Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270107067108/av3132sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270107067108/av3132Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270107067108/av3132IIsup3.hkl |
CCDC references: 681555; 681556
The preparation of the glycoluril monomers (I) and (II) followed a well established methodology (Yin et al., 2006; Li et al., 2006), but ethanol was used as a solvent. When diethoxycarbonyl- or diphenylglycoluril are combined with equivalent ethyl amines in the presence of anhydrous formaldehyde in ethanol at reflux, the expected compounds, the new glycolurils, were obtained in good yields. EtOH and the ethyl amines were freshly distilled. A suspension of diethoxycarbonylglycoluril (1.43 g, 5 mmol) or diphenylglycoluril (1.47 g, 5 mmol) in anhydrous formaldehyde (0.3 g, 10 mmol) and EtOH (50 ml) was brought to reflux under magnetic stirring. A solution of ethylamine (5 mmol) in EtOH (10 ml) was added dropwise (over 1 h) to the mixture. Refluxing was continued for 10–12 h, monitored by thin-layer chromatography. The solvent was removed under reduced pressure and the products were separated by column chromatography (silica gel) in 80% and 50% isolated yields, respectively. Crystals of (I) and (II) suitable for X-ray data collection were obtained by slow evaporation of dichloroethane–methanol solutions (4:1 v/v) at 293 K.
For both (I) and (II), all H atoms bonded to C atoms were initially located in difference Fourier maps and then constrained to their ideal geometry positions, with C—H = 0.96 (methyl) or 0.97 Å (methylene), and with Uiso(H) = 1.5Ueq(methyl C) or 1.2Ueq(methylene C). H atoms bonded to amine N atoms were found in difference maps; the N—H distances were refined freely [Please give range of refined distances] and Uiso(H) = 1.2Ueq(N).
For both compounds, data collection: SMART (Bruker, 2001); cell refinement: SMART (Bruker, 2001); data reduction: SAINT-Plus (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: PLATON (Spek, 2003).
C14H21N5O6 | F(000) = 1504 |
Mr = 355.36 | Dx = 1.358 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 2051 reflections |
a = 23.898 (2) Å | θ = 2.2–22.3° |
b = 10.4791 (9) Å | µ = 0.11 mm−1 |
c = 15.9302 (13) Å | T = 296 K |
β = 119.412 (1)° | Block, colourless |
V = 3475.2 (5) Å3 | 0.20 × 0.20 × 0.10 mm |
Z = 8 |
Bruker SMART APEX CCD area-detector diffractometer | 3061 independent reflections |
Radiation source: fine focus sealed Siemens Mo tube | 2206 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.046 |
0.3° wide ω exposures scans | θmax = 25.0°, θmin = 2.2° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −24→28 |
Tmin = 0.979, Tmax = 0.989 | k = −12→12 |
10973 measured reflections | l = −18→18 |
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)] = 0.069 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.172 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.07 | w = 1/[σ2(Fo2) + (0.0728P)2 + 4.4873P] where P = (Fo2 + 2Fc2)/3 |
3061 reflections | (Δ/σ)max < 0.001 |
236 parameters | Δρmax = 0.22 e Å−3 |
0 restraints | Δρmin = −0.41 e Å−3 |
C14H21N5O6 | V = 3475.2 (5) Å3 |
Mr = 355.36 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 23.898 (2) Å | µ = 0.11 mm−1 |
b = 10.4791 (9) Å | T = 296 K |
c = 15.9302 (13) Å | 0.20 × 0.20 × 0.10 mm |
β = 119.412 (1)° |
Bruker SMART APEX CCD area-detector diffractometer | 3061 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2206 reflections with I > 2σ(I) |
Tmin = 0.979, Tmax = 0.989 | Rint = 0.046 |
10973 measured reflections |
R[F2 > 2σ(F2)] = 0.069 | 0 restraints |
wR(F2) = 0.172 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.07 | Δρmax = 0.22 e Å−3 |
3061 reflections | Δρmin = −0.41 e Å−3 |
236 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 | ||
C1 | 0.17081 (14) | 0.3335 (3) | 0.2399 (2) | 0.0357 (7) | |
C2 | 0.16144 (14) | −0.0151 (3) | 0.2027 (2) | 0.0417 (8) | |
C3 | 0.17397 (14) | 0.1757 (3) | 0.1383 (2) | 0.0369 (7) | |
C4 | 0.17494 (15) | 0.2013 (3) | 0.0443 (2) | 0.0450 (8) | |
C5 | 0.1455 (3) | 0.3511 (6) | −0.0811 (4) | 0.1038 (18) | |
H5A | 0.1715 | 0.4275 | −0.0673 | 0.125* | |
H5B | 0.1643 | 0.2854 | −0.1022 | 0.125* | |
C6 | 0.0812 (4) | 0.3775 (7) | −0.1567 (5) | 0.157 (3) | |
H6A | 0.0558 | 0.3013 | −0.1716 | 0.235* | |
H6B | 0.0823 | 0.4061 | −0.2131 | 0.235* | |
