Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270113010706/sf3191sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270113010706/sf3191IIsup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270113010706/sf3191IVsup3.hkl | |
Chemical Markup Language (CML) file https://doi.org/10.1107/S0108270113010706/sf3191IIsup4.cml |
CCDC references: 950442; 950443
For related literature, see: Hellal et al. (2006); Kosturkiewicz et al. (1992); Kourany-Lefoll, Pais, Sevenet, Guittet, Montagnac, Fontain, Guenard & Adeline (1992); Liang (2004); Neubert & Snider (2003); Runge & Bowden (2007); Tan et al. (2012); Trujillo-Ferrara, García-Báez, Padilla-Martínez, Martínez-Martínez & Farfan-García (2004).
Propane-1,3-diamine (14.9 g, 201.0 mmol) and 3a,4,7,7a-tetrahydro-4,7-epoxyisobenzofuran-1,3-dione (4.8 g, 28.9 mmol), (I), were refluxed at 353 K for 2 h. The resulting solution was poured into H2O and extracted with dichloromethane (2 × 30 ml). The combined organic layers were dried with Na2SO4 and concentrated. A translucent solid was obtained by recrystallization in toluene to yield compound (II) [yield 23.5%; m.p. 393 K (decomposition)]. Crystals suitable for X-ray diffraction were obtained by slow evaporation from a layered solution of n-heptane and saturated dichloromethane [Which phase was (II) in?]. 1H NMR and 13C{1H} NMR data are available in the Supplementary materials.
Compound (IV) was prepared in analogy with (II), using ethylenediamine (5 ml, 74.9 mmol) and (I) (5.0 g, 30.1 mmol). Compound (IV) was obtained as a white solid by recrystallization from a mixture of dichloromethane and ether (1:3 v/v) [yield 9.9%; m.p. 399 K (decomposition)]. Crystals suitable for X-ray diffraction were obtained by precipitation out of a dichloromethane–ether (1:3 v/v) solution at 253 K. 1H NMR (300 MHz, CDCl3, δ, p.p.m.): 6.45 (s, 2H, H4A and H5A), 5.20 (s, 2H, H3A and H6A), 3.48 (t, 2H, J = 6.3, H9A and H9B), 2.80 (t, 4H, J = 6.3 Hz, H2A, H7A, H10A and H10B), 1.01 (br, 2H, H11A and H11B); 13C{1H} NMR (75 MHz, CDCl3, δ, p.p.m.): 176.4 (C1A and C8A), 136.4 (C4A and C5A), 80.8 (C3A and C6A), 47.3 (C2A and C7A), 41.9 (C9A), 39.7 (C10A).
The amine H atoms were located in a difference Fourier map and both positional and isotropic displacement parameters were refined. All other H atoms were positioned geometrically and refined using a riding model, with C—H = 0.95–0.99 Å and Uiso(H) = 1.2Ueq(C).
For both compounds, data collection: CrystalClear (Rigaku, 2008); cell refinement: CrystalClear (Rigaku, 2008); data reduction: CrystalClear (Rigaku, 2008); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SIR97 (Altomare et al., 1999) within WinGX (Farrugia, 2012); molecular graphics: ORTEP-3 (Farrugia, 2012); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and publCIF (Westrip, 2010).
C11H12N2O2 | F(000) = 432 |
Mr = 204.23 | Dx = 1.424 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71069 Å |
Hall symbol: -P 2ybc | Cell parameters from 21982 reflections |
a = 4.916 (2) Å | θ = 7.3–55.0° |
b = 8.998 (3) Å | µ = 0.10 mm−1 |
c = 21.604 (6) Å | T = 100 K |
β = 94.445 (7)° | Block, colourless |
V = 952.8 (6) Å3 | 0.38 × 0.14 × 0.09 mm |
Z = 4 |
Rigaku AFC12 with Saturn 724+ CCD area-detector diffractometer | 2193 independent reflections |
Radiation source: fine-focus sealed tube | 2031 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.031 |
ω scans | θmax = 27.5°, θmin = 3.6° |
Absorption correction: multi-scan (ABSCOR; Higashi, 1999) | h = −6→6 |
Tmin = 0.822, Tmax = 1.000 | k = −11→11 |
21174 measured reflections | l = −27→27 |
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)] = 0.037 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.100 | H-atom parameters constrained |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0501P)2 + 0.4632P] where P = (Fo2 + 2Fc2)/3 |
2193 reflections | (Δ/σ)max < 0.001 |
136 parameters | Δρmax = 0.36 e Å−3 |
0 restraints | Δρmin = −0.18 e Å−3 |
C11H12N2O2 | V = 952.8 (6) Å3 |
Mr = 204.23 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 4.916 (2) Å | µ = 0.10 mm−1 |
b = 8.998 (3) Å | T = 100 K |
c = 21.604 (6) Å | 0.38 × 0.14 × 0.09 mm |
β = 94.445 (7)° |
Rigaku AFC12 with Saturn 724+ CCD area-detector diffractometer | 2193 independent reflections |
