1,4-Di­aza­spiro­[4.5]­decane-2,3-dione

The spirane 1,4-di­aza­spiro­[4.5]­decane-2,3-dione, C₈H₁₂N₂O₂, or 2,2-penta­methyl­ene-4,5-imidazolidinedione, has been prepared and found to crystallize with two independent mol­ecules in the asymmetric unit. Though nearly identical in geometry, the two distinct mol­ecules undergo two different styles of co-operative hydrogen bonding, namely a planar and a canted arrangement.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.046
• wR factor = 0.106
• Data-to-parameter ratio = 17.9

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


 Alert Level C:



PLAT_369  Alert C Long   C(sp2)-C(sp2) Bond  C7     -   C8     =       1.53 Ang.


 0 Alert Level A = Potentially serious problem

 0 Alert Level B = Potential problem

 1 Alert Level C = Please check

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S1. Comment

As part of a research program concerning alternative methods for the synthesis of gem-bis(difluoramino)alkanes, we required the title compound, (I) (Davis, Chapman & Johnson, 2002). The 2,2-dialkyl-4,5-imidazolidinedione ring system is seldom seen in the literature in spite of a convenient method of preparation (Gruber et al., 1971). Compound (I) was synthesized from cyclohexanone by the patented procedure. To our knowledge, this is the first structural determination of this heterocyclic ring system.

Crystals of (I) suitable for diffraction were grown from supersaturated acetonitrile solutions. There are two independent molecules in the asymmetric unit, which are effectively identical in geometry and bond distances (Fig. 1). The imidazolidinedione ring is planar in each independent molecule. The torsion angles within the five-membered rings range between between 0.2 (2) and 1.3 (2)°. The cyclohexane rings adopts chair conformations. These features are similar to those observed in the crystal structure of the related heterocycle, 1β-methyl-4α-isopropylcyclohexyl-spiro-5'-hydantoin (Gałdecki et al., 1986).

The C—C bond lengths between the carbonyl groups appear anomolously long [1.528 (2) and 1.521 (2) Å], but this trait is mirrored in other structurally characterized oxamide derivatives (Chen et al., 1991).

Both molecules within the asymmetric unit are involved in the hydrogen-bonding network (Fig. 2). One molecule forms a planar co-operative hydrogen-bonding arrangement [1.98 (1) Å] with a symmetry-related amide functionality. The other portion of the dione, opposite this planar arrangement, ties into the canted hydrogen-bonding network with one longer hydrogen bond [2.06 (1) Å]. The infinite canted network is composed solely of the second molecule of the asymmetric unit. This co-operative network, with multiple hydrogen bonds between complimentary functional groups, is analogous to that seen in the structurally similar 1,1-bisacetamidocyclohexane (Davis, Stasko & Chapman, 2002). The planes of the two imidazolidinediones are tilted by approximately 130 (1)°, resulting in a shallow herring-bone arrangement, with hydrogen bonds between the amides [2.11 (1) Å].

S2. Experimental

Cyanogen (7 ml) were collected in a graduated test tube cooled to 248 K, which was then stoppered by a septum. The tube was then connected via Teflon spaghetti to a vigorously stirred mixture of cyclohexanone (10 g, 10.6 ml, 102 mmol) in 5% NaOH (75 ml, 94 mmol), and cooled in an ice bath. The 248 K bath was removed and the Teflon tubing was immersed in the ketone mixture. After the cyanogen had bubbled through the reaction mixture (approximately 30 min), the tubing and the ice bath were removed and the reaction stirred for 24 h. The mixture was then cooled in an ice bath and neutralized with 50% H₂SO₄, causing the product to precipitate. The mixture was filtered and the product washed with H₂O and then suction dried. The product was recrystallized from MeCN (4.7 g, 28%); m.p. 573 K (decomposition); ¹H NMR (DMSO-d₆, p.p.m.): δ 9.98 (bs, 2H), 1.62–1.4 (m, 8H), 1.39–1.1 (m, 2H); ¹³C NMR (DMSO-d₆, p.p.m.): δ 159.65, 68.09, 38.30, 24.16, 21.90.

