Pseudopolymorphism of N-acetyl-L-phenylalanine methyl ester

The structures of two pseudopolymorphs of N-acetyl-L-phenylalanine methyl ester, L-AcFOMe, were determined at both 293 (2) and 150 (2) K. At room temperature, the orthorhombic phase C₁₂H₁₅NO₃ (I), with space group P2₁2₁2₁, converts into the tetragonal phase C₁₂H₁₅NO₃·0.5H₂O (II), with space group P4₁2₁2, in the presence of water. In the structures of both pseudopolymorphs, alternating layers of hydrophilic and hydrophobic intermolecular interaction can be distinguished. In the hydrophilic layers the structures are stabilized by moderate hydrogen bonds of the type N—H...O for the anhydrous L-AcFOMe and of types N—H...O and O—H...O for the hemihydrate. Weak C—H...π interactions are observed within the hydrophobic layers: for (I) they are of type III [Malone et al. (1997). J. Chem. Soc. Faraday Trans. 93, 3429–3436], whereas typical type I edge-to-face interactions are present for (II). The differences between the hydrogen-bonding networks of (I) and (II) are discussed in terms of graph-set analysis.

S1. Experimental

(type here to add preparation details)

S2. Refinement

(type here to add refinement details)

Computing details

For all compounds, data collection: COLLECT (Nonius, 1997); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: HKL DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); ORTEP-3 for Windows (Farrugia, 1997); Mercury (Version 1.4; Macrae et al., 2006); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

Figures

(Ia) N-Acetyl-L-phenylalanine methyl ester

Crystal data

C12H15NO3	Dx = 1.205 Mg m^−3
Mr = 221.25	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P212121	Cell parameters from 1546 reflections
a = 4.9910 (1) Å	θ = 1.0–27.5°
b = 8.7145 (2) Å	µ = 0.09 mm^−1
c = 28.0411 (7) Å	T = 293 K
V = 1219.62 (5) Å^3	Prism, colourless
Z = 4	0.32 × 0.20 × 0.16 mm
F(000) = 472

Data collection

KappaCCD diffractometer	1656 independent reflections
Radiation source: fine-focus sealed tube	1126 reflections with I > 2σ(I)
Horizontally mounted graphite crystal monochromator	Rint = 0.025
Detector resolution: 9 pixels mm^-1	θmax = 27.5°, θmin = 3.2°
ϕ scans and ω scans to fill asymmetric unit	h = −6→6
Absorption correction: multi-scan HKL DENZO and SCALEPACK (Otwinowski & Minor, 1997)	k = −11→11
Tmin = 0.973, Tmax = 0.986	l = −35→36
8443 measured reflections

Refinement

Refinement on F^2	H atoms treated by a mixture of independent and constrained refinement
Least-squares matrix: full	w = 1/[σ^2(Fo^2) + (0.0634P)^2 + 0.0884P] where P = (Fo^2 + 2Fc^2)/3
R[F^2 > 2σ(F^2)] = 0.042	(Δ/σ)max < 0.001
wR(F^2) = 0.116	Δρmax = 0.14 e Å^−3
S = 0.98	Δρmin = −0.17 e Å^−3
1656 reflections	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
151 parameters	Extinction coefficient: 0.047 (8)
0 restraints

