2-Oxo-2-phenyl-N-[(R)-1-phenyl­ethyl]acetamide and N,N-dimethyl-2-(1-naphth­yl)-2-oxoacetamide: possibility of Yang photocyclization in a crystal

The crystal structures of 2-oxo-2-phenyl-N-[(R)-1-phenyl­ethyl]acetamide, C₁₆H₁₅NO₂, (I), and N,N-dimethyl-2-(1-naph­thyl)-2-oxoacetamide, C₁₄H₁₃NO₂, (II), were determined in an attempt to understand the reason for the lack of Yang photocyclization in their respective crystals. In the case of (I), the long distance between the O atom of the carbonyl group and the [gamma]-H atom, and between the C atom of the carbonyl group and the [gamma]-C atom, preclude Yang photocyclization. For (II), the deviation of the [gamma]-H atom from the plane of the carbonyl group and inter­actions between the naphthalene rings are regarded as possible reasons for the chemical inertia. The two independent mol­ecules of (I) differ in their conformation. N-H...O hydrogen bonds link molecules of (I) into chains extended along the b axis.

S1. Comment

Structural changes in crystals due to photochemical reactions are the main subject of our studies. In particular, we examine geometric changes at the reaction centre and the movement of molecules and their fragments in crystals. Studies of this type enable us to determine and understand the pathway of chemical reactions in the crystalline state and to gain knowledge of the differences and similarities that are characteristic for a given type of reaction proceeding in different compounds.

Studies of this type concern intermolecular (Fernandes & Levendis, 2004; Ohba & Ito, 2003; Turowska-Tyrk, 2001, 2003; Turowska-Tyrk & Trzop, 2003) and intramolecular photochemical reactions (Cotton et al., 2007; Turowska-Tyrk, Bąkowicz, Scheffer & Xia, 2006; Turowska-Tyrk, Trzop, Scheffer & Chen, 2006; Turowska-Tyrk, Bąkowicz & Scheffer, 2007; Turowska-Tyrk, Łabęcka, Scheffer & Xia, 2007; Trzop & Turowska-Tyrk, 2008; Zheng et al., 2007). In this paper, we present the structures of the two title compounds, (I) and (II), which can potentially undergo an intramolecular Yang photocyclization.

Compound (I) crystallizes in the triclinic space group P1 with two crystallographically independent molecules in the asymmetric unit. Fig. 1 presents projections of molecules A and B on the planes of their respective carbonyl groups, clearly showing the conformational differences. The largest difference is in the torsion angles N1—C9—C10—C11 and C16—C9—C10—C11, which are 96.2 (6) and -28.3 (7)°, respectively, for molecule A, and 37.6 (7) and -85.9 (6)°, respectively, for molecule B. Hydrogen bonds of the type N—H···O link molecules A and B into infinite chains in the b-axis direction (Fig. 2 and Table 1).

Compound (II) crystallizes in the orthorhombic space group Pbca with only one molecule in the asymmetric unit (Fig. 3). In contrast with compound (I), there are no classical hydrogen bonds. The naphthalene rings are arranged in parallel pairs, with a perpendicular distance between the rings of 3.506 (1) Å (Fig. 4).

Compounds (I) and (II) have a characteristic molecular fragment, namely the carbonyl group and a γ-H atom. Compounds with such a structure can potentially undergo an intramolecular Norrish type II photochemical reaction. A mechanism for this reaction is presented in the second scheme (Aoyama et al., 1979; Lavy et al., 2008; Yang et al., 2005). The first step is a γ-H abstraction by the carbonyl O atom and the formation of a biradical which can then undergo three reaction types: a Yang photocyclization leading to the formation of a cyclobutane ring (path a), a 1,4-hydrogen shift leading to the formation of a five-membered ring (path b) or a return to the initial reactant (path c).

Several geometric demands must be fulfilled in order that Yang photocyclization can proceed (Natarajan et al., 2005; Xia et al., 2005). They concern the following parameters: the (C)O···γ-H (d) distance, the (O)C···γC (D) distance, the deviation of γ-H from the mean plane of the carbonyl group (ω), the C═O···γ-H (Δ) angle and the γ-C—γ-H···O (Θ) angle. The ideal and average literature values for these parameters, together with the data for compound (II), are given in Table 2. For compound (I) the geometric demands are not fulfilled. The values of d and D are too large, 3.72 and 3.46 Å, respectively, which indicates the chemical inertia of compound (I) in the crystalline state. It seems that compound (II) meets the geometric demands for Yang photocyclization, although the influence of the ω parameter is not fully clear. Nevertheless, despite UV–Vis irradiation of a crystal with a 100 W Hg lamp (7 h), Yang photocyclization did not proceed. We did not observe any changes in the cell constants over the irradiation time and the structure determined after irradiation revealed only molecules of the reactant.

