organic compounds
7-Isopropylidene-N2,N3,N5,N6-tetramethoxy-N2,N3,N5,N6-tetramethylbicyclo[2.2.1]hepta-2,5-diene-2,3,5,6-tetracarboxamide
aInstitut für Organische Chemie, Universität Kiel, Otto-Hahn-Platz 4, 24118 Kiel, Germany, and bInstitut für Anorganische Chemie, Universität Kiel, Otto-Hahn-Platz 6/7, 24118 Kiel, Germany
*Correspondence e-mail: cnaether@ac.uni-kiel.de, rherges@oc.uni-kiel.de
Although the molecular structure of the title compound, C22H32N4O8, displays a twofold symmetry of the molecule including the methoxy and methyl substituents, no crystallographic twofold symmetry is observed in the X-ray structure analysis. The carbonyl O atoms alternately point to different sides of the plane defined by the carbonyl C atoms. Two methoxy groups are oriented inside the molecules cavity. The H atoms of two methyl groups are disordered over two orientations and were refined using a split model.
CCDC reference: 878002
Related literature
For background to this work, see: Winkler et al. (2003a, 2012). For the structure of 7-isopropylidenenorborna-2,5-diene-2,3,5,6-tetracarboxylic acid tetrakis(diethylamide), see: Winkler et al. (2003b).
Experimental
Crystal data
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Data collection: X-AREA (Stoe & Cie, 2008); cell X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: XCIF in SHELXTL.
Supporting information
CCDC reference: 878002
10.1107/S1600536814004255/im2450sup1.cif
contains datablocks I, New_Global_Publ_Block. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536814004255/im2450Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536814004255/im2450Isup3.cml
7-Isopropylidenenorborna-2,5-diene-2,3,5,6-tetracarboxylic acid (250 mg, 0.81 mmol), suspended in anhydrous ethyl acetate (40 ml), was cooled to 0 °C and sonicated. After 5 min, diisopropyl ethylamine (2.20 ml, 13.0 mmol) was added and the mixture was sonicated for another 5 min. After the addition of N,O-dimethylhydroxylamine-hydrochloride (318 mg, 3.24 mmol) and n-propyl phosphonic acid anhydride (T3P) (2.43 ml, 4.05 mmol) (50% solution in ethyl acetate), the mixture was sonicated for 30 min and stirred at RT for 16 h. The mixture was then heated to reflux for 5 h. The reaction was stopped by addition of water (25 ml). After extraction with ethyl acetate, the combined organic phases were washed with 50 ml of brine and dried over magensium sulfate. After removal of the solvent, recrystallization from ethyl acetate afforded colorless crystals in 51% yield. mp.: 168 °C
Hydrogen atoms were positioned with idealized geometry (methyl H atoms allowed to rotate but not to tip) and were refined isotropically with Uiso(H) = 1.2 Ueq(C)) (1.5 for methyl H atoms) using a riding model. The H atoms of two methyl groups are disordered and were refined using a split model with two orientations rotated by 60° and sof of 60:40.