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
N1	0.9648 (4)	0.1871 (2)	0.14259 (7)	0.0530 (5)
H1	1.146 (6)	0.202 (3)	0.1465 (8)	0.054 (6)*
C1	0.8270 (5)	−0.0331 (3)	0.19033 (9)	0.0585 (6)
O1	0.9347 (5)	0.0111 (2)	0.22578 (7)	0.0987 (8)
C2	0.8724 (5)	0.0303 (2)	0.14076 (8)	0.0498 (5)
H2	0.6988	0.0305	0.1245	0.060*
O2	0.6520 (4)	−0.1475 (2)	0.18916 (6)	0.0760 (6)
C3	1.0621 (5)	−0.0715 (2)	0.11151 (8)	0.0571 (6)
H3A	1.2445	−0.0557	0.1224	0.069*
H3B	1.0168	−0.1784	0.1169	0.069*
C4	1.0461 (5)	−0.0373 (2)	0.05895 (8)	0.0504 (5)
C5	0.8514 (6)	−0.1080 (3)	0.03140 (10)	0.0622 (6)
H5	0.7361	−0.1787	0.0454	0.075*
C6	1.2140 (5)	0.0674 (3)	0.03718 (9)	0.0606 (6)
H6	1.3465	0.1160	0.0549	0.073*
C7	0.8262 (6)	−0.0749 (3)	−0.01654 (10)	0.0699 (7)
H7	0.6959	−0.1240	−0.0347	0.084*
C8	1.1867 (6)	0.1007 (3)	−0.01082 (10)	0.0702 (7)
H8	1.3009	0.1714	−0.0251	0.084*
C9	0.9932 (6)	0.0303 (3)	−0.03738 (10)	0.0681 (7)
H9	0.9747	0.0538	−0.0696	0.082*
C10	0.7934 (5)	0.3036 (3)	0.14765 (8)	0.0514 (6)
O10	0.5508 (3)	0.28266 (19)	0.14871 (7)	0.0675 (5)
C11	0.9138 (7)	0.4596 (3)	0.15162 (10)	0.0693 (7)
H11A	0.7909	0.5342	0.1392	0.083*
H11B	1.0777	0.4630	0.1337	0.083*
H11C	0.9503	0.4819	0.1845	0.083*
C12	0.5831 (9)	−0.2164 (4)	0.23451 (11)	0.0963 (11)
H12A	0.4550	−0.2970	0.2295	0.116*
H12B	0.5071	−0.1398	0.2551	0.116*
H12C	0.7414	−0.2580	0.2490	0.116*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0353 (10)	0.0541 (10)	0.0695 (13)	−0.0007 (9)	0.0004 (9)	−0.0018 (9)
C1	0.0505 (14)	0.0616 (13)	0.0633 (15)	0.0024 (13)	−0.0022 (12)	0.0026 (12)
O1	0.122 (2)	0.1120 (15)	0.0615 (12)	−0.0335 (17)	−0.0175 (12)	0.0068 (10)
C2	0.0365 (11)	0.0548 (11)	0.0582 (13)	−0.0003 (11)	−0.0013 (10)	0.0023 (10)
O2	0.0780 (12)	0.0822 (11)	0.0679 (11)	−0.0206 (11)	0.0039 (10)	0.0176 (9)
C3	0.0491 (13)	0.0552 (12)	0.0670 (15)	0.0064 (12)	0.0012 (12)	0.0051 (11)
C4	0.0426 (11)	0.0456 (10)	0.0630 (14)	0.0069 (11)	0.0052 (11)	−0.0036 (10)
C5	0.0553 (14)	0.0561 (13)	0.0752 (16)	−0.0077 (13)	0.0053 (14)	−0.0066 (12)
C6	0.0487 (14)	0.0639 (14)	0.0691 (16)	−0.0046 (12)	−0.0015 (12)	0.0000 (12)
C7	0.0669 (16)	0.0735 (16)	0.0692 (16)	−0.0016 (16)	−0.0077 (14)	−0.0174 (13)
C8	0.0592 (15)	0.0782 (16)	0.0732 (17)	−0.0038 (15)	0.0128 (15)	0.0101 (13)
C9	0.0648 (17)	0.0774 (16)	0.0622 (15)	0.0109 (15)	0.0040 (14)	−0.0030 (13)
C10	0.0475 (13)	0.0601 (13)	0.0467 (12)	0.0045 (12)	−0.0013 (11)	0.0023 (10)
O10	0.0434 (9)	0.0736 (11)	0.0856 (13)	0.0077 (10)	0.0026 (9)	−0.0030 (9)
C11	0.0733 (17)	0.0579 (13)	0.0769 (16)	−0.0003 (15)	−0.0063 (15)	−0.0054 (11)
C12	0.109 (3)	0.094 (2)	0.086 (2)	−0.003 (2)	0.0220 (19)	0.0322 (16)

Geometric parameters (Å, º)

