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Acta Crystallogr Sect E Struct Rep Online. 2008 August 1; 64(Pt 8): o1555.
Published online 2008 July 19. doi:  10.1107/S1600536808022113
PMCID: PMC2961972

7,11-Bis(4-methyl­phen­yl)-2,4,8,10-tetra­azaspiro­[5.5]undecane-1,3,5,9-tetra­one

Abstract

In the mol­ecule of the title compound, C21H20N4O4, the two methyl­phenyl rings are oriented at a dihedral angle of 59.32 (4)°. The other two rings have flattened-boat conformations. In the crystal structure, inter­molecular N—H(...)O hydrogen bonds link the mol­ecules. There are C—H(...)π contacts between a methyl­phenyl ring and methyl and methine groups.

Related literature

For general background, see: Pradhan et al. (2006 [triangle]); Useglio et al. (2006 [triangle]); Kazmierski et al. (2006 [triangle]). For bond-length data, see: Allen et al. (1987 [triangle]). For ring conformation puckering parameters, see: Cremer & Pople (1975 [triangle]).

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Object name is e-64-o1555-scheme1.jpg

Experimental

Crystal data

  • C21H20N4O4
  • M r = 392.41
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-o1555-efi1.jpg
  • a = 8.852 (2) Å
  • b = 12.538 (3) Å
  • c = 17.259 (4) Å
  • β = 104.483 (18)°
  • V = 1854.6 (8) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.1 mm−1
  • T = 298 (2) K
  • 0.15 × 0.11 × 0.1 mm

Data collection

  • Stoe IPDSII diffractometer
  • Absorption correction: numerical (X-SHAPE; Stoe & Cie, 2005 [triangle]) T min = 0.979, T max = 0.991
  • 17766 measured reflections
  • 4456 independent reflections
  • 3107 reflections with I > 2σ(I)
  • R int = 0.093

Refinement

  • R[F 2 > 2σ(F 2)] = 0.081
  • wR(F 2) = 0.148
  • S = 1.13
  • 4456 reflections
  • 278 parameters
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.43 e Å−3
  • Δρmin = −0.44 e Å−3

Data collection: X-AREA (Stoe & Cie, 2005 [triangle]); cell refinement: X-AREA; data reduction: X-RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 [triangle]); software used to prepare material for publication: WinGX (Farrugia, 1999 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808022113/hk2496sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808022113/hk2496Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

The authors are grateful to the Islamic Azad University, Dorood Branch, for financial support.

supplementary crystallographic information

Comment

Spiro compounds having cyclic structures fused at a central carbon are of recent interest, due to their interesting conformational feature and structural implications on biological systems (Pradhan et al., 2006). The asymmetric characteristic of the molecule due to the chiral spiro carbon is one of the important criteria of the biological activities. For example, some spiro compounds show antibacterial and antiviral activities (Useglio et al., 2006, Kazmierski et al., 2006). We report herein the synthesis and crystal structure of the title compound.

In the molecule of the title compound (Fig. 1), the bond lengths (Allen et al., 1987) and angles are within normal ranges. Ring A (C1-C3/C5-C7) and C (C11-C14/C16/C17) are, of course, planar and they are oriented at a dihedral angle of A/C = 59.32 (4)°. Rings B (N1/N2/C8-C10/C18) and D (N3/N4/C18-C21) have flattened-boat [[var phi] = -54.22 (2)°, θ = 129.53 (3)° (for ring B) and [var phi] = 52.72 (3)°, θ = 21.44 (3)° (for ring D)] conformations, having total puckering amplitudes, QT, of 1.186 (3) and 0.174 (3) Å, respectively (Cremer & Pople, 1975).

In the crystal structure, intermolecular N-H···O hydrogen bonds (Table 1) link the molecules (Fig. 2), in which they may be effective in the stabilization of the structure. The C—H···π contacts (Table 1) between the ring C and the methyl and methine groups further stabilize the structure.

Experimental

For the preparation of the title compound, a mixture of 4-methylbenzaldehyde (0.24 g, 2 mmol), barbituric acid (0.13 g, 1 mmol), and urea (0.06 g, 1 mmol) was heated at 373 K. After 2 h, the reaction mixture was washed with water (10 ml). The residue recrystallized from ethanol to afford the pure product (yield; 0.25 g, 65%, m.p. 519-521 K).