Data collection: X-AREA (Stoe & Cie, 2008); cell
X-AREA (Stoe & Cie, 2008); data reduction: X-AREA (Stoe & Cie, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: XCIF in SHELXTL (Sheldrick, 2008).Fig. 1. Crystal structure of the title compound with labeling and displacement ellipsoids drawn at the 50% probability level. Disordering is shown with full and open bonds. |
C22H32N4O8 | Z = 2 |
Mr = 480.52 | F(000) = 512 |
Triclinic, P1 | Dx = 1.281 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 9.5830 (9) Å | Cell parameters from 3915 reflections |
b = 10.2662 (8) Å | θ = 4–28° |
c = 13.3792 (16) Å | µ = 0.10 mm−1 |
α = 94.648 (12)° | T = 200 K |
β = 91.548 (13)° | Block, colorless |
γ = 108.013 (10)° | 0.3 × 0.3 × 0.2 mm |
V = 1245.7 (2) Å3 |
Stoe IPDS-1 diffractometer | 3431 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.040 |
Graphite monochromator | θmax = 26.0°, θmin = 2.9° |
Phi scans | h = −11→11 |
10017 measured reflections | k = −12→12 |
4788 independent reflections | l = −16→16 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.045 | H-atom parameters constrained |
wR(F2) = 0.119 | w = 1/[σ2(Fo2) + (0.0701P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.00 | (Δ/σ)max < 0.001 |
4788 reflections | Δρmax = 0.19 e Å−3 |
318 parameters | Δρmin = −0.19 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.079 (8) |
C22H32N4O8 | γ = 108.013 (10)° |
Mr = 480.52 | V = 1245.7 (2) Å3 |
Triclinic, P1 | Z = 2 |
a = 9.5830 (9) Å | Mo Kα radiation |
b = 10.2662 (8) Å | µ = 0.10 mm−1 |
c = 13.3792 (16) Å | T = 200 K |
α = 94.648 (12)° | 0.3 × 0.3 × 0.2 mm |
β = 91.548 (13)° |
Stoe IPDS-1 diffractometer | 3431 reflections with I > 2σ(I) |
10017 measured reflections | Rint = 0.040 |
4788 independent reflections |
R[F2 > 2σ(F2)] = 0.045 | 0 restraints |
wR(F2) = 0.119 | H-atom parameters constrained |
S = 1.00 | Δρmax = 0.19 e Å−3 |
4788 reflections | Δρmin = −0.19 e Å−3 |
318 parameters |
Experimental. 1H-NMR (500 MHz, 300 K, CDCl3, TMS): δ = 4.65 (s, 2H, H-1,4), 3.62 (s, 12H, H12), 3.25 (s, 12H, H-11), 1.53 (s, 6H, H-9) p.p.m.. 13C-NMR (125 MHz, 300 K, CDCl3, TMS): δ = 165.8 (C-10), 160.5 (C-7), 151.1 (C-2,3,5,6), 100.4 (C-8), 61.6 (C-12), 56.5 (C-1,4), 32.1 (C-11), 18.3 (C-9) p.p.m.. MS (EI, 70 eV): m/z(%)= 480 (2) [M]+, 421 (24), 420 (100), 329 (14), 328 (13), 269 (13), 268 (46), 240 (21), 220 (26). MS (CI, isobutane): m/z(%)= 481 (100) [M+H]+. UV/Vis (CHCl3): λ(max)(lg ε)= 262 nm (3.855), 314 nm (2.881). |
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 | Occ. (<1) | |
C1 | 0.81447 (18) | 0.39743 (16) | 0.81937 (12) | 0.0298 (3) | |
C2 | 0.67642 (18) | 0.36772 (16) | 0.78212 (13) | 0.0300 (3) | |