N1—C10	1.336 (3)	C6—C8	1.384 (4)
N1—C2	1.443 (3)	C6—H6	0.9300
N1—H1	0.92 (3)	C7—C9	1.370 (4)
C1—O1	1.194 (3)	C7—H7	0.9300
C1—O2	1.326 (3)	C8—C9	1.365 (4)
C1—C2	1.513 (3)	C8—H8	0.9300
C2—C3	1.535 (3)	C9—H9	0.9300
C2—H2	0.9800	C10—O10	1.225 (3)
O2—C12	1.448 (3)	C10—C11	1.490 (3)
C3—C4	1.506 (3)	C11—H11A	0.9600
C3—H3A	0.9700	C11—H11B	0.9600
C3—H3B	0.9700	C11—H11C	0.9600
C4—C6	1.382 (3)	C12—H12A	0.9600
C4—C5	1.386 (3)	C12—H12B	0.9600
C5—C7	1.380 (4)	C12—H12C	0.9600
C5—H5	0.9300
C10—N1—C2	121.3 (2)	C4—C6—H6	119.7
C10—N1—H1	121 (2)	C8—C6—H6	119.7
C2—N1—H1	117 (2)	C9—C7—C5	120.0 (3)
O1—C1—O2	124.0 (2)	C9—C7—H7	120.0
O1—C1—C2	125.5 (2)	C5—C7—H7	120.0
O2—C1—C2	110.5 (2)	C9—C8—C6	120.4 (3)
N1—C2—C1	111.2 (2)	C9—C8—H8	119.8
N1—C2—C3	111.7 (2)	C6—C8—H8	119.8
C1—C2—C3	111.9 (2)	C8—C9—C7	119.9 (3)
N1—C2—H2	107.3	C8—C9—H9	120.1
C1—C2—H2	107.3	C7—C9—H9	120.1
C3—C2—H2	107.3	O10—C10—N1	121.5 (2)
C1—O2—C12	116.5 (2)	O10—C10—C11	122.2 (2)
C4—C3—C2	112.1 (2)	N1—C10—C11	116.3 (2)
C4—C3—H3A	109.2	C10—C11—H11A	109.5
C2—C3—H3A	109.2	C10—C11—H11B	109.5
C4—C3—H3B	109.2	H11A—C11—H11B	109.5
C2—C3—H3B	109.2	C10—C11—H11C	109.5
H3A—C3—H3B	107.9	H11A—C11—H11C	109.5
C6—C4—C5	118.2 (2)	H11B—C11—H11C	109.5
C6—C4—C3	122.1 (2)	O2—C12—H12A	109.5
C5—C4—C3	119.7 (2)	O2—C12—H12B	109.5
C7—C5—C4	120.9 (3)	H12A—C12—H12B	109.5
C7—C5—H5	119.5	O2—C12—H12C	109.5
C4—C5—H5	119.5	H12A—C12—H12C	109.5
C4—C6—C8	120.6 (2)	H12B—C12—H12C	109.5
C10—N1—C2—C1	−82.6 (3)	C2—C3—C4—C5	−85.4 (2)
C10—N1—C2—C3	151.8 (2)	C6—C4—C5—C7	0.2 (3)
O1—C1—C2—N1	−25.1 (4)	C3—C4—C5—C7	177.8 (2)
O2—C1—C2—N1	155.9 (2)	C5—C4—C6—C8	0.2 (3)
O1—C1—C2—C3	100.5 (3)	C3—C4—C6—C8	−177.4 (2)
O2—C1—C2—C3	−78.6 (2)	C4—C5—C7—C9	−0.7 (4)
O1—C1—O2—C12	2.7 (4)	C4—C6—C8—C9	0.0 (4)
C2—C1—O2—C12	−178.2 (2)	C6—C8—C9—C7	−0.6 (4)
N1—C2—C3—C4	−71.4 (3)	C5—C7—C9—C8	0.9 (4)
C1—C2—C3—C4	163.3 (2)	C2—N1—C10—O10	−3.4 (3)
C2—C3—C4—C6	92.1 (3)	C2—N1—C10—C11	176.9 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O10^i	0.92 (3)	2.14 (3)	3.046 (3)	168 (2)
C12—H12C···O1^ii	0.96	2.68	3.560 (4)	153
C11—H11C···O1^iii	0.96	2.59	3.548 (3)	174
C12—H12B···O10^iv	0.96	2.80	3.342 (4)	117
C9—H9···O10^v	0.93	2.66	3.533 (3)	156
C8—H8···CG1^v	0.93	3.12	3.88 (4)	141

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

(Ib) N-Acetyl-L-phenylalanine methyl ester

Crystal data

C12H15NO3	Dx = 1.243 Mg m^−3
Mr = 221.25	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P212121	Cell parameters from 2846 reflections
a = 4.9488 (2) Å	θ = 1.0–30.0°
b = 8.6359 (6) Å	µ = 0.09 mm^−1
c = 27.6622 (10) Å	T = 150 K
V = 1182.21 (10) Å^3	Prism, colourless
Z = 4	0.32 × 0.20 × 0.16 mm
F(000) = 472