H6C | 0.0626 | 0.4427 | −0.1358 | 0.235* | |
C7 | 0.10693 (13) | 0.1752 (2) | 0.1334 (2) | 0.0352 (7) | |
C8 | 0.05016 (15) | 0.1789 (3) | 0.0301 (2) | 0.0432 (8) | |
C9 | −0.04711 (19) | 0.2766 (4) | −0.0793 (3) | 0.0722 (12) | |
H9A | −0.0754 | 0.2055 | −0.0879 | 0.087* | |
H9B | −0.0341 | 0.2708 | −0.1281 | 0.087* | |
C10 | −0.0806 (3) | 0.3966 (5) | −0.0894 (4) | 0.1050 (17) | |
H10A | −0.0877 | 0.4077 | −0.0355 | 0.158* | |
H10B | −0.1212 | 0.3954 | −0.1480 | 0.158* | |
H10C | −0.0551 | 0.4660 | −0.0915 | 0.158* | |
C11 | 0.07313 (14) | 0.2671 (3) | 0.2454 (2) | 0.0414 (8) | |
H11A | 0.0853 | 0.3351 | 0.2925 | 0.050* | |
H11B | 0.0278 | 0.2771 | 0.1994 | 0.050* | |
C12 | 0.06719 (16) | 0.0436 (3) | 0.2241 (3) | 0.0485 (8) | |
H12A | 0.0219 | 0.0485 | 0.1766 | 0.058* | |
H12B | 0.0748 | −0.0383 | 0.2564 | 0.058* | |
C13 | 0.14668 (17) | 0.1292 (4) | 0.3792 (3) | 0.0594 (10) | |
H13A | 0.1791 | 0.1533 | 0.3623 | 0.071* | |
H13B | 0.1531 | 0.0399 | 0.3976 | 0.071* | |
C14 | 0.1555 (3) | 0.2066 (6) | 0.4628 (3) | 0.1041 (17) | |
H14A | 0.1538 | 0.2956 | 0.4474 | 0.156* | |
H14B | 0.1964 | 0.1873 | 0.5176 | 0.156* | |
H14C | 0.1219 | 0.1871 | 0.4774 | 0.156* | |
N1 | 0.20655 (13) | 0.2775 (2) | 0.2060 (2) | 0.0437 (7) | |
H1 | 0.2470 (17) | 0.302 (3) | 0.222 (2) | 0.052* | |
N2 | 0.19845 (13) | 0.0500 (2) | 0.1748 (2) | 0.0454 (7) | |
H2 | 0.2345 (17) | 0.017 (3) | 0.175 (2) | 0.054* | |
N3 | 0.11016 (11) | 0.2801 (2) | 0.19456 (17) | 0.0345 (6) | |
N4 | 0.10575 (11) | 0.0516 (2) | 0.17482 (19) | 0.0398 (6) | |
N5 | 0.08274 (12) | 0.1450 (2) | 0.2943 (2) | 0.0446 (7) | |
O1 | 0.18833 (10) | 0.41850 (19) | 0.30059 (16) | 0.0477 (6) | |
O2 | 0.17362 (10) | −0.1192 (2) | 0.24359 (18) | 0.0548 (6) | |
O3 | 0.20115 (14) | 0.1339 (3) | 0.0142 (2) | 0.0730 (8) | |
O4 | 0.14544 (13) | 0.3091 (2) | 0.00594 (18) | 0.0666 (7) | |
O5 | 0.04553 (12) | 0.1026 (2) | −0.02871 (18) | 0.0681 (8) | |
O6 | 0.00918 (10) | 0.2715 (2) | 0.01628 (16) | 0.0523 (6) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0301 (16) | 0.0309 (15) | 0.0442 (18) | −0.0038 (13) | 0.0168 (15) | −0.0004 (14) |
C2 | 0.0300 (17) | 0.0315 (16) | 0.064 (2) | 0.0012 (13) | 0.0234 (16) | −0.0026 (15) |
C3 | 0.0285 (16) | 0.0304 (15) | 0.0528 (19) | −0.0008 (12) | 0.0206 (15) | −0.0027 (13) |
C4 | 0.0365 (18) | 0.0437 (18) | 0.057 (2) | −0.0048 (15) | 0.0242 (17) | −0.0041 (16) |
C5 | 0.104 (4) | 0.127 (4) | 0.106 (4) | 0.029 (3) | 0.070 (4) | 0.052 (3) |
C6 | 0.160 (7) | 0.186 (7) | 0.125 (6) | −0.021 (6) | 0.070 (6) | 0.033 (5) |
C7 | 0.0288 (16) | 0.0274 (14) | 0.0503 (18) | −0.0020 (12) | 0.0203 (15) | −0.0023 (13) |
C8 | 0.0307 (17) | 0.0372 (16) | 0.059 (2) | −0.0055 (14) | 0.0205 (16) | −0.0058 (16) |
C9 | 0.053 (2) | 0.081 (3) | 0.056 (2) | 0.012 (2) | 0.007 (2) | 0.006 (2) |
C10 | 0.084 (4) | 0.086 (3) | 0.101 (4) | 0.022 (3) | 0.012 (3) | 0.016 (3) |
C11 | 0.0341 (17) | 0.0364 (16) | 0.058 (2) | 0.0042 (13) | 0.0258 (16) | −0.0016 (14) |
C12 | 0.0385 (19) | 0.0353 (16) | 0.075 (2) | −0.0040 (14) | 0.0301 (18) | 0.0045 (16) |
C13 | 0.052 (2) | 0.066 (2) | 0.057 (2) | 0.0028 (18) | 0.0242 (19) | 0.0156 (19) |
C14 | 0.101 (4) | 0.135 (5) | 0.067 (3) | 0.015 (3) | 0.033 (3) | 0.003 (3) |
N1 | 0.0299 (14) | 0.0444 (15) | 0.0611 (18) | −0.0109 (12) | 0.0257 (14) | −0.0146 (13) |
N2 | 0.0342 (15) | 0.0330 (13) | 0.077 (2) | 0.0057 (12) | 0.0337 (15) | 0.0059 (13) |
N3 | 0.0300 (13) | 0.0263 (11) | 0.0485 (14) | −0.0007 (10) | 0.0203 (12) | −0.0014 (11) |
N4 | 0.0275 (13) | 0.0275 (12) | 0.0678 (17) | 0.0005 (10) | 0.0259 (13) | −0.0003 (12) |
N5 | 0.0358 (15) | 0.0433 (15) | 0.0600 (18) | 0.0016 (12) | 0.0276 (14) | 0.0059 (13) |
O1 | 0.0444 (13) | 0.0397 (12) | 0.0600 (14) | −0.0118 (10) | 0.0264 (11) | −0.0160 (11) |
O2 | 0.0442 (14) | 0.0327 (11) | 0.0909 (18) | 0.0078 (10) | 0.0358 (13) | 0.0141 (12) |
O3 | 0.085 (2) | 0.0712 (17) | 0.086 (2) | 0.0085 (15) | 0.0604 (18) | −0.0081 (15) |
O4 | 0.0718 (18) | 0.0664 (16) | 0.0748 (18) | 0.0185 (14) | 0.0463 (15) | 0.0265 (14) |
O5 | 0.0523 (16) | 0.0684 (16) | 0.0658 (16) | −0.0008 (13) | 0.0152 (13) | −0.0293 (14) |
O6 | 0.0377 (13) | 0.0538 (13) | 0.0491 (14) | 0.0078 (11) | 0.0088 (11) | 0.0011 (11) |
C1—O1 | 1.226 (3) | C9—O6 | 1.456 (4) |
C1—N1 | 1.349 (4) | C9—C10 | 1.457 (6) |
C1—N3 | 1.381 (4) | C9—H9A | 0.9700 |
C2—O2 | 1.230 (3) | C9—H9B | 0.9700 |
C2—N2 | 1.353 (4) | C10—H10A | 0.9600 |
