of a tetranitro Tröger's base analogue and was prepared in racemic form by reacting 4-methoxy-2-methyl-3,5-dinitroaniline with diglycolic acid in polyphosphoric acid (PPA) as shown in Fig. 2. The molecular structure of (I) is shown in Fig. 1. It is interesting to note that in addition to (I), there are two other reports of simple dibenzo Tröger's base analogues with dihedral angles greater than 100° that bear substituents in the 2,4,8- and 10-positions (Sucholeiki et al., 1988; Faroughi et al., 2006), at the upper end of the the range of 82° (Solano et al., 2005) to 108° (Faroughi et al., 2006), that are the lower and upper limits, respectively, that have been measured for for over twenty simple dibenzo Tröger's base analogues. These results would tend to suggest that the placement of substituents in these positions may lead to an increase in the cavity size of the Tröger's base systems, at least in the crystalline state.
Although the compound was prepared in racemic form, the crystal chosen for analysis crystallized in enantiopure form, however the absolute configuration of the structure has not been established by X-ray methods. This appears to be the fourth example of conglomerate crystallization among Tröger's base systems (Kostyanovsky et al., 2003; Sergeyev et al., 2005; Lenev et al., 2006).
We were interested in preparing a range of nitro-substituted Tröger's base compounds as precursors for supramolecular recognition elements.
For related literature on mononitro-substituted Tröger's base analogues, see: Webb & Wilcox (1990); Pardo et al., (1996). For dinitro-substituted Tröger's base analogues, see: Mederski et al. (2003); Li et al. (2005); Bhuiyan et al. (2007).
For related literature, see: Faroughi et al. (2006); Jensen & Wärnmark (2001); Kostyanovsky et al. (2003); Lenev et al. (2006); Mederski et al. (2003); Sergeyev et al. (2005); Solano et al. (2005); Sucholeiki et al. (1988).
Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT (Bruker, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2003); software used to prepare material for publication: modiCIFer (Guzei, 2005).
Fig. 1. The molecular structure of (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. | |
Fig. 2. The preparation of (I). |
C19H18N6O10 | Dx = 1.557 Mg m−3 |
Mr = 490.39 | Melting point: 509 K |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 6736 reflections |
a = 8.629 (2) Å | θ = 2.4–28.3° |
b = 9.155 (2) Å | µ = 0.13 mm−1 |
c = 26.484 (5) Å | T = 150 K |
V = 2092.2 (8) Å3 | Plate, pale yellow |
Z = 4 | 0.50 × 0.47 × 0.20 mm |
F(000) = 1016 |
Bruker CCD-1000 area-detector diffractometer | 2951 independent reflections |
