Buy article online - an online subscription or single-article purchase is required to access this article.
Download citation
Download citation
link to html
The six-membered ring in the title compound, C10H17NO4, has a half-chair conformation and lies to one side of the central chromophore. Mol­ecules are connected into a supra­molecular chain via N—H...O hydrogen-bonding inter­actions and these are consolidated into a three-dimensional structure via C—H...O inter­actions. Two C atoms and two O atoms in the ring are disordered over two positions; the site occupancy factors are ca 0.7 and 0.3.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807049252/ng2332sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807049252/ng2332Isup2.hkl
Contains datablock I

CCDC reference: 667344

Key indicators

  • Single-crystal X-ray study
  • T = 120 K
  • Mean [sigma](C-C) = 0.003 Å
  • Disorder in main residue
  • R factor = 0.038
  • wR factor = 0.100
  • Data-to-parameter ratio = 9.4

checkCIF/PLATON results

No syntax errors found



Alert level C PLAT301_ALERT_3_C Main Residue Disorder ......................... 21.00 Perc. PLAT366_ALERT_2_C Short? C(sp?)-C(sp?) Bond C1 - C2 ... 1.33 Ang.
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 26.50 From the CIF: _reflns_number_total 1369 Count of symmetry unique reflns 1380 Completeness (_total/calc) 99.20% 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 2 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 1 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 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

Recently, we reported that 1,2-dioxines can be converted to a wide variety of carbohydrates by dihydroxylation of the olefin, followed by cleavage of the peroxide bond (Robinson et al., 2006). To extend this methodology further, a number of amino dioxines were synthesized, such as the title compound, C10H17NO4 (I), that could potentially be converted to amino sugars by the same method.

The molecular structure of (I), Fig. 1, features a six-membered ring with a half-chair conformation so that the O atoms lie on either side of the plane defined by the four C atoms. The ring is characterized by a puckering amplitude = 0.618 (2) Å, and values of θ = 52.10 (19)° and φ = 28.0 (3)° (Cremer & Pople, 1975). The overall conformation of the molecule is such that the ring lies to one side of the central chromophore. Molecules are connected into a supramolecular chain aligned along the b axis by N—H···O hydrogen bonding interactions (Fig. 2 & Table 1). Chains are consolidated into a 3-D structure via C—H···O interactions (Fig. 3).

Related literature top

For the synthesis of the t-butyl 2-formylallylcarbamate reactant, see Erkkila & Pihko (2006). For the conversion of 1,2-dioxines to carbohydrates, see Robinson et al. (2006) and Pedersen & Rosenbohm (2001) for some experimental techiques. For calculations on ring puckering, see Cremer & Pople (1975).

Experimental top

Diphenylmethylphosphonium iodide (41.8 g, 103 mmol) was suspended in anhydrous THF (350 ml) and cooled to 0 °C. Potassium tert-butoxide (11.56 g, 103 mmol) was added in one portion to give a yellow slurry that was allowed to warm to room temperature. tert-butyl 2-formylallylcarbamate (Erkkila & Pihko, 2006) (17.4 g, 94 mmol) was dissolved in anhydrous THF (150 ml) and added to the above suspension by cannula. The resulting mixture was stirred vigorusly overnight under an atmosphere of nitrogen. Half saturated aqueous ammonium chloride (50 ml) was added and the THF removed in vacuo. The aqueous phase was transferred to a separatory funnel with water (200 ml) and extracted with 20% ethyl acetate in hexanes, v/v (200 ml + 3 x 100 ml). The combined organic phases were dried (Na2SO4), filtered and concentrated in vacuo to give a yellow gum. Purification by Dry Column Vacuum Chromatography (Pedersen & Rosenbohm, 2001) (id 6 cm; 20 ml fractions; 10 x hexanes; 2–20% EtOAc in hexanes, v/v - 2% increments; 10 x 20% EtOAc in hexanes, v/v) gave tert-butyl 2-methylenebut-3-enylcarbamate (3.0 g, 17%) as a tan liquid. This diene (3.0 g, 16.4 mmol) was dissolved in dichloromethane (90 ml), Rose Bengal bis-triethylammonium salt (100 mg) was added and the solution photolysed for 24 h whilst a stream of oxygen was bubbled through the solution. The solvent was removed in vacuo to give a pink gum that was purified by Dry Column Vacuum Chromatography (id 4 cm; 20 ml fractions; 8 x hexanes; 5 - 60% EtOAc in hexanes, v/v - 5% increments) to give dioxine (I) (0.90 g, 26%) as needles.

