Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270104007012/gg1207sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270104007012/gg1207Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270104007012/gg1207IIsup3.hkl | |
Portable Document Format (PDF) file https://doi.org/10.1107/S0108270104007012/gg1207sup4.pdf |
CCDC references: 241239; 241240
Compound (I) was prepared as follows. A solution of N,N,N',N'-dipiperidylchloroformamidinium chloride (7.53 g, 30 mmol) in dry MeCN was added dropwise under vigorous stirring to an ice-cooled solution of 1,3-diaminopropane (1.11 g, 15 mmol) and triethylamine (4.18 ml, 3.03 g, 30 mmol) in dry MeCN. After 3 h at reflux, a solution of NaOH (1.2 g, 30 mmol) in water was added. The solvents and NEt3 were then evaporated under vacuum. In order to deprotonate the bis-hydrochloride, 50 wt% KOH (aq., 15 ml) was added and the free base was extracted into the MeCN phase (3 × 20 ml). The organic phase was dried with Na2SO4 over charcoal. After filtration over Celite, the solvent was evaporated under reduced pressure. The pure product, (I), was obtained as a white powder (yield 66%, 4.26 g). Colourless crystals of (I) suitable for X-ray diffraction were obtained by crystallization from a cold saturated MeCN solution. Spectroscopic analysis: 1H NMR (500 MHz, CDCl3, δ, p.p.m.): 1.48–1.61 (m, 24H, Pip-CH2), 1.80 (q, 2H, CH2), 3.02 (t, 16H, Pip-CH2), 3.18 (t, 4H, CH2); 13C NMR (125 MHz, CDCl3, δ, p.p.m.): 24.8 (Pip), 25.9 (Pip), 34.5 (C13), 46.7 (C12, C14), 49.1 (Pip), 160.0 (Cquart.); IR (KBr, ν, cm−1, important bands): 2927 (versus), 1626 (versus, C═N), 1608 (s, C═N), 1398 (s), 1367 (s), 1246 (s), 1209 (s). EI—MS: m/z (%) 430 (42) [M+], 346 (10) [M+—Pip], 237 (13), 222 (81), 196 (12), 154 (41), 126 (43), 85 (51) [HPip], 84 (100) [Pip], 69 (22). Compound (II) was prepared as follows. A solution of N,N'-dimethylpropylenechloroformamidinium chloride (7.33 g, 40 mmol) in dry MeCN was added dropwise under vigorous stirring to an ice-cooled solution of 1,3-diaminopropane (1.48 g, 20 mmol) and triethylamine (5.57 ml, 4.04 g, 40 mmol) in dry MeCN. After 3 h at reflux, a solution of NaOH (1.6 g, 40 mmol) in water was added. Further treatment was carried out as for (I). The pure product, (II), was obtained as a colourless oil which crystallized after 2 months to give needles suitable for X-ray diffraction (yield 92%, 5.4 g, 18.4 mmol). Spectroscopic analysis: 1H NMR (500 MHz, CDCl3, δ, p.p.m.): 1.50 (m, 2H, CH2), 1.68 (m, 4H, CH2), 2.70 (s, 12H, CH3), 2.95 (m, 8H, CH2), 3.02 (t, 4H, CH2); 13C NMR (125 MHz, CDCl3, δ, p.p.m.): 20.9 (CH2), 32.3 (C8), 39.3 (CH3), 45.8 (C7, 9), 48.4 (CH2), 157.5 (Cquart.); IR (KBr, ν, cm−1, important bands): 2921 (s), 2858 (s), 1621 (versus, C═N), 1576 (s, C═N), 1541 (s). CI—MS: m/z 294 (25) [M+]. The formamidinium salts were prepared using the literature procedures of Kantlehner et al. (1984).
For both compounds, all H atoms were placed in calculated positions, with C—H distances in the range 0.98–0.99 Å Please check added text, and refined as riding on their attached C atoms, with Uiso(H) = 1.2Ueq(C).
For both compounds, data collection: SMART (Bruker, 2002); cell refinement: SMART; data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXTL (Bruker, 2002); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL and PLATON (Spek, 2002); software used to prepare material for publication: SHELXTL.
C25H46N6 | F(000) = 952 |
Mr = 430.68 | Dx = 1.141 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 3799 reflections |
a = 10.0619 (7) Å | θ = 2.3–27.5° |
b = 19.8127 (13) Å | µ = 0.07 mm−1 |
c = 12.7511 (8) Å | T = 120 K |
β = 99.594 (2)° | Prism, colourless |
V = 2506.4 (3) Å3 | 0.40 × 0.35 × 0.20 mm |
Z = 4 |
Bruker SMART CCD area-detector diffractometer | 6205 independent reflections |
Radiation source: sealed tube | 4055 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.044 |
ϕ and ω scans | θmax = 28.3°, θmin = 1.9° |
Absorption correction: multi-scan (SADABS; Bruker, 2002) | h = −13→13 |
Tmin = 0.951, Tmax = 0.989 | k = −22→26 |
19511 measured reflections | l = −12→17 |
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)] = 0.042 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.090 | H-atom parameters constrained |
S = 0.86 | w = 1/[σ2(Fo2) + (0.0397P)2] where P = (Fo2 + 2Fc2)/3 |
6205 reflections | (Δ/σ)max < 0.001 |
