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The title compound, C11H16O4, a diol ester of the nonexistent orthocarbonic acid C(OH)4, was prepared for the purpose of collecting NMR data on orthocarbonates and for comparison with similar silicon compounds. The mol­ecule shows chemical but not crystallographic C2 symmetry. The 1,3-dioxane rings adopt chair conformations. The central C atom is in a distorted tetra­hedral environment of four O atoms.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807034915/bt2444sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807034915/bt2444Isup2.hkl
Contains datablock I

CCDC reference: 659096

Key indicators

  • Single-crystal X-ray study
  • T = 200 K
  • Mean [sigma](C-C) = 0.003 Å
  • R factor = 0.041
  • wR factor = 0.098
  • Data-to-parameter ratio = 10.5

checkCIF/PLATON results

No syntax errors found



Alert level G REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is correct. If it is not, please give the correct count in the _publ_section_exptl_refinement section of the submitted CIF. From the CIF: _diffrn_reflns_theta_max 27.56 From the CIF: _reflns_number_total 1442 Count of symmetry unique reflns 1452 Completeness (_total/calc) 99.31% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 0 Fraction of Friedel pairs measured 0.000 Are heavy atom types Z>Si present no
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 0 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 0 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check

Comment top

The title compound, C11H16O4, a diol ester of the nonexistent orthocarbonic acid C(OH)4, was prepared for the purpose of collecting NMR data on orthocarbonates and for comparison with similar silicon compounds. It was obtained as the product of the reaction between dichlorodiphenoxymethane and 1,1-bis(hydroxymethyl)cyclopropane.

The molecular structure (Fig. 1) shows C2 symmetry. The 1,3-dioxane rings adopt chair conformations. The central carbon atom is in a distorted tetrahedral environment of four oxygen atoms. O11 and O21 are equatorial substituents, O13 and O23 are axial substituents, of their opposing six-membered rings. Due to the anomeric effect, the axial C10–O bonds are slightly, but significantly, longer than the corresponding equatorial bonds. The endocyclic O–C–O angles are significantly larger than the exocyclic ones.

The molecular packing is shown in Fig. 2.

Related literature top

For related literature, see: Bromley et al. (1998); Flack (1983); Mues & Buysch (1990); Narasimhamurthy et al. (1990).

Experimental top

The title compound was prepared according to a literature procedure (Mues & Buysch, 1990) by the reaction of dichlorodiphenoxymethane, (PhO)2CCl2, with 1,1-bis(hydroxymethyl)cyclopropane. The crude product was recrystallized from boiling ethyl acetate.

Spectroscopic data: 1H NMR (400 MHz, CDCl3, 22 °C) δ/p.p.m.: 3.79 (s, 8 H, OCH2), 0.55 (s, 8 H, CH2). 13C{1H} NMR (101 MHz, CDCl3, 24 °C) δ/p.p.m.: 114.8 (CO4), 69.1 (OCH2), 16.2 (Cq), 8.9 (CH2). HRMS m/z calculated for C11H16O4 (M+): 212.1043; found: 212.1043.

Refinement top

All H atoms were located in a difference map and refined as riding on their parent atoms. One common isotropic displacement parameter for all H atoms was refined to Uiso(H) = 0.0420 (17).

Due to the absence of significant anomalous scattering the absolute structure parameter (Flack, 1983), which is -3.1 with an estimated standard deviation of 1.2 for the unmerged data set, is meaningless. Thus, Friedel opposites (995 pairs) have been merged and the absolute configuration has been arbitrarily chosen.

Structure description top

The title compound, C11H16O4, a diol ester of the nonexistent orthocarbonic acid C(OH)4, was prepared for the purpose of collecting NMR data on orthocarbonates and for comparison with similar silicon compounds. It was obtained as the product of the reaction between dichlorodiphenoxymethane and 1,1-bis(hydroxymethyl)cyclopropane.

The molecular structure (Fig. 1) shows C2 symmetry. The 1,3-dioxane rings adopt chair conformations. The central carbon atom is in a distorted tetrahedral environment of four oxygen atoms. O11 and O21 are equatorial substituents, O13 and O23 are axial substituents, of their opposing six-membered rings. Due to the anomeric effect, the axial C10–O bonds are slightly, but significantly, longer than the corresponding equatorial bonds. The endocyclic O–C–O angles are significantly larger than the exocyclic ones.

