Comparison of the structural motifs of aceto­acetanilides and related azo pigments

The structures of three methyl-substituted acetoacetanilides and of an azo pigment derived from one of them are presented and discussed together with a review of related known crystal structures. By considering the position of any aromatic substituents it is possible to predict whether the simple acetoacetanilides adopt planar structures with intramolecular hydrogen bonding or twisted structures featuring intermolecular hydrogen bonding. However, we find that the same crystal engineering rules cannot be applied to the related azo pigments: this is apparently due to the presence of an sp² atom which facilitates the adoption of planar conformations. The thermal properties of the acetoacetanilides were measured by DSC and are discussed with reference to their crystal structures.

S1. Comment

SEE TEXT

S2. Experimental

SEE TEXT

Computing details

Data collection: SMART (Siemens, 1995) for (9); MSC/Rigaku diffractometer control for (10), (11), (12). Cell refinement: local program for (9); MSC/Rigaku diffractometer control for (10), (11), (12). Data reduction: SAINT (Siemens, 1995) for (9); TEXSAN for (10), (11), (12). Program(s) used to solve structure: SHELXS (Sheldrick, 1990) for (9); SHELXS97 (Sheldrick, 1990) for (10), (11), (12). For all compounds, program(s) used to refine structure: SHELXL97 (Sheldrick, 1997). Molecular graphics: ORTEP II for (9). For all compounds, software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

(9)

Crystal data

C17H16N4O4	F(000) = 712
Mr = 340.34	Dx = 1.401 Mg m^−3
Monoclinic, P21/n	Synchrotron radiation, λ = 0.6891 Å
Hall symbol: -P 2yac	Cell parameters from 5749 reflections
a = 14.111 (6) Å	θ = 2.5–23°
b = 7.567 (3) Å	µ = 0.10 mm^−1
c = 15.338 (6) Å	T = 150 K
β = 99.967 (10)°	Plate, light yellow
V = 1613.0 (11) Å^3	0.20 × 0.04 × 0.02 mm
Z = 4

Data collection

Bruker SMART CCD diffractometer	2445 independent reflections
Radiation source: Station 9.8, Daresbury SRS	1600 reflections with I > 2σ(I)
Si111 monochromator	Rint = 0.069
ω rotation with narrow frames scans	θmax = 23.0°, θmin = 2.9°
Absorption correction: empirical (using intensity measurements) SADABS - see comment below	h = −16→15
Tmin = 0.980, Tmax = 0.999	k = −8→8
5749 measured reflections	l = −11→17

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)] = 0.066	Riding
wR(F^2) = 0.166	Calculated w = 1/[σ^2(Fo^2) + (0.0959P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.00	(Δ/σ)max = 0.001
2445 reflections	Δρmax = 0.34 e Å^−3
231 parameters	Δρmin = −0.28 e Å^−3
0 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.068 (9)

Special details

Experimental. A standard Station 9.8 experiment was performed. For further details see Clegg et al. J. Chem. Soc. Dalton Trans. 1998, 3037. Decay of the incident beam was corrected using SADABS (Sheldrick 1997, a program for Scaling and Correction of Area Detector Data). The figure given in _diffrn_standards_decay_% includes this beam decay.

