Ethyl 9-dicyano­methyl­ene-2,5,7-trinitro­fluorene-4-carboxyl­ate

Batsanov, A.S.; Perepichka, I.F.

doi:10.1107/S1600536806003175

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 62| Part 3| March 2006| Pages o885-o887

https://doi.org/10.1107/S1600536806003175

Ethyl 9-dicyanomethylene-2,5,7-trinitrofluorene-4-carboxylate

Andrei S. Batsanov ^a ^* and Igor F. Perepichka ^b

^aDepartment of Chemistry, University of Durham, South Road, Durham DH1 3LE, England, and ^bL. M. Litvinenko Institute of Physical Organic and Coal Chemistry, National Academy of Sciences of Ukraine, Donetsk 83114, Ukraine
^*Correspondence e-mail: a.s.batsanov@durham.ac.uk

(Received 24 January 2006; accepted 26 January 2006; online 3 February 2006)

The title compound, C₁₉H₉N₅O₈, has a warped fluorene ring system due to steric repulsion between the 4-ethoxycarbonyl and 5-nitro groups.

Comment

The title compound, (I), has been obtained in the course of our studies of electron acceptors of the fluorene series and their charge-transfer complexes and radical ion salts with π-electron donors, e.g. tetrathiafulvalene family donors (Perepichka et al., 1998 , 2000 , 2002 ; Batsanov et al., 2001 , 2002 ; Kuz'mina et al., 2002 ).

The molecular structure of (I) is strongly influenced by steric repulsion between the nitro and ethoxycarbonyl groups in positions 4 and 5, respectively. This overcrowding, indicated, for example, by the short (intramolecular) non-bonding distances N4⋯O5 [2.730 (5) Å] and C17⋯O4 [2.711 (6) Å], causes the above-mentioned substituents to tilt out of the fluorene plane in opposite directions. Furthermore, the fluorene aromatic system itself loses planarity and adopts a warped (twisted) conformation, the deviations (Å) of its C atoms from the mean plane being: C1 −0.186 (4), C2 −0.149 (4), C3 0.135 (4), C4 0.245 (4), C5 −0.226 (4), C6 −0.145 (4), C7 0.070 (4), C8 0.138 (4), C9 0.033 (4), C10 −0.039 (4), C11 0.060 (5), C12 −0.013 (5) and C13 0.078 (4). Similar distortions are typical for other fluorene derivatives with bulky substituents in positions 4 and 5, e.g. 9-dicyanomethylene-2,4,5,7-tetranitrofluorene (Silverman et al., 1974 ; Batsanov et al., 2001), 9-dicyanomethylene-4,5-dinitrofluorene-2,7-disulfonamide (Batsanov & Perepichka, 2004 ) or 9-dicyanomethylene-4-bromo-2,5,7-trinitrofluorene (Perepichka et al., 2002).

Figure 1
The molecular structure of (I)

. Atomic displacement ellipsoids are drawn at the 50% probability level.