C3 | 0.63158 (18) | 0.21966 (17) | 0.73104 (13) | 0.0308 (4) | |
H3 | 0.5240 | 0.1707 | 0.7187 | 0.037* | |
C4 | 0.72948 (19) | 0.21953 (16) | 0.64136 (13) | 0.0301 (3) | |
C5 | 0.86786 (18) | 0.24874 (16) | 0.67833 (12) | 0.0295 (3) | |
C6 | 0.86494 (18) | 0.27007 (16) | 0.79390 (13) | 0.0302 (3) | |
H6 | 0.9515 | 0.2636 | 0.8343 | 0.036* | |
C7 | 0.71645 (19) | 0.15921 (17) | 0.80360 (13) | 0.0319 (4) | |
C8 | 0.6783 (2) | 0.04726 (18) | 0.85174 (13) | 0.0386 (4) | |
C9 | 0.5221 (3) | −0.0464 (2) | 0.84862 (16) | 0.0501 (5) | |
H9A | 0.4600 | −0.0117 | 0.8055 | 0.075* | |
H9B | 0.4866 | −0.0493 | 0.9167 | 0.075* | |
H9C | 0.5180 | −0.1393 | 0.8217 | 0.075* | |
C10 | 0.7892 (3) | 0.0025 (2) | 0.91079 (16) | 0.0505 (5) | |
H10A | 0.8882 | 0.0643 | 0.9024 | 0.076* | |
H10B | 0.7832 | −0.0917 | 0.8862 | 0.076* | |
H10C | 0.7682 | 0.0059 | 0.9821 | 0.076* | |
C11 | 0.89827 (19) | 0.52489 (18) | 0.88315 (13) | 0.0341 (4) | |
O1 | 0.85560 (18) | 0.55873 (16) | 0.96400 (11) | 0.0500 (4) | |
N1 | 1.02489 (18) | 0.60006 (17) | 0.84779 (12) | 0.0404 (4) | |
C12 | 1.1278 (3) | 0.7203 (2) | 0.90131 (19) | 0.0544 (5) | |
H12A | 1.0857 | 0.7446 | 0.9633 | 0.082* | 0.60 |
H12B | 1.1485 | 0.7971 | 0.8592 | 0.082* | 0.60 |
H12C | 1.2193 | 0.7010 | 0.9178 | 0.082* | 0.60 |
H12D | 1.2166 | 0.7505 | 0.8636 | 0.082* | 0.40 |
H12E | 1.1539 | 0.6980 | 0.9677 | 0.082* | 0.40 |
H12F | 1.0831 | 0.7942 | 0.9091 | 0.082* | 0.40 |
O2 | 1.06466 (14) | 0.55339 (13) | 0.75543 (10) | 0.0359 (3) | |
C13 | 1.0318 (3) | 0.6292 (2) | 0.67700 (16) | 0.0481 (5) | |
H13A | 0.9303 | 0.6306 | 0.6808 | 0.072* | |
H13B | 1.0437 | 0.5849 | 0.6115 | 0.072* | |
H13C | 1.0990 | 0.7237 | 0.6853 | 0.072* | |
C14 | 0.58711 (19) | 0.46339 (18) | 0.78346 (13) | 0.0335 (4) | |
O3 | 0.63333 (18) | 0.57977 (14) | 0.75583 (12) | 0.0502 (4) | |
N2 | 0.45160 (17) | 0.41573 (17) | 0.81724 (13) | 0.0403 (4) | |
C15 | 0.3392 (2) | 0.4826 (3) | 0.81249 (18) | 0.0535 (5) | |
H15A | 0.3831 | 0.5771 | 0.7954 | 0.080* | |
H15B | 0.2957 | 0.4839 | 0.8778 | 0.080* | |
H15C | 0.2627 | 0.4319 | 0.7610 | 0.080* | |
O4 | 0.40977 (16) | 0.28673 (14) | 0.85165 (12) | 0.0482 (4) | |
C16 | 0.4368 (4) | 0.3012 (3) | 0.9592 (2) | 0.0717 (8) | |
H16A | 0.5405 | 0.3524 | 0.9763 | 0.108* | |
H16B | 0.4134 | 0.2099 | 0.9837 | 0.108* | |
H16C | 0.3749 | 0.3512 | 0.9908 | 0.108* | |
C17 | 0.6746 (2) | 0.17624 (18) | 0.53508 (13) | 0.0354 (4) | |
O5 | 0.7086 (2) | 0.08738 (17) | 0.48378 (11) | 0.0580 (4) | |
N3 | 0.57718 (19) | 0.23375 (16) | 0.49947 (12) | 0.0396 (4) | |
C18 | 0.5110 (3) | 0.2035 (3) | 0.39838 (16) | 0.0542 (5) | |
H18A | 0.4217 | 0.2308 | 0.3958 | 0.081* | 0.60 |
H18B | 0.4859 | 0.1046 | 0.3786 | 0.081* | 0.60 |
H18C | 0.5807 | 0.2546 | 0.3522 | 0.081* | 0.60 |
