Butallyl-onal 1,4-dioxane hemisolvate.

THE ASYMMETRIC UNIT OF THE TITLE COMPOUND [SYSTEMATIC NAME: 5-(1-bromo-prop-2-en-1-yl)-5-sec-butyl-pyrimidine-2,4,6-trione 1,4-dioxane hemisolvate], C(11)H(15)BrN(2)O(3)·0.5C(4)H(8)O(2), contains one half-mol-ecule of 1,4-dioxane and one mol-ecule of butallyl-onal, with an almost planar barbiturate ring [largest deviation from the mean plane = 0.049 (5) Å]. The centrosymmetric dioxane mol-ecule adopts a nearly ideal chair conformation. The barbiturate mol-ecules are linked together by an N-H⋯O hydrogen bond, giving a single-stranded chain. Additionally, each dioxane mol-ecule acts as a bridge between two anti-parallel strands of hydrogen-bonded barbiturate mol-ecules via two hydrogen bonds, N-H⋯O(dioxane)O⋯H-N. Thus, a ladder structure is obtained, with the connected barbiturate mol-ecules forming the 'stiles' and the bridging dioxane mol-ecules the 'rungs'.

Related literature

For the preparation of butallyl­onal, see: J. D. Riedel Akt.-Ges. (1924 ▶); Boedecker (1929 ▶). For related structures, see: Al-Saqqar et al. (2004 ▶); Gelbrich et al. (2007 ▶, 2010 ▶); Craven et al. (1969 ▶); Gatehouse & Craven (1971 ▶); Lewis et al. (2004 ▶); Zencirci et al. (2009 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C11H15BrN2O3·0.5C4H8O2

M = 347.21

Monoclinic,

a = 10.494 (2) Å

b = 6.7679 (8) Å

c = 21.864 (3) Å

β = 97.294 (15)°

V = 1540.3 (4) Å3

Z = 4

Mo Kα radiation

μ = 2.68 mm−1

T = 293 K

0.25 × 0.08 × 0.07 mm

Data collection

Oxford Diffraction Xcalibur Ruby Gemini ultra diffractometer

Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2007 ▶) T min = 0.990, T max = 1.000

9189 measured reflections

2714 independent reflections

1171 reflections with I > 2σ(I)

R int = 0.100

Refinement

R[F 2 > 2σ(F 2)] = 0.064

wR(F 2) = 0.145

S = 0.95

2714 reflections

189 parameters

2 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.56 e Å−3

Δρmin = −0.33 e Å−3

Data collection: CrysAlis PRO (Oxford Diffraction, 2007 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: XP in SHELXTL (Sheldrick, 2008 ▶) and Mercury (Bruno et al., 2002 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810038651/fj2340sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810038651/fj2340Isup2.hkl

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

C11H15BrN2O3·0.5C4H8O2	F(000) = 712
Mr = 347.21	Dx = 1.497 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 837 reflections
a = 10.494 (2) Å	θ = 2.5–28.5°
b = 6.7679 (8) Å	µ = 2.68 mm−1
c = 21.864 (3) Å	T = 293 K
β = 97.294 (15)°	Prism, colourless
V = 1540.3 (4) Å3	0.25 × 0.08 × 0.07 mm
Z = 4

Oxford Diffraction Xcalibur Ruby Gemini ultra diffractometer	2714 independent reflections
Radiation source: Enhance Ultra (Cu) X-ray Source	1171 reflections with I > 2σ(I)
mirror	Rint = 0.100
Detector resolution: 10.3575 pixels mm-1	θmax = 25.1°, θmin = 3.2°
ω scans	h = −10→12
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2007)	k = −8→8
Tmin = 0.990, Tmax = 1.000	l = −25→26
9189 measured reflections

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)] = 0.064	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.145	H atoms treated by a mixture of independent and constrained refinement
S = 0.95	w = 1/[σ2(Fo2) + (0.0409P)2] where P = (Fo2 + 2Fc2)/3
2714 reflections	(Δ/σ)max < 0.001
189 parameters	Δρmax = 0.56 e Å−3
2 restraints	Δρmin = −0.33 e Å−3

Experimental. CrysAlisPro, Oxford Diffraction Ltd., Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