Refinement

H1B, H2B, H3 and H4D atoms (for NH) were located in difference syntheses and refined isotropically [N-H = 0.77 (4)-0.87 (4) Å and Uiso(H) = 0.032 (8) -0.076 (14) Å2]. The remaining H atoms were positioned geometrically, with C-H = 0.93, 0.98 and 0.96 Å for aromatic, methine and methyl H, respectively, and constrained to ride on their parent atoms with Uiso(H) = 1.2Ueq(C).

Figures

Fig. 1.
The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
Fig. 2.
A partial packing diagram of the title compound. Hydrogen bonds are shown as dashed lines.

Crystal data

C21H20N4O4F000 = 824
Mr = 392.41Dx = 1.405 Mg m3
Monoclinic, P21/nMo Kα radiation λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 2021 reflections
a = 8.852 (2) Åθ = 2.0–28.1º
b = 12.538 (3) ŵ = 0.1 mm1
c = 17.259 (4) ÅT = 298 (2) K
β = 104.483 (18)ºPrism, yellow
V = 1854.6 (8) Å30.15 × 0.11 × 0.1 mm
Z = 4

Data collection

Stoe IPDSII diffractometerRint = 0.093
rotation method scansθmax = 28.1º
Absorption correction: Numericalshape of crystal determined optically (X-SHAPE; Stoe & Cie, 2005))θmin = 2.0º
Tmin = 0.979, Tmax = 0.991h = −11→11
17766 measured reflectionsk = −16→16
4456 independent reflectionsl = −22→22
3107 reflections with I > 2σ(I)

Refinement

Refinement on F2H atoms treated by a mixture of independent and constrained refinement
Least-squares matrix: full  w = 1/[σ2(Fo2) + (0.0701P)2 + 0.8069P] where P = (Fo2 + 2Fc2)/3
R[F2 > 2σ(F2)] = 0.081(Δ/σ)max = 0.003
wR(F2) = 0.148Δρmax = 0.43 e Å3
S = 1.13Δρmin = −0.44 e Å3
4456 reflectionsExtinction correction: none
278 parameters