There can be several reasons for this inertia of compound (II). One of them was mentioned above: the value of the ω parameter differs by about 13° from the largest value observed for compounds undergoing Yang photocyclization (Turowska-Tyrk, Bąkowicz & Scheffer, 2007). Interactions between the naphthalene rings (Fig. 4) could be another cause. Such an explanation was proposed for 2,4,6-triisopropylbenzophenones (Ito et al., 2009). The next reason for the chemical inertia of (II) can be related to the size of the reaction cavity. Such a reason was given in the case of inclusion compounds (Zouev et al., 2006), styrylcoumarins (Moorthy et al., 2006) and 2,4,6-triisopropylbenzophenones (Ito et al., 1998). Interactions between naphthalene rings, as well as a small reaction cavity, restrain the molecular movements necessary for the chemical reaction to proceed. In order to make molecular movements easier, the crystal of compound (II) was irradiated at a higher temperature (323 K), but this did not help to induce a reaction. It is also possible that the photochemical reaction did not proceed owing to the absorption of UV–Vis radiation by a naphthalene group in a molecule (Natarajan et al., 2005). The lack of photochemical reaction of compound (II) cannot be a result of rotation of a methyl group because such rotation is not observed in the crystal.

S2. Experimental

Compound (I) having the R configuration and compound (II) were purchased from Sigma–Aldrich. [Recrystallisation from which solvent?]

S3. Refinement

H atoms for (I) were positioned geometrically and treated as riding, with C—H = 0.93–0.98 Å and U_iso = 1.5U_eq(C) for a methyl group or 1.2U_eq(C) for other groups. The N-bound H atom was located in a difference Fourier map and refined without constraints. For (II), only the H atoms on C14 were treated as riding.

Computing details

For both compounds, data collection: CrysAlis CCD (Oxford Diffraction, 2003); cell refinement: CrysAlis CCD (Oxford Diffraction, 2003); data reduction: CrysAlis RED (Oxford Diffraction, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures

	Fig. 1. Views of molecules A and B of (I), with the atom-numbering schemes. Displacement ellipsoids are drawn at the 20% probability level. H atoms have been omitted.
	Fig. 2. The hydrogen bonds in the structure of (I). Only H atoms taking part in hydrogen bonds are shown. [Symmetry code: (i) x, 1 + y, z.]
	Fig. 3. A view of the molecule of (II), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 20% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 4. A stereoscopic view of the crystal lattice fragment of (II), illustrating the π–π stacking of the naphthyl groups .

(I) 2-Oxo-2-phenyl-N-[(R)-1-phenylethyl]acetamide

Crystal data

C16H15NO2	Z = 2
Mr = 253.29	F(000) = 268
Triclinic, P1	Dx = 1.243 Mg m^−3
Hall symbol: P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.593 (2) Å	Cell parameters from 1169 reflections
b = 9.761 (2) Å	θ = 2.7–19.7°
c = 10.054 (3) Å	µ = 0.08 mm^−1
α = 93.32 (2)°	T = 299 K
β = 114.45 (3)°	Block, colourless
γ = 113.75 (3)°	0.50 × 0.30 × 0.15 mm
V = 676.6 (3) Å^3

Data collection

Kuma KM4 CCD diffractometer	1671 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.043
Graphite monochromator	θmax = 25.0°, θmin = 3.1°
ω scans	h = −10→10
3656 measured reflections	k = −9→11
2248 independent reflections	l = −11→11

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)] = 0.061	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.170	w = 1/[σ^2(Fo^2) + (0.1105P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max < 0.001
2248 reflections	Δρmax = 0.36 e Å^−3
349 parameters	Δρmin = −0.20 e Å^−3
3 restraints	Absolute structure: The absolute structure was assigned according to the information from Sigma–Aldrich.
Primary atom site location: structure-invariant direct methods