H18D | 0.5705 | 0.1625 | 0.3553 | 0.081* | 0.40 |
H18E | 0.5063 | 0.2887 | 0.3725 | 0.081* | 0.40 |
H18F | 0.4115 | 0.1387 | 0.3989 | 0.081* | 0.40 |
O6 | 0.56596 (14) | 0.35176 (13) | 0.55432 (10) | 0.0365 (3) | |
C19 | 0.6728 (2) | 0.4717 (2) | 0.52256 (16) | 0.0458 (5) | |
H19A | 0.7707 | 0.4607 | 0.5275 | 0.069* | |
H19B | 0.6721 | 0.5533 | 0.5658 | 0.069* | |
H19C | 0.6484 | 0.4829 | 0.4528 | 0.069* | |
C20 | 1.00122 (19) | 0.26034 (17) | 0.62073 (14) | 0.0341 (4) | |
O7 | 1.03798 (18) | 0.33922 (16) | 0.55533 (12) | 0.0524 (4) | |
N4 | 1.08090 (18) | 0.18055 (17) | 0.64597 (14) | 0.0440 (4) | |
C21 | 1.2220 (2) | 0.1841 (3) | 0.6077 (2) | 0.0571 (6) | |
H21A | 1.2963 | 0.2065 | 0.6636 | 0.086* | |
H21B | 1.2503 | 0.2543 | 0.5601 | 0.086* | |
H21C | 1.2149 | 0.0940 | 0.5735 | 0.086* | |
O8 | 1.02474 (18) | 0.08363 (15) | 0.71379 (11) | 0.0482 (4) | |
C22 | 0.9419 (3) | −0.0452 (2) | 0.6592 (2) | 0.0641 (7) | |
H22A | 0.8626 | −0.0316 | 0.6176 | 0.096* | |
H22B | 0.8998 | −0.1127 | 0.7067 | 0.096* | |
H22C | 1.0070 | −0.0787 | 0.6160 | 0.096* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0281 (8) | 0.0296 (8) | 0.0321 (8) | 0.0086 (6) | 0.0069 (7) | 0.0048 (6) |
C2 | 0.0280 (8) | 0.0302 (8) | 0.0329 (8) | 0.0100 (6) | 0.0074 (7) | 0.0046 (6) |
C3 | 0.0276 (8) | 0.0304 (8) | 0.0345 (8) | 0.0083 (6) | 0.0046 (7) | 0.0044 (6) |
C4 | 0.0324 (8) | 0.0270 (7) | 0.0340 (8) | 0.0126 (6) | 0.0055 (7) | 0.0057 (6) |
C5 | 0.0325 (8) | 0.0260 (7) | 0.0343 (8) | 0.0139 (6) | 0.0072 (7) | 0.0068 (6) |
C6 | 0.0278 (8) | 0.0298 (8) | 0.0345 (8) | 0.0103 (6) | 0.0035 (7) | 0.0063 (6) |
C7 | 0.0342 (9) | 0.0296 (8) | 0.0327 (8) | 0.0103 (7) | 0.0049 (7) | 0.0045 (6) |
C8 | 0.0508 (11) | 0.0304 (8) | 0.0314 (8) | 0.0079 (8) | 0.0054 (8) | 0.0028 (7) |
C9 | 0.0607 (13) | 0.0370 (9) | 0.0391 (10) | −0.0051 (9) | 0.0060 (9) | 0.0051 (8) |
C10 | 0.0727 (15) | 0.0383 (10) | 0.0409 (10) | 0.0163 (10) | −0.0020 (10) | 0.0119 (8) |
C11 | 0.0319 (9) | 0.0348 (8) | 0.0361 (9) | 0.0112 (7) | 0.0035 (7) | 0.0034 (7) |
O1 | 0.0539 (9) | 0.0508 (8) | 0.0419 (8) | 0.0134 (7) | 0.0120 (7) | −0.0069 (6) |
N1 | 0.0347 (8) | 0.0413 (8) | 0.0370 (8) | 0.0016 (6) | 0.0022 (7) | −0.0029 (6) |
C12 | 0.0439 (12) | 0.0444 (11) | 0.0608 (13) | −0.0028 (9) | −0.0015 (10) | −0.0091 (10) |
O2 | 0.0321 (6) | 0.0378 (6) | 0.0402 (7) | 0.0133 (5) | 0.0062 (5) | 0.0065 (5) |
C13 | 0.0540 (12) | 0.0472 (11) | 0.0474 (11) | 0.0191 (9) | 0.0053 (9) | 0.0147 (9) |
C14 | 0.0330 (9) | 0.0386 (9) | 0.0322 (8) | 0.0157 (7) | 0.0058 (7) | 0.0043 (7) |
O3 | 0.0551 (9) | 0.0389 (7) | 0.0660 (9) | 0.0240 (6) | 0.0220 (7) | 0.0156 (7) |
N2 | 0.0333 (8) | 0.0482 (9) | 0.0475 (9) | 0.0210 (7) | 0.0119 (7) | 0.0148 (7) |
C15 | 0.0409 (11) | 0.0715 (14) | 0.0590 (13) | 0.0354 (11) | 0.0030 (10) | −0.0013 (11) |