Computing details

Data collection: XSCANS (Siemens, 1994); cell refinement: XSCANS; data reduction: SHELXTL (Bruker, 2000); program(s) used to solve structure: SHELXTL; program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. ORTEP drawing (SHELXTL; Bruker, 2000) of the title compound, illustrating the numbering scheme and showing displacement ellipsoids at the 50% probability level.
	Fig. 2. The hydrogen-bonding array in (I) (left: planar and right: canted)

(I)

Crystal data

C8H12N2O2	F(000) = 720
Mr = 168.20	Dx = 1.312 Mg m^−3
Monoclinic, P21/c	Melting point: 300 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 13.671 (3) Å	Cell parameters from 18 reflections
b = 10.641 (2) Å	θ = 2–22.5°
c = 11.781 (2) Å	µ = 0.10 mm^−1
β = 96.60 (3)°	T = 293 K
V = 1702.4 (6) Å^3	Oblong prism, colourless
Z = 8	0.5 × 0.5 × 0.2 mm

Data collection

Bruker P4 diffractometer	Rint = 0.019
Radiation source: fine-focus sealed tube	θmax = 27.5°, θmin = 1.5°
Graphite monochromator	h = −17→17
ω scans	k = −13→0
4084 measured reflections	l = 0→15
3893 independent reflections	3 standard reflections every 48 reflections
2650 reflections with I > 2σ(I)	intensity decay: none

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.107	H-atom parameters constrained
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0385P)^2 + 0.4243P] where P = (Fo^2 + 2Fc^2)/3
3893 reflections	(Δ/σ)max < 0.001
217 parameters	Δρmax = 0.19 e Å^−3
0 restraints	Δρmin = −0.17 e Å^−3

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.

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 (Ų)

