The title compound [systematic name: 1'-aminocyclohexanespiro-4'-imidazole-2',5'(3'H,4'H)-dione], C8H13N3O2, has been synthesized and was found to crystallize in two different structures, both monoclinic and both with the same P21/c space group. In the first structure, there are two molecules in the asymmetric unit, one of which uses all of its hydrogen-bond donors and acceptors and forms undulating layers, while the other forms chains propagating perpendicular to the layers. In the second structure, there is only one independent molecule and the packing is based on a chain structure mediated by hydrogen bonding between the hydantoin moieties and further grouped into hydrophilic layers separated by layers of the hydrophobic cyclohexyl groups.
Supporting information
CCDC references: 282216; 282217
The compound 3-amino-1,3-diazaspiro[4.5]decane-2,4-dione was obtained according to the method of Naydenova et al. (2002). The first polymorph, (I), was obtained by re-crystallization of the title compound from methanol. The second, (II), emerged from a methanol solution containing (I):B(OH)3 (Ratio?) in an attempt to obtain a borate compound.
H atoms attached to the N atoms of polymorph (I) were placed in positions found from the electron-density map and refined with Uiso(H) = 1.2Ueq(N). The rest of the H atoms were placed in idealized positions (C—H = 0.97 Å and N—H = 0.86 Å) and were constrained to ride on their parent atoms, with Uiso(H) = 1.2Ueq(C,N).
For both compounds, data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
(I) 3-amino-1,3-diazaspiro[4.5]decane-2,4-dione or 1'-aminocyclohexanespiro-4'-imidazole-2',5'(3'H,4'H)-dione
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Crystal data top
C8H13N3O2 | F(000) = 784 |
Mr = 183.21 | Dx = 1.364 Mg m−3 |
Monoclinic, P21/c | Melting point: 438 K |
Hall symbol: -P 2ybc | Mo Kα radiation, λ = 0.71073 Å |
a = 14.0813 (13) Å | Cell parameters from 22 reflections |
b = 10.2094 (19) Å | θ = 16.7–17.7° |
c = 12.372 (3) Å | µ = 0.10 mm−1 |
β = 91.621 (14)° | T = 290 K |
V = 1777.9 (6) Å3 | Prism, white |
Z = 8 | 0.24 × 0.21 × 0.12 mm |
Data collection top
Enraf-Nonius CAD-4 diffractometer | Rint = 0.076 |
Radiation source: fine-focus sealed tube | θmax = 26.0°, θmin = 1.5° |
Graphite monochromator | h = −17→17 |
non–profiled ω/2θ scans | k = −12→12 |
7138 measured reflections | l = −15→0 |
3509 independent reflections | 3 standard reflections every 500 reflections |
1946 reflections with I > 2σ(I) | intensity decay: 3% |
Refinement top
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)] = 0.050 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.118 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.99 | w = 1/[σ2(Fo2) + (0.0418P)2] where P = (Fo2 + 2Fc2)/3 |
3509 reflections | (Δ/σ)max < 0.001 |
253 parameters | Δρmax = 0.17 e Å−3 |
0 restraints | Δρmin = −0.22 e Å−3 |
Crystal data top
C8H13N3O2 | V = 1777.9 (6) Å3 |
Mr = 183.21 | Z = 8 |
Monoclinic, P21/c | Mo Kα radiation |
a = 14.0813 (13) Å | µ = 0.10 mm−1 |
b = 10.2094 (19) Å | T = 290 K |
c = 12.372 (3) Å | 0.24 × 0.21 × 0.12 mm |
β = 91.621 (14)° | |
Data collection top
Enraf-Nonius CAD-4 diffractometer | Rint = 0.076 |
7138 measured reflections | 3 standard reflections every 500 reflections |