Absorption correction: multi-scan (ABSCOR; Higashi, 1999) | 2031 reflections with I > 2σ(I) |
Tmin = 0.822, Tmax = 1.000 | Rint = 0.031 |
21174 measured reflections |
R[F2 > 2σ(F2)] = 0.037 | 0 restraints |
wR(F2) = 0.100 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.36 e Å−3 |
2193 reflections | Δρmin = −0.18 e Å−3 |
136 parameters |
Experimental. 1H NMR (300 MHz, CDCl3, δ, p.p.m.): 6.44 (s, 2H), 5.20 (s, 1H), 5.16 (s, 1H), 3.52 (t, 2H, J = 6.0), 3.47 (t, 2H, J = 5.6), 2.85 (d, 1H, J = 7.2), 2.69 (d, 1H, J = 6.9), 1.81–1.73 (m, 2H); 13C{H1}NMR (300 MHz, CDCl3, δ, p.p.m.): 173.4, 155.3, 136.0 (CH), 82.4 (CH), 80.1 (CH), 46.4 (CH), 45.3 (CH), 44.3 (CH2), 37.5 (CH2), 18.7 (CH2). HRMS (CI+), calculated for C11H12O2N2: [M + H]+ 205.0977; found: 205.0977. |
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 | ||
C11 | −0.0103 (3) | 0.26831 (14) | 0.40558 (6) | 0.0228 (3) | |
H11B | 0.0009 | 0.3512 | 0.4344 | 0.027* | |
H11A | −0.2009 | 0.2404 | 0.3988 | 0.027* | |
C10 | 0.0904 (3) | 0.31934 (13) | 0.34407 (6) | 0.0230 (3) | |
H10B | −0.0324 | 0.3941 | 0.3255 | 0.028* | |
H10A | 0.2699 | 0.3637 | 0.3514 | 0.028* | |
C9 | 0.1047 (3) | 0.18828 (13) | 0.29981 (6) | 0.0212 (3) | |
H9A | −0.0775 | 0.1533 | 0.2868 | 0.025* | |
H9B | 0.1938 | 0.2177 | 0.2632 | 0.025* | |
C8 | 0.4126 (2) | −0.03622 (13) | 0.30657 (5) | 0.0173 (2) | |
C7 | 0.5411 (2) | −0.13572 (12) | 0.35729 (5) | 0.0159 (2) | |
H7 | 0.7407 | −0.1378 | 0.3583 | 0.019* | |
C6 | 0.4117 (2) | −0.29402 (12) | 0.35416 (5) | 0.0167 (2) | |
H6 | 0.4043 | −0.3421 | 0.3134 | 0.020* | |
C5 | 0.5539 (2) | −0.38203 (13) | 0.40695 (6) | 0.0196 (2) | |
H5 | 0.6827 | −0.4569 | 0.4039 | 0.024* | |
C4 | 0.4574 (2) | −0.33056 (13) | 0.45853 (6) | 0.0208 (3) | |
H4 | 0.5027 | −0.3625 | 0.4990 | 0.025* | |
C3 | 0.2574 (2) | −0.20859 (13) | 0.43766 (5) | 0.0182 (2) | |
H3 | 0.1207 | −0.1844 | 0.4668 | 0.022* | |
C2 | 0.4360 (2) | −0.07520 (12) | 0.41816 (5) | 0.0161 (2) | |
H2 | 0.5839 | −0.0507 | 0.4495 | 0.019* | |
C1 | 0.2649 (2) | 0.05812 (12) | 0.39800 (5) | 0.0163 (2) | |
N1 | 0.2610 (2) | 0.07085 (11) | 0.33328 (4) | 0.0176 (2) | |
N2 | 0.1435 (2) | 0.14183 (11) | 0.43429 (5) | 0.0208 (2) | |
O1 | 0.15021 (16) | −0.26290 (9) | 0.37768 (4) | 0.0184 (2) | |
O2 | 0.43549 (19) | −0.04727 (10) | 0.25087 (4) | 0.0246 (2) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C11 | 0.0250 (6) | 0.0193 (6) | 0.0246 (6) | 0.0092 (5) | 0.0052 (5) | 0.0013 (5) |
C10 | 0.0246 (6) | 0.0171 (6) | 0.0276 (6) | 0.0049 (5) | 0.0027 (5) | 0.0040 (5) |
C9 | 0.0224 (6) | 0.0198 (6) | 0.0213 (6) | 0.0046 (5) | 0.0016 (4) | 0.0053 (4) |
C8 | 0.0154 (5) | 0.0168 (5) | 0.0202 (5) | −0.0013 (4) | 0.0042 (4) | 0.0013 (4) |
C7 | 0.0128 (5) | 0.0163 (5) | 0.0187 (5) | 0.0015 (4) | 0.0031 (4) | 0.0002 (4) |
C6 | 0.0156 (5) | 0.0157 (5) | 0.0193 (5) | 0.0020 (4) | 0.0044 (4) | −0.0014 (4) |
C5 | 0.0175 (5) | 0.0141 (5) | 0.0274 (6) | 0.0035 (4) | 0.0022 (4) | 0.0017 (4) |
C4 | 0.0234 (6) | 0.0161 (5) | 0.0227 (6) | 0.0027 (4) | 0.0009 (5) | 0.0041 (4) |
C3 | 0.0204 (5) | 0.0174 (5) | 0.0175 (5) | 0.0038 (4) | 0.0058 (4) | 0.0021 (4) |
C2 | 0.0171 (5) | 0.0150 (5) | 0.0160 (5) | 0.0028 (4) | 0.0003 (4) | −0.0006 (4) |
C1 | 0.0162 (5) | 0.0150 (5) | 0.0179 (5) | 0.0005 (4) | 0.0017 (4) | 0.0007 (4) |
N1 | 0.0191 (5) | 0.0166 (5) | 0.0171 (5) | 0.0030 (4) | 0.0021 (4) | 0.0020 (4) |
N2 | 0.0243 (5) | 0.0174 (5) | 0.0212 (5) | 0.0058 (4) | 0.0045 (4) | 0.0004 (4) |
O1 | 0.0131 (4) | 0.0196 (4) | 0.0227 (4) | 0.0009 (3) | 0.0027 (3) | 0.0006 (3) |
O2 | 0.0316 (5) | 0.0250 (5) | 0.0181 (4) | 0.0024 (4) | 0.0080 (4) | 0.0016 (3) |
C1—C2 | 1.5100 (17) | C7—C6 | 1.5591 (17) |
C2—C7 | 1.5485 (15) | C7—H7 | 0.9800 |
C7—C8 | 1.5147 (16) | C6—O1 | 1.4460 (18) |
N1—C8 | 1.3722 (16) | C6—C5 | 1.5143 (16) |
O2—C8 | 1.2212 (15) | C6—H6 | 0.9800 |
C11—N2 | 1.4762 (16) | C5—C4 | 1.3279 (17) |
C11—C10 | 1.5245 (17) | C5—H5 | 0.9300 |
C11—H11B | 0.9700 | C4—C3 | 1.5185 (17) |
C11—H11A | 0.9700 | C4—H4 | 0.9300 |
C10—C9 | 1.5233 (18) | C3—O1 | 1.4455 (14) |
C10—H10B | 0.9700 | C3—C2 | 1.5642 (17) |
C10—H10A | 0.9700 | C3—H3 | 0.9800 |
C9—N1 | 1.4642 (15) | C2—H2 | 0.9800 |
C9—H9A | 0.9700 | C1—N2 | 1.2690 (16) |
C9—H9B | 0.9700 | C1—N1 | 1.4017 (15) |
C1—C2—C7 | 104.45 (9) | O1—C6—C5 | 101.99 (9) |
C2—C7—C8 | 104.99 (9) | O1—C6—C7 | 100.29 (9) |