	x	y	z	Uiso*/Ueq
C1	0.32731 (12)	0.86746 (16)	0.12085 (14)	0.0383 (4)
C2	0.33565 (14)	0.72644 (17)	0.10294 (18)	0.0516 (5)
H2A	0.2812	0.6845	0.1331	0.062*
H2B	0.3312	0.7088	0.0217	0.062*
C3	0.43173 (17)	0.6751 (2)	0.1613 (2)	0.0702 (7)
H3A	0.4327	0.5845	0.1522	0.084*
H3B	0.4860	0.7098	0.1252	0.084*
C4	0.44498 (19)	0.7072 (2)	0.2868 (2)	0.0805 (8)
H4A	0.5088	0.6775	0.3209	0.097*
H4B	0.3948	0.6650	0.3245	0.097*
C5	0.43793 (16)	0.8474 (2)	0.30485 (18)	0.0636 (6)
H5A	0.4921	0.8889	0.2737	0.076*
H5B	0.4434	0.8652	0.3861	0.076*
C6	0.34097 (14)	0.8994 (2)	0.24759 (16)	0.0513 (5)
H6A	0.3400	0.9900	0.2571	0.062*
H6B	0.2869	0.8644	0.2839	0.062*
C7	0.35490 (12)	1.01554 (15)	−0.01835 (14)	0.0348 (4)
C8	0.24401 (12)	1.00212 (16)	−0.01507 (14)	0.0381 (4)
O1	0.39473 (9)	1.08625 (12)	−0.08078 (11)	0.0484 (3)
O2	0.18071 (9)	1.06051 (13)	−0.07319 (12)	0.0547 (4)
N1	0.39717 (9)	0.93657 (13)	0.05961 (12)	0.0367 (3)
H1N	0.4599	0.9270	0.0728	0.044*
N2	0.23482 (10)	0.91574 (14)	0.06483 (13)	0.0443 (4)
H2N	0.1785	0.8906	0.0819	0.053*
C1'	0.08781 (11)	0.19799 (14)	0.63932 (14)	0.0334 (4)
C2'	0.19343 (12)	0.23222 (16)	0.68478 (15)	0.0402 (4)
H1A'	0.2096	0.3134	0.6544	0.048*
H1B'	0.1987	0.2392	0.7674	0.048*
C3'	0.26666 (13)	0.1351 (2)	0.65232 (17)	0.0518 (5)
H3A'	0.2560	0.0565	0.6908	0.062*
H3B'	0.3330	0.1633	0.6779	0.062*
C4'	0.25660 (14)	0.11315 (19)	0.52413 (17)	0.0528 (5)
H4A'	0.2728	0.1897	0.4857	0.063*
H4B'	0.3023	0.0482	0.5065	0.063*
C5'	0.15236 (14)	0.07371 (19)	0.48163 (17)	0.0514 (5)
H5A'	0.1463	0.0630	0.3993	0.062*
H5B'	0.1382	−0.0064	0.5155	0.062*
C6'	0.07863 (13)	0.17054 (17)	0.51187 (14)	0.0423 (4)
H6A'	0.0126	0.1405	0.4872	0.051*
H6B'	0.0884	0.2478	0.4709	0.051*
C7'	−0.02114 (11)	0.12538 (15)	0.76330 (14)	0.0341 (4)
C8'	−0.04380 (12)	0.26304 (15)	0.73739 (15)	0.0373 (4)
O1'	−0.06356 (8)	0.06075 (10)	0.82871 (11)	0.0457 (3)
O2'	−0.10632 (9)	0.32540 (11)	0.77781 (12)	0.0503 (3)
