Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807042742/hk2317sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807042742/hk2317Isup2.hkl |
CCDC reference: 663714
Key indicators
- Single-crystal X-ray study
- T = 273 K
- Mean (C-C) = 0.002 Å
- R factor = 0.033
- wR factor = 0.090
- Data-to-parameter ratio = 17.7
checkCIF/PLATON results
No syntax errors found
Alert level B PLAT024_ALERT_4_B Merging of Friedel Pairs is STRONGLY Indicated . !
Alert level G REFLT03_ALERT_4_G ALERT: MoKa measured Friedel data cannot be used to determine absolute structure in a light-atom study EXCEPT under VERY special conditions. It is preferred that Friedel data is merged in such cases. From the CIF: _diffrn_reflns_theta_max 28.18 From the CIF: _reflns_number_total 1843 Count of symmetry unique reflns 1110 Completeness (_total/calc) 166.04% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 733 Fraction of Friedel pairs measured 0.660 Are heavy atom types Z>Si present no PLAT791_ALERT_1_G Confirm the Absolute Configuration of C1 = . S PLAT791_ALERT_1_G Confirm the Absolute Configuration of C6 = . R
0 ALERT level A = In general: serious problem 1 ALERT level B = Potentially serious problem 0 ALERT level C = Check and explain 3 ALERT level G = General alerts; check 2 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 2 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
Hexahydrophthalic anhydride (20 mmol) and urea (10 mmol) was added to a 25 ml flask. After the mixture was heated at reflux for 1 h, 5 ml of ice water was added, then the crystals of (I) were obtained by filtration. Crystals of (I) suitable for X-ray analysis were obtained by slow evaporation of an ethyl acetate solution.
H1A (for NH) was located in difference syntheses and only its position was refined [N—H = 0.860 (17) Å, Uiso(H) = 0.044 Å2]. The remaining H atoms were positioned geometrically, with C—H = 0.98 and 0.97 Å for methine, and methylene H, and constrained to ride on their parent atoms, with Uiso(H) = 1.2Ueq(C).
Hexahydrophthalimide is a key intermediate for the synthesis of hypoglycemic drug mitiglinide (Yamaguchi et al., 1998). As part of our studies in this area, we report herein the synthesis and crystal structure of the title compound, (I).
In the molecule of the title compound, (I), (Fig. 1) the bond lengths and angles are generally within normal ranges (Allen et al., 1987).
Ring A (C1—C6) is not planar, having total puckering amplitude, QT, of 0.519 (3) Å, and chair conformation [φ = -47.93 (3)° and θ = 161.98 (3)°] (Cremer & Pople, 1975). Ring B (C1/C6—C8/N1) has envelope conformation with atom C6 displaced by -0.394 (3) Å from the plane of the other four ring atoms.
In the crystal structure, the intermolecular N—H···O hydrogen bonds (Table 1) link the molecules (Fig. 2), in which they seem to be effective in the stabilization of the structure.
For related literature, see: Yamaguchi et al. (1998). For general background, see: Cremer & Pople (1975). For bond-length data, see: Allen et al. (1987).
Data collection: CAD-4 Software (Enraf–Nonius, 1985); cell refinement: CAD-4 Software (Enraf–Nonius, 1985); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Siemens, 1996); software used to prepare material for publication: PLATON (Spek, 2003).
C8H11NO2 | F(000) = 328 |
Mr = 153.18 | Dx = 1.333 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 25 reflections |
a = 6.7574 (12) Å | θ = 2.8–18.0° |
b = 7.8615 (14) Å | µ = 0.10 mm−1 |
c = 14.371 (3) Å | T = 273 K |
V = 763.4 (2) Å3 | Block, colorless |
Z = 4 | 0.30 × 0.26 × 0.24 mm |