C2—N4 | 1.370 (4) | C10—H10B | 0.9600 |
C3—N2 | 1.443 (4) | C10—H10C | 0.9600 |
C3—N1 | 1.443 (4) | C11—N5 | 1.456 (4) |
C3—C4 | 1.532 (5) | C11—N3 | 1.470 (4) |
C3—C7 | 1.565 (4) | C11—H11A | 0.9700 |
C4—O3 | 1.190 (4) | C11—H11B | 0.9700 |
C4—O4 | 1.313 (4) | C12—N5 | 1.452 (4) |
C5—C6 | 1.439 (8) | C12—N4 | 1.478 (4) |
C5—O4 | 1.455 (5) | C12—H12A | 0.9700 |
C5—H5A | 0.9700 | C12—H12B | 0.9700 |
C5—H5B | 0.9700 | C13—N5 | 1.470 (4) |
C6—H6A | 0.9600 | C13—C14 | 1.483 (6) |
C6—H6B | 0.9600 | C13—H13A | 0.9700 |
C6—H6C | 0.9600 | C13—H13B | 0.9700 |
C7—N3 | 1.446 (3) | C14—H14A | 0.9600 |
C7—N4 | 1.460 (3) | C14—H14B | 0.9600 |
C7—C8 | 1.536 (4) | C14—H14C | 0.9600 |
C8—O5 | 1.194 (4) | N1—H1 | 0.91 (3) |
C8—O6 | 1.318 (4) | N2—H2 | 0.93 (3) |
O1—C1—N1 | 126.4 (3) | N5—C11—N3 | 113.4 (2) |
O1—C1—N3 | 124.8 (3) | N5—C11—H11A | 108.9 |
N1—C1—N3 | 108.8 (2) | N3—C11—H11A | 108.9 |
O2—C2—N2 | 126.7 (3) | N5—C11—H11B | 108.9 |
O2—C2—N4 | 124.3 (3) | N3—C11—H11B | 108.9 |
N2—C2—N4 | 108.9 (3) | H11A—C11—H11B | 107.7 |
N2—C3—N1 | 114.2 (3) | N5—C12—N4 | 112.1 (2) |
N2—C3—C4 | 110.9 (2) | N5—C12—H12A | 109.2 |
N1—C3—C4 | 109.9 (2) | N4—C12—H12A | 109.2 |
N2—C3—C7 | 102.7 (2) | N5—C12—H12B | 109.2 |
N1—C3—C7 | 101.7 (2) | N4—C12—H12B | 109.2 |
C4—C3—C7 | 117.3 (2) | H12A—C12—H12B | 107.9 |
O3—C4—O4 | 126.2 (3) | N5—C13—C14 | 112.9 (3) |
O3—C4—C3 | 123.6 (3) | N5—C13—H13A | 109.0 |
O4—C4—C3 | 110.1 (3) | C14—C13—H13A | 109.0 |
C6—C5—O4 | 110.8 (4) | N5—C13—H13B | 109.0 |
C6—C5—H5A | 109.5 | C14—C13—H13B | 109.0 |
O4—C5—H5A | 109.5 | H13A—C13—H13B | 107.8 |
C6—C5—H5B | 109.5 | C13—C14—H14A | 109.5 |
O4—C5—H5B | 109.5 | C13—C14—H14B | 109.5 |
H5A—C5—H5B | 108.1 | H14A—C14—H14B | 109.5 |
N3—C7—N4 | 112.1 (2) | C13—C14—H14C | 109.5 |
N3—C7—C8 | 115.5 (2) | H14A—C14—H14C | 109.5 |
N4—C7—C8 | 107.7 (2) | H14B—C14—H14C | 109.5 |
N3—C7—C3 | 104.5 (2) | C1—N1—C3 | 114.0 (2) |
N4—C7—C3 | 103.1 (2) | C1—N1—H1 | 124 (2) |
C8—C7—C3 | 113.4 (2) | C3—N1—H1 | 122 (2) |
O5—C8—O6 | 125.9 (3) | C2—N2—C3 | 113.0 (2) |
O5—C8—C7 | 121.1 (3) | C2—N2—H2 | 125 (2) |
O6—C8—C7 | 113.0 (3) | C3—N2—H2 | 122 (2) |
O6—C9—C10 | 108.8 (4) | C1—N3—C7 | 110.8 (2) |
O6—C9—H9A | 109.9 | C1—N3—C11 | 120.7 (2) |
C10—C9—H9A | 109.9 | C7—N3—C11 | 117.0 (2) |
O6—C9—H9B | 109.9 | C2—N4—C7 | 111.6 (2) |
C10—C9—H9B | 109.9 | C2—N4—C12 | 123.9 (3) |
H9A—C9—H9B | 108.3 | C7—N4—C12 | 116.5 (2) |
C9—C10—H10A | 109.5 | C12—N5—C11 | 108.5 (2) |
C9—C10—H10B | 109.5 | C12—N5—C13 | 112.5 (3) |
H10A—C10—H10B | 109.5 | C11—N5—C13 | 114.2 (2) |
C9—C10—H10C | 109.5 | C4—O4—C5 | 116.9 (3) |
H10A—C10—H10C | 109.5 | C8—O6—C9 | 115.5 (3) |
H10B—C10—H10C | 109.5 | ||
N2—C3—C4—O3 | −10.3 (4) | N1—C1—N3—C11 | 147.5 (3) |
N1—C3—C4—O3 | 116.9 (3) | N4—C7—N3—C1 | 105.9 (3) |
C7—C3—C4—O3 | −127.7 (3) | C8—C7—N3—C1 | −130.3 (3) |
N2—C3—C4—O4 | 172.3 (3) | C3—C7—N3—C1 | −5.0 (3) |
N1—C3—C4—O4 | −60.5 (3) | N4—C7—N3—C11 | −37.8 (3) |
C7—C3—C4—O4 | 54.9 (3) | C8—C7—N3—C11 | 86.0 (3) |
N2—C3—C7—N3 | 121.3 (2) | C3—C7—N3—C11 | −148.8 (2) |
N1—C3—C7—N3 | 2.9 (3) | N5—C11—N3—C1 | −91.8 (3) |
C4—C3—C7—N3 | −116.9 (3) | N5—C11—N3—C7 | 48.2 (3) |
N2—C3—C7—N4 | 4.0 (3) | O2—C2—N4—C7 | 176.6 (3) |
N1—C3—C7—N4 | −114.4 (2) | N2—C2—N4—C7 | −5.7 (4) |
C4—C3—C7—N4 | 125.8 (3) | O2—C2—N4—C12 | 28.9 (5) |
N2—C3—C7—C8 | −112.2 (3) | N2—C2—N4—C12 | −153.3 (3) |
N1—C3—C7—C8 | 129.4 (2) | N3—C7—N4—C2 | −111.0 (3) |
C4—C3—C7—C8 | 9.6 (3) | C8—C7—N4—C2 | 120.9 (3) |
N3—C7—C8—O5 | 174.2 (3) | C3—C7—N4—C2 | 0.8 (3) |
N4—C7—C8—O5 | −59.8 (4) | N3—C7—N4—C12 | 39.2 (3) |
C3—C7—C8—O5 | 53.7 (4) | C8—C7—N4—C12 | −88.8 (3) |
N3—C7—C8—O6 | −6.6 (4) | C3—C7—N4—C12 | 151.0 (3) |
N4—C7—C8—O6 | 119.5 (3) | N5—C12—N4—C2 | 95.4 (3) |
C3—C7—C8—O6 | −127.1 (3) | N5—C12—N4—C7 | −50.8 (4) |
O1—C1—N1—C3 | 177.1 (3) | N4—C12—N5—C11 | 57.0 (3) |
N3—C1—N1—C3 | −3.3 (3) | N4—C12—N5—C13 | −70.4 (3) |
N2—C3—N1—C1 | −109.7 (3) | N3—C11—N5—C12 | −56.0 (3) |
C4—C3—N1—C1 | 125.0 (3) | N3—C11—N5—C13 | 70.4 (3) |
C7—C3—N1—C1 | 0.1 (3) | C14—C13—N5—C12 | −162.6 (3) |
O2—C2—N2—C3 | −173.6 (3) | C14—C13—N5—C11 | 73.0 (4) |
N4—C2—N2—C3 | 8.7 (4) | O3—C4—O4—C5 | −0.8 (6) |
N1—C3—N2—C2 | 101.4 (3) | C3—C4—O4—C5 | 176.5 (4) |
C4—C3—N2—C2 | −133.9 (3) | C6—C5—O4—C4 | 127.1 (5) |
C7—C3—N2—C2 | −7.8 (3) | O5—C8—O6—C9 | 1.6 (5) |
O1—C1—N3—C7 | −175.1 (3) | C7—C8—O6—C9 | −177.6 (3) |
N1—C1—N3—C7 | 5.3 (3) | C10—C9—O6—C8 | −168.8 (4) |
