Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270109004818/uk3005sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270109004818/uk3005Isup2.hkl |
CCDC reference: 678813
For related literature, see: Alphen (1933); Alvaro et al. (2007); Archelas & Morin (1984); Davies et al. (1992); Neunhoeffer & Fruhauf (1969); Nielsen et al. (1979, 1998); Nitravati & Sikhibhushan (1939); Potts & Husain (1972); Potts et al. (1974); Reed & Schleyer (1988); Senderowitz et al. (1992); Stanforth et al. (2002); Watson et al. (1990).
Aqueous glyoxal (40% w/w, 1.15 ml, 0.01 mol) was added dropwise to a stirred solution of 1,1',2,2'-tetrakis(phenylamino)ethane (3.94 g, 0.01 mol) in ethanol (50 ml) as solvent. The solution temperature was kept at 273 K during the reaction. The mixture was put aside for 24 h at a temperature of 278–283 K. The resulting white precipitate was filtered off and washed with cold ethanol to give 2.53 g (55% yield) of N3,N6,2,5,7-pentaphenyl-2,5,7-triazabicyclo[2,2,1]heptane-3,6-diamine (m.p. 428 K). 1H NMR (CDCl3): δH 6.59–7.30 (m, 25H, CHAr), 5.69 (s, 2H, CH), 4.93 (d, 2H, J = 10 Hz, CH), 3.69 (d, 2H, J = 10 Hz, NH) p.p.m. Addition of D2O to the NMR sample caused the NH signals to disappeared and the CH doublet quickly converted to a singlet. 13C NMR (CDCl3): δC 144.8, 144.2, 143.6, 129.3, 129.7, 122.1, 119.4, 118.7, 117.4, 113.7, 113.2 (CHAr), 76.0 (CH), 72.4 (CH) p.p.m.
The H atoms of the NH groups were located in a difference Fourier map and refined using rigid model with Uiso(H) values fixed at 1.2|Ueq(N). The C-bound H atoms were placed in calculated positions and refined using a riding model with fixed displacement parameters [Uiso(H) = 1.2Ueq(C) or 1.5Ueq(C) for CH and CH3 H atoms, respectively].
Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus (Bruker, 2001); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
Fig. 1. The molecular structure of (I), showing the atom-numbering scheme. H atoms bound to C atoms have been omitted. |
C34H31N5·C8H10 | F(000) = 1312 |
Mr = 615.80 | Dx = 1.230 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 2274 reflections |
a = 12.9790 (8) Å | θ = 2.4–26.8° |
b = 18.0643 (11) Å | µ = 0.07 mm−1 |
c = 14.1838 (8) Å | T = 100 K |
β = 90.682 (2)° | Plate, light-yellow |
V = 3325.2 (3) Å3 | 0.21 × 0.18 × 0.05 mm |
Z = 4 |
Bruker SMART APEXII CCD area-detector diffractometer | 6265 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.051 |
Graphite monochromator | θmax = 30.1°, θmin = 1.8° |
ϕ and ω scans | h = −18→18 |
37513 measured reflections | k = −25→25 |
9690 independent reflections | l = −19→19 |
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: mixed |
wR(F2) = 0.125 | H-atom parameters constrained |
S = 1.01 | w = 1/[σ2(Fo2) + (0.054P)2 + 0.65P] where P = (Fo2 + 2Fc2)/3 |
9690 reflections | (Δ/σ)max < 0.001 |
426 parameters | Δρmax = 0.46 e Å−3 |
0 restraints | Δρmin = −0.22 e Å−3 |
C34H31N5·C8H10 | V = 3325.2 (3) Å3 |
Mr = 615.80 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 12.9790 (8) Å | µ = 0.07 mm−1 |
b = 18.0643 (11) Å | T = 100 K |
c = 14.1838 (8) Å | 0.21 × 0.18 × 0.05 mm |
β = 90.682 (2)° |
