In the title compound, C
34H
30O
12P
2, which was synthesized
via the esterification of dimethyl 2,5-dioxo-1,4-cyclohexanedicarboxylate with diphenyl chlorophosphate, the molecule has crystallographic inversion symmetry. The dihedral angles between the plane of the cyclohexa-1,4-diene ring and those of the two benzene rings of the substituent phosphate groups are 41.0 (1) and 89.5 (1)°, while that with the ester group is 3.1 (3)°. In the crystal, only weak intermolecular C—H

O hydrogen bonds are present.
Supporting information
CCDC reference: 1057648
Key indicators
- Single-crystal X-ray study
- T = 113 K
- Mean
(C-C)= 0.003 Å
- R factor = 0.045
- wR factor = 0.099
- Data-to-parameter ratio = 17.2
checkCIF/PLATON results
No syntax errors found
No errors found in this datablock
The title compound was synthesized using the basic procedure of Chaignaud
et al. (2008) (Fig. 2), as follows:
A solution of LiHMDS (1 M in THF, 7.9 mL) in THF (20 mL) was cooled to
-78 °C under nitrogen. Subsequently, a mixture of dimethyl
2,5-dioxo-1,4-cyclohexanedicarboxylate (3.19 mmol), diphenyl chlorophosphate
(6.67 mmol) and HMPA (8.90 mmol) in anhydrous THF (5 mL) were added dropwise
over 5 min. The mixture was stirred at -78 °C for 1h under nitrogen and
after completion of the reaction, the mixture was diluted with water (30 mL)
and extracted with ethyl acetate (3×15 mL), dried with anhydrous
MgSO4 and filtered. Subsequently, the product obtained by evaporation of
the solvent was recrystallized from ethyl acetate giving a white solid in
10% yield (m.p. 118–120 °C).
H atoms were were positioned geometrically and refined using a riding model
with C—H = 0.95–0.99 Å and Uiso(H) = 1.2Ueq(C)
(aromatic) or 1.5Ueq(C) (methyl).
Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: CrystalStructure (Rigaku, 2005).
Dimethyl
2,5-bis[(diphenoxyphosphoryl)oxy]cyclohexa-1,4-diene-1,4-dicarboxylate
top
Crystal data top
C34H30O12P2 | F(000) = 720 |
Mr = 692.52 | Dx = 1.461 Mg m−3 |
Monoclinic, P21/c | Melting point = 391–393 K |
Hall symbol: -P 2ybc | Mo Kα radiation, λ = 0.71073 Å |
a = 12.272 (10) Å | Cell parameters from 5446 reflections |
b = 10.629 (8) Å | θ = 1.7–28.3° |
c = 13.174 (10) Å | µ = 0.21 mm−1 |
β = 113.644 (10)° | T = 113 K |
V = 1574 (2) Å3 | Prism, colorless |
Z = 2 | 0.20 × 0.18 × 0.12 mm |
Data collection top
Rigaku Saturn724 CCD diffractometer | 3758 independent reflections |
Radiation source: rotating anode | 2264 reflections with I > 2σ(I) |
Multilayer monochromator | Rint = 0.100 |
Detector resolution: 14.22 pixels mm-1 | θmax = 28.0°, θmin = 1.8° |
ω and ϕ scans | h = −16→16 |
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005) | k = −13→13 |
Tmin = 0.960, Tmax = 0.976 | l = −17→17 |
15948 measured reflections | |
Refinement top