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
C1A	0.8298 (8)	0.2058 (6)	0.2069 (6)	0.0645 (13)
H1A	0.7285	0.1553	0.1084	0.077*
C2A	1.0168 (9)	0.2522 (7)	0.2349 (7)	0.0745 (15)
H2A	1.0420	0.2341	0.1560	0.089*
C3A	1.1649 (9)	0.3251 (7)	0.3797 (8)	0.0825 (17)
H3A	1.2918	0.3573	0.3994	0.099*
C4A	1.1285 (8)	0.3511 (8)	0.4957 (8)	0.0850 (18)
H4A	1.2305	0.3985	0.5942	0.102*
C5A	0.9448 (8)	0.3086 (7)	0.4690 (6)	0.0745 (15)
H5A	0.9219	0.3300	0.5486	0.089*
C6A	0.7901 (7)	0.2328 (5)	0.3219 (5)	0.0537 (11)
C7A	0.5919 (8)	0.1911 (6)	0.2926 (6)	0.0644 (13)
C8A	0.4269 (7)	0.0721 (6)	0.1422 (7)	0.0626 (12)
C9A	0.1641 (7)	0.0279 (6)	−0.1094 (6)	0.0637 (13)
H9A	0.1572	−0.0750	−0.1229	0.076*
C10A	−0.0292 (6)	0.0056 (5)	−0.1274 (6)	0.0557 (11)
C11A	−0.1068 (8)	0.0993 (6)	−0.1885 (7)	0.0701 (14)
H11A	−0.0375	0.1832	−0.2154	0.084*
C12A	−0.2912 (10)	0.0683 (9)	−0.2104 (8)	0.091 (2)
H12A	−0.3458	0.1305	−0.2531	0.110*
C13A	−0.3893 (9)	−0.0540 (9)	−0.1684 (8)	0.089 (2)
H13A	−0.5116	−0.0752	−0.1827	0.107*
C14A	−0.3115 (11)	−0.1440 (9)	−0.1069 (9)	0.095 (2)
H14A	−0.3793	−0.2267	−0.0778	0.114*
C15A	−0.1334 (9)	−0.1143 (7)	−0.0869 (7)	0.0786 (15)
H15A	−0.0812	−0.1779	−0.0443	0.094*
C16A	0.2142 (10)	0.0996 (9)	−0.2256 (8)	0.0927 (19)
H16A	0.3368	0.1089	−0.2088	0.139*
H16B	0.2215	0.2007	−0.2156	0.139*
H16C	0.1159	0.0345	−0.3258	0.139*
N1A	0.3198 (6)	0.1215 (5)	0.0463 (5)	0.0621 (11)
HN1A	0.345 (8)	0.227 (7)	0.076 (6)	0.074*
O1A	0.5531 (6)	0.2432 (6)	0.3800 (5)	0.0995 (15)
O2A	0.4054 (6)	−0.0616 (4)	0.1194 (5)	0.0880 (13)
C1B	−0.0127 (8)	0.5380 (6)	0.0496 (6)	0.0611 (12)
H1B	0.0883	0.5585	0.1452	0.073*
C2B	−0.1918 (9)	0.5111 (7)	0.0328 (8)	0.0761 (16)
H2B	−0.2110	0.5146	0.1172	0.091*
C3B	−0.3401 (8)	0.4795 (7)	−0.1084 (9)	0.0837 (18)
H3B	−0.4602	0.4623	−0.1200	0.100*
C4B	−0.3131 (9)	0.4732 (9)	−0.2303 (8)	0.100 (2)
H4B	−0.4161	0.4481	−0.3262	0.120*
C5B	−0.1350 (8)	0.5033 (8)	−0.2154 (7)	0.0814 (17)
H5B	−0.1175	0.5024	−0.3006	0.098*
C6B	0.0160 (6)	0.5343 (5)	−0.0763 (5)	0.0529 (11)
C7B	0.2036 (7)	0.5603 (5)	−0.0624 (5)	0.0573 (12)
C8B	0.3506 (7)	0.5522 (5)	0.0814 (6)	0.0544 (11)
C9B	0.6092 (7)	0.6812 (6)	0.3414 (6)	0.0599 (12)
H9B	0.5664	0.5741	0.3497	0.072*
C10B	0.8102 (7)	0.7420 (5)	0.3616 (5)	0.0534 (11)
C11B	0.8882 (8)	0.8619 (6)	0.3067 (7)	0.0733 (15)
H11B	0.8122	0.9040	0.2486	0.088*
C12B	1.0776 (9)	0.9209 (7)	0.3363 (8)	0.0857 (18)
H12B	1.1290	1.0043	0.3004	0.103*
C13B	1.1892 (9)	0.8598 (8)	0.4163 (9)	0.0877 (18)
H13B	1.3166	0.8998	0.4346	0.105*
C14B	1.1143 (9)	0.7380 (9)	0.4709 (8)	0.091 (2)
H14B	1.1907	0.6952	0.5269	0.110*
C15B	0.9268 (9)	0.6801 (7)	0.4424 (7)	0.0784 (16)
H15B	0.8763	0.5966	0.4786	0.094*
C16B	0.6068 (9)	0.7743 (10)	0.4662 (7)	0.096 (2)
H16D	0.4769	0.7328	0.4513	0.144*
H16E	0.6529	0.8810	0.4634	0.144*