Bruker SMART APEXII CCD area-detector diffractometer | 6265 reflections with I > 2σ(I) |
37513 measured reflections | Rint = 0.051 |
9690 independent reflections |
R[F2 > 2σ(F2)] = 0.047 | 0 restraints |
wR(F2) = 0.125 | H-atom parameters constrained |
S = 1.01 | Δρmax = 0.46 e Å−3 |
9690 reflections | Δρmin = −0.22 e Å−3 |
426 parameters |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 | ||
C1 | 0.08017 (10) | 0.23478 (7) | 0.13062 (9) | 0.0222 (3) | |
H1 | 0.0185 | 0.2551 | 0.1633 | 0.027* | |
N2 | 0.05715 (8) | 0.19761 (6) | 0.04043 (7) | 0.0216 (2) | |
C3 | 0.14464 (10) | 0.14990 (7) | 0.01949 (9) | 0.0203 (3) | |
H3 | 0.1800 | 0.1674 | −0.0386 | 0.024* | |
C4 | 0.21279 (10) | 0.16615 (7) | 0.10870 (9) | 0.0199 (2) | |
H4 | 0.2654 | 0.1273 | 0.1235 | 0.024* | |
N5 | 0.25405 (8) | 0.24093 (6) | 0.10064 (8) | 0.0232 (2) | |
C6 | 0.16807 (11) | 0.29172 (7) | 0.11520 (9) | 0.0248 (3) | |
H6 | 0.1544 | 0.3215 | 0.0570 | 0.030* | |
N7 | 0.13637 (8) | 0.17847 (6) | 0.18370 (7) | 0.0204 (2) | |
C7 | −0.00767 (9) | 0.22662 (7) | −0.02940 (9) | 0.0196 (2) | |
C8 | −0.07693 (10) | 0.28382 (7) | −0.00886 (9) | 0.0239 (3) | |
H8 | −0.0762 | 0.3058 | 0.0520 | 0.029* | |
C9 | −0.14640 (11) | 0.30834 (7) | −0.07694 (10) | 0.0264 (3) | |
H9 | −0.1935 | 0.3467 | −0.0620 | 0.032* | |
C10 | −0.14826 (11) | 0.27773 (7) | −0.16652 (10) | 0.0269 (3) | |
H10 | −0.1962 | 0.2948 | −0.2127 | 0.032* | |
C11 | −0.07914 (11) | 0.22189 (7) | −0.18766 (9) | 0.0251 (3) | |
H11 | −0.0794 | 0.2010 | −0.2491 | 0.030* | |
C12 | −0.00941 (10) | 0.19598 (7) | −0.12034 (9) | 0.0221 (3) | |
H12 | 0.0372 | 0.1574 | −0.1359 | 0.027* | |
N3 | 0.11079 (8) | 0.07407 (6) | 0.00786 (8) | 0.0204 (2) | |
H3N | 0.0638 | 0.0613 | 0.0480 | 0.025* | |
C13 | 0.18058 (9) | 0.01903 (7) | −0.01788 (9) | 0.0196 (2) | |
C14 | 0.16269 (10) | −0.05423 (7) | 0.00897 (10) | 0.0248 (3) | |
H14 | 0.1054 | −0.0656 | 0.0474 | 0.030* | |
C15 | 0.22770 (12) | −0.11036 (8) | −0.01996 (11) | 0.0316 (3) | |
H15 | 0.2141 | −0.1600 | −0.0021 | 0.038* | |
C16 | 0.31267 (12) | −0.09454 (9) | −0.07491 (11) | 0.0355 (4) | |
H16 | 0.3578 | −0.1330 | −0.0940 | 0.043* | |
C17 | 0.33073 (12) | −0.02223 (9) | −0.10148 (11) | 0.0349 (3) | |
H17 | 0.3885 | −0.0112 | −0.1395 | 0.042* | |
C18 | 0.26597 (10) | 0.03464 (8) | −0.07365 (10) | 0.0266 (3) | |
H18 | 0.2796 | 0.0841 | −0.0925 | 0.032* | |
C19 | 0.33985 (10) | 0.25826 (8) | 0.04651 (9) | 0.0255 (3) | |
C20 | 0.40916 (11) | 0.20348 (8) | 0.01878 (10) | 0.0287 (3) | |
H20 | 0.3972 | 0.1534 | 0.0357 | 0.034* | |
C21 | 0.49555 (12) | 0.22175 (10) | −0.03348 (11) | 0.0368 (4) | |
H21 | 0.5420 | 0.1838 | −0.0517 | 0.044* | |
C22 | 0.51489 (13) | 0.29407 (11) | −0.05928 (12) | 0.0430 (4) | |
H22 | 0.5736 | 0.3060 | −0.0957 | 0.052* | |
C23 | 0.44762 (14) | 0.34856 (10) | −0.03131 (12) | 0.0430 (4) | |
H23 | 0.4607 | 0.3985 | −0.0484 | 0.052* | |
C24 | 0.36076 (12) | 0.33210 (8) | 0.02156 (10) | 0.0338 (3) | |
H24 | 0.3158 | 0.3706 | 0.0407 | 0.041* | |
N6 | 0.19078 (10) | 0.33972 (6) | 0.19409 (8) | 0.0293 (3) | |
H6N | 0.2065 | 0.3141 | 0.2445 | 0.035* | |
C25 | 0.14162 (10) | 0.40711 (7) | 0.21058 (10) | 0.0237 (3) | |