O1—C1—N3—C11 | −32.9 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2···O1i | 0.93 (3) | 1.98 (4) | 2.886 (3) | 166 (3) |
N1—H1···O2ii | 0.91 (3) | 1.89 (4) | 2.786 (3) | 170 (3) |
C13—H13B···O3iii | 0.97 | 2.45 | 3.342 (4) | 153 |
Symmetry codes: (i) −x+1/2, y−1/2, −z+1/2; (ii) −x+1/2, y+1/2, −z+1/2; (iii) x, −y, z+1/2. |
C20H21N5O2 | F(000) = 768 |
Mr = 363.42 | Dx = 1.358 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 2090 reflections |
a = 8.0724 (5) Å | θ = 2.6–21.4° |
b = 11.6462 (7) Å | µ = 0.09 mm−1 |
c = 19.2338 (12) Å | T = 295 K |
β = 100.462 (1)° | Block, colourless |
V = 1778.16 (19) Å3 | 0.20 × 0.20 × 0.10 mm |
Z = 4 |
Bruker SMART APEX CCD area-detector diffractometer | 3860 independent reflections |
Radiation source: fine focus sealed Siemens Mo tube | 2581 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.058 |
0.3° wide ω exposures scans | θmax = 27.0°, θmin = 2.1° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −10→9 |
Tmin = 0.982, Tmax = 0.991 | k = −14→14 |
16184 measured reflections | l = −24→24 |
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)] = 0.063 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.159 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0709P)2 + 0.4735P] where P = (Fo2 + 2Fc2)/3 |
3860 reflections | (Δ/σ)max < 0.001 |
251 parameters | Δρmax = 0.28 e Å−3 |
0 restraints | Δρmin = −0.21 e Å−3 |
C20H21N5O2 | V = 1778.16 (19) Å3 |
Mr = 363.42 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 8.0724 (5) Å | µ = 0.09 mm−1 |
b = 11.6462 (7) Å | T = 295 K |
c = 19.2338 (12) Å | 0.20 × 0.20 × 0.10 mm |
β = 100.462 (1)° |
Bruker SMART APEX CCD area-detector diffractometer | 3860 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2581 reflections with I > 2σ(I) |
Tmin = 0.982, Tmax = 0.991 | Rint = 0.058 |
16184 measured reflections |
R[F2 > 2σ(F2)] = 0.063 | 0 restraints |
wR(F2) = 0.159 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | Δρmax = 0.28 e Å−3 |
3860 reflections | Δρmin = −0.21 e Å−3 |
251 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 | ||
C1 | 0.6718 (3) | 0.68744 (19) | 0.17062 (11) | 0.0291 (5) | |
C2 | 0.7753 (3) | 0.7129 (2) | 0.11401 (12) | 0.0364 (6) | |
C3 | 0.8332 (3) | 0.8224 (3) | 0.10483 (15) | 0.0554 (8) | |
H3 | 0.8148 | 0.8808 | 0.1355 | 0.066* | |
C4 | 0.9187 (4) | 0.8459 (4) | 0.0501 (2) | 0.0841 (12) | |
H4 | 0.9598 | 0.9194 | 0.0450 | 0.101* | |
C5 | 0.9428 (4) | 0.7610 (5) | 0.0035 (2) | 0.0976 (16) | |
H5 | 0.9982 | 0.7772 | −0.0337 | 0.117* | |
C6 | 0.8854 (4) | 0.6531 (4) | 0.01190 (17) | 0.0835 (12) | |
H6 | 0.9018 | 0.5957 | −0.0198 | 0.100* | |
C7 | 0.8028 (3) | 0.6279 (3) | 0.06721 (13) | 0.0560 (8) | |
H7 | 0.7657 | 0.5535 | 0.0729 | 0.067* | |
C8 | 0.4729 (3) | 0.69466 (18) | 0.14481 (10) | 0.0263 (5) | |
C9 | 0.4133 (3) | 0.73594 (19) | 0.06922 (10) | 0.0279 (5) | |
C10 | 0.3957 (3) | 0.8517 (2) | 0.05468 (12) | 0.0427 (6) | |
H10 | 0.4153 | 0.9046 | 0.0915 | 0.051* | |
C11 | 0.3490 (3) | 0.8901 (3) | −0.01449 (15) | 0.0565 (8) | |
H11 | 0.3381 | 0.9684 | −0.0237 | 0.068* | |
C12 | 0.3189 (3) | 0.8137 (3) | −0.06903 (14) | 0.0591 (8) | |
H12 | 0.2868 | 0.8395 | −0.1153 | 0.071* | |
C13 | 0.3364 (4) | 0.6988 (3) | −0.05513 (13) | 0.0594 (8) | |
H13 | 0.3166 | 0.6464 | −0.0922 | 0.071* | |
C14 | 0.3832 (3) | 0.6596 (2) | 0.01343 (11) | 0.0425 (6) | |
H14 | 0.3945 | 0.5812 | 0.0221 | 0.051* | |
C15 | 0.5532 (3) | 0.8141 (2) | 0.24338 (11) | 0.0341 (5) | |
C16 | 0.5426 (3) | 0.5117 (2) | 0.19058 (10) | 0.0311 (5) | |
C17 | 0.2468 (3) | 0.7614 (2) | 0.20744 (12) | 0.0369 (6) | |
H17A | 0.2318 | 0.8093 | 0.2471 | 0.044* | |
H17B | 0.1707 | 0.7891 | 0.1659 | 0.044* | |
C18 | 0.2402 (3) | 0.5693 (2) | 0.16625 (11) | 0.0344 (5) | |
H18A | 0.1651 | 0.5878 | 0.1223 | 0.041* | |
H18B | 0.2186 | 0.4905 | 0.1782 | 0.041* | |
C19 | 0.2732 (4) | 0.6034 (3) | 0.29320 (12) | 0.0527 (7) | |
H19A | 0.2798 | 0.5202 | 0.2931 | 0.063* | |
H19B | 0.3865 | 0.6332 | 0.3073 | 0.063* | |
C20 | 0.1691 (5) | 0.6403 (4) | 0.34440 (16) | 0.0899 (12) | |
H20A | 0.1698 | 0.7226 | 0.3473 | 0.135* | |
H20B | 0.2140 | 0.6086 | 0.3900 | 0.135* | |
H20C | 0.0557 | 0.6138 | 0.3293 | 0.135* | |
N1 | 0.6980 (3) | 0.76980 (19) | 0.22757 (10) | 0.0407 (5) | |
H1 | 0.797 (3) | 0.809 (2) | 0.2453 (13) | 0.049* | |
N2 | 0.6905 (2) | 0.56991 (18) | 0.19555 (10) | 0.0367 (5) | |
H2 | 0.787 (3) | 0.531 (2) | 0.2024 (12) | 0.044* | |
