2-Phenyl­malonpiperadide and 2-phenyl­malonmorpholide

The structures of 2-phenyl­malonpiperadide [systematic name: 2-phenyl-1,3-bis­(piperidin-1-yl)­propane-1,3-dione, C₁₉H₂₆N₂O₂, (I)] and 2-phenyl­malonmorpholide [systematic name: 1,3-dimorpholino-2-phenyl­propane-1,3-dione, C₁₇H₂₂N₂O₄, (II)], have been determined and both their molecular conformations and packing arrangements compared. Although chemically similar, compounds (I) and (II) exhibit different molecular conformations. The only general conformational similarities are that their respective carbonyl groups are orientated in the same direction and the heterocyclic rings exist in the chair arrangement. General similarities in the packing arrangements arise due to both compounds having the same space group (P2₁2₁2₁) and a similar alignment of their phenyl-substituted backbone with respect to the c axis. Similar C—H...O hydrogen-bonding associations are listed for the carbonyl O atoms, while only one of the morpholine O atoms is involved in any such association.

S1. Comment

Symmetrical malonamides can be prepared by two classical methods (Burgada, 1964) with both involving the reaction of two molar equivalents of an amine with either diethyl malonate or malonyldichloride. A third, more modern but less efficient, synthesis involves the reaction of a two molar equivalence of a base or amine with 3-oxopyrazolo[1,2-a]pyrazol-8-ylium-1-olate (Zvilichovsky & David, 1982), a compound also derived from either diethyl malonate or malonyldichloride. The nucleophilic cleavage of derivatives of 3-oxopyrazolo[1,2-a]pyrazol-8-ylium-1-olate to produce symmetrical malonamides was also investigated by Potts et al. (1988), who studied their decomposition using morpholine, aniline or water. Experimental runs were performed in tetrahydrofuran at 298 K and took from a few s to several days for a complete reaction, depending on the substituents of the initial pyrazolo[1,2a]pyrazole with one of the slowest reactants being seen for 5,7-dimethyl-2-phenyl-1-oxo-1H-pyrazolo[1,2-a]pyrazol-4-ylium-3-olate. We decided to continue investigating the nucleophilic cleavage of this specific compound using a variety of nucleophiles including both piperidine and morpholine with all resultant products being 2-phenylmalonamide derivatives. Interestingly, a search of the April 2003 release of the Cambridge Structural Database (Allen, 2002) reveals that there are 37 reported structures of malonamides, including both symmetrical and unsymmetrical analogues, yet of these there is only one 2-phenylmalonamide derivative, that being the amide itself (Sakamoto et al., 2000). Reported here are the crystal structures of both 2-phenylmalonpiperadide, (I), and 2-phenylmalonmorpholide, (II).

Compounds (I) and (II) share crystallographic similarities by both packing in the same non-centrosymmetric space group and sharing similar cell dimensions and cell volumes. The only chemical difference between the two is the substitution of the piperidyl 4-position CH₂ groups in (I) for the morpholine O atoms in (II), with the loss of ca 104 ų in cell volume. However, these two O atoms have the potential to cause a difference in the solid-state packing of (II), as opposed to (I), because exposed O atoms can act as hydrogen-bond acceptors, in addition to the two malonamide carbonyl O atoms. Comparative molecular conformations for (I) and (II) are shown in Figs 1 and 2, respectively, while selected torsion angles are listed in Tables 1 and 3.

With both the saturated heterocyclic rings systems in the chair conformation and the carbonyl groups orientated in the same direction for both molecules, the important torsion angles become those containing the C16—C2 bond, specifically N4—C1—C2—C16 and C16—C2—C3—N10, because the backbone torsion angles for the two compounds, N4—C1—C2—C3 and C1—C2—C3—N10, are inversely similar. The conformation of 2-phenylmalonamide itself differs from both (I) and (II), with the carbonyl groups arranged in opposing directions and the backbone chain being much flatter. Comparative torsion angles are 98.15 (N1—C1—C2—C4), 101.16 (C4—C2—C3—N2), −26.26 (N1—C1—C2—C3) and 134.11° (C1—C2—C3—N4) (note that in 2-phenylmalonamide atom C4 = C16).

The C—H···O hydrogen-bonding associations for compounds (I) and (II) are listed in Tables 2 and 4, respectively, and although both compounds arrange very differently the malonamide carbonyl O atoms in each are involved in the same number of intermolecular C—H···O associations. In addition, there is only one listed association to a morpholine O atom (O13) indicating that the morpholine O atoms do not have much effect on the difference in molecular packing. The unit cells for (I) and (II), both viewed down the a axis, are shown in Figs 3 and 4. Interestingly, the phenyl rings in both compounds are arranged almost perpendicular to the c axis orientating the main length of the backbone in the same direction as the c axis. However, apart from these general packing similarities the two structures remain considerably different. The occurrence of crystallographic differences between chemically similar compounds, such as (I) and (II), is interesting and in the structures discussed in this paper have no apparent cause. Additional comparative compounds would be those containing thiomorpholine, piperazine or any minor 4-position derivative of piperidine or piperazine.