280 parameters | Δρmax = 0.22 e Å−3 |
0 restraints | Δρmin = −0.15 e Å−3 |
C25H46N6 | V = 2506.4 (3) Å3 |
Mr = 430.68 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 10.0619 (7) Å | µ = 0.07 mm−1 |
b = 19.8127 (13) Å | T = 120 K |
c = 12.7511 (8) Å | 0.40 × 0.35 × 0.20 mm |
β = 99.594 (2)° |
Bruker SMART CCD area-detector diffractometer | 6205 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2002) | 4055 reflections with I > 2σ(I) |
Tmin = 0.951, Tmax = 0.989 | Rint = 0.044 |
19511 measured reflections |
R[F2 > 2σ(F2)] = 0.042 | 0 restraints |
wR(F2) = 0.090 | H-atom parameters constrained |
S = 0.86 | Δρmax = 0.22 e Å−3 |
6205 reflections | Δρmin = −0.15 e Å−3 |
280 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 | ||
N1 | 1.25914 (9) | 0.24511 (5) | 0.10722 (7) | 0.0270 (2) | |
N2 | 1.27042 (9) | 0.14622 (5) | 0.01131 (7) | 0.0265 (2) | |
N3 | 1.33223 (10) | 0.14286 (5) | 0.19724 (7) | 0.0289 (2) | |
N4 | 0.97422 (9) | 0.25464 (4) | 0.26632 (7) | 0.0243 (2) | |
N5 | 0.87013 (9) | 0.16025 (4) | 0.17075 (7) | 0.0253 (2) | |
N6 | 0.94131 (9) | 0.15528 (4) | 0.35501 (7) | 0.0241 (2) | |
C1 | 1.28848 (11) | 0.18249 (6) | 0.10722 (9) | 0.0255 (3) | |
C2 | 1.18668 (12) | 0.17841 (6) | −0.08015 (9) | 0.0301 (3) | |
H2A | 1.2382 | 0.2148 | −0.1084 | 0.036* | |
H2B | 1.1059 | 0.1987 | −0.0579 | 0.036* | |
C3 | 1.14425 (12) | 0.12590 (6) | −0.16583 (9) | 0.0322 (3) | |
H3A | 1.0901 | 0.1478 | −0.2286 | 0.039* | |
H3B | 1.0872 | 0.0914 | −0.1389 | 0.039* | |
C4 | 1.26648 (13) | 0.09197 (6) | −0.19865 (9) | 0.0337 (3) | |
H4A | 1.3163 | 0.1251 | −0.2354 | 0.040* | |
H4B | 1.2364 | 0.0549 | −0.2490 | 0.040* | |
C5 | 1.35952 (12) | 0.06390 (6) | −0.10228 (9) | 0.0321 (3) | |
H5A | 1.3149 | 0.0256 | −0.0723 | 0.039* | |
H5B | 1.4432 | 0.0469 | −0.1242 | 0.039* | |
C6 | 1.39421 (11) | 0.11804 (6) | −0.01823 (9) | 0.0290 (3) | |
H6A | 1.4509 | 0.0985 | 0.0454 | 0.035* | |
H6B | 1.4462 | 0.1544 | −0.0460 | 0.035* | |
C7 | 1.30596 (13) | 0.07070 (6) | 0.19894 (9) | 0.0346 (3) | |
H7A | 1.3829 | 0.0457 | 0.1786 | 0.042* | |
H7B | 1.2244 | 0.0598 | 0.1468 | 0.042* | |
C8 | 1.28547 (14) | 0.04928 (7) | 0.30954 (10) | 0.0417 (3) | |
H8A | 1.2734 | −0.0003 | 0.3112 | 0.050* | |
H8B | 1.2028 | 0.0707 | 0.3266 | 0.050* | |
C9 | 1.40589 (15) | 0.06966 (7) | 0.39265 (10) | 0.0481 (4) | |
H9A | 1.3868 | 0.0591 | 0.4645 | 0.058* | |
H9B | 1.4861 | 0.0434 | 0.3815 | 0.058* | |
C10 | 1.43533 (13) | 0.14439 (7) | 0.38541 (10) | 0.0418 (3) | |
H10A | 1.5194 | 0.1555 | 0.4345 | 0.050* | |
H10B | 1.3610 | 0.1708 | 0.4073 | 0.050* | |
C11 | 1.45031 (12) | 0.16359 (7) | 0.27276 (9) | 0.0350 (3) | |
H11A | 1.4621 | 0.2131 | 0.2684 | 0.042* | |
H11B | 1.5317 | 0.1416 | 0.2542 | 0.042* | |
C12 | 1.24621 (12) | 0.27921 (6) | 0.20667 (8) | 0.0273 (3) | |
H12A | 1.3295 | 0.3049 | 0.2329 | 0.033* | |
H12B | 1.2334 | 0.2454 | 0.2613 | 0.033* | |
C13 | 1.12667 (11) | 0.32669 (5) | 0.18786 (9) | 0.0271 (3) | |
H13A | 1.1331 | 0.3557 | 0.1257 | 0.032* | |
H13B | 1.1287 | 0.3563 | 0.2507 | 0.032* | |
C14 | 0.99451 (11) | 0.28821 (5) | 0.16803 (8) | 0.0255 (3) | |
H14A | 0.9192 | 0.3197 | 0.1443 | 0.031* | |
H14B | 0.9965 | 0.2543 | 0.1113 | 0.031* | |
C15 | 0.92822 (11) | 0.19442 (5) | 0.26243 (8) | 0.0230 (2) | |
C16 | 0.88042 (12) | 0.08746 (5) | 0.15955 (9) | 0.0284 (3) | |
H16A | 0.7967 | 0.0657 | 0.1738 | 0.034* | |
H16B | 0.9566 | 0.0701 | 0.2118 | 0.034* | |
C17 | 0.90245 (12) | 0.07037 (6) | 0.04781 (9) | 0.0296 (3) | |
H17A | 0.9048 | 0.0207 | 0.0395 | 0.035* | |
H17B | 0.9904 | 0.0887 | 0.0362 | 0.035* | |
C18 | 0.79051 (12) | 0.09971 (6) | −0.03509 (9) | 0.0310 (3) | |
H18A | 0.8118 | 0.0917 | −0.1071 | 0.037* | |
H18B | 0.7045 | 0.0766 | −0.0303 | 0.037* | |
C19 | 0.77476 (12) | 0.17513 (6) | −0.01814 (8) | 0.0285 (3) | |
H19A | 0.8545 | 0.1992 | −0.0356 | 0.034* | |
H19B | 0.6942 | 0.1918 | −0.0665 | 0.034* | |
C20 | 0.76026 (11) | 0.19008 (6) | 0.09617 (8) | 0.0261 (3) | |
H20A | 0.7596 | 0.2396 | 0.1071 | 0.031* | |
H20B | 0.6733 | 0.1719 | 0.1102 | 0.031* | |
C21 | 1.03450 (12) | 0.18007 (6) | 0.44712 (8) | 0.0273 (3) | |
H21A | 0.9925 | 0.2179 | 0.4805 | 0.033* | |
H21B | 1.1176 | 0.1971 | 0.4241 | 0.033* | |
C22 | 1.06958 (12) | 0.12344 (6) | 0.52727 (9) | 0.0296 (3) | |
H22A | 1.1296 | 0.1411 | 0.5908 | 0.036* | |
H22B | 1.1188 | 0.0875 | 0.4956 | 0.036* | |
C23 | 0.94348 (12) | 0.09371 (6) | 0.56044 (9) | 0.0316 (3) | |