H16F	0.6891	0.7682	0.5630	0.144*
N1B	0.4691 (6)	0.6779 (4)	0.1952 (5)	0.0584 (10)
HN1B	0.447 (8)	0.766 (7)	0.172 (6)	0.070*
O1B	0.2394 (6)	0.5755 (7)	−0.1671 (5)	0.1039 (16)
O2B	0.3527 (6)	0.4268 (4)	0.0846 (5)	0.0849 (12)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1A	0.065 (3)	0.069 (3)	0.053 (3)	0.031 (2)	0.023 (3)	0.012 (2)
C2A	0.078 (4)	0.079 (3)	0.076 (4)	0.040 (3)	0.041 (3)	0.024 (3)
C3A	0.061 (4)	0.082 (4)	0.101 (5)	0.033 (3)	0.035 (4)	0.027 (3)
C4A	0.058 (4)	0.102 (5)	0.068 (4)	0.040 (3)	0.008 (3)	0.005 (3)
C5A	0.076 (4)	0.092 (4)	0.054 (3)	0.050 (3)	0.021 (3)	0.012 (3)
C6A	0.056 (3)	0.054 (2)	0.052 (3)	0.033 (2)	0.019 (2)	0.014 (2)
C7A	0.069 (3)	0.069 (3)	0.062 (3)	0.040 (3)	0.028 (3)	0.019 (2)
C8A	0.062 (3)	0.056 (3)	0.085 (4)	0.037 (2)	0.038 (3)	0.029 (2)
C9A	0.058 (3)	0.054 (2)	0.069 (3)	0.028 (2)	0.021 (3)	0.004 (2)
C10A	0.050 (3)	0.055 (3)	0.055 (3)	0.025 (2)	0.020 (2)	0.009 (2)
C11A	0.073 (3)	0.060 (3)	0.082 (4)	0.038 (3)	0.034 (3)	0.020 (3)
C12A	0.080 (4)	0.109 (5)	0.085 (4)	0.064 (4)	0.023 (4)	0.008 (4)
C13A	0.057 (3)	0.099 (5)	0.095 (5)	0.028 (3)	0.033 (4)	−0.004 (4)
C14A	0.089 (5)	0.088 (4)	0.108 (5)	0.031 (4)	0.057 (4)	0.026 (4)
C15A	0.075 (4)	0.069 (3)	0.087 (4)	0.031 (3)	0.037 (3)	0.024 (3)
C16A	0.073 (4)	0.115 (5)	0.083 (4)	0.036 (4)	0.041 (4)	0.013 (4)
N1A	0.056 (2)	0.045 (2)	0.075 (3)	0.0262 (18)	0.021 (2)	0.0081 (19)
O1A	0.085 (3)	0.143 (4)	0.081 (3)	0.065 (3)	0.040 (2)	0.006 (3)
O2A	0.088 (3)	0.059 (2)	0.108 (3)	0.041 (2)	0.033 (2)	0.023 (2)
C1B	0.062 (3)	0.071 (3)	0.058 (3)	0.035 (2)	0.031 (3)	0.020 (2)
C2B	0.078 (4)	0.082 (4)	0.099 (5)	0.044 (3)	0.060 (4)	0.033 (3)
C3B	0.051 (3)	0.082 (4)	0.111 (5)	0.029 (3)	0.036 (4)	0.013 (3)
C4B	0.056 (4)	0.137 (6)	0.074 (4)	0.051 (4)	0.002 (3)	−0.004 (4)
C5B	0.067 (4)	0.115 (5)	0.053 (3)	0.044 (3)	0.021 (3)	0.010 (3)
C6B	0.048 (2)	0.053 (2)	0.054 (3)	0.024 (2)	0.021 (2)	0.010 (2)
C7B	0.051 (3)	0.063 (3)	0.052 (3)	0.023 (2)	0.025 (2)	0.005 (2)
C8B	0.048 (3)	0.052 (3)	0.063 (3)	0.024 (2)	0.027 (2)	0.009 (2)
C9B	0.059 (3)	0.065 (3)	0.056 (3)	0.034 (2)	0.022 (2)	0.017 (2)
C10B	0.057 (3)	0.058 (3)	0.051 (3)	0.036 (2)	0.022 (2)	0.013 (2)
C11B	0.071 (3)	0.075 (3)	0.088 (4)	0.045 (3)	0.038 (3)	0.037 (3)
C12B	0.078 (4)	0.085 (4)	0.109 (5)	0.041 (3)	0.053 (4)	0.041 (4)
C13B	0.066 (4)	0.100 (4)	0.102 (5)	0.044 (3)	0.039 (4)	0.021 (4)
C14B	0.071 (4)	0.116 (5)	0.100 (5)	0.062 (4)	0.032 (4)	0.043 (4)
C15B	0.075 (4)	0.083 (4)	0.093 (4)	0.049 (3)	0.040 (3)	0.042 (3)
C16B	0.070 (4)	0.144 (6)	0.067 (4)	0.054 (4)	0.027 (3)	0.007 (4)
N1B	0.056 (2)	0.049 (2)	0.061 (2)	0.0297 (18)	0.016 (2)	0.0092 (18)
O1B	0.077 (3)	0.164 (5)	0.068 (3)	0.047 (3)	0.042 (2)	0.025 (3)
O2B	0.091 (3)	0.0501 (19)	0.099 (3)	0.0392 (18)	0.029 (2)	0.0066 (18)