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
Br1	0.64263 (9)	0.24500 (13)	0.04609 (4)	0.0951 (4)
N1	0.4336 (5)	0.4954 (6)	0.1405 (2)	0.0504 (15)
H1	0.435 (6)	0.6246 (17)	0.138 (2)	0.061*
N3	0.3225 (5)	0.2096 (6)	0.1096 (2)	0.0468 (14)
H3	0.253 (3)	0.163 (7)	0.087 (2)	0.056*
O2	0.2482 (5)	0.5076 (6)	0.0762 (2)	0.0786 (16)
O6	0.6264 (5)	0.4897 (5)	0.1981 (2)	0.0752 (16)
O4	0.3920 (4)	−0.0903 (5)	0.13692 (18)	0.0579 (13)
C2	0.3306 (7)	0.4133 (8)	0.1065 (3)	0.0519 (18)
C4	0.4088 (6)	0.0884 (8)	0.1410 (3)	0.0450 (16)
C5	0.5229 (6)	0.1748 (6)	0.1812 (3)	0.0386 (15)
C6	0.5334 (7)	0.4010 (8)	0.1731 (3)	0.0505 (18)
C7	0.6478 (6)	0.0760 (8)	0.1667 (3)	0.0501 (17)
H7A	0.7191	0.1616	0.1817	0.060*
H7B	0.6588	−0.0463	0.1899	0.060*
C8	0.6567 (6)	0.0305 (9)	0.1013 (3)	0.0606 (19)
C9	0.6782 (7)	−0.1521 (11)	0.0779 (3)	0.084 (2)
H9A	0.6886	−0.2609	0.1040	0.101*
H9B	0.6823	−0.1675	0.0360	0.101*
C10	0.5050 (7)	0.1407 (8)	0.2512 (3)	0.0605 (19)
H10	0.5815	0.1959	0.2756	0.073*
C12	0.4966 (9)	−0.0656 (10)	0.2707 (4)	0.097 (3)
H12A	0.5544	−0.1461	0.2499	0.117*
H12B	0.4099	−0.1140	0.2593	0.117*
C13	0.5331 (10)	−0.0833 (13)	0.3418 (3)	0.129 (4)
H13D	0.6067	−0.0020	0.3546	0.193*
H13E	0.5530	−0.2184	0.3525	0.193*
H13F	0.4622	−0.0404	0.3622	0.193*
C14	0.3888 (8)	0.2595 (10)	0.2694 (3)	0.103 (3)
H14A	0.4032	0.3982	0.2640	0.154*
H14B	0.3793	0.2338	0.3117	0.154*
H14C	0.3120	0.2201	0.2436	0.154*
O1S	0.1014 (4)	0.0764 (5)	0.04030 (19)	0.0650 (14)
C1S	0.0085 (7)	0.2010 (7)	0.0056 (3)	0.072 (2)
H1S1	0.0491	0.3243	−0.0036	0.086*
H1S2	−0.0595	0.2313	0.0303	0.086*
C2S	0.0465 (7)	−0.1081 (8)	0.0515 (3)	0.066 (2)
H2S1	−0.0200	−0.0899	0.0781	0.080*
H2S2	0.1119	−0.1938	0.0727	0.080*

	U11	U22	U33	U12	U13	U23
Br1	0.1010 (8)	0.1162 (6)	0.0699 (6)	0.0078 (6)	0.0173 (5)	0.0284 (5)
N1	0.050 (4)	0.025 (2)	0.070 (3)	−0.006 (3)	−0.019 (3)	0.003 (3)
N3	0.048 (4)	0.025 (2)	0.062 (3)	−0.006 (2)	−0.014 (3)	0.002 (2)
O2	0.068 (4)	0.046 (2)	0.112 (4)	0.003 (2)	−0.028 (3)	0.021 (2)
O6	0.072 (4)	0.051 (2)	0.092 (4)	−0.017 (2)	−0.032 (3)	−0.008 (2)
O4	0.063 (3)	0.027 (2)	0.078 (3)	−0.0022 (19)	−0.011 (2)	0.0016 (19)
C2	0.056 (5)	0.037 (3)	0.061 (4)	0.004 (3)	0.000 (4)	0.009 (3)
C4	0.057 (5)	0.036 (3)	0.042 (4)	−0.002 (3)	0.006 (3)	0.006 (3)
C5	0.043 (4)	0.027 (3)	0.044 (4)	0.001 (3)	−0.003 (3)	0.005 (2)
C6	0.059 (5)	0.042 (3)	0.046 (4)	0.009 (4)	−0.011 (4)	0.002 (3)
C7	0.044 (5)	0.047 (3)	0.059 (4)	0.000 (3)	0.003 (3)	−0.001 (3)
C8	0.049 (5)	0.066 (4)	0.068 (5)	−0.003 (4)	0.009 (4)	−0.002 (4)
C9	0.091 (7)	0.098 (5)	0.068 (5)	0.003 (5)	0.031 (5)	0.005 (4)
C10	0.082 (6)	0.050 (3)	0.052 (4)	0.020 (4)	0.017 (4)	0.006 (3)
C12	0.107 (8)	0.084 (5)	0.103 (7)	−0.001 (5)	0.023 (6)	0.008 (5)
C13	0.144 (9)	0.186 (8)	0.060 (6)	0.060 (8)	0.029 (6)	0.072 (6)
C14	0.132 (8)	0.114 (6)	0.067 (5)	0.072 (6)	0.032 (5)	0.019 (5)
O1S	0.058 (3)	0.046 (2)	0.080 (3)	−0.003 (2)	−0.031 (3)	0.001 (2)
C1S	0.071 (5)	0.041 (3)	0.097 (6)	0.006 (3)	−0.016 (4)	−0.002 (4)
C2S	0.073 (6)	0.056 (4)	0.063 (5)	0.004 (4)	−0.014 (4)	0.012 (3)