H23A | 0.9683 | 0.0546 | 0.6080 | 0.038* | |
H23B | 0.9000 | 0.1280 | 0.6000 | 0.038* | |
C24 | 0.84572 (12) | 0.07132 (6) | 0.46295 (9) | 0.0307 (3) | |
H24A | 0.8850 | 0.0331 | 0.4285 | 0.037* | |
H24B | 0.7608 | 0.0557 | 0.4846 | 0.037* | |
C25 | 0.81598 (11) | 0.12915 (6) | 0.38472 (9) | 0.0270 (3) | |
H25A | 0.7553 | 0.1133 | 0.3202 | 0.032* | |
H25B | 0.7696 | 0.1658 | 0.4172 | 0.032* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0287 (6) | 0.0318 (6) | 0.0218 (5) | −0.0027 (4) | 0.0077 (4) | −0.0017 (4) |
N2 | 0.0248 (5) | 0.0338 (6) | 0.0212 (5) | 0.0026 (4) | 0.0046 (4) | −0.0019 (4) |
N3 | 0.0300 (6) | 0.0329 (6) | 0.0229 (5) | 0.0009 (5) | 0.0016 (4) | −0.0003 (4) |
N4 | 0.0277 (5) | 0.0251 (5) | 0.0209 (5) | 0.0003 (4) | 0.0064 (4) | 0.0015 (4) |
N5 | 0.0288 (6) | 0.0218 (5) | 0.0237 (5) | 0.0021 (4) | −0.0007 (4) | 0.0013 (4) |
N6 | 0.0237 (5) | 0.0273 (5) | 0.0211 (5) | −0.0031 (4) | 0.0029 (4) | 0.0033 (4) |
C1 | 0.0211 (6) | 0.0334 (7) | 0.0225 (6) | −0.0024 (5) | 0.0053 (5) | −0.0008 (5) |
C2 | 0.0327 (7) | 0.0341 (7) | 0.0236 (6) | 0.0019 (5) | 0.0049 (5) | 0.0002 (5) |
C3 | 0.0357 (7) | 0.0374 (7) | 0.0224 (7) | −0.0031 (6) | 0.0014 (5) | 0.0017 (5) |
C4 | 0.0452 (8) | 0.0339 (7) | 0.0231 (7) | −0.0068 (6) | 0.0088 (6) | −0.0055 (5) |
C5 | 0.0332 (7) | 0.0323 (7) | 0.0324 (7) | −0.0018 (6) | 0.0101 (5) | −0.0053 (5) |
C6 | 0.0249 (7) | 0.0352 (7) | 0.0278 (7) | −0.0028 (5) | 0.0074 (5) | −0.0031 (5) |
C7 | 0.0399 (8) | 0.0339 (7) | 0.0304 (7) | 0.0045 (6) | 0.0069 (6) | 0.0017 (5) |
C8 | 0.0474 (9) | 0.0439 (8) | 0.0350 (8) | 0.0053 (7) | 0.0103 (6) | 0.0096 (6) |
C9 | 0.0483 (9) | 0.0649 (10) | 0.0314 (8) | 0.0150 (8) | 0.0078 (6) | 0.0140 (7) |
C10 | 0.0330 (8) | 0.0657 (10) | 0.0246 (7) | 0.0046 (7) | −0.0014 (5) | 0.0009 (6) |
C11 | 0.0260 (7) | 0.0509 (8) | 0.0269 (7) | 0.0033 (6) | 0.0012 (5) | −0.0011 (6) |
C12 | 0.0323 (7) | 0.0297 (6) | 0.0206 (6) | −0.0064 (5) | 0.0062 (5) | −0.0017 (5) |
C13 | 0.0386 (7) | 0.0233 (6) | 0.0199 (6) | −0.0043 (5) | 0.0066 (5) | −0.0004 (5) |
C14 | 0.0326 (7) | 0.0237 (6) | 0.0202 (6) | 0.0010 (5) | 0.0047 (5) | 0.0006 (4) |
C15 | 0.0213 (6) | 0.0251 (6) | 0.0229 (6) | 0.0034 (5) | 0.0047 (4) | 0.0005 (5) |
C16 | 0.0325 (7) | 0.0239 (6) | 0.0271 (7) | 0.0007 (5) | 0.0003 (5) | 0.0005 (5) |
C17 | 0.0317 (7) | 0.0257 (6) | 0.0321 (7) | 0.0021 (5) | 0.0075 (5) | −0.0018 (5) |
C18 | 0.0346 (7) | 0.0333 (7) | 0.0250 (7) | 0.0000 (6) | 0.0053 (5) | −0.0023 (5) |
C19 | 0.0300 (7) | 0.0319 (7) | 0.0227 (6) | 0.0018 (5) | 0.0017 (5) | 0.0023 (5) |
C20 | 0.0248 (6) | 0.0273 (6) | 0.0254 (6) | 0.0028 (5) | 0.0021 (5) | 0.0013 (5) |
C21 | 0.0294 (7) | 0.0300 (6) | 0.0221 (6) | −0.0030 (5) | 0.0030 (5) | 0.0012 (5) |
C22 | 0.0314 (7) | 0.0347 (7) | 0.0222 (6) | 0.0037 (5) | 0.0029 (5) | 0.0034 (5) |
C23 | 0.0397 (8) | 0.0309 (6) | 0.0266 (7) | 0.0058 (6) | 0.0123 (5) | 0.0073 (5) |
C24 | 0.0327 (7) | 0.0289 (6) | 0.0330 (7) | −0.0006 (5) | 0.0126 (5) | 0.0046 (5) |
C25 | 0.0238 (6) | 0.0298 (6) | 0.0282 (7) | −0.0003 (5) | 0.0064 (5) | 0.0015 (5) |
N1—C1 | 1.2753 (14) | C10—H10A | 0.9900 |
N1—C12 | 1.4616 (13) | C10—H10B | 0.9900 |
N2—C1 | 1.4039 (14) | C11—H11A | 0.9900 |
N2—C2 | 1.4661 (14) | C11—H11B | 0.9900 |
N2—C6 | 1.4702 (14) | C12—C13 | 1.5144 (16) |
N3—C1 | 1.3999 (14) | C12—H12A | 0.9900 |
N3—C7 | 1.4548 (14) | C12—H12B | 0.9900 |
N3—C11 | 1.4581 (14) | C13—C14 | 1.5171 (15) |
N4—C15 | 1.2776 (13) | C13—H13A | 0.9900 |
N4—C14 | 1.4629 (13) | C13—H13B | 0.9900 |
N5—C15 | 1.3924 (13) | C14—H14A | 0.9900 |
N5—C16 | 1.4546 (13) | C14—H14B | 0.9900 |
N5—C20 | 1.4579 (13) | C16—C17 | 1.5162 (15) |
N6—C15 | 1.4002 (13) | C16—H16A | 0.9900 |
N6—C21 | 1.4604 (13) | C16—H16B | 0.9900 |
N6—C25 | 1.4700 (13) | C17—C18 | 1.5254 (16) |
C2—C3 | 1.5176 (15) | C17—H17A | 0.9900 |
C2—H2A | 0.9900 | C17—H17B | 0.9900 |
C2—H2B | 0.9900 | C18—C19 | 1.5219 (15) |
C3—C4 | 1.5201 (17) | C18—H18A | 0.9900 |
C3—H3A | 0.9900 | C18—H18B | 0.9900 |
C3—H3B | 0.9900 | C19—C20 | 1.5180 (15) |
C4—C5 | 1.5206 (16) | C19—H19A | 0.9900 |
C4—H4A | 0.9900 | C19—H19B | 0.9900 |
C4—H4B | 0.9900 | C20—H20A | 0.9900 |
C5—C6 | 1.5153 (15) | C20—H20B | 0.9900 |
C5—H5A | 0.9900 | C21—C22 | 1.5192 (15) |
C5—H5B | 0.9900 | C21—H21A | 0.9900 |
C6—H6A | 0.9900 | C21—H21B | 0.9900 |
C6—H6B | 0.9900 | C22—C23 | 1.5214 (16) |
C7—C8 | 1.5193 (16) | C22—H22A | 0.9900 |