Geometric parameters (Å, º)

C1A—C6A	1.373 (7)	C1B—C2B	1.386 (7)
C1A—C2A	1.375 (7)	C1B—C6B	1.387 (7)
C1A—H1A	0.9300	C1B—H1B	0.9300
C2A—C3A	1.365 (9)	C2B—C3B	1.368 (10)
C2A—H2A	0.9300	C2B—H2B	0.9300
C3A—C4A	1.361 (9)	C3B—C4B	1.340 (10)
C3A—H3A	0.9300	C3B—H3B	0.9300
C4A—C5A	1.358 (8)	C4B—C5B	1.376 (9)
C4A—H4A	0.9300	C4B—H4B	0.9300
C5A—C6A	1.398 (7)	C5B—C6B	1.365 (7)
C5A—H5A	0.9300	C5B—H5B	0.9300
C6A—C7A	1.472 (7)	C6B—C7B	1.471 (6)
C7A—O1A	1.212 (7)	C7B—O1B	1.215 (6)
C7A—C8A	1.530 (8)	C7B—C8B	1.507 (7)
C8A—O2A	1.236 (6)	C8B—O2B	1.234 (6)
C8A—N1A	1.298 (7)	C8B—N1B	1.311 (6)
C9A—N1A	1.480 (7)	C9B—N1B	1.452 (6)
C9A—C10A	1.515 (7)	C9B—C10B	1.500 (7)
C9A—C16A	1.519 (9)	C9B—C16B	1.518 (8)
C9A—H9A	0.9800	C9B—H9B	0.9800
C10A—C15A	1.361 (7)	C10B—C11B	1.368 (7)
C10A—C11A	1.370 (7)	C10B—C15B	1.378 (7)
C11A—C12A	1.403 (8)	C11B—C12B	1.376 (8)
C11A—H11A	0.9300	C11B—H11B	0.9300
C12A—C13A	1.362 (10)	C12B—C13B	1.342 (9)
C12A—H12A	0.9300	C12B—H12B	0.9300
C13A—C14A	1.340 (10)	C13B—C14B	1.371 (10)
C13A—H13A	0.9300	C13B—H13B	0.9300
C14A—C15A	1.360 (8)	C14B—C15B	1.365 (8)
C14A—H14A	0.9300	C14B—H14B	0.9300
C15A—H15A	0.9300	C15B—H15B	0.9300
C16A—H16A	0.9600	C16B—H16D	0.9600
C16A—H16B	0.9600	C16B—H16E	0.9600
C16A—H16C	0.9600	C16B—H16F	0.9600
N1A—HN1A	0.97 (6)	N1B—HN1B	0.98 (6)
C6A—C1A—C2A	121.1 (5)	C2B—C1B—C6B	120.0 (5)
C6A—C1A—H1A	119.5	C2B—C1B—H1B	120.0
C2A—C1A—H1A	119.5	C6B—C1B—H1B	120.0
C3A—C2A—C1A	119.3 (6)	C3B—C2B—C1B	119.6 (6)
C3A—C2A—H2A	120.4	C3B—C2B—H2B	120.2
C1A—C2A—H2A	120.4	C1B—C2B—H2B	120.2
C4A—C3A—C2A	120.5 (6)	C4B—C3B—C2B	120.2 (6)
C4A—C3A—H3A	119.7	C4B—C3B—H3B	119.9
C2A—C3A—H3A	119.7	C2B—C3B—H3B	119.9
C5A—C4A—C3A	120.7 (6)	C3B—C4B—C5B	120.9 (6)
C5A—C4A—H4A	119.6	C3B—C4B—H4B	119.5
C3A—C4A—H4A	119.6	C5B—C4B—H4B	119.5
C4A—C5A—C6A	119.9 (6)	C6B—C5B—C4B	120.4 (6)
C4A—C5A—H5A	120.0	C6B—C5B—H5B	119.8
C6A—C5A—H5A	120.0	C4B—C5B—H5B	119.8
C1A—C6A—C5A	118.4 (5)	C5B—C6B—C1B	118.7 (5)
C1A—C6A—C7A	121.7 (4)	C5B—C6B—C7B	120.0 (4)
C5A—C6A—C7A	119.8 (5)	C1B—C6B—C7B	121.2 (4)
O1A—C7A—C6A	124.3 (5)	O1B—C7B—C6B	122.4 (5)
O1A—C7A—C8A	119.1 (5)	O1B—C7B—C8B	118.1 (5)
C6A—C7A—C8A	116.6 (4)	C6B—C7B—C8B	119.2 (4)
O2A—C8A—N1A	124.7 (5)	O2B—C8B—N1B	123.6 (5)
O2A—C8A—C7A	118.9 (5)	O2B—C8B—C7B	117.7 (4)
N1A—C8A—C7A	116.4 (4)	N1B—C8B—C7B	118.7 (4)
N1A—C9A—C10A	110.1 (4)	N1B—C9B—C10B	113.9 (4)
N1A—C9A—C16A	110.4 (4)	N1B—C9B—C16B	109.0 (4)
C10A—C9A—C16A	113.8 (5)	C10B—C9B—C16B	111.1 (4)
N1A—C9A—H9A	107.4	N1B—C9B—H9B	107.5
C10A—C9A—H9A	107.4	C10B—C9B—H9B	107.5
C16A—C9A—H9A	107.4	C16B—C9B—H9B	107.5
C15A—C10A—C11A	118.4 (5)	C11B—C10B—C15B	117.3 (5)
C15A—C10A—C9A	119.4 (5)	C11B—C10B—C9B	122.7 (4)
C11A—C10A—C9A	122.1 (4)	C15B—C10B—C9B	119.9 (5)
C10A—C11A—C12A	119.8 (5)	C10B—C11B—C12B	120.8 (5)
C10A—C11A—H11A	120.1	C10B—C11B—H11B	119.6
C12A—C11A—H11A	120.1	C12B—C11B—H11B	119.6