N1'	0.05108 (9)	0.09383 (12)	0.70384 (12)	0.0339 (3)
H1N'	0.0745	0.0189	0.7030	0.041*
N2'	0.01973 (10)	0.29677 (13)	0.66560 (13)	0.0427 (4)
H2N'	0.0207	0.3710	0.6369	0.051*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0312 (8)	0.0425 (9)	0.0429 (10)	0.0001 (7)	0.0113 (7)	0.0078 (8)
C2	0.0511 (11)	0.0399 (10)	0.0653 (13)	−0.0042 (8)	0.0127 (10)	0.0083 (9)
C3	0.0646 (14)	0.0406 (11)	0.105 (2)	0.0097 (10)	0.0099 (13)	0.0225 (12)
C4	0.0687 (15)	0.0790 (17)	0.0899 (19)	−0.0049 (13)	−0.0071 (13)	0.0507 (15)
C5	0.0632 (13)	0.0810 (16)	0.0452 (11)	−0.0108 (11)	−0.0002 (10)	0.0206 (11)
C6	0.0505 (11)	0.0650 (13)	0.0405 (10)	−0.0021 (9)	0.0142 (8)	0.0067 (9)
C7	0.0369 (8)	0.0326 (8)	0.0365 (8)	0.0042 (7)	0.0106 (7)	0.0012 (7)
C8	0.0376 (9)	0.0396 (9)	0.0382 (9)	0.0054 (7)	0.0084 (7)	−0.0020 (8)
O1	0.0444 (7)	0.0498 (8)	0.0526 (8)	0.0021 (6)	0.0128 (6)	0.0199 (6)
O2	0.0437 (7)	0.0644 (9)	0.0549 (8)	0.0140 (6)	0.0011 (6)	0.0089 (7)
N1	0.0301 (6)	0.0397 (8)	0.0416 (8)	0.0021 (6)	0.0097 (6)	0.0104 (6)
N2	0.0294 (7)	0.0551 (9)	0.0502 (9)	0.0014 (6)	0.0123 (6)	0.0087 (7)
C1'	0.0355 (8)	0.0259 (7)	0.0393 (9)	−0.0018 (6)	0.0069 (7)	0.0030 (7)
C2'	0.0397 (9)	0.0422 (9)	0.0389 (9)	−0.0111 (7)	0.0054 (7)	0.0008 (8)
C3'	0.0363 (9)	0.0622 (12)	0.0569 (12)	0.0012 (9)	0.0063 (8)	0.0090 (10)
C4'	0.0502 (11)	0.0536 (11)	0.0584 (12)	0.0046 (9)	0.0224 (9)	0.0043 (10)
C5'	0.0638 (12)	0.0488 (11)	0.0440 (10)	−0.0090 (9)	0.0167 (9)	−0.0056 (9)
C6'	0.0406 (9)	0.0470 (10)	0.0386 (9)	−0.0088 (8)	0.0018 (7)	0.0056 (8)
C7'	0.0316 (8)	0.0286 (8)	0.0425 (9)	−0.0033 (6)	0.0057 (7)	−0.0011 (7)
C8'	0.0344 (8)	0.0301 (8)	0.0479 (10)	−0.0009 (7)	0.0062 (7)	−0.0004 (7)
O1'	0.0452 (7)	0.0335 (6)	0.0630 (8)	−0.0005 (5)	0.0259 (6)	0.0068 (6)
O2'	0.0454 (7)	0.0361 (7)	0.0724 (9)	0.0067 (6)	0.0197 (7)	−0.0012 (6)
N1'	0.0347 (7)	0.0251 (6)	0.0433 (8)	0.0007 (5)	0.0110 (6)	0.0034 (6)
N2'	0.0446 (8)	0.0266 (7)	0.0590 (9)	0.0027 (6)	0.0154 (7)	0.0094 (7)