N3 | 0.4207 (2) | 0.77285 (16) | 0.19596 (9) | 0.0295 (4) | |
N4 | 0.4148 (2) | 0.57886 (15) | 0.15536 (9) | 0.0286 (4) | |
N5 | 0.2025 (2) | 0.64405 (18) | 0.22146 (9) | 0.0369 (5) | |
O1 | 0.5438 (2) | 0.88198 (15) | 0.29134 (8) | 0.0477 (5) | |
O2 | 0.5242 (2) | 0.41385 (15) | 0.21175 (9) | 0.0454 (5) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0238 (12) | 0.0291 (12) | 0.0338 (10) | 0.0020 (9) | 0.0034 (9) | 0.0014 (9) |
C2 | 0.0196 (11) | 0.0481 (16) | 0.0409 (12) | 0.0031 (11) | 0.0035 (9) | 0.0087 (11) |
C3 | 0.0370 (15) | 0.0591 (19) | 0.0693 (17) | −0.0017 (14) | 0.0080 (13) | 0.0240 (15) |
C4 | 0.0405 (19) | 0.113 (3) | 0.100 (3) | 0.001 (2) | 0.0178 (18) | 0.063 (3) |
C5 | 0.041 (2) | 0.187 (5) | 0.071 (2) | 0.029 (3) | 0.0283 (17) | 0.063 (3) |
C6 | 0.061 (2) | 0.141 (4) | 0.0544 (18) | 0.033 (2) | 0.0267 (16) | 0.008 (2) |
C7 | 0.0442 (17) | 0.080 (2) | 0.0469 (15) | 0.0114 (15) | 0.0159 (12) | −0.0048 (14) |
C8 | 0.0246 (11) | 0.0240 (12) | 0.0300 (10) | 0.0004 (9) | 0.0041 (8) | −0.0003 (8) |
C9 | 0.0180 (11) | 0.0334 (13) | 0.0312 (10) | 0.0007 (9) | 0.0018 (8) | 0.0048 (9) |
C10 | 0.0431 (15) | 0.0370 (15) | 0.0452 (13) | −0.0041 (12) | 0.0007 (11) | 0.0103 (11) |
C11 | 0.0476 (17) | 0.0552 (19) | 0.0640 (18) | −0.0046 (14) | 0.0029 (14) | 0.0333 (15) |
C12 | 0.0452 (17) | 0.094 (3) | 0.0379 (14) | −0.0017 (17) | 0.0060 (12) | 0.0263 (16) |
C13 | 0.065 (2) | 0.084 (3) | 0.0302 (13) | 0.0060 (17) | 0.0109 (12) | −0.0034 (13) |
C14 | 0.0494 (16) | 0.0444 (16) | 0.0336 (12) | 0.0058 (13) | 0.0073 (10) | −0.0028 (11) |
C15 | 0.0343 (13) | 0.0328 (13) | 0.0342 (11) | −0.0013 (11) | 0.0030 (10) | −0.0034 (10) |
C16 | 0.0322 (13) | 0.0300 (13) | 0.0318 (10) | 0.0029 (10) | 0.0076 (9) | 0.0054 (9) |
C17 | 0.0295 (13) | 0.0428 (15) | 0.0389 (12) | 0.0060 (11) | 0.0075 (10) | −0.0016 (10) |
C18 | 0.0269 (12) | 0.0353 (14) | 0.0402 (12) | −0.0024 (10) | 0.0037 (10) | 0.0060 (10) |
C19 | 0.0546 (18) | 0.064 (2) | 0.0408 (13) | 0.0025 (15) | 0.0123 (12) | 0.0127 (12) |
C20 | 0.112 (3) | 0.112 (3) | 0.0503 (17) | 0.010 (3) | 0.0277 (18) | 0.0061 (19) |
N1 | 0.0271 (11) | 0.0489 (14) | 0.0448 (11) | −0.0057 (10) | 0.0030 (9) | −0.0178 (10) |
N2 | 0.0231 (11) | 0.0353 (12) | 0.0503 (11) | 0.0057 (9) | 0.0033 (9) | 0.0109 (9) |
N3 | 0.0251 (10) | 0.0308 (11) | 0.0319 (9) | 0.0022 (8) | 0.0039 (8) | −0.0056 (8) |
N4 | 0.0239 (10) | 0.0271 (11) | 0.0338 (9) | 0.0007 (8) | 0.0026 (7) | 0.0051 (8) |
N5 | 0.0296 (11) | 0.0445 (13) | 0.0376 (10) | 0.0007 (9) | 0.0092 (8) | 0.0058 (9) |
O1 | 0.0473 (11) | 0.0506 (12) | 0.0442 (9) | −0.0006 (9) | 0.0056 (8) | −0.0220 (8) |
O2 | 0.0406 (10) | 0.0374 (11) | 0.0585 (10) | 0.0057 (8) | 0.0101 (8) | 0.0193 (8) |
C1—N1 | 1.442 (3) | C13—C14 | 1.382 (3) |
C1—N2 | 1.449 (3) | C13—H13 | 0.9300 |
C1—C2 | 1.517 (3) | C14—H14 | 0.9300 |
C1—C8 | 1.594 (3) | C15—O1 | 1.227 (3) |
C2—C3 | 1.381 (4) | C15—N3 | 1.361 (3) |
C2—C7 | 1.383 (4) | C15—N1 | 1.361 (3) |
C3—C4 | 1.386 (4) | C16—O2 | 1.229 (3) |
C3—H3 | 0.9300 | C16—N2 | 1.361 (3) |
C4—C5 | 1.372 (6) | C16—N4 | 1.371 (3) |
C4—H4 | 0.9300 | C17—N5 | 1.451 (3) |
C5—C6 | 1.358 (6) | C17—N3 | 1.467 (3) |
C5—H5 | 0.9300 | C17—H17A | 0.9700 |
C6—C7 | 1.386 (4) | C17—H17B | 0.9700 |
C6—H6 | 0.9300 | C18—N5 | 1.447 (3) |
C7—H7 | 0.9300 | C18—N4 | 1.466 (3) |
C8—N4 | 1.454 (3) | C18—H18A | 0.9700 |
C8—N3 | 1.458 (3) | C18—H18B | 0.9700 |
C8—C9 | 1.524 (3) | C19—C20 | 1.470 (4) |
C9—C10 | 1.379 (3) | C19—N5 | 1.472 (3) |
C9—C14 | 1.380 (3) | C19—H19A | 0.9700 |
C10—C11 | 1.389 (3) | C19—H19B | 0.9700 |
C10—H10 | 0.9300 | C20—H20A | 0.9600 |
C11—C12 | 1.363 (4) | C20—H20B | 0.9600 |
C11—H11 | 0.9300 | C20—H20C | 0.9600 |
C12—C13 | 1.367 (4) | N1—H1 | 0.93 (3) |
C12—H12 | 0.9300 | N2—H2 | 0.89 (3) |
N1—C1—N2 | 112.64 (18) | C13—C14—H14 | 119.7 |
N1—C1—C2 | 113.02 (19) | O1—C15—N3 | 125.6 (2) |
N2—C1—C2 | 112.63 (18) | O1—C15—N1 | 125.8 (2) |
N1—C1—C8 | 101.63 (16) | N3—C15—N1 | 108.55 (19) |
N2—C1—C8 | 101.02 (17) | O2—C16—N2 | 126.6 (2) |
C2—C1—C8 | 114.87 (16) | O2—C16—N4 | 124.6 (2) |
C3—C2—C7 | 118.7 (2) | N2—C16—N4 | 108.81 (19) |
C3—C2—C1 | 121.1 (2) | N5—C17—N3 | 112.84 (19) |
C7—C2—C1 | 120.1 (2) | N5—C17—H17A | 109.0 |
C2—C3—C4 | 120.4 (3) | N3—C17—H17A | 109.0 |
C2—C3—H3 | 119.8 | N5—C17—H17B | 109.0 |
C4—C3—H3 | 119.8 | N3—C17—H17B | 109.0 |
C5—C4—C3 | 120.2 (4) | H17A—C17—H17B | 107.8 |