S2. Experimental

For (I), a 2:1 molar ratio of piperidine (0.71 g, 8.33 mmol) and 5,7-dimethyl-2-phenyl-1-oxo-1H-pyrazolo[1,2-a]pyrazol-4-ylium-3-olate (1.00 g, 4.20 mmol) was refluxed in tetrahydrofuran (THF, 100 ml) for 48 h. Upon cooling the reaction, the solvent was removed under reduced pressure. The crude product was redissolved in minimal THF and precipitated by pouring into cool deionized water (100 ml). Collection in vacuo yielded an off-white powder (0.94 g, 72%; m.p. 416–419 K). Spectroscopic analysis, IR (ν_max, KBr, cm⁻¹: 1647 (s) and 1626 (s) (CO); ¹H NMR (400 MHz, d₆-DMSO, Me₄Si, p.p.m.): 1.40 (m, 12H, CH₂), 3.40 (m, 8H, NCH₂), 5.40 (s, 1H), 7.30 (m, 5H, ArH); m/z (ES): 315 (MH⁺, 15%), 337 (M + Na, 39%), 651 (2M + Na, 100%). Compound (II) was produced using a method analogous to that used for (I), using morpholine (1.45 g, 1.67 mmol) and 5,7-dimethyl-2-phenyl-1-oxo-1H-pyrazolo[1,2-a]pyrazol-4-ylium-3-olate (2.00 g, 8.33 mmol). The final product was collected in vacuo as a white powder (2.33 g, 88%, m.p. 459–461 K). Spectroscopic analysis, IR (ν_max, KBr, cm⁻¹: 1658 (s) and 1633 (s) (CO); ¹H NMR (400 MHz, d₆-DMSO, Me₄Si, p.p.m.): 3.27–3.63 (br m, 16H, NCH₂ & OCH₂), 5.51 (s, 1H), 7.21–7.39 (m, 5H, ArH); m/z (ES): 319 (MH⁺, 30%), 341 (M + Na, 100%), 659 (2M + Na, 73%). Crystals of both were grown from CHCl₃ solutions.

S3. Refinement

All H atoms were included in the refinement, at calculated positions, in the riding-model approximation, with C—H set at 0.95 (aryl H), 0.99 (CH₂) and 1.00 Å (C—H). The isotropic displacement parameters were set equal to 1.25U_eq of the carrier atom. The high R_int value for (I) was the result of weak high-angle data. The numbers of Friedel pairs for (I) and (II) are 1386 and 1195, respectively. In the absence of large atoms in both structures or strong anomalous dispersion effects, the Friedel opposites were merged prior to refinement.

Computing details

For both compounds, data collection: DENZO (Otwinowski & Minor, 1997) and COLLECT (Nonius, 1998); cell refinement: DENZO and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLUTON94 (Spek, 1994) and PLATON97 (Spek, 1997); software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. The molecular configuration and atom-numbering scheme for (I). Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. The molecular configuration and atom-numbering scheme for (II). Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 3. Packing diagram of (I), viewed down the a axis.
	Fig. 4. Packing diagram of (II), viewed down the a axis.

(I) 2-phenyl-1,3-bis(piperidin-1-yl)propane-1,3-dione

Crystal data

C19H26N2O2	Dx = 1.259 Mg m^−3
Mr = 314.42	Melting point: 416-419 K K
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 6419 reflections
a = 6.1652 (3) Å	θ = 2.9–27.5°
b = 10.2718 (5) Å	µ = 0.08 mm^−1
c = 26.1962 (17) Å	T = 120 K
V = 1658.95 (16) Å^3	Plate, colourless
Z = 4	0.15 × 0.10 × 0.04 mm
F(000) = 680

Data collection

Bruker Nonius KappaCCD area-detector diffractometer	2177 independent reflections
Radiation source: Bruker–Nonius FR591 rotating anode	1013 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.176
Detector resolution: 9.091 pixels mm^-1	θmax = 27.5°, θmin = 3.1°
ϕ and ω scans	h = −7→7
Absorption correction: multi-scan (SORTAV; Blessing, 1995)	k = −9→13
Tmin = 0.988, Tmax = 0.997	l = −34→25
6936 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.069	H-atom parameters constrained
wR(F^2) = 0.177	w = 1/[σ^2(Fo^2) + (0.0705P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.94	(Δ/σ)max < 0.001
2177 reflections	Δρmax = 0.34 e Å^−3
209 parameters	Δρmin = −0.34 e Å^−3
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.012 (3)