Refinement top

All H atoms were included in the riding-model approximation, with C—H = 0.95 to 0.99 Å and N—H = 0.88 Å, and with Uiso(H) = 1.2Ueq(C, N) and Uiso(H) = 1.5Ueq(methyl-C). Disorder was noted in the C4—O1—O2—C4 residue of the six-membered ring and two positions were discerned for the O atoms. The major component (anisotropic) had a site occupancy factor = 0.706 (5). The absolute structure could not be determined with confidence so the Friedel pairs were averaged.

Structure description top

Recently, we reported that 1,2-dioxines can be converted to a wide variety of carbohydrates by dihydroxylation of the olefin, followed by cleavage of the peroxide bond (Robinson et al., 2006). To extend this methodology further, a number of amino dioxines were synthesized, such as the title compound, C10H17NO4 (I), that could potentially be converted to amino sugars by the same method.

The molecular structure of (I), Fig. 1, features a six-membered ring with a half-chair conformation so that the O atoms lie on either side of the plane defined by the four C atoms. The ring is characterized by a puckering amplitude = 0.618 (2) Å, and values of θ = 52.10 (19)° and φ = 28.0 (3)° (Cremer & Pople, 1975). The overall conformation of the molecule is such that the ring lies to one side of the central chromophore. Molecules are connected into a supramolecular chain aligned along the b axis by N—H···O hydrogen bonding interactions (Fig. 2 & Table 1). Chains are consolidated into a 3-D structure via C—H···O interactions (Fig. 3).

For the synthesis of the t-butyl 2-formylallylcarbamate reactant, see Erkkila & Pihko (2006). For the conversion of 1,2-dioxines to carbohydrates, see Robinson et al. (2006) and Pedersen & Rosenbohm (2001) for some experimental techiques. For calculations on ring puckering, see Cremer & Pople (1975).

Computing details top

Data collection: CrystalClear (Rigaku Americas Corporation, 2005); cell refinement: CrystalClear (Rigaku Americas Corporation, 2005); data reduction: CrystalClear (Rigaku Americas Corporation, 2005); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