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
O1	0.09586 (16)	0.7620 (3)	0.03614 (13)	0.0300 (7)
O2	−0.19376 (18)	0.7401 (4)	−0.09218 (16)	0.0421 (8)
O3	−0.0133 (2)	0.2248 (5)	0.51310 (17)	0.0615 (10)
O4	0.1373 (2)	0.2916 (4)	0.54092 (16)	0.0449 (8)
N1	−0.0122 (2)	0.8410 (4)	−0.08688 (16)	0.0239 (7)
H1	−0.0738	0.8375	−0.1097	0.053 (13)*
N2	−0.05818 (19)	0.5990 (4)	0.10490 (16)	0.0239 (7)
N3	0.02814 (19)	0.5886 (4)	0.15595 (16)	0.0250 (7)
H3	0.0797	0.6305	0.1381	0.049 (12)*
N4	0.0589 (2)	0.2875 (4)	0.49128 (18)	0.0328 (8)
C1	0.0467 (3)	0.9254 (5)	−0.1393 (2)	0.0256 (8)
C2	0.0012 (3)	1.0040 (5)	−0.2186 (2)	0.0277 (9)
C3	0.0559 (3)	1.0795 (5)	−0.2731 (2)	0.0340 (10)
H3A	0.0246	1.1319	−0.3267	0.041*
C4	0.1564 (3)	1.0833 (6)	−0.2534 (2)	0.0386 (10)
H4	0.1928	1.1396	−0.2921	0.046*
C5	0.2016 (3)	1.0031 (5)	−0.1764 (2)	0.0386 (10)
H5	0.2698	1.0011	−0.1626	0.046*
C6	0.1477 (2)	0.9256 (5)	−0.1193 (2)	0.0285 (9)
H6	0.1794	0.8720	−0.0662	0.034*
C7	0.0118 (2)	0.7648 (5)	−0.0071 (2)	0.0241 (8)
C8	−0.0685 (2)	0.6790 (5)	0.0285 (2)	0.0239 (8)
C9	−0.1710 (2)	0.6745 (5)	−0.0188 (2)	0.0287 (9)
C10	−0.2453 (3)	0.5892 (6)	0.0259 (3)	0.0409 (11)
H10A	−0.3093	0.6084	−0.0095	0.061*
H10B	−0.2429	0.6412	0.0847	0.061*
H10C	−0.2326	0.4620	0.0317	0.061*
C11	0.0339 (2)	0.5092 (5)	0.2386 (2)	0.0247 (8)
C12	0.1231 (2)	0.5148 (5)	0.2954 (2)	0.0295 (9)
H12	0.1771	0.5689	0.2768	0.035*
C13	0.1314 (2)	0.4411 (5)	0.3782 (2)	0.0279 (9)
H13	0.1912	0.4439	0.4177	0.034*
C14	0.0526 (2)	0.3634 (5)	0.4032 (2)	0.0252 (8)
C15	−0.0376 (2)	0.3564 (5)	0.3473 (2)	0.0270 (9)
H15	−0.0913	0.3015	0.3658	0.032*
C16	−0.0448 (2)	0.4316 (5)	0.2655 (2)	0.0259 (9)
H16	−0.1049	0.4305	0.2265	0.031*
C21	−0.1069 (3)	0.9980 (6)	−0.2422 (2)	0.0343 (9)
H21A	−0.1273	1.0491	−0.3012	0.051*
H21B	−0.1351	1.0660	−0.1986	0.051*
H21C	−0.1287	0.8751	−0.2421	0.051*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0183 (14)	0.0419 (17)	0.0258 (12)	−0.0028 (12)	−0.0068 (10)	0.0042 (11)
O2	0.0198 (14)	0.062 (2)	0.0386 (15)	0.0007 (13)	−0.0101 (11)	0.0197 (14)
O3	0.0374 (19)	0.106 (3)	0.0379 (16)	−0.0211 (18)	−0.0033 (13)	0.0277 (16)
O4	0.0331 (17)	0.064 (2)	0.0314 (14)	0.0039 (14)	−0.0130 (12)	0.0094 (13)
N1	0.0176 (16)	0.0249 (17)	0.0250 (15)	−0.0007 (13)	−0.0083 (12)	0.0007 (12)
N2	0.0180 (16)	0.0260 (18)	0.0248 (15)	0.0032 (13)	−0.0046 (12)	0.0020 (13)
N3	0.0130 (15)	0.0336 (19)	0.0260 (14)	0.0009 (13)	−0.0035 (12)	0.0013 (13)
N4	0.029 (2)	0.042 (2)	0.0243 (15)	0.0053 (15)	−0.0027 (14)	0.0033 (14)
C1	0.026 (2)	0.025 (2)	0.0255 (17)	−0.0004 (16)	0.0027 (15)	−0.0035 (15)
C2	0.033 (2)	0.026 (2)	0.0225 (17)	−0.0018 (17)	−0.0001 (15)	−0.0019 (15)
C3	0.045 (3)	0.031 (2)	0.0257 (18)	0.0052 (19)	0.0051 (17)	0.0037 (16)
C4	0.040 (2)	0.042 (3)	0.038 (2)	0.000 (2)	0.0162 (18)	0.0066 (18)
C5	0.030 (2)	0.043 (3)	0.042 (2)	−0.001 (2)	0.0041 (17)	0.0024 (19)
C6	0.0194 (19)	0.036 (2)	0.0287 (18)	0.0017 (17)	−0.0003 (15)	0.0029 (16)
C7	0.0171 (19)	0.028 (2)	0.0255 (17)	−0.0014 (16)	−0.0019 (14)	−0.0032 (15)
C8	0.0153 (18)	0.026 (2)	0.0274 (18)	0.0017 (15)	−0.0034 (14)	0.0007 (15)
C9	0.0128 (18)	0.035 (2)	0.036 (2)	0.0036 (16)	−0.0022 (15)	0.0028 (17)
C10	0.017 (2)	0.056 (3)	0.048 (2)	0.0043 (19)	−0.0016 (16)	0.012 (2)
C11	0.0225 (19)	0.025 (2)	0.0244 (17)	0.0047 (16)	−0.0029 (14)	0.0005 (15)
C12	0.0146 (18)	0.041 (2)	0.0303 (18)	−0.0048 (17)	−0.0024 (14)	0.0036 (17)
C13	0.0176 (18)	0.031 (2)	0.0299 (19)	0.0031 (16)	−0.0099 (14)	0.0027 (16)
C14	0.0212 (19)	0.029 (2)	0.0218 (17)	0.0064 (16)	−0.0059 (14)	0.0021 (14)
C15	0.0166 (18)	0.032 (2)	0.0317 (19)	0.0009 (16)	0.0018 (14)	0.0011 (16)
C16	0.0137 (18)	0.035 (2)	0.0258 (18)	0.0008 (16)	−0.0066 (14)	−0.0014 (15)
C21	0.035 (2)	0.040 (2)	0.0244 (18)	−0.0004 (19)	−0.0071 (16)	0.0045 (16)