O4 | 0.0421 (8) | 0.0422 (7) | 0.0591 (9) | 0.0097 (6) | 0.0181 (7) | 0.0065 (6) |
C16 | 0.100 (2) | 0.0689 (16) | 0.0577 (15) | 0.0341 (15) | 0.0352 (15) | 0.0287 (13) |
C17 | 0.0401 (9) | 0.0314 (8) | 0.0363 (9) | 0.0137 (7) | 0.0036 (7) | 0.0015 (7) |
O5 | 0.0851 (12) | 0.0572 (9) | 0.0439 (8) | 0.0443 (9) | −0.0027 (8) | −0.0100 (7) |
N3 | 0.0459 (9) | 0.0369 (8) | 0.0373 (8) | 0.0169 (7) | −0.0064 (7) | −0.0024 (6) |
C18 | 0.0593 (14) | 0.0574 (13) | 0.0419 (11) | 0.0152 (11) | −0.0148 (10) | −0.0004 (9) |
O6 | 0.0350 (7) | 0.0360 (6) | 0.0417 (7) | 0.0153 (5) | 0.0043 (5) | 0.0050 (5) |
C19 | 0.0511 (12) | 0.0370 (9) | 0.0491 (11) | 0.0115 (8) | 0.0054 (9) | 0.0109 (8) |
C20 | 0.0327 (9) | 0.0320 (8) | 0.0402 (9) | 0.0140 (7) | 0.0066 (7) | 0.0007 (7) |
O7 | 0.0570 (9) | 0.0550 (9) | 0.0540 (9) | 0.0244 (7) | 0.0276 (7) | 0.0211 (7) |
N4 | 0.0372 (9) | 0.0429 (8) | 0.0589 (10) | 0.0215 (7) | 0.0097 (8) | 0.0075 (7) |
C21 | 0.0368 (11) | 0.0684 (14) | 0.0708 (15) | 0.0283 (10) | 0.0042 (10) | −0.0142 (11) |
O8 | 0.0591 (9) | 0.0453 (8) | 0.0506 (8) | 0.0309 (7) | 0.0012 (7) | 0.0072 (6) |
C22 | 0.0818 (18) | 0.0351 (10) | 0.0781 (17) | 0.0223 (11) | 0.0060 (14) | 0.0040 (10) |
C1—C2 | 1.335 (3) | C14—O3 | 1.230 (2) |
C1—C11 | 1.489 (2) | C14—N2 | 1.343 (2) |
C1—C6 | 1.545 (2) | N2—O4 | 1.381 (2) |
C2—C14 | 1.488 (2) | N2—C15 | 1.447 (2) |
C2—C3 | 1.541 (2) | C15—H15A | 0.9800 |
C3—C7 | 1.535 (2) | C15—H15B | 0.9800 |
C3—C4 | 1.543 (2) | C15—H15C | 0.9800 |
C3—H3 | 1.0000 | O4—C16 | 1.443 (3) |
C4—C5 | 1.337 (3) | C16—H16A | 0.9800 |
C4—C17 | 1.486 (3) | C16—H16B | 0.9800 |
C5—C20 | 1.488 (2) | C16—H16C | 0.9800 |
C5—C6 | 1.546 (2) | C17—O5 | 1.226 (2) |
C6—C7 | 1.539 (2) | C17—N3 | 1.345 (2) |
C6—H6 | 1.0000 | N3—O6 | 1.400 (2) |
C7—C8 | 1.320 (2) | N3—C18 | 1.446 (3) |
C8—C9 | 1.506 (3) | C18—H18A | 0.9800 |
C8—C10 | 1.510 (3) | C18—H18B | 0.9800 |
C9—H9A | 0.9800 | C18—H18C | 0.9800 |
C9—H9B | 0.9800 | C18—H18D | 0.9800 |
C9—H9C | 0.9800 | C18—H18E | 0.9800 |
C10—H10A | 0.9800 | C18—H18F | 0.9800 |
C10—H10B | 0.9800 | O6—C19 | 1.440 (2) |
C10—H10C | 0.9800 | C19—H19A | 0.9800 |
C11—O1 | 1.228 (2) | C19—H19B | 0.9800 |
C11—N1 | 1.343 (2) | C19—H19C | 0.9800 |
N1—O2 | 1.394 (2) | C20—O7 | 1.225 (2) |
N1—C12 | 1.441 (3) | C20—N4 | 1.336 (2) |
C12—H12A | 0.9800 | N4—O8 | 1.394 (2) |
C12—H12B | 0.9800 | N4—C21 | 1.450 (2) |
C12—H12C | 0.9800 | C21—H21A | 0.9800 |
C12—H12D | 0.9800 | C21—H21B | 0.9800 |
C12—H12E | 0.9800 | C21—H21C | 0.9800 |
C12—H12F | 0.9800 | O8—C22 | 1.441 (3) |
O2—C13 | 1.440 (2) | C22—H22A | 0.9800 |
C13—H13A | 0.9800 | C22—H22B | 0.9800 |
C13—H13B | 0.9800 | C22—H22C | 0.9800 |
C13—H13C | 0.9800 | ||
C2—C1—C11 | 125.72 (15) | H13A—C13—H13C | 109.5 |
C2—C1—C6 | 107.71 (14) | H13B—C13—H13C | 109.5 |