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)] = 0.045 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.099 | H-atom parameters constrained |
S = 1.00 | w = 1/[σ2(Fo2) + (0.012P)2] where P = (Fo2 + 2Fc2)/3 |
3758 reflections | (Δ/σ)max = 0.002 |
218 parameters | Δρmax = 0.54 e Å−3 |
0 restraints | Δρmin = −0.62 e Å−3 |
Crystal data top
C34H30O12P2 | V = 1574 (2) Å3 |
Mr = 692.52 | Z = 2 |
Monoclinic, P21/c | Mo Kα radiation |
a = 12.272 (10) Å | µ = 0.21 mm−1 |
b = 10.629 (8) Å | T = 113 K |
c = 13.174 (10) Å | 0.20 × 0.18 × 0.12 mm |
β = 113.644 (10)° | |
Data collection top
Rigaku Saturn724 CCD diffractometer | 3758 independent reflections |
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005) | 2264 reflections with I > 2σ(I) |
Tmin = 0.960, Tmax = 0.976 | Rint = 0.100 |
15948 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.045 | 0 restraints |
wR(F2) = 0.099 | H-atom parameters constrained |
S = 1.00 | Δρmax = 0.54 e Å−3 |
3758 reflections | Δρmin = −0.62 e Å−3 |
218 parameters | |
Special details top
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 | Uiso*/Ueq | |
P1 | 0.17401 (5) | 0.72276 (5) | 0.24500 (4) | 0.01714 (15) | |
O1 | 0.12748 (11) | 0.81381 (12) | 0.31240 (10) | 0.0189 (3) | |
O2 | 0.26861 (12) | 0.64338 (12) | 0.34149 (11) | 0.0211 (3) | |
O3 | 0.21532 (12) | 0.77428 (12) | 0.16508 (10) | 0.0194 (3) | |
O4 | 0.06126 (12) | 0.63451 (12) | 0.19634 (10) | 0.0187 (3) | |
O5 | −0.16106 (13) | 0.79217 (13) | −0.10725 (11) | 0.0285 (4) | |
O6 | −0.06056 (12) | 0.82652 (13) | 0.07360 (11) | 0.0259 (4) | |
C1 | 0.20189 (18) | 0.91573 (18) | 0.36916 (16) | 0.0181 (5) | |
C2 | 0.20083 (19) | 1.02272 (19) | 0.30979 (17) | 0.0229 (5) | |
H2 | 0.1545 | 1.0266 | 0.2323 | 0.027* | |
C3 | 0.2684 (2) | 1.1239 (2) | 0.36526 (18) | 0.0288 (6) | |
H3 | 0.2690 | 1.1986 | 0.3259 | 0.035* | |
C4 | 0.3353 (2) | 1.1172 (2) | 0.47791 (18) | 0.0310 (6) | |
H4 | 0.3818 | 1.1873 | 0.5159 | 0.037* | |
C5 | 0.3350 (2) | 1.0088 (2) | 0.53572 (18) | 0.0298 (6) | |
H5 | 0.3816 | 1.0046 | 0.6132 | 0.036* | |
C6 | 0.26714 (19) | 0.90613 (19) | 0.48111 (17) | 0.0237 (5) | |
H6 | 0.2659 | 0.8313 | 0.5201 | 0.028* | |
C7 | 0.37059 (18) | 0.58701 (19) | 0.33647 (16) | 0.0193 (5) | |
C8 | 0.45474 (17) | 0.6591 (2) | 0.31964 (15) | 0.0221 (5) | |
H8 | 0.4432 | 0.7469 | 0.3063 | 0.027* | |
C9 | 0.55660 (19) | 0.6006 (2) | 0.32263 (17) | 0.0294 (6) | |
H9 | 0.6158 | 0.6483 | 0.3105 | 0.035* | |
C10 | 0.5728 (2) | 0.4722 (2) | 0.34328 (17) | 0.0317 (6) | |
H10 | 0.6431 | 0.4326 | 0.3455 | 0.038* | |
C11 | 0.4874 (2) | 0.4024 (2) | 0.36046 (17) | 0.0290 (6) | |
H11 | 0.4987 | 0.3147 | 0.3747 | 0.035* | |
C12 | 0.38516 (19) | 0.46028 (19) | 0.35698 (17) | 0.0247 (5) | |
H12 | 0.3256 | 0.4128 | 0.3687 | 0.030* | |