O2—C8—C7 | 126.84 (11) | C5—C6—C7 | 106.39 (10) |
O2—C8—N1 | 124.47 (11) | O1—C6—H6 | 115.4 |
N1—C8—C7 | 108.68 (10) | C5—C6—H6 | 115.4 |
C8—N1—C1 | 113.35 (9) | C7—C6—H6 | 115.4 |
N1—C1—C2 | 108.46 (9) | C4—C5—C6 | 105.99 (10) |
N2—C11—C10 | 114.08 (10) | C4—C5—H5 | 127.0 |
N2—C11—H11B | 108.7 | C6—C5—H5 | 127.0 |
C10—C11—H11B | 108.7 | C5—C4—C3 | 105.56 (10) |
N2—C11—H11A | 108.7 | C5—C4—H4 | 127.2 |
C10—C11—H11A | 108.7 | C3—C4—H4 | 127.2 |
H11B—C11—H11A | 107.6 | O1—C3—C4 | 101.80 (9) |
C9—C10—C11 | 110.36 (10) | O1—C3—C2 | 101.02 (9) |
C9—C10—H10B | 109.6 | C4—C3—C2 | 105.69 (11) |
C11—C10—H10B | 109.6 | O1—C3—H3 | 115.5 |
C9—C10—H10A | 109.6 | C4—C3—H3 | 115.5 |
C11—C10—H10A | 109.6 | C2—C3—H3 | 115.5 |
H10B—C10—H10A | 108.1 | C1—C2—C7 | 104.45 (9) |
N1—C9—C10 | 107.25 (10) | C1—C2—C3 | 112.04 (11) |
N1—C9—H9A | 110.3 | C7—C2—C3 | 100.96 (9) |
C10—C9—H9A | 110.3 | C1—C2—H2 | 112.8 |
N1—C9—H9B | 110.3 | C7—C2—H2 | 112.8 |
C10—C9—H9B | 110.3 | C3—C2—H2 | 112.8 |
H9A—C9—H9B | 108.5 | N2—C1—N1 | 126.67 (11) |
C8—C7—C6 | 111.27 (10) | N2—C1—C2 | 124.86 (11) |
C2—C7—C6 | 101.33 (9) | C8—N1—C9 | 125.47 (10) |
C8—C7—H7 | 112.8 | C1—N1—C9 | 121.17 (9) |
C2—C7—H7 | 112.8 | C1—N2—C11 | 116.62 (11) |
C6—C7—H7 | 112.8 | C3—O1—C6 | 96.21 (9) |
N2—C11—C10—C9 | 52.43 (15) | C4—C3—C2—C7 | 71.22 (11) |
C11—C10—C9—N1 | −51.50 (14) | C7—C2—C1—N2 | −178.87 (11) |
O2—C8—C7—C2 | −177.88 (11) | C3—C2—C1—N2 | 72.70 (15) |
N1—C8—C7—C2 | 1.78 (12) | C7—C2—C1—N1 | 2.03 (12) |
O2—C8—C7—C6 | −69.07 (16) | C3—C2—C1—N1 | −106.39 (10) |
N1—C8—C7—C6 | 110.59 (11) | O2—C8—N1—C1 | 179.14 (11) |
C8—C7—C6—O1 | −73.71 (11) | C7—C8—N1—C1 | −0.53 (13) |
C2—C7—C6—O1 | 37.46 (10) | O2—C8—N1—C9 | −0.25 (19) |
C8—C7—C6—C5 | −179.57 (9) | C7—C8—N1—C9 | −179.92 (10) |
C2—C7—C6—C5 | −68.40 (11) | N2—C1—N1—C8 | 179.92 (11) |
O1—C6—C5—C4 | −31.12 (12) | C2—C1—N1—C8 | −1.00 (13) |
C7—C6—C5—C4 | 73.52 (13) | N2—C1—N1—C9 | −0.66 (18) |
C6—C5—C4—C3 | −0.78 (12) | C2—C1—N1—C9 | 178.41 (10) |
C5—C4—C3—O1 | 32.45 (12) | C10—C9—N1—C8 | −152.25 (11) |
C5—C4—C3—C2 | −72.72 (12) | C10—C9—N1—C1 | 28.41 (14) |
C8—C7—C2—C1 | −2.26 (11) | N1—C1—N2—C11 | −2.07 (18) |
C6—C7—C2—C1 | −118.15 (10) | C2—C1—N2—C11 | 179.00 (11) |
C8—C7—C2—C3 | 114.14 (11) | C10—C11—N2—C1 | −24.52 (16) |
C6—C7—C2—C3 | −1.75 (10) | C4—C3—O1—C6 | −49.60 (10) |
O1—C3—C2—C1 | 76.14 (10) | C2—C3—O1—C6 | 59.19 (10) |
C4—C3—C2—C1 | −178.13 (9) | C5—C6—O1—C3 | 49.17 (10) |
O1—C3—C2—C7 | −34.51 (10) | C7—C6—O1—C3 | −60.20 (9) |
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3···N2i | 0.98 | 2.61 | 3.570 (4) | 165 |
C6—H6···O2ii | 0.98 | 2.48 | 3.3421 (19) | 147 |
C7—H7···O1iii | 0.98 | 2.32 | 3.2040 (18) | 150 |
C10—H10B···O2iv | 0.97 | 2.53 | 3.393 (4) | 148 |
Symmetry codes: (i) −x, −y, −z+1; (ii) −x+1, y−1/2, −z+1/2; (iii) x+1, y, z; (iv) −x, y+1/2, −z+1/2. |
C10H12N2O3 | F(000) = 880 |
Mr = 208.22 | Dx = 1.424 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71075 Å |
Hall symbol: -P 2ybc | Cell parameters from 4078 reflections |
a = 17.840 (2) Å | θ = 2.6–27.5° |
b = 6.8747 (6) Å | µ = 0.11 mm−1 |
c = 16.2125 (17) Å | T = 153 K |
β = 102.419 (5)° | Prism, colourless |
V = 1941.9 (3) Å3 | 0.48 × 0.25 × 0.07 mm |
Z = 8 |
Rigaku Mercury2 diffractometer | 4439 independent reflections |
Radiation source: fine-focus sealed tube | 3478 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.033 |
Detector resolution: 13.6612 pixels mm-1 | θmax = 27.5°, θmin = 2.3° |
ω scans | h = −23→23 |
Absorption correction: multi-scan (ABSCOR; Higashi, 1999) | k = −8→8 |
Tmin = 0.923, Tmax = 1.000 | l = −21→21 |
19826 measured reflections |
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)] = 0.046 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.125 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.07 | w = 1/[σ2(Fo2) + (0.056P)2 + 0.7213P] where P = (Fo2 + 2Fc2)/3 |
4439 reflections | (Δ/σ)max < 0.001 |
287 parameters | Δρmax = 0.22 e Å−3 |
0 restraints | Δρmin = −0.22 e Å−3 |
C10H12N2O3 | V = 1941.9 (3) Å3 |
Mr = 208.22 | Z = 8 |
Monoclinic, P21/c | Mo Kα radiation |
a = 17.840 (2) Å | µ = 0.11 mm−1 |
b = 6.8747 (6) Å | T = 153 K |
c = 16.2125 (17) Å | 0.48 × 0.25 × 0.07 mm |
β = 102.419 (5)° |
Rigaku Mercury2 diffractometer | 4439 independent reflections |
Absorption correction: multi-scan (ABSCOR; Higashi, 1999) | 3478 reflections with I > 2σ(I) |