C5—C4—H4 | 119.9 | N5—C18—N4 | 113.27 (18) |
C3—C4—H4 | 119.9 | N5—C18—H18A | 108.9 |
C6—C5—C4 | 119.8 (3) | N4—C18—H18A | 108.9 |
C6—C5—H5 | 120.1 | N5—C18—H18B | 108.9 |
C4—C5—H5 | 120.1 | N4—C18—H18B | 108.9 |
C5—C6—C7 | 120.6 (4) | H18A—C18—H18B | 107.7 |
C5—C6—H6 | 119.7 | C20—C19—N5 | 111.2 (2) |
C7—C6—H6 | 119.7 | C20—C19—H19A | 109.4 |
C2—C7—C6 | 120.3 (3) | N5—C19—H19A | 109.4 |
C2—C7—H7 | 119.8 | C20—C19—H19B | 109.4 |
C6—C7—H7 | 119.8 | N5—C19—H19B | 109.4 |
N4—C8—N3 | 110.19 (16) | H19A—C19—H19B | 108.0 |
N4—C8—C9 | 111.82 (16) | C19—C20—H20A | 109.5 |
N3—C8—C9 | 111.53 (17) | C19—C20—H20B | 109.5 |
N4—C8—C1 | 103.87 (16) | H20A—C20—H20B | 109.5 |
N3—C8—C1 | 102.77 (15) | C19—C20—H20C | 109.5 |
C9—C8—C1 | 116.06 (16) | H20A—C20—H20C | 109.5 |
C10—C9—C14 | 118.3 (2) | H20B—C20—H20C | 109.5 |
C10—C9—C8 | 120.33 (19) | C15—N1—C1 | 114.12 (19) |
C14—C9—C8 | 121.3 (2) | C15—N1—H1 | 116.8 (16) |
C9—C10—C11 | 120.6 (2) | C1—N1—H1 | 126.8 (15) |
C9—C10—H10 | 119.7 | C16—N2—C1 | 114.20 (18) |
C11—C10—H10 | 119.7 | C16—N2—H2 | 119.4 (17) |
C12—C11—C10 | 120.4 (3) | C1—N2—H2 | 124.4 (16) |
C12—C11—H11 | 119.8 | C15—N3—C8 | 112.62 (18) |
C10—C11—H11 | 119.8 | C15—N3—C17 | 126.04 (18) |
C11—C12—C13 | 119.4 (2) | C8—N3—C17 | 116.55 (17) |
C11—C12—H12 | 120.3 | C16—N4—C8 | 111.40 (17) |
C13—C12—H12 | 120.3 | C16—N4—C18 | 122.86 (18) |
C12—C13—C14 | 120.7 (3) | C8—N4—C18 | 115.65 (17) |
C12—C13—H13 | 119.6 | C18—N5—C17 | 109.79 (17) |
C14—C13—H13 | 119.6 | C18—N5—C19 | 113.4 (2) |
C9—C14—C13 | 120.6 (3) | C17—N5—C19 | 114.3 (2) |
C9—C14—H14 | 119.7 | ||
N1—C1—C2—C3 | −23.1 (3) | N2—C1—N1—C15 | −101.6 (2) |
N2—C1—C2—C3 | −152.1 (2) | C2—C1—N1—C15 | 129.4 (2) |
C8—C1—C2—C3 | 92.9 (3) | C8—C1—N1—C15 | 5.7 (2) |
N1—C1—C2—C7 | 161.6 (2) | O2—C16—N2—C1 | −175.6 (2) |
N2—C1—C2—C7 | 32.5 (3) | N4—C16—N2—C1 | 6.5 (2) |
C8—C1—C2—C7 | −82.4 (3) | N1—C1—N2—C16 | 106.0 (2) |
C7—C2—C3—C4 | −0.6 (4) | C2—C1—N2—C16 | −124.7 (2) |
C1—C2—C3—C4 | −176.0 (2) | C8—C1—N2—C16 | −1.7 (2) |
C2—C3—C4—C5 | 1.6 (4) | O1—C15—N3—C8 | 179.3 (2) |
C3—C4—C5—C6 | −1.2 (5) | N1—C15—N3—C8 | 0.8 (3) |
C4—C5—C6—C7 | −0.1 (5) | O1—C15—N3—C17 | −26.3 (4) |
C3—C2—C7—C6 | −0.7 (4) | N1—C15—N3—C17 | 155.3 (2) |
C1—C2—C7—C6 | 174.7 (2) | N4—C8—N3—C15 | 112.8 (2) |
C5—C6—C7—C2 | 1.0 (5) | C9—C8—N3—C15 | −122.4 (2) |
N1—C1—C8—N4 | −119.56 (17) | C1—C8—N3—C15 | 2.6 (2) |
N2—C1—C8—N4 | −3.42 (19) | N4—C8—N3—C17 | −44.3 (2) |
C2—C1—C8—N4 | 118.06 (19) | C9—C8—N3—C17 | 80.5 (2) |
N1—C1—C8—N3 | −4.7 (2) | C1—C8—N3—C17 | −154.46 (17) |
N2—C1—C8—N3 | 111.44 (17) | N5—C17—N3—C15 | −103.2 (2) |
C2—C1—C8—N3 | −127.07 (19) | N5—C17—N3—C8 | 50.4 (2) |
N1—C1—C8—C9 | 117.3 (2) | O2—C16—N4—C8 | 173.2 (2) |
N2—C1—C8—C9 | −126.58 (19) | N2—C16—N4—C8 | −8.9 (2) |
C2—C1—C8—C9 | −5.1 (3) | O2—C16—N4—C18 | 29.4 (3) |
N4—C8—C9—C10 | 154.5 (2) | N2—C16—N4—C18 | −152.67 (19) |
N3—C8—C9—C10 | 30.6 (3) | N3—C8—N4—C16 | −101.92 (19) |
C1—C8—C9—C10 | −86.6 (3) | C9—C8—N4—C16 | 133.45 (18) |
N4—C8—C9—C14 | −28.5 (3) | C1—C8—N4—C16 | 7.6 (2) |
N3—C8—C9—C14 | −152.4 (2) | N3—C8—N4—C18 | 44.7 (2) |
C1—C8—C9—C14 | 90.4 (3) | C9—C8—N4—C18 | −80.0 (2) |
C14—C9—C10—C11 | −0.1 (4) | C1—C8—N4—C18 | 154.14 (16) |
C8—C9—C10—C11 | 177.0 (2) | N5—C18—N4—C16 | 90.4 (2) |
C9—C10—C11—C12 | 0.3 (4) | N5—C18—N4—C8 | −52.0 (2) |
C10—C11—C12—C13 | −0.5 (4) | N4—C18—N5—C17 | 54.1 (2) |
C11—C12—C13—C14 | 0.3 (4) | N4—C18—N5—C19 | −75.1 (2) |
C10—C9—C14—C13 | −0.1 (4) | N3—C17—N5—C18 | −53.0 (2) |
C8—C9—C14—C13 | −177.1 (2) | N3—C17—N5—C19 | 75.7 (2) |
C12—C13—C14—C9 | 0.0 (4) | C20—C19—N5—C18 | −150.6 (3) |
O1—C15—N1—C1 | 177.0 (2) | C20—C19—N5—C17 | 82.5 (3) |
N3—C15—N1—C1 | −4.5 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2···O1i | 0.89 (3) | 2.20 (3) | 3.043 (3) | 158 (2) |
N1—H1···O2ii | 0.93 (3) | 1.96 (3) | 2.873 (3) | 168 (2) |
C18—H18B···O1iii | 0.97 | 2.62 | 3.370 (3) | 134 (1) |
C17—H17A···O2iv | 0.97 | 2.64 | 3.404 (3) | 135 (1) |
Symmetry codes: (i) −x+3/2, y−1/2, −z+1/2; (ii) −x+3/2, y+1/2, −z+1/2; (iii) −x+1/2, y−1/2, −z+1/2; (iv) −x+1/2, y+1/2, −z+1/2. |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | C14H21N5O6 | C20H21N5O2 |
Mr | 355.36 | 363.42 |
Crystal system, space group | Monoclinic, C2/c | Monoclinic, P21/n |
Temperature (K) | 296 | 295 |
a, b, c (Å) | 23.898 (2), 10.4791 (9), 15.9302 (13) | 8.0724 (5), 11.6462 (7), 19.2338 (12) |