Br1—C8	1.881 (6)	C10—C12	1.466 (8)
N1—C6	1.351 (7)	C10—C14	1.553 (9)
N1—C2	1.351 (7)	C10—H10	0.9800
N1—H1	0.876 (10)	C12—C13	1.558 (9)
N3—C4	1.344 (6)	C12—H12A	0.9700
N3—C2	1.384 (7)	C12—H12B	0.9700
N3—H3	0.89 (4)	C13—H13D	0.9600
O2—C2	1.203 (6)	C13—H13E	0.9600
O6—C6	1.215 (6)	C13—H13F	0.9600
O4—C4	1.224 (5)	C14—H14A	0.9600
C4—C5	1.510 (7)	C14—H14B	0.9600
C5—C7	1.540 (8)	C14—H14C	0.9600
C5—C6	1.547 (7)	O1S—C2S	1.410 (7)
C5—C10	1.583 (8)	O1S—C1S	1.431 (7)
C7—C8	1.479 (8)	C1S—C2Si	1.452 (8)
C7—H7A	0.9700	C1S—H1S1	0.9700
C7—H7B	0.9700	C1S—H1S2	0.9700
C8—C9	1.366 (8)	C2S—C1Si	1.452 (8)
C9—H9A	0.9300	C2S—H2S1	0.9700
C9—H9B	0.9300	C2S—H2S2	0.9700
C6—N1—C2	127.5 (5)	C14—C10—C5	111.4 (5)
C6—N1—H1	119 (4)	C12—C10—H10	106.3
C2—N1—H1	113 (4)	C14—C10—H10	106.3
C4—N3—C2	126.3 (5)	C5—C10—H10	106.3
C4—N3—H3	121 (3)	C10—C12—C13	110.3 (6)
C2—N3—H3	112 (3)	C10—C12—H12A	109.6
O2—C2—N1	123.6 (5)	C13—C12—H12A	109.6
O2—C2—N3	120.8 (6)	C10—C12—H12B	109.6
N1—C2—N3	115.6 (5)	C13—C12—H12B	109.6
O4—C4—N3	118.9 (5)	H12A—C12—H12B	108.1
O4—C4—C5	121.4 (5)	C12—C13—H13D	109.5
N3—C4—C5	119.6 (4)	C12—C13—H13E	109.5
C4—C5—C7	110.2 (4)	H13D—C13—H13E	109.5
C4—C5—C6	112.3 (5)	C12—C13—H13F	109.5
C7—C5—C6	109.4 (5)	H13D—C13—H13F	109.5
C4—C5—C10	108.8 (5)	H13E—C13—H13F	109.5
C7—C5—C10	110.2 (5)	C10—C14—H14A	109.5
C6—C5—C10	105.9 (4)	C10—C14—H14B	109.5
O6—C6—N1	121.9 (5)	H14A—C14—H14B	109.5
O6—C6—C5	120.2 (5)	C10—C14—H14C	109.5
N1—C6—C5	117.8 (5)	H14A—C14—H14C	109.5
C8—C7—C5	116.7 (5)	H14B—C14—H14C	109.5
C8—C7—H7A	108.1	C2S—O1S—C1S	110.4 (4)
C5—C7—H7A	108.1	O1S—C1S—C2Si	111.7 (5)
C8—C7—H7B	108.1	O1S—C1S—H1S1	109.3
C5—C7—H7B	108.1	C2Si—C1S—H1S1	109.3
H7A—C7—H7B	107.3	O1S—C1S—H1S2	109.3
C9—C8—C7	125.7 (6)	C2Si—C1S—H1S2	109.3
C9—C8—Br1	117.5 (6)	H1S1—C1S—H1S2	107.9
C7—C8—Br1	116.8 (4)	O1S—C2S—C1Si	111.1 (5)
C8—C9—H9A	120.0	O1S—C2S—H2S1	109.4
C8—C9—H9B	120.0	C1Si—C2S—H2S1	109.4
H9A—C9—H9B	120.0	O1S—C2S—H2S2	109.4
C12—C10—C14	110.0 (7)	C1Si—C2S—H2S2	109.4
C12—C10—C5	116.0 (5)	H2S1—C2S—H2S2	108.0

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O4ii	0.88 (1)	1.98 (2)	2.837 (5)	166 (6)
N3—H3···O1S	0.89 (4)	1.87 (4)	2.757 (6)	177 (5)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O4i	0.88 (1)	1.98 (2)	2.837 (5)	166 (6)
N3—H3⋯O1S	0.89 (4)	1.87 (4)	2.757 (6)	177 (5)

Symmetry code: (i) .