C26 | 0.13831 (10) | 0.43333 (8) | 0.30303 (10) | 0.0271 (3) | |
H26 | 0.1645 | 0.4035 | 0.3530 | 0.033* | |
C27 | 0.09744 (11) | 0.50221 (8) | 0.32283 (11) | 0.0322 (3) | |
H27 | 0.0956 | 0.5191 | 0.3862 | 0.039* | |
C28 | 0.05907 (11) | 0.54686 (8) | 0.25103 (12) | 0.0350 (4) | |
H28 | 0.0317 | 0.5944 | 0.2645 | 0.042* | |
C29 | 0.06147 (11) | 0.52081 (8) | 0.15963 (12) | 0.0335 (3) | |
H29 | 0.0349 | 0.5509 | 0.1101 | 0.040* | |
C30 | 0.10181 (11) | 0.45170 (8) | 0.13839 (11) | 0.0298 (3) | |
H30 | 0.1024 | 0.4348 | 0.0750 | 0.036* | |
C31 | 0.08365 (10) | 0.11447 (7) | 0.21679 (9) | 0.0207 (3) | |
C32 | −0.02321 (10) | 0.10652 (8) | 0.21077 (9) | 0.0251 (3) | |
H32 | −0.0643 | 0.1451 | 0.1848 | 0.030* | |
C33 | −0.06913 (11) | 0.04215 (8) | 0.24287 (10) | 0.0310 (3) | |
H33 | −0.1419 | 0.0369 | 0.2388 | 0.037* | |
C34 | −0.01044 (12) | −0.01435 (9) | 0.28066 (11) | 0.0348 (3) | |
H34 | −0.0425 | −0.0588 | 0.3010 | 0.042* | |
C35 | 0.09573 (12) | −0.00614 (8) | 0.28888 (11) | 0.0328 (3) | |
H35 | 0.1363 | −0.0447 | 0.3157 | 0.039* | |
C36 | 0.14240 (10) | 0.05823 (8) | 0.25789 (10) | 0.0258 (3) | |
H36 | 0.2148 | 0.0641 | 0.2647 | 0.031* | |
C37 | 0.27607 (12) | 0.10462 (10) | 0.65063 (12) | 0.0406 (4) | |
C38 | 0.34250 (13) | 0.13323 (12) | 0.72068 (13) | 0.0516 (5) | |
H38 | 0.4033 | 0.1068 | 0.7376 | 0.062* | |
C39 | 0.32040 (13) | 0.19952 (12) | 0.76539 (12) | 0.0494 (5) | |
H39 | 0.3671 | 0.2180 | 0.8118 | 0.059* | |
C40 | 0.23312 (13) | 0.23899 (10) | 0.74450 (11) | 0.0424 (4) | |
C41 | 0.16802 (12) | 0.21196 (9) | 0.67356 (11) | 0.0368 (4) | |
H41 | 0.1078 | 0.2390 | 0.6566 | 0.044* | |
C42 | 0.18987 (12) | 0.14637 (9) | 0.62744 (11) | 0.0361 (4) | |
H42 | 0.1447 | 0.1296 | 0.5788 | 0.043* | |
C43 | 0.29846 (16) | 0.03312 (11) | 0.60203 (15) | 0.0582 (5) | |
H43A | 0.2376 | 0.0174 | 0.5657 | 0.087* | |
H43B | 0.3158 | −0.0047 | 0.6491 | 0.087* | |
H43C | 0.3567 | 0.0398 | 0.5595 | 0.087* | |
C44 | 0.20722 (17) | 0.30908 (11) | 0.79704 (13) | 0.0580 (6) | |
H44A | 0.2578 | 0.3169 | 0.8480 | 0.087* | |
H44B | 0.1382 | 0.3047 | 0.8238 | 0.087* | |
H44C | 0.2089 | 0.3512 | 0.7535 | 0.087* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0264 (6) | 0.0213 (6) | 0.0187 (6) | 0.0049 (5) | −0.0053 (5) | −0.0029 (5) |
N2 | 0.0235 (5) | 0.0225 (5) | 0.0186 (5) | 0.0065 (4) | −0.0050 (4) | −0.0033 (4) |
C3 | 0.0217 (6) | 0.0186 (6) | 0.0205 (6) | 0.0017 (5) | −0.0017 (5) | −0.0006 (5) |
C4 | 0.0203 (6) | 0.0186 (6) | 0.0208 (6) | −0.0007 (5) | −0.0024 (5) | 0.0018 (5) |
N5 | 0.0268 (6) | 0.0188 (5) | 0.0239 (6) | −0.0016 (5) | −0.0032 (4) | 0.0013 (4) |
C6 | 0.0330 (7) | 0.0195 (6) | 0.0217 (6) | 0.0028 (6) | −0.0082 (5) | −0.0008 (5) |
N7 | 0.0210 (5) | 0.0198 (5) | 0.0203 (5) | 0.0027 (4) | −0.0033 (4) | 0.0001 (4) |
C7 | 0.0199 (6) | 0.0198 (6) | 0.0190 (6) | −0.0003 (5) | −0.0028 (5) | 0.0004 (5) |
C8 | 0.0290 (7) | 0.0208 (6) | 0.0218 (6) | 0.0024 (5) | −0.0050 (5) | −0.0020 (5) |
C9 | 0.0294 (7) | 0.0189 (6) | 0.0308 (7) | 0.0040 (5) | −0.0074 (6) | 0.0004 (5) |
C10 | 0.0311 (7) | 0.0231 (7) | 0.0262 (7) | 0.0003 (6) | −0.0116 (6) | 0.0043 (5) |
C11 | 0.0308 (7) | 0.0243 (7) | 0.0201 (6) | −0.0031 (6) | −0.0045 (5) | 0.0002 (5) |