3509 independent reflections | intensity decay: 3% |
1946 reflections with I > 2σ(I) | |
Refinement top
R[F2 > 2σ(F2)] = 0.050 | 0 restraints |
wR(F2) = 0.118 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.99 | Δρmax = 0.17 e Å−3 |
3509 reflections | Δρmin = −0.22 e Å−3 |
253 parameters | |
Special details top
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
C12 | 0.29709 (18) | 0.2288 (2) | 0.51071 (19) | 0.0308 (6) | |
C22 | 0.47066 (17) | 0.8373 (2) | 0.6324 (2) | 0.0295 (6) | |
C14 | 0.18345 (18) | 0.3747 (3) | 0.5643 (2) | 0.0343 (6) | |
C24 | 0.40278 (17) | 0.6545 (3) | 0.5548 (2) | 0.0321 (6) | |
C15 | 0.16190 (17) | 0.3399 (2) | 0.4466 (2) | 0.0325 (6) | |
C25 | 0.34991 (17) | 0.7726 (2) | 0.5102 (2) | 0.0292 (6) | |
C16 | 0.16869 (19) | 0.4624 (3) | 0.3771 (2) | 0.0419 (7) | |
H16A | 0.1278 | 0.5297 | 0.4059 | 0.050* | |
H16B | 0.2334 | 0.4949 | 0.3810 | 0.050* | |
C26 | 0.24553 (17) | 0.7697 (3) | 0.5402 (2) | 0.0364 (6) | |
H26A | 0.2181 | 0.6864 | 0.5181 | 0.044* | |
H26B | 0.2413 | 0.7763 | 0.6181 | 0.044* | |
C17 | 0.1402 (2) | 0.4373 (3) | 0.2600 (2) | 0.0496 (8) | |
H17A | 0.1411 | 0.5193 | 0.2204 | 0.060* | |
H17B | 0.1860 | 0.3788 | 0.2283 | 0.060* | |
C27 | 0.18856 (18) | 0.8796 (3) | 0.4878 (2) | 0.0442 (7) | |
H27A | 0.2100 | 0.9629 | 0.5173 | 0.053* | |
H27B | 0.1220 | 0.8691 | 0.5041 | 0.053* | |
C18 | 0.0430 (2) | 0.3778 (3) | 0.2494 (2) | 0.0589 (9) | |
H18A | 0.0288 | 0.3578 | 0.1741 | 0.071* | |
H18B | −0.0037 | 0.4403 | 0.2735 | 0.071* | |
C28 | 0.19975 (19) | 0.8794 (3) | 0.3659 (2) | 0.0488 (8) | |
H28A | 0.1729 | 0.7994 | 0.3358 | 0.059* | |
H28B | 0.1650 | 0.9527 | 0.3344 | 0.059* | |
C19 | 0.0366 (2) | 0.2537 (4) | 0.3160 (3) | 0.0611 (9) | |
H19A | 0.0786 | 0.1880 | 0.2870 | 0.073* | |
H19B | −0.0278 | 0.2200 | 0.3108 | 0.073* | |
C110 | 0.06373 (19) | 0.2787 (3) | 0.4342 (2) | 0.0487 (8) | |
H10A | 0.0173 | 0.3366 | 0.4653 | 0.058* | |
H10B | 0.0627 | 0.1966 | 0.4735 | 0.058* | |
C210 | 0.36108 (19) | 0.7790 (3) | 0.3875 (2) | 0.0388 (7) | |
H10C | 0.4275 | 0.7921 | 0.3718 | 0.047* | |
H10D | 0.3411 | 0.6964 | 0.3555 | 0.047* | |
C29 | 0.30283 (18) | 0.8891 (3) | 0.3372 (2) | 0.0416 (7) | |
H29A | 0.3281 | 0.9725 | 0.3623 | 0.050* | |
H29B | 0.3079 | 0.8861 | 0.2593 | 0.050* | |
N11 | 0.23769 (16) | 0.2457 (2) | 0.42589 (17) | 0.0370 (6) | |
H11A | 0.2509 (19) | 0.223 (3) | 0.363 (2) | 0.044* | |
N13 | 0.26132 (14) | 0.30399 (19) | 0.59455 (16) | 0.0306 (5) | |
N21 | 0.40031 (15) | 0.8788 (2) | 0.56619 (18) | 0.0343 (6) | |
H21A | 0.3904 (18) | 0.957 (3) | 0.554 (2) | 0.041* | |
N23 | 0.47156 (14) | 0.69975 (19) | 0.62394 (16) | 0.0307 (5) | |
N14 | 0.30742 (16) | 0.3144 (3) | 0.69722 (18) | 0.0371 (6) | |
H14A | 0.3461 (19) | 0.246 (3) | 0.702 (2) | 0.045* | |
H14B | 0.3479 (18) | 0.382 (3) | 0.693 (2) | 0.045* | |
N24 | 0.54226 (17) | 0.6240 (2) | 0.6756 (2) | 0.0402 (6) | |
H24A | 0.5131 (18) | 0.561 (3) | 0.719 (2) | 0.048* | |
H24B | 0.5705 (19) | 0.579 (3) | 0.628 (2) | 0.048* | |
O11 | 0.36752 (13) | 0.16118 (18) | 0.52101 (14) | 0.0421 (5) | |
O21 | 0.52261 (12) | 0.90065 (17) | 0.69158 (14) | 0.0383 (5) | |
O12 | 0.14119 (14) | 0.4521 (2) | 0.61864 (15) | 0.0553 (6) | |