Radiation source: fine-focus sealed tube | 2796 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.024 |
ω scans | θmax = 28.4°, θmin = 1.5° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −11→11 |
Tmin = 0.913, Tmax = 0.975 | k = −12→11 |
20912 measured reflections | l = −35→35 |
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)] = 0.031 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.087 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0569P)2 + 0.4264P] where P = (Fo2 + 2Fc2)/3 |
2951 reflections | (Δ/σ)max < 0.001 |
320 parameters | Δρmax = 0.33 e Å−3 |
0 restraints | Δρmin = −0.25 e Å−3 |
C19H18N6O10 | V = 2092.2 (8) Å3 |
Mr = 490.39 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 8.629 (2) Å | µ = 0.13 mm−1 |
b = 9.155 (2) Å | T = 150 K |
c = 26.484 (5) Å | 0.50 × 0.47 × 0.20 mm |
Bruker CCD-1000 area-detector diffractometer | 2951 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2796 reflections with I > 2σ(I) |
Tmin = 0.913, Tmax = 0.975 | Rint = 0.024 |
20912 measured reflections |
R[F2 > 2σ(F2)] = 0.031 | 0 restraints |
wR(F2) = 0.087 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.33 e Å−3 |
2951 reflections | Δρmin = −0.25 e Å−3 |
320 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 | ||
O1 | −0.24794 (17) | 0.33842 (19) | 0.07709 (8) | 0.0502 (5) | |
O2 | −0.08837 (18) | 0.48777 (15) | 0.04288 (6) | 0.0389 (4) | |
O3 | −0.16534 (14) | 0.11061 (15) | 0.01060 (4) | 0.0271 (3) | |
O4 | 0.0242 (2) | −0.11653 (17) | −0.02943 (5) | 0.0412 (4) | |
O5 | 0.0452 (3) | −0.23330 (16) | 0.04133 (7) | 0.0519 (4) | |
O6 | −0.03451 (19) | 0.5055 (2) | 0.31937 (6) | 0.0516 (5) | |
O7 | 0.1945 (2) | 0.5605 (2) | 0.34557 (6) | 0.0503 (4) | |
O8 | 0.16799 (16) | 0.21859 (15) | 0.34025 (4) | 0.0293 (3) | |
O9 | 0.42213 (18) | −0.03735 (17) | 0.25715 (6) | 0.0405 (4) | |
O10 | 0.1932 (2) | −0.04848 (15) | 0.29035 (6) | 0.0390 (3) | |
N1 | −0.12096 (16) | 0.36974 (16) | 0.06071 (5) | 0.0229 (3) | |
N2 | 0.04626 (19) | −0.12154 (16) | 0.01626 (6) | 0.0293 (3) | |
N3 | 0.30705 (16) | 0.42473 (15) | 0.14649 (5) | 0.0204 (3) | |
N4 | 0.38756 (16) | 0.18709 (16) | 0.11780 (5) | 0.0205 (3) | |
N5 | 0.10563 (19) | 0.49762 (18) | 0.31727 (5) | 0.0289 (3) | |
N6 | 0.29756 (19) | 0.01726 (17) | 0.26895 (5) | 0.0267 (3) | |
C1 | −0.00005 (17) | 0.25689 (17) | 0.06230 (6) | 0.0192 (3) | |
C2 | −0.03352 (19) | 0.12601 (18) | 0.03837 (6) | 0.0210 (3) | |
C3 | −0.2842 (2) | 0.0221 (3) | 0.03419 (7) | 0.0362 (4) | |
H3A | −0.2384 | −0.0695 | 0.0462 | 0.054* | |
H3B | −0.3657 | 0.0005 | 0.0095 | 0.054* | |
H3C | −0.3288 | 0.0754 | 0.0628 | 0.054* | |
C4 | 0.0768 (2) | 0.01678 (18) | 0.04267 (6) | 0.0217 (3) | |
C5 | 0.21390 (19) | 0.03065 (17) | 0.06985 (6) | 0.0202 (3) | |