Geometric parameters (Å, º)

O1—C7	1.254 (4)	C2—C21	1.507 (5)
O2—C9	1.221 (4)	C3—C4	1.399 (6)
O3—N4	1.221 (4)	C4—C5	1.381 (5)
O4—N4	1.230 (4)	C5—C6	1.385 (5)
N1—C7	1.342 (4)	C7—C8	1.490 (5)
N1—C1	1.405 (5)	C8—C9	1.502 (5)
N2—C8	1.304 (4)	C9—C10	1.496 (5)
N2—N3	1.331 (4)	C11—C16	1.381 (5)
N3—C11	1.392 (4)	C11—C12	1.403 (5)
N4—C14	1.457 (4)	C12—C13	1.373 (5)
C1—C2	1.405 (5)	C13—C14	1.371 (5)
C1—C6	1.406 (5)	C14—C15	1.406 (5)
C2—C3	1.358 (5)	C15—C16	1.366 (5)
C7—N1—C1	129.5 (3)	N1—C7—C8	115.7 (3)
C8—N2—N3	120.3 (3)	N2—C8—C7	123.9 (3)
N2—N3—C11	117.6 (3)	N2—C8—C9	111.9 (3)
O3—N4—O4	122.9 (3)	C7—C8—C9	124.2 (3)
O3—N4—C14	119.2 (3)	O2—C9—C10	120.3 (3)
O4—N4—C14	117.9 (3)	O2—C9—C8	121.0 (3)
C2—C1—N1	117.5 (3)	C10—C9—C8	118.7 (3)
C2—C1—C6	118.8 (3)	C16—C11—N3	122.2 (3)
N1—C1—C6	123.6 (3)	C16—C11—C12	120.6 (3)
C3—C2—C1	119.2 (3)	N3—C11—C12	117.2 (3)
C3—C2—C21	121.6 (3)	C13—C12—C11	119.1 (3)
C1—C2—C21	119.2 (3)	C14—C13—C12	119.3 (3)
C2—C3—C4	122.6 (3)	C13—C14—C15	122.5 (3)
C5—C4—C3	118.4 (3)	C13—C14—N4	120.4 (3)
C4—C5—C6	120.3 (4)	C15—C14—N4	117.0 (3)
C5—C6—C1	120.6 (3)	C16—C15—C14	117.4 (3)
O1—C7—N1	123.7 (3)	C15—C16—C11	121.1 (3)
O1—C7—C8	120.6 (3)
C8—N2—N3—C11	177.0 (3)	N1—C7—C8—C9	−0.2 (5)
C7—N1—C1—C2	−176.1 (3)	N2—C8—C9—O2	−178.6 (3)
C7—N1—C1—C6	8.0 (6)	C7—C8—C9—O2	1.6 (6)
N1—C1—C2—C3	−176.9 (3)	N2—C8—C9—C10	1.9 (5)
C6—C1—C2—C3	−0.8 (5)	C7—C8—C9—C10	−177.9 (4)
N1—C1—C2—C21	1.5 (5)	N2—N3—C11—C16	4.6 (5)
C6—C1—C2—C21	177.6 (3)	N2—N3—C11—C12	−173.7 (3)
C1—C2—C3—C4	−0.2 (6)	C16—C11—C12—C13	0.4 (5)
C21—C2—C3—C4	−178.6 (4)	N3—C11—C12—C13	178.7 (3)
C2—C3—C4—C5	1.5 (6)	C11—C12—C13—C14	0.2 (5)
C3—C4—C5—C6	−1.8 (6)	C12—C13—C14—C15	−0.3 (6)
C4—C5—C6—C1	0.7 (6)	C12—C13—C14—N4	−178.7 (3)
C2—C1—C6—C5	0.6 (5)	O3—N4—C14—C13	177.3 (4)
N1—C1—C6—C5	176.4 (3)	O4—N4—C14—C13	−1.8 (5)
C1—N1—C7—O1	2.0 (6)	O3—N4—C14—C15	−1.2 (5)
C1—N1—C7—C8	−177.2 (3)	O4—N4—C14—C15	179.7 (3)
N3—N2—C8—C7	−0.8 (5)	C13—C14—C15—C16	−0.2 (6)
N3—N2—C8—C9	179.5 (3)	N4—C14—C15—C16	178.2 (3)
O1—C7—C8—N2	0.8 (5)	C14—C15—C16—C11	0.8 (6)
N1—C7—C8—N2	−179.9 (3)	N3—C11—C16—C15	−179.2 (3)
O1—C7—C8—C9	−179.5 (3)	C12—C11—C16—C15	−0.9 (6)