The molecular packing is shown in Fig. 2.

For related literature, see: Bromley et al. (1998); Flack (1983); Mues & Buysch (1990); Narasimhamurthy et al. (1990).

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2005); cell refinement: CrysAlis RED (Oxford Diffraction, 2005); data reduction: CrysAlis RED; program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1996); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), with atom labels and anisotropic displacement ellipsoids (drawn at 50% probability level) for non-H atoms.
[Figure 2] Fig. 2. The packing of (I), viewed along [1 0 0]. H atoms omitted for clarity.
5,7,13,14-Tetraoxatrispiro[2.2.2.29.26.23]pentadecane top
Crystal data top
C11H16O4F(000) = 456
Mr = 212.24Dx = 1.331 (1) Mg m3
Orthorhombic, P212121Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2abθ = 4.4–27.5°
a = 6.2980 (8) ŵ = 0.10 mm1
b = 7.1520 (8) ÅT = 200 K
c = 23.508 (3) ÅBlock, colourless
V = 1058.9 (2) Å30.26 × 0.19 × 0.10 mm
Z = 4
Data collection top
Oxford XCalibur3
diffractometer
1237 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.044
Graphite monochromatorθmax = 27.6°, θmin = 4.4°
ω scansh = 85
6256 measured reflectionsk = 89
1442 independent reflectionsl = 2830
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.041Hydrogen site location: difference Fourier map
wR(F2) = 0.098Only H-atom displacement parameters refined
S = 1.08 w = 1/[σ2(Fo2) + (0.0525P)2]
where P = (Fo2 + 2Fc2)/3
1442 reflections(Δ/σ)max < 0.001
137 parametersΔρmax = 0.16 e Å3
0 restraintsΔρmin = 0.17 e Å3
Crystal data top
C11H16O4V = 1058.9 (2) Å3
Mr = 212.24Z = 4
Orthorhombic, P212121Mo Kα radiation
a = 6.2980 (8) ŵ = 0.10 mm1
b = 7.1520 (8) ÅT = 200 K
c = 23.508 (3) Å0.26 × 0.19 × 0.10 mm
Data collection top
Oxford XCalibur3
diffractometer
1237 reflections with I > 2σ(I)
6256 measured reflectionsRint = 0.044
1442 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0410 restraints
wR(F2) = 0.098Only H-atom displacement parameters refined
S = 1.08Δρmax = 0.16 e Å3
1442 reflectionsΔρmin = 0.17 e Å3
137 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 > 2σ(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
xyzUiso*/Ueq
O110.6614 (3)0.7090 (2)0.06259 (6)0.0344 (4)
O130.6407 (3)0.8773 (2)0.14710 (6)0.0336 (4)
O210.6058 (3)0.5650 (2)0.14343 (6)0.0352 (4)
O230.3442 (2)0.7528 (2)0.10339 (6)0.0318 (4)
C100.5614 (4)0.7292 (3)0.11423 (9)0.0296 (5)
C110.6546 (4)0.8783 (3)0.02814 (9)0.0348 (5)
H1110.50610.90620.01720.0420 (17)*
H1120.73850.86020.00700.0420 (17)*
C120.7440 (4)1.0372 (3)0.06173 (10)0.0317 (5)
C130.6326 (4)1.0554 (3)0.11755 (9)0.0345 (5)
H1310.70211.15320.14080.0420 (17)*
H1320.48301.09250.11130.0420 (17)*
C140.8256 (4)1.2072 (3)0.03185 (11)0.0405 (6)
H1410.80461.32980.05050.0420 (17)*
H1420.81791.20950.01020.0420 (17)*
C150.9787 (4)1.0718 (3)0.05907 (11)0.0388 (6)
H1511.06450.99120.03370.0420 (17)*
H1521.05121.11160.09440.0420 (17)*
C210.4940 (4)0.5515 (4)0.19660 (10)0.0364 (5)
H2110.54670.64850.22310.0420 (17)*
H2120.52060.42760.21400.0420 (17)*
C220.2604 (4)0.5770 (3)0.18734 (10)0.0321 (5)
C230.2164 (4)0.7525 (3)0.15418 (9)0.0347 (5)
H2310.06410.75830.14390.0420 (17)*
H2320.25070.86340.17770.0420 (17)*
C240.1061 (4)0.5146 (4)0.23182 (9)0.0421 (6)
H2410.02280.59140.23780.0420 (17)*
H2420.16390.45550.26660.0420 (17)*
C250.1253 (4)0.4088 (3)0.17680 (10)0.0412 (6)
H2510.19480.28470.17780.0420 (17)*
H2520.00810.42050.14900.0420 (17)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O110.0381 (9)0.0323 (8)0.0328 (8)0.0006 (7)0.0067 (8)0.0034 (6)
O130.0376 (9)0.0336 (8)0.0296 (7)0.0023 (7)0.0019 (8)0.0025 (6)
O210.0300 (8)0.0349 (8)0.0408 (8)0.0072 (7)0.0012 (8)0.0047 (7)