O22 | 0.38657 (13) | 0.54017 (17) | 0.53346 (15) | 0.0442 (5) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C12 | 0.0397 (15) | 0.0251 (14) | 0.0276 (14) | −0.0024 (12) | 0.0026 (12) | 0.0009 (11) |
C22 | 0.0319 (14) | 0.0277 (14) | 0.0288 (14) | −0.0015 (11) | 0.0000 (11) | −0.0024 (12) |
C14 | 0.0343 (14) | 0.0371 (15) | 0.0315 (15) | −0.0002 (12) | 0.0013 (12) | −0.0037 (13) |
C24 | 0.0340 (14) | 0.0307 (15) | 0.0316 (15) | −0.0050 (11) | 0.0019 (12) | −0.0009 (12) |
C15 | 0.0354 (14) | 0.0317 (14) | 0.0304 (14) | 0.0023 (11) | 0.0008 (11) | −0.0032 (12) |
C25 | 0.0307 (13) | 0.0256 (14) | 0.0311 (14) | −0.0035 (11) | −0.0037 (11) | −0.0003 (11) |
C16 | 0.0459 (16) | 0.0364 (16) | 0.0431 (17) | 0.0021 (13) | −0.0033 (13) | 0.0024 (14) |
C26 | 0.0383 (15) | 0.0365 (16) | 0.0344 (14) | −0.0050 (12) | −0.0001 (12) | 0.0026 (13) |
C17 | 0.0582 (19) | 0.0541 (19) | 0.0364 (17) | 0.0146 (16) | −0.0007 (14) | 0.0075 (15) |
C27 | 0.0304 (15) | 0.0466 (18) | 0.0554 (19) | 0.0011 (13) | −0.0013 (13) | 0.0075 (15) |
C18 | 0.059 (2) | 0.078 (3) | 0.0392 (18) | 0.0175 (18) | −0.0153 (15) | −0.0098 (17) |
C28 | 0.0474 (18) | 0.0470 (19) | 0.0509 (19) | −0.0024 (14) | −0.0179 (14) | 0.0101 (15) |
C19 | 0.0473 (18) | 0.075 (2) | 0.061 (2) | −0.0124 (17) | −0.0132 (16) | −0.0176 (19) |
C110 | 0.0415 (16) | 0.055 (2) | 0.0491 (18) | −0.0118 (14) | 0.0015 (14) | −0.0023 (15) |
C210 | 0.0415 (16) | 0.0411 (17) | 0.0340 (15) | −0.0057 (12) | 0.0024 (12) | −0.0020 (13) |
C29 | 0.0515 (18) | 0.0448 (17) | 0.0281 (15) | −0.0054 (14) | −0.0064 (13) | 0.0044 (13) |
N11 | 0.0474 (13) | 0.0390 (13) | 0.0247 (12) | 0.0075 (11) | −0.0004 (11) | −0.0056 (11) |
N13 | 0.0351 (12) | 0.0331 (12) | 0.0233 (11) | −0.0019 (10) | −0.0023 (9) | −0.0021 (10) |
N21 | 0.0388 (13) | 0.0217 (11) | 0.0416 (14) | −0.0007 (10) | −0.0135 (10) | 0.0013 (10) |
N23 | 0.0353 (12) | 0.0237 (11) | 0.0329 (12) | 0.0006 (9) | −0.0049 (10) | 0.0040 (9) |
N14 | 0.0378 (14) | 0.0455 (15) | 0.0275 (12) | −0.0027 (11) | −0.0069 (10) | −0.0023 (11) |
N24 | 0.0440 (15) | 0.0312 (14) | 0.0449 (16) | 0.0038 (11) | −0.0087 (12) | 0.0061 (11) |
O11 | 0.0466 (11) | 0.0369 (11) | 0.0426 (11) | 0.0124 (9) | −0.0015 (9) | −0.0007 (9) |
O21 | 0.0393 (11) | 0.0347 (10) | 0.0402 (11) | −0.0015 (8) | −0.0101 (9) | −0.0082 (9) |
O12 | 0.0575 (13) | 0.0682 (15) | 0.0402 (12) | 0.0215 (11) | −0.0002 (10) | −0.0170 (11) |
O22 | 0.0523 (12) | 0.0271 (10) | 0.0526 (12) | −0.0067 (9) | −0.0069 (9) | −0.0010 (9) |
Geometric parameters (Å, º) top
C12—O11 | 1.212 (3) | C27—C28 | 1.521 (4) |
C12—N11 | 1.335 (3) | C27—H27A | 0.9700 |
C12—N13 | 1.396 (3) | C27—H27B | 0.9700 |
C22—O21 | 1.208 (3) | C18—C19 | 1.515 (4) |
C22—N21 | 1.336 (3) | C18—H18A | 0.9700 |
C22—N23 | 1.408 (3) | C18—H18B | 0.9700 |
C14—O12 | 1.205 (3) | C28—C29 | 1.507 (4) |
C14—N13 | 1.356 (3) | C28—H28A | 0.9700 |
C14—C15 | 1.521 (3) | C28—H28B | 0.9700 |
C24—O22 | 1.217 (3) | C19—C110 | 1.523 (4) |
C24—N23 | 1.355 (3) | C19—H19A | 0.9700 |
C24—C25 | 1.513 (3) | C19—H19B | 0.9700 |
C15—N11 | 1.465 (3) | C110—H10A | 0.9700 |
C15—C110 | 1.521 (3) | C110—H10B | 0.9700 |
C15—C16 | 1.522 (3) | C210—C29 | 1.515 (4) |
C25—N21 | 1.460 (3) | C210—H10C | 0.9700 |
C25—C26 | 1.526 (3) | C210—H10D | 0.9700 |