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/Ueq
O11.0239 (3)0.62989 (17)0.65204 (12)0.0446 (5)
O21.0451 (3)0.60240 (17)0.43863 (13)0.0463 (6)
O30.7614 (3)0.63921 (19)0.18421 (13)0.0522 (6)
O40.6359 (3)0.85414 (18)0.36650 (13)0.0520 (6)
N10.8229 (3)0.6195 (2)0.54163 (15)0.0417 (6)
H1B0.809 (5)0.559 (4)0.553 (3)0.076 (14)*
N20.9943 (3)0.7595 (2)0.55764 (14)0.0403 (6)
H2B1.069 (4)0.787 (3)0.582 (2)0.046 (10)*
N30.8909 (3)0.6150 (2)0.31407 (15)0.0393 (6)
H30.936 (4)0.563 (3)0.3020 (19)0.032 (8)*
N40.7093 (3)0.7516 (2)0.27656 (14)0.0381 (6)
H4D0.646 (4)0.787 (3)0.239 (2)0.045 (9)*
C10.4632 (4)0.5999 (3)0.3870 (2)0.0453 (7)
H10.42280.66650.39440.054*
C20.3664 (4)0.5232 (3)0.3421 (2)0.0516 (8)
H20.26220.53970.31960.062*
C30.4211 (4)0.4227 (3)0.33000 (18)0.0455 (7)
C40.3157 (5)0.3384 (3)0.2819 (2)0.0634 (10)
H4A0.31230.27760.31520.076*
H4B0.35560.31720.23740.076*
H4C0.21250.36680.26260.076*
C50.5765 (4)0.4012 (3)0.3651 (2)0.0489 (8)
H50.61620.3340.35870.059*
C60.6746 (4)0.4773 (2)0.40958 (19)0.0448 (7)
H60.77870.46060.4320.054*
C70.6191 (3)0.5784 (2)0.42101 (16)0.0363 (6)
C80.7243 (3)0.6631 (2)0.46862 (16)0.0357 (6)
H80.65680.71660.48420.043*
C90.9505 (4)0.6683 (2)0.58658 (16)0.0361 (6)
C100.9253 (3)0.8080 (2)0.48001 (16)0.0349 (6)
H100.85110.86210.48850.042*
C111.0480 (4)0.8656 (2)0.44822 (17)0.0374 (7)
C121.0027 (4)0.9543 (2)0.39888 (18)0.0417 (7)
H120.89840.97460.38440.05*
C131.1118 (4)1.0120 (2)0.3715 (2)0.0491 (8)
H131.07921.06950.33740.059*
C141.2688 (4)0.9861 (2)0.3938 (2)0.0474 (8)
C151.3894 (5)1.0521 (3)0.3674 (3)0.0694 (11)
H15A1.38661.1240.38620.083*
H15B1.36731.05210.31010.083*
H15C1.49111.02240.38920.083*
C161.3123 (4)0.8966 (3)0.4421 (2)0.0511 (8)
H161.41680.87680.45680.061*
C171.2051 (4)0.8368 (3)0.46843 (19)0.0455 (8)
H171.23750.77690.49990.055*
C180.8296 (3)0.7230 (2)0.42113 (15)0.0340 (6)
C190.9342 (3)0.6434 (2)0.39333 (16)0.0335 (6)
C200.7848 (3)0.6665 (2)0.25345 (17)0.0356 (6)
C210.7178 (3)0.7831 (2)0.35308 (16)0.0343 (6)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.0555 (13)0.0453 (11)0.0249 (10)−0.0030 (10)−0.0049 (9)0.0011 (8)
O20.0490 (13)0.0443 (11)0.0358 (11)0.0170 (10)−0.0075 (10)−0.0017 (9)
O30.0634 (15)0.0587 (14)0.0279 (11)0.0076 (12)−0.0013 (10)−0.0114 (10)
O40.0593 (14)0.0517 (13)0.0381 (12)0.0261 (11)−0.0007 (10)−0.0024 (10)
N10.0491 (15)0.0430 (14)0.0264 (12)−0.0046 (12)−0.0030 (11)0.0014 (10)
N20.0495 (15)0.0402 (13)0.0231 (11)−0.0030 (12)−0.0059 (11)−0.0012 (10)
N30.0442 (14)0.0381 (13)0.0312 (13)0.0117 (11)0.0012 (10)−0.0082 (10)
N40.0440 (14)0.0405 (13)0.0233 (11)0.0111 (11)−0.0040 (10)0.0010 (10)
C10.0410 (16)0.0415 (16)0.0491 (19)0.0038 (13)0.0031 (14)−0.0023 (13)
C20.0364 (16)0.059 (2)0.053 (2)−0.0003 (15)−0.0014 (14)0.0024 (16)
C30.0520 (19)0.0473 (17)0.0335 (15)−0.0100 (14)0.0041 (14)0.0023 (13)
C40.070 (2)0.051 (2)0.060 (2)−0.0199 (18)0.0006 (19)−0.0005 (17)
C50.059 (2)0.0394 (16)0.0446 (18)0.0011 (15)0.0052 (15)−0.0016 (13)
C60.0437 (17)0.0436 (16)0.0422 (17)0.0069 (13)0.0012 (14)−0.0002 (13)
C70.0394 (15)0.0402 (15)0.0259 (13)0.0013 (12)0.0017 (11)0.0023 (11)
C80.0411 (15)0.0398 (14)0.0231 (12)0.0060 (12)0.0023 (11)−0.0020 (11)
C90.0441 (16)0.0401 (14)0.0214 (12)0.0050 (12)0.0034 (11)−0.0023 (11)
C100.0435 (15)0.0327 (13)0.0233 (13)0.0067 (12)−0.0014 (11)−0.0034 (10)
C110.0508 (17)0.0291 (13)0.0283 (13)0.0034 (12)0.0025 (12)−0.0022 (11)
C120.0504 (18)0.0349 (14)0.0375 (16)0.0116 (13)0.0067 (13)0.0021 (12)
C130.072 (2)0.0317 (14)0.0444 (18)0.0090 (15)0.0163 (16)0.0030 (13)
C140.058 (2)0.0382 (15)0.0455 (18)0.0030 (14)0.0127 (15)−0.0037 (13)
C150.074 (3)0.054 (2)0.081 (3)−0.007 (2)0.021 (2)0.009 (2)
C160.0467 (18)0.0494 (18)0.053 (2)0.0031 (15)0.0053 (15)0.0036 (15)
C170.0488 (18)0.0423 (16)0.0401 (17)0.0082 (14)0.0012 (14)0.0065 (13)
C180.0415 (15)0.0334 (13)0.0221 (12)0.0081 (12)−0.0018 (11)−0.0019 (10)
C190.0374 (15)0.0328 (13)0.0263 (13)0.0054 (11)0.0001 (11)−0.0011 (10)
C200.0372 (15)0.0376 (14)0.0277 (13)−0.0025 (12)0.0002 (11)−0.0015 (11)
C210.0367 (14)0.0347 (13)0.0265 (13)0.0078 (12)−0.0013 (11)0.0006 (11)