Enraf–Nonius CAD-4 diffractometer | 1699 reflections with I > 2σ(I) |
Radiation source: sealed tube | Rint = 0.057 |
Graphite monochromator | θmax = 28.2°, θmin = 2.8° |
φ and ω scans | h = −8→8 |
Absorption correction: ψ scan (North et al., 1968) | k = −10→6 |
Tmin = 0.97, Tmax = 0.98 | l = −19→14 |
4773 measured reflections | 3 standard reflections every 120 min |
1843 independent reflections | intensity decay: 1% |
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)] = 0.033 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.090 | w = 1/[σ2(Fo2) + (0.0566P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.07 | (Δ/σ)max < 0.001 |
1843 reflections | Δρmax = 0.22 e Å−3 |
104 parameters | Δρmin = −0.14 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.42 (2) |
C8H11NO2 | V = 763.4 (2) Å3 |
Mr = 153.18 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 6.7574 (12) Å | µ = 0.10 mm−1 |
b = 7.8615 (14) Å | T = 273 K |
c = 14.371 (3) Å | 0.30 × 0.26 × 0.24 mm |
Enraf–Nonius CAD-4 diffractometer | 1699 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.057 |
Tmin = 0.97, Tmax = 0.98 | 3 standard reflections every 120 min |
4773 measured reflections | intensity decay: 1% |
1843 independent reflections |
R[F2 > 2σ(F2)] = 0.033 | 0 restraints |
wR(F2) = 0.090 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.07 | Δρmax = 0.22 e Å−3 |
1843 reflections | Δρmin = −0.14 e Å−3 |
104 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
O1 | 0.47695 (15) | 0.91918 (12) | 0.12610 (7) | 0.0494 (3) | |
O2 | −0.03151 (14) | 0.63013 (12) | 0.25855 (7) | 0.0477 (3) | |
N1 | 0.20581 (16) | 0.80816 (13) | 0.20032 (7) | 0.0368 (3) | |
H1A | 0.148 (2) | 0.903 (2) | 0.2135 (11) | 0.044* | |
C1 | 0.26087 (16) | 0.51872 (14) | 0.17742 (8) | 0.0325 (3) | |
H1 | 0.2780 | 0.4225 | 0.2200 | 0.039* | |
C2 | 0.16634 (17) | 0.46046 (16) | 0.08509 (8) | 0.0385 (3) | |
H2A | 0.0623 | 0.3789 | 0.0982 | 0.046* | |
H2B | 0.1066 | 0.5577 | 0.0545 | 0.046* | |
C3 | 0.3167 (2) | 0.37982 (18) | 0.02014 (9) | 0.0454 (3) | |
H3A | 0.3715 | 0.2787 | 0.0490 | 0.055* | |
H3B | 0.2521 | 0.3461 | −0.0372 | 0.055* | |
C4 | 0.48208 (18) | 0.50434 (17) | −0.00141 (8) | 0.0454 (3) | |
H4A | 0.4270 | 0.6053 | −0.0303 | 0.054* | |
H4B | 0.5737 | 0.4528 | −0.0451 | 0.054* | |
C5 | 0.59260 (17) | 0.55445 (19) | 0.08653 (10) | 0.0455 (3) | |
H5A | 0.6858 | 0.6443 | 0.0717 | 0.055* | |
H5B | 0.6678 | 0.4574 | 0.1085 | 0.055* | |
C6 | 0.45644 (16) | 0.61537 (15) | 0.16426 (8) | 0.0350 (3) | |
H6 | 0.5305 | 0.6043 | 0.2226 | 0.042* | |
C7 | 0.38956 (17) | 0.79860 (15) | 0.15769 (7) | 0.0344 (3) | |
C8 | 0.12617 (18) | 0.65170 (15) | 0.21917 (8) | 0.0340 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0569 (6) | 0.0393 (5) | 0.0521 (5) | −0.0139 (5) | 0.0103 (4) | 0.0003 (4) |
O2 | 0.0505 (5) | 0.0376 (5) | 0.0551 (5) | −0.0033 (4) | 0.0209 (4) | −0.0017 (4) |
N1 | 0.0439 (5) | 0.0273 (5) | 0.0393 (5) | 0.0005 (4) | 0.0070 (4) | −0.0023 (4) |
C1 | 0.0356 (5) | 0.0284 (5) | 0.0334 (5) | 0.0012 (4) | 0.0010 (4) | 0.0028 (4) |
C2 | 0.0345 (5) | 0.0386 (6) | 0.0424 (6) | −0.0026 (5) | −0.0014 (5) | −0.0081 (5) |
C3 | 0.0486 (7) | 0.0418 (7) | 0.0459 (7) | 0.0001 (6) | 0.0026 (6) | −0.0123 (5) |
C4 | 0.0481 (7) | 0.0446 (7) | 0.0435 (7) | 0.0051 (6) | 0.0121 (6) | −0.0024 (6) |
C5 | 0.0320 (5) | 0.0462 (7) | 0.0584 (8) | 0.0024 (5) | 0.0070 (5) | −0.0020 (6) |
C6 | 0.0318 (5) | 0.0369 (6) | 0.0363 (5) | 0.0003 (5) | −0.0047 (4) | −0.0001 (5) |
C7 | 0.0380 (6) | 0.0349 (6) | 0.0304 (5) | −0.0050 (5) | −0.0011 (4) | −0.0025 (4) |