C25—C210 | 1.532 (3) | C29—H29A | 0.9700 |
C16—C17 | 1.514 (4) | C29—H29B | 0.9700 |
C16—H16A | 0.9700 | N11—H11A | 0.83 (3) |
C16—H16B | 0.9700 | N13—N14 | 1.414 (3) |
C26—C27 | 1.514 (3) | N21—H21A | 0.83 (3) |
C26—H26A | 0.9700 | N23—N24 | 1.401 (3) |
C26—H26B | 0.9700 | N14—H14A | 0.89 (3) |
C17—C18 | 1.500 (4) | N14—H14B | 0.90 (3) |
C17—H17A | 0.9700 | N24—H24A | 0.94 (3) |
C17—H17B | 0.9700 | N24—H24B | 0.86 (3) |
| | | |
O11—C12—N11 | 130.5 (2) | C17—C18—H18B | 109.4 |
O11—C12—N13 | 123.1 (2) | C19—C18—H18B | 109.4 |
N11—C12—N13 | 106.4 (2) | H18A—C18—H18B | 108.0 |
O21—C22—N21 | 128.8 (2) | C29—C28—C27 | 111.1 (2) |
O21—C22—N23 | 124.9 (2) | C29—C28—H28A | 109.4 |
N21—C22—N23 | 106.2 (2) | C27—C28—H28A | 109.4 |
O12—C14—N13 | 127.1 (2) | C29—C28—H28B | 109.4 |
O12—C14—C15 | 126.8 (2) | C27—C28—H28B | 109.4 |
N13—C14—C15 | 106.1 (2) | H28A—C28—H28B | 108.0 |
O22—C24—N23 | 126.2 (2) | C18—C19—C110 | 111.4 (3) |
O22—C24—C25 | 126.7 (2) | C18—C19—H19A | 109.4 |
N23—C24—C25 | 107.1 (2) | C110—C19—H19A | 109.4 |
N11—C15—C110 | 112.1 (2) | C18—C19—H19B | 109.4 |
N11—C15—C14 | 101.21 (19) | C110—C19—H19B | 109.4 |
C110—C15—C14 | 110.4 (2) | H19A—C19—H19B | 108.0 |
N11—C15—C16 | 112.5 (2) | C15—C110—C19 | 111.7 (2) |
C110—C15—C16 | 110.6 (2) | C15—C110—H10A | 109.3 |
C14—C15—C16 | 109.6 (2) | C19—C110—H10A | 109.3 |
N21—C25—C24 | 101.00 (19) | C15—C110—H10B | 109.3 |
N21—C25—C26 | 110.9 (2) | C19—C110—H10B | 109.3 |
C24—C25—C26 | 111.3 (2) | H10A—C110—H10B | 107.9 |
N21—C25—C210 | 112.1 (2) | C29—C210—C25 | 111.6 (2) |
C24—C25—C210 | 109.4 (2) | C29—C210—H10C | 109.3 |
C26—C25—C210 | 111.6 (2) | C25—C210—H10C | 109.3 |
C17—C16—C15 | 112.5 (2) | C29—C210—H10D | 109.3 |
C17—C16—H16A | 109.1 | C25—C210—H10D | 109.3 |
C15—C16—H16A | 109.1 | H10C—C210—H10D | 108.0 |
C17—C16—H16B | 109.1 | C28—C29—C210 | 111.6 (2) |
C15—C16—H16B | 109.1 | C28—C29—H29A | 109.3 |
H16A—C16—H16B | 107.8 | C210—C29—H29A | 109.3 |
C27—C26—C25 | 112.6 (2) | C28—C29—H29B | 109.3 |
C27—C26—H26A | 109.1 | C210—C29—H29B | 109.3 |
C25—C26—H26A | 109.1 | H29A—C29—H29B | 108.0 |
C27—C26—H26B | 109.1 | C12—N11—C15 | 113.0 (2) |
C25—C26—H26B | 109.1 | C12—N11—H11A | 122.8 (19) |
H26A—C26—H26B | 107.8 | C15—N11—H11A | 122.0 (19) |
C18—C17—C16 | 111.6 (2) | C14—N13—C12 | 113.2 (2) |
C18—C17—H17A | 109.3 | C14—N13—N14 | 123.7 (2) |
C16—C17—H17A | 109.3 | C12—N13—N14 | 122.9 (2) |
C18—C17—H17B | 109.3 | C22—N21—C25 | 113.4 (2) |
C16—C17—H17B | 109.3 | C22—N21—H21A | 122.6 (18) |
H17A—C17—H17B | 108.0 | C25—N21—H21A | 123.7 (18) |
C26—C27—C28 | 110.8 (2) | C24—N23—N24 | 125.9 (2) |
C26—C27—H27A | 109.5 | C24—N23—C22 | 112.3 (2) |
C28—C27—H27A | 109.5 | N24—N23—C22 | 121.6 (2) |
C26—C27—H27B | 109.5 | N13—N14—H14A | 105.4 (18) |
C28—C27—H27B | 109.5 | N13—N14—H14B | 106.1 (17) |
H27A—C27—H27B | 108.1 | H14A—N14—H14B | 103 (2) |
C17—C18—C19 | 111.1 (2) | N23—N24—H24A | 108.8 (17) |
C17—C18—H18A | 109.4 | N23—N24—H24B | 108.5 (19) |
C19—C18—H18A | 109.4 | H24A—N24—H24B | 104 (3) |
| | | |
C25—C26—C27—C28 | 54.2 (3) | C15—C16—C17—C18 | 54.7 (3) |
C26—C27—C28—C29 | −56.6 (3) | C16—C17—C18—C19 | −55.4 (3) |
C27—C28—C29—C210 | 57.3 (3) | C17—C18—C19—C110 | 55.9 (4) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N11—H11A···N14i | 0.83 (3) | 2.26 (3) | 3.083 (3) | 170 (3) |