Geometric parameters (Å, º)

C1—N2	1.451 (2)	C1'—N2'	1.461 (2)
C1—N1	1.460 (2)	C1'—N1'	1.4650 (19)
C1—C2	1.521 (2)	C1'—C6'	1.521 (2)
C1—C6	1.522 (3)	C1'—C2'	1.525 (2)
C2—C3	1.513 (3)	C2'—C3'	1.518 (3)
C2—H2A	0.9700	C2'—H1A'	0.9700
C2—H2B	0.9700	C2'—H1B'	0.9700
C3—C4	1.509 (4)	C3'—C4'	1.519 (3)
C3—H3A	0.9700	C3'—H3A'	0.9700
C3—H3B	0.9700	C3'—H3B'	0.9700
C4—C5	1.512 (3)	C4'—C5'	1.514 (3)
C4—H4A	0.9700	C4'—H4A'	0.9700
C4—H4B	0.9700	C4'—H4B'	0.9700
C5—C6	1.521 (3)	C5'—C6'	1.512 (3)
C5—H5A	0.9700	C5'—H5A'	0.9700
C5—H5B	0.9700	C5'—H5B'	0.9700
C6—H6A	0.9700	C6'—H6A'	0.9700
C6—H6B	0.9700	C6'—H6B'	0.9700
C7—O1	1.2229 (19)	C7'—O1'	1.2271 (19)
C7—N1	1.327 (2)	C7'—N1'	1.318 (2)
C7—C8	1.528 (2)	C7'—C8'	1.521 (2)
C8—O2	1.211 (2)	C8'—O2'	1.2211 (19)
C8—N2	1.332 (2)	C8'—N2'	1.329 (2)
N1—H1N	0.8600	N1'—H1N'	0.8600
N2—H2N	0.8600	N2'—H2N'	0.8600
N2—C1—N1	100.50 (13)	N2'—C1'—N1'	99.78 (12)
N2—C1—C2	111.18 (15)	N2'—C1'—C6'	111.42 (14)
N1—C1—C2	111.39 (14)	N1'—C1'—C6'	111.88 (13)
N2—C1—C6	111.67 (15)	N2'—C1'—C2'	110.75 (13)
N1—C1—C6	111.02 (14)	N1'—C1'—C2'	111.44 (13)
C2—C1—C6	110.72 (15)	C6'—C1'—C2'	111.10 (13)
C3—C2—C1	111.61 (17)	C3'—C2'—C1'	111.95 (15)
C3—C2—H2A	109.3	C3'—C2'—H1A'	109.2
C1—C2—H2A	109.3	C1'—C2'—H1A'	109.2
C3—C2—H2B	109.3	C3'—C2'—H1B'	109.2
C1—C2—H2B	109.3	C1'—C2'—H1B'	109.2
H2A—C2—H2B	108.0	H1A'—C2'—H1B'	107.9
C4—C3—C2	111.3 (2)	C2'—C3'—C4'	111.60 (16)
C4—C3—H3A	109.4	C2'—C3'—H3A'	109.3
C2—C3—H3A	109.4	C4'—C3'—H3A'	109.3
C4—C3—H3B	109.4	C2'—C3'—H3B'	109.3
C2—C3—H3B	109.4	C4'—C3'—H3B'	109.3
H3A—C3—H3B	108.0	H3A'—C3'—H3B'	108.0
C3—C4—C5	111.05 (17)	C5'—C4'—C3'	110.21 (15)
C3—C4—H4A	109.4	C5'—C4'—H4A'	109.6
C5—C4—H4A	109.4	C3'—C4'—H4A'	109.6
C3—C4—H4B	109.4	C5'—C4'—H4B'	109.6
C5—C4—H4B	109.4	C3'—C4'—H4B'	109.6
H4A—C4—H4B	108.0	H4A'—C4'—H4B'	108.1
C4—C5—C6	111.30 (19)	C6'—C5'—C4'	111.14 (15)
C4—C5—H5A	109.4	C6'—C5'—H5A'	109.4
C6—C5—H5A	109.4	C4'—C5'—H5A'	109.4
C4—C5—H5B	109.4	C6'—C5'—H5B'	109.4
C6—C5—H5B	109.4	C4'—C5'—H5B'	109.4
H5A—C5—H5B	108.0	H5A'—C5'—H5B'	108.0
C5—C6—C1	110.87 (17)	C5'—C6'—C1'	112.45 (15)
C5—C6—H6A	109.5	C5'—C6'—H6A'	109.1
C1—C6—H6A	109.5	C1'—C6'—H6A'	109.1
C5—C6—H6B	109.5	C5'—C6'—H6B'	109.1
C1—C6—H6B	109.5	C1'—C6'—H6B'	109.1
H6A—C6—H6B	108.1	H6A'—C6'—H6B'	107.8
O1—C7—N1	128.11 (15)	O1'—C7'—N1'	128.89 (15)
O1—C7—C8	125.76 (15)	O1'—C7'—C8'	124.46 (14)
N1—C7—C8	106.12 (14)	N1'—C7'—C8'	106.65 (14)
O2—C8—N2	129.36 (16)	O2'—C8'—N2'	129.72 (16)
O2—C8—C7	125.75 (16)	O2'—C8'—C7'	125.50 (15)
N2—C8—C7	104.89 (14)	N2'—C8'—C7'	104.77 (14)
C7—N1—C1	113.79 (13)	C7'—N1'—C1'	113.91 (13)
C7—N1—H1N	123.1	C7'—N1'—H1N'	123.0
C1—N1—H1N	123.1	C1'—N1'—H1N'	123.0
C8—N2—C1	114.68 (13)	C8'—N2'—C1'	114.79 (13)
C8—N2—H2N	122.7	C8'—N2'—H2N'	122.6
C1—N2—H2N	122.7	C1'—N2'—H2N'	122.6

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O1^i	0.86	1.98	2.8376 (19)	172
N2—H2N···O1′^ii	0.86	2.06	2.7915 (19)	143
N1′—H1N′···O2′^iii	0.86	2.11	2.9561 (19)	167
N2′—H2N′···O1′^iv	0.86	2.13	2.8714 (19)	144

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