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

	x	y	z	Uiso*/Ueq
C1	0.9803 (9)	0.2467 (6)	0.1834 (2)	0.0289 (14)
O1	0.9011 (6)	0.3469 (4)	0.19950 (14)	0.0328 (10)
C2	1.1346 (8)	0.2493 (5)	0.1361 (2)	0.0242 (13)
H2	1.2586	0.1884	0.1421	0.030*
C3	1.0037 (9)	0.2022 (5)	0.0903 (2)	0.0276 (14)
O3	0.8046 (6)	0.2120 (4)	0.09015 (15)	0.0364 (12)
N4	0.9471 (7)	0.1286 (4)	0.20548 (17)	0.0287 (12)
C5	0.7861 (10)	0.1181 (7)	0.2474 (2)	0.0370 (17)
H51	0.7481	0.2060	0.2600	0.046*
H52	0.8488	0.0680	0.2761	0.046*
C6	0.5838 (10)	0.0500 (6)	0.2278 (2)	0.0372 (16)
H61	0.4764	0.0420	0.2557	0.047*
H62	0.5178	0.1020	0.2000	0.047*
C7	0.6426 (10)	−0.0836 (6)	0.2080 (2)	0.0424 (17)
H71	0.6956	−0.1379	0.2367	0.053*
H72	0.5116	−0.1258	0.1937	0.053*
C8	0.8154 (9)	−0.0758 (6)	0.1673 (2)	0.0379 (16)
H81	0.7548	−0.0336	0.1365	0.047*
H82	0.8621	−0.1648	0.1579	0.047*
C9	1.0098 (10)	0.0014 (5)	0.1861 (2)	0.0365 (16)
H91	1.0838	−0.0480	0.2134	0.046*
H92	1.1138	0.0128	0.1576	0.046*
N10	1.1110 (7)	0.1500 (4)	0.04983 (17)	0.0266 (12)
C11	0.9889 (9)	0.0865 (5)	0.0089 (2)	0.0309 (15)
H111	1.0442	0.1156	−0.0247	0.039*
H112	0.8337	0.1107	0.0113	0.039*
C12	1.0134 (10)	−0.0602 (5)	0.0138 (2)	0.0313 (15)
H121	0.9479	−0.0896	0.0463	0.039*
H122	0.9352	−0.1034	−0.0146	0.039*
C13	1.2499 (10)	−0.0990 (6)	0.0124 (2)	0.0385 (16)
H131	1.3102	−0.0801	−0.0219	0.048*
H132	1.2628	−0.1937	0.0185	0.048*
C14	1.3803 (10)	−0.0252 (6)	0.0528 (2)	0.0354 (16)
H141	1.3343	−0.0537	0.0872	0.044*
H142	1.5363	−0.0457	0.0489	0.044*
C15	1.3465 (9)	0.1212 (6)	0.0476 (2)	0.0317 (15)
H151	1.4227	0.1672	0.0755	0.040*
H152	1.4070	0.1518	0.0147	0.040*
C16	1.2215 (9)	0.3858 (5)	0.1280 (2)	0.0246 (14)
C17	1.4316 (9)	0.4170 (6)	0.1421 (2)	0.0275 (14)
H17	1.5256	0.3514	0.1549	0.034*
C18	1.5047 (10)	0.5438 (6)	0.1375 (2)	0.0333 (16)
H18	1.6483	0.5650	0.1477	0.042*
C19	1.3699 (10)	0.6408 (6)	0.1180 (2)	0.0355 (16)
H19	1.4202	0.7279	0.1148	0.044*
C20	1.1603 (10)	0.6076 (6)	0.1034 (2)	0.0363 (16)
H20	1.0660	0.6726	0.0903	0.045*
C21	1.0878 (10)	0.4805 (6)	0.1078 (2)	0.0313 (15)
H21	0.9455	0.4585	0.0969	0.039*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.028 (3)	0.033 (4)	0.025 (3)	0.001 (3)	−0.008 (3)	−0.005 (3)
O1	0.037 (2)	0.029 (2)	0.032 (2)	0.000 (2)	0.001 (2)	−0.007 (2)
C2	0.022 (3)	0.023 (3)	0.028 (3)	0.005 (3)	−0.011 (2)	0.000 (3)
C3	0.032 (3)	0.020 (3)	0.030 (4)	−0.003 (3)	−0.004 (3)	0.009 (3)
O3	0.017 (2)	0.053 (3)	0.040 (3)	0.0046 (19)	−0.0048 (19)	−0.007 (2)
N4	0.033 (3)	0.024 (3)	0.029 (3)	0.006 (2)	0.001 (2)	−0.005 (3)
C5	0.044 (4)	0.043 (4)	0.024 (3)	0.002 (3)	0.008 (3)	0.004 (3)
C6	0.032 (3)	0.050 (4)	0.030 (3)	0.001 (3)	0.001 (3)	0.000 (3)
C7	0.036 (4)	0.049 (5)	0.042 (4)	−0.007 (4)	−0.003 (3)	−0.004 (4)
C8	0.035 (3)	0.041 (4)	0.038 (4)	−0.002 (3)	−0.001 (3)	0.000 (3)
C9	0.038 (4)	0.031 (4)	0.041 (4)	0.008 (3)	0.001 (3)	−0.003 (3)
N10	0.022 (2)	0.026 (3)	0.031 (3)	0.000 (2)	−0.001 (2)	−0.006 (2)
C11	0.028 (3)	0.036 (4)	0.029 (3)	−0.004 (3)	0.000 (3)	0.000 (3)
C12	0.039 (4)	0.026 (3)	0.029 (3)	−0.005 (3)	0.007 (3)	−0.005 (3)
C13	0.049 (4)	0.024 (4)	0.042 (4)	0.002 (3)	0.011 (3)	0.006 (3)
C14	0.031 (4)	0.038 (4)	0.037 (4)	0.009 (3)	0.008 (3)	0.011 (3)
C15	0.029 (3)	0.033 (4)	0.033 (3)	0.004 (3)	0.001 (3)	−0.001 (3)
C16	0.032 (3)	0.021 (4)	0.021 (3)	−0.001 (3)	−0.002 (3)	−0.006 (3)
C17	0.022 (3)	0.034 (4)	0.026 (3)	−0.002 (3)	−0.002 (3)	−0.009 (3)
C18	0.027 (3)	0.044 (4)	0.029 (3)	−0.006 (3)	0.006 (3)	−0.012 (3)
C19	0.055 (4)	0.027 (4)	0.025 (3)	0.001 (3)	0.009 (3)	−0.002 (3)
C20	0.039 (4)	0.043 (5)	0.027 (3)	0.003 (3)	−0.002 (3)	0.007 (3)
C21	0.034 (3)	0.033 (4)	0.027 (3)	−0.010 (3)	−0.006 (3)	0.002 (3)