N21—H21A···O11ii | 0.83 (3) | 2.14 (3) | 2.970 (3) | 179 (3) |
N14—H14A···N24iii | 0.89 (3) | 2.49 (3) | 3.247 (3) | 144 (2) |
N14—H14B···O21iii | 0.90 (3) | 2.29 (3) | 2.865 (3) | 121 (2) |
N24—H24A···O21iii | 0.94 (3) | 2.04 (3) | 2.970 (3) | 167 (2) |
N24—H24B···O22iv | 0.86 (3) | 2.43 (3) | 3.264 (3) | 166 (2) |
Symmetry codes: (i) x, −y+1/2, z−1/2; (ii) x, y+1, z; (iii) −x+1, y−1/2, −z+3/2; (iv) −x+1, −y+1, −z+1. |
(II) 3-amino-1,3-diazaspiro[4.5]decane-2,4-dione or 1'-aminocyclohexanespiro-4'-imidazole-2',5'(3'H,4'H)-dione
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Crystal data top
C8H13N3O2 | F(000) = 392 |
Mr = 183.21 | Dx = 1.313 Mg m−3 |
Monoclinic, P21/c | Melting point: 395 K |
Hall symbol: -P 2ybc | Mo Kα radiation, λ = 0.71073 Å |
a = 6.1743 (12) Å | Cell parameters from 22 reflections |
b = 26.765 (3) Å | θ = 18.0–19.0° |
c = 6.0257 (12) Å | µ = 0.10 mm−1 |
β = 111.425 (11)° | T = 290 K |
V = 927.0 (3) Å3 | Prismatic, pale yellow |
Z = 4 | 0.21 × 0.18 × 0.12 mm |
Data collection top
Enraf–Nonius CAD-4 diffractometer | Rint = 0.100 |
Radiation source: fine-focus sealed tube | θmax = 28.0°, θmin = 1.5° |
Graphite monochromator | h = −8→7 |
non–profiled ω/2θ scans | k = −35→35 |
4768 measured reflections | l = 0→7 |
2218 independent reflections | 3 standard reflections every 500 reflections |
1178 reflections with I > 2σ(I) | intensity decay: 1% |
Refinement top
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)] = 0.055 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.138 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.050P)2] where P = (Fo2 + 2Fc2)/3 |
2218 reflections | (Δ/σ)max < 0.001 |
120 parameters | Δρmax = 0.19 e Å−3 |
0 restraints | Δρmin = −0.20 e Å−3 |
Crystal data top
C8H13N3O2 | V = 927.0 (3) Å3 |
Mr = 183.21 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 6.1743 (12) Å | µ = 0.10 mm−1 |
b = 26.765 (3) Å | T = 290 K |
c = 6.0257 (12) Å | 0.21 × 0.18 × 0.12 mm |
β = 111.425 (11)° | |
Data collection top
Enraf–Nonius CAD-4 diffractometer | Rint = 0.100 |
4768 measured reflections | 3 standard reflections every 500 reflections |
2218 independent reflections | intensity decay: 1% |
1178 reflections with I > 2σ(I) | |
Refinement top
R[F2 > 2σ(F2)] = 0.055 | 0 restraints |
wR(F2) = 0.138 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.19 e Å−3 |
2218 reflections | Δρmin = −0.20 e Å−3 |
120 parameters | |
Special details top
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
O1 | 0.3992 (3) | 0.26965 (6) | 0.9050 (3) | 0.0558 (5) | |
O2 | 0.8487 (3) | 0.35472 (6) | 0.5762 (3) | 0.0599 (5) | |
N1 | 0.3256 (3) | 0.33844 (6) | 0.6603 (3) | 0.0423 (5) | |
H1 | 0.1834 | 0.3438 | 0.6449 | 0.051* | |
N3 | 0.6766 (3) | 0.30605 (6) | 0.7774 (3) | 0.0401 (4) | |
N4 | 0.8539 (3) | 0.27084 (7) | 0.8850 (4) | 0.0543 (5) | |
H4C | 0.8291 | 0.2562 | 1.0062 | 0.065* | 0.20 (3) |
H4A | 0.9911 | 0.2862 | 0.9384 | 0.065* | |
H4B | 0.8535 | 0.2478 | 0.7782 | 0.065* | 0.80 (3) |
C2 | 0.4556 (4) | 0.30085 (8) | 0.7921 (4) | 0.0401 (5) | |
C4 | 0.6838 (3) | 0.34292 (7) | 0.6297 (4) | 0.0393 (5) | |
C5 | 0.4508 (3) | 0.36897 (7) | 0.5469 (4) | 0.0351 (5) | |
C6 | 0.3420 (4) | 0.36786 (8) | 0.2758 (4) | 0.0482 (6) | |