(10)

Crystal data

C12H15NO2	F(000) = 220
Mr = 205.25	Dx = 1.272 Mg m^−3
Monoclinic, P21/m	Mo Kα radiation, λ = 0.71069 Å
Hall symbol: -P 2y1	Cell parameters from 25 reflections
a = 8.8636 (15) Å	θ = 16.9–17.9°
b = 6.605 (3) Å	µ = 0.09 mm^−1
c = 9.2381 (17) Å	T = 123 K
β = 97.804 (14)°	Cut needle, colourless
V = 535.9 (3) Å^3	0.70 × 0.35 × 0.20 mm
Z = 2

Data collection

Rigaku AFC7S Diffractometer	Rint = 0.023
Radiation source: fine-focus sealed tube	θmax = 27.0°, θmin = 3.0°
Graphite monochromator	h = −11→11
ω/2θ scans	k = −8→8
2714 measured reflections	l = −11→11
1279 independent reflections	3 standard reflections every 150 reflections
1031 reflections with I > 2σ(I)	intensity decay: none

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)] = 0.033	Riding
wR(F^2) = 0.099	Calculated w = 1/[σ^2(Fo^2) + (0.0409P)^2 + 0.1624P] where P = (Fo^2 + 2Fc^2)/3
S = 1.07	(Δ/σ)max < 0.001
1279 reflections	Δρmax = 0.30 e Å^−3
94 parameters	Δρmin = −0.22 e Å^−3
0 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.027 (5)

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. All H atoms placed in calculated positions and in riding modes. The orientations of the C41 and C10 methyl groups were obtained by refining rotation about the C—Me bond. These methyl groups have disordered H atom positions with occupancy 50:50.

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	Occ. (<1)
N1	0.03732 (14)	0.2500	0.54875 (13)	0.0165 (3)
H1	0.0797	0.2500	0.6406	0.020*
O1	−0.19623 (13)	0.2500	0.40767 (12)	0.0245 (3)
O2	0.03134 (14)	0.2500	0.84143 (12)	0.0321 (4)
C1	0.13908 (17)	0.2500	0.44372 (16)	0.0159 (3)
C2	0.29615 (18)	0.2500	0.49644 (17)	0.0178 (3)
C3	0.39932 (18)	0.2500	0.39533 (17)	0.0193 (3)
H3	0.5052	0.2500	0.4301	0.023*
C4	0.35274 (18)	0.2500	0.24467 (17)	0.0196 (3)
C5	0.19730 (19)	0.2500	0.19597 (16)	0.0193 (4)
H5	0.1632	0.2500	0.0939	0.023*
C6	0.09070 (18)	0.2500	0.29336 (16)	0.0182 (3)
H6	−0.0150	0.2500	0.2577	0.022*
C7	−0.11684 (18)	0.2500	0.52705 (16)	0.0165 (3)
C8	−0.19503 (17)	0.2500	0.66439 (16)	0.0172 (3)
H8A	−0.2624	0.3702	0.6579	0.021*	0.50
H8B	−0.2624	0.1298	0.6579	0.021*	0.50
C9	−0.10690 (19)	0.2500	0.81601 (17)	0.0218 (4)
C10	−0.2021 (2)	0.2500	0.94029 (18)	0.0292 (4)
H10A	−0.3068	0.2894	0.9032	0.044*	0.50
H10B	−0.1591	0.3465	1.0153	0.044*	0.50
H10C	−0.2019	0.1141	0.9828	0.044*	0.50
C21	0.35046 (18)	0.2500	0.65812 (17)	0.0238 (4)
H21A	0.3127	0.1284	0.7046	0.036*
H21B	0.4614	0.2500	0.6748	0.036*
C41	0.4685 (2)	0.2500	0.13861 (18)	0.0263 (4)
H41A	0.5636	0.3109	0.1853	0.039*	0.50
H41B	0.4290	0.3286	0.0517	0.039*	0.50
H41C	0.4878	0.1105	0.1100	0.039*	0.50