Data collection

KappaCCD diffractometer	2019 independent reflections
Radiation source: fine-focus sealed tube	1736 reflections with I > 2σ(I)
Horizontally mounted graphite crystal monochromator	Rint = 0.028
Detector resolution: 9 pixels mm^-1	θmax = 30.1°, θmin = 3.2°
ω scans at χ = 55 deg	h = −6→6
Absorption correction: multi-scan HKL DENZO and SCALEPACK (Otwinowski & Minor, 1997)	k = −12→12
Tmin = 0.972, Tmax = 0.986	l = −38→38
8592 measured reflections

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Primary atom site location: structure-invariant direct methods
R[F^2 > 2σ(F^2)] = 0.039	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.096	w = 1/[σ^2(Fo^2) + (0.0476P)^2 + 0.1338P] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max < 0.001
2019 reflections	Δρmax = 0.20 e Å^−3
150 parameters	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
N1	0.9756 (3)	0.17369 (15)	0.14176 (5)	0.0230 (3)
H1	1.165 (5)	0.189 (2)	0.1458 (8)	0.041 (6)*
C1	0.8299 (3)	−0.05130 (18)	0.18902 (6)	0.0253 (3)
O1	0.9382 (3)	−0.00806 (16)	0.22535 (5)	0.0473 (4)
C2	0.8774 (3)	0.01612 (17)	0.13890 (5)	0.0214 (3)
H2	0.6989	0.0189	0.1220	0.026*
O2	0.6494 (3)	−0.16546 (14)	0.18699 (4)	0.0339 (3)
C3	1.0673 (4)	−0.08635 (17)	0.10878 (6)	0.0243 (3)
H3A	1.2552	−0.0728	0.1203	0.029*
H3B	1.0171	−0.1964	0.1132	0.029*
C4	1.0517 (3)	−0.04506 (17)	0.05556 (5)	0.0219 (3)
C5	0.8513 (4)	−0.11234 (18)	0.02703 (6)	0.0266 (3)
H5	0.7321	−0.1866	0.0407	0.032*
C6	1.2237 (3)	0.06351 (19)	0.03498 (6)	0.0267 (3)
H6	1.3609	0.1101	0.0541	0.032*
C7	0.8253 (4)	−0.07116 (19)	−0.02125 (6)	0.0285 (4)
H7	0.6892	−0.1179	−0.0406	0.034*
C8	1.1968 (4)	0.1047 (2)	−0.01344 (6)	0.0305 (4)
H8	1.3158	0.1789	−0.0273	0.037*
C9	0.9970 (4)	0.03776 (19)	−0.04141 (6)	0.0298 (4)
H9	0.9775	0.0664	−0.0744	0.036*
C10	0.8025 (3)	0.29163 (18)	0.14876 (6)	0.0226 (3)
O10	0.5566 (2)	0.27063 (13)	0.15013 (5)	0.0301 (3)
C11	0.9267 (4)	0.44933 (18)	0.15400 (6)	0.0301 (4)
H11A	0.8127	0.5261	0.1377	0.036*
H11B	1.1069	0.4494	0.1393	0.036*
H11C	0.9414	0.4755	0.1884	0.036*
C12	0.5786 (5)	−0.2361 (2)	0.23292 (7)	0.0435 (5)
H12A	0.4453	−0.3182	0.2275	0.052*
H12B	0.5019	−0.1573	0.2544	0.052*
H12C	0.7409	−0.2803	0.2478	0.052*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0180 (6)	0.0219 (6)	0.0289 (7)	−0.0006 (5)	0.0001 (5)	−0.0009 (5)
C1	0.0242 (8)	0.0274 (7)	0.0243 (7)	0.0023 (7)	−0.0007 (7)	0.0005 (6)
O1	0.0644 (10)	0.0519 (8)	0.0255 (6)	−0.0168 (8)	−0.0088 (7)	0.0017 (6)
C2	0.0180 (7)	0.0235 (7)	0.0226 (7)	−0.0006 (6)	−0.0017 (6)	0.0009 (6)
O2	0.0366 (7)	0.0369 (6)	0.0281 (6)	−0.0095 (6)	0.0014 (6)	0.0081 (5)
C3	0.0251 (8)	0.0230 (7)	0.0248 (7)	0.0030 (7)	−0.0015 (7)	0.0012 (6)
C4	0.0209 (7)	0.0205 (7)	0.0243 (7)	0.0037 (6)	0.0026 (6)	−0.0014 (6)
C5	0.0270 (8)	0.0246 (7)	0.0281 (8)	−0.0018 (7)	0.0031 (7)	−0.0003 (6)
C6	0.0219 (8)	0.0276 (7)	0.0305 (8)	−0.0007 (7)	−0.0009 (7)	0.0005 (7)
C7	0.0299 (8)	0.0291 (8)	0.0266 (8)	−0.0004 (8)	−0.0028 (7)	−0.0048 (6)
C8	0.0266 (8)	0.0327 (8)	0.0321 (9)	−0.0012 (7)	0.0065 (7)	0.0066 (7)
C9	0.0312 (9)	0.0344 (8)	0.0238 (8)	0.0072 (7)	0.0031 (7)	0.0027 (7)
C10	0.0239 (8)	0.0273 (7)	0.0165 (7)	0.0024 (6)	−0.0007 (6)	0.0020 (6)
O10	0.0206 (6)	0.0331 (6)	0.0366 (7)	0.0029 (5)	0.0017 (5)	−0.0005 (5)
C11	0.0311 (9)	0.0267 (7)	0.0325 (8)	0.0002 (7)	−0.0041 (8)	−0.0028 (7)
C12	0.0504 (12)	0.0443 (10)	0.0360 (10)	−0.0032 (10)	0.0110 (9)	0.0160 (8)