Experimental

To a suspension of 2,5,7-trinitro-9-oxofluorene-4-carboxylic acid (10.0 g, 27.8 mmol), (II), in thionyl chloride (50 ml) a catalytic amount of N,N-dimethylformamide (2 drops) was added. The mixture was refluxed for 2 h (full dissolution occurring in 15–20 min) and then evaporated under reduced pressure until dry. Ethanol (50 ml) was added to the residue, the mixture was refluxed for 3 h and left to cool for crystallization. The precipitate was filtered off, washed with cold ethanol (2 × 20 ml) and dried to yield crude compound (III) (9.1 g, 84%; m.p. 426–430 K). This was dissolved in boiling dioxane (25 ml), filtered hot and the filtrate was diluted with hot ethanol (100 ml). On cooling, the solid was filtered off, washed with ethanol and dried. This procedure was repeated to give pure compound (III) (7.2 g, 67%) as yellow crystals (m.p. 434–435 K). ¹H NMR (200 MHz, acetone-d₆): δ 8.99 (1H, d, J = 2.0 Hz, H-3), 8.83 (1H, d, J = 2.0 Hz, H-6), 8.78 (1H, d, J = 2.2 Hz, H-8), 8.69 (1H, d, J = 2.2 Hz, H-1), 4.42 (2H, q, J = 7.2 Hz, CH2), 1.43 (3H, t, J = 7.2 Hz, CH3). ¹³C NMR (50 MHz, acetone-d₆): δ 186.21 (C=O), 165.44 (–CO₂–), 150.71, 150.56, 147.36, 144.19, 140.30, 140.08, 139.18, 132.90, 131.05, 126.38, 122.95, 122.00, 63.84 (CH₂), 14.32 (CH₃). MS (EI): m/z 387 (M⁺, 100%). HRMS (EI): m/z 387.03447; calculated exact mass: 387.03388. Analysis found: C 49.52, H 2.40, N 10.89%; C₁₆H₉N₃O₉ requires: C 49.62, H 2.34, N 10.85%.

Compound (III) (5.0 g, 12.9 mmol) was dissolved in N,N-dimethylformamide (25 ml), malonitrile (2.2 g, 33.3 mmol) was added to this solution and the mixture was stirred at room temperature for 1 h (the product began to precipitate in 30 min). 2-Propanol (100 ml) was added to the mixture and it was allowed to stand at 273 K for 1–2 h. The solid was filtered off, washed with 2-propanol and dried to yield crude compound (I) (5.2 g, 93%; m.p. 539–543 K). It was dissolved in boiling dioxane (75 ml), hot 2-propanol was added to the solution and the product left to crystallize. The solid was filtered off, washed with 2-propanol and dried. The purification procedure was repeated once more, to afford pure compound (I) (4.8 g, 85%) as bright-yellow crystals (m.p. 543–545 K). ¹H NMR (200 MHz, acetone-d₆ + half a drop CF₃CO₂D): δ 9.69 (1H, d, J = 2.0 Hz, H-8), 9.60 (1H, d, J = 2.0 Hz, H-1), 9.04 (1H, d, J = 2.0 Hz, H-6), 8.88 (1H, d J = 2.0 Hz, H-3), 4.43 (2H, q, J = 7.2 Hz, CH2), 1.44 (3H, t, J = 7.2 Hz, CH3). ¹³C NMR (100 MHz, acetone-d₆ + 0.5 drop CF₃CO₂D): δ 165.30 (–CO₂–), 154.81, 141.14, 140.14, 139.25, 137.49, 133.05, 130.49, 125.76, 124.75, 123.70, 121.52, 117.74, 113.96, 113.37, 113.32, 110.17, 63.96 (CH₂), 14.36 (CH₃). MS (EI): m/z 435 (M⁺, 100%). Analysis found: C 52.52, H 2.03, N 16.15%; C₁₉H₉N₅O₈ requires: C 52.42, H 2.08, N 16.09%. Compound (I) was dissolved in hot acetonitrile and left to cool slowly to yield single crystals of X-ray quality.

Crystal data

C₁₉H₉N₅O₈
M_r = 435.31
Monoclinic, P 2₁ /c
a = 19.481 (2) Å
b = 8.620 (1) Å
c = 10.814 (1) Å
β = 99.40 (1)°
V = 1791.6 (3) Å³
Z = 4
D_x = 1.615 Mg m⁻³
Mo Kα radiation
Cell parameters from 1107 reflections
θ = 3.1–22.6°
μ = 0.13 mm⁻¹
T = 110 (2) K
Prism, yellow
0.18 × 0.07 × 0.07 mm

Data collection

Bruker SMART 1 K CCD area-detector diffractometer
ω scans
Absorption correction: none
7993 measured reflections
3079 independent reflections
1518 reflections with I > 2σ(I)
R_int = 0.126
θ_max = 25.0°
h = −13 → 22
k = −9 → 10
l = −12 → 12