C12 | 0.0230 (6) | 0.0219 (6) | 0.0213 (6) | −0.0001 (5) | −0.0018 (5) | −0.0013 (5) |
N3 | 0.0179 (5) | 0.0197 (5) | 0.0238 (5) | −0.0002 (4) | 0.0022 (4) | −0.0017 (4) |
C13 | 0.0180 (6) | 0.0203 (6) | 0.0204 (6) | −0.0005 (5) | −0.0035 (5) | −0.0029 (5) |
C14 | 0.0227 (6) | 0.0232 (7) | 0.0284 (7) | −0.0031 (5) | −0.0049 (5) | 0.0011 (5) |
C15 | 0.0363 (8) | 0.0208 (7) | 0.0374 (8) | 0.0019 (6) | −0.0112 (7) | −0.0032 (6) |
C16 | 0.0341 (8) | 0.0314 (8) | 0.0409 (9) | 0.0124 (7) | −0.0044 (7) | −0.0117 (7) |
C17 | 0.0274 (7) | 0.0384 (8) | 0.0390 (8) | 0.0035 (7) | 0.0072 (6) | −0.0082 (7) |
C18 | 0.0252 (7) | 0.0248 (7) | 0.0299 (7) | −0.0016 (6) | 0.0051 (5) | −0.0027 (6) |
C19 | 0.0276 (7) | 0.0290 (7) | 0.0197 (6) | −0.0077 (6) | −0.0086 (5) | 0.0036 (5) |
C20 | 0.0272 (7) | 0.0347 (8) | 0.0241 (7) | −0.0062 (6) | −0.0032 (5) | 0.0049 (6) |
C21 | 0.0281 (7) | 0.0538 (10) | 0.0283 (8) | −0.0077 (7) | −0.0024 (6) | 0.0065 (7) |
C22 | 0.0326 (8) | 0.0626 (12) | 0.0336 (8) | −0.0183 (8) | −0.0051 (7) | 0.0144 (8) |
C23 | 0.0475 (10) | 0.0449 (10) | 0.0364 (9) | −0.0260 (8) | −0.0144 (7) | 0.0181 (7) |
C24 | 0.0414 (8) | 0.0298 (8) | 0.0298 (8) | −0.0102 (7) | −0.0120 (6) | 0.0066 (6) |
N6 | 0.0437 (7) | 0.0202 (6) | 0.0239 (6) | 0.0039 (5) | −0.0129 (5) | −0.0015 (5) |
C25 | 0.0241 (6) | 0.0188 (6) | 0.0282 (7) | −0.0043 (5) | −0.0045 (5) | 0.0003 (5) |
C26 | 0.0258 (7) | 0.0270 (7) | 0.0285 (7) | −0.0060 (6) | −0.0010 (5) | −0.0011 (6) |
C27 | 0.0269 (7) | 0.0312 (8) | 0.0387 (8) | −0.0054 (6) | 0.0066 (6) | −0.0090 (6) |
C28 | 0.0253 (7) | 0.0240 (7) | 0.0558 (10) | −0.0011 (6) | 0.0089 (7) | −0.0046 (7) |
C29 | 0.0305 (7) | 0.0243 (7) | 0.0455 (9) | 0.0012 (6) | −0.0021 (7) | 0.0067 (7) |
C30 | 0.0347 (8) | 0.0235 (7) | 0.0311 (7) | 0.0013 (6) | −0.0050 (6) | 0.0019 (6) |
C31 | 0.0224 (6) | 0.0225 (6) | 0.0172 (6) | 0.0001 (5) | −0.0006 (5) | −0.0028 (5) |
C32 | 0.0230 (6) | 0.0317 (7) | 0.0208 (6) | 0.0017 (6) | −0.0008 (5) | −0.0053 (5) |
C33 | 0.0228 (7) | 0.0402 (8) | 0.0302 (7) | −0.0054 (6) | 0.0046 (6) | −0.0083 (6) |
C34 | 0.0354 (8) | 0.0310 (8) | 0.0381 (8) | −0.0081 (7) | 0.0115 (7) | −0.0008 (7) |
C35 | 0.0340 (8) | 0.0288 (7) | 0.0359 (8) | 0.0011 (6) | 0.0051 (6) | 0.0066 (6) |
C36 | 0.0229 (6) | 0.0273 (7) | 0.0272 (7) | 0.0009 (5) | 0.0008 (5) | 0.0034 (6) |
C37 | 0.0313 (8) | 0.0476 (10) | 0.0429 (9) | −0.0056 (7) | 0.0034 (7) | 0.0233 (8) |
C38 | 0.0312 (8) | 0.0770 (14) | 0.0464 (10) | −0.0079 (9) | −0.0061 (7) | 0.0350 (10) |
C39 | 0.0383 (9) | 0.0752 (14) | 0.0343 (9) | −0.0257 (9) | −0.0099 (7) | 0.0185 (9) |
C40 | 0.0462 (10) | 0.0529 (10) | 0.0280 (8) | −0.0219 (8) | −0.0048 (7) | 0.0163 (7) |
C41 | 0.0326 (8) | 0.0431 (9) | 0.0345 (8) | −0.0118 (7) | −0.0036 (6) | 0.0125 (7) |
C42 | 0.0287 (7) | 0.0457 (9) | 0.0338 (8) | −0.0110 (7) | −0.0035 (6) | 0.0126 (7) |
C43 | 0.0523 (11) | 0.0581 (12) | 0.0645 (13) | 0.0095 (10) | 0.0117 (10) | 0.0212 (10) |
C44 | 0.0793 (14) | 0.0602 (12) | 0.0345 (9) | −0.0315 (11) | −0.0096 (9) | 0.0081 (9) |
C1—N7 | 1.4562 (16) | C22—C23 | 1.377 (3) |
C1—N2 | 1.4722 (16) | C22—H22 | 0.9500 |