Geometric parameters (Å, º)

C3—O3	1.231 (6)	C5—C6	1.519 (8)
C3—N10	1.361 (7)	C5—H51	0.99
C3—C2	1.524 (7)	C5—H52	0.99
C2—C16	1.516 (7)	C6—C7	1.510 (8)
C2—C1	1.562 (8)	C6—H61	0.99
C2—H2	1.00	C6—H62	0.99
C1—O1	1.215 (6)	C7—C8	1.509 (8)
C1—N4	1.360 (7)	C7—H71	0.99
N10—C11	1.464 (7)	C7—H72	0.99
N10—C15	1.483 (7)	C8—C9	1.518 (8)
C11—C12	1.520 (8)	C8—H81	0.99
C11—H111	0.99	C8—H82	0.99
C11—H112	0.99	C9—H91	0.99
C12—C13	1.512 (8)	C9—H92	0.99
C12—H121	0.99	C16—C21	1.380 (8)
C12—H122	0.99	C16—C17	1.384 (7)
C13—C14	1.530 (8)	C17—C18	1.384 (8)
C13—H131	0.99	C17—H17	0.95
C13—H132	0.99	C18—C19	1.394 (8)
C14—C15	1.524 (8)	C18—H18	0.95
C14—H141	0.99	C19—C20	1.390 (8)
C14—H142	0.99	C19—H19	0.95
C15—H151	0.99	C20—C21	1.384 (8)
C15—H152	0.99	C20—H20	0.95
N4—C9	1.454 (7)	C21—H21	0.95
N4—C5	1.484 (7)
O3—C3—N10	121.0 (5)	N4—C5—C6	109.4 (5)
O3—C3—C2	120.3 (5)	N4—C5—H51	109.8
N10—C3—C2	118.7 (5)	C6—C5—H51	109.8
C16—C2—C3	111.8 (4)	N4—C5—H52	109.8
C16—C2—C1	110.0 (5)	C6—C5—H52	109.8
C3—C2—C1	107.2 (4)	H51—C5—H52	108.2
C16—C2—H2	109.3	C7—C6—C5	109.7 (5)
C3—C2—H2	109.3	C7—C6—H61	109.7
C1—C2—H2	109.3	C5—C6—H61	109.7
O1—C1—N4	123.2 (5)	C7—C6—H62	109.7
O1—C1—C2	120.4 (5)	C5—C6—H62	109.7
N4—C1—C2	116.4 (5)	H61—C6—H62	108.2
C3—N10—C11	119.8 (4)	C8—C7—C6	111.3 (5)
C3—N10—C15	125.9 (4)	C8—C7—H71	109.4
C11—N10—C15	112.7 (4)	C6—C7—H71	109.4
N10—C11—C12	109.2 (5)	C8—C7—H72	109.4
N10—C11—H111	109.8	C6—C7—H72	109.4
C12—C11—H111	109.8	H71—C7—H72	108.0
N10—C11—H112	109.8	C7—C8—C9	110.9 (5)
C12—C11—H112	109.8	C7—C8—H81	109.5
H111—C11—H112	108.3	C9—C8—H81	109.5
C13—C12—C11	110.8 (5)	C7—C8—H82	109.5
C13—C12—H121	109.5	C9—C8—H82	109.5
C11—C12—H121	109.5	H81—C8—H82	108.0
C13—C12—H122	109.5	N4—C9—C8	111.8 (5)
C11—C12—H122	109.5	N4—C9—H91	109.2
H121—C12—H122	108.1	C8—C9—H91	109.2
C12—C13—C14	111.1 (5)	N4—C9—H92	109.2
C12—C13—H131	109.4	C8—C9—H92	109.2
C14—C13—H131	109.4	H91—C9—H92	107.9
C12—C13—H132	109.4	C21—C16—C17	119.8 (5)
C14—C13—H132	109.4	C21—C16—C2	119.6 (5)
H131—C13—H132	108.0	C17—C16—C2	120.5 (5)
C15—C14—C13	110.8 (5)	C16—C17—C18	119.9 (6)
C15—C14—H141	109.5	C16—C17—H17	120.0
C13—C14—H141	109.5	C18—C17—H17	120.0
C15—C14—H142	109.5	C17—C18—C19	120.7 (6)