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.067
wR(F²) = 0.172
S = 1.03
3079 reflections
292 parameters
H-atom parameters constrained
w = 1/[σ²(F_o²) + (0.0632P)² + 0.5406P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max < 0.001
Δρ_max = 0.41 e Å⁻³
Δρ_min = −0.37 e Å⁻³
Extinction correction: SHELXTL
Extinction coefficient: 0.018 (2)

Table 1
Selected geometric parameters (Å, °)

N15—C15	1.152 (6)
N16—C16	1.147 (6)
C9—C14	1.352 (7)
C9—C10	1.465 (7)
C9—C13	1.495 (6)
C10—C11	1.412 (6)
C11—C12	1.502 (7)
C12—C13	1.397 (7)
C14—C16	1.444 (7)
C14—C15	1.446 (7)

C2—C1—C10	116.9 (4)
C3—C2—C1	123.3 (4)
C2—C3—C4	118.0 (5)
C3—C4—C11	121.4 (4)
C6—C5—C12	117.7 (5)
C7—C6—C5	119.2 (5)
C6—C7—C8	124.3 (5)
C7—C8—C13	116.0 (5)

The diffraction was rather weak, with a mean I/σ(I) ratio of 5.2. The methyl group was refined as a rigid body (C—H = 0.98 Å) rotating around the C—C bond, with a common (refined) U_iso value for all three H atoms. Other H atoms were treated as riding in idealized positions, with Csp³—H = 0.99 Å and Csp²—H = 0.95 Å, and U_iso(H) = 1.3U_eq(C) and 1.2U_eq(C), respectively.

Data collection: SMART (Bruker, 1997 ); cell refinement: SAINT (Bruker, 1999 ); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Bruker, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536806003175/bt6807sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536806003175/bt6807Isup2.hkl

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SMART; data reduction: SAINT (Bruker, 1999); program(s) used to solve structure: SHELXTL (Bruker, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Ethyl 9-dicyanomethylene-2,5,7-trinitrofluorene-4-carboxylate top

Crystal data top

C₁₉H₉N₅O₈	F(000) = 888
M_r = 435.31	D_x = 1.615 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1107 reflections
a = 19.481 (2) Å	θ = 3.1–22.6°
b = 8.620 (1) Å	µ = 0.13 mm⁻¹
c = 10.814 (1) Å	T = 110 K
β = 99.40 (1)°	Prism, yellow
V = 1791.6 (3) Å³	0.18 × 0.07 × 0.07 mm
Z = 4

Data collection top

Bruker SMART 1 K CCD area-detector diffractometer	1518 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.126
Graphite monochromator	θ_max = 25.0°, θ_min = 2.1°
Detector resolution: 8 pixels mm^-1	h = −13→22
ω scans	k = −9→10
7993 measured reflections	l = −12→12
3079 independent reflections

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)] = 0.067	H-atom parameters constrained
wR(F²) = 0.172	w = 1/[σ²(F_o²) + (0.0632P)² + 0.5406P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max < 0.001
3079 reflections	Δρ_max = 0.41 e Å⁻³
292 parameters	Δρ_min = −0.37 e Å⁻³
0 restraints	Extinction correction: SHELXTL, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.018 (2)

Special details top

Experimental. The data collection nominally covered over a hemisphere of reciprocal space, by a combination of 4 sets of ω scans; each set at different φ and/or 2θ angles and each scan (46.5 sec exposure) covering 0.3° in ω. Crystal to detector distance 6.03 cm.

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.