C1—C6 | 1.5536 (19) | C23—C24 | 1.393 (2) |
C1—H1 | 1.0000 | C23—H23 | 0.9500 |
N2—C7 | 1.3941 (16) | C24—H24 | 0.9500 |
N2—C3 | 1.4590 (16) | N6—C25 | 1.3955 (17) |
C3—N3 | 1.4474 (16) | N6—H6N | 0.8744 |
C3—C4 | 1.5630 (17) | C25—C26 | 1.3954 (19) |
C3—H3 | 1.0000 | C25—C30 | 1.3970 (19) |
C4—N5 | 1.4581 (16) | C26—C27 | 1.383 (2) |
C4—N7 | 1.4798 (16) | C26—H26 | 0.9500 |
C4—H4 | 1.0000 | C27—C28 | 1.387 (2) |
N5—C19 | 1.3957 (17) | C27—H27 | 0.9500 |
N5—C6 | 1.4612 (17) | C28—C29 | 1.380 (2) |
C6—N6 | 1.4431 (17) | C28—H28 | 0.9500 |
C6—H6 | 1.0000 | C29—C30 | 1.388 (2) |
N7—C31 | 1.4257 (16) | C29—H29 | 0.9500 |
C7—C8 | 1.4025 (18) | C30—H30 | 0.9500 |
C7—C12 | 1.4036 (17) | C31—C36 | 1.3938 (19) |
C8—C9 | 1.3860 (18) | C31—C32 | 1.3960 (18) |
C8—H8 | 0.9500 | C32—C33 | 1.386 (2) |
C9—C10 | 1.3856 (19) | C32—H32 | 0.9500 |
C9—H9 | 0.9500 | C33—C34 | 1.378 (2) |
C10—C11 | 1.3853 (19) | C33—H33 | 0.9500 |
C10—H10 | 0.9500 | C34—C35 | 1.389 (2) |
C11—C12 | 1.3889 (18) | C34—H34 | 0.9500 |
C11—H11 | 0.9500 | C35—C36 | 1.385 (2) |
C12—H12 | 0.9500 | C35—H35 | 0.9500 |
N3—C13 | 1.3965 (16) | C36—H36 | 0.9500 |
N3—H3N | 0.8704 | C37—C42 | 1.386 (2) |
C13—C14 | 1.3974 (18) | C37—C38 | 1.406 (3) |
C13—C18 | 1.3979 (18) | C37—C43 | 1.494 (3) |
C14—C15 | 1.384 (2) | C38—C39 | 1.387 (3) |
C14—H14 | 0.9500 | C38—H38 | 0.9500 |
C15—C16 | 1.388 (2) | C39—C40 | 1.368 (3) |
C15—H15 | 0.9500 | C39—H39 | 0.9500 |
C16—C17 | 1.380 (2) | C40—C41 | 1.394 (2) |
C16—H16 | 0.9500 | C40—C44 | 1.509 (3) |
C17—C18 | 1.3878 (19) | C41—C42 | 1.384 (2) |
C17—H17 | 0.9500 | C41—H41 | 0.9500 |
C18—H18 | 0.9500 | C42—H42 | 0.9500 |
C19—C20 | 1.397 (2) | C43—H43A | 0.9800 |
C19—C24 | 1.407 (2) | C43—H43B | 0.9800 |
C20—C21 | 1.391 (2) | C43—H43C | 0.9800 |
C20—H20 | 0.9500 | C44—H44A | 0.9800 |
C21—C22 | 1.381 (2) | C44—H44B | 0.9800 |
C21—H21 | 0.9500 | C44—H44C | 0.9800 |
N7—C1—N2 | 103.06 (10) | C20—C21—H21 | 119.5 |
N7—C1—C6 | 99.85 (10) | C23—C22—C21 | 118.82 (15) |
N2—C1—C6 | 108.75 (10) | C23—C22—H22 | 120.6 |
N7—C1—H1 | 114.5 | C21—C22—H22 | 120.6 |
N2—C1—H1 | 114.5 | C22—C23—C24 | 121.49 (15) |
C6—C1—H1 | 114.5 | C22—C23—H23 | 119.3 |
C7—N2—C3 | 122.82 (10) | C24—C23—H23 | 119.3 |
C7—N2—C1 | 124.09 (10) | C23—C24—C19 | 119.82 (16) |
C3—N2—C1 | 107.21 (10) | C23—C24—H24 | 120.1 |
N3—C3—N2 | 110.26 (10) | C19—C24—H24 | 120.1 |
N3—C3—C4 | 115.99 (10) | C25—N6—C6 | 124.37 (11) |
N2—C3—C4 | 99.12 (9) | C25—N6—H6N | 115.3 |
N3—C3—H3 | 110.3 | C6—N6—H6N | 111.1 |
N2—C3—H3 | 110.3 | C26—C25—N6 | 118.22 (12) |
C4—C3—H3 | 110.3 | C26—C25—C30 | 118.55 (13) |
N5—C4—N7 | 99.61 (10) | N6—C25—C30 | 123.09 (13) |
N5—C4—C3 | 108.38 (10) | C27—C26—C25 | 120.83 (14) |
N7—C4—C3 | 103.45 (10) | C27—C26—H26 | 119.6 |
N5—C4—H4 | 114.6 | C25—C26—H26 | 119.6 |
N7—C4—H4 | 114.6 | C26—C27—C28 | 120.63 (14) |
C3—C4—H4 | 114.6 | C26—C27—H27 | 119.7 |
C19—N5—C4 | 123.17 (11) | C28—C27—H27 | 119.7 |
C19—N5—C6 | 123.54 (11) | C29—C28—C27 | 118.66 (14) |
C4—N5—C6 | 106.79 (10) | C29—C28—H28 | 120.7 |
N6—C6—N5 | 109.73 (11) | C27—C28—H28 | 120.7 |
N6—C6—C1 | 115.61 (11) | C28—C29—C30 | 121.56 (14) |
N5—C6—C1 | 99.64 (10) | C28—C29—H29 | 119.2 |