C6 | 0.3289 (2) | −0.09185 (19) | 0.07389 (7) | 0.0274 (3) | |
H6A | 0.2939 | −0.1617 | 0.0995 | 0.041* | |
H6B | 0.4302 | −0.0525 | 0.0836 | 0.041* | |
H6C | 0.3376 | −0.1414 | 0.0412 | 0.041* | |
C7 | 0.24331 (18) | 0.16794 (17) | 0.09196 (5) | 0.0180 (3) | |
C8 | 0.13757 (18) | 0.28300 (17) | 0.08822 (5) | 0.0181 (3) | |
C9 | 0.17197 (19) | 0.43057 (17) | 0.11245 (6) | 0.0205 (3) | |
H9A | 0.1917 | 0.5034 | 0.0856 | 0.025* | |
H9B | 0.0800 | 0.4631 | 0.1318 | 0.025* | |
C10 | 0.42902 (19) | 0.34144 (19) | 0.12147 (6) | 0.0232 (3) | |
H10A | 0.5268 | 0.3514 | 0.1407 | 0.028* | |
H10B | 0.4463 | 0.3813 | 0.0872 | 0.028* | |
C11 | 0.38882 (19) | 0.12370 (18) | 0.16884 (6) | 0.0217 (3) | |
H11A | 0.4975 | 0.1073 | 0.1794 | 0.026* | |
H11B | 0.3361 | 0.0277 | 0.1680 | 0.026* | |
C12 | 0.30895 (18) | 0.22120 (17) | 0.20748 (6) | 0.0199 (3) | |
C13 | 0.27142 (18) | 0.36599 (17) | 0.19513 (6) | 0.0189 (3) | |
C14 | 0.20377 (19) | 0.46122 (18) | 0.23053 (6) | 0.0204 (3) | |
C15 | 0.1778 (2) | 0.61959 (19) | 0.21860 (6) | 0.0273 (3) | |
H15A | 0.0893 | 0.6292 | 0.1957 | 0.041* | |
H15B | 0.2707 | 0.6599 | 0.2025 | 0.041* | |
H15C | 0.1566 | 0.6732 | 0.2499 | 0.041* | |
C16 | 0.17340 (19) | 0.40371 (19) | 0.27790 (6) | 0.0221 (3) | |
C17 | 0.20533 (19) | 0.26139 (18) | 0.29235 (6) | 0.0223 (3) | |
C18 | 0.2990 (3) | 0.1949 (2) | 0.37300 (6) | 0.0335 (4) | |
H18A | 0.3633 | 0.1159 | 0.3594 | 0.050* | |
H18B | 0.2623 | 0.1679 | 0.4068 | 0.050* | |
H18C | 0.3605 | 0.2847 | 0.3751 | 0.050* | |
C19 | 0.27199 (19) | 0.17181 (18) | 0.25601 (6) | 0.0216 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0255 (7) | 0.0472 (9) | 0.0781 (12) | 0.0093 (7) | 0.0215 (7) | 0.0217 (9) |
O2 | 0.0358 (7) | 0.0257 (6) | 0.0553 (9) | 0.0065 (6) | 0.0150 (7) | 0.0123 (6) |
O3 | 0.0214 (5) | 0.0388 (7) | 0.0213 (5) | −0.0075 (5) | −0.0039 (4) | 0.0033 (5) |
O4 | 0.0496 (8) | 0.0450 (8) | 0.0290 (6) | −0.0131 (8) | 0.0026 (6) | −0.0152 (6) |
O5 | 0.0773 (12) | 0.0237 (6) | 0.0548 (9) | −0.0119 (8) | −0.0092 (10) | −0.0007 (6) |
O6 | 0.0351 (8) | 0.0801 (13) | 0.0394 (8) | 0.0226 (9) | 0.0029 (7) | −0.0153 (9) |
O7 | 0.0524 (9) | 0.0621 (10) | 0.0363 (7) | −0.0002 (9) | −0.0028 (7) | −0.0274 (7) |
O8 | 0.0311 (7) | 0.0394 (7) | 0.0174 (5) | 0.0006 (6) | −0.0004 (5) | 0.0032 (5) |
O9 | 0.0401 (8) | 0.0389 (7) | 0.0426 (8) | 0.0175 (7) | −0.0053 (6) | 0.0050 (7) |
O10 | 0.0501 (9) | 0.0298 (7) | 0.0371 (7) | −0.0035 (7) | 0.0030 (7) | 0.0049 (6) |
N1 | 0.0191 (6) | 0.0267 (7) | 0.0229 (6) | 0.0022 (6) | 0.0006 (5) | 0.0020 (5) |
N2 | 0.0309 (7) | 0.0242 (7) | 0.0329 (7) | −0.0076 (6) | 0.0027 (6) | −0.0084 (6) |
N3 | 0.0205 (6) | 0.0222 (6) | 0.0187 (6) | −0.0035 (5) | 0.0011 (5) | −0.0020 (5) |