Geometric parameters (Å, °)

C1—C71.384 (4)C11—C121.398 (4)
C1—C21.388 (5)C12—C131.381 (5)
C1—H10.93C12—H120.93
C2—C31.385 (5)C13—C141.384 (5)
C2—H20.93C13—H130.93
C3—C51.384 (5)C14—C161.393 (5)
C3—C41.513 (5)C14—C151.509 (5)
C4—H4A0.96C15—H15A0.96
C4—H4B0.96C15—H15B0.96
C4—H4C0.96C15—H15C0.96
C5—C61.385 (4)C16—C171.372 (5)
C5—H50.93C16—H160.93
C6—C71.390 (4)C17—H170.93
C6—H60.93C18—C191.518 (4)
C7—C81.512 (4)C18—C211.531 (4)
C8—N11.449 (4)C19—O21.207 (3)
C8—C181.577 (4)C19—N31.372 (3)
C8—H80.98C20—O31.210 (3)
C9—O11.250 (3)C20—N41.370 (4)
C9—N21.344 (4)C20—N31.379 (4)
C9—N11.346 (4)C21—O41.207 (3)
C10—N21.459 (3)C21—N41.362 (4)
C10—C111.516 (4)N1—H1B0.80 (5)
C10—C181.568 (4)N2—H2B0.77 (4)
C10—H100.98N3—H30.82 (3)
C11—C171.393 (4)N4—H4D0.87 (4)
C7—C1—C2120.8 (3)C12—C13—C14121.4 (3)
C7—C1—H1119.6C12—C13—H13119.3
C2—C1—H1119.6C14—C13—H13119.3
C3—C2—C1121.6 (3)C13—C14—C16117.6 (3)
C3—C2—H2119.2C13—C14—C15121.6 (3)
C1—C2—H2119.2C16—C14—C15120.8 (3)
C5—C3—C2117.2 (3)C14—C15—H15A109.5
C5—C3—C4120.9 (3)C14—C15—H15B109.5
C2—C3—C4121.9 (3)H15A—C15—H15B109.5
C3—C4—H4A109.5C14—C15—H15C109.5
C3—C4—H4B109.5H15A—C15—H15C109.5
H4A—C4—H4B109.5H15B—C15—H15C109.5
C3—C4—H4C109.5C17—C16—C14121.8 (3)
H4A—C4—H4C109.5C17—C16—H16119.1
H4B—C4—H4C109.5C14—C16—H16119.1
C3—C5—C6121.7 (3)C16—C17—C11120.3 (3)
C3—C5—H5119.2C16—C17—H17119.8
C6—C5—H5119.2C11—C17—H17119.8
C5—C6—C7120.8 (3)C19—C18—C21114.1 (2)
C5—C6—H6119.6C19—C18—C10112.2 (2)
C7—C6—H6119.6C21—C18—C10107.7 (2)
C1—C7—C6117.9 (3)C19—C18—C8109.7 (2)
C1—C7—C8120.4 (3)C21—C18—C8106.3 (2)
C6—C7—C8121.7 (3)C10—C18—C8106.3 (2)
N1—C8—C7111.3 (2)O2—C19—N3121.0 (3)
N1—C8—C18109.0 (2)O2—C19—C18122.5 (2)
C7—C8—C18114.6 (2)N3—C19—C18116.5 (2)
N1—C8—H8107.2O3—C20—N4122.2 (3)
C7—C8—H8107.2O3—C20—N3122.1 (3)
C18—C8—H8107.2N4—C20—N3115.7 (2)
O1—C9—N2122.1 (3)O4—C21—N4120.6 (2)
O1—C9—N1121.1 (3)O4—C21—C18121.3 (3)
N2—C9—N1116.8 (3)N4—C21—C18118.0 (2)
N2—C10—C11110.9 (2)C9—N1—C8124.5 (3)
N2—C10—C18110.2 (2)C9—N1—H1B117 (3)
C11—C10—C18114.1 (2)C8—N1—H1B118 (3)
N2—C10—H10107C9—N2—C10127.1 (3)
C11—C10—H10107C9—N2—H2B118 (3)
C18—C10—H10107C10—N2—H2B114 (3)
C17—C11—C12118.3 (3)C19—N3—C20127.0 (3)
C17—C11—C10123.1 (3)C19—N3—H3115 (2)
C12—C11—C10118.5 (3)C20—N3—H3118 (2)