N6—C6—H6 | 110.5 | C30—C29—H29 | 119.2 |
N5—C6—H6 | 110.5 | C29—C30—C25 | 119.77 (14) |
C1—C6—H6 | 110.5 | C29—C30—H30 | 120.1 |
C31—N7—C1 | 119.81 (10) | C25—C30—H30 | 120.1 |
C31—N7—C4 | 116.30 (10) | C36—C31—C32 | 119.26 (12) |
C1—N7—C4 | 93.97 (9) | C36—C31—N7 | 117.80 (11) |
N2—C7—C8 | 120.81 (11) | C32—C31—N7 | 122.94 (12) |
N2—C7—C12 | 120.51 (11) | C33—C32—C31 | 119.81 (13) |
C8—C7—C12 | 118.56 (12) | C33—C32—H32 | 120.1 |
C9—C8—C7 | 120.26 (12) | C31—C32—H32 | 120.1 |
C9—C8—H8 | 119.9 | C34—C33—C32 | 120.74 (13) |
C7—C8—H8 | 119.9 | C34—C33—H33 | 119.6 |
C10—C9—C8 | 121.03 (13) | C32—C33—H33 | 119.6 |
C10—C9—H9 | 119.5 | C33—C34—C35 | 119.77 (14) |
C8—C9—H9 | 119.5 | C33—C34—H34 | 120.1 |
C11—C10—C9 | 119.00 (12) | C35—C34—H34 | 120.1 |
C11—C10—H10 | 120.5 | C36—C35—C34 | 120.00 (14) |
C9—C10—H10 | 120.5 | C36—C35—H35 | 120.0 |
C10—C11—C12 | 120.99 (12) | C34—C35—H35 | 120.0 |
C10—C11—H11 | 119.5 | C35—C36—C31 | 120.36 (13) |
C12—C11—H11 | 119.5 | C35—C36—H36 | 119.8 |
C11—C12—C7 | 120.14 (12) | C31—C36—H36 | 119.8 |
C11—C12—H12 | 119.9 | C42—C37—C38 | 117.01 (18) |
C7—C12—H12 | 119.9 | C42—C37—C43 | 121.47 (17) |
C13—N3—C3 | 120.43 (10) | C38—C37—C43 | 121.52 (17) |
C13—N3—H3N | 116.3 | C39—C38—C37 | 120.81 (17) |
C3—N3—H3N | 113.0 | C39—C38—H38 | 119.6 |
N3—C13—C14 | 119.51 (11) | C37—C38—H38 | 119.6 |
N3—C13—C18 | 121.70 (12) | C40—C39—C38 | 121.75 (17) |
C14—C13—C18 | 118.73 (12) | C40—C39—H39 | 119.1 |
C15—C14—C13 | 120.60 (13) | C38—C39—H39 | 119.1 |
C15—C14—H14 | 119.7 | C39—C40—C41 | 117.84 (18) |
C13—C14—H14 | 119.7 | C39—C40—C44 | 121.27 (17) |
C14—C15—C16 | 120.46 (14) | C41—C40—C44 | 120.89 (17) |
C14—C15—H15 | 119.8 | C42—C41—C40 | 120.98 (16) |
C16—C15—H15 | 119.8 | C42—C41—H41 | 119.5 |
C17—C16—C15 | 119.14 (13) | C40—C41—H41 | 119.5 |
C17—C16—H16 | 120.4 | C41—C42—C37 | 121.54 (16) |
C15—C16—H16 | 120.4 | C41—C42—H42 | 119.2 |
C16—C17—C18 | 121.17 (14) | C37—C42—H42 | 119.2 |
C16—C17—H17 | 119.4 | C37—C43—H43A | 109.5 |
C18—C17—H17 | 119.4 | C37—C43—H43B | 109.5 |
C17—C18—C13 | 119.90 (13) | H43A—C43—H43B | 109.5 |
C17—C18—H18 | 120.0 | C37—C43—H43C | 109.5 |
C13—C18—H18 | 120.0 | H43A—C43—H43C | 109.5 |
N5—C19—C20 | 121.10 (12) | H43B—C43—H43C | 109.5 |
N5—C19—C24 | 120.56 (14) | C40—C44—H44A | 109.5 |
C20—C19—C24 | 118.29 (13) | C40—C44—H44B | 109.5 |
C21—C20—C19 | 120.51 (14) | H44A—C44—H44B | 109.5 |
C21—C20—H20 | 119.7 | C40—C44—H44C | 109.5 |
C19—C20—H20 | 119.7 | H44A—C44—H44C | 109.5 |
C22—C21—C20 | 121.06 (16) | H44B—C44—H44C | 109.5 |
C22—C21—H21 | 119.5 | ||
N7—C1—N2—C7 | 171.35 (11) | C14—C15—C16—C17 | −0.9 (2) |
C6—C1—N2—C7 | −83.33 (14) | C15—C16—C17—C18 | 0.5 (2) |
N7—C1—N2—C3 | −35.18 (13) | C16—C17—C18—C13 | −0.1 (2) |
C6—C1—N2—C3 | 70.14 (12) | N3—C13—C18—C17 | −176.89 (13) |
C7—N2—C3—N3 | −83.24 (14) | C14—C13—C18—C17 | 0.2 (2) |
C1—N2—C3—N3 | 122.87 (11) | C4—N5—C19—C20 | −18.77 (18) |
C7—N2—C3—C4 | 154.60 (11) | C6—N5—C19—C20 | −166.70 (12) |
C1—N2—C3—C4 | 0.71 (12) | C4—N5—C19—C24 | 163.68 (12) |
N3—C3—C4—N5 | 170.34 (10) | C6—N5—C19—C24 | 15.75 (19) |
N2—C3—C4—N5 | −71.72 (12) | N5—C19—C20—C21 | −178.63 (12) |
N3—C3—C4—N7 | −84.57 (12) | C24—C19—C20—C21 | −1.0 (2) |