C13 | 0.02855 (17) | 0.57494 (18) | 0.09354 (16) | 0.0173 (5) | |
C14 | −0.04157 (18) | 0.62776 (18) | −0.00080 (16) | 0.0167 (5) | |
C15 | −0.07850 (18) | 0.55461 (17) | −0.10704 (15) | 0.0186 (5) | |
H15A | −0.1664 | 0.5490 | −0.1412 | 0.022* | |
H15B | −0.0532 | 0.6015 | −0.1588 | 0.022* | |
C16 | −0.09356 (18) | 0.75651 (19) | −0.01748 (16) | 0.0196 (5) | |
C17 | −0.11425 (19) | 0.95035 (18) | 0.05728 (18) | 0.0302 (6) | |
H17A | −0.0905 | 0.9985 | 0.0061 | 0.045* | |
H17B | −0.0876 | 0.9943 | 0.1286 | 0.045* | |
H17C | −0.2011 | 0.9420 | 0.0262 | 0.045* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
P1 | 0.0148 (3) | 0.0166 (3) | 0.0186 (3) | −0.0009 (2) | 0.0052 (2) | −0.0017 (2) |
O1 | 0.0177 (8) | 0.0178 (8) | 0.0225 (8) | −0.0025 (6) | 0.0093 (7) | −0.0050 (6) |
O2 | 0.0168 (8) | 0.0239 (8) | 0.0207 (8) | 0.0035 (7) | 0.0056 (7) | 0.0029 (6) |
O3 | 0.0193 (8) | 0.0208 (8) | 0.0194 (7) | −0.0011 (6) | 0.0090 (7) | 0.0005 (6) |
O4 | 0.0166 (7) | 0.0197 (8) | 0.0182 (8) | −0.0054 (6) | 0.0055 (6) | −0.0040 (6) |
O5 | 0.0344 (9) | 0.0248 (9) | 0.0226 (8) | 0.0067 (7) | 0.0078 (8) | 0.0036 (7) |
O6 | 0.0235 (8) | 0.0227 (8) | 0.0258 (9) | 0.0062 (7) | 0.0038 (7) | −0.0043 (7) |
C1 | 0.0165 (11) | 0.0177 (11) | 0.0200 (11) | −0.0006 (9) | 0.0070 (9) | −0.0040 (9) |
C2 | 0.0272 (13) | 0.0221 (12) | 0.0168 (11) | 0.0012 (10) | 0.0060 (10) | −0.0016 (9) |
C3 | 0.0354 (14) | 0.0208 (13) | 0.0301 (13) | −0.0050 (11) | 0.0131 (12) | −0.0028 (10) |
C4 | 0.0334 (14) | 0.0261 (14) | 0.0310 (14) | −0.0123 (11) | 0.0103 (12) | −0.0132 (11) |
C5 | 0.0276 (13) | 0.0379 (15) | 0.0179 (12) | −0.0024 (11) | 0.0029 (10) | −0.0045 (10) |
C6 | 0.0271 (13) | 0.0225 (13) | 0.0217 (12) | 0.0013 (10) | 0.0101 (10) | 0.0023 (10) |
C7 | 0.0143 (11) | 0.0238 (12) | 0.0158 (11) | 0.0044 (9) | 0.0017 (9) | −0.0044 (9) |
C8 | 0.0171 (11) | 0.0216 (12) | 0.0237 (12) | −0.0007 (10) | 0.0041 (10) | −0.0038 (9) |
C9 | 0.0161 (12) | 0.0398 (15) | 0.0307 (14) | −0.0035 (11) | 0.0077 (11) | −0.0036 (11) |
C10 | 0.0184 (12) | 0.0442 (16) | 0.0264 (13) | 0.0096 (12) | 0.0026 (11) | −0.0099 (11) |
C11 | 0.0289 (13) | 0.0248 (13) | 0.0296 (13) | 0.0069 (11) | 0.0077 (11) | −0.0034 (11) |
C12 | 0.0216 (12) | 0.0228 (13) | 0.0275 (12) | −0.0006 (10) | 0.0074 (10) | −0.0010 (10) |
C13 | 0.0147 (10) | 0.0186 (11) | 0.0189 (11) | −0.0052 (9) | 0.0071 (9) | −0.0058 (9) |
C14 | 0.0144 (10) | 0.0169 (11) | 0.0188 (11) | −0.0012 (9) | 0.0066 (9) | −0.0009 (9) |
C15 | 0.0154 (11) | 0.0201 (12) | 0.0182 (11) | −0.0005 (9) | 0.0046 (9) | −0.0002 (9) |
C16 | 0.0158 (11) | 0.0240 (13) | 0.0199 (11) | −0.0025 (9) | 0.0079 (10) | 0.0003 (9) |
C17 | 0.0270 (13) | 0.0246 (13) | 0.0355 (14) | 0.0094 (11) | 0.0088 (12) | −0.0039 (11) |
Geometric parameters (Å, º) top