C13A—C12A—C11A	119.2 (6)	C13B—C12B—C11B	120.9 (6)
C13A—C12A—H12A	120.4	C13B—C12B—H12B	119.5
C11A—C12A—H12A	120.4	C11B—C12B—H12B	119.5
C14A—C13A—C12A	120.8 (6)	C12B—C13B—C14B	119.6 (6)
C14A—C13A—H13A	119.6	C12B—C13B—H13B	120.2
C12A—C13A—H13A	119.6	C14B—C13B—H13B	120.2
C13A—C14A—C15A	119.9 (6)	C15B—C14B—C13B	119.5 (5)
C13A—C14A—H14A	120.0	C15B—C14B—H14B	120.3
C15A—C14A—H14A	120.0	C13B—C14B—H14B	120.3
C14A—C15A—C10A	121.9 (6)	C14B—C15B—C10B	121.8 (5)
C14A—C15A—H15A	119.0	C14B—C15B—H15B	119.1
C10A—C15A—H15A	119.0	C10B—C15B—H15B	119.1
C9A—C16A—H16A	109.5	C9B—C16B—H16D	109.5
C9A—C16A—H16B	109.5	C9B—C16B—H16E	109.5
H16A—C16A—H16B	109.5	H16D—C16B—H16E	109.5
C9A—C16A—H16C	109.5	C9B—C16B—H16F	109.5
H16A—C16A—H16C	109.5	H16D—C16B—H16F	109.5
H16B—C16A—H16C	109.5	H16E—C16B—H16F	109.5
C8A—N1A—C9A	124.3 (4)	C8B—N1B—C9B	123.3 (4)
C8A—N1A—HN1A	119 (3)	C8B—N1B—HN1B	112 (3)
C9A—N1A—HN1A	117 (3)	C9B—N1B—HN1B	124 (3)
C6A—C1A—C2A—C3A	0.5 (8)	C6B—C1B—C2B—C3B	0.6 (8)
C1A—C2A—C3A—C4A	0.4 (9)	C1B—C2B—C3B—C4B	0.6 (10)
C2A—C3A—C4A—C5A	−1.7 (10)	C2B—C3B—C4B—C5B	−2.2 (11)
C3A—C4A—C5A—C6A	2.1 (9)	C3B—C4B—C5B—C6B	2.6 (11)
C2A—C1A—C6A—C5A	−0.1 (7)	C4B—C5B—C6B—C1B	−1.3 (9)
C2A—C1A—C6A—C7A	176.8 (5)	C4B—C5B—C6B—C7B	177.6 (6)
C4A—C5A—C6A—C1A	−1.2 (8)	C2B—C1B—C6B—C5B	−0.3 (7)
C4A—C5A—C6A—C7A	−178.2 (5)	C2B—C1B—C6B—C7B	−179.1 (5)
C1A—C6A—C7A—O1A	−161.9 (6)	C5B—C6B—C7B—O1B	9.9 (8)
C5A—C6A—C7A—O1A	15.0 (8)	C1B—C6B—C7B—O1B	−171.2 (6)
C1A—C6A—C7A—C8A	19.1 (6)	C5B—C6B—C7B—C8B	−164.0 (5)
C5A—C6A—C7A—C8A	−164.0 (5)	C1B—C6B—C7B—C8B	14.9 (6)
O1A—C7A—C8A—O2A	−114.8 (6)	O1B—C7B—C8B—O2B	−80.3 (7)
C6A—C7A—C8A—O2A	64.3 (6)	C6B—C7B—C8B—O2B	93.8 (6)
O1A—C7A—C8A—N1A	65.9 (7)	O1B—C7B—C8B—N1B	99.3 (6)
C6A—C7A—C8A—N1A	−115.1 (5)	C6B—C7B—C8B—N1B	−86.6 (5)
N1A—C9A—C10A—C15A	−86.2 (6)	N1B—C9B—C10B—C11B	37.6 (7)
C16A—C9A—C10A—C15A	149.3 (5)	C16B—C9B—C10B—C11B	−85.9 (7)
N1A—C9A—C10A—C11A	96.2 (6)	N1B—C9B—C10B—C15B	−144.5 (5)
C16A—C9A—C10A—C11A	−28.3 (7)	C16B—C9B—C10B—C15B	92.0 (6)
C15A—C10A—C11A—C12A	−1.2 (8)	C15B—C10B—C11B—C12B	−2.2 (8)
C9A—C10A—C11A—C12A	176.5 (5)	C9B—C10B—C11B—C12B	175.7 (5)
C10A—C11A—C12A—C13A	0.9 (9)	C10B—C11B—C12B—C13B	1.8 (10)
C11A—C12A—C13A—C14A	0.0 (10)	C11B—C12B—C13B—C14B	−0.8 (11)
C12A—C13A—C14A—C15A	−0.5 (11)	C12B—C13B—C14B—C15B	0.3 (11)
C13A—C14A—C15A—C10A	0.2 (10)	C13B—C14B—C15B—C10B	−0.9 (11)
C11A—C10A—C15A—C14A	0.7 (9)	C11B—C10B—C15B—C14B	1.8 (9)
C9A—C10A—C15A—C14A	−177.0 (6)	C9B—C10B—C15B—C14B	−176.2 (6)
O2A—C8A—N1A—C9A	−4.5 (8)	O2B—C8B—N1B—C9B	−3.7 (8)
C7A—C8A—N1A—C9A	174.8 (4)	C7B—C8B—N1B—C9B	176.7 (4)
C10A—C9A—N1A—C8A	118.2 (5)	C10B—C9B—N1B—C8B	98.7 (5)
C16A—C9A—N1A—C8A	−115.4 (6)	C16B—C9B—N1B—C8B	−136.7 (5)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1A—HN1A···O2B	0.97 (6)	1.92 (6)	2.864 (5)	166 (5)
N1B—HN1B···O2A^i	0.98 (6)	1.91 (6)	2.889 (5)	178 (5)