N2—C3—C4—N7 | 33.37 (11) | C19—C20—C21—C22 | −0.1 (2) |
N7—C4—N5—C19 | 171.54 (11) | C20—C21—C22—C23 | 0.8 (2) |
C3—C4—N5—C19 | −80.71 (14) | C21—C22—C23—C24 | −0.4 (2) |
N7—C4—N5—C6 | −35.99 (12) | C22—C23—C24—C19 | −0.7 (2) |
C3—C4—N5—C6 | 71.75 (12) | N5—C19—C24—C23 | 179.03 (13) |
C19—N5—C6—N6 | −86.22 (15) | C20—C19—C24—C23 | 1.4 (2) |
C4—N5—C6—N6 | 121.44 (11) | N5—C6—N6—C25 | 160.49 (12) |
C19—N5—C6—C1 | 152.00 (11) | C1—C6—N6—C25 | −87.84 (16) |
C4—N5—C6—C1 | −0.34 (12) | C6—N6—C25—C26 | 154.66 (13) |
N7—C1—C6—N6 | −80.18 (13) | C6—N6—C25—C30 | −29.8 (2) |
N2—C1—C6—N6 | 172.30 (10) | N6—C25—C26—C27 | 175.20 (13) |
N7—C1—C6—N5 | 37.28 (11) | C30—C25—C26—C27 | −0.6 (2) |
N2—C1—C6—N5 | −70.24 (11) | C25—C26—C27—C28 | −0.2 (2) |
N2—C1—N7—C31 | −69.98 (13) | C26—C27—C28—C29 | 0.7 (2) |
C6—C1—N7—C31 | 177.99 (10) | C27—C28—C29—C30 | −0.5 (2) |
N2—C1—N7—C4 | 53.50 (11) | C28—C29—C30—C25 | −0.3 (2) |
C6—C1—N7—C4 | −58.53 (10) | C26—C25—C30—C29 | 0.8 (2) |
N5—C4—N7—C31 | −175.54 (10) | N6—C25—C30—C29 | −174.73 (13) |
C3—C4—N7—C31 | 72.78 (12) | C1—N7—C31—C36 | 172.93 (11) |
N5—C4—N7—C1 | 58.29 (10) | C4—N7—C31—C36 | 61.07 (15) |
C3—C4—N7—C1 | −53.39 (11) | C1—N7—C31—C32 | −7.92 (18) |
C3—N2—C7—C8 | −166.66 (12) | C4—N7—C31—C32 | −119.77 (13) |
C1—N2—C7—C8 | −17.16 (19) | C36—C31—C32—C33 | −2.02 (19) |
C3—N2—C7—C12 | 17.33 (18) | N7—C31—C32—C33 | 178.85 (12) |
C1—N2—C7—C12 | 166.83 (12) | C31—C32—C33—C34 | −0.1 (2) |
N2—C7—C8—C9 | −175.07 (12) | C32—C33—C34—C35 | 1.6 (2) |
C12—C7—C8—C9 | 1.02 (19) | C33—C34—C35—C36 | −0.9 (2) |
C7—C8—C9—C10 | −0.7 (2) | C34—C35—C36—C31 | −1.2 (2) |
C8—C9—C10—C11 | −0.1 (2) | C32—C31—C36—C35 | 2.7 (2) |
C9—C10—C11—C12 | 0.7 (2) | N7—C31—C36—C35 | −178.16 (12) |
C10—C11—C12—C7 | −0.4 (2) | C42—C37—C38—C39 | 1.4 (2) |
N2—C7—C12—C11 | 175.62 (12) | C43—C37—C38—C39 | −179.74 (16) |
C8—C7—C12—C11 | −0.47 (19) | C37—C38—C39—C40 | 1.0 (2) |
N2—C3—N3—C13 | 176.38 (10) | C38—C39—C40—C41 | −2.5 (2) |
C4—C3—N3—C13 | −72.03 (15) | C38—C39—C40—C44 | 176.89 (15) |
C3—N3—C13—C14 | 152.73 (12) | C39—C40—C41—C42 | 1.5 (2) |
C3—N3—C13—C18 | −30.17 (18) | C44—C40—C41—C42 | −177.82 (15) |
N3—C13—C14—C15 | 176.51 (12) | C40—C41—C42—C37 | 0.9 (2) |
C18—C13—C14—C15 | −0.68 (19) | C38—C37—C42—C41 | −2.3 (2) |
C13—C14—C15—C16 | 1.0 (2) | C43—C37—C42—C41 | 178.82 (15) |
Experimental details
Crystal data | |
Chemical formula | C34H31N5·C8H10 |
Mr | 615.80 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 100 |
a, b, c (Å) | 12.9790 (8), 18.0643 (11), 14.1838 (8) |
β (°) | 90.682 (2) |
V (Å3) | 3325.2 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.07 |
Crystal size (mm) | 0.21 × 0.18 × 0.05 |
Data collection | |
Diffractometer | Bruker SMART APEXII CCD area-detector diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 37513, 9690, 6265 |
Rint | 0.051 |
(sin θ/λ)max (Å−1) | 0.705 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.047, 0.125, 1.01 |
No. of reflections | 9690 |
No. of parameters | 426 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.46, −0.22 |
Computer programs: APEX2 (Bruker, 2005), SAINT-Plus (Bruker, 2001), SHELXTL (Sheldrick, 2008).