C7—H7A | 0.9900 | C22—H22B | 0.9900 |
C7—H7B | 0.9900 | C23—C24 | 1.5173 (16) |
C8—C9 | 1.5251 (19) | C23—H23A | 0.9900 |
C8—H8A | 0.9900 | C23—H23B | 0.9900 |
C8—H8B | 0.9900 | C24—C25 | 1.5160 (15) |
C9—C10 | 1.5157 (18) | C24—H24A | 0.9900 |
C9—H9A | 0.9900 | C24—H24B | 0.9900 |
C9—H9B | 0.9900 | C25—H25A | 0.9900 |
C10—C11 | 1.5175 (17) | C25—H25B | 0.9900 |
C1—N1—C12 | 120.24 (9) | C13—C12—H12A | 109.8 |
C1—N2—C2 | 116.36 (9) | N1—C12—H12B | 109.8 |
C1—N2—C6 | 115.17 (9) | C13—C12—H12B | 109.8 |
C2—N2—C6 | 111.14 (9) | H12A—C12—H12B | 108.2 |
C1—N3—C7 | 122.03 (9) | C12—C13—C14 | 111.42 (9) |
C1—N3—C11 | 119.59 (10) | C12—C13—H13A | 109.3 |
C7—N3—C11 | 113.39 (10) | C14—C13—H13A | 109.3 |
C15—N4—C14 | 119.52 (9) | C12—C13—H13B | 109.3 |
C15—N5—C16 | 122.52 (9) | C14—C13—H13B | 109.3 |
C15—N5—C20 | 121.14 (9) | H13A—C13—H13B | 108.0 |
C16—N5—C20 | 113.36 (9) | N4—C14—C13 | 109.23 (9) |
C15—N6—C21 | 116.70 (9) | N4—C14—H14A | 109.8 |
C15—N6—C25 | 116.62 (9) | C13—C14—H14A | 109.8 |
C21—N6—C25 | 112.00 (9) | N4—C14—H14B | 109.8 |
N1—C1—N3 | 125.94 (10) | C13—C14—H14B | 109.8 |
N1—C1—N2 | 120.11 (10) | H14A—C14—H14B | 108.3 |
N3—C1—N2 | 113.86 (10) | N4—C15—N5 | 125.82 (10) |
N2—C2—C3 | 109.26 (10) | N4—C15—N6 | 120.12 (10) |
N2—C2—H2A | 109.8 | N5—C15—N6 | 113.95 (9) |
C3—C2—H2A | 109.8 | N5—C16—C17 | 109.73 (9) |
N2—C2—H2B | 109.8 | N5—C16—H16A | 109.7 |
C3—C2—H2B | 109.8 | C17—C16—H16A | 109.7 |
H2A—C2—H2B | 108.3 | N5—C16—H16B | 109.7 |
C2—C3—C4 | 110.97 (10) | C17—C16—H16B | 109.7 |
C2—C3—H3A | 109.4 | H16A—C16—H16B | 108.2 |
C4—C3—H3A | 109.4 | C16—C17—C18 | 111.06 (10) |
C2—C3—H3B | 109.4 | C16—C17—H17A | 109.4 |
C4—C3—H3B | 109.4 | C18—C17—H17A | 109.4 |
H3A—C3—H3B | 108.0 | C16—C17—H17B | 109.4 |
C3—C4—C5 | 110.90 (9) | C18—C17—H17B | 109.4 |
C3—C4—H4A | 109.5 | H17A—C17—H17B | 108.0 |
C5—C4—H4A | 109.5 | C19—C18—C17 | 110.98 (9) |
C3—C4—H4B | 109.5 | C19—C18—H18A | 109.4 |
C5—C4—H4B | 109.5 | C17—C18—H18A | 109.4 |
H4A—C4—H4B | 108.0 | C19—C18—H18B | 109.4 |
C6—C5—C4 | 110.54 (10) | C17—C18—H18B | 109.4 |
C6—C5—H5A | 109.5 | H18A—C18—H18B | 108.0 |
C4—C5—H5A | 109.5 | C20—C19—C18 | 110.91 (9) |
C6—C5—H5B | 109.5 | C20—C19—H19A | 109.5 |
C4—C5—H5B | 109.5 | C18—C19—H19A | 109.5 |
H5A—C5—H5B | 108.1 | C20—C19—H19B | 109.5 |
N2—C6—C5 | 110.18 (9) | C18—C19—H19B | 109.5 |
N2—C6—H6A | 109.6 | H19A—C19—H19B | 108.0 |
C5—C6—H6A | 109.6 | N5—C20—C19 | 111.31 (9) |
N2—C6—H6B | 109.6 | N5—C20—H20A | 109.4 |
C5—C6—H6B | 109.6 | C19—C20—H20A | 109.4 |
H6A—C6—H6B | 108.1 | N5—C20—H20B | 109.4 |
N3—C7—C8 | 109.96 (10) | C19—C20—H20B | 109.4 |
N3—C7—H7A | 109.7 | H20A—C20—H20B | 108.0 |
C8—C7—H7A | 109.7 | N6—C21—C22 | 109.79 (9) |
N3—C7—H7B | 109.7 | N6—C21—H21A | 109.7 |
C8—C7—H7B | 109.7 | C22—C21—H21A | 109.7 |
H7A—C7—H7B | 108.2 | N6—C21—H21B | 109.7 |
C7—C8—C9 | 110.85 (11) | C22—C21—H21B | 109.7 |
C7—C8—H8A | 109.5 | H21A—C21—H21B | 108.2 |
C9—C8—H8A | 109.5 | C21—C22—C23 | 111.22 (10) |
C7—C8—H8B | 109.5 | C21—C22—H22A | 109.4 |
C9—C8—H8B | 109.5 | C23—C22—H22A | 109.4 |
H8A—C8—H8B | 108.1 | C21—C22—H22B | 109.4 |
C10—C9—C8 | 110.92 (11) | C23—C22—H22B | 109.4 |
C10—C9—H9A | 109.5 | H22A—C22—H22B | 108.0 |
C8—C9—H9A | 109.5 | C24—C23—C22 | 110.01 (10) |
C10—C9—H9B | 109.5 | C24—C23—H23A | 109.7 |
C8—C9—H9B | 109.5 | C22—C23—H23A | 109.7 |
H9A—C9—H9B | 108.0 | C24—C23—H23B | 109.7 |
C9—C10—C11 | 110.71 (11) | C22—C23—H23B | 109.7 |
C9—C10—H10A | 109.5 | H23A—C23—H23B | 108.2 |
C11—C10—H10A | 109.5 | C25—C24—C23 | 110.37 (10) |
C9—C10—H10B | 109.5 | C25—C24—H24A | 109.6 |
C11—C10—H10B | 109.5 | C23—C24—H24A | 109.6 |
H10A—C10—H10B | 108.1 | C25—C24—H24B | 109.6 |
N3—C11—C10 | 110.85 (10) | C23—C24—H24B | 109.6 |
N3—C11—H11A | 109.5 | H24A—C24—H24B | 108.1 |
C10—C11—H11A | 109.5 | N6—C25—C24 | 110.61 (9) |
N3—C11—H11B | 109.5 | N6—C25—H25A | 109.5 |
C10—C11—H11B | 109.5 | C24—C25—H25A | 109.5 |
H11A—C11—H11B | 108.1 | N6—C25—H25B | 109.5 |
N1—C12—C13 | 109.44 (9) | C24—C25—H25B | 109.5 |
N1—C12—H12A | 109.8 | H25A—C25—H25B | 108.1 |
C12—N1—C1—N3 | −11.06 (17) | C15—N4—C14—C13 | −138.49 (10) |
C12—N1—C1—N2 | 165.14 (9) | C12—C13—C14—N4 | 68.79 (11) |
C7—N3—C1—N1 | 151.32 (12) | C14—N4—C15—N5 | −12.98 (16) |
C11—N3—C1—N1 | −55.32 (16) | C14—N4—C15—N6 | 163.03 (9) |
C7—N3—C1—N2 | −25.09 (14) | C16—N5—C15—N4 | 148.62 (11) |
C11—N3—C1—N2 | 128.28 (11) | C20—N5—C15—N4 | −52.19 (16) |