Geometric parameters (Å, º)

N1—C10	1.345 (2)	C6—C8	1.392 (2)
N1—C2	1.447 (2)	C6—H6	0.9500
N1—H1	0.95 (2)	C7—C9	1.385 (2)
C1—O1	1.199 (2)	C7—H7	0.9500
C1—O2	1.332 (2)	C8—C9	1.382 (2)
C1—C2	1.522 (2)	C8—H8	0.9500
C2—C3	1.536 (2)	C9—H9	0.9500
C2—H2	1.0000	C10—O10	1.231 (2)
O2—C12	1.452 (2)	C10—C11	1.501 (2)
C3—C4	1.517 (2)	C11—H11A	0.9800
C3—H3A	0.9900	C11—H11B	0.9800
C3—H3B	0.9900	C11—H11C	0.9800
C4—C6	1.388 (2)	C12—H12A	0.9800
C4—C5	1.394 (2)	C12—H12B	0.9800
C5—C7	1.388 (2)	C12—H12C	0.9800
C5—H5	0.9500
C10—N1—C2	120.4 (1)	C4—C6—H6	119.7
C10—N1—H1	120 (1)	C8—C6—H6	119.7
C2—N1—H1	118 (1)	C9—C7—C5	120.3 (2)
O1—C1—O2	124.5 (2)	C9—C7—H7	119.8
O1—C1—C2	125.1 (2)	C5—C7—H7	119.8
O2—C1—C2	110.4 (1)	C9—C8—C6	120.0 (2)
N1—C2—C1	111.2 (1)	C9—C8—H8	120.0
N1—C2—C3	111.5 (1)	C6—C8—H8	120.0
C1—C2—C3	111.6 (1)	C8—C9—C7	119.9 (2)
N1—C2—H2	107.4	C8—C9—H9	120.1
C1—C2—H2	107.4	C7—C9—H9	120.1
C3—C2—H2	107.4	O10—C10—N1	121.5 (2)
C1—O2—C12	115.8 (1)	O10—C10—C11	122.4 (2)
C4—C3—C2	111.1 (1)	N1—C10—C11	116.1 (1)
C4—C3—H3A	109.4	C10—C11—H11A	109.5
C2—C3—H3A	109.4	C10—C11—H11B	109.5
C4—C3—H3B	109.4	H11A—C11—H11B	109.5
C2—C3—H3B	109.4	C10—C11—H11C	109.5
H3A—C3—H3B	108.0	H11A—C11—H11C	109.5
C6—C4—C5	119.0 (2)	H11B—C11—H11C	109.5
C6—C4—C3	121.7 (2)	O2—C12—H12A	109.5
C5—C4—C3	119.2 (1)	O2—C12—H12B	109.5
C7—C5—C4	120.3 (2)	H12A—C12—H12B	109.5
C7—C5—H5	119.9	O2—C12—H12C	109.5
C4—C5—H5	119.9	H12A—C12—H12C	109.5
C4—C6—C8	120.6 (2)	H12B—C12—H12C	109.5
C10—N1—C2—C1	−81.2 (2)	C2—C3—C4—C5	−85.5 (2)
C10—N1—C2—C3	153.6 (1)	C6—C4—C5—C7	0.1 (2)
O1—C1—C2—N1	−23.9 (2)	C3—C4—C5—C7	177.1 (2)
O2—C1—C2—N1	155.9 (1)	C5—C4—C6—C8	0.0 (2)
O1—C1—C2—C3	101.3 (2)	C3—C4—C6—C8	−176.9 (2)
O2—C1—C2—C3	−79.0 (2)	C4—C5—C7—C9	−0.4 (3)
O1—C1—O2—C12	1.9 (3)	C4—C6—C8—C9	0.2 (3)
C2—C1—O2—C12	−177.9 (2)	C6—C8—C9—C7	−0.5 (3)
N1—C2—C3—C4	−71.0 (2)	C5—C7—C9—C8	0.6 (2)
C1—C2—C3—C4	164.0 (1)	C2—N1—C10—O10	−4.2 (2)
C2—C3—C4—C6	91.4 (2)	C2—N1—C10—C11	176.7 (1)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O10^i	0.95 (2)	2.06 (2)	3.003 (2)	168 (2)
C12—H12C···O1^ii	0.98	2.63	3.545 (3)	155
C11—H11C···O1^iii	0.98	2.46	3.424 (2)	166
C12—H12B···O10^iv	0.98	2.73	3.304 (2)	118
C9—H9···O10^v	0.95	2.55	3.445 (2)	156
C8—H8···CG1^v	0.95	3.04	3.81 (4)	139