C13—C14—H142	109.5	C17—C18—H18	119.6
H141—C14—H142	108.1	C19—C18—H18	119.6
N10—C15—C14	109.1 (4)	C20—C19—C18	118.6 (6)
N10—C15—H151	109.9	C20—C19—H19	120.7
C14—C15—H151	109.9	C18—C19—H19	120.7
N10—C15—H152	109.9	C21—C20—C19	120.6 (6)
C14—C15—H152	109.9	C21—C20—H20	119.7
H151—C15—H152	108.3	C19—C20—H20	119.7
C1—N4—C9	127.8 (5)	C16—C21—C20	120.3 (5)
C1—N4—C5	118.7 (5)	C16—C21—H21	119.9
C9—N4—C5	111.8 (5)	C20—C21—H21	119.9
O1—C1—C2—C16	19.1 (7)	O1—C1—N4—C5	7.7 (8)
N4—C1—C2—C16	−159.0 (5)	C2—C1—N4—C5	−174.3 (4)
O1—C1—C2—C3	−102.6 (6)	C1—N4—C5—C6	106.2 (6)
N4—C1—C2—C3	79.3 (5)	C9—N4—C5—C6	−60.1 (6)
C16—C2—C3—O3	−96.3 (6)	N4—C5—C6—C7	58.8 (7)
C1—C2—C3—O3	24.2 (7)	C5—C6—C7—C8	−56.3 (7)
C16—C2—C3—N10	83.4 (6)	C6—C7—C8—C9	52.9 (7)
C1—C2—C3—N10	−156.1 (5)	C1—N4—C9—C8	−107.4 (6)
O3—C3—N10—C11	−9.4 (8)	C5—N4—C9—C8	57.3 (6)
C2—C3—N10—C11	170.9 (4)	C7—C8—C9—N4	−53.1 (7)
O3—C3—N10—C15	−173.6 (5)	C3—C2—C16—C21	44.3 (7)
C2—C3—N10—C15	6.7 (7)	C1—C2—C16—C21	−74.6 (6)
C3—N10—C11—C12	−104.9 (5)	C3—C2—C16—C17	−137.5 (5)
C15—N10—C11—C12	61.3 (6)	C1—C2—C16—C17	103.6 (6)
N10—C11—C12—C13	−57.2 (6)	C21—C16—C17—C18	2.2 (8)
C11—C12—C13—C14	54.3 (7)	C2—C16—C17—C18	−176.0 (5)
C12—C13—C14—C15	−53.6 (6)	C16—C17—C18—C19	−1.0 (8)
C3—N10—C15—C14	104.7 (6)	C17—C18—C19—C20	0.1 (8)
C11—N10—C15—C14	−60.5 (6)	C18—C19—C20—C21	−0.4 (9)
C13—C14—C15—N10	55.2 (6)	C17—C16—C21—C20	−2.5 (9)
O1—C1—N4—C9	171.5 (5)	C2—C16—C21—C20	175.7 (5)
C2—C1—N4—C9	−10.5 (7)	C19—C20—C21—C16	1.6 (9)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C5—H51···O1	0.99	2.34	2.757 (7)	104
C9—H91···O1^i	0.99	2.52	3.436 (7)	153
C11—H112···O3	0.99	2.32	2.735 (7)	104
C15—H151···O3^ii	0.99	2.43	3.177 (7)	132
C17—H17···O1^ii	0.95	2.59	3.340 (7)	136

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

(II) 1,3-dimorpholino-2-phenylpropane-1,3-dione

Crystal data

C17H22N2O4	Dx = 1.360 Mg m^−3
Mr = 318.37	Melting point: 459-461 K K
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 6411 reflections
a = 8.3900 (1) Å	θ = 1.0–30.5°
b = 10.8464 (2) Å	µ = 0.10 mm^−1
c = 17.0838 (4) Å	T = 120 K
V = 1554.65 (5) Å^3	Block, colourless
Z = 4	0.60 × 0.40 × 0.26 mm
F(000) = 680