C2—N2—C1—N1 | −15.11 (15) | C16—N5—C15—N6 | −27.61 (14) |
C6—N2—C1—N1 | 117.55 (12) | C20—N5—C15—N6 | 131.58 (10) |
C2—N2—C1—N3 | 161.53 (9) | C21—N6—C15—N4 | −13.71 (15) |
C6—N2—C1—N3 | −65.81 (12) | C25—N6—C15—N4 | 122.44 (11) |
C1—N2—C2—C3 | −163.65 (9) | C21—N6—C15—N5 | 162.75 (9) |
C6—N2—C2—C3 | 61.88 (12) | C25—N6—C15—N5 | −61.10 (12) |
N2—C2—C3—C4 | −57.35 (12) | C15—N5—C16—C17 | −140.15 (10) |
C2—C3—C4—C5 | 53.40 (13) | C20—N5—C16—C17 | 59.19 (12) |
C3—C4—C5—C6 | −52.60 (13) | N5—C16—C17—C18 | −56.29 (13) |
C1—N2—C6—C5 | 163.11 (9) | C16—C17—C18—C19 | 53.66 (13) |
C2—N2—C6—C5 | −61.84 (12) | C17—C18—C19—C20 | −51.69 (13) |
C4—C5—C6—N2 | 56.37 (13) | C15—N5—C20—C19 | 140.92 (10) |
C1—N3—C7—C8 | −146.44 (11) | C16—N5—C20—C19 | −58.12 (12) |
C11—N3—C7—C8 | 58.69 (13) | C18—C19—C20—N5 | 53.25 (13) |
N3—C7—C8—C9 | −55.56 (14) | C15—N6—C21—C22 | −162.75 (9) |
C7—C8—C9—C10 | 53.88 (15) | C25—N6—C21—C22 | 59.17 (12) |
C8—C9—C10—C11 | −53.08 (15) | N6—C21—C22—C23 | −56.61 (12) |
C1—N3—C11—C10 | 146.00 (10) | C21—C22—C23—C24 | 54.76 (13) |
C7—N3—C11—C10 | −58.46 (13) | C22—C23—C24—C25 | −54.43 (13) |
C9—C10—C11—N3 | 54.57 (14) | C15—N6—C25—C24 | 162.09 (9) |
C1—N1—C12—C13 | −138.97 (10) | C21—N6—C25—C24 | −59.79 (12) |
N1—C12—C13—C14 | 70.29 (11) | C23—C24—C25—N6 | 56.74 (12) |
C15H30N6 | Z = 2 |
Mr = 294.45 | F(000) = 324 |
Triclinic, P1 | Dx = 1.191 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 6.9057 (7) Å | Cell parameters from 718 reflections |
b = 7.6661 (7) Å | θ = 2.5–21.1° |
c = 16.3568 (16) Å | µ = 0.08 mm−1 |
α = 89.307 (3)° | T = 120 K |
β = 82.355 (2)° | Prism, colourless |
γ = 73.152 (2)° | 0.20 × 0.15 × 0.10 mm |
V = 821.07 (14) Å3 |
Bruker SMART CCD area-detector diffractometer | 4053 independent reflections |
Radiation source: sealed tube | 1931 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.047 |
π and ω scans | θmax = 28.3°, θmin = 1.3° |
Absorption correction: multi-scan (SADABS; Bruker, 2002) | h = −8→9 |
Tmin = 0.910, Tmax = 0.989 | k = −9→10 |
7147 measured reflections | l = −21→21 |
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)] = 0.054 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.113 | H-atom parameters constrained |
S = 0.84 | w = 1/[σ2(Fo2) + (0.0224P)2 + 0.0587P] where P = (Fo2 + 2Fc2)/3 |
4053 reflections | (Δ/σ)max < 0.001 |
194 parameters | Δρmax = 0.23 e Å−3 |
0 restraints | Δρmin = −0.17 e Å−3 |
C15H30N6 | γ = 73.152 (2)° |
Mr = 294.45 | V = 821.07 (14) Å3 |
Triclinic, P1 | Z = 2 |
a = 6.9057 (7) Å | Mo Kα radiation |
b = 7.6661 (7) Å | µ = 0.08 mm−1 |
c = 16.3568 (16) Å | T = 120 K |
α = 89.307 (3)° | 0.20 × 0.15 × 0.10 mm |
β = 82.355 (2)° |
Bruker SMART CCD area-detector diffractometer | 4053 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2002) | 1931 reflections with I > 2σ(I) |
Tmin = 0.910, Tmax = 0.989 | Rint = 0.047 |
7147 measured reflections |
R[F2 > 2σ(F2)] = 0.054 | 0 restraints |
wR(F2) = 0.113 | H-atom parameters constrained |
S = 0.84 | Δρmax = 0.23 e Å−3 |
4053 reflections | Δρmin = −0.17 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 | ||
N1 | −0.2269 (3) | 1.0989 (3) | 0.09859 (12) | 0.0293 (5) | |
N2 | −0.0566 (3) | 1.2593 (2) | 0.16972 (11) | 0.0253 (5) | |
N3 | 0.0595 (3) | 0.9345 (2) | 0.15180 (11) | 0.0250 (5) | |
N4 | 0.3994 (3) | 0.5215 (2) | 0.35211 (11) | 0.0209 (5) | |
N5 | 0.7371 (3) | 0.5082 (2) | 0.37725 (11) | 0.0188 (4) | |
N6 | 0.6318 (3) | 0.2455 (2) | 0.36994 (11) | 0.0213 (5) | |
C1 | −0.2592 (4) | 0.9284 (3) | 0.07584 (15) | 0.0396 (7) | |
H1A | −0.1676 | 0.8772 | 0.0254 | 0.059* | |
H1B | −0.4012 | 0.9503 | 0.0662 | 0.059* | |
H1C | −0.2305 | 0.8424 | 0.1206 | 0.059* | |
C2 | −0.3155 (4) | 1.2520 (3) | 0.04755 (15) | 0.0326 (7) | |
H2A | −0.4647 | 1.2713 | 0.0520 | 0.039* | |
H2B | −0.2569 | 1.2213 | −0.0109 | 0.039* | |
C3 | −0.2761 (4) | 1.4269 (3) | 0.07296 (15) | 0.0396 (7) | |
H3A | −0.1565 | 1.4449 | 0.0371 | 0.048* | |
H3B | −0.3961 | 1.5323 | 0.0672 | 0.048* | |
C4 | −0.2360 (4) | 1.4129 (3) | 0.16166 (14) | 0.0360 (7) | |
H4A | −0.2132 | 1.5272 | 0.1798 | 0.043* | |
H4B | −0.3563 | 1.3956 | 0.1973 | 0.043* | |
C5 | 0.1348 (4) | 1.3044 (3) | 0.15106 (15) | 0.0364 (7) | |
H5A | 0.2487 | 1.1919 | 0.1444 | 0.055* | |
H5B | 0.1505 | 1.3795 | 0.1964 | 0.055* | |
H5C | 0.1341 | 1.3721 | 0.0999 | 0.055* | |
C6 | −0.0630 (4) | 1.0903 (3) | 0.13949 (13) | 0.0236 (6) | |