Parameters | nN3 → σ*C—N2i | nN7 → σ*C—N2 | nN5 → σ*C—N7 | nN6 → σ*C—N5 |
N'—C | 1.4474 (16) | 1.4562 (16) | 1.4581 (16) | 1.4431 (17) |
C—N'' | 1.4590 (16) | 1.4722 (16) | 1.4798 (16) | 1.4612 (17) |
N'—C—N'' | 110.26 (10) | 103.06 (10) | 99.61 (10) | 109.73 (11) |
Pyr N' | 349.7 | 330.08 (17) | 353.50 (18) | 350.8 |
Pyr N'' | 354.12 (17) | 354.12 (17) | 330.08 (17) | 353.50 (18) |
Notes: (i) nN' → σ*C-N"; (ii) pyramidality of the N atoms (the sum of the three angles around N; s.u. values are estimated from the sum of s.u. values when they are available). |
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Polyazapolycyclics (Nielsen et al., 1979), an important precursor for the syntheses of high-density and energetic compounds (Nielsen et al. 1998), are constituted of saturated rings with multiple N atoms and are generally synthesized under catalytic reaction conditions. Several azanorbornane or azabicyclo[2,2,1]heptane (Archelas & Morin, 1984) and diazanorbornan derivatives (Alvaro et al., 2007) have been synthesized and characterized so far, but triazanorbornane derivatives have seldom been reported (Nitravati & Sikhibhushan, 1939, 1941; Alphen,1933). The synthesis and molecular structure of 2,5,7-triazabicyclo[2,2,1]heptanes have been presented in a few papers without using X-ray crystal structure analysis (Potts & Husain, 1972; Potts et al.,1974; Neunhoeffer & Fruhauf, 1969, 1970; Stanforth et al., 2002). In order to reveal the structural features of this norbornane-like triazacyclo[2,2,1]heptane skeleton, the crystal structure of the title compound, (I), was carried out.
Catalytic reaction of 1,1',2,2'-tetrakis(phenylamino)ethane (Kliegman & Barnes, 1970) in the presence of ethanol as solvent and glyoxal as catalyst led to the formation of (I), which is reported for the first time. Single crystals were formed by recrystallization from xylene solution.
There is one independent molecule and one xylene crystalline solvent molecule in the asymmetric unit. The crystal structure is racemic, so all S- and all R-configuration molecules are included. The molecular structure of (I) is shown in Fig. 1. The geometry is designated as a norbornane skeleton, which consists of a six-membered piperazine ring and a ring formed by an N atom bridging between the C1 and C4 positions. Despite the presence of two NH groups, N3 and N6, each carrying lone-pair electrons potentially available for hydrogen-bond formation, there are, in fact, no intra- or intermolecular C—H···N hydrogen bonds. As shown in the scheme, the skeleton has a good local twofold-axis symmetry, namely through the bridge N7 and almost perpendicular to the least-squares plane of the piperazine ring. It is noteworthy that the symmetry involves not only the skeleton but also the peripheral phenyl groups, except for that attached to the bridge atom N7.
The anomeric effect in N—C—N systems and its implications on structural stability, reactivity and conformational behavior have been studied extensively (Senderowitz et al., 1992). The occurrence of anomeric effects in a system influences many structural and electronic properties. The general concept of the anomeric effect involves a stabilizing interaction between a lone pair on N and an antiperiplanar σ* orbital of the adjacent C—N bond (nN → σ*C—N), which is best described as `negative hyperconjugation' (Reed & Schleyer, 1988).
In (I), four unequal anomeric effects are observed in the N'—C—N" fragments, and these effects are manifested by the bond distances and N pyramidality. In the nN' → σ*C—N" systems, the significance of the anomeric effect is indicated by the amount of geometrical deformation caused by the effect. Within the N'—C—N" unit, the N'—C bond is shorter than the C—N" bond. On the other hand, the pyramidality angle of N' (the sum of the three bond angles around N') is larger than that of N". These geometric parameters related to the anomeric effect are shown in Table 1. Among them, the nN5 → σ*C—N7 system shows a prominent anomeric interaction and the largest bond-length difference is 0.021 (2) Å, which is comparable to that reported for an analogous molecule (ca 0.01 Å; Senderowitz et al., 1992).
Conversely, the pyramidality angle differences in the N'—C—N" units are not so indicative. The differences within the N5—C4—N7 and N7—C1—N2 systems are 23.6 (2) and 24.1 (2)°, respectively, and these are much larger than those for the N6—C6—N5 and N3—C3—N2 groups (2.9 and 4.3°, respectively). Moreover, the calculated pyramidality angles for atoms N3 and N6 are not accurate because they include H atoms, whose positions were determined from a difference Fourier synthesis. Thus the anomeric effect on the pyramidality angle is not clear in this molecule. It could be that the anomeric effect on the angle is buried among the steric effects caused by the crowding of the substituent groups, which would strongly affect the molecular structure.
Reflecting the local twofold-axis symmetry, the corresponding N atoms in this symmetric skeleton (N2 and N5, N3 and N6) have nearly the same pyramidality angles. The pyramidality angle of N7 [330.07 (17)°] is rather small, and the attached phenyl group inclines from the local twofold axis towards atoms N2, C3 and N3. Corresponding to this inclination, the C32—C31—N7 angle [122.92 (12)°] is distorted from the ideal angle of 120°, which is attributable to the short contact between the voluminous phenyl ring and the skeleton. For example, the H32A···H1A separation (atom C1 is the bridgehead) is only 2.282 Å. Same distortion is seen in another norbornane derivative [122.5 (4)°; Watson et al., 1990] for the phenyl ring on the bridging atom.
The angle at the bridging N atom, C1—N7—C4, is 93.96 (10)°. Although this bridge angle is comparable to those reported for norbornane and diazanorbornane (Davies et al., 1992), it still indicates of the presence ring presure [please clarify what is meant by this].