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

	x	y	z	U_iso*/U_eq
O1	0.53613 (17)	0.2322 (4)	0.2237 (4)	0.0309 (9)
O2	0.55693 (17)	0.2996 (4)	0.4205 (3)	0.0321 (10)
O3	0.34804 (18)	0.4135 (4)	0.6081 (3)	0.0330 (10)
O4	0.28475 (17)	0.5939 (4)	0.5031 (3)	0.0293 (9)
O5	0.21531 (18)	0.2915 (4)	0.4372 (3)	0.0323 (10)
O6	0.13270 (17)	0.4589 (4)	0.4749 (3)	0.0302 (10)
O7	−0.00294 (18)	0.6632 (5)	0.0855 (4)	0.0407 (11)
O8	0.04476 (17)	0.6932 (5)	−0.0813 (4)	0.0385 (11)
N2	0.5196 (2)	0.2939 (5)	0.3175 (5)	0.0264 (11)
N4	0.3258 (2)	0.4838 (5)	0.5107 (4)	0.0271 (11)
N7	0.0466 (2)	0.6547 (5)	0.0287 (4)	0.0309 (12)
N15	0.4359 (2)	0.4704 (5)	−0.1171 (4)	0.0264 (11)
N16	0.2283 (2)	0.6451 (5)	−0.2394 (4)	0.0317 (12)
C1	0.4162 (2)	0.4011 (6)	0.1842 (5)	0.0216 (12)
H1	0.4389	0.3905	0.1133	0.026*
C2	0.4497 (2)	0.3643 (5)	0.3044 (5)	0.0198 (12)
C3	0.4208 (3)	0.3903 (6)	0.4109 (5)	0.0246 (12)
H3	0.4471	0.3747	0.4920	0.029*
C4	0.3523 (2)	0.4397 (5)	0.3960 (5)	0.0202 (12)
C5	0.1783 (3)	0.4889 (6)	0.2876 (5)	0.0245 (13)
C6	0.1152 (2)	0.5433 (6)	0.2194 (5)	0.0272 (13)
H6	0.0741	0.5440	0.2561	0.033*
C7	0.1136 (2)	0.5954 (6)	0.0985 (5)	0.0225 (12)
C8	0.1697 (2)	0.5900 (6)	0.0349 (5)	0.0252 (13)
H8	0.1657	0.6200	−0.0506	0.030*
C9	0.3006 (2)	0.5089 (6)	0.0615 (5)	0.0206 (12)
C10	0.3476 (2)	0.4543 (5)	0.1728 (4)	0.0190 (12)
C11	0.3132 (2)	0.4608 (5)	0.2780 (4)	0.0191 (12)
C12	0.2382 (3)	0.4980 (6)	0.2302 (5)	0.0237 (12)
C13	0.2325 (2)	0.5381 (6)	0.1038 (5)	0.0204 (12)
C14	0.3158 (2)	0.5339 (6)	−0.0545 (5)	0.0222 (12)
C15	0.3831 (3)	0.4987 (6)	−0.0877 (5)	0.0224 (12)
C16	0.2665 (3)	0.5949 (6)	−0.1573 (5)	0.0235 (12)
C17	0.1782 (2)	0.4036 (6)	0.4085 (5)	0.0261 (13)
C18	0.1288 (3)	0.3746 (6)	0.5921 (4)	0.0294 (14)
H181	0.1753	0.3702	0.6450	0.038*
H182	0.1123	0.2671	0.5734	0.038*
C19	0.0786 (3)	0.4606 (7)	0.6594 (5)	0.0380 (15)
H191	0.0952	0.5670	0.6766	0.049 (10)*
H192	0.0753	0.4081	0.7385	0.049 (10)*
H193	0.0327	0.4629	0.6066	0.049 (10)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.025 (2)	0.034 (2)	0.036 (2)	0.0071 (17)	0.0116 (17)	0.0019 (19)