C7 | 0.1953 (3) | 0.9168 (3) | 0.21408 (13) | 0.0234 (6) | |
H7A | 0.1365 | 1.0158 | 0.2564 | 0.028* | |
H7B | 0.3290 | 0.9278 | 0.1882 | 0.028* | |
C8 | 0.2248 (3) | 0.7333 (3) | 0.25451 (14) | 0.0241 (6) | |
H8A | 0.0901 | 0.7227 | 0.2793 | 0.029* | |
H8B | 0.2831 | 0.6353 | 0.2117 | 0.029* | |
C9 | 0.3636 (3) | 0.7061 (3) | 0.32051 (13) | 0.0227 (6) | |
H9A | 0.4954 | 0.7254 | 0.2972 | 0.027* | |
H9B | 0.3002 | 0.7965 | 0.3662 | 0.027* | |
C10 | 0.5794 (3) | 0.4339 (3) | 0.36795 (13) | 0.0181 (5) | |
C11 | 0.6909 (3) | 0.6615 (3) | 0.43606 (14) | 0.0262 (6) | |
H11A | 0.5498 | 0.7370 | 0.4354 | 0.039* | |
H11B | 0.7843 | 0.7350 | 0.4206 | 0.039* | |
H11C | 0.7078 | 0.6153 | 0.4916 | 0.039* | |
C12 | 0.9377 (3) | 0.3784 (3) | 0.38082 (13) | 0.0223 (6) | |
H12A | 1.0342 | 0.4435 | 0.3947 | 0.027* | |
H12B | 0.9917 | 0.3154 | 0.3265 | 0.027* | |
C13 | 0.9170 (3) | 0.2400 (3) | 0.44633 (14) | 0.0236 (6) | |
H13A | 1.0529 | 0.1572 | 0.4535 | 0.028* | |
H13B | 0.8523 | 0.3028 | 0.4999 | 0.028* | |
C14 | 0.7854 (3) | 0.1338 (3) | 0.41670 (14) | 0.0222 (6) | |
H14A | 0.8732 | 0.0290 | 0.3816 | 0.027* | |
H14B | 0.7168 | 0.0852 | 0.4649 | 0.027* | |
C15 | 0.5040 (4) | 0.1503 (3) | 0.33783 (15) | 0.0321 (7) | |
H15A | 0.4098 | 0.1241 | 0.3833 | 0.048* | |
H15B | 0.5899 | 0.0358 | 0.3105 | 0.048* | |
H15C | 0.4258 | 0.2267 | 0.2980 | 0.048* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0335 (13) | 0.0300 (12) | 0.0265 (12) | −0.0067 (10) | −0.0174 (10) | 0.0075 (10) |
N2 | 0.0305 (12) | 0.0192 (11) | 0.0245 (12) | −0.0029 (9) | −0.0080 (10) | 0.0043 (9) |
N3 | 0.0287 (12) | 0.0216 (11) | 0.0238 (11) | −0.0022 (9) | −0.0119 (9) | 0.0049 (9) |
N4 | 0.0199 (11) | 0.0145 (10) | 0.0290 (12) | −0.0046 (8) | −0.0077 (9) | 0.0082 (8) |
N5 | 0.0206 (11) | 0.0139 (10) | 0.0235 (11) | −0.0053 (8) | −0.0080 (9) | 0.0012 (8) |
N6 | 0.0235 (11) | 0.0125 (10) | 0.0321 (12) | −0.0072 (9) | −0.0147 (9) | 0.0041 (9) |
C1 | 0.0401 (17) | 0.0415 (17) | 0.0433 (18) | −0.0160 (14) | −0.0186 (14) | 0.0064 (14) |
C2 | 0.0265 (15) | 0.0413 (16) | 0.0264 (15) | −0.0023 (12) | −0.0092 (12) | 0.0127 (12) |
C3 | 0.0485 (19) | 0.0307 (16) | 0.0316 (16) | 0.0033 (13) | −0.0112 (14) | 0.0118 (12) |
C4 | 0.0465 (18) | 0.0226 (14) | 0.0311 (16) | 0.0035 (12) | −0.0090 (13) | 0.0043 (11) |
C5 | 0.0537 (19) | 0.0282 (15) | 0.0329 (16) | −0.0194 (13) | −0.0095 (14) | 0.0096 (12) |
C6 | 0.0273 (14) | 0.0267 (14) | 0.0177 (13) | −0.0085 (11) | −0.0045 (11) | 0.0038 (11) |
C7 | 0.0256 (14) | 0.0193 (13) | 0.0243 (14) | −0.0039 (11) | −0.0056 (11) | 0.0049 (10) |
C8 | 0.0236 (13) | 0.0199 (13) | 0.0301 (14) | −0.0057 (10) | −0.0091 (11) | 0.0027 (10) |
C9 | 0.0272 (14) | 0.0158 (12) | 0.0254 (14) | −0.0053 (10) | −0.0069 (11) | 0.0038 (10) |
C10 | 0.0242 (13) | 0.0160 (12) | 0.0167 (12) | −0.0094 (10) | −0.0043 (10) | 0.0030 (9) |
C11 | 0.0324 (15) | 0.0195 (13) | 0.0294 (14) | −0.0091 (11) | −0.0104 (12) | 0.0010 (11) |
C12 | 0.0181 (13) | 0.0234 (13) | 0.0282 (14) | −0.0079 (10) | −0.0086 (11) | 0.0026 (10) |
C13 | 0.0219 (13) | 0.0220 (13) | 0.0264 (14) | −0.0030 (11) | −0.0098 (11) | 0.0052 (11) |
C14 | 0.0241 (14) | 0.0143 (12) | 0.0278 (14) | −0.0038 (10) | −0.0066 (11) | 0.0052 (10) |
C15 | 0.0354 (16) | 0.0212 (14) | 0.0459 (17) | −0.0125 (12) | −0.0188 (13) | 0.0060 (12) |
N1—C6 | 1.375 (3) | C4—H4B | 0.9900 |
N1—C1 | 1.449 (3) | C5—H5A | 0.9800 |
N1—C2 | 1.464 (3) | C5—H5B | 0.9800 |
N2—C6 | 1.407 (3) | C5—H5C | 0.9800 |
N2—C5 | 1.454 (3) | C7—C8 | 1.518 (3) |
N2—C4 | 1.461 (3) | C7—H7A | 0.9900 |
N3—C6 | 1.279 (2) | C7—H7B | 0.9900 |
N3—C7 | 1.453 (3) | C8—C9 | 1.510 (3) |
N4—C10 | 1.289 (2) | C8—H8A | 0.9900 |
N4—C9 | 1.464 (2) | C8—H8B | 0.9900 |
N5—C10 | 1.393 (3) | C9—H9A | 0.9900 |
N5—C12 | 1.461 (2) | C9—H9B | 0.9900 |
N5—C11 | 1.462 (2) | C11—H11A | 0.9800 |
N6—C10 | 1.385 (2) | C11—H11B | 0.9800 |
N6—C15 | 1.446 (3) | C11—H11C | 0.9800 |
N6—C14 | 1.455 (2) | C12—C13 | 1.521 (3) |
C1—H1A | 0.9800 | C12—H12A | 0.9900 |
C1—H1B | 0.9800 | C12—H12B | 0.9900 |
C1—H1C | 0.9800 | C13—C14 | 1.509 (3) |
C2—C3 | 1.516 (3) | C13—H13A | 0.9900 |
C2—H2A | 0.9900 | C13—H13B | 0.9900 |
C2—H2B | 0.9900 | C14—H14A | 0.9900 |
C3—C4 | 1.510 (3) | C14—H14B | 0.9900 |
C3—H3A | 0.9900 | C15—H15A | 0.9800 |
C3—H3B | 0.9900 | C15—H15B | 0.9800 |
C4—H4A | 0.9900 | C15—H15C | 0.9800 |
C6—N1—C1 | 117.68 (19) | C8—C7—H7A | 109.6 |
C6—N1—C2 | 123.2 (2) | N3—C7—H7B | 109.6 |