β (°) | 119.412 (1) | 100.462 (1) |
V (Å3) | 3475.2 (5) | 1778.16 (19) |
Z | 8 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.11 | 0.09 |
Crystal size (mm) | 0.20 × 0.20 × 0.10 | 0.20 × 0.20 × 0.10 |
Data collection | ||
Diffractometer | Bruker SMART APEX CCD area-detector diffractometer | Bruker SMART APEX CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.979, 0.989 | 0.982, 0.991 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 10973, 3061, 2206 | 16184, 3860, 2581 |
Rint | 0.046 | 0.058 |
(sin θ/λ)max (Å−1) | 0.595 | 0.639 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.069, 0.172, 1.07 | 0.063, 0.159, 1.04 |
No. of reflections | 3061 | 3860 |
No. of parameters | 236 | 251 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.22, −0.41 | 0.28, −0.21 |
Computer programs: SMART (Bruker, 2001), SAINT-Plus (Bruker, 2001), SHELXS97 (Sheldrick, 1997a), SHELXL97 (Sheldrick, 1997a), PLATON (Spek, 2003).
C1—N1 | 1.349 (4) | C7—N4 | 1.460 (3) |
C1—N3 | 1.381 (4) | C11—N5 | 1.456 (4) |
C2—N2 | 1.353 (4) | C11—N3 | 1.470 (4) |
C2—N4 | 1.370 (4) | C12—N5 | 1.452 (4) |
C3—N2 | 1.443 (4) | C12—N4 | 1.478 (4) |
C3—N1 | 1.443 (4) | C13—N5 | 1.470 (4) |
C7—N3 | 1.446 (3) | ||
N1—C3—C7—N3 | 2.9 (3) | C4—C3—C7—C8 | 9.6 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2···O1i | 0.93 (3) | 1.98 (4) | 2.886 (3) | 166 (3) |
N1—H1···O2ii | 0.91 (3) | 1.89 (4) | 2.786 (3) | 170 (3) |
C13—H13B···O3iii | 0.97 | 2.45 | 3.342 (4) | 153 |
Symmetry codes: (i) −x+1/2, y−1/2, −z+1/2; (ii) −x+1/2, y+1/2, −z+1/2; (iii) x, −y, z+1/2. |
C1—N1 | 1.442 (3) | C16—N4 | 1.371 (3) |
C1—N2 | 1.449 (3) | C17—N5 | 1.451 (3) |
C8—N4 | 1.454 (3) | C17—N3 | 1.467 (3) |
C8—N3 | 1.458 (3) | C18—N5 | 1.447 (3) |
C15—N3 | 1.361 (3) | C18—N4 | 1.466 (3) |
C15—N1 | 1.361 (3) | C19—N5 | 1.472 (3) |
C16—N2 | 1.361 (3) | ||
N1—C1—C8—N3 | −4.7 (2) | C2—C1—C8—C9 | −5.1 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2···O1i | 0.89 (3) | 2.20 (3) | 3.043 (3) | 158 (2) |
N1—H1···O2ii | 0.93 (3) | 1.96 (3) | 2.873 (3) | 168 (2) |
C18—H18B···O1iii | 0.97 | 2.62 | 3.370 (3) | 134 (1) |
C17—H17A···O2iv | 0.97 | 2.64 | 3.404 (3) | 135 (1) |
Symmetry codes: (i) −x+3/2, y−1/2, −z+1/2; (ii) −x+3/2, y+1/2, −z+1/2; (iii) −x+1/2, y−1/2, −z+1/2; (iv) −x+1/2, y+1/2, −z+1/2. |
Glycoluril, a biurea compound known for about 130 years, has established an impressive career as a building block for molecular and supramolecular chemistry during the past two decades. For example, glycoluril derivatives have been used in a variety of applications, including polymer cross-linking (Jacobs et al., 1996), explosives (Yinon et al., 1994), the stabilization of organic compounds against photodegradation (Krause et al., 1997), textile waste stream purification (Karcher et al., 1999) and combinatorial chemistry, and furthermore in the fields of cucurbituril chemistry (Freeman et al., 1981; Kim et al., 2000; Pryor & Rebek, 1999; Lee et al., 2003; Burnett et al., 2003) and anion sensors (Kang et al., 2004; Kang & Kim, 2005). The intriguing structural feature in a number of glycoluril derivatives is the twisting observed about the bridgehead dihedral angle, and the rigid and non-planar glycoluril skeleton, with well defined geometry, is more favourable for constructing a three-dimensional structure, which suggests that glycoluril derivatives have significant potential as building blocks in crystal engineering studies. Rebek and co-workers have reported that achiral glycolurils form chiral hydrogen-bonded ribbons in the solid state, and subsequently observed four complementary hydrogen bonds between sulfamides and ureas linking adjacent hydrogen-bonded ribbons (Johnson et al., 2002, 2003). Isaacs and co-workers have reported similar hydrogen-bonded ribbons in a related syn-protected glycoluril derivative (Wu et al., 2002). One of our laboratory interests is to develop a robust supramolecular synthon based on glycoluril for crystal engineering (Wang et al., 2006; Chen et al., 2007). As part of our research programme aimed at the study of hydogen-bonding interactions involving glycoluril, the present work has been undertaken. We report here the two-dimensional hydrogen-bonded networks formed by two novel glycoluril derivatives, (I) and (II), that adopt an unusual twisted conformation in the solid state (Matta et al., 2000; Li et al., 1994; Duspara et al., 2001).