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

(IIa) N-Acetyl-L-phenylalanine methyl ester hemihydrate

Crystal data

2(C12H15NO3)·H2O	Dx = 1.256 Mg m^−3
Mr = 460.52	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, P41212	Cell parameters from 3565 reflections
a = 7.1582 (1) Å	θ = 2.9–33.7°
c = 47.5286 (6) Å	µ = 0.09 mm^−1
V = 2435.36 (6) Å^3	T = 293 K
Z = 4	Prism, colourless
F(000) = 984	0.32 × 0.12 × 0.12 mm

Data collection

KappaCCD diffractometer	1738 independent reflections
Radiation source: fine-focus sealed tube	1270 reflections with I > 2σ(I)
Horizontally mounted graphite crystal monochromator	Rint = 0.026
Detector resolution: 9 pixels mm^-1	θmax = 27.5°, θmin = 3.0°
ω scans at χ = 55 deg	h = −9→9
Absorption correction: multi-scan HKL DENZO and SCALEPACK (Otwinowski & Minor, 1997)	k = −6→6
Tmin = 0.971, Tmax = 0.989	l = −61→61
11430 measured reflections

Refinement

Refinement on F^2	H-atom parameters constrained
Least-squares matrix: full	w = 1/[σ^2(Fo^2) + (0.0566P)^2 + 0.2801P] where P = (Fo^2 + 2Fc^2)/3
R[F^2 > 2σ(F^2)] = 0.045	(Δ/σ)max < 0.001
wR(F^2) = 0.119	Δρmax = 0.17 e Å^−3
S = 1.06	Δρmin = −0.17 e Å^−3
1738 reflections	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
152 parameters	Extinction coefficient: 0.019 (3)
0 restraints