C1—N1—C2 | 114.15 (19) | C8—C7—H7B | 109.6 |
C6—N2—C5 | 117.32 (19) | H7A—C7—H7B | 108.2 |
C6—N2—C4 | 115.3 (2) | C9—C8—C7 | 112.94 (19) |
C5—N2—C4 | 113.35 (18) | C9—C8—H8A | 109.0 |
C6—N3—C7 | 119.93 (19) | C7—C8—H8A | 109.0 |
C10—N4—C9 | 119.16 (19) | C9—C8—H8B | 109.0 |
C10—N5—C12 | 116.26 (17) | C7—C8—H8B | 109.0 |
C10—N5—C11 | 117.15 (18) | H8A—C8—H8B | 107.8 |
C12—N5—C11 | 112.79 (17) | N4—C9—C8 | 110.21 (18) |
C10—N6—C15 | 119.63 (17) | N4—C9—H9A | 109.6 |
C10—N6—C14 | 124.42 (18) | C8—C9—H9A | 109.6 |
C15—N6—C14 | 114.84 (16) | N4—C9—H9B | 109.6 |
N1—C1—H1A | 109.5 | C8—C9—H9B | 109.6 |
N1—C1—H1B | 109.5 | H9A—C9—H9B | 108.1 |
H1A—C1—H1B | 109.5 | N4—C10—N6 | 118.5 (2) |
N1—C1—H1C | 109.5 | N4—C10—N5 | 126.45 (19) |
H1A—C1—H1C | 109.5 | N6—C10—N5 | 114.86 (18) |
H1B—C1—H1C | 109.5 | N5—C11—H11A | 109.5 |
N1—C2—C3 | 112.3 (2) | N5—C11—H11B | 109.5 |
N1—C2—H2A | 109.1 | H11A—C11—H11B | 109.5 |
C3—C2—H2A | 109.1 | N5—C11—H11C | 109.5 |
N1—C2—H2B | 109.1 | H11A—C11—H11C | 109.5 |
C3—C2—H2B | 109.1 | H11B—C11—H11C | 109.5 |
H2A—C2—H2B | 107.9 | N5—C12—C13 | 108.85 (18) |
C4—C3—C2 | 108.46 (19) | N5—C12—H12A | 109.9 |
C4—C3—H3A | 110.0 | C13—C12—H12A | 109.9 |
C2—C3—H3A | 110.0 | N5—C12—H12B | 109.9 |
C4—C3—H3B | 110.0 | C13—C12—H12B | 109.9 |
C2—C3—H3B | 110.0 | H12A—C12—H12B | 108.3 |
H3A—C3—H3B | 108.4 | C14—C13—C12 | 106.78 (18) |
N2—C4—C3 | 109.89 (19) | C14—C13—H13A | 110.4 |
N2—C4—H4A | 109.7 | C12—C13—H13A | 110.4 |
C3—C4—H4A | 109.7 | C14—C13—H13B | 110.4 |
N2—C4—H4B | 109.7 | C12—C13—H13B | 110.4 |
C3—C4—H4B | 109.7 | H13A—C13—H13B | 108.6 |
H4A—C4—H4B | 108.2 | N6—C14—C13 | 112.10 (16) |
N2—C5—H5A | 109.5 | N6—C14—H14A | 109.2 |
N2—C5—H5B | 109.5 | C13—C14—H14A | 109.2 |
H5A—C5—H5B | 109.5 | N6—C14—H14B | 109.2 |
N2—C5—H5C | 109.5 | C13—C14—H14B | 109.2 |
H5A—C5—H5C | 109.5 | H14A—C14—H14B | 107.9 |
H5B—C5—H5C | 109.5 | N6—C15—H15A | 109.5 |
N3—C6—N1 | 119.2 (2) | N6—C15—H15B | 109.5 |
N3—C6—N2 | 125.9 (2) | H15A—C15—H15B | 109.5 |
N1—C6—N2 | 114.7 (2) | N6—C15—H15C | 109.5 |
N3—C7—C8 | 110.09 (19) | H15A—C15—H15C | 109.5 |
N3—C7—H7A | 109.6 | H15B—C15—H15C | 109.5 |
C6—N1—C2—C3 | −25.0 (3) | C10—N4—C9—C8 | 140.1 (2) |
C1—N1—C2—C3 | −179.4 (2) | C7—C8—C9—N4 | −175.28 (18) |
N1—C2—C3—C4 | −23.0 (3) | C9—N4—C10—N6 | −158.05 (19) |
C6—N2—C4—C3 | −54.4 (3) | C9—N4—C10—N5 | 16.4 (3) |
C5—N2—C4—C3 | 84.8 (3) | C15—N6—C10—N4 | 12.9 (3) |
C2—C3—C4—N2 | 60.7 (3) | C14—N6—C10—N4 | −154.4 (2) |
C7—N3—C6—N1 | −162.0 (2) | C15—N6—C10—N5 | −162.2 (2) |
C7—N3—C6—N2 | 12.8 (3) | C14—N6—C10—N5 | 30.5 (3) |
C1—N1—C6—N3 | 3.7 (3) | C12—N5—C10—N4 | −169.8 (2) |
C2—N1—C6—N3 | −149.8 (2) | C11—N5—C10—N4 | 52.7 (3) |
C1—N1—C6—N2 | −171.64 (19) | C12—N5—C10—N6 | 4.9 (3) |
C2—N1—C6—N2 | 34.8 (3) | C11—N5—C10—N6 | −132.69 (19) |
C5—N2—C6—N3 | 54.5 (3) | C10—N5—C12—C13 | −52.2 (2) |
C4—N2—C6—N3 | −168.0 (2) | C11—N5—C12—C13 | 87.2 (2) |
C5—N2—C6—N1 | −130.5 (2) | N5—C12—C13—C14 | 65.2 (2) |
C4—N2—C6—N1 | 7.0 (3) | C10—N6—C14—C13 | −13.7 (3) |
C6—N3—C7—C8 | 145.6 (2) | C15—N6—C14—C13 | 178.40 (19) |
N3—C7—C8—C9 | −179.60 (18) | C12—C13—C14—N6 | −33.3 (2) |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | C25H46N6 | C15H30N6 |
Mr | 430.68 | 294.45 |
Crystal system, space group | Monoclinic, P21/n | Triclinic, P1 |
Temperature (K) | 120 | 120 |
a, b, c (Å) | 10.0619 (7), 19.8127 (13), 12.7511 (8) | 6.9057 (7), 7.6661 (7), 16.3568 (16) |
α, β, γ (°) | 90, 99.594 (2), 90 | 89.307 (3), 82.355 (2), 73.152 (2) |
V (Å3) | 2506.4 (3) | 821.07 (14) |
Z | 4 | 2 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.07 | 0.08 |
Crystal size (mm) | 0.40 × 0.35 × 0.20 | 0.20 × 0.15 × 0.10 |
Data collection | ||
Diffractometer | Bruker SMART CCD area-detector diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2002) | Multi-scan (SADABS; Bruker, 2002) |
Tmin, Tmax | 0.951, 0.989 | 0.910, 0.989 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 19511, 6205, 4055 | 7147, 4053, 1931 |
Rint | 0.044 | 0.047 |
(sin θ/λ)max (Å−1) | 0.668 | 0.667 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.042, 0.090, 0.86 | 0.054, 0.113, 0.84 |
No. of reflections | 6205 | 4053 |
No. of parameters | 280 | 194 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.22, −0.15 | 0.23, −0.17 |
Computer programs: SMART (Bruker, 2002), SMART, SAINT (Bruker, 2002), SHELXTL (Bruker, 2002), SHELXTL and PLATON (Spek, 2002).