Tmin = 0.923, Tmax = 1.000 | Rint = 0.033 |
19826 measured reflections |
R[F2 > 2σ(F2)] = 0.046 | 0 restraints |
wR(F2) = 0.125 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.07 | Δρmax = 0.22 e Å−3 |
4439 reflections | Δρmin = −0.22 e Å−3 |
287 parameters |
Experimental. HRMS (CI+), calculated for C10H13O3N2: [M + H]+ 209.0921; found: 209.0922. Analysis, calculated for C10H12O3N2: C 57.68, H 5.81, N 13.45; found: C 57.27, H 5.51, N 12.96. |
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 | ||
C1A | 0.11191 (8) | 0.5549 (2) | 0.21220 (9) | 0.0245 (3) | |
C8B | 0.30204 (9) | 0.7661 (2) | 0.03009 (9) | 0.0236 (3) | |
C2A | 0.05896 (8) | 0.3813 (2) | 0.19748 (9) | 0.0240 (3) | |
H2A | 0.0264 | 0.3709 | 0.2389 | 0.029* | |
C7B | 0.38202 (9) | 0.8530 (2) | 0.04465 (9) | 0.0240 (3) | |
H7B | 0.3878 | 0.9480 | 0.0014 | 0.029* | |
C3A | 0.01235 (8) | 0.3770 (2) | 0.10399 (9) | 0.0270 (3) | |
H3A | −0.0135 | 0.4988 | 0.0833 | 0.032* | |
C6B | 0.40781 (9) | 0.9334 (2) | 0.13638 (9) | 0.0292 (3) | |
H6B | 0.3716 | 1.0224 | 0.1546 | 0.035* | |
C4A | −0.03908 (9) | 0.1990 (3) | 0.09612 (10) | 0.0312 (4) | |
H4A | −0.0920 | 0.1969 | 0.0913 | 0.037* | |
C5B | 0.48865 (10) | 1.0111 (3) | 0.14447 (10) | 0.0375 (4) | |
H5B | 0.5037 | 1.1408 | 0.1464 | 0.045* | |
C5A | 0.00715 (9) | 0.0472 (2) | 0.09755 (9) | 0.0303 (4) | |
H5A | −0.0067 | −0.0834 | 0.0943 | 0.036* | |
C4B | 0.53341 (10) | 0.8565 (3) | 0.14828 (11) | 0.0368 (4) | |
H4B | 0.5864 | 0.8554 | 0.1538 | 0.044* | |
C6A | 0.08715 (9) | 0.1305 (2) | 0.10547 (9) | 0.0257 (3) | |
H6A | 0.1239 | 0.0454 | 0.0859 | 0.031* | |
C3B | 0.48096 (9) | 0.6824 (2) | 0.14183 (10) | 0.0285 (3) | |
H3B | 0.5057 | 0.5604 | 0.1640 | 0.034* | |
C7A | 0.11273 (8) | 0.2044 (2) | 0.19850 (9) | 0.0235 (3) | |
H7A | 0.1067 | 0.1060 | 0.2403 | 0.028* | |
C2B | 0.43554 (8) | 0.6755 (2) | 0.04771 (9) | 0.0250 (3) | |
H2B | 0.4690 | 0.6848 | 0.0072 | 0.030* | |
C8A | 0.19280 (8) | 0.2911 (2) | 0.21489 (8) | 0.0232 (3) | |
C1B | 0.38243 (9) | 0.5025 (2) | 0.03199 (9) | 0.0252 (3) | |
C9A | 0.25164 (8) | 0.6263 (2) | 0.22864 (9) | 0.0259 (3) | |
H9A | 0.2357 | 0.7442 | 0.1969 | 0.031* | |
H9B | 0.2925 | 0.5673 | 0.2063 | 0.031* | |
C9B | 0.24321 (9) | 0.4292 (2) | 0.01472 (9) | 0.0262 (3) | |
H9C | 0.2002 | 0.4915 | 0.0319 | 0.031* | |
H9D | 0.2579 | 0.3165 | 0.0506 | 0.031* | |
C10A | 0.28184 (9) | 0.6778 (2) | 0.32148 (9) | 0.0265 (3) | |
H10A | 0.2393 | 0.7229 | 0.3450 | 0.032* | |
H10B | 0.3022 | 0.5611 | 0.3518 | 0.032* | |
C10B | 0.21842 (9) | 0.3630 (2) | −0.07725 (10) | 0.0305 (4) | |
H10C | 0.1980 | 0.4741 | −0.1117 | 0.037* | |
H10D | 0.2633 | 0.3175 | −0.0963 | 0.037* | |
N1A | 0.18672 (7) | 0.49184 (18) | 0.21772 (7) | 0.0237 (3) | |
N1B | 0.30777 (7) | 0.56515 (18) | 0.02627 (7) | 0.0232 (3) | |
N2A | 0.34167 (8) | 0.8271 (2) | 0.33524 (9) | 0.0313 (3) | |
N2B | 0.16070 (9) | 0.2086 (2) | −0.09061 (9) | 0.0316 (3) | |
O1A | 0.09422 (7) | 0.72480 (16) | 0.21678 (8) | 0.0350 (3) | |
O3B | 0.24162 (6) | 0.85307 (17) | 0.02391 (7) | 0.0328 (3) | |
O2A | 0.07133 (6) | 0.31402 (16) | 0.06088 (6) | 0.0266 (2) | |
O2B | 0.42195 (6) | 0.75223 (16) | 0.18321 (6) | 0.0280 (3) | |
O3A | 0.25344 (6) | 0.20386 (17) | 0.22252 (7) | 0.0330 (3) | |
O1B | 0.40037 (7) | 0.33208 (16) | 0.02779 (8) | 0.0360 (3) | |
H11A | 0.3196 (12) | 0.944 (3) | 0.3100 (13) | 0.055 (6)* | |
H11B | 0.3779 (12) | 0.794 (3) | 0.3075 (12) | 0.042 (5)* | |
H11C | 0.1829 (12) | 0.101 (3) | −0.0609 (13) | 0.046 (6)* | |
H11D | 0.1210 (14) | 0.253 (3) | −0.0666 (14) | 0.058 (7)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1A | 0.0261 (8) | 0.0258 (8) | 0.0221 (7) | −0.0004 (6) | 0.0066 (6) | −0.0001 (6) |
C8B | 0.0276 (8) | 0.0259 (7) | 0.0170 (6) | −0.0005 (6) | 0.0040 (5) | 0.0004 (6) |
C2A | 0.0232 (7) | 0.0260 (8) | 0.0239 (7) | −0.0017 (6) | 0.0074 (6) | 0.0001 (6) |
C7B | 0.0283 (8) | 0.0222 (7) | 0.0211 (7) | −0.0036 (6) | 0.0043 (6) | 0.0005 (6) |
C3A | 0.0231 (7) | 0.0305 (8) | 0.0270 (8) | 0.0019 (6) | 0.0042 (6) | 0.0018 (6) |
C6B | 0.0365 (9) | 0.0242 (8) | 0.0245 (7) | 0.0009 (6) | 0.0016 (6) | −0.0029 (6) |
C4A | 0.0238 (8) | 0.0413 (9) | 0.0275 (8) | −0.0059 (7) | 0.0030 (6) | −0.0023 (7) |
C5B | 0.0414 (10) | 0.0347 (9) | 0.0314 (9) | −0.0126 (8) | −0.0032 (7) | −0.0048 (7) |