C11—C1—C6 | 126.28 (15) | O3—C14—N2 | 121.23 (16) |
C1—C2—C14 | 126.22 (16) | O3—C14—C2 | 122.67 (15) |
C1—C2—C3 | 107.02 (14) | N2—C14—C2 | 116.10 (15) |
C14—C2—C3 | 126.62 (15) | C14—N2—O4 | 118.04 (14) |
C7—C3—C2 | 98.31 (13) | C14—N2—C15 | 125.53 (17) |
C7—C3—C4 | 96.76 (12) | O4—N2—C15 | 116.18 (16) |
C2—C3—C4 | 107.50 (13) | N2—C15—H15A | 109.5 |
C7—C3—H3 | 117.0 | N2—C15—H15B | 109.5 |
C2—C3—H3 | 117.0 | H15A—C15—H15B | 109.5 |
C4—C3—H3 | 117.0 | N2—C15—H15C | 109.5 |
C5—C4—C17 | 126.88 (15) | H15A—C15—H15C | 109.5 |
C5—C4—C3 | 107.59 (15) | H15B—C15—H15C | 109.5 |
C17—C4—C3 | 125.07 (15) | N2—O4—C16 | 108.98 (17) |
C4—C5—C20 | 127.32 (16) | O4—C16—H16A | 109.5 |
C4—C5—C6 | 107.01 (14) | O4—C16—H16B | 109.5 |
C20—C5—C6 | 125.67 (15) | H16A—C16—H16B | 109.5 |
C7—C6—C1 | 97.69 (12) | O4—C16—H16C | 109.5 |
C7—C6—C5 | 96.70 (13) | H16A—C16—H16C | 109.5 |
C1—C6—C5 | 107.58 (12) | H16B—C16—H16C | 109.5 |
C7—C6—H6 | 117.2 | O5—C17—N3 | 121.17 (18) |
C1—C6—H6 | 117.2 | O5—C17—C4 | 122.52 (16) |
C5—C6—H6 | 117.2 | N3—C17—C4 | 116.18 (15) |
C8—C7—C3 | 132.86 (17) | C17—N3—O6 | 117.33 (15) |
C8—C7—C6 | 132.60 (17) | C17—N3—C18 | 124.05 (17) |
C3—C7—C6 | 94.40 (13) | O6—N3—C18 | 116.83 (15) |
C7—C8—C9 | 122.14 (19) | N3—C18—H18A | 109.5 |
C7—C8—C10 | 122.15 (19) | N3—C18—H18B | 109.5 |
C9—C8—C10 | 115.68 (17) | H18A—C18—H18B | 109.5 |
C8—C9—H9A | 109.5 | N3—C18—H18C | 109.5 |
C8—C9—H9B | 109.5 | H18A—C18—H18C | 109.5 |
H9A—C9—H9B | 109.5 | H18B—C18—H18C | 109.5 |
C8—C9—H9C | 109.5 | N3—C18—H18D | 109.5 |
H9A—C9—H9C | 109.5 | N3—C18—H18E | 109.5 |
H9B—C9—H9C | 109.5 | H18D—C18—H18E | 109.5 |
C8—C10—H10A | 109.5 | N3—C18—H18F | 109.5 |
C8—C10—H10B | 109.5 | H18D—C18—H18F | 109.5 |
H10A—C10—H10B | 109.5 | H18E—C18—H18F | 109.5 |
C8—C10—H10C | 109.5 | N3—O6—C19 | 109.55 (14) |
H10A—C10—H10C | 109.5 | O6—C19—H19A | 109.5 |
H10B—C10—H10C | 109.5 | O6—C19—H19B | 109.5 |
O1—C11—N1 | 121.74 (18) | H19A—C19—H19B | 109.5 |
O1—C11—C1 | 122.24 (16) | O6—C19—H19C | 109.5 |
N1—C11—C1 | 116.02 (15) | H19A—C19—H19C | 109.5 |
C11—N1—O2 | 117.70 (15) | H19B—C19—H19C | 109.5 |
C11—N1—C12 | 124.80 (17) | O7—C20—N4 | 121.58 (16) |
O2—N1—C12 | 117.35 (15) | O7—C20—C5 | 122.68 (15) |
N1—C12—H12A | 109.5 | N4—C20—C5 | 115.73 (15) |
N1—C12—H12B | 109.5 | C20—N4—O8 | 118.28 (15) |
H12A—C12—H12B | 109.5 | C20—N4—C21 | 125.56 (18) |
N1—C12—H12C | 109.5 | O8—N4—C21 | 116.16 (17) |
H12A—C12—H12C | 109.5 | N4—C21—H21A | 109.5 |
H12B—C12—H12C | 109.5 | N4—C21—H21B | 109.5 |
N1—C12—H12D | 109.5 | H21A—C21—H21B | 109.5 |
N1—C12—H12E | 109.5 | N4—C21—H21C | 109.5 |
H12D—C12—H12E | 109.5 | H21A—C21—H21C | 109.5 |
N1—C12—H12F | 109.5 | H21B—C21—H21C | 109.5 |
H12D—C12—H12F | 109.5 | N4—O8—C22 | 109.25 (17) |
H12E—C12—H12F | 109.5 | O8—C22—H22A | 109.5 |