Data collection

Bruker–Nonius KappaCCD area-detector diffractometer	2032 independent reflections
Radiation source: Bruker Nonius FR591 rotating anode	1909 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.066
Detector resolution: 9.091 pixels mm^-1	θmax = 27.5°, θmin = 2.2°
ϕ and ω scans	h = −9→10
Absorption correction: multi-scan (SORTAV; Blessing, 1995)	k = −11→14
Tmin = 0.944, Tmax = 0.975	l = −18→22
9999 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.039	H-atom parameters constrained
wR(F^2) = 0.103	w = 1/[σ^2(Fo^2) + (0.0639P)^2 + 0.2187P] where P = (Fo^2 + 2Fc^2)/3
S = 1.12	(Δ/σ)max < 0.001
2032 reflections	Δρmax = 0.38 e Å^−3
209 parameters	Δρmin = −0.35 e Å^−3
0 restraints	Extinction correction: SHELXL07, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.067 (7)

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

	x	y	z	Uiso*/Ueq
C1	0.9933 (2)	0.34874 (16)	0.78954 (10)	0.0154 (4)
O1	1.02680 (19)	0.24983 (11)	0.75851 (8)	0.0231 (3)
C2	0.9005 (2)	0.44671 (17)	0.74398 (10)	0.0147 (4)
H2	0.9537	0.5285	0.7507	0.018*
C3	0.9009 (2)	0.41155 (17)	0.65666 (10)	0.0174 (4)
O3	0.78446 (18)	0.36214 (15)	0.62747 (8)	0.0273 (4)
N4	1.03130 (19)	0.37393 (14)	0.86451 (9)	0.0170 (3)
C5	1.1032 (2)	0.27872 (18)	0.91380 (11)	0.0207 (4)
H51	1.2087	0.3066	0.9327	0.026*
H52	1.1183	0.2022	0.8831	0.026*
C6	0.9946 (3)	0.25402 (18)	0.98249 (12)	0.0255 (5)
H61	0.8921	0.2205	0.9632	0.032*
H62	1.0440	0.1912	1.0168	0.032*
O7	0.9653 (2)	0.36275 (13)	1.02649 (8)	0.0276 (4)
C8	0.8912 (2)	0.45425 (19)	0.97879 (12)	0.0232 (4)
H81	0.8726	0.5295	1.0103	0.029*
H82	0.7865	0.4235	0.9606	0.029*
C9	0.9936 (2)	0.48630 (16)	0.90849 (10)	0.0178 (4)
H91	0.9360	0.5450	0.8743	0.022*
H92	1.0934	0.5262	0.9262	0.022*
N10	1.0324 (2)	0.44033 (16)	0.61470 (9)	0.0201 (4)
C11	1.0427 (3)	0.4011 (2)	0.53262 (11)	0.0242 (5)
H111	1.0619	0.4736	0.4987	0.030*
H112	0.9408	0.3626	0.5165	0.030*
C12	1.1765 (3)	0.30997 (19)	0.52314 (12)	0.0260 (5)
H121	1.1533	0.2352	0.5544	0.033*
H122	1.1847	0.2853	0.4675	0.033*
O13	1.32469 (18)	0.36189 (15)	0.54814 (8)	0.0277 (4)
C14	1.3176 (3)	0.3948 (2)	0.62909 (11)	0.0248 (4)
H141	1.4207	0.4313	0.6452	0.031*
H142	1.2995	0.3198	0.6609	0.031*
C15	1.1845 (2)	0.48672 (17)	0.64430 (11)	0.0190 (4)