C13—C12—C11120.4 (3)C21—N4—C20126.5 (2)
C13—C12—H12119.8C21—N4—H4D117 (2)
C11—C12—H12119.8C20—N4—H4D117 (2)
C7—C1—C2—C30.4 (5)N1—C8—C18—C1965.8 (3)
C1—C2—C3—C50.5 (5)C7—C8—C18—C19−59.7 (3)
C1—C2—C3—C4179.3 (4)N1—C8—C18—C21−170.3 (2)
C2—C3—C5—C6−1.0 (5)C7—C8—C18—C2164.2 (3)
C4—C3—C5—C6−179.8 (3)N1—C8—C18—C10−55.8 (3)
C3—C5—C6—C70.5 (5)C7—C8—C18—C10178.7 (2)
C2—C1—C7—C6−0.8 (5)C21—C18—C19—O2167.7 (3)
C2—C1—C7—C8178.9 (3)C10—C18—C19—O244.8 (4)
C5—C6—C7—C10.4 (5)C8—C18—C19—O2−73.1 (3)
C5—C6—C7—C8−179.4 (3)C21—C18—C19—N3−16.2 (4)
C1—C7—C8—N1136.0 (3)C10—C18—C19—N3−139.0 (3)
C6—C7—C8—N1−44.2 (4)C8—C18—C19—N3103.0 (3)
C1—C7—C8—C18−99.7 (3)C19—C18—C21—O4−174.6 (3)
C6—C7—C8—C1880.0 (3)C10—C18—C21—O4−49.3 (4)
N2—C10—C11—C1727.2 (4)C8—C18—C21—O464.3 (3)
C18—C10—C11—C17−98.0 (3)C19—C18—C21—N47.6 (4)
N2—C10—C11—C12−150.1 (3)C10—C18—C21—N4132.9 (3)
C18—C10—C11—C1284.6 (3)C8—C18—C21—N4−113.5 (3)
C17—C11—C12—C13−0.4 (4)O1—C9—N1—C8174.7 (3)
C10—C11—C12—C13177.0 (3)N2—C9—N1—C8−5.4 (5)
C11—C12—C13—C14−1.9 (5)C7—C8—N1—C9164.5 (3)
C12—C13—C14—C162.8 (5)C18—C8—N1—C937.2 (4)
C12—C13—C14—C15−176.9 (3)O1—C9—N2—C10175.3 (3)
C13—C14—C16—C17−1.4 (5)N1—C9—N2—C10−4.6 (5)
C15—C14—C16—C17178.4 (4)C11—C10—N2—C9−146.8 (3)
C14—C16—C17—C11−0.9 (5)C18—C10—N2—C9−19.4 (4)
C12—C11—C17—C161.8 (5)O2—C19—N3—C20−168.4 (3)
C10—C11—C17—C16−175.5 (3)C18—C19—N3—C2015.4 (4)
N2—C10—C18—C19−72.4 (3)O3—C20—N3—C19175.2 (3)
C11—C10—C18—C1953.3 (3)N4—C20—N3—C19−3.9 (5)
N2—C10—C18—C21161.2 (2)O4—C21—N4—C20−173.8 (3)
C11—C10—C18—C21−73.2 (3)C18—C21—N4—C204.0 (4)
N2—C10—C18—C847.6 (3)O3—C20—N4—C21174.2 (3)
C11—C10—C18—C8173.3 (2)N3—C20—N4—C21−6.7 (4)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1B···O2i0.80 (5)2.39 (5)3.004 (3)135 (4)
N2—H2B···O3ii0.77 (4)2.32 (3)3.065 (4)164 (3)
N3—H3···O1i0.82 (4)2.54 (4)3.181 (3)136 (3)
N4—H4D···O1iii0.87 (4)1.92 (4)2.785 (3)174 (3)
C4—H4B···Cg4iv0.963.023.721 (3)131
C10—H10···Cg4v0.983.113.914 (3)141

Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) x+1/2, −y+3/2, z+1/2; (iii) x−1/2, −y+3/2, z−1/2; (iv) −x+3/2, y−1/2, −z+1/2; (v) −x+1, −y+1, −z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HK2496).

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