N1—O2—C13 | 110.50 (14) | O8—C22—H22B | 109.5 |
O2—C13—H13A | 109.5 | H22A—C22—H22B | 109.5 |
O2—C13—H13B | 109.5 | O8—C22—H22C | 109.5 |
H13A—C13—H13B | 109.5 | H22A—C22—H22C | 109.5 |
O2—C13—H13C | 109.5 | H22B—C22—H22C | 109.5 |
Experimental details
Crystal data | |
Chemical formula | C22H32N4O8 |
Mr | 480.52 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 200 |
a, b, c (Å) | 9.5830 (9), 10.2662 (8), 13.3792 (16) |
α, β, γ (°) | 94.648 (12), 91.548 (13), 108.013 (10) |
V (Å3) | 1245.7 (2) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.10 |
Crystal size (mm) | 0.3 × 0.3 × 0.2 |
Data collection | |
Diffractometer | Stoe IPDS1 diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 10017, 4788, 3431 |
Rint | 0.040 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.045, 0.119, 1.00 |
No. of reflections | 4788 |
No. of parameters | 318 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.19, −0.19 |
Computer programs: X-AREA (Stoe & Cie, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XP in SHELXTL (Sheldrick, 2008), XCIF in SHELXTL (Sheldrick, 2008).
Acknowledgements
We gratefully acknowledge financial support by the Deutsche Forschungsgemeinschaft via SFB 677. We thank Jürgen Brockmann, Archimica Frankfurt, Germany for a free sample of T3P(R).
References
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Stoe & Cie (2008). X-AREA, X-RED32 and X-SHAPE. Stoe & Cie, Darmstadt, Germany. Google Scholar
Winkler, T., Bayrhuber, M., Sahlmann, B. & Herges, R. (2012). Dalton Trans. 41 7037–7040. Web of Science CrossRef CAS PubMed Google Scholar
Winkler, T., Dix, I., Jones, P. G. & Herges, R. (2003a). Angew. Chem. 115, 3665–3668. CrossRef Google Scholar
Winkler, T., Herges, R., Jones, P. G. & Dix, I. (2003b). Acta Cryst. E59, o1101–o1102. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
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The tertiary tetra amides of norbornadiene and quadricyclane are interesting compounds because of their ability to form stable complexes with alkali and alkaline earth metal cations. (Winkler et al., 2003a; Winkler et al., 2012) To enable further synthetic modifications, the tetrakis(N,O-dimethylhydroxyl amide) was synthesized. For the identification of this compound, a structure determination was performed.
In the structure of the title compound, the carbonyl atoms alternately point to different sides of the plane defined by the carbony C atoms. In contrast to the tetrakis(diethyl amide) (Winkler et al., 2003b), the methoxy substituents are small enough to point inside of the cavity of the molecule. although the molecule displays twofold symmetry no crystallographic twofold symmetry is oberved experimentally. In addition, no intramolecular hydrogen bonds are found.