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
N1	0.1621 (3)	0.1351 (3)	0.21800 (3)	0.0401 (5)
H1	0.1807	0.0253	0.2256	0.048*
C1	−0.1544 (4)	0.1807 (4)	0.19968 (5)	0.0443 (6)
O1	−0.2369 (3)	0.1170 (4)	0.21906 (4)	0.0745 (7)
C2	0.0499 (3)	0.1447 (3)	0.19260 (4)	0.0398 (6)
H2	0.0962	0.2468	0.1808	0.048*
O2	−0.2328 (2)	0.2886 (3)	0.18015 (3)	0.0531 (5)
C3	0.0631 (3)	−0.0394 (4)	0.17608 (5)	0.0446 (6)
H3A	0.0402	−0.1426	0.1888	0.054*
H3B	−0.0342	−0.0412	0.1619	0.054*
C4	0.2496 (3)	−0.0680 (3)	0.16196 (5)	0.0401 (6)
C5	0.2855 (4)	0.0142 (4)	0.13604 (5)	0.0487 (7)
H5	0.1934	0.0857	0.1274	0.058*
C6	0.3884 (4)	−0.1737 (4)	0.17408 (5)	0.0452 (6)
H6	0.3666	−0.2316	0.1913	0.054*
C7	0.4556 (4)	−0.0087 (4)	0.12293 (5)	0.0560 (8)
H7	0.4774	0.0470	0.1056	0.067*
C8	0.5602 (4)	−0.1952 (4)	0.16101 (5)	0.0519 (7)
H8	0.6534	−0.2653	0.1696	0.062*
C9	0.5931 (4)	−0.1137 (4)	0.13546 (5)	0.0558 (7)
H9	0.7079	−0.1292	0.1266	0.067*
C10	0.2155 (3)	0.2901 (4)	0.23140 (5)	0.0416 (6)
O10	0.1785 (3)	0.4469 (3)	0.22203 (4)	0.0571 (5)
C11	0.3251 (4)	0.2628 (4)	0.25810 (5)	0.0574 (8)
H11A	0.4532	0.2967	0.2549	0.069*
H11B	0.3185	0.1341	0.2637	0.069*
H11C	0.2737	0.3401	0.2727	0.069*
C12	−0.4319 (4)	0.3171 (4)	0.18295 (6)	0.0593 (8)
H12A	−0.4754	0.3952	0.1679	0.071*
H12B	−0.4578	0.3763	0.2006	0.071*
H12C	−0.4947	0.1987	0.1822	0.071*
O5	0.2188 (2)	−0.2188 (2)	0.2500	0.0471 (6)
H51	0.3284	−0.1991	0.2565	0.057*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0437 (12)	0.0337 (11)	0.0428 (10)	0.0011 (9)	−0.0066 (9)	−0.0036 (9)
C1	0.0439 (15)	0.0470 (15)	0.0421 (12)	0.0025 (12)	−0.0001 (11)	−0.0038 (12)
O1	0.0538 (13)	0.1087 (19)	0.0611 (11)	0.0080 (12)	0.0146 (10)	0.0282 (12)
C2	0.0386 (13)	0.0415 (14)	0.0392 (11)	−0.0022 (11)	0.0007 (11)	−0.0025 (11)
O2	0.0395 (10)	0.0621 (12)	0.0577 (10)	0.0069 (9)	0.0024 (8)	0.0097 (9)
C3	0.0400 (14)	0.0464 (15)	0.0474 (13)	−0.0018 (11)	−0.0020 (11)	−0.0083 (12)
C4	0.0438 (15)	0.0384 (14)	0.0381 (11)	−0.0017 (11)	−0.0010 (10)	−0.0103 (10)
C5	0.0549 (17)	0.0468 (16)	0.0446 (13)	0.0059 (13)	−0.0026 (13)	−0.0027 (11)
C6	0.0481 (15)	0.0491 (16)	0.0383 (11)	−0.0003 (12)	−0.0021 (11)	0.0008 (11)
C7	0.068 (2)	0.0572 (18)	0.0431 (13)	−0.0035 (15)	0.0061 (14)	0.0006 (13)
C8	0.0432 (15)	0.0573 (18)	0.0552 (14)	0.0048 (13)	−0.0059 (12)	−0.0030 (14)
C9	0.0475 (17)	0.065 (2)	0.0550 (14)	−0.0032 (15)	0.0093 (13)	−0.0114 (15)
C10	0.0380 (13)	0.0429 (15)	0.0439 (12)	−0.0014 (12)	0.0028 (11)	−0.0077 (12)
O10	0.0740 (14)	0.0366 (10)	0.0606 (10)	0.0006 (10)	−0.0076 (10)	−0.0084 (9)
C11	0.0646 (19)	0.0596 (18)	0.0479 (14)	−0.0038 (14)	−0.0093 (13)	−0.0077 (12)
C12	0.0404 (16)	0.0607 (19)	0.0770 (18)	0.0048 (14)	−0.0031 (14)	−0.0018 (16)
O5	0.0415 (9)	0.0415 (9)	0.0585 (13)	0.0010 (11)	−0.0076 (8)	−0.0076 (8)

Geometric parameters (Å, º)