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0130 (6)	0.0238 (7)	0.0126 (6)	0.000	0.0013 (5)	0.000
O1	0.0144 (6)	0.0401 (7)	0.0184 (6)	0.000	0.0000 (4)	0.000
O2	0.0182 (6)	0.0595 (10)	0.0179 (6)	0.000	0.0004 (5)	0.000
C1	0.0144 (7)	0.0169 (7)	0.0165 (7)	0.000	0.0029 (6)	0.000
C2	0.0150 (7)	0.0199 (8)	0.0180 (7)	0.000	0.0005 (6)	0.000
C3	0.0138 (7)	0.0228 (8)	0.0215 (8)	0.000	0.0026 (6)	0.000
C4	0.0204 (8)	0.0180 (8)	0.0213 (7)	0.000	0.0063 (6)	0.000
C5	0.0220 (8)	0.0206 (8)	0.0151 (7)	0.000	0.0023 (6)	0.000
C6	0.0168 (7)	0.0200 (8)	0.0172 (7)	0.000	−0.0004 (6)	0.000
C7	0.0152 (7)	0.0173 (8)	0.0169 (7)	0.000	0.0016 (6)	0.000
C8	0.0133 (7)	0.0202 (8)	0.0184 (7)	0.000	0.0034 (6)	0.000
C9	0.0207 (8)	0.0264 (9)	0.0190 (7)	0.000	0.0049 (6)	0.000
C10	0.0277 (9)	0.0424 (11)	0.0188 (7)	0.000	0.0080 (7)	0.000
C21	0.0136 (7)	0.0396 (10)	0.0177 (7)	0.000	0.0001 (6)	0.000
C41	0.0248 (8)	0.0332 (10)	0.0230 (8)	0.000	0.0104 (7)	0.000

Geometric parameters (Å, º)

N1—C7	1.3538 (19)	C3—C4	1.397 (2)
N1—C1	1.4116 (19)	C4—C5	1.390 (2)
O1—C7	1.2251 (19)	C4—C41	1.512 (2)
O2—C9	1.216 (2)	C5—C6	1.390 (2)
C1—C6	1.397 (2)	C7—C8	1.526 (2)
C1—C2	1.411 (2)	C8—C9	1.508 (2)
C2—C3	1.393 (2)	C9—C10	1.514 (2)
C2—C21	1.506 (2)
C7—N1—C1	128.64 (13)	C3—C4—C41	120.73 (14)
C6—C1—C2	119.89 (14)	C4—C5—C6	121.42 (14)
C6—C1—N1	123.02 (13)	C5—C6—C1	119.97 (14)
C2—C1—N1	117.09 (13)	O1—C7—N1	125.32 (14)
C3—C2—C1	118.38 (14)	O1—C7—C8	118.57 (14)
C3—C2—C21	120.97 (14)	N1—C7—C8	116.11 (13)
C1—C2—C21	120.65 (14)	C9—C8—C7	122.39 (13)
C2—C3—C4	122.41 (14)	O2—C9—C8	124.10 (14)
C5—C4—C3	117.93 (14)	O2—C9—C10	120.27 (15)
C5—C4—C41	121.34 (14)	C8—C9—C10	115.63 (14)
C7—N1—C1—C6	0.0	C41—C4—C5—C6	180.0
C7—N1—C1—C2	180.0	C4—C5—C6—C1	0.0
C6—C1—C2—C3	0.0	C2—C1—C6—C5	0.0
N1—C1—C2—C3	180.0	N1—C1—C6—C5	180.0
C6—C1—C2—C21	180.0	C1—N1—C7—O1	0.0
N1—C1—C2—C21	0.0	C1—N1—C7—C8	180.0
C1—C2—C3—C4	0.0	O1—C7—C8—C9	180.0
C21—C2—C3—C4	180.0	N1—C7—C8—C9	0.0
C2—C3—C4—C5	0.0	C7—C8—C9—O2	0.0
C2—C3—C4—C41	180.0	C7—C8—C9—C10	180.0
C3—C4—C5—C6	0.0

(11)

Crystal data

C11H13NO2	F(000) = 816
Mr = 191.22	Dx = 1.239 Mg m^−3
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71069 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 19 reflections
a = 26.766 (5) Å	θ = 6.6–9.1°
b = 9.3754 (18) Å	µ = 0.09 mm^−1
c = 8.1729 (13) Å	T = 123 K
V = 2050.9 (6) Å^3	Plate, colourless
Z = 8	0.70 × 0.40 × 0.15 mm