N4 | 0.0160 (6) | 0.0244 (6) | 0.0211 (6) | 0.0001 (5) | −0.0001 (5) | −0.0031 (5) |
N5 | 0.0331 (8) | 0.0341 (8) | 0.0196 (6) | 0.0090 (7) | 0.0013 (6) | −0.0031 (6) |
N6 | 0.0333 (8) | 0.0261 (7) | 0.0209 (6) | 0.0035 (6) | −0.0078 (6) | 0.0011 (5) |
C1 | 0.0176 (7) | 0.0212 (7) | 0.0187 (6) | 0.0011 (6) | 0.0023 (5) | 0.0020 (5) |
C2 | 0.0201 (7) | 0.0260 (7) | 0.0167 (6) | −0.0049 (6) | 0.0004 (6) | 0.0008 (6) |
C3 | 0.0268 (9) | 0.0514 (12) | 0.0302 (9) | −0.0165 (9) | −0.0057 (7) | 0.0059 (9) |
C4 | 0.0245 (8) | 0.0199 (7) | 0.0207 (7) | −0.0043 (6) | 0.0026 (6) | −0.0032 (6) |
C5 | 0.0213 (7) | 0.0200 (7) | 0.0192 (6) | 0.0005 (6) | 0.0038 (6) | −0.0011 (6) |
C6 | 0.0284 (8) | 0.0227 (7) | 0.0310 (8) | 0.0053 (7) | 0.0030 (7) | −0.0027 (6) |
C7 | 0.0173 (7) | 0.0206 (7) | 0.0163 (6) | −0.0006 (6) | 0.0025 (5) | −0.0017 (5) |
C8 | 0.0184 (7) | 0.0202 (7) | 0.0157 (6) | −0.0026 (6) | 0.0036 (5) | −0.0007 (5) |
C9 | 0.0232 (7) | 0.0193 (7) | 0.0189 (6) | −0.0003 (6) | 0.0005 (6) | −0.0004 (5) |
C10 | 0.0182 (7) | 0.0290 (8) | 0.0226 (7) | −0.0057 (6) | 0.0027 (6) | −0.0046 (6) |
C11 | 0.0192 (7) | 0.0251 (7) | 0.0209 (7) | 0.0048 (6) | −0.0011 (6) | −0.0027 (6) |
C12 | 0.0170 (6) | 0.0230 (7) | 0.0198 (6) | 0.0008 (6) | −0.0017 (6) | −0.0023 (6) |
C13 | 0.0165 (6) | 0.0217 (7) | 0.0185 (6) | −0.0026 (6) | −0.0011 (5) | −0.0021 (5) |
C14 | 0.0185 (7) | 0.0222 (7) | 0.0204 (7) | −0.0006 (6) | −0.0016 (6) | −0.0032 (6) |
C15 | 0.0355 (9) | 0.0218 (7) | 0.0245 (7) | 0.0031 (7) | 0.0004 (7) | −0.0027 (6) |
C16 | 0.0201 (7) | 0.0282 (8) | 0.0180 (7) | 0.0024 (6) | −0.0014 (6) | −0.0053 (6) |
C17 | 0.0212 (7) | 0.0288 (8) | 0.0168 (6) | 0.0001 (7) | −0.0021 (6) | 0.0000 (6) |
C18 | 0.0414 (10) | 0.0366 (10) | 0.0227 (8) | 0.0015 (9) | −0.0101 (7) | 0.0019 (7) |
C19 | 0.0207 (7) | 0.0240 (7) | 0.0201 (7) | 0.0011 (6) | −0.0039 (6) | 0.0004 (6) |
O1—N1 | 1.213 (2) | C4—C5 | 1.391 (2) |
O2—N1 | 1.212 (2) | C5—C7 | 1.410 (2) |
O3—C2 | 1.3618 (19) | C5—C6 | 1.501 (2) |
O3—C3 | 1.449 (2) | C6—H6A | 0.9800 |
O4—N2 | 1.226 (2) | C6—H6B | 0.9800 |
O5—N2 | 1.220 (2) | C6—H6C | 0.9800 |
O6—N5 | 1.213 (2) | C7—C8 | 1.397 (2) |
O7—N5 | 1.217 (2) | C8—C9 | 1.525 (2) |
O8—C17 | 1.366 (2) | C9—H9A | 0.9900 |
O8—C18 | 1.441 (2) | C9—H9B | 0.9900 |
O9—N6 | 1.226 (2) | C10—H10A | 0.9900 |
O10—N6 | 1.223 (2) | C10—H10B | 0.9900 |
N1—C1 | 1.469 (2) | C11—C12 | 1.523 (2) |
N2—C4 | 1.470 (2) | C11—H11A | 0.9900 |
N3—C13 | 1.4295 (19) | C11—H11B | 0.9900 |
N3—C10 | 1.459 (2) | C12—C19 | 1.399 (2) |
N3—C9 | 1.475 (2) | C12—C13 | 1.403 (2) |
N4—C7 | 1.431 (2) | C13—C14 | 1.407 (2) |
N4—C10 | 1.461 (2) | C14—C16 | 1.386 (2) |