P1—O1 | 1.5677 (19) | C11—C12 | 1.382 (4) |
P1—O2 | 1.5785 (19) | C13—C14 | 1.320 (3) |
P1—O3 | 1.4469 (19) | C13—C15i | 1.489 (3) |
P1—O4 | 1.579 (2) | C14—C15 | 1.503 (3) |
O1—C1 | 1.421 (3) | C14—C16 | 1.489 (3) |
O2—C7 | 1.413 (3) | C2—H2 | 0.9500 |
O4—C13 | 1.400 (3) | C3—H3 | 0.9500 |
O5—C16 | 1.201 (3) | C4—H4 | 0.9500 |
O6—C16 | 1.330 (3) | C5—H5 | 0.9500 |
O6—C17 | 1.449 (3) | C6—H6 | 0.9500 |
C1—C2 | 1.377 (3) | C8—H8 | 0.9500 |
C1—C6 | 1.371 (3) | C9—H9 | 0.9500 |
C2—C3 | 1.376 (3) | C10—H10 | 0.9500 |
C3—C4 | 1.380 (3) | C11—H11 | 0.9500 |
C4—C5 | 1.382 (3) | C12—H12 | 0.9500 |
C5—C6 | 1.386 (3) | C15—H15A | 0.9900 |
C7—C8 | 1.374 (3) | C15—H15B | 0.9900 |
C7—C12 | 1.371 (3) | C17—H17A | 0.9800 |
C8—C9 | 1.383 (3) | C17—H17B | 0.9800 |
C9—C10 | 1.390 (3) | C17—H17C | 0.9800 |
C10—C11 | 1.375 (4) | | |
| | | |
O1—P1—O2 | 101.02 (7) | O5—C16—C14 | 121.40 (18) |
O1—P1—O3 | 119.47 (8) | O6—C16—C14 | 115.08 (17) |
O1—P1—O4 | 97.92 (8) | C1—C2—H2 | 121.00 |
O2—P1—O3 | 115.41 (9) | C3—C2—H2 | 121.00 |
O2—P1—O4 | 104.54 (8) | C2—C3—H3 | 120.00 |
O3—P1—O4 | 115.79 (8) | C4—C3—H3 | 120.00 |
P1—O1—C1 | 117.75 (13) | C3—C4—H4 | 120.00 |
P1—O2—C7 | 124.62 (13) | C5—C4—H4 | 120.00 |
P1—O4—C13 | 121.73 (14) | C4—C5—H5 | 120.00 |
C16—O6—C17 | 114.76 (16) | C6—C5—H5 | 120.00 |
O1—C1—C2 | 118.23 (17) | C1—C6—H6 | 121.00 |
O1—C1—C6 | 118.96 (17) | C5—C6—H6 | 121.00 |
C2—C1—C6 | 122.74 (19) | C7—C8—H8 | 121.00 |
C1—C2—C3 | 118.52 (19) | C9—C8—H8 | 121.00 |
C2—C3—C4 | 120.2 (2) | C8—C9—H9 | 120.00 |
C3—C4—C5 | 120.3 (2) | C10—C9—H9 | 120.00 |
C4—C5—C6 | 120.3 (2) | C9—C10—H10 | 120.00 |
C1—C6—C5 | 118.03 (19) | C11—C10—H10 | 120.00 |
O2—C7—C8 | 120.56 (18) | C10—C11—H11 | 120.00 |
O2—C7—C12 | 117.1 (2) | C12—C11—H11 | 120.00 |
C8—C7—C12 | 122.2 (2) | C7—C12—H12 | 120.00 |
C7—C8—C9 | 118.3 (2) | C11—C12—H12 | 120.00 |
C8—C9—C10 | 120.3 (2) | C14—C15—H15A | 109.00 |
C9—C10—C11 | 120.2 (2) | C14—C15—H15B | 109.00 |
C10—C11—C12 | 119.8 (2) | H15A—C15—H15B | 108.00 |
C7—C12—C11 | 119.3 (2) | C13i—C15—H15A | 109.00 |
O4—C13—C14 | 122.97 (18) | C13i—C15—H15B | 109.00 |
O4—C13—C15i | 110.99 (16) | O6—C17—H17A | 109.00 |
C14—C13—C15i | 125.99 (18) | O6—C17—H17B | 109.00 |
C13—C14—C15 | 119.73 (18) | O6—C17—H17C | 109.00 |
C13—C14—C16 | 127.52 (18) | H17A—C17—H17B | 109.00 |
C15—C14—C16 | 112.75 (16) | H17A—C17—H17C | 109.00 |
C13i—C15—C14 | 114.28 (16) | H17B—C17—H17C | 109.00 |
O5—C16—O6 | 123.51 (19) | | |
| | | |
O2—P1—O1—C1 | 75.66 (14) | C3—C4—C5—C6 | −0.3 (4) |
O3—P1—O1—C1 | −52.09 (15) | C4—C5—C6—C1 | 0.4 (4) |
O4—P1—O1—C1 | −177.76 (12) | O2—C7—C8—C9 | 175.83 (17) |
O1—P1—O2—C7 | −151.58 (15) | C12—C7—C8—C9 | 0.6 (3) |
O3—P1—O2—C7 | −21.23 (17) | O2—C7—C12—C11 | −175.66 (18) |
O4—P1—O2—C7 | 107.15 (15) | C8—C7—C12—C11 | −0.3 (3) |