Data collection

Rigaku AFC7S Diffractometer	Rint = 0.039
Radiation source: fine-focus sealed tube	θmax = 27.5°, θmin = 2.7°
Graphite monochromator	h = −34→34
ω/2θ scans	k = −12→12
4726 measured reflections	l = −10→10
2363 independent reflections	3 standard reflections every 150 reflections
1401 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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.103	All H-atom parameters refined
S = 0.99	Calculated w = 1/[σ^2(Fo^2) + (0.048P)^2 + 0.0959P] where P = (Fo^2 + 2Fc^2)/3
2363 reflections	(Δ/σ)max = 0.040
168 parameters	Δρmax = 0.18 e Å^−3
0 restraints	Δρmin = −0.20 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	Occ. (<1)
O1	0.25827 (4)	−0.29631 (10)	0.03770 (14)	0.0314 (3)
O2	0.17274 (5)	−0.12578 (13)	0.21003 (14)	0.0419 (3)
N1	0.29137 (4)	−0.07245 (13)	0.03422 (14)	0.0216 (3)
C1	0.34058 (5)	−0.10045 (15)	0.08792 (17)	0.0217 (3)
C2	0.37706 (5)	0.00066 (15)	0.05131 (18)	0.0248 (3)
C3	0.42603 (6)	−0.01927 (18)	0.10250 (18)	0.0291 (3)
C4	0.43982 (5)	−0.13953 (18)	0.19110 (18)	0.0302 (3)
C5	0.40313 (6)	−0.23921 (18)	0.2264 (2)	0.0312 (3)
C6	0.35386 (5)	−0.22121 (15)	0.1774 (2)	0.0269 (3)
C7	0.25437 (5)	−0.16820 (15)	0.00963 (17)	0.0218 (3)
C8	0.20664 (5)	−0.10706 (15)	−0.05909 (18)	0.0221 (3)
C9	0.16489 (5)	−0.10829 (15)	0.06541 (19)	0.0263 (3)
C10	0.11356 (7)	−0.0837 (3)	−0.0007 (3)	0.0444 (5)
C41	0.49270 (6)	−0.1597 (2)	0.2518 (2)	0.0476 (5)
H41A	0.4960	−0.2544	0.3014	0.057*	0.50
H41B	0.5004	−0.0865	0.3336	0.057*	0.50
H41C	0.5160	−0.1512	0.1598	0.057*	0.50
H41D	0.5123	−0.0737	0.2285	0.057*	0.50
H41E	0.5079	−0.2416	0.1963	0.057*	0.50
H41F	0.4923	−0.1768	0.3701	0.057*	0.50
H1	0.3675 (5)	0.0820 (19)	−0.012 (2)	0.026 (4)*
H2	0.4495 (6)	0.059 (2)	0.077 (2)	0.039 (5)*
H3	0.4122 (6)	−0.3239 (19)	0.288 (2)	0.036 (5)*
H4	0.3303 (6)	−0.2908 (18)	0.206 (2)	0.034 (5)*
H5	0.2843 (6)	0.016 (2)	0.011 (2)	0.029 (4)*
H6	0.2103 (5)	−0.0112 (17)	−0.0939 (18)	0.019 (4)*
H7	0.1981 (5)	−0.1678 (17)	−0.153 (2)	0.024 (4)*
H8	0.1113 (8)	0.011 (3)	−0.046 (3)	0.061 (6)*
H9	0.1063 (9)	−0.153 (3)	−0.088 (3)	0.078 (8)*
H10	0.0900 (9)	−0.087 (3)	0.082 (4)	0.078 (8)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0286 (5)	0.0204 (5)	0.0453 (7)	−0.0015 (4)	−0.0056 (5)	0.0010 (4)
O2	0.0507 (7)	0.0514 (7)	0.0237 (6)	0.0185 (6)	0.0060 (5)	0.0076 (5)
N1	0.0212 (6)	0.0178 (6)	0.0257 (6)	0.0012 (4)	−0.0016 (5)	0.0008 (5)
C1	0.0213 (6)	0.0235 (7)	0.0202 (7)	0.0007 (5)	0.0007 (5)	−0.0012 (5)
C2	0.0274 (8)	0.0238 (7)	0.0232 (7)	−0.0014 (6)	−0.0014 (6)	0.0015 (6)
C3	0.0248 (8)	0.0363 (8)	0.0262 (8)	−0.0062 (6)	−0.0005 (6)	0.0014 (7)
C4	0.0225 (7)	0.0430 (9)	0.0249 (7)	0.0025 (6)	−0.0001 (6)	0.0025 (7)
C5	0.0280 (7)	0.0344 (8)	0.0310 (8)	0.0063 (7)	−0.0007 (6)	0.0080 (7)
C6	0.0253 (7)	0.0269 (8)	0.0285 (8)	0.0003 (6)	0.0019 (6)	0.0033 (6)
C7	0.0235 (7)	0.0209 (7)	0.0210 (6)	−0.0010 (5)	0.0002 (5)	−0.0027 (5)
C8	0.0244 (7)	0.0217 (7)	0.0202 (6)	−0.0028 (5)	−0.0017 (5)	−0.0004 (5)
C9	0.0287 (7)	0.0224 (7)	0.0278 (7)	0.0050 (6)	0.0025 (6)	0.0035 (6)
C10	0.0264 (9)	0.0579 (12)	0.0488 (11)	0.0084 (8)	0.0048 (8)	0.0159 (10)
C41	0.0253 (8)	0.0708 (13)	0.0465 (10)	0.0023 (9)	−0.0037 (7)	0.0149 (10)

Geometric parameters (Å, º)