H6A | 0.4513 | 0.3817 | 0.2106 | 0.058* | |
H6B | 0.3120 | 0.3334 | 0.2229 | 0.058* | |
C7 | 0.1166 (4) | 0.39713 (10) | 0.1806 (4) | 0.0614 (7) | |
H7A | 0.0002 | 0.3808 | 0.2281 | 0.074* | |
H7B | 0.0604 | 0.3976 | 0.0078 | 0.074* | |
C8 | 0.1502 (5) | 0.45033 (10) | 0.2734 (5) | 0.0716 (8) | |
H8A | 0.2533 | 0.4679 | 0.2111 | 0.086* | |
H8B | 0.0015 | 0.4675 | 0.2176 | 0.086* | |
C9 | 0.2515 (5) | 0.45138 (8) | 0.5418 (5) | 0.0613 (7) | |
H9A | 0.1412 | 0.4368 | 0.6037 | 0.074* | |
H9B | 0.2779 | 0.4858 | 0.5958 | 0.074* | |
C10 | 0.4793 (4) | 0.42277 (8) | 0.6389 (4) | 0.0500 (6) | |
H10A | 0.5347 | 0.4225 | 0.8117 | 0.060* | |
H10B | 0.5950 | 0.4396 | 0.5920 | 0.060* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.0618 (11) | 0.0550 (9) | 0.0619 (11) | 0.0031 (8) | 0.0358 (9) | 0.0150 (8) |
O2 | 0.0344 (9) | 0.0718 (11) | 0.0820 (13) | −0.0001 (8) | 0.0314 (9) | 0.0135 (9) |
N1 | 0.0314 (9) | 0.0468 (11) | 0.0553 (12) | 0.0050 (8) | 0.0236 (9) | 0.0094 (9) |
N3 | 0.0308 (9) | 0.0438 (10) | 0.0449 (11) | 0.0036 (8) | 0.0128 (8) | 0.0013 (9) |
N4 | 0.0403 (11) | 0.0558 (12) | 0.0624 (13) | 0.0111 (9) | 0.0136 (10) | 0.0065 (11) |
C2 | 0.0414 (12) | 0.0423 (12) | 0.0414 (12) | −0.0012 (10) | 0.0208 (10) | −0.0027 (10) |
C4 | 0.0304 (11) | 0.0433 (12) | 0.0463 (13) | −0.0049 (9) | 0.0164 (10) | −0.0038 (10) |
C5 | 0.0283 (10) | 0.0383 (11) | 0.0414 (12) | −0.0036 (8) | 0.0161 (9) | −0.0006 (9) |
C6 | 0.0440 (13) | 0.0599 (14) | 0.0430 (13) | −0.0031 (11) | 0.0187 (11) | −0.0008 (11) |
C7 | 0.0461 (14) | 0.0843 (19) | 0.0470 (15) | 0.0063 (13) | 0.0091 (12) | 0.0108 (13) |
C8 | 0.0652 (18) | 0.0674 (18) | 0.080 (2) | 0.0223 (14) | 0.0240 (16) | 0.0239 (16) |
C9 | 0.0670 (17) | 0.0418 (13) | 0.081 (2) | 0.0064 (12) | 0.0337 (15) | 0.0007 (13) |
C10 | 0.0516 (14) | 0.0421 (12) | 0.0555 (14) | −0.0045 (11) | 0.0189 (11) | −0.0042 (11) |
Geometric parameters (Å, º) top
O1—C2 | 1.206 (2) | C6—C7 | 1.515 (3) |
O2—C4 | 1.216 (2) | C6—H6A | 0.9700 |
N1—C2 | 1.350 (3) | C6—H6B | 0.9700 |
N1—C5 | 1.455 (2) | C7—C8 | 1.516 (3) |
N1—H1 | 0.8600 | C7—H7A | 0.9700 |
N3—C4 | 1.341 (2) | C7—H7B | 0.9700 |
N3—C2 | 1.406 (3) | C8—C9 | 1.506 (4) |
N3—N4 | 1.410 (2) | C8—H8A | 0.9700 |
N4—H4C | 0.8900 | C8—H8B | 0.9700 |
N4—H4A | 0.8900 | C9—C10 | 1.519 (3) |
N4—H4B | 0.8900 | C9—H9A | 0.9700 |
C4—C5 | 1.510 (3) | C9—H9B | 0.9700 |
C5—C6 | 1.523 (3) | C10—H10A | 0.9700 |
C5—C10 | 1.530 (3) | C10—H10B | 0.9700 |
| | | |
C2—N1—C5 | 113.01 (17) | C7—C6—H6B | 109.1 |
C2—N1—H1 | 123.5 | C5—C6—H6B | 109.1 |
C5—N1—H1 | 123.5 | H6A—C6—H6B | 107.9 |
C4—N3—C2 | 112.52 (17) | C6—C7—C8 | 111.3 (2) |
C4—N3—N4 | 126.06 (17) | C6—C7—H7A | 109.4 |
C2—N3—N4 | 120.88 (17) | C8—C7—H7A | 109.4 |
N3—N4—H4C | 109.5 | C6—C7—H7B | 109.4 |
N3—N4—H4A | 109.5 | C8—C7—H7B | 109.4 |
H4C—N4—H4A | 109.5 | H7A—C7—H7B | 108.0 |
N3—N4—H4B | 109.5 | C9—C8—C7 | 111.1 (2) |
H4C—N4—H4B | 109.5 | C9—C8—H8A | 109.4 |
H4A—N4—H4B | 109.5 | C7—C8—H8A | 109.4 |
O1—C2—N1 | 128.0 (2) | C9—C8—H8B | 109.4 |
O1—C2—N3 | 126.2 (2) | C7—C8—H8B | 109.4 |
N1—C2—N3 | 105.74 (17) | H8A—C8—H8B | 108.0 |
O2—C4—N3 | 126.9 (2) | C8—C9—C10 | 111.5 (2) |
O2—C4—C5 | 125.55 (19) | C8—C9—H9A | 109.3 |