Figures top
[Figure 1] Fig. 1. Molecular structure of (I) showing atom-labelling scheme and displacement ellipsoids at the 50% probability level. The minor component of the disorder was omitted for clarity.
[Figure 2] Fig. 2. View of the supramolecular chain in (I) mediated by N—H···O hydrogen bonds, shown as orange-dashed lines. Colour code: red (oxygen), blue (nitrogen), grey (carbon) and green (hydrogen).
[Figure 3] Fig. 3. View of the unit-cell contents of (I) down the b axis. Colour code for atoms as for Fig. 2. Hydrogen bonding contacts of the type N—H···O and C—H···O are shown as orange- and blue-dashed lines, respectively.
tert-Butyl N-(3,6-dihydro-1,2-dioxin-4-ylmethyl)carbamate top
Crystal data top
C10H17NO4F(000) = 464
Mr = 215.25Dx = 1.239 Mg m3
Orthorhombic, P212121Mo Kα radiation, λ = 0.71070 Å
Hall symbol: P 2ac 2abCell parameters from 4236 reflections
a = 9.435 (4) Åθ = 2.2–30.4°
b = 9.628 (4) ŵ = 0.10 mm1
c = 12.698 (6) ÅT = 120 K
V = 1153.6 (9) Å3Prism, colorless
Z = 40.40 × 0.40 × 0.10 mm
Data collection top
Rigaku AFC12κ/SATURN724
diffractometer
1347 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.027
Graphite monochromatorθmax = 26.5°, θmin = 2.7°
ω scansh = 1011
11678 measured reflectionsk = 1012
1369 independent reflectionsl = 1515
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)] = 0.038Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.100H-atom parameters constrained
S = 1.07 w = 1/[σ2(Fo2) + (0.0581P)2 + 0.2125P]
where P = (Fo2 + 2Fc2)/3
1369 reflections(Δ/σ)max < 0.001
145 parametersΔρmax = 0.14 e Å3
0 restraintsΔρmin = 0.16 e Å3
Crystal data top
C10H17NO4V = 1153.6 (9) Å3
Mr = 215.25Z = 4
Orthorhombic, P212121Mo Kα radiation
a = 9.435 (4) ŵ = 0.10 mm1
b = 9.628 (4) ÅT = 120 K
c = 12.698 (6) Å0.40 × 0.40 × 0.10 mm
Data collection top
Rigaku AFC12κ/SATURN724
diffractometer
1347 reflections with I > 2σ(I)
11678 measured reflectionsRint = 0.027
1369 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0380 restraints
wR(F2) = 0.100H-atom parameters constrained
S = 1.07Δρmax = 0.14 e Å3
1369 reflectionsΔρmin = 0.16 e Å3
145 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
xyzUiso*/UeqOcc. (<1)
O30.45338 (14)0.52172 (13)0.69574 (12)0.0403 (3)
O40.33495 (14)0.72768 (13)0.68622 (11)0.0370 (3)
C30.8147 (3)0.6760 (3)1.05230 (18)0.0568 (6)0.706 (5)
H3A0.88920.60701.06900.068*0.706 (5)
H3B0.83850.76361.08910.068*0.706 (5)
C40.6062 (2)0.5477 (2)0.92708 (15)0.0393 (4)0.706 (5)
H4A0.51470.59710.93470.047*0.706 (5)
H4B0.59050.46710.88010.047*0.706 (5)
O10.6742 (3)0.6237 (2)1.09082 (16)0.0500 (8)0.706 (5)
O20.6513 (2)0.4980 (2)1.02975 (15)0.0429 (7)0.706 (5)
C3A0.8147 (3)0.6760 (3)1.05230 (18)0.0568 (6)0.294 (5)
H3C0.91370.67531.07820.068*0.294 (5)
H3D0.76210.75011.08960.068*0.294 (5)
C4A0.6062 (2)0.5477 (2)0.92708 (15)0.0393 (4)0.294 (5)
H4C0.51130.55910.89490.047*0.294 (5)
H4D0.63610.44970.91990.047*0.294 (5)
O1A0.7525 (6)0.5504 (6)1.0696 (4)0.0480 (18)*0.294 (5)
O2A0.6048 (6)0.5901 (6)1.0373 (4)0.0443 (16)*0.294 (5)
N10.56110 (16)0.72726 (15)0.73168 (12)0.0330 (3)
H10.55140.81810.73290.040*
C10.71146 (19)0.64320 (18)0.87711 (14)0.0317 (4)
C20.8118 (2)0.7010 (2)0.93588 (16)0.0402 (5)
H20.88170.75820.90410.048*
C50.69754 (18)0.6658 (2)0.76017 (14)0.0336 (4)
H5A0.77480.72780.73600.040*
H5B0.70830.57570.72350.040*
C60.45012 (19)0.64797 (18)0.70358 (13)0.0314 (4)
C70.2026 (2)0.6673 (2)0.64337 (17)0.0412 (5)
C80.1393 (2)0.5642 (2)0.7209 (2)0.0512 (6)
H8A0.20160.48320.72680.077*
H8B0.04580.53470.69600.077*
H8C0.12980.60840.79010.077*
C90.1067 (2)0.7929 (3)0.6341 (3)0.0623 (7)
H9A0.08930.83170.70420.093*
H9B0.01640.76510.60220.093*
H9C0.15230.86320.58970.093*
C100.2326 (3)0.6033 (3)0.53635 (19)0.0593 (7)
H10A0.29470.52250.54500.089*
H10B0.27920.67210.49120.089*
H10C0.14330.57400.50380.089*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O30.0397 (7)0.0282 (7)0.0530 (8)0.0002 (5)0.0028 (6)0.0033 (6)