O1—C7	1.2273 (17)	C3—C4	1.390 (2)
O2—C9	1.2117 (18)	C4—C5	1.386 (2)
N1—C7	1.3516 (18)	C4—C41	1.512 (2)
N1—C1	1.4129 (17)	C5—C6	1.389 (2)
C1—C2	1.3935 (19)	C7—C8	1.5088 (19)
C1—C6	1.394 (2)	C8—C9	1.511 (2)
C2—C3	1.388 (2)	C9—C10	1.494 (2)
C7—N1—C1	127.28 (12)	C4—C5—C6	122.08 (14)
C2—C1—C6	119.11 (13)	C5—C6—C1	119.48 (14)
C2—C1—N1	117.40 (13)	O1—C7—N1	124.06 (13)
C6—C1—N1	123.47 (13)	O1—C7—C8	120.88 (12)
C3—C2—C1	120.35 (14)	N1—C7—C8	115.06 (12)
C2—C3—C4	121.13 (14)	C7—C8—C9	111.88 (12)
C5—C4—C3	117.84 (14)	O2—C9—C10	122.20 (15)
C5—C4—C41	120.72 (15)	O2—C9—C8	121.97 (13)
C3—C4—C41	121.41 (15)	C10—C9—C8	115.81 (14)
C7—N1—C1—C2	157.92 (13)	C4—C5—C6—C1	0.9 (2)
C7—N1—C1—C6	−23.5 (2)	C2—C1—C6—C5	−0.8 (2)
C6—C1—C2—C3	0.4 (2)	N1—C1—C6—C5	−179.38 (14)
N1—C1—C2—C3	179.08 (13)	C1—N1—C7—O1	3.0 (2)
C1—C2—C3—C4	−0.1 (2)	C1—N1—C7—C8	−176.08 (13)
C2—C3—C4—C5	0.2 (2)	O1—C7—C8—C9	70.81 (18)
C2—C3—C4—C41	−178.04 (16)	N1—C7—C8—C9	−110.10 (14)
C3—C4—C5—C6	−0.6 (2)	C7—C8—C9—O2	15.5 (2)
C41—C4—C5—C6	177.65 (16)	C7—C8—C9—C10	−165.72 (15)

(12)

Crystal data

C11H13NO2	F(000) = 408
Mr = 191.22	Dx = 1.350 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71069 Å
Hall symbol: -P 2ybc	Cell parameters from 24 reflections
a = 7.3247 (10) Å	θ = 10.1–17.7°
b = 12.108 (2) Å	µ = 0.09 mm^−1
c = 10.7479 (14) Å	T = 123 K
β = 99.357 (13)°	Needle, colourless
V = 940.5 (2) Å^3	0.55 × 0.15 × 0.10 mm
Z = 4

Data collection

Rigaku AFC7S diffractometer	Rint = 0.027
Radiation source: fine-focus sealed tube	θmax = 26.5°, θmin = 2.6°
Graphite monochromator	h = 0→9
ω/2θ scans	k = 0→15
2104 measured reflections	l = −13→13
1951 independent reflections	3 standard reflections every 150 reflections
1168 reflections with I > 2σ(I)	intensity decay: none

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)] = 0.043	All H-atom parameters refined
wR(F^2) = 0.128	Calculated w = 1/[σ^2(Fo^2) + (0.0432P)^2 + 0.2688P] where P = (Fo^2 + 2Fc^2)/3
S = 1.07	(Δ/σ)max < 0.001
1951 reflections	Δρmax = 0.22 e Å^−3
180 parameters	Δρmin = −0.20 e Å^−3
0 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0070 (18)