N1—C1 | 1.2753 (14) | N4—C14 | 1.4629 (13) |
N1—C12 | 1.4616 (13) | N5—C15 | 1.3924 (13) |
N2—C1 | 1.4039 (14) | N6—C15 | 1.4002 (13) |
N3—C1 | 1.3999 (14) | C12—C13 | 1.5144 (16) |
N4—C15 | 1.2776 (13) | C13—C14 | 1.5171 (15) |
C1—N1—C12 | 120.24 (9) | C12—C13—C14 | 111.42 (9) |
C15—N4—C14 | 119.52 (9) | N4—C14—C13 | 109.23 (9) |
N1—C1—N3 | 125.94 (10) | N4—C15—N5 | 125.82 (10) |
N1—C1—N2 | 120.11 (10) | N4—C15—N6 | 120.12 (10) |
N3—C1—N2 | 113.86 (10) | N5—C15—N6 | 113.95 (9) |
N1—C12—C13 | 109.44 (9) | ||
C12—N1—C1—N2 | 165.14 (9) | C14—N4—C15—N6 | 163.03 (9) |
C6—N2—C1—N1 | 117.55 (12) | C25—N6—C15—N4 | 122.44 (11) |
N1—C6 | 1.375 (3) | N4—C9 | 1.464 (2) |
N2—C6 | 1.407 (3) | N5—C10 | 1.393 (3) |
N3—C6 | 1.279 (2) | N6—C10 | 1.385 (2) |
N3—C7 | 1.453 (3) | C7—C8 | 1.518 (3) |
N4—C10 | 1.289 (2) | C8—C9 | 1.510 (3) |
C6—N3—C7 | 119.93 (19) | C9—C8—C7 | 112.94 (19) |
C10—N4—C9 | 119.16 (19) | N4—C9—C8 | 110.21 (18) |
N3—C6—N1 | 119.2 (2) | N4—C10—N6 | 118.5 (2) |
N3—C6—N2 | 125.9 (2) | N4—C10—N5 | 126.45 (19) |
N1—C6—N2 | 114.7 (2) | N6—C10—N5 | 114.86 (18) |
N3—C7—C8 | 110.09 (19) | ||
C7—N3—C6—N2 | 12.8 (3) | C9—N4—C10—N5 | 16.4 (3) |
In the search for bifunctional N-donor ligands able to stabilize unusually high metal oxidation states, we have extended our studies to guanidyl-type systems. The first derivative, the ligand bis(tetramethylguanidino)propylene (btmgp), and its complexes with Cu, Fe and Ni, have recently been investigated (Harmjanz, 1997; Waden, 1999; Pohl et al., 2000; Schneider, 2000; Herres, 2002). We have now developed the title compounds, (I) [a piperidine derivative, bis(dipiperidylguanidino)propylene] and (II) [a propylene derivative, 1,3-bis(dimethylpropyleneguanidino)propane], as novel ligands for use in biomimetic coordination chemistry. In Cu—O2 chemistry in particular, the modification of the guanidyl moieties within the ligands is expected to control the formation of different Cu—O2 species (Herres et al., 2004). \sch
The molecule of (I) lies roughly on a non-crystallographic twofold axis running through C13, with a trans arrangement of the guanidino groups relative to the C12—C13—C14 centre. The resulting torsion angles are N1—C12—C13—C14 70.3 (1) and N4—C14—C13—C12 68.8 (1)°. The C—N single bonds range from 1.392 (1) to 1.404 (1) Å, while the C═N double bonds, C1═N1 and C14═N4, are similar, with a mean of 1.276 (1) Å. The mean of the N2—C1—N3 and N5—C15—N6 angles is 113.91 (10)°, and the mean of the C1—N1—C12 and C15—N4—C14 angles is 119.88 (9)°. Thus, the guanidino double bonds in (I) are clearly localized. The same is valid for the related compound, (II). Here, the corresponding C—N single bond lengths range from 1.375 (3) to 1.407 (3) Å, and the mean of the C6═N3 and C10═N4 double bonds is 1.284 (2) Å. The mean of the N1—C6—N2 and N5—C10—N6 angles is 114.8 (2)° and the mean of the C6—N3—C7 and C9—N4—C10 angles is 119.5 (2)°.
Similar double-bond localization is observed in bis(tetramethylguanidino)naphthalene (Raab et al., 2002), with equally unprotonated imine N and NR2 amino groups having a mean C═N bond length of 1.282 (3) Å and a mean C—N bond length of 1.384 (1) Å. In bis(tetramethylguanidino)biphenyl (Pruszynski et al., 1992), with a protonated imine N, strong delocalization is observed among the three C—N bonds, which are in the range 1.31 (1)–1.34 (1) Å. 2-Cyanoguanidine, with C—N bonds in the range 1.3327 (3)–1.3441 (3) Å (Hirshfeld & Hope, 1980), and, to a lesser extent, tetrabenzylcyanoguanidine, with C═N 1.315 and C—N 1.370 Å (no s.u.s given; Shiba et al., 1993), also show delocalization, but this is due to the cyano groups attached to the imine N atom. Substitution of the NH2 groups in cyanoguanidine with NBz2 leads to the observed increase in localization.
For compound (I), the shortest non-bonding intramolecular C—H···A distance is C14—H14B···N5, with H···N 2.45 Å Should this be C···N?, while the shortest intermolecular distance results from a C4—H4A···N4i interaction, with H···N 2.86 Å Should this be C···N? [symmetry code: (i) x + 1/2, 1/2 − y, z − 1/2]. For compound (II), the corresponding distances are C2—H2B···N3ii 2.62 Å (Fig. 2) and C12—H12B···N2iii 2.68 Å [symmetry codes: (ii) −x, 2 − y, −z; (iii) x + 1, y − 1, z]. The former interaction generates a hydrogen-bonded dimer with graph set R22(10) (Fig. 2).