O1—P1—O4—C13 | 149.57 (14) | C7—C8—C9—C10 | −0.6 (3) |
O2—P1—O4—C13 | −106.81 (14) | C8—C9—C10—C11 | 0.3 (3) |
O3—P1—O4—C13 | 21.34 (17) | C9—C10—C11—C12 | 0.1 (3) |
P1—O1—C1—C2 | 81.9 (2) | C10—C11—C12—C7 | −0.1 (3) |
P1—O1—C1—C6 | −101.1 (2) | O4—C13—C14—C15 | −176.33 (19) |
P1—O2—C7—C8 | 59.5 (2) | O4—C13—C14—C16 | 2.7 (4) |
P1—O2—C7—C12 | −125.04 (17) | C15i—C13—C14—C15 | 0.7 (4) |
P1—O4—C13—C14 | −88.2 (2) | C15i—C13—C14—C16 | 179.7 (2) |
P1—O4—C13—C15i | 94.39 (18) | O4—C13—C15i—C14i | 176.67 (18) |
C17—O6—C16—O5 | 1.1 (3) | C14—C13—C15i—C14i | −0.7 (3) |
C17—O6—C16—C14 | −178.27 (19) | C13—C14—C15—C13i | −0.6 (3) |
O1—C1—C2—C3 | 177.0 (2) | C16—C14—C15—C13i | −179.77 (19) |
C6—C1—C2—C3 | 0.2 (4) | C13—C14—C16—O5 | −176.4 (2) |
O1—C1—C6—C5 | −177.2 (2) | C13—C14—C16—O6 | 2.9 (4) |
C2—C1—C6—C5 | −0.4 (4) | C15—C14—C16—O5 | 2.7 (3) |
C1—C2—C3—C4 | 0.0 (4) | C15—C14—C16—O6 | −177.98 (19) |
C2—C3—C4—C5 | 0.1 (4) | | |
Symmetry code: (i) −x, −y+1, −z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2···O5ii | 0.95 | 2.56 | 3.191 (4) | 124 |
C6—H6···O3iii | 0.95 | 2.50 | 3.345 (4) | 148 |
C9—H9···O5iv | 0.95 | 2.59 | 3.405 (4) | 144 |
C10—H10···O3v | 0.95 | 2.46 | 3.381 (4) | 163 |
C15—H15B···O1vi | 0.99 | 2.56 | 3.409 (4) | 144 |
Symmetry codes: (ii) −x, −y+2, −z; (iii) x, −y+3/2, z+1/2; (iv) x+1, −y+3/2, z+1/2; (v) −x+1, y−1/2, −z+1/2; (vi) x, −y+3/2, z−1/2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C6—H6···O3i | 0.95 | 2.50 | 3.345 (4) | 148 |
C9—H9···O5ii | 0.95 | 2.59 | 3.405 (4) | 144 |
C10—H10···O3iii | 0.95 | 2.46 | 3.381 (4) | 163 |
C15—H15B···O1iv | 0.99 | 2.56 | 3.409 (4) | 144 |
Symmetry codes: (i) x, −y+3/2, z+1/2; (ii) x+1, −y+3/2, z+1/2; (iii) −x+1, y−1/2, −z+1/2; (iv) x, −y+3/2, z−1/2. |
1,4-Cyclohexadiene is a useful and fundamental structural motif found in a wide range of organic materials and biologically active molecules (El-Rayyes & Al-Hajjar, 1978). The synthetic routes for the preparation of derivatives of this parent compound have been reported (Chaignaud et al., 2008) but their crystal structures were not described.
The title compound, C34H30O12P2, was synthesized by the esterification of dimethyl 2,5-dioxo-1,4-cyclohexanedicarboxylate with diphenyl chlorophosphate using the reported procedure of Chaignaud et al. (2008) and the structure is reported herein.
The molecule of the title compound has crystallographic inversion symmetry (Fig. 1), with dihedral angles between the cyclohexa-1,4-diene ring and the two benzene rings of the substituent phosphate group of 41.0 (1) [C1–C6] and 89.5 (1)° [C7–C12]. The ester group is essentially coplanar with the cyclohexadiene group [dihedral angle = 3.1 (3)°]. In the crystal, only weak intermolecular C—H···O hydrogen bonds are present (Table 1).