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
O1	0.0678 (3)	0.52659 (14)	0.27430 (15)	0.0271 (4)
O2	0.2796 (2)	0.72230 (14)	0.59108 (14)	0.0238 (4)
N1	0.2256 (3)	0.52332 (17)	0.47681 (18)	0.0183 (5)
C1	0.2560 (3)	0.40959 (19)	0.4996 (2)	0.0161 (5)
C2	0.3564 (3)	0.38052 (19)	0.61879 (19)	0.0164 (5)
C3	0.3869 (3)	0.2686 (2)	0.6453 (2)	0.0198 (5)
C4	0.3206 (3)	0.1868 (2)	0.5581 (2)	0.0219 (5)
C5	0.2231 (3)	0.2174 (2)	0.4420 (2)	0.0217 (5)
C6	0.1907 (3)	0.3274 (2)	0.4124 (2)	0.0200 (5)
C7	0.1379 (3)	0.57432 (19)	0.3709 (2)	0.0169 (5)
C8	0.1285 (3)	0.6996 (2)	0.3758 (2)	0.0175 (5)
C9	0.2060 (3)	0.76505 (19)	0.4926 (2)	0.0187 (5)
C10	0.1891 (4)	0.8882 (2)	0.4800 (2)	0.0230 (5)
C21	0.4236 (4)	0.4663 (2)	0.7163 (2)	0.0205 (5)
H1	0.446 (4)	0.251 (2)	0.726 (2)	0.027 (7)*
H2	0.345 (3)	0.112 (2)	0.583 (2)	0.023 (7)*
H3	0.184 (4)	0.159 (2)	0.384 (2)	0.031 (8)*
H4	0.120 (3)	0.3503 (19)	0.333 (2)	0.011 (6)*
H5	0.264 (4)	0.572 (2)	0.535 (2)	0.022 (7)*
H6	0.012 (4)	0.717 (2)	0.359 (2)	0.029 (7)*
H7	0.182 (4)	0.729 (2)	0.305 (2)	0.033 (8)*
H8	0.090 (4)	0.909 (2)	0.408 (3)	0.033 (7)*
H9	0.311 (4)	0.916 (2)	0.460 (2)	0.030 (7)*
H10	0.170 (4)	0.918 (2)	0.562 (3)	0.033 (7)*
H11	0.501 (4)	0.523 (2)	0.685 (3)	0.031 (8)*
H12	0.314 (4)	0.509 (2)	0.734 (2)	0.032 (7)*
H13	0.492 (4)	0.435 (2)	0.787 (3)	0.034 (8)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0400 (11)	0.0204 (9)	0.0166 (8)	−0.0011 (8)	−0.0079 (7)	−0.0023 (7)
O2	0.0291 (10)	0.0224 (9)	0.0178 (8)	0.0009 (8)	−0.0026 (7)	−0.0011 (7)
N1	0.0228 (11)	0.0157 (10)	0.0151 (10)	−0.0005 (8)	−0.0009 (8)	−0.0028 (8)
C1	0.0151 (12)	0.0173 (11)	0.0164 (10)	0.0010 (8)	0.0039 (9)	0.0014 (9)
C2	0.0151 (11)	0.0197 (12)	0.0146 (10)	−0.0012 (9)	0.0035 (9)	−0.0009 (9)
C3	0.0175 (12)	0.0229 (13)	0.0183 (12)	0.0006 (10)	0.0006 (9)	0.0020 (9)
C4	0.0221 (13)	0.0179 (13)	0.0262 (12)	0.0039 (10)	0.0048 (10)	0.0020 (10)
C5	0.0241 (13)	0.0188 (12)	0.0225 (12)	0.0001 (10)	0.0043 (10)	−0.0050 (10)
C6	0.0204 (12)	0.0245 (13)	0.0144 (11)	0.0017 (10)	0.0009 (9)	0.0011 (9)
C7	0.0177 (12)	0.0194 (11)	0.0137 (10)	−0.0002 (9)	0.0028 (9)	0.0014 (9)
C8	0.0165 (12)	0.0196 (12)	0.0156 (10)	0.0028 (9)	0.0004 (9)	0.0016 (9)
C9	0.0169 (11)	0.0192 (12)	0.0203 (11)	−0.0037 (10)	0.0036 (9)	−0.0003 (10)
C10	0.0273 (14)	0.0181 (12)	0.0223 (12)	−0.0032 (11)	−0.0003 (10)	0.0005 (10)
C21	0.0223 (12)	0.0204 (12)	0.0163 (11)	−0.0010 (11)	−0.0045 (10)	0.0014 (10)

Geometric parameters (Å, º)

O1—C7	1.225 (3)	C2—C21	1.500 (3)
O2—C9	1.222 (3)	C3—C4	1.396 (3)
N1—C7	1.361 (3)	C4—C5	1.384 (3)
N1—C1	1.410 (3)	C5—C6	1.381 (3)
C1—C6	1.397 (3)	C7—C8	1.520 (3)
C1—C2	1.414 (3)	C8—C9	1.514 (3)
C2—C3	1.395 (3)	C9—C10	1.501 (3)
C7—N1—C1	128.9 (2)	C6—C5—C4	120.6 (2)
C6—C1—N1	123.5 (2)	C5—C6—C1	120.4 (2)
C6—C1—C2	120.1 (2)	O1—C7—N1	124.8 (2)
N1—C1—C2	116.4 (2)	O1—C7—C8	119.0 (2)
C3—C2—C1	118.0 (2)	N1—C7—C8	116.2 (2)
C3—C2—C21	120.4 (2)	C9—C8—C7	122.5 (2)
C1—C2—C21	121.6 (2)	O2—C9—C10	121.2 (2)
C2—C3—C4	121.7 (2)	O2—C9—C8	123.3 (2)
C5—C4—C3	119.2 (2)	C10—C9—C8	115.5 (2)
C7—N1—C1—C6	−2.3 (4)	C4—C5—C6—C1	−0.1 (4)
C7—N1—C1—C2	178.5 (2)	N1—C1—C6—C5	−178.9 (2)
C6—C1—C2—C3	0.0 (3)	C2—C1—C6—C5	0.2 (3)
N1—C1—C2—C3	179.2 (2)	C1—N1—C7—O1	0.3 (4)
C6—C1—C2—C21	−178.1 (2)	C1—N1—C7—C8	−179.8 (2)
N1—C1—C2—C21	1.1 (3)	O1—C7—C8—C9	178.0 (2)
C1—C2—C3—C4	−0.3 (3)	N1—C7—C8—C9	−2.0 (3)
C21—C2—C3—C4	177.8 (2)	C7—C8—C9—O2	−0.8 (4)
C2—C3—C4—C5	0.5 (4)	C7—C8—C9—C10	178.6 (2)
C3—C4—C5—C6	−0.3 (4)