N3—C4—C5 | 107.48 (16) | C10—C9—H9A | 109.3 |
N1—C5—C4 | 101.03 (16) | C8—C9—H9B | 109.3 |
N1—C5—C6 | 112.99 (17) | C10—C9—H9B | 109.3 |
C4—C5—C6 | 109.81 (17) | H9A—C9—H9B | 108.0 |
N1—C5—C10 | 111.65 (17) | C9—C10—C5 | 111.54 (19) |
C4—C5—C10 | 110.20 (17) | C9—C10—H10A | 109.3 |
C6—C5—C10 | 110.76 (17) | C5—C10—H10A | 109.3 |
C7—C6—C5 | 112.35 (19) | C9—C10—H10B | 109.3 |
C7—C6—H6A | 109.1 | C5—C10—H10B | 109.3 |
C5—C6—H6A | 109.1 | H10A—C10—H10B | 108.0 |
| | | |
C5—C6—C7—C8 | 54.6 (3) | C7—C8—C9—C10 | 56.3 (3) |
C6—C7—C8—C9 | −55.5 (3) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O2i | 0.86 | 1.98 | 2.833 (2) | 174 |
N4—H4A···O1ii | 0.89 | 2.64 | 3.325 (3) | 135 |
N4—H4B···N4iii | 0.89 | 2.42 | 3.2127 (14) | 148 |
N4—H4C···N4iv | 0.89 | 2.35 | 3.2127 (14) | 165 |
Symmetry codes: (i) x−1, y, z; (ii) x+1, y, z; (iii) x, −y+1/2, z−1/2; (iv) x, −y+1/2, z+1/2. |
Experimental details
| (I) | (II) |
Crystal data |
Chemical formula | C8H13N3O2 | C8H13N3O2 |
Mr | 183.21 | 183.21 |
Crystal system, space group | Monoclinic, P21/c | Monoclinic, P21/c |
Temperature (K) | 290 | 290 |
a, b, c (Å) | 14.0813 (13), 10.2094 (19), 12.372 (3) | 6.1743 (12), 26.765 (3), 6.0257 (12) |
β (°) | 91.621 (14) | 111.425 (11) |
V (Å3) | 1777.9 (6) | 927.0 (3) |
Z | 8 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.10 | 0.10 |
Crystal size (mm) | 0.24 × 0.21 × 0.12 | 0.21 × 0.18 × 0.12 |
|
Data collection |
Diffractometer | Enraf-Nonius CAD-4 diffractometer | Enraf–Nonius CAD-4 diffractometer |
Absorption correction | – | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7138, 3509, 1946 | 4768, 2218, 1178 |
Rint | 0.076 | 0.100 |
(sin θ/λ)max (Å−1) | 0.617 | 0.660 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.050, 0.118, 0.99 | 0.055, 0.138, 1.04 |
No. of reflections | 3509 | 2218 |
No. of parameters | 253 | 120 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.17, −0.22 | 0.19, −0.20 |
Selected torsion angles (º) for (I) topC25—C26—C27—C28 | 54.2 (3) | C15—C16—C17—C18 | 54.7 (3) |
C26—C27—C28—C29 | −56.6 (3) | C16—C17—C18—C19 | −55.4 (3) |
C27—C28—C29—C210 | 57.3 (3) | C17—C18—C19—C110 | 55.9 (4) |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
N11—H11A···N14i | 0.83 (3) | 2.26 (3) | 3.083 (3) | 170 (3) |
N21—H21A···O11ii | 0.83 (3) | 2.14 (3) | 2.970 (3) | 179 (3) |
N14—H14A···N24iii | 0.89 (3) | 2.49 (3) | 3.247 (3) | 144 (2) |
N14—H14B···O21iii | 0.90 (3) | 2.29 (3) | 2.865 (3) | 121 (2) |
N24—H24A···O21iii | 0.94 (3) | 2.04 (3) | 2.970 (3) | 167 (2) |
N24—H24B···O22iv | 0.86 (3) | 2.43 (3) | 3.264 (3) | 166 (2) |
Symmetry codes: (i) x, −y+1/2, z−1/2; (ii) x, y+1, z; (iii) −x+1, y−1/2, −z+3/2; (iv) −x+1, −y+1, −z+1. |
Selected torsion angles (º) for (II) topC5—C6—C7—C8 | 54.6 (3) | C7—C8—C9—C10 | 56.3 (3) |
C6—C7—C8—C9 | −55.5 (3) | | |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O2i | 0.86 | 1.98 | 2.833 (2) | 174 |
N4—H4A···O1ii | 0.89 | 2.64 | 3.325 (3) | 135 |
N4—H4B···N4iii | 0.89 | 2.42 | 3.2127 (14) | 148 |
N4—H4C···N4iv | 0.89 | 2.35 | 3.2127 (14) | 165 |
Symmetry codes: (i) x−1, y, z; (ii) x+1, y, z; (iii) x, −y+1/2, z−1/2; (iv) x, −y+1/2, z+1/2. |