O2	0.022 (2)	0.039 (3)	0.031 (2)	0.0037 (18)	−0.0046 (18)	0.0040 (18)
O3	0.034 (2)	0.044 (3)	0.019 (2)	0.0073 (19)	−0.0010 (16)	0.0118 (19)
O4	0.023 (2)	0.038 (2)	0.028 (2)	0.0037 (19)	0.0053 (16)	−0.0030 (18)
O5	0.030 (2)	0.028 (2)	0.040 (2)	0.0083 (19)	0.0079 (17)	0.0064 (18)
O6	0.022 (2)	0.038 (2)	0.031 (2)	0.0013 (17)	0.0063 (17)	0.0005 (18)
O7	0.019 (2)	0.058 (3)	0.046 (3)	0.0080 (19)	0.0083 (19)	0.014 (2)
O8	0.023 (2)	0.062 (3)	0.028 (2)	0.0122 (19)	−0.0031 (17)	0.006 (2)
N2	0.022 (2)	0.021 (3)	0.036 (3)	−0.001 (2)	0.004 (2)	0.006 (2)
N4	0.022 (3)	0.030 (3)	0.029 (3)	0.004 (2)	0.001 (2)	0.004 (2)
N7	0.020 (3)	0.039 (3)	0.033 (3)	0.005 (2)	0.001 (2)	0.005 (2)
N15	0.021 (3)	0.033 (3)	0.025 (3)	−0.001 (2)	0.005 (2)	−0.001 (2)
N16	0.025 (3)	0.040 (3)	0.030 (3)	0.003 (2)	0.004 (2)	0.003 (2)
C1	0.019 (3)	0.015 (3)	0.030 (3)	0.000 (2)	0.001 (2)	0.000 (2)
C2	0.019 (3)	0.013 (3)	0.028 (3)	0.003 (2)	0.005 (2)	0.003 (2)
C3	0.025 (3)	0.022 (3)	0.024 (3)	−0.002 (2)	−0.002 (2)	0.003 (2)
C4	0.021 (3)	0.015 (3)	0.023 (3)	0.002 (2)	0.001 (2)	−0.001 (2)
C5	0.019 (3)	0.028 (3)	0.028 (3)	0.003 (2)	0.008 (2)	0.001 (2)
C6	0.015 (3)	0.036 (4)	0.031 (3)	0.000 (2)	0.005 (2)	−0.003 (3)
C7	0.015 (3)	0.029 (3)	0.023 (3)	0.003 (2)	−0.001 (2)	0.000 (2)
C8	0.021 (3)	0.033 (3)	0.020 (3)	−0.004 (2)	−0.001 (2)	−0.001 (2)
C9	0.013 (3)	0.019 (3)	0.030 (3)	−0.002 (2)	0.003 (2)	−0.005 (2)
C10	0.014 (3)	0.019 (3)	0.023 (3)	−0.003 (2)	0.000 (2)	−0.002 (2)
C11	0.018 (3)	0.016 (3)	0.024 (3)	0.004 (2)	0.006 (2)	−0.001 (2)
C12	0.022 (3)	0.023 (3)	0.025 (3)	0.005 (2)	0.001 (2)	−0.002 (2)
C13	0.020 (3)	0.019 (3)	0.022 (3)	−0.002 (2)	0.001 (2)	−0.001 (2)
C14	0.021 (3)	0.022 (3)	0.024 (3)	−0.003 (2)	0.003 (2)	0.000 (2)
C15	0.023 (3)	0.025 (3)	0.018 (3)	−0.002 (2)	−0.002 (2)	0.003 (2)
C16	0.018 (3)	0.029 (3)	0.023 (3)	−0.001 (2)	0.001 (2)	−0.005 (3)
C17	0.012 (3)	0.032 (4)	0.034 (3)	−0.003 (3)	0.004 (2)	−0.002 (3)
C18	0.028 (3)	0.040 (4)	0.020 (3)	−0.004 (3)	0.001 (2)	0.007 (3)
C19	0.036 (3)	0.052 (4)	0.027 (3)	−0.007 (3)	0.010 (3)	0.002 (3)