The molecular structures of (I) and (II) (Fig. 1) are built up from three fused rings, namely two nearly planar imidazole five-membered rings that adopt envelope conformations, with the C═O groups at the flap positions, and one six-membered triazacyclohexane ring that adopts a chair conformation. These rings bear two CO2Et groups in (I) and two Ph groups in (II) on their `convex' faces, respectively. The bond lengths and angles in both compounds are similar to those reported previously (Johnson et al., 2002, 2003; Wu et al., 2002; Wang et al., 2006; Chen et al., 2007). Selected geometric parameters for (I) and (II) are listed in Tables 1 and 3, respectively. The ═O···O═distances are 5.657 (2) Å in (I) and 5.691 (2) Å in (II). All Csp2—N and Csp3—N distances lie in the ranges 1.349 (4)–1.381 (4) and 1.442 (3)–1.478 (4) Å, respectively. Obviously, the N—C(carbonyl) bond distances are much shorter than the other N—C bond distances in the three fused rings, indicating some electron delocalization within these rings. Again, the cis-fused five-membered rings bearing CO2Et or Ph groups enforce their cup-shaped geometry. The angles between the mean planes defined by the five-membered rings are 115.1 (1)° in (I) and 112.9 (1)° in (II). The glycoluril units are both almost coplanar, which is indicated by the key torsion angles [in (I), N1—C3—C7—N3 = 2.9 (3)° and C4—C3—C7—C8 = 9.6 (3)°; in (II), N1—C1—C8—N3 = -4.7 (2)° and C2—C1—C8—C9 = -5.1 (3)°]. These slight differences are thought to be due to the different substitutes on the `convex' faces.
In their supramolecular structures formed via N—H···O and C—H···O hydrogen bonds, the molecules of both (I) and (II) are linked into two-dimensional networks. In (I), the crystal packing can be easily analysed in terms of two simple substructures. In the first substructure, amide atoms N1 and N2 in the molecule at (x, y, z) act as hydrogen-bond donors, via atoms H1 and H2, respectively, to carboxyl atom O2 in the molecule at (-x + 1/2, y + 1/2, -z + 1/2) and atom O1 at (-x + 1/2, y - 1/2, -z + 1/2), both producing one-dimensional chains running parallel to the [010] direction generated by the 21 screw axis at (1/4, y, 1/4). These two types of [010] chains are interlinked by the approximately centrosymmetric R22(8) (Bernstein et al. 1995) hydrogen-bonding motif centred at (0.257, 0.295, 0.249), forming a one-dimensional chain structure along the [010] direction (Fig. 2, Table 2). Four chains of this type pass through each unit cell; two of these, running along the (1/4, y, 1/4) and (3/4, y, 3/4) directions, respectively, are antiparallel to the other two, which run along the (3/4, y, 1/4) and (1/4, y, 3/4) directions, respectively. As reported by Wu et al. (2002), if all the CO2Et groups were located on one side of the molecule, this would lead to cyclic structures for these analogues. We do not observe these cyclic structures in the solid state of (I), which may be due to the unfavourable entropy associated with the formation of cyclic structures. In the second substructure, ethyl atom C13 in the molecule at (x, y, z) acts as a hydrogen-bond donor, via atom H13B, to carboxyl atom O3 in the molecule at (x, -y, z + 1/2), forming the other one-dimensional chain along the [001] direction generated by a c-glide plane at y = 0, which suffices to link the [010] chains into a two-dimensional network (Fig. 3) running parallel to the (100) direction. No direction-specific interactions between adjacent two-dimensional networks are observed.
Similar to compound (I), molecules in compound (II) also form one-dimensional hydrogen-bonded tapes in the solid state along the [010] direction (Fig. 4, Table 4). Structure (II) also can be easily analysed in terms of two one-dimensional substructures. In the first substructure, two amide atoms, N1 and N2, in the molecule at (x, y, z) act as hydrogen-bond donors, via atoms H1 and H2, respectively, to carboxyl atom O2 in the molecule at (-x + 3/2, y + 1/2, -z + 1/2) and atom O1 at (-x + 3/2, y - 1/2, -z + 1/2), both producing one-dimensional chains running parallel to the [010] direction generated by the 21 screw axis at (3/4, y, 3/4). These two type [010] chains are interlinked by the approximately centrosymmetric R22(8) (Bernstein et al. 1995) hydrogen-bonding motif centred at (0.966, 0.400, 0.279), forming a one-dimensional chain structure along the [010] direction. In comparison with the formation of the four chains in each unit cell in compound (I), only two one-dimensional chains pass through each unit cell in (II); these two chains run along the (3/4, y, 1/4) and (1/4, y, 3/4) directions, respectively. The second substructure is constructed by C—H···O hydrogen bonds. Methylene atoms C17 and C18 in the molecule at (x, y, z) act as hydrogen-bond donors, via atoms H17A and H18B, respectively, to carboxyl atom O2 in the molecule at (-x + 1/2, y + 1/2, -z + 1/2) and atom O1 at (-x + 1/2, y - 1/2, -z + 1/2), forming the other one-dimensional tape along the [100] direction, which suffices to link the [010] tapes into a two-dimensional network running parallel to the (001) direction (Fig. 5). There are no direction-specific interactions between adjacent two-dimensional frameworks in (II) either.
As noted above, the same one-dimensional hydrogen-bonded chains along the [010] direction are found here for (I) and (II). This may be ascribed to the same motifs of these two novel glycoluril derivatives, which both bear two free syn-urea N—H groups and two ureidyl C═O. The C—H···O hydrogen bonds {along the [001] direction in (I) and along the [100] direction in (II)} link these one-dimensional helical chains into two-dimensional networks.