N4—C11 | 1.471 (2) | C14—C15 | 1.501 (2) |
N5—C16 | 1.472 (2) | C15—H15A | 0.9800 |
N6—C19 | 1.473 (2) | C15—H15B | 0.9800 |
C1—C2 | 1.386 (2) | C15—H15C | 0.9800 |
C1—C8 | 1.392 (2) | C16—C17 | 1.386 (2) |
C2—C4 | 1.385 (2) | C17—C19 | 1.389 (2) |
C3—H3A | 0.9800 | C18—H18A | 0.9800 |
C3—H3B | 0.9800 | C18—H18B | 0.9800 |
C3—H3C | 0.9800 | C18—H18C | 0.9800 |
C2—O3—C3 | 114.59 (13) | C7—C8—C9 | 120.73 (14) |
C17—O8—C18 | 114.64 (14) | N3—C9—C8 | 112.28 (13) |
O2—N1—O1 | 124.03 (16) | N3—C9—H9A | 109.1 |
O2—N1—C1 | 118.24 (14) | C8—C9—H9A | 109.1 |
O1—N1—C1 | 117.72 (14) | N3—C9—H9B | 109.1 |
O5—N2—O4 | 124.57 (16) | C8—C9—H9B | 109.1 |
O5—N2—C4 | 117.72 (15) | H9A—C9—H9B | 107.9 |
O4—N2—C4 | 117.71 (15) | N3—C10—N4 | 111.05 (13) |
C13—N3—C10 | 111.58 (13) | N3—C10—H10A | 109.4 |
C13—N3—C9 | 113.24 (12) | N4—C10—H10A | 109.4 |
C10—N3—C9 | 108.16 (12) | N3—C10—H10B | 109.4 |
C7—N4—C10 | 111.31 (13) | N4—C10—H10B | 109.4 |
C7—N4—C11 | 113.42 (13) | H10A—C10—H10B | 108.0 |
C10—N4—C11 | 108.57 (13) | N4—C11—C12 | 112.52 (13) |
O6—N5—O7 | 124.88 (18) | N4—C11—H11A | 109.1 |
O6—N5—C16 | 117.60 (17) | C12—C11—H11A | 109.1 |
O7—N5—C16 | 117.52 (16) | N4—C11—H11B | 109.1 |
O10—N6—O9 | 124.29 (16) | C12—C11—H11B | 109.1 |
O10—N6—C19 | 118.07 (16) | H11A—C11—H11B | 107.8 |
O9—N6—C19 | 117.63 (16) | C19—C12—C13 | 117.83 (15) |
C2—C1—C8 | 123.48 (15) | C19—C12—C11 | 122.07 (15) |
C2—C1—N1 | 116.55 (14) | C13—C12—C11 | 120.10 (14) |
C8—C1—N1 | 119.94 (14) | C12—C13—C14 | 121.72 (14) |
O3—C2—C4 | 122.92 (15) | C12—C13—N3 | 121.06 (14) |
O3—C2—C1 | 120.70 (15) | C14—C13—N3 | 117.17 (14) |
C4—C2—C1 | 116.32 (15) | C16—C14—C13 | 116.51 (15) |
O3—C3—H3A | 109.5 | C16—C14—C15 | 121.97 (15) |
O3—C3—H3B | 109.5 | C13—C14—C15 | 121.35 (15) |
H3A—C3—H3B | 109.5 | C14—C15—H15A | 109.5 |
O3—C3—H3C | 109.5 | C14—C15—H15B | 109.5 |
H3A—C3—H3C | 109.5 | H15A—C15—H15B | 109.5 |
H3B—C3—H3C | 109.5 | C14—C15—H15C | 109.5 |
C2—C4—C5 | 124.14 (15) | H15A—C15—H15C | 109.5 |
C2—C4—N2 | 117.37 (15) | H15B—C15—H15C | 109.5 |
C5—C4—N2 | 118.49 (15) | C14—C16—C17 | 124.73 (15) |
C4—C5—C7 | 116.71 (14) | C14—C16—N5 | 119.63 (15) |
C4—C5—C6 | 122.07 (15) | C17—C16—N5 | 115.62 (14) |
C7—C5—C6 | 121.17 (15) | O8—C17—C16 | 118.64 (15) |
C5—C6—H6A | 109.5 | O8—C17—C19 | 124.86 (16) |
C5—C6—H6B | 109.5 | C16—C17—C19 | 116.49 (15) |
H6A—C6—H6B | 109.5 | O8—C18—H18A | 109.5 |
C5—C6—H6C | 109.5 | O8—C18—H18B | 109.5 |
H6A—C6—H6C | 109.5 | H18A—C18—H18B | 109.5 |
H6B—C6—H6C | 109.5 | O8—C18—H18C | 109.5 |
C8—C7—C5 | 121.68 (14) | H18A—C18—H18C | 109.5 |
C8—C7—N4 | 120.63 (14) | H18B—C18—H18C | 109.5 |
C5—C7—N4 | 117.67 (14) | C17—C19—C12 | 122.68 (15) |
C1—C8—C7 | 117.55 (14) | C17—C19—N6 | 117.90 (15) |