Geometric parameters (Å, º) top

O1—N2	1.234 (5)	C5—C12	1.412 (7)
O2—N2	1.228 (5)	C5—C17	1.500 (7)
O3—N4	1.231 (5)	C6—C7	1.378 (7)
O4—N4	1.235 (5)	C6—H6	0.9500
O5—C17	1.217 (6)	C7—C8	1.384 (6)
O6—C17	1.317 (6)	C8—C13	1.398 (7)
O6—C18	1.474 (6)	C8—H8	0.9500
O7—N7	1.228 (5)	C9—C14	1.352 (7)
O8—N7	1.230 (5)	C9—C10	1.465 (7)
N2—C2	1.476 (6)	C9—C13	1.495 (6)
N4—C4	1.469 (6)	C10—C11	1.412 (6)
N7—C7	1.487 (6)	C11—C12	1.502 (7)
N15—C15	1.152 (6)	C12—C13	1.397 (7)
N16—C16	1.147 (6)	C14—C16	1.444 (7)
C1—C2	1.393 (6)	C14—C15	1.446 (7)
C1—C10	1.401 (6)	C18—C19	1.505 (7)
C1—H1	0.9501	C18—H181	0.9900
C2—C3	1.381 (6)	C18—H182	0.9900
C3—C4	1.385 (6)	C19—H191	0.9800
C3—H3	0.9500	C19—H192	0.9800
C4—C11	1.388 (6)	C19—H193	0.9799
C5—C6	1.407 (7)

C17—O6—C18	115.1 (4)	C14—C9—C13	126.6 (4)
O2—N2—O1	124.6 (4)	C10—C9—C13	105.6 (4)
O2—N2—C2	118.1 (4)	C1—C10—C11	120.9 (4)
O1—N2—C2	117.3 (4)	C1—C10—C9	129.5 (4)
O3—N4—O4	124.7 (4)	C11—C10—C9	109.6 (4)
O3—N4—C4	118.1 (4)	C4—C11—C10	118.3 (4)
O4—N4—C4	117.1 (4)	C4—C11—C12	134.5 (4)
O7—N7—O8	124.5 (4)	C10—C11—C12	107.1 (4)
O7—N7—C7	117.6 (4)	C13—C12—C5	120.3 (4)
O8—N7—C7	117.9 (4)	C13—C12—C11	107.9 (4)
C2—C1—C10	116.9 (4)	C5—C12—C11	131.6 (5)
C2—C1—H1	121.5	C12—C13—C8	121.6 (4)
C10—C1—H1	121.7	C12—C13—C9	108.9 (4)
C3—C2—C1	123.3 (4)	C8—C13—C9	129.4 (5)
C3—C2—N2	118.8 (4)	C9—C14—C16	123.6 (4)
C1—C2—N2	117.9 (4)	C9—C14—C15	122.7 (4)
C2—C3—C4	118.0 (5)	C16—C14—C15	113.7 (4)
C2—C3—H3	121.0	N15—C15—C14	178.3 (5)
C4—C3—H3	121.0	N16—C16—C14	178.7 (6)
C3—C4—C11	121.4 (4)	O5—C17—O6	125.0 (5)
C3—C4—N4	116.5 (4)	O5—C17—C5	121.7 (5)
C11—C4—N4	121.8 (4)	O6—C17—C5	113.2 (5)
C6—C5—C12	117.7 (5)	O6—C18—C19	107.6 (4)
C6—C5—C17	119.7 (4)	O6—C18—H181	110.2
C12—C5—C17	122.0 (4)	C19—C18—H181	110.1
C7—C6—C5	119.2 (5)	O6—C18—H182	110.3
C7—C6—H6	120.3	C19—C18—H182	110.2
C5—C6—H6	120.4	H181—C18—H182	108.5
C6—C7—C8	124.3 (5)	C18—C19—H191	109.5
C6—C7—N7	118.4 (4)	C18—C19—H192	109.6
C8—C7—N7	117.2 (5)	H191—C19—H192	109.5
C7—C8—C13	116.0 (5)	C18—C19—H193	109.4
C7—C8—H8	122.0	H191—C19—H193	109.5
C13—C8—H8	122.0	H192—C19—H193	109.5
C14—C9—C10	127.7 (4)