O40.0308 (6)0.0281 (6)0.0521 (7)0.0014 (5)0.0070 (6)0.0002 (6)
C30.0668 (15)0.0525 (13)0.0513 (12)0.0174 (13)0.0236 (12)0.0077 (10)
C40.0340 (9)0.0463 (11)0.0376 (9)0.0043 (8)0.0034 (8)0.0026 (8)
O10.0606 (15)0.0528 (14)0.0366 (10)0.0119 (12)0.0015 (11)0.0054 (9)
O20.0519 (12)0.0383 (12)0.0384 (10)0.0098 (10)0.0043 (9)0.0065 (8)
C3A0.0668 (15)0.0525 (13)0.0513 (12)0.0174 (13)0.0236 (12)0.0077 (10)
C4A0.0340 (9)0.0463 (11)0.0376 (9)0.0043 (8)0.0034 (8)0.0026 (8)
N10.0326 (8)0.0274 (7)0.0390 (8)0.0008 (6)0.0047 (6)0.0008 (6)
C10.0297 (8)0.0268 (8)0.0386 (9)0.0035 (7)0.0015 (7)0.0013 (7)
C20.0384 (10)0.0337 (9)0.0484 (10)0.0047 (9)0.0084 (9)0.0022 (8)
C50.0274 (8)0.0344 (9)0.0391 (9)0.0002 (7)0.0009 (7)0.0005 (7)
C60.0330 (9)0.0282 (8)0.0329 (8)0.0008 (7)0.0008 (7)0.0002 (7)
C70.0292 (9)0.0395 (10)0.0551 (11)0.0065 (8)0.0074 (9)0.0022 (9)
C80.0383 (10)0.0475 (12)0.0677 (14)0.0083 (9)0.0038 (10)0.0065 (11)
C90.0337 (10)0.0512 (13)0.102 (2)0.0017 (11)0.0148 (12)0.0145 (14)
C100.0469 (12)0.0782 (18)0.0527 (12)0.0201 (13)0.0100 (10)0.0062 (12)
Geometric parameters (Å, º) top
O3—C61.220 (2)N1—C61.344 (2)
O4—C61.349 (2)N1—C51.462 (2)
O4—C71.481 (2)N1—H10.8800
C3—O11.500 (4)C1—C21.327 (3)
C3—C21.498 (3)C1—C51.507 (3)
C3—H3A0.9900C2—H20.9500
C3—H3B0.9900C5—H5A0.9900
C4—O21.453 (3)C5—H5B0.9900
C4—C11.495 (3)C7—C91.515 (3)
C4—H4A0.9900C7—C101.519 (3)
C4—H4B0.9900C7—C81.520 (3)
O1—O21.454 (3)C8—H8A0.9800
C3A—O1A1.362 (6)C8—H8B0.9800
C3A—C21.498 (3)C8—H8C0.9800
C3A—H3C0.9900C9—H9A0.9800
C3A—H3D0.9900C9—H9B0.9800
C4A—O2A1.458 (6)C9—H9C0.9800
C4A—C11.495 (3)C10—H10A0.9800
C4A—H4C0.9900C10—H10B0.9800
C4A—H4D0.9900C10—H10C0.9800
O1A—O2A1.502 (8)
C6—O4—C7121.07 (14)C1—C2—C3A120.0 (2)
O1—C3—C2111.0 (2)C1—C2—H2120.0
O1—C3—H3A109.4C3—C2—H2120.0
C2—C3—H3A109.4C3A—C2—H2120.0
O1—C3—H3B109.4N1—C5—C1112.28 (15)
C2—C3—H3B109.4N1—C5—H5A109.1
H3A—C3—H3B108.0C1—C5—H5A109.1
O2—C4—C1112.89 (17)N1—C5—H5B109.1
O2—C4—H4A109.0C1—C5—H5B109.1
C1—C4—H4A109.0H5A—C5—H5B107.9
O2—C4—H4B109.0O3—C6—N1124.61 (17)
C1—C4—H4B109.0O3—C6—O4125.03 (17)
H4A—C4—H4B107.8N1—C6—O4110.36 (14)
O2—O1—C3103.7 (2)O4—C7—C9102.64 (17)
C4—O2—O1104.33 (18)O4—C7—C10109.30 (17)
O1A—C3A—C2107.1 (3)C9—C7—C10111.4 (2)
O1A—C3A—H3C110.3O4—C7—C8110.44 (17)
C2—C3A—H3C110.3C9—C7—C8109.71 (19)
O1A—C3A—H3D110.3C10—C7—C8112.8 (2)
C2—C3A—H3D110.3C7—C8—H8A109.5
H3C—C3A—H3D108.6C7—C8—H8B109.5
O2A—C4A—C1104.0 (3)H8A—C8—H8B109.5
O2A—C4A—H4C111.0C7—C8—H8C109.5
C1—C4A—H4C111.0H8A—C8—H8C109.5
O2A—C4A—H4D111.0H8B—C8—H8C109.5
C1—C4A—H4D111.0C7—C9—H9A109.5
H4C—C4A—H4D109.0C7—C9—H9B109.5
C3A—O1A—O2A97.5 (4)H9A—C9—H9B109.5
C4A—O2A—O1A100.5 (4)C7—C9—H9C109.5
C6—N1—C5121.46 (14)H9A—C9—H9C109.5
C6—N1—H1119.3H9B—C9—H9C109.5
C5—N1—H1119.3C7—C10—H10A109.5
C2—C1—C4119.53 (17)C7—C10—H10B109.5
C2—C1—C4A119.53 (17)H10A—C10—H10B109.5
C2—C1—C5123.74 (18)C7—C10—H10C109.5
C4—C1—C5116.71 (16)H10A—C10—H10C109.5
C4A—C1—C5116.71 (16)H10B—C10—H10C109.5
C1—C2—C3120.0 (2)
C2—C3—O1—O258.0 (2)C5—C1—C2—C3A178.1 (2)
C1—C4—O2—O157.4 (2)O1—C3—C2—C118.2 (3)
C3—O1—O2—C477.6 (2)O1—C3—C2—C3A0 (100)
C2—C3A—O1A—O2A67.3 (4)O1A—C3A—C2—C127.2 (4)
C1—C4A—O2A—O1A66.0 (4)O1A—C3A—C2—C30 (100)
C3A—O1A—O2A—C4A93.9 (4)C6—N1—C5—C193.6 (2)
O2—C4—C1—C216.9 (3)C2—C1—C5—N1120.2 (2)
O2—C4—C1—C4A0 (11)C4—C1—C5—N160.9 (2)
O2—C4—C1—C5162.06 (17)C4A—C1—C5—N160.9 (2)
O2A—C4A—C1—C224.3 (3)C5—N1—C6—O32.6 (3)
O2A—C4A—C1—C40 (38)C5—N1—C6—O4176.90 (14)
O2A—C4A—C1—C5156.7 (3)C7—O4—C6—O37.0 (3)
C4—C1—C2—C33.0 (3)C7—O4—C6—N1173.47 (15)
C4A—C1—C2—C33.0 (3)C6—O4—C7—C9178.27 (18)
C5—C1—C2—C3178.1 (2)C6—O4—C7—C1059.9 (2)
C4—C1—C2—C3A3.0 (3)C6—O4—C7—C864.8 (2)
C4A—C1—C2—C3A3.0 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O3i0.882.162.984 (2)156
C3—H3A···O3ii0.992.523.425 (3)152
C4—H4B···O4iii0.992.553.446 (3)150
Symmetry codes: (i) x+1, y+1/2, z+3/2; (ii) x+3/2, y+1, z+1/2; (iii) x+1, y1/2, z+3/2.