C8 | 0.0400 (6) | 0.0316 (5) | 0.0303 (5) | −0.0023 (5) | 0.0027 (4) | 0.0004 (4) |
C1—C8 | 1.5104 (16) | C4—H4B | 0.9700 |
C1—C6 | 1.5360 (15) | C5—C6 | 1.5243 (17) |
C1—C2 | 1.5423 (16) | C5—H5A | 0.9700 |
C1—H1 | 0.9800 | C5—H5B | 0.9700 |
C2—C3 | 1.5186 (17) | C6—C7 | 1.5127 (17) |
C2—H2A | 0.9700 | C6—H6 | 0.9800 |
C2—H2B | 0.9700 | C7—O1 | 1.2055 (14) |
C3—C4 | 1.5173 (18) | C7—N1 | 1.3867 (15) |
C3—H3A | 0.9700 | C8—O2 | 1.2183 (15) |
C3—H3B | 0.9700 | C8—N1 | 1.3696 (14) |
C4—C5 | 1.5199 (19) | N1—H1A | 0.860 (17) |
C4—H4A | 0.9700 | ||
C8—C1—C6 | 103.01 (9) | H4A—C4—H4B | 108.0 |
C8—C1—C2 | 107.32 (9) | C4—C5—C6 | 113.21 (10) |
C6—C1—C2 | 113.41 (9) | C4—C5—H5A | 108.9 |
C8—C1—H1 | 110.9 | C6—C5—H5A | 108.9 |
C6—C1—H1 | 110.9 | C4—C5—H5B | 108.9 |
C2—C1—H1 | 110.9 | C6—C5—H5B | 108.9 |
C3—C2—C1 | 112.06 (10) | H5A—C5—H5B | 107.7 |
C3—C2—H2A | 109.2 | C7—C6—C5 | 115.70 (10) |
C1—C2—H2A | 109.2 | C7—C6—C1 | 102.81 (9) |
C3—C2—H2B | 109.2 | C5—C6—C1 | 117.01 (10) |
C1—C2—H2B | 109.2 | C7—C6—H6 | 106.9 |
H2A—C2—H2B | 107.9 | C5—C6—H6 | 106.9 |
C4—C3—C2 | 110.42 (10) | C1—C6—H6 | 106.9 |
C4—C3—H3A | 109.6 | O1—C7—N1 | 124.22 (12) |
C2—C3—H3A | 109.6 | O1—C7—C6 | 128.75 (11) |
C4—C3—H3B | 109.6 | N1—C7—C6 | 106.95 (9) |
C2—C3—H3B | 109.6 | O2—C8—N1 | 124.09 (11) |
H3A—C3—H3B | 108.1 | O2—C8—C1 | 127.97 (11) |
C3—C4—C5 | 111.06 (10) | N1—C8—C1 | 107.83 (10) |
C3—C4—H4A | 109.4 | C8—N1—C7 | 112.99 (10) |
C5—C4—H4A | 109.4 | C8—N1—H1A | 123.5 (10) |
C3—C4—H4B | 109.4 | C7—N1—H1A | 123.5 (10) |
C5—C4—H4B | 109.4 |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O2i | 0.860 (17) | 1.995 (17) | 2.8537 (15) | 175.8 (14) |
Symmetry code: (i) −x, y+1/2, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C8H11NO2 |
Mr | 153.18 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 273 |
a, b, c (Å) | 6.7574 (12), 7.8615 (14), 14.371 (3) |
V (Å3) | 763.4 (2) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.10 |
Crystal size (mm) | 0.30 × 0.26 × 0.24 |
Data collection | |
Diffractometer | Enraf–Nonius CAD-4 |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.97, 0.98 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4773, 1843, 1699 |
Rint | 0.057 |
(sin θ/λ)max (Å−1) | 0.664 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.033, 0.090, 1.07 |
No. of reflections | 1843 |
No. of parameters | 104 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.22, −0.14 |
Computer programs: CAD-4 Software (Enraf–Nonius, 1985), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Siemens, 1996), PLATON (Spek, 2003).
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O2i | 0.860 (17) | 1.995 (17) | 2.8537 (15) | 175.8 (14) |
Symmetry code: (i) −x, y+1/2, −z+1/2. |
Hexahydrophthalimide is a key intermediate for the synthesis of hypoglycemic drug mitiglinide (Yamaguchi et al., 1998). As part of our studies in this area, we report herein the synthesis and crystal structure of the title compound, (I).
In the molecule of the title compound, (I), (Fig. 1) the bond lengths and angles are generally within normal ranges (Allen et al., 1987).
Ring A (C1—C6) is not planar, having total puckering amplitude, QT, of 0.519 (3) Å, and chair conformation [φ = -47.93 (3)° and θ = 161.98 (3)°] (Cremer & Pople, 1975). Ring B (C1/C6—C8/N1) has envelope conformation with atom C6 displaced by -0.394 (3) Å from the plane of the other four ring atoms.
In the crystal structure, the intermolecular N—H···O hydrogen bonds (Table 1) link the molecules (Fig. 2), in which they seem to be effective in the stabilization of the structure.