O230.0246 (7)0.0404 (8)0.0303 (7)0.0003 (7)0.0017 (7)0.0030 (7)
C100.0285 (11)0.0304 (11)0.0299 (10)0.0008 (9)0.0012 (9)0.0001 (9)
C110.0364 (13)0.0385 (12)0.0294 (11)0.0017 (11)0.0032 (11)0.0028 (9)
C120.0291 (11)0.0323 (11)0.0336 (11)0.0020 (10)0.0000 (10)0.0035 (9)
C130.0379 (13)0.0283 (11)0.0374 (11)0.0007 (11)0.0011 (11)0.0040 (9)
C140.0390 (13)0.0346 (12)0.0478 (13)0.0018 (11)0.0009 (12)0.0080 (10)
C150.0297 (12)0.0367 (13)0.0499 (14)0.0004 (10)0.0015 (12)0.0004 (11)
C210.0365 (13)0.0378 (13)0.0350 (12)0.0011 (11)0.0026 (11)0.0073 (10)
C220.0310 (11)0.0355 (13)0.0299 (11)0.0011 (10)0.0003 (10)0.0011 (9)
C230.0297 (11)0.0392 (13)0.0352 (11)0.0048 (10)0.0036 (10)0.0016 (10)
C240.0409 (15)0.0496 (14)0.0359 (12)0.0013 (11)0.0071 (12)0.0060 (11)
C250.0412 (15)0.0391 (13)0.0432 (13)0.0065 (12)0.0047 (12)0.0001 (10)
Geometric parameters (Å, º) top
O11—C101.375 (2)C14—H1410.9900
O11—C111.457 (2)C14—H1420.9900
O13—C101.403 (2)C15—H1510.9900
O13—C131.452 (2)C15—H1520.9900
O21—C101.389 (2)C21—C221.498 (3)
O21—C211.438 (3)C21—H2110.9900
O23—C101.401 (3)C21—H2120.9900
O23—C231.440 (2)C22—C251.494 (3)
C11—C121.494 (3)C22—C241.495 (3)
C11—H1110.9900C22—C231.504 (3)
C11—H1120.9900C23—H2310.9900
C12—C131.494 (3)C23—H2320.9900
C12—C141.495 (3)C24—C251.503 (3)
C12—C151.500 (3)C24—H2410.9900
C13—H1310.9900C24—H2420.9900
C13—H1320.9900C25—H2510.9900
C14—C151.509 (3)C25—H2520.9900
C10—O11—C11112.96 (16)C12—C15—H151117.8
C10—O13—C13112.74 (15)C14—C15—H151117.8
C10—O21—C21112.81 (16)C12—C15—H152117.8
C10—O23—C23113.24 (16)C14—C15—H152117.8
O11—C10—O21104.80 (16)H151—C15—H152114.9
O11—C10—O23107.41 (17)O21—C21—C22110.28 (19)
O21—C10—O23112.86 (17)O21—C21—H211109.6
O11—C10—O13113.70 (17)C22—C21—H211109.6
O21—C10—O13107.14 (15)O21—C21—H212109.6
O23—C10—O13110.89 (17)C22—C21—H212109.6
O11—C11—C12109.09 (17)H211—C21—H212108.1
O11—C11—H111109.9C25—C22—C2460.39 (16)
C12—C11—H111109.9C25—C22—C21119.0 (2)
O11—C11—H112109.9C24—C22—C21120.0 (2)
C12—C11—H112109.9C25—C22—C23118.8 (2)
H111—C11—H112108.3C24—C22—C23119.5 (2)
C13—C12—C11110.71 (19)C21—C22—C23111.0 (2)
C13—C12—C14120.2 (2)O23—C23—C22109.15 (18)
C11—C12—C14120.0 (2)O23—C23—H231109.9
C13—C12—C15119.0 (2)C22—C23—H231109.9
C11—C12—C15118.4 (2)O23—C23—H232109.9
C14—C12—C1560.49 (16)C22—C23—H232109.9
O13—C13—C12109.11 (17)H231—C23—H232108.3
O13—C13—H131109.9C22—C24—C2559.77 (15)
C12—C13—H131109.9C22—C24—H241117.8
O13—C13—H132109.9C25—C24—H241117.8
C12—C13—H132109.9C22—C24—H242117.8
H131—C13—H132108.3C25—C24—H242117.8
C12—C14—C1559.92 (15)H241—C24—H242114.9
C12—C14—H141117.8C22—C25—C2459.84 (16)
C15—C14—H141117.8C22—C25—H251117.8
C12—C14—H142117.8C24—C25—H251117.8
C15—C14—H142117.8C22—C25—H252117.8
H141—C14—H142114.9C24—C25—H252117.8
C12—C15—C1459.60 (15)H251—C25—H252114.9
C11—O11—C10—O21172.98 (17)C14—C12—C13—O13158.8 (2)
C11—O11—C10—O2366.8 (2)C15—C12—C13—O1388.0 (2)
C11—O11—C10—O1356.3 (2)C13—C12—C14—C15108.4 (3)
C21—O21—C10—O11173.57 (17)C11—C12—C14—C15107.7 (3)
C21—O21—C10—O2357.0 (2)C13—C12—C15—C14110.3 (2)
C21—O21—C10—O1365.3 (2)C11—C12—C15—C14110.3 (2)
C23—O23—C10—O11172.79 (16)C10—O21—C21—C2254.1 (3)
C23—O23—C10—O2157.8 (2)O21—C21—C22—C2591.4 (2)
C23—O23—C10—O1362.4 (2)O21—C21—C22—C24162.05 (19)
C13—O13—C10—O1156.2 (2)O21—C21—C22—C2351.9 (3)
C13—O13—C10—O21171.48 (18)C10—O23—C23—C2254.5 (2)
C13—O13—C10—O2365.0 (2)C25—C22—C23—O2391.6 (2)
C10—O11—C11—C1254.8 (2)C24—C22—C23—O23161.94 (19)
O11—C11—C12—C1354.2 (3)C21—C22—C23—O2351.8 (3)
O11—C11—C12—C14158.8 (2)C21—C22—C24—C25108.4 (3)
O11—C11—C12—C1588.3 (2)C23—C22—C24—C25108.3 (2)
C10—O13—C13—C1254.3 (3)C21—C22—C25—C24110.0 (2)
C11—C12—C13—O1354.2 (3)C23—C22—C25—C24109.5 (2)