C10—C1—C2—C3	−5.7 (7)	C1—C10—C11—C4	11.1 (7)
C10—C1—C2—N2	174.2 (4)	C9—C10—C11—C4	−169.1 (4)
O2—N2—C2—C3	−19.5 (6)	C1—C10—C11—C12	−171.2 (4)
O1—N2—C2—C3	160.0 (4)	C9—C10—C11—C12	8.6 (5)
O2—N2—C2—C1	160.6 (4)	C6—C5—C12—C13	−9.2 (7)
O1—N2—C2—C1	−19.9 (6)	C17—C5—C12—C13	161.8 (5)
C1—C2—C3—C4	7.2 (7)	C6—C5—C12—C11	175.6 (5)
N2—C2—C3—C4	−172.7 (4)	C17—C5—C12—C11	−13.4 (9)
C2—C3—C4—C11	0.8 (7)	C4—C11—C12—C13	167.2 (5)
C2—C3—C4—N4	−173.0 (4)	C10—C11—C12—C13	−9.9 (5)
O3—N4—C4—C3	−33.3 (6)	C4—C11—C12—C5	−17.1 (10)
O4—N4—C4—C3	143.6 (4)	C10—C11—C12—C5	165.8 (5)
O3—N4—C4—C11	152.9 (5)	C5—C12—C13—C8	8.5 (8)
O4—N4—C4—C11	−30.2 (6)	C11—C12—C13—C8	−175.2 (4)
C12—C5—C6—C7	3.2 (8)	C5—C12—C13—C9	−169.0 (4)
C17—C5—C6—C7	−168.0 (5)	C11—C12—C13—C9	7.2 (5)
C5—C6—C7—C8	4.0 (8)	C7—C8—C13—C12	−1.5 (7)
C5—C6—C7—N7	−179.1 (4)	C7—C8—C13—C9	175.5 (5)
O7—N7—C7—C6	4.4 (7)	C14—C9—C13—C12	−179.7 (5)
O8—N7—C7—C6	−176.2 (5)	C10—C9—C13—C12	−2.0 (5)
O7—N7—C7—C8	−178.4 (5)	C14—C9—C13—C8	3.0 (8)
O8—N7—C7—C8	1.0 (7)	C10—C9—C13—C8	−179.4 (5)
C6—C7—C8—C13	−4.8 (8)	C10—C9—C14—C16	−177.0 (5)
N7—C7—C8—C13	178.2 (4)	C13—C9—C14—C16	0.1 (8)
C2—C1—C10—C11	−3.7 (7)	C10—C9—C14—C15	4.3 (8)
C2—C1—C10—C9	176.5 (5)	C13—C9—C14—C15	−178.5 (5)
C14—C9—C10—C1	−6.9 (9)	C18—O6—C17—O5	0.3 (7)
C13—C9—C10—C1	175.5 (5)	C18—O6—C17—C5	177.6 (4)
C14—C9—C10—C11	173.3 (5)	C6—C5—C17—O5	140.5 (5)
C13—C9—C10—C11	−4.3 (5)	C12—C5—C17—O5	−30.4 (8)
C3—C4—C11—C10	−9.7 (7)	C6—C5—C17—O6	−36.9 (7)
N4—C4—C11—C10	163.8 (4)	C12—C5—C17—O6	152.2 (5)
C3—C4—C11—C12	173.5 (5)	C17—O6—C18—C19	175.8 (4)
N4—C4—C11—C12	−13.0 (8)

Acknowledgements

The authors thank Professor M. R. Bryce for fruitful advice.

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