Symmetry code: (i) x, y+1, z.

(II) N,N-dimethyl-2-(1-naphthyl)-2-oxoacetamide

Crystal data

C14H13NO2	F(000) = 960
Mr = 227.25	Dx = 1.283 Mg m^−3
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 936 reflections
a = 8.981 (3) Å	θ = 2.6–18.3°
b = 24.056 (8) Å	µ = 0.09 mm^−1
c = 10.895 (3) Å	T = 299 K
V = 2353.8 (13) Å^3	Block, colourless
Z = 8	0.50 × 0.20 × 0.05 mm

Data collection

Kuma KM4 CCD diffractometer	1229 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.051
Graphite monochromator	θmax = 25.0°, θmin = 3.4°
ω scans	h = −10→9
11922 measured reflections	k = −28→28
2058 independent reflections	l = −9→12

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)] = 0.063	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.158	w = 1/[σ^2(Fo^2) + (0.0663P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.11	(Δ/σ)max < 0.001
2058 reflections	Δρmax = 0.11 e Å^−3
196 parameters	Δρmin = −0.15 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0052 (13)

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	0.1743 (3)	0.39550 (12)	0.4483 (2)	0.0546 (7)
C2	0.0678 (3)	0.36805 (15)	0.3810 (3)	0.0656 (8)
H2	0.062 (3)	0.3255 (11)	0.392 (2)	0.066 (8)*
C3	−0.0270 (4)	0.39654 (16)	0.3015 (3)	0.0749 (9)
H3	−0.099 (3)	0.3766 (11)	0.258 (3)	0.089 (10)*
C4	−0.0158 (3)	0.45193 (16)	0.2900 (3)	0.0711 (9)
H4	−0.078 (3)	0.4738 (12)	0.230 (3)	0.097 (10)*
C5	0.0905 (3)	0.48238 (12)	0.3564 (2)	0.0588 (7)
C6	0.1031 (4)	0.54031 (15)	0.3419 (3)	0.0726 (9)
H6	0.033 (3)	0.5577 (11)	0.285 (3)	0.091 (10)*
C7	0.2047 (4)	0.56962 (16)	0.4045 (3)	0.0795 (10)
H7	0.209 (3)	0.6100 (13)	0.394 (2)	0.088 (10)*
C8	0.2990 (4)	0.54249 (14)	0.4870 (3)	0.0758 (9)
H8	0.375 (3)	0.5638 (12)	0.530 (3)	0.088 (10)*
C9	0.2910 (3)	0.48672 (13)	0.5042 (3)	0.0631 (8)
H9	0.362 (3)	0.4677 (11)	0.559 (2)	0.081 (9)*
C10	0.1883 (3)	0.45430 (11)	0.4387 (2)	0.0523 (7)
C11	0.2690 (3)	0.36091 (12)	0.5270 (2)	0.0659 (8)
C12	0.2552 (3)	0.29838 (12)	0.5177 (3)	0.0670 (8)
C13	0.1006 (6)	0.2988 (2)	0.7022 (4)	0.0929 (12)
H13A	0.102 (4)	0.3429 (17)	0.686 (3)	0.143 (15)*
H13B	0.148 (5)	0.2937 (15)	0.773 (4)	0.138 (17)*
H13C	−0.001 (6)	0.2831 (18)	0.708 (4)	0.17 (2)*
C14	0.1840 (4)	0.21094 (13)	0.6054 (3)	0.1028 (12)
H14A	0.2474	0.1976	0.5409	0.154*
H14B	0.0844	0.1976	0.5923	0.154*
H14C	0.2200	0.1976	0.6830	0.154*
N1	0.1840 (3)	0.27131 (10)	0.6054 (2)	0.0709 (7)
O1	0.3681 (3)	0.37800 (9)	0.5937 (2)	0.1033 (9)
O2	0.3189 (3)	0.27624 (9)	0.4311 (2)	0.0994 (8)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0487 (16)	0.067 (2)	0.0480 (15)	−0.0017 (14)	0.0021 (12)	−0.0017 (13)
C2	0.0601 (19)	0.073 (2)	0.0638 (18)	−0.0031 (17)	0.0021 (14)	−0.0008 (16)
C3	0.064 (2)	0.095 (3)	0.066 (2)	−0.0132 (19)	−0.0147 (16)	−0.0012 (18)
C4	0.066 (2)	0.091 (3)	0.0562 (18)	0.0007 (18)	−0.0059 (15)	0.0105 (17)
C5	0.0568 (18)	0.074 (2)	0.0457 (15)	0.0037 (15)	0.0086 (13)	0.0045 (14)
C6	0.081 (2)	0.076 (2)	0.0606 (19)	0.0098 (19)	0.0094 (17)	0.0106 (17)
C7	0.096 (3)	0.065 (2)	0.077 (2)	−0.002 (2)	0.019 (2)	0.0048 (19)
C8	0.078 (2)	0.072 (3)	0.078 (2)	−0.0110 (19)	0.0006 (18)	−0.0056 (18)
C9	0.0639 (19)	0.064 (2)	0.0617 (18)	−0.0037 (16)	−0.0017 (15)	−0.0031 (15)
C10	0.0476 (15)	0.0637 (18)	0.0456 (14)	−0.0013 (13)	0.0080 (12)	−0.0002 (13)
C11	0.0668 (19)	0.067 (2)	0.0633 (17)	−0.0026 (15)	−0.0064 (15)	−0.0043 (15)
C12	0.0640 (19)	0.065 (2)	0.0720 (19)	0.0070 (15)	−0.0029 (16)	−0.0057 (16)
C13	0.103 (3)	0.105 (4)	0.071 (2)	0.007 (3)	0.011 (2)	−0.001 (2)
C14	0.112 (3)	0.066 (2)	0.131 (3)	0.006 (2)	−0.008 (2)	0.018 (2)
N1	0.0752 (18)	0.0575 (17)	0.0801 (17)	0.0079 (12)	−0.0015 (14)	0.0090 (13)
O1	0.1117 (19)	0.0809 (16)	0.1173 (18)	−0.0056 (14)	−0.0566 (15)	0.0065 (13)
O2	0.0990 (18)	0.0953 (17)	0.1038 (17)	0.0091 (13)	0.0248 (14)	−0.0238 (14)

