7-Iso­propyl­idene-N2,N3,N5,N6-tetra­meth­oxy-N2,N3,N5,N6-tetra­methylbi­cyclo­[2.2.1]hepta-2,5-diene-2,3,5,6-tetra­carboxamide

Sahlmann, B.; Näther, C.; Herges, R.

doi:10.1107/S1600536814004255

organic compounds

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ISSN: 2056-9890

Volume 70| Part 4| April 2014| Page o438

doi:10.1107/S1600536814004255

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7-Isopropylidene-N²,N³,N⁵,N⁶-tetramethoxy-N²,N³,N⁵,N⁶-tetramethylbicyclo[2.2.1]hepta-2,5-diene-2,3,5,6-tetracarboxamide

Benjamin Sahlmann,^a Christian Näther ^b ^* and Rainer Herges ^a

^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

(Received 21 February 2014; accepted 24 February 2014; online 15 March 2014)

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

C₂₂H₃₂N₄O₈
M_r = 480.52
Triclinic, $[P \overline 1]$
a = 9.5830 (9) Å
b = 10.2662 (8) Å
c = 13.3792 (16) Å
α = 94.648 (12)°
β = 91.548 (13)°
γ = 108.013 (10)°
V = 1245.7 (2) Å³
Z = 2
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 200 K
0.3 × 0.3 × 0.2 mm

Data collection

Stoe IPDS-1 diffractometer
10017 measured reflections
4788 independent reflections
3431 reflections with I > 2σ(I)
R_int = 0.040

Refinement

R[F² > 2σ(F²)] = 0.045
wR(F²) = 0.119
S = 1.00
4788 reflections
318 parameters
H-atom parameters constrained
Δρ_max = 0.19 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Data collection: X-AREA (Stoe & Cie, 2008 ); cell refinement: 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

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: 10.1107/S1600536814004255/im2450sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814004255/im2450Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536814004255/im2450Isup3.cml

checkCIF report

Comment top

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.

Related literature top

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 top

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

Computing details top

Data collection: X-AREA (Stoe & Cie, 2008); cell refinement: 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).

Figures top

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.

7-Isopropylidene-N²,N³,N⁵,N⁶-tetramethoxy-N²,N³,N⁵,N⁶-tetramethylbicyclo[2.2.1]hepta-2,5-diene-2,3,5,6-tetracarboxamide top

Crystal data top

C₂₂H₃₂N₄O₈	Z = 2
M_r = 480.52	F(000) = 512
Triclinic, P1	D_x = 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

Data collection top

Stoe IPDS-1 diffractometer	3431 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.040
Graphite monochromator	θ_max = 26.0°, θ_min = 2.9°
Phi scans	h = −11→11
10017 measured reflections	k = −12→12
4788 independent reflections	l = −16→16

Refinement top

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(F_o²) + (0.0701P)²] where P = (F_o² + 2F_c²)/3
S = 1.00	(Δ/σ)_max < 0.001
4788 reflections	Δρ_max = 0.19 e Å⁻³
318 parameters	Δρ_min = −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)

Crystal data top

C₂₂H₃₂N₄O₈	γ = 108.013 (10)°
M_r = 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)°

Data collection top

Stoe IPDS-1 diffractometer	3431 reflections with I > 2σ(I)
10017 measured reflections	R_int = 0.040
4788 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	0 restraints
wR(F²) = 0.119	H-atom parameters constrained
S = 1.00	Δρ_max = 0.19 e Å⁻³
4788 reflections	Δρ_min = −0.19 e Å⁻³
318 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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
M_r	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
R_int	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
Δρ_max, Δρ_min (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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