C5A | 0.0319 (9) | 0.0330 (9) | 0.0241 (7) | −0.0087 (7) | 0.0016 (6) | −0.0020 (6) |
C4B | 0.0277 (8) | 0.0445 (10) | 0.0350 (9) | −0.0103 (7) | −0.0003 (7) | −0.0051 (8) |
C6A | 0.0300 (8) | 0.0243 (7) | 0.0222 (7) | 0.0000 (6) | 0.0045 (6) | −0.0013 (6) |
C3B | 0.0218 (7) | 0.0323 (8) | 0.0305 (8) | 0.0017 (6) | 0.0039 (6) | −0.0012 (6) |
C7A | 0.0262 (8) | 0.0230 (7) | 0.0210 (7) | −0.0008 (6) | 0.0046 (6) | 0.0020 (6) |
C2B | 0.0226 (7) | 0.0267 (8) | 0.0271 (7) | −0.0040 (6) | 0.0081 (6) | −0.0027 (6) |
C8A | 0.0274 (8) | 0.0253 (7) | 0.0166 (6) | 0.0011 (6) | 0.0040 (5) | 0.0007 (5) |
C1B | 0.0256 (8) | 0.0254 (8) | 0.0255 (7) | −0.0022 (6) | 0.0076 (6) | −0.0018 (6) |
C9A | 0.0263 (8) | 0.0296 (8) | 0.0224 (7) | −0.0061 (6) | 0.0064 (6) | −0.0004 (6) |
C9B | 0.0251 (7) | 0.0300 (8) | 0.0241 (7) | −0.0080 (6) | 0.0067 (6) | −0.0002 (6) |
C10A | 0.0277 (8) | 0.0294 (8) | 0.0222 (7) | 0.0009 (6) | 0.0053 (6) | −0.0026 (6) |
C10B | 0.0326 (9) | 0.0330 (8) | 0.0256 (8) | −0.0105 (7) | 0.0055 (6) | 0.0006 (6) |
N1A | 0.0234 (6) | 0.0245 (6) | 0.0232 (6) | −0.0026 (5) | 0.0053 (5) | −0.0005 (5) |
N1B | 0.0215 (6) | 0.0244 (6) | 0.0243 (6) | −0.0037 (5) | 0.0061 (5) | −0.0029 (5) |
N2A | 0.0265 (7) | 0.0367 (8) | 0.0299 (7) | −0.0024 (6) | 0.0043 (6) | −0.0078 (6) |
N2B | 0.0306 (8) | 0.0315 (8) | 0.0318 (7) | −0.0080 (6) | 0.0045 (6) | −0.0007 (6) |
O1A | 0.0358 (6) | 0.0245 (6) | 0.0455 (7) | 0.0029 (5) | 0.0104 (5) | −0.0029 (5) |
O3B | 0.0289 (6) | 0.0349 (6) | 0.0332 (6) | 0.0055 (5) | 0.0037 (5) | 0.0013 (5) |
O2A | 0.0281 (6) | 0.0301 (6) | 0.0220 (5) | 0.0009 (4) | 0.0061 (4) | 0.0037 (4) |
O2B | 0.0295 (6) | 0.0317 (6) | 0.0222 (5) | 0.0040 (5) | 0.0045 (4) | 0.0028 (4) |
O3A | 0.0266 (6) | 0.0342 (6) | 0.0365 (6) | 0.0056 (5) | 0.0028 (5) | 0.0007 (5) |
O1B | 0.0316 (6) | 0.0257 (6) | 0.0519 (7) | 0.0003 (5) | 0.0113 (5) | −0.0047 (5) |
C1A—C2A | 1.509 (2) | C6A—O2A | 1.4515 (17) |
C2A—C7A | 1.547 (2) | C6A—C7A | 1.5639 (19) |
C7A—C8A | 1.518 (2) | C6A—H6A | 0.9800 |
C8A—N1A | 1.3858 (19) | C3B—O2B | 1.4465 (18) |
C8A—O3A | 1.2197 (18) | C3B—C2B | 1.567 (2) |
C1A—N1A | 1.3877 (19) | C3B—H3B | 0.9800 |
C1A—O1A | 1.2166 (19) | C7A—H7A | 0.9800 |
C8B—O3B | 1.2177 (18) | C2B—C1B | 1.508 (2) |
C8B—N1B | 1.3878 (19) | C2B—H2B | 0.9800 |
C8B—C7B | 1.518 (2) | C1B—O1B | 1.2203 (19) |
C2A—C3A | 1.565 (2) | C1B—N1B | 1.3838 (19) |
C2A—H2A | 0.9800 | C9A—N1A | 1.4624 (18) |
C7B—C2B | 1.543 (2) | C9A—C10A | 1.527 (2) |
C7B—C6B | 1.560 (2) | C9A—H9A | 0.9700 |
C7B—H7B | 0.9800 | C9A—H9B | 0.9700 |
C3A—O2A | 1.4490 (18) | C9B—N1B | 1.4637 (18) |
C3A—C4A | 1.518 (2) | C9B—C10B | 1.530 (2) |
C3A—H3A | 0.9800 | C9B—H9C | 0.9700 |
C6B—O2B | 1.4520 (19) | C9B—H9D | 0.9700 |
C6B—C5B | 1.517 (2) | C10A—N2A | 1.463 (2) |
C6B—H6B | 0.9800 | C10A—H10A | 0.9700 |
C4A—C5A | 1.327 (2) | C10A—H10B | 0.9700 |
C4A—H4A | 0.9300 | C10B—N2B | 1.462 (2) |
C5B—C4B | 1.323 (3) | C10B—H10C | 0.9700 |
C5B—H5B | 0.9300 | C10B—H10D | 0.9700 |
C5A—C6A | 1.517 (2) | N2A—H11A | 0.95 (2) |
C5A—H5A | 0.9300 | N2A—H11B | 0.89 (2) |
C4B—C3B | 1.509 (2) | N2B—H11C | 0.93 (2) |
C4B—H4B | 0.9300 | N2B—H11D | 0.93 (2) |
C1A—C2A—C7A | 104.74 (12) | O2B—C3B—H3B | 115.4 |
C8A—C7A—C2A | 104.56 (11) | C4B—C3B—H3B | 115.4 |
O3A—C8A—C7A | 127.27 (14) | C2B—C3B—H3B | 115.4 |
O3A—C8A—N1A | 124.08 (14) | C8A—C7A—C6A | 111.40 (12) |
N1A—C8A—C7A | 108.63 (12) | C2A—C7A—C6A | 101.17 (11) |
C8A—N1A—C1A | 112.94 (12) | C8A—C7A—H7A | 112.9 |
N1A—C1A—C2A | 108.91 (12) | C2A—C7A—H7A | 112.9 |
O1A—C1A—N1A | 123.67 (14) | C6A—C7A—H7A | 112.9 |
O1A—C1A—C2A | 127.40 (14) | C1B—C2B—C7B | 104.84 (12) |
O3B—C8B—N1B | 123.88 (14) | C1B—C2B—C3B | 111.28 (12) |
O3B—C8B—C7B | 127.28 (14) | C7B—C2B—C3B | 101.20 (11) |
N1B—C8B—C7B | 108.83 (12) | C1B—C2B—H2B | 112.9 |
C1A—C2A—C3A | 110.64 (12) | C7B—C2B—H2B | 112.9 |
C7A—C2A—C3A | 101.22 (11) | C3B—C2B—H2B | 112.9 |
C1A—C2A—H2A | 113.1 | O1B—C1B—N1B | 123.73 (14) |
C7A—C2A—H2A | 113.1 | O1B—C1B—C2B | 127.16 (14) |
C3A—C2A—H2A | 113.1 | N1B—C1B—C2B | 109.06 (12) |
C8B—C7B—C2B | 104.39 (12) | N1A—C9A—C10A | 111.62 (12) |
C8B—C7B—C6B | 111.23 (12) | N1A—C9A—H9A | 109.3 |
C2B—C7B—C6B | 101.29 (11) | C10A—C9A—H9A | 109.3 |
C8B—C7B—H7B | 113.0 | N1A—C9A—H9B | 109.3 |
C2B—C7B—H7B | 113.0 | C10A—C9A—H9B | 109.3 |
C6B—C7B—H7B | 113.0 | H9A—C9A—H9B | 108.0 |
O2A—C3A—C4A | 101.96 (12) | N1B—C9B—C10B | 111.67 (12) |
O2A—C3A—C2A | 100.56 (11) | N1B—C9B—H9C | 109.3 |
C4A—C3A—C2A | 106.40 (12) | C10B—C9B—H9C | 109.3 |
O2A—C3A—H3A | 115.4 | N1B—C9B—H9D | 109.3 |
C4A—C3A—H3A | 115.4 | C10B—C9B—H9D | 109.3 |
C2A—C3A—H3A | 115.4 | H9C—C9B—H9D | 107.9 |
O2B—C6B—C5B | 101.63 (12) | N2A—C10A—C9A | 113.85 (12) |
O2B—C6B—C7B | 100.20 (11) | N2A—C10A—H10A | 108.8 |
C5B—C6B—C7B | 106.68 (13) | C9A—C10A—H10A | 108.8 |
O2B—C6B—H6B | 115.5 | N2A—C10A—H10B | 108.8 |
C5B—C6B—H6B | 115.5 | C9A—C10A—H10B | 108.8 |
C7B—C6B—H6B | 115.5 | H10A—C10A—H10B | 107.7 |
C5A—C4A—C3A | 105.67 (14) | N2B—C10B—C9B | 114.02 (12) |
C5A—C4A—H4A | 127.2 | N2B—C10B—H10C | 108.7 |
C3A—C4A—H4A | 127.2 | C9B—C10B—H10C | 108.7 |
C4B—C5B—C6B | 105.93 (15) | N2B—C10B—H10D | 108.7 |
C4B—C5B—H5B | 127.0 | C9B—C10B—H10D | 108.7 |
C6B—C5B—H5B | 127.0 | H10C—C10B—H10D | 107.6 |
C4A—C5A—C6A | 105.94 (14) | C8A—N1A—C1A | 112.94 (12) |
C4A—C5A—H5A | 127.0 | C8A—N1A—C9A | 124.59 (13) |
C6A—C5A—H5A | 127.0 | C1A—N1A—C9A | 122.43 (13) |
C5B—C4B—C3B | 105.95 (14) | C1B—N1B—C8B | 112.70 (12) |
C5B—C4B—H4B | 127.0 | C1B—N1B—C9B | 121.96 (13) |
C3B—C4B—H4B | 127.0 | C8B—N1B—C9B | 125.31 (12) |
O2A—C6A—C5A | 101.96 (12) | C10A—N2A—H11A | 107.9 (13) |
O2A—C6A—C7A | 100.54 (11) | C10A—N2A—H11B | 109.0 (13) |
C5A—C6A—C7A | 106.15 (12) | H11A—N2A—H11B | 106.3 (18) |
O2A—C6A—H6A | 115.4 | C10B—N2B—H11C | 107.2 (13) |
C5A—C6A—H6A | 115.4 | C10B—N2B—H11D | 105.9 (14) |
C7A—C6A—H6A | 115.4 | H11C—N2B—H11D | 109.0 (18) |
O2B—C3B—C4B | 101.94 (13) | C3A—O2A—C6A | 95.91 (10) |
O2B—C3B—C2B | 100.73 (11) | C3B—O2B—C6B | 95.97 (11) |
C4B—C3B—C2B | 105.93 (13) | ||
O1A—C1A—C2A—C7A | −179.51 (15) | O2B—C3B—C2B—C7B | 34.90 (14) |
N1A—C1A—C2A—C7A | 2.19 (15) | C4B—C3B—C2B—C7B | −70.95 (14) |
O1A—C1A—C2A—C3A | 72.18 (19) | C2A—C7A—C8A—O3A | 178.38 (14) |
N1A—C1A—C2A—C3A | −106.12 (13) | C6A—C7A—C8A—O3A | −73.16 (18) |
O3B—C8B—C7B—C2B | 179.53 (14) | C2A—C7A—C8A—N1A | −3.32 (15) |
N1B—C8B—C7B—C2B | 0.71 (15) | C6A—C7A—C8A—N1A | 105.14 (13) |
O3B—C8B—C7B—C6B | 71.08 (19) | C7B—C2B—C1B—O1B | 178.86 (15) |
N1B—C8B—C7B—C6B | −107.74 (14) | C3B—C2B—C1B—O1B | −72.5 (2) |
C1A—C2A—C3A—O2A | 74.43 (14) | C7B—C2B—C1B—N1B | −3.73 (15) |
C7A—C2A—C3A—O2A | −36.17 (13) | C3B—C2B—C1B—N1B | 104.86 (14) |
C1A—C2A—C3A—C4A | −179.63 (12) | N1A—C9A—C10A—N2A | −174.08 (13) |
C7A—C2A—C3A—C4A | 69.77 (14) | N1B—C9B—C10B—N2B | 172.66 (14) |
C8B—C7B—C6B—O2B | 72.99 (14) | O3A—C8A—N1A—C1A | −176.58 (13) |
C2B—C7B—C6B—O2B | −37.46 (14) | C7A—C8A—N1A—C1A | 5.05 (16) |
C8B—C7B—C6B—C5B | 178.53 (13) | O3A—C8A—N1A—C9A | 1.2 (2) |
C2B—C7B—C6B—C5B | 68.07 (14) | C7A—C8A—N1A—C9A | −177.21 (12) |
O2A—C3A—C4A—C5A | 32.38 (15) | O1A—C1A—N1A—C8A | 177.01 (14) |
C2A—C3A—C4A—C5A | −72.54 (15) | C2A—C1A—N1A—C8A | −4.61 (16) |
O2B—C6B—C5B—C4B | 31.39 (16) | O1A—C1A—N1A—C9A | −0.8 (2) |
C7B—C6B—C5B—C4B | −73.11 (16) | C2A—C1A—N1A—C9A | 177.59 (12) |
C3A—C4A—C5A—C6A | −0.51 (16) | C10A—C9A—N1A—C8A | −93.08 (16) |
C6B—C5B—C4B—C3B | 0.50 (18) | C10A—C9A—N1A—C1A | 84.46 (16) |
C4A—C5A—C6A—O2A | −31.43 (15) | O1B—C1B—N1B—C8B | −178.00 (14) |
C4A—C5A—C6A—C7A | 73.40 (15) | C2B—C1B—N1B—C8B | 4.48 (16) |
C5B—C4B—C3B—O2B | −32.42 (16) | O1B—C1B—N1B—C9B | 0.1 (2) |
C5B—C4B—C3B—C2B | 72.55 (16) | C2B—C1B—N1B—C9B | −177.36 (12) |
C1A—C2A—C7A—C8A | 0.67 (14) | O3B—C8B—N1B—C1B | 177.87 (13) |
C3A—C2A—C7A—C8A | 115.74 (12) | C7B—C8B—N1B—C1B | −3.27 (16) |
C1A—C2A—C7A—C6A | −115.15 (12) | O3B—C8B—N1B—C9B | −0.2 (2) |
C3A—C2A—C7A—C6A | −0.08 (13) | C7B—C8B—N1B—C9B | 178.66 (12) |
O2A—C6A—C7A—C8A | −74.40 (14) | C10B—C9B—N1B—C1B | −79.01 (17) |
C5A—C6A—C7A—C8A | 179.74 (12) | C10B—C9B—N1B—C8B | 98.90 (17) |
O2A—C6A—C7A—C2A | 36.24 (13) | C4A—C3A—O2A—C6A | −49.59 (12) |
C5A—C6A—C7A—C2A | −69.62 (14) | C2A—C3A—O2A—C6A | 59.87 (12) |
C8B—C7B—C2B—C1B | 1.77 (14) | C5A—C6A—O2A—C3A | 49.24 (12) |
C6B—C7B—C2B—C1B | 117.39 (12) | C7A—C6A—O2A—C3A | −59.95 (12) |
C8B—C7B—C2B—C3B | −114.03 (12) | C4B—C3B—O2B—C6B | 49.64 (13) |
C6B—C7B—C2B—C3B | 1.59 (14) | C2B—C3B—O2B—C6B | −59.36 (12) |
O2B—C3B—C2B—C1B | −76.04 (14) | C5B—C6B—O2B—C3B | −49.14 (13) |
C4B—C3B—C2B—C1B | 178.11 (13) | C7B—C6B—O2B—C3B | 60.42 (12) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2A—H11A···O3Ai | 0.95 (2) | 2.42 (2) | 3.3599 (18) | 169.1 (18) |
N2A—H11B···O2B | 0.89 (2) | 2.33 (2) | 3.1480 (18) | 151.8 (17) |
N2B—H11C···O3Bii | 0.92 (2) | 2.30 (2) | 3.2175 (19) | 174.4 (18) |
N2B—H11D···O2A | 0.93 (2) | 2.45 (2) | 3.2838 (19) | 148.7 (19) |
C2B—H2B···O1Biii | 0.98 | 2.52 | 3.408 (2) | 151 |
Symmetry codes: (i) x, y+1, z; (ii) x, y−1, z; (iii) −x+1, −y+1, −z. |
Experimental details
(II) | (IV) | |
Crystal data | ||
Chemical formula | C11H12N2O2 | C10H12N2O3 |
Mr | 204.23 | 208.22 |
Crystal system, space group | Monoclinic, P21/c | Monoclinic, P21/c |
Temperature (K) | 100 | 153 |
a, b, c (Å) | 4.916 (2), 8.998 (3), 21.604 (6) | 17.840 (2), 6.8747 (6), 16.2125 (17) |
β (°) | 94.445 (7) | 102.419 (5) |
V (Å3) | 952.8 (6) | 1941.9 (3) |
Z | 4 | 8 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.10 | 0.11 |
Crystal size (mm) | 0.38 × 0.14 × 0.09 | 0.48 × 0.25 × 0.07 |
Data collection | ||
Diffractometer | Rigaku AFC12 with Saturn 724+ CCD area-detector diffractometer | Rigaku Mercury2 diffractometer |
Absorption correction | Multi-scan (ABSCOR; Higashi, 1999) | Multi-scan (ABSCOR; Higashi, 1999) |
Tmin, Tmax | 0.822, 1.000 | 0.923, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 21174, 2193, 2031 | 19826, 4439, 3478 |
Rint | 0.031 | 0.033 |
(sin θ/λ)max (Å−1) | 0.649 | 0.649 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.037, 0.100, 1.05 | 0.046, 0.125, 1.07 |
No. of reflections | 2193 | 4439 |
No. of parameters | 136 | 287 |
H-atom treatment | H-atom parameters constrained | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.36, −0.18 | 0.22, −0.22 |
Computer programs: CrystalClear (Rigaku, 2008), SIR97 (Altomare et al., 1999) within WinGX (Farrugia, 2012), ORTEP-3 (Farrugia, 2012), SHELXL97 (Sheldrick, 2008) and publCIF (Westrip, 2010).
C1—C2 | 1.5100 (17) | N1—C8 | 1.3722 (16) |
C2—C7 | 1.5485 (15) | O2—C8 | 1.2212 (15) |
C7—C8 | 1.5147 (16) | ||
C1—C2—C7 | 104.45 (9) | N1—C8—C7 | 108.68 (10) |
C2—C7—C8 | 104.99 (9) | C8—N1—C1 | 113.35 (9) |
O2—C8—C7 | 126.84 (11) | N1—C1—C2 | 108.46 (9) |
O2—C8—N1 | 124.47 (11) |
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3···N2i | 0.98 | 2.613 | 3.570 (4) | 165.1 |
C6—H6···O2ii | 0.98 | 2.475 | 3.3421 (19) | 147.4 |
C7—H7···O1iii | 0.98 | 2.320 | 3.2040 (18) | 150.2 |
C10—H10B···O2iv | 0.97 | 2.534 | 3.393 (4) | 147.6 |
Symmetry codes: (i) −x, −y, −z+1; (ii) −x+1, y−1/2, −z+1/2; (iii) x+1, y, z; (iv) −x, y+1/2, −z+1/2. |
C1A—C2A | 1.509 (2) | C8A—N1A | 1.3858 (19) |
C2A—C7A | 1.547 (2) | C8A—O3A | 1.2197 (18) |
C7A—C8A | 1.518 (2) | C1A—N1A | 1.3877 (19) |
C1A—C2A—C7A | 104.74 (12) | N1A—C8A—C7A | 108.63 (12) |
C8A—C7A—C2A | 104.56 (11) | C8A—N1A—C1A | 112.94 (12) |
O3A—C8A—C7A | 127.27 (14) | N1A—C1A—C2A | 108.91 (12) |
O3A—C8A—N1A | 124.08 (14) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2A—H11A···O3Ai | 0.95 (2) | 2.42 (2) | 3.3599 (18) | 169.1 (18) |
N2A—H11B···O2B | 0.89 (2) | 2.33 (2) | 3.1480 (18) | 151.8 (17) |
N2B—H11C···O3Bii | 0.92 (2) | 2.30 (2) | 3.2175 (19) | 174.4 (18) |
N2B—H11D···O2A | 0.93 (2) | 2.45 (2) | 3.2838 (19) | 148.7 (19) |
C2B—H2B···O1Biii | 0.98 | 2.52 | 3.408 (2) | 151.1 |
Symmetry codes: (i) x, y+1, z; (ii) x, y−1, z; (iii) −x+1, −y+1, −z. |
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3,4,6a,7,10,10a-Hexahydro-7,10-epoxypyrimido[2,1-a]isoindol-6(2H)-one, (II), is an important intermediate in the synthesis of phloeodictine A1, which has been shown to have antimicrobial properties (Neubert & Snider, 2003), as well as exhibiting significant cytotoxicity towards KB human nasopharyngeal carcinoma cells (Kourany-Lefoll et al., 1992). Additionally, cyclic amidines are commonly used in medicinal chemistry (Hellal et al., 2006). However, despite these important applications, the crystal structures of these compounds have not been well studied. In this work, 2-(2-aminoethyl)-3a,4,7,7a-tetrahydro-1H-4,7-epoxyisoindole-1,3(2H)-dione, (IV), serves as a model for understanding the preferential formation of the cyclic compound, (II), via intramolecular condensation over the homologous acyclic precursor 2-(3-aminopropyl)-3a,4,7,7a-tetrahydro-1H-4,7-epoxyisoindole-1,3(2H)-dione, (III) (see scheme), and for probing how the formation of the amidine ring influences the structural and electronic properties of this biologically relevant molecule.