H151	1.1757	0.5021	0.7013	0.024*
H152	1.2101	0.5659	0.6184	0.024*
C16	0.7307 (2)	0.45459 (17)	0.77398 (10)	0.0159 (4)
C17	0.6589 (2)	0.56884 (18)	0.78233 (10)	0.0192 (4)
H17	0.7158	0.6413	0.7684	0.024*
C18	0.5037 (2)	0.57841 (19)	0.81094 (11)	0.0226 (4)
H18	0.4554	0.6571	0.8171	0.028*
C19	0.4205 (2)	0.4727 (2)	0.83027 (11)	0.0228 (4)
H19	0.3145	0.4789	0.8495	0.028*
C20	0.4906 (2)	0.3580 (2)	0.82179 (11)	0.0222 (4)
H20	0.4329	0.2855	0.8349	0.028*
C21	0.6463 (2)	0.34934 (18)	0.79396 (11)	0.0192 (4)
H21	0.6949	0.2707	0.7886	0.024*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0131 (8)	0.0174 (8)	0.0157 (8)	0.0004 (7)	0.0019 (6)	−0.0005 (7)
O1	0.0298 (8)	0.0184 (7)	0.0209 (7)	0.0062 (6)	0.0015 (6)	−0.0029 (5)
C2	0.0164 (9)	0.0158 (8)	0.0120 (8)	−0.0003 (7)	0.0009 (6)	−0.0022 (6)
C3	0.0183 (9)	0.0201 (9)	0.0139 (8)	0.0014 (7)	−0.0010 (7)	−0.0021 (7)
O3	0.0233 (7)	0.0400 (8)	0.0188 (7)	−0.0058 (7)	−0.0020 (6)	−0.0085 (6)
N4	0.0153 (7)	0.0197 (7)	0.0160 (7)	0.0031 (6)	−0.0010 (6)	−0.0001 (6)
C5	0.0195 (9)	0.0249 (9)	0.0178 (9)	0.0047 (8)	−0.0002 (7)	0.0028 (8)
C6	0.0309 (11)	0.0237 (9)	0.0219 (9)	−0.0008 (9)	0.0051 (9)	0.0034 (8)
O7	0.0405 (9)	0.0254 (7)	0.0169 (6)	0.0004 (7)	0.0052 (6)	0.0015 (6)
C8	0.0236 (10)	0.0241 (9)	0.0218 (9)	−0.0013 (9)	0.0041 (8)	−0.0026 (8)
C9	0.0194 (9)	0.0179 (8)	0.0161 (8)	−0.0008 (7)	−0.0017 (7)	−0.0025 (7)
N10	0.0203 (8)	0.0274 (8)	0.0127 (7)	−0.0012 (7)	0.0010 (6)	−0.0038 (6)
C11	0.0292 (11)	0.0313 (10)	0.0121 (8)	−0.0013 (9)	0.0025 (7)	−0.0045 (8)
C12	0.0343 (12)	0.0220 (9)	0.0218 (9)	−0.0026 (9)	0.0080 (9)	−0.0029 (8)
O13	0.0265 (8)	0.0341 (8)	0.0225 (7)	0.0016 (7)	0.0082 (6)	−0.0021 (6)
C14	0.0238 (10)	0.0318 (11)	0.0187 (9)	0.0014 (8)	0.0032 (8)	0.0009 (8)
C15	0.0196 (9)	0.0207 (9)	0.0167 (8)	−0.0030 (7)	0.0022 (7)	−0.0008 (7)
C16	0.0173 (9)	0.0195 (8)	0.0109 (7)	0.0000 (7)	−0.0009 (6)	−0.0015 (7)
C17	0.0195 (9)	0.0191 (9)	0.0189 (8)	−0.0002 (7)	0.0019 (7)	0.0013 (7)
C18	0.0198 (9)	0.0256 (10)	0.0224 (9)	0.0064 (8)	0.0019 (8)	0.0012 (8)
C19	0.0152 (9)	0.0359 (11)	0.0173 (9)	−0.0029 (9)	0.0016 (6)	−0.0004 (8)
C20	0.0222 (10)	0.0277 (9)	0.0168 (8)	−0.0083 (9)	−0.0007 (7)	0.0005 (8)
C21	0.0207 (9)	0.0192 (9)	0.0178 (8)	−0.0012 (8)	−0.0026 (7)	−0.0015 (7)