C1—C8—C9 | 121.71 (14) | C12—C19—N6 | 119.36 (15) |
O2—N1—C1—C2 | −123.01 (17) | C7—N4—C10—N3 | 56.74 (17) |
O1—N1—C1—C2 | 56.5 (2) | C11—N4—C10—N3 | −68.78 (16) |
O2—N1—C1—C8 | 58.8 (2) | C7—N4—C11—C12 | −79.62 (16) |
O1—N1—C1—C8 | −121.7 (2) | C10—N4—C11—C12 | 44.66 (17) |
C3—O3—C2—C4 | 76.4 (2) | N4—C11—C12—C19 | 168.27 (14) |
C3—O3—C2—C1 | −106.45 (19) | N4—C11—C12—C13 | −12.4 (2) |
C8—C1—C2—O3 | −175.31 (14) | C19—C12—C13—C14 | 2.2 (2) |
N1—C1—C2—O3 | 6.6 (2) | C11—C12—C13—C14 | −177.18 (14) |
C8—C1—C2—C4 | 2.0 (2) | C19—C12—C13—N3 | 179.33 (14) |
N1—C1—C2—C4 | −176.08 (13) | C11—C12—C13—N3 | 0.0 (2) |
O3—C2—C4—C5 | 178.54 (15) | C10—N3—C13—C12 | −20.9 (2) |
C1—C2—C4—C5 | 1.3 (2) | C9—N3—C13—C12 | 101.40 (17) |
O3—C2—C4—N2 | −0.9 (2) | C10—N3—C13—C14 | 156.36 (14) |
C1—C2—C4—N2 | −178.10 (14) | C9—N3—C13—C14 | −81.33 (17) |
O5—N2—C4—C2 | −123.3 (2) | C12—C13—C14—C16 | −1.2 (2) |
O4—N2—C4—C2 | 57.0 (2) | N3—C13—C14—C16 | −178.47 (14) |
O5—N2—C4—C5 | 57.3 (2) | C12—C13—C14—C15 | 174.14 (15) |
O4—N2—C4—C5 | −122.48 (18) | N3—C13—C14—C15 | −3.1 (2) |
C2—C4—C5—C7 | −3.3 (2) | C13—C14—C16—C17 | 0.2 (2) |
N2—C4—C5—C7 | 176.13 (14) | C15—C14—C16—C17 | −175.08 (16) |
C2—C4—C5—C6 | 179.20 (15) | C13—C14—C16—N5 | 178.75 (15) |
N2—C4—C5—C6 | −1.4 (2) | C15—C14—C16—N5 | 3.4 (3) |
C4—C5—C7—C8 | 2.1 (2) | O6—N5—C16—C14 | 88.4 (2) |
C6—C5—C7—C8 | 179.65 (14) | O7—N5—C16—C14 | −92.3 (2) |
C4—C5—C7—N4 | −176.71 (14) | O6—N5—C16—C17 | −93.0 (2) |
C6—C5—C7—N4 | 0.9 (2) | O7—N5—C16—C17 | 86.4 (2) |
C10—N4—C7—C8 | −20.73 (19) | C18—O8—C17—C16 | −109.32 (18) |
C11—N4—C7—C8 | 102.05 (17) | C18—O8—C17—C19 | 71.6 (2) |
C10—N4—C7—C5 | 158.08 (14) | C14—C16—C17—O8 | −179.42 (15) |
C11—N4—C7—C5 | −79.14 (16) | N5—C16—C17—O8 | 2.0 (2) |
C2—C1—C8—C7 | −3.0 (2) | C14—C16—C17—C19 | −0.3 (2) |
N1—C1—C8—C7 | 174.98 (13) | N5—C16—C17—C19 | −178.84 (15) |
C2—C1—C8—C9 | 177.82 (14) | O8—C17—C19—C12 | −179.61 (15) |
N1—C1—C8—C9 | −4.1 (2) | C16—C17—C19—C12 | 1.3 (2) |
C5—C7—C8—C1 | 0.9 (2) | O8—C17—C19—N6 | 3.2 (2) |
N4—C7—C8—C1 | 179.63 (13) | C16—C17—C19—N6 | −175.87 (15) |
C5—C7—C8—C9 | −179.99 (13) | C13—C12—C19—C17 | −2.3 (2) |
N4—C7—C8—C9 | −1.2 (2) | C11—C12—C19—C17 | 177.10 (15) |
C13—N3—C9—C8 | −80.15 (16) | C13—C12—C19—N6 | 174.90 (14) |
C10—N3—C9—C8 | 44.05 (17) | C11—C12—C19—N6 | −5.7 (2) |
C1—C8—C9—N3 | 168.06 (13) | O10—N6—C19—C17 | 44.5 (2) |
C7—C8—C9—N3 | −11.0 (2) | O9—N6—C19—C17 | −136.02 (17) |
C13—N3—C10—N4 | 55.74 (17) | O10—N6—C19—C12 | −132.75 (17) |
C9—N3—C10—N4 | −69.45 (17) | O9—N6—C19—C12 | 46.7 (2) |
Experimental details
Crystal data | |
Chemical formula | C19H18N6O10 |
Mr | 490.39 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 150 |