Hydantoins and cycloalkanespirohydantoins are the subjects of extensive investigation due to their biological properties. As part of our research on the characterization of the biological activity of aminocycloalkanespiro-5-hydantoins and their metal complexes, the title compound was synthesized and its biological activity was investigated. The study shows very pronounced atropine-sensitive contractile effects on guinea pig ileum longitudinal muscles (Naydenova et al., 2002). These results contrast with the anticonvulsive properties of hydantoins. The contractile effects are explained by the presence of the –NH2 radical in position 3 and are also related to the cycloalkane ring size (Avenado & Gonzalez, 1985).
Both structural modifications of the title compound, (I) and (II), are built up of molecules with almost identical geometry (Fig. 1). The hydantoin moieties are essentially planar, with r.m.s. deviations of 0.014, 0.003 and 0.017 Å for the two molecules in (I) and the one molecule in (II), respectively. The bond distances and angles within the hydantoin units are comparable with those observed in other spiro-5-hydantoins (Gauthier et al., 1997). The cyclohexane rings adopt chair conformations with similar endocyclic torsion angles (Tables 1 and 3). Analogous features are observed in the crystal structures of related heterocyclic molecules (Stasko et al., 2002; Gauthier et al., 1997).
The presence of a hydantoin ring, of which nearly all the atoms can be involved in hydrogen bonds, and a cyclohexane ring, acting as an impediment to hydrogen-bond formation, suggests a variety of possible hydrogen-bonding networks, resulting in different molecular packing in (I) and (II).
The two independent molecules in (I) participate in hydrogen bonding in quite different manners. All possible hydrogen donors and acceptors in the first molecule (A) are involved in a total of six intermolecular hydrogen bonds (two of which are weak), while the second molecule (B) participates in only four hydrogen bonds and atom O12 is not involved in any such interactions (Table 2). Two N—H···O bonds involving the H atoms of the amino group at N24 link neighbouring molecules A to form undulating layers parallel to (100). In contrast, molecules B are linked through N11···N14(x, 1/2 − y, z − 1/2) hydrogen bonds and form infinite chains threaded through the troughs of the undulating layers. The remaining three hydrogen bonds connect molecules A and B and also stabilize the structural motif (Fig 2).
The hydrogen-bonding network for the second polymorph, (II), is presented in Table 4. The molecules in (II) form chains via two hydrogen bonds, N1···O2(x − 1, y, z) and O1···N4(x − 1, y, z), the first being significantly stronger than the second. The additional weak hydrogen bond N4···N4(x, 1/2 − y, 1/2 + z) mediates two-dimensional packing of the chains into infinite layers parallel to (010) (Fig. 3).
We note the similar hydrogen-bonding contributions of the amino groups, which are simultaneously donors of two and acceptors of one hydrogen bond each in both (I) and (II). Another analogy between the polymorphs is that they contain layers based on hydrogen bonding of the hydantoin moieties, with cyclohexyl groups which block the formation of strong non-covalent interactions in the direction perpendicular to the plane of the layers.