Experimental details

Crystal data
Chemical formulaC10H17NO4
Mr215.25
Crystal system, space groupOrthorhombic, P212121
Temperature (K)120
a, b, c (Å)9.435 (4), 9.628 (4), 12.698 (6)
V3)1153.6 (9)
Z4
Radiation typeMo Kα
µ (mm1)0.10
Crystal size (mm)0.40 × 0.40 × 0.10
Data collection
DiffractometerRigaku AFC12κ/SATURN724
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
11678, 1369, 1347
Rint0.027
(sin θ/λ)max1)0.628
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.038, 0.100, 1.07
No. of reflections1369
No. of parameters145
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.14, 0.16

Computer programs: CrystalClear (Rigaku Americas Corporation, 2005), SIR92 (Altomare et al., 1994), SHELXL97 (Sheldrick, 1997), ORTEPII (Johnson, 1976) and DIAMOND (Brandenburg, 2006).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O3i0.882.162.984 (2)156
C3—H3A···O3ii0.992.523.425 (3)152
C4—H4B···O4iii0.992.553.446 (3)150
Symmetry codes: (i) x+1, y+1/2, z+3/2; (ii) x+3/2, y+1, z+1/2; (iii) x+1, y1/2, z+3/2.
 

Subscribe to Acta Crystallographica Section E: Crystallographic Communications

The full text of this article is available to subscribers to the journal.

If you have already registered and are using a computer listed in your registration details, please email support@iucr.org for assistance.

Buy online

You may purchase this article in PDF and/or HTML formats. For purchasers in the European Community who do not have a VAT number, VAT will be added at the local rate. Payments to the IUCr are handled by WorldPay, who will accept payment by credit card in several currencies. To purchase the article, please complete the form below (fields marked * are required), and then click on `Continue'.
E-mail address* 
Repeat e-mail address* 
(for error checking) 

Format*   PDF (US $40)
   HTML (US $40)
   PDF+HTML (US $50)
In order for VAT to be shown for your country javascript needs to be enabled.

VAT number 
(non-UK EC countries only) 
Country* 
 

Terms and conditions of use
Contact us

Follow Acta Cryst. E
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds