Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807035684/pv2017sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807035684/pv2017Isup2.hkl |
CCDC reference: 660329
Key indicators
- Single-crystal X-ray study
- T = 291 K
- Mean (C-C) = 0.003 Å
- R factor = 0.052
- wR factor = 0.139
- Data-to-parameter ratio = 14.3
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical . ? PLAT480_ALERT_4_C Long H...A H-Bond Reported H8B .. O1 .. 2.71 Ang. PLAT480_ALERT_4_C Long H...A H-Bond Reported H7A .. O1 .. 2.71 Ang.
Alert level G PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 78
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 3 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 1 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 1 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
Into a three-necked round-bottomed flask equipped with a mechanical stirrer were introduced dienamine, (I), (28.4 g, 0.1 mol), ethanol (95%, 50 ml) and glyoxal (18 g, 40%). The mixture was then heated at about 333 K with stirring for 30 min under an inert atmosphere. Natural cooling of the reaction mixture overnight gave a crystalline product (yield: 18%). which was recrystallized from ethyl acetate. Single crystals of (II) were obtained by cooling of the hot solution of the above product in ethyl acetate very slowly over one week. 1HNMR(CDCl3, 400 MHz): δ 4.17 (q, J = 7.2 Hz, 4H, 2CH2), δ 3.66 (s, 4H, 2CH2), δ 3.23 (q, J = 2.4 Hz, 4H, 2CH2), δ 2.40 (t, J = 2.4 Hz, 6H, 2CH3), δ 1.27 (t, J = 7.2 Hz, 6H, 2CH3).
H atoms were placed in idealized positions and were allowed to ride on the respective parent atoms with C—H = 0.98 Å and N—H = 0.86 Å, and with Uiso(H) = xUeq(carrier atom), where x = 1.2 for C—H and N—H.
The reaction of ethylenediamine with ethyl acetoacetate yields dienamine,(I) (scheme 1), cyclization of which with glyoxal and thereafter rearrangement yields bicyclic pyrrolinone (II). We have reported the structure of the dienamine,(I) (Zhang et al., 2004). We have now prepared several novel ethylenedi(2-pyrrolin-5-one) derivatives (Zhang et al., 2007), but unfortunately, only the title compound, (II) has provided crystals suitable for single-crystal structure determination. We report here the molecular and supramolecular structure of the title compound, (II).
The structural unit in the title compound (Fig. 1) adopts a low-energy anti conformation with torsion angle N1—C4—C4i—N1i [symmetry code: (i) 1 - x,1 - y,1 - z] 180.0 (2)°. The anti-conformation is thought to result from a van der Waals repulsion effect between the two pyrrolinone rings. The pyrrolinone rings are perfectly planar, with a mean deviation of 0.006 Å. The dihedral angle between the planes of the two rings is 0 °, indicating that the two rings are parallel to one another. Within the pyrrolinone rings, there is a clear distinction between single and double bonds. The lengths for C2═C3 and C1═O1 bonds [1.349 (3) and 1.211 (3) Å, respectively] are shorter than the corresponding bonds found in the precursor (I) [1.370 (4) and 1.222 (4) Å, respectively; Zhang et al., 2004]. Conversely, the N1—C3 and C1—C2 bonds are longer [1.411 (3) and 1.459 (3) Å versus 1.342 (4) and 1.439 (4) Å, respectively]. It is also interestingly found that within pyrrolinone rings, the distance of 1.385 Å for N1—C9 is shorter than that of 1.411 Å for N1—C3 bond, indicating that as compared with C3═C2, the C9═O3 bond is in π-π conjugation with the N1 atom. The sum of the three angles around each of the N1, C3 and C2 atoms is 359.98 (2)°, implying that the N6, C3 and C2 atoms take on sp2 hybridization.
In the molecule (II), there are two intramolecular C—H···O hydrogen bonds (Table 1), which, though not strong, contribute to the relatively stable co-planarity for the structural unit O2/C1/C2/C3/C7. This presumably sets the stage in turn for the interactions within the crystal lattice.
The molecules of compound (II) are linked by six independent C—H···O hydrogen bonds (Table 1) into a three-dimensional framework structure, whose formation is rather easily analysed in terms of two simple substructures, one of which is one-dimensional and the other is two-dimensional.
In the one-dimensional substructure, the methylene C8 atom in the pyrrolinone ring acts as a hydrogen-bond donor, via H8B, to the acyl atoms, thus forming the centrosymmetric R22(24) dimer (Bernstein et al., 1995) centred at (0,1/2,1/2); details of hydrogen-bonding geometry has been given in Table 1. Propagation by translation of these two hydrogen bonds generates a C(4) C(4) (Bernstein et al., 1995) hydrogen-bonded chains (column) along the a axis.
The column centred at (0,1/2,1/2) associates further via two independent bifurcated donor hydrogen bonds and two bifurcated acceptor hydrogen bonds with nearby four columns centred at (0,0,0), (0,1,0),(0,0,1) and (0,1,1), respectively. These lateral interactions reinforce structures by adding hydrogen bonds and extending them forming a two-dimensional substructure. The methyl atom C7 acts as a hydrogen-bond donor, via atoms H7A and H7C, to O atoms forming a two-dimensional hydrogen-bonded substructure (details in Table 1). The combination of the one- and two-dimensional substructures suffices to generate the three-dimensional framework structure (Fig. 2).
For related literature, see: Bernstein et al. (1995); Zhang et al. (2004, 2007).
Data collection: SMART (Bruker, YEAR?); cell refinement: SMART; data reduction: SAINT (Bruker, YEAR?); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL.
C18H24N2O6 | F(000) = 388 |
Mr = 364.39 | Dx = 1.306 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 1143 reflections |
a = 4.5403 (10) Å | θ = 2.5–20.9° |
b = 12.418 (3) Å | µ = 0.10 mm−1 |
c = 16.439 (4) Å | T = 291 K |
β = 91.812 (3)° | Block, colourless |
V = 926.4 (4) Å3 | 0.30 × 0.15 × 0.12 mm |
Z = 2 |
Bruker SMART CCD area-detector diffractometer | 1716 independent reflections |
Radiation source: fine-focus sealed tube | 1164 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.032 |
φ and ω scans | θmax = 25.5°, θmin = 2.5° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1997a) | h = −5→5 |
Tmin = 0.971, Tmax = 0.988 | k = −15→14 |
6085 measured reflections | l = −19→19 |
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)] = 0.052 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.139 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0615P)2 + 0.2115P] where P = (Fo2 + 2Fc2)/3 |
1716 reflections | (Δ/σ)max < 0.001 |
120 parameters | Δρmax = 0.17 e Å−3 |
78 restraints | Δρmin = −0.14 e Å−3 |
C18H24N2O6 | V = 926.4 (4) Å3 |
Mr = 364.39 | Z = 2 |
Monoclinic, P21/n | Mo Kα radiation |
a = 4.5403 (10) Å | µ = 0.10 mm−1 |
b = 12.418 (3) Å | T = 291 K |
c = 16.439 (4) Å | 0.30 × 0.15 × 0.12 mm |
β = 91.812 (3)° |
Bruker SMART CCD area-detector diffractometer | 1716 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1997a) | 1164 reflections with I > 2σ(I) |
Tmin = 0.971, Tmax = 0.988 | Rint = 0.032 |
6085 measured reflections |
R[F2 > 2σ(F2)] = 0.052 | 78 restraints |
wR(F2) = 0.139 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.17 e Å−3 |
1716 reflections | Δρmin = −0.14 e Å−3 |
120 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 | 1.1869 (4) | 0.81344 (14) | 0.73896 (11) | 0.0720 (6) | |
O2 | 1.1711 (4) | 0.64213 (13) | 0.78091 (9) | 0.0626 (5) | |
O3 | 0.3884 (4) | 0.74182 (16) | 0.49802 (11) | 0.0807 (6) | |
N1 | 0.5743 (4) | 0.60518 (15) | 0.57889 (11) | 0.0524 (5) | |
C1 | 1.0922 (5) | 0.72278 (18) | 0.73102 (13) | 0.0509 (6) | |
C2 | 0.8829 (5) | 0.69234 (17) | 0.66586 (12) | 0.0472 (5) | |
C3 | 0.7712 (4) | 0.59462 (17) | 0.64654 (12) | 0.0451 (5) | |
C4 | 0.4149 (5) | 0.5203 (2) | 0.53604 (14) | 0.0590 (6) | |
H4A | 0.2245 | 0.5473 | 0.5169 | 0.071* | |
H4B | 0.3813 | 0.4611 | 0.5731 | 0.071* | |
C5 | 1.3733 (6) | 0.6677 (2) | 0.84821 (14) | 0.0687 (7) | |
H5A | 1.2941 | 0.7254 | 0.8808 | 0.082* | |
H5B | 1.5615 | 0.6908 | 0.8280 | 0.082* | |
C6 | 1.4108 (8) | 0.5687 (3) | 0.89787 (18) | 0.1009 (11) | |
H6A | 1.2285 | 0.5517 | 0.9230 | 0.151* | |
H6B | 1.5615 | 0.5803 | 0.9392 | 0.151* | |
H6C | 1.4668 | 0.5101 | 0.8636 | 0.151* | |
C7 | 0.8173 (6) | 0.48586 (17) | 0.68252 (15) | 0.0613 (7) | |
H7A | 0.9800 | 0.4881 | 0.7212 | 0.092* | |
H7B | 0.8593 | 0.4354 | 0.6402 | 0.092* | |
H7C | 0.6425 | 0.4639 | 0.7094 | 0.092* | |
C8 | 0.7540 (5) | 0.77494 (18) | 0.60915 (14) | 0.0566 (6) | |
H8A | 0.9063 | 0.8096 | 0.5784 | 0.068* | |
H8B | 0.6477 | 0.8294 | 0.6387 | 0.068* | |
C9 | 0.5496 (5) | 0.7116 (2) | 0.55439 (14) | 0.0575 (6) |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0810 (13) | 0.0532 (10) | 0.0810 (12) | −0.0135 (9) | −0.0110 (10) | −0.0072 (9) |
O2 | 0.0747 (12) | 0.0589 (10) | 0.0531 (9) | −0.0057 (8) | −0.0155 (8) | −0.0015 (8) |
O3 | 0.0725 (13) | 0.1035 (15) | 0.0649 (11) | 0.0129 (10) | −0.0145 (10) | 0.0175 (10) |
N1 | 0.0479 (11) | 0.0587 (12) | 0.0502 (10) | −0.0034 (9) | −0.0018 (8) | −0.0048 (9) |
C1 | 0.0487 (13) | 0.0517 (14) | 0.0526 (13) | 0.0012 (11) | 0.0036 (10) | −0.0060 (11) |
C2 | 0.0488 (13) | 0.0452 (12) | 0.0476 (11) | −0.0003 (10) | 0.0020 (10) | −0.0016 (10) |
C3 | 0.0407 (12) | 0.0518 (13) | 0.0427 (11) | −0.0015 (10) | 0.0026 (9) | −0.0025 (10) |
C4 | 0.0465 (13) | 0.0757 (17) | 0.0549 (13) | −0.0113 (12) | 0.0001 (10) | −0.0131 (12) |
C5 | 0.0692 (17) | 0.085 (2) | 0.0506 (14) | −0.0030 (14) | −0.0114 (12) | −0.0105 (13) |
C6 | 0.138 (3) | 0.090 (2) | 0.0721 (19) | 0.016 (2) | −0.0422 (19) | −0.0024 (17) |
C7 | 0.0724 (16) | 0.0497 (14) | 0.0615 (14) | −0.0048 (12) | −0.0037 (12) | 0.0025 (11) |
C8 | 0.0581 (15) | 0.0505 (13) | 0.0610 (14) | 0.0040 (11) | 0.0015 (12) | 0.0022 (11) |
C9 | 0.0514 (14) | 0.0681 (16) | 0.0532 (14) | 0.0061 (12) | 0.0037 (11) | 0.0049 (12) |
O1—C1 | 1.211 (3) | C4—H4B | 0.9700 |
O2—C1 | 1.336 (3) | C5—C6 | 1.482 (4) |
O2—C5 | 1.450 (3) | C5—H5A | 0.9700 |
O3—C9 | 1.221 (3) | C5—H5B | 0.9700 |
N1—C9 | 1.385 (3) | C6—H6A | 0.9600 |
N1—C3 | 1.411 (3) | C6—H6B | 0.9600 |
N1—C4 | 1.449 (3) | C6—H6C | 0.9600 |
C1—C2 | 1.459 (3) | C7—H7A | 0.9600 |
C2—C3 | 1.349 (3) | C7—H7B | 0.9600 |
C2—C8 | 1.493 (3) | C7—H7C | 0.9600 |
C3—C7 | 1.487 (3) | C8—C9 | 1.496 (3) |
C4—C4i | 1.521 (4) | C8—H8A | 0.9700 |
C4—H4A | 0.9700 | C8—H8B | 0.9700 |
C1—O2—C5 | 117.06 (18) | C6—C5—H5B | 110.3 |
C9—N1—C3 | 111.19 (18) | H5A—C5—H5B | 108.5 |
C9—N1—C4 | 121.21 (19) | C5—C6—H6A | 109.5 |
C3—N1—C4 | 127.58 (19) | C5—C6—H6B | 109.5 |
O1—C1—O2 | 122.9 (2) | H6A—C6—H6B | 109.5 |
O1—C1—C2 | 122.7 (2) | C5—C6—H6C | 109.5 |
O2—C1—C2 | 114.35 (19) | H6A—C6—H6C | 109.5 |
C3—C2—C1 | 129.6 (2) | H6B—C6—H6C | 109.5 |
C3—C2—C8 | 109.52 (19) | C3—C7—H7A | 109.5 |
C1—C2—C8 | 120.90 (19) | C3—C7—H7B | 109.5 |
C2—C3—N1 | 109.02 (18) | H7A—C7—H7B | 109.5 |
C2—C3—C7 | 132.5 (2) | C3—C7—H7C | 109.5 |
N1—C3—C7 | 118.43 (18) | H7A—C7—H7C | 109.5 |
N1—C4—C4i | 111.2 (2) | H7B—C7—H7C | 109.5 |
N1—C4—H4A | 109.4 | C2—C8—C9 | 103.77 (19) |
C4i—C4—H4A | 109.4 | C2—C8—H8A | 111.0 |
N1—C4—H4B | 109.4 | C9—C8—H8A | 111.0 |
C4i—C4—H4B | 109.4 | C2—C8—H8B | 111.0 |
H4A—C4—H4B | 108.0 | C9—C8—H8B | 111.0 |
O2—C5—C6 | 107.3 (2) | H8A—C8—H8B | 109.0 |
O2—C5—H5A | 110.3 | O3—C9—N1 | 123.7 (2) |
C6—C5—H5A | 110.3 | O3—C9—C8 | 129.8 (2) |
O2—C5—H5B | 110.3 | N1—C9—C8 | 106.47 (19) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
C7—H7A···O2 | 0.96 | 2.31 | 2.966 (4) | 125 |
C8—H8B···O1ii | 0.97 | 2.71 | 3.429 (3) | 131 |
C7—H7C···O1iii | 0.96 | 2.55 | 3.417 (3) | 150 |
C7—H7A···O1iv | 0.96 | 2.71 | 3.337 (3) | 123 |
Symmetry codes: (ii) x−1, y, z; (iii) −x+3/2, y−1/2, −z+3/2; (iv) −x+5/2, y−1/2, −z+3/2. |
Experimental details
Crystal data | |
Chemical formula | C18H24N2O6 |
Mr | 364.39 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 291 |
a, b, c (Å) | 4.5403 (10), 12.418 (3), 16.439 (4) |
β (°) | 91.812 (3) |
V (Å3) | 926.4 (4) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.10 |
Crystal size (mm) | 0.30 × 0.15 × 0.12 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1997a) |
Tmin, Tmax | 0.971, 0.988 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6085, 1716, 1164 |
Rint | 0.032 |
(sin θ/λ)max (Å−1) | 0.606 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.052, 0.139, 1.04 |
No. of reflections | 1716 |
No. of parameters | 120 |
No. of restraints | 78 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.17, −0.14 |
Computer programs: SMART (Bruker, YEAR?), SMART, SAINT (Bruker, SHELXS97 (Sheldrick, 1997a), SHELXL97 (Sheldrick, 1997a), SHELXTL (Sheldrick, 1997b), SHELXTL.
D—H···A | D—H | H···A | D···A | D—H···A |
C7—H7A···O2 | 0.96 | 2.31 | 2.966 (4) | 125 |
C8—H8B···O1i | 0.97 | 2.71 | 3.429 (3) | 131 |
C7—H7C···O1ii | 0.96 | 2.55 | 3.417 (3) | 150 |
C7—H7A···O1iii | 0.96 | 2.71 | 3.337 (3) | 123 |
Symmetry codes: (i) x−1, y, z; (ii) −x+3/2, y−1/2, −z+3/2; (iii) −x+5/2, y−1/2, −z+3/2. |
The reaction of ethylenediamine with ethyl acetoacetate yields dienamine,(I) (scheme 1), cyclization of which with glyoxal and thereafter rearrangement yields bicyclic pyrrolinone (II). We have reported the structure of the dienamine,(I) (Zhang et al., 2004). We have now prepared several novel ethylenedi(2-pyrrolin-5-one) derivatives (Zhang et al., 2007), but unfortunately, only the title compound, (II) has provided crystals suitable for single-crystal structure determination. We report here the molecular and supramolecular structure of the title compound, (II).
The structural unit in the title compound (Fig. 1) adopts a low-energy anti conformation with torsion angle N1—C4—C4i—N1i [symmetry code: (i) 1 - x,1 - y,1 - z] 180.0 (2)°. The anti-conformation is thought to result from a van der Waals repulsion effect between the two pyrrolinone rings. The pyrrolinone rings are perfectly planar, with a mean deviation of 0.006 Å. The dihedral angle between the planes of the two rings is 0 °, indicating that the two rings are parallel to one another. Within the pyrrolinone rings, there is a clear distinction between single and double bonds. The lengths for C2═C3 and C1═O1 bonds [1.349 (3) and 1.211 (3) Å, respectively] are shorter than the corresponding bonds found in the precursor (I) [1.370 (4) and 1.222 (4) Å, respectively; Zhang et al., 2004]. Conversely, the N1—C3 and C1—C2 bonds are longer [1.411 (3) and 1.459 (3) Å versus 1.342 (4) and 1.439 (4) Å, respectively]. It is also interestingly found that within pyrrolinone rings, the distance of 1.385 Å for N1—C9 is shorter than that of 1.411 Å for N1—C3 bond, indicating that as compared with C3═C2, the C9═O3 bond is in π-π conjugation with the N1 atom. The sum of the three angles around each of the N1, C3 and C2 atoms is 359.98 (2)°, implying that the N6, C3 and C2 atoms take on sp2 hybridization.
In the molecule (II), there are two intramolecular C—H···O hydrogen bonds (Table 1), which, though not strong, contribute to the relatively stable co-planarity for the structural unit O2/C1/C2/C3/C7. This presumably sets the stage in turn for the interactions within the crystal lattice.
The molecules of compound (II) are linked by six independent C—H···O hydrogen bonds (Table 1) into a three-dimensional framework structure, whose formation is rather easily analysed in terms of two simple substructures, one of which is one-dimensional and the other is two-dimensional.
In the one-dimensional substructure, the methylene C8 atom in the pyrrolinone ring acts as a hydrogen-bond donor, via H8B, to the acyl atoms, thus forming the centrosymmetric R22(24) dimer (Bernstein et al., 1995) centred at (0,1/2,1/2); details of hydrogen-bonding geometry has been given in Table 1. Propagation by translation of these two hydrogen bonds generates a C(4) C(4) (Bernstein et al., 1995) hydrogen-bonded chains (column) along the a axis.
The column centred at (0,1/2,1/2) associates further via two independent bifurcated donor hydrogen bonds and two bifurcated acceptor hydrogen bonds with nearby four columns centred at (0,0,0), (0,1,0),(0,0,1) and (0,1,1), respectively. These lateral interactions reinforce structures by adding hydrogen bonds and extending them forming a two-dimensional substructure. The methyl atom C7 acts as a hydrogen-bond donor, via atoms H7A and H7C, to O atoms forming a two-dimensional hydrogen-bonded substructure (details in Table 1). The combination of the one- and two-dimensional substructures suffices to generate the three-dimensional framework structure (Fig. 2).