In initial work focused on preparing (III) from (I) (see scheme), 1H NMR data indicated a break in symmetry between atoms H3 and H6 and between atoms H2 and H7. This suggested that the proton coupling could be affected by hydrogen bonding between the amine H atoms and one of the carbonyl O atoms, or that the actual structure differed from theoretical expectations altogether. Mass spectrometry was used to probe the first hypothesis and revealed that H2O elimination had occurred, indicating that the desired product was not obtained. However, through single-crystal X-ray crystallography, we were able to identify the material as compound (II), an unexpected yet interesting product of the reaction. Notably, model compound (IV) was easily obtained by substituting ethylenediamine for propane-1,3-diamine during the synthesis, demonstrating that the longer carbon chain is required for facile formation of the amidine ring.
Compound (IV) contains two molecules in the asymmetric unit, which are hydrogen-bonded dimers with a noncrystallographic inversion center at x = 1/4, y = 0.53 (near 1/2) and z = 0.12 (near 1/8). Molecules (IVA) and (IVB) are nearly identical, with the exception of the C3—C4 bond lengths [C3A—C4A = 1.518 (2) Å and C3B—C4B = 1.509 (2) Å]. When comparing this bond with the analogous C5—C6 bonds, molecules (IVA) and (IVB) both have a bond length of 1.517 (2) Å. Looking at the molecule of (II), the C3—C4 bond length is 1.5185 (17) Å. This leads us to believe that C3B—C4B has undergone some distortion.
With the exception of C3B—C4B, the bond lengths and angles in the bicyclic ring for both (II) and (IV) agree with previously reported compounds containing the same functionality (Trujillo-Ferrara et al., 2004; Tan et al., 2012). Therefore, further discussion will focus on the amidine and central five-membered rings. However, it is also important to note that the bicyclic ring, with inherent internal ring strain, gives the molecules ROMP (ring-opening metathesis polymerization) reactivity, making these compounds available for uses in polymer chemistry (Trnka & Grubbs, 2001; Runge & Bowden, 2007).
When comparing the angles and bond lengths of the central five-membered ring of (II) (see Table 1) with those of (IV) (see Table 2), it appears that no distortion has occurred due to the formation of the amidine ring. The C7—C8—N1 angle of (II) and the C7A—C8A—N1A angle of (IV) are 108.68 (10) and 108.63 (12)°, respectively. Additionally, the C1—N1—C8 angle in (II) [113.35 (9)°] and the C1A—N1A—C8A angle in (IV) [112.94 (12)°] are approximately equal, supporting the conjecture that little or no distortion has occurred. The N2—C1—N1 angle in (II) is 126.67 (11)°, which is slightly greater than the average N—C═N angle (121.53 °) reported by Kosturkiewicz et al. (1992) for 28 amidine complexes. This is due to the additional flexibility during the formation of the compound, which is not uncommon for ring-fused cyclic amidine complexes. In fact, 2-[(1,3-benzodioxol-5-yl)methylene]-6,7-dihydro-5H-thiazolo[3,2-a]pyrimidin-3-one was reported to have an even larger N—C═N bond angle of 128.46° (Liang, 2004).
In both (II) and (IV), hydrogen bonding dictates the packing structure. In (II), there are no classical hydrogen bonds, but weaker interactions [compared with N—H···O hydrogen bonds in (IV)], such as C—H···O and C—H···N, exist between the molecules. Compound (II) packs in a head-to-tail fashion (see bond d in Fig. 3) with respect to the ether groups, with hydrogen bonding occurring between atoms O1 and H7, while compound (IV) packs in a head-to-head fashion (see bonds a and b in Fig. 4), with hydrogen bonding present between atoms O2A and H11D and between O2B and H11B. This bonding structure causes a stair step in the packing of (II). In (II) (see bonds a–c in Fig. 3), the molecule is inverted in each row, so that bonding occurs in a head-to-head/tail-to-tail fashion, resulting in hydrogen bonding occurring between atoms N2 and H3, between O2 and H6, and between O2 and H10B of adjacent molecules. The bonds between atoms N2 and H3 are significantly closer to linearity, as indicated by the bonding angle (see Table 3), which indicates that these bonds are stronger and therefore dictate the packing structure. In (IV), the bonds closest to linearity are between the carbonyls and the amine H atoms (see Table 4). Hydrogen bonding also occurs between atoms O3B and H11C, and between O3A and H11A (see bonds c and d in Fig. 4).
In addition to affecting the structural properties of (II), the formation of the amidine ring seems to have had notable perturbations on the distribution of charge compared with that of the other ring-fused amidine compounds. The N—C and C═N bond lengths are highly indicative of electron-density distribution across bonds. Previous studies reported the difference between the bond lengths of the analogous N—C and C═N bonds in the amidine rings (Δ bond distance) as, on average, 0.0670 Å for the 28 compounds studied (Kosturkiewicz et al., 1992), while the Δ bond distance in (II) was measured as 0.133 Å. From these data it was concluded that, compared with other ring-fused amidine complexes, (II) exhibits very little delocalization across the N—C and C═N bonds. Kosturkiewicz et al. (1992) speculated that the low level of delocalization is caused by the presence of an R group at the central C atom, which is consistent with the five-membered ring attached to atom C4 in (II). Other cyclic amidines also display large Δ bond distances, including 2-[(1,3-benzodioxol-5-yl)methylene]-6,7-dihydro-5H-thiazolo[3,2-a]pyrimidin-3-one, where the Δ bond distance is 0.131 Å (Liang, 2004).
This large discrepancy in the N—C bond lengths also contributes to the previously discussed higher-than-average N1—C1—N2 angle in the six-membered ring of (II). If there were a higher level of delocalization across the N1—C1—N2 bond, it would be expected that the bond angles of C10—C9—N1 [107.25 (10)°] and N2—C11—C10 [114.08 (10)°] would be equivalent, but this is not the case. The same line of reasoning can be applied when considering the C9—N1—C1 [121.17 (9)°] and C1—N2—C11 [116.62 (11)°] angles.
In conclusion, we have determined that the formation of cyclic compound (II) does not cause noticeable perturbations in the structure of the bicyclic ring or the central five-membered ring, compared with the linear compound, (IV). However, the formation of the cyclic compound does lead to perturbations in the N—C═N bonds, as indicated by the large bond angle and the large discrepancy in bond lengths between the N—C and C═N bonds.