Experimental details

Crystal data
Chemical formulaC11H16O4
Mr212.24
Crystal system, space groupOrthorhombic, P212121
Temperature (K)200
a, b, c (Å)6.2980 (8), 7.1520 (8), 23.508 (3)
V3)1058.9 (2)
Z4
Radiation typeMo Kα
µ (mm1)0.10
Crystal size (mm)0.26 × 0.19 × 0.10
Data collection
DiffractometerOxford XCalibur3
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
6256, 1442, 1237
Rint0.044
(sin θ/λ)max1)0.651
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.041, 0.098, 1.08
No. of reflections1442
No. of parameters137
H-atom treatmentOnly H-atom displacement parameters refined
Δρmax, Δρmin (e Å3)0.16, 0.17

Computer programs: CrysAlis CCD (Oxford Diffraction, 2005), CrysAlis RED (Oxford Diffraction, 2005), CrysAlis RED, SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 1997), ORTEPIII (Burnett & Johnson, 1996), SHELXL97.

Selected geometric parameters (Å, º) top
O11—C101.375 (2)O21—C101.389 (2)
O13—C101.403 (2)O23—C101.401 (3)
O11—C10—O21104.80 (16)O21—C10—O13107.14 (15)
O11—C10—O23107.41 (17)O23—C10—O13110.89 (17)
O21—C10—O23112.86 (17)O11—C11—C12109.09 (17)
O11—C10—O13113.70 (17)
 

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