Geometric parameters (Å, º)

C1—C2	1.375 (4)	C8—H8	0.97 (3)
C1—C10	1.424 (4)	C9—C10	1.403 (4)
C1—C11	1.467 (4)	C9—H9	0.98 (3)
C2—C3	1.394 (4)	C11—O1	1.220 (3)
C2—H2	1.03 (3)	C11—C12	1.513 (4)
C3—C4	1.342 (4)	C12—O2	1.225 (3)
C3—H3	0.94 (3)	C12—N1	1.321 (3)
C4—C5	1.404 (4)	C13—N1	1.453 (4)
C4—H4	1.00 (3)	C13—H13A	1.07 (4)
C5—C6	1.407 (4)	C13—H13B	0.89 (4)
C5—C10	1.425 (3)	C13—H13C	0.99 (5)
C6—C7	1.340 (4)	C14—N1	1.452 (4)
C6—H6	0.97 (3)	C14—H14A	0.9600
C7—C8	1.397 (5)	C14—H14B	0.9600
C7—H7	0.98 (3)	C14—H14C	0.9600
C8—C9	1.356 (4)
C2—C1—C10	119.9 (3)	C10—C9—H9	118.3 (16)
C2—C1—C11	116.3 (3)	C9—C10—C1	124.9 (3)
C10—C1—C11	123.7 (3)	C9—C10—C5	117.5 (3)
C1—C2—C3	121.3 (3)	C1—C10—C5	117.6 (3)
C1—C2—H2	116.7 (14)	O1—C11—C1	125.4 (3)
C3—C2—H2	122.0 (14)	O1—C11—C12	115.8 (3)
C4—C3—C2	120.0 (3)	C1—C11—C12	118.5 (3)
C4—C3—H3	120.9 (17)	O2—C12—N1	124.7 (3)
C2—C3—H3	119.1 (17)	O2—C12—C11	116.5 (3)
C3—C4—C5	121.4 (3)	N1—C12—C11	118.8 (3)
C3—C4—H4	122.7 (17)	N1—C13—H13A	109 (2)
C5—C4—H4	115.8 (17)	N1—C13—H13B	109 (3)
C4—C5—C6	120.9 (3)	H13A—C13—H13B	106 (3)
C4—C5—C10	119.7 (3)	N1—C13—H13C	110 (3)
C6—C5—C10	119.4 (3)	H13A—C13—H13C	114 (4)
C7—C6—C5	121.2 (3)	H13B—C13—H13C	109 (4)
C7—C6—H6	122.3 (17)	N1—C14—H14A	109.5
C5—C6—H6	116.5 (17)	N1—C14—H14B	109.5
C6—C7—C8	119.7 (4)	H14A—C14—H14B	109.5
C6—C7—H7	119.2 (17)	N1—C14—H14C	109.5
C8—C7—H7	121.1 (17)	H14A—C14—H14C	109.5
C9—C8—C7	121.2 (4)	H14B—C14—H14C	109.5
C9—C8—H8	119.5 (17)	C12—N1—C14	119.5 (3)
C7—C8—H8	119.2 (17)	C12—N1—C13	123.4 (3)
C8—C9—C10	121.0 (3)	C14—N1—C13	117.1 (3)
C8—C9—H9	120.6 (16)
C10—C1—C2—C3	0.8 (4)	C4—C5—C10—C9	−179.1 (2)
C11—C1—C2—C3	−178.9 (3)	C6—C5—C10—C9	1.6 (3)
C1—C2—C3—C4	−0.4 (5)	C4—C5—C10—C1	0.9 (3)
C2—C3—C4—C5	0.3 (5)	C6—C5—C10—C1	−178.4 (2)
C3—C4—C5—C6	178.7 (3)	C2—C1—C11—O1	−179.4 (3)
C3—C4—C5—C10	−0.6 (4)	C10—C1—C11—O1	0.9 (4)
C4—C5—C6—C7	−179.7 (3)	C2—C1—C11—C12	6.9 (4)
C10—C5—C6—C7	−0.4 (4)	C10—C1—C11—C12	−172.8 (2)
C5—C6—C7—C8	−0.8 (5)	O1—C11—C12—O2	−95.0 (3)
C6—C7—C8—C9	0.8 (5)	C1—C11—C12—O2	79.4 (3)
C7—C8—C9—C10	0.5 (5)	O1—C11—C12—N1	81.2 (4)
C8—C9—C10—C1	178.4 (3)	C1—C11—C12—N1	−104.4 (3)
C8—C9—C10—C5	−1.7 (4)	O2—C12—N1—C14	2.8 (4)
C2—C1—C10—C9	179.0 (2)	C11—C12—N1—C14	−173.1 (3)
C11—C1—C10—C9	−1.3 (4)	O2—C12—N1—C13	−175.5 (3)
C2—C1—C10—C5	−1.0 (4)	C11—C12—N1—C13	8.6 (5)
C11—C1—C10—C5	178.7 (2)