Geometric parameters (Å, º)

C1—O1	1.229 (2)	C11—C12	1.505 (3)
C1—N4	1.348 (2)	C11—H111	0.99
C1—C2	1.530 (2)	C11—H112	0.99
C2—C16	1.516 (2)	C12—O13	1.430 (3)
C2—C3	1.540 (2)	C12—H121	0.99
C2—H2	1.00	C12—H122	0.99
C3—O3	1.220 (2)	O13—C14	1.429 (2)
C3—N10	1.353 (3)	C14—C15	1.519 (3)
N4—C5	1.463 (2)	C14—H141	0.99
N4—C9	1.466 (2)	C14—H142	0.99
C5—C6	1.509 (3)	C15—H151	0.99
C5—H51	0.99	C15—H152	0.99
C5—H52	0.99	C16—C17	1.385 (3)
C6—O7	1.420 (2)	C16—C21	1.386 (3)
C6—H61	0.99	C17—C18	1.395 (3)
C6—H62	0.99	C17—H17	0.95
O7—C8	1.427 (3)	C18—C19	1.382 (3)
C8—C9	1.517 (3)	C18—H18	0.95
C8—H81	0.99	C19—C20	1.384 (3)
C8—H82	0.99	C19—H19	0.95
C9—H91	0.99	C20—C21	1.393 (3)
C9—H92	0.99	C20—H20	0.95
N10—C15	1.462 (2)	C21—H21	0.95
N10—C11	1.468 (2)
O1—C1—N4	122.18 (17)	N10—C11—C12	109.69 (17)
O1—C1—C2	120.21 (16)	N10—C11—H111	109.7
N4—C1—C2	117.57 (15)	C12—C11—H111	109.7
C16—C2—C1	110.20 (14)	N10—C11—H112	109.7
C16—C2—C3	110.07 (15)	C12—C11—H112	109.7
C1—C2—C3	108.65 (14)	H111—C11—H112	108.2
C16—C2—H2	109.3	O13—C12—C11	110.98 (16)
C1—C2—H2	109.3	O13—C12—H121	109.4
C3—C2—H2	109.3	C11—C12—H121	109.4
O3—C3—N10	122.54 (16)	O13—C12—H122	109.4
O3—C3—C2	120.20 (17)	C11—C12—H122	109.4
N10—C3—C2	117.24 (16)	H121—C12—H122	108.0
C1—N4—C5	120.09 (16)	C14—O13—C12	110.55 (15)
C1—N4—C9	127.19 (15)	O13—C14—C15	111.10 (16)
C5—N4—C9	112.38 (15)	O13—C14—H141	109.4
N4—C5—C6	108.92 (16)	C15—C14—H141	109.4
N4—C5—H51	109.9	O13—C14—H142	109.4
C6—C5—H51	109.9	C15—C14—H142	109.4
N4—C5—H52	109.9	H141—C14—H142	108.0
C6—C5—H52	109.9	N10—C15—C14	110.89 (15)
H51—C5—H52	108.3	N10—C15—H151	109.5
O7—C6—C5	111.64 (16)	C14—C15—H151	109.5
O7—C6—H61	109.3	N10—C15—H152	109.5
C5—C6—H61	109.3	C14—C15—H152	109.5
O7—C6—H62	109.3	H151—C15—H152	108.0
C5—C6—H62	109.3	C17—C16—C21	119.26 (16)
H61—C6—H62	108.0	C17—C16—C2	119.60 (16)
C6—O7—C8	110.54 (16)	C21—C16—C2	121.13 (17)
O7—C8—C9	111.40 (16)	C16—C17—C18	120.59 (18)
O7—C8—H81	109.3	C16—C17—H17	119.7
C9—C8—H81	109.3	C18—C17—H17	119.7
O7—C8—H82	109.3	C19—C18—C17	119.57 (18)
C9—C8—H82	109.3	C19—C18—H18	120.2
H81—C8—H82	108.0	C17—C18—H18	120.2
N4—C9—C8	109.71 (15)	C18—C19—C20	120.39 (17)
N4—C9—H91	109.7	C18—C19—H19	119.8
C8—C9—H91	109.7	C20—C19—H19	119.8
N4—C9—H92	109.7	C19—C20—C21	119.66 (19)
C8—C9—H92	109.7	C19—C20—H20	120.2
H91—C9—H92	108.2	C21—C20—H20	120.2
C3—N10—C15	127.47 (14)	C16—C21—C20	120.52 (19)
C3—N10—C11	119.14 (16)	C16—C21—H21	119.7
C15—N10—C11	112.29 (15)	C20—C21—H21	119.7
O1—C1—C2—C16	106.91 (18)	O3—C3—N10—C11	−5.7 (3)
N4—C1—C2—C16	−71.0 (2)	C2—C3—N10—C11	175.85 (16)
O1—C1—C2—C3	−13.8 (2)	C3—N10—C11—C12	−115.2 (2)
N4—C1—C2—C3	168.29 (15)	C15—N10—C11—C12	53.7 (2)
C16—C2—C3—O3	−20.3 (2)	N10—C11—C12—O13	−57.7 (2)
C1—C2—C3—O3	100.5 (2)	C11—C12—O13—C14	60.9 (2)
C16—C2—C3—N10	158.25 (16)	C12—O13—C14—C15	−58.5 (2)
C1—C2—C3—N10	−81.0 (2)	C3—N10—C15—C14	115.8 (2)
O1—C1—N4—C5	−5.1 (3)	C11—N10—C15—C14	−52.0 (2)
C2—C1—N4—C5	172.81 (15)	O13—C14—C15—N10	54.0 (2)
O1—C1—N4—C9	−177.95 (17)	C1—C2—C16—C17	139.41 (17)
C2—C1—N4—C9	0.0 (3)	C3—C2—C16—C17	−100.77 (19)
C1—N4—C5—C6	−119.06 (19)	C1—C2—C16—C21	−40.0 (2)
C9—N4—C5—C6	54.8 (2)	C3—C2—C16—C21	79.8 (2)
N4—C5—C6—O7	−57.5 (2)	C21—C16—C17—C18	0.4 (3)
C5—C6—O7—C8	60.1 (2)	C2—C16—C17—C18	−179.03 (15)
C6—O7—C8—C9	−58.5 (2)	C16—C17—C18—C19	−0.7 (3)
C1—N4—C9—C8	119.39 (19)	C17—C18—C19—C20	0.3 (3)
C5—N4—C9—C8	−53.9 (2)	C18—C19—C20—C21	0.3 (3)
O7—C8—C9—N4	55.0 (2)	C17—C16—C21—C20	0.3 (3)
O3—C3—N10—C15	−172.72 (18)	C2—C16—C21—C20	179.70 (16)
C2—C3—N10—C15	8.8 (3)	C19—C20—C21—C16	−0.6 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O1^i	1.00	2.41	3.344 (2)	155
C17—H17···O1^i	0.95	2.50	3.361 (2)	150
C5—H52···O1	0.99	2.32	2.747 (2)	105
C9—H92···O13^ii	0.99	2.51	3.275 (2)	134
C11—H112···O3	0.99	2.31	2.738 (3)	105
C12—H122···O3^iii	0.99	2.43	3.305 (2)	148

Symmetry codes: (i) −x+2, y+1/2, −z+3/2; (ii) −x+5/2, −y+1, z+1/2; (iii) x+1/2, −y+1/2, −z+1.