a, b, c (Å) | 8.629 (2), 9.155 (2), 26.484 (5) |
V (Å3) | 2092.2 (8) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.13 |
Crystal size (mm) | 0.50 × 0.47 × 0.20 |
Data collection | |
Diffractometer | Bruker CCD-1000 area-detector |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.913, 0.975 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 20912, 2951, 2796 |
Rint | 0.024 |
(sin θ/λ)max (Å−1) | 0.669 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.031, 0.087, 1.04 |
No. of reflections | 2951 |
No. of parameters | 320 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.33, −0.25 |
Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 2003), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2003), modiCIFer (Guzei, 2005).
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For over 100 years since the first synthesis of Tröger's base it was believed that analogues bearing electron-withdrawing groups could not be prepared in good yields, if at all. This belief was dispelled with the first synthesis of dihalogenated analogues (Jensen & Wärnmark, 2001), tetrabromo (Faroughi et al., 2006) and dinitro analogues (Mederski et al., 2003; Li et al., 2005; Bhuiyan et al., 2007). Compound (I) is the first example of a tetranitro Tröger's base analogue and was prepared in racemic form by reacting 4-methoxy-2-methyl-3,5-dinitroaniline with diglycolic acid in polyphosphoric acid (PPA) as shown in Fig. 2. The molecular structure of (I) is shown in Fig. 1. It is interesting to note that in addition to (I), there are two other reports of simple dibenzo Tröger's base analogues with dihedral angles greater than 100° that bear substituents in the 2,4,8- and 10-positions (Sucholeiki et al., 1988; Faroughi et al., 2006), at the upper end of the the range of 82° (Solano et al., 2005) to 108° (Faroughi et al., 2006), that are the lower and upper limits, respectively, that have been measured for for over twenty simple dibenzo Tröger's base analogues. These results would tend to suggest that the placement of substituents in these positions may lead to an increase in the cavity size of the Tröger's base systems, at least in the crystalline state.
Although the compound was prepared in racemic form, the crystal chosen for analysis crystallized in enantiopure form, however the absolute configuration of the structure has not been established by X-ray methods. This appears to be the fourth example of conglomerate crystallization among Tröger's base systems (Kostyanovsky et al., 2003; Sergeyev et al., 2005; Lenev et al., 2006).
We were interested in preparing a range of nitro-substituted Tröger's base compounds as precursors for supramolecular recognition elements.