N1—C10	1.335 (3)	C6—C8	1.387 (4)
N1—C2	1.452 (3)	C6—H6	0.9300
N1—H1	0.8752	C7—C9	1.374 (4)
C1—O1	1.186 (3)	C7—H7	0.9300
C1—O2	1.332 (3)	C8—C9	1.368 (4)
C1—C2	1.523 (3)	C8—H8	0.9300
C2—C3	1.537 (3)	C9—H9	0.9300
C2—H2	0.9800	C10—O10	1.236 (3)
O2—C12	1.445 (3)	C10—C11	1.505 (3)
C3—C4	1.509 (3)	C11—H11A	0.9600
C3—H3A	0.9700	C11—H11B	0.9600
C3—H3B	0.9700	C11—H11C	0.9600
C4—C6	1.375 (3)	C12—H12A	0.9600
C4—C5	1.389 (3)	C12—H12B	0.9600
C5—C7	1.377 (4)	C12—H12C	0.9600
C5—H5	0.9300	O5—H51	0.8547
C10—N1—C2	121.0 (2)	C4—C6—H6	119.5
C10—N1—H1	120.4	C8—C6—H6	119.5
C2—N1—H1	118.0	C9—C7—C5	120.1 (3)
O1—C1—O2	123.7 (2)	C9—C7—H7	119.9
O1—C1—C2	125.8 (3)	C5—C7—H7	119.9
O2—C1—C2	110.5 (2)	C9—C8—C6	120.2 (3)
N1—C2—C1	110.85 (19)	C9—C8—H8	119.9
N1—C2—C3	110.5 (2)	C6—C8—H8	119.9
C1—C2—C3	108.5 (2)	C8—C9—C7	119.7 (3)
N1—C2—H2	109.0	C8—C9—H9	120.2
C1—C2—H2	109.0	C7—C9—H9	120.2
C3—C2—H2	109.0	O10—C10—N1	121.4 (2)
C1—O2—C12	115.7 (2)	O10—C10—C11	122.2 (2)
C4—C3—C2	113.4 (2)	N1—C10—C11	116.3 (2)
C4—C3—H3A	108.9	C10—C11—H11A	109.5
C2—C3—H3A	108.9	C10—C11—H11B	109.5
C4—C3—H3B	108.9	H11A—C11—H11B	109.5
C2—C3—H3B	108.9	C10—C11—H11C	109.5
H3A—C3—H3B	107.7	H11A—C11—H11C	109.5
C6—C4—C5	118.1 (2)	H11B—C11—H11C	109.5
C6—C4—C3	121.9 (2)	O2—C12—H12A	109.5
C5—C4—C3	120.0 (2)	O2—C12—H12B	109.5
C7—C5—C4	121.0 (2)	H12A—C12—H12B	109.5
C7—C5—H5	119.5	O2—C12—H12C	109.5
C4—C5—H5	119.5	H12A—C12—H12C	109.5
C4—C6—C8	120.9 (2)	H12B—C12—H12C	109.5
C10—N1—C2—C1	−78.8 (3)	C2—C3—C4—C5	−82.9 (3)
C10—N1—C2—C3	160.8 (2)	C6—C4—C5—C7	−0.4 (4)
O1—C1—C2—N1	−38.1 (4)	C3—C4—C5—C7	179.4 (2)
O2—C1—C2—N1	144.9 (2)	C5—C4—C6—C8	1.0 (4)
O1—C1—C2—C3	83.5 (3)	C3—C4—C6—C8	−178.7 (2)
O2—C1—C2—C3	−93.6 (2)	C4—C5—C7—C9	−0.1 (4)
O1—C1—O2—C12	−3.3 (4)	C4—C6—C8—C9	−1.2 (4)
C2—C1—O2—C12	173.9 (2)	C6—C8—C9—C7	0.7 (4)
N1—C2—C3—C4	−72.0 (3)	C5—C7—C9—C8	0.0 (4)
C1—C2—C3—C4	166.3 (2)	C2—N1—C10—O10	−3.3 (3)
C2—C3—C4—C6	96.8 (3)	C2—N1—C10—C11	177.7 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O5	0.88	2.11	2.983 (3)	171
O5—H51···O10^i	0.85	1.91	2.753 (2)	168
C11—H11B···O10^i	0.96	2.88	3.679 (4)	142
C12—H12B···O10^ii	0.96	2.84	3.477 (3)	125
C11—H11C···O1^iii	0.96	2.92	3.351 (4)	109
C5—H5···CG1^iv	0.93	2.82	3.66 (4)	151
C12—H12C···CG1^ii	0.96	2.62	3.44 (5)	143

Symmetry codes: (i) −y+1, −x, −z+1/2; (ii) x−1, y, z; (iii) −y, −x, −z+1/2; (iv) −x+1/2, y+1/2, −z+1/4.

(IIb) N-Acetyl-L-phenylalanine methyl ester hemihydrate

Crystal data

2(C12H15NO3)·H2O	Dx = 1.291 Mg m^−3
Mr = 460.52	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, P41212	Cell parameters from 2051 reflections
a = 7.0900 (1) Å	θ = 2.9–27.5°
c = 47.1426 (5) Å	µ = 0.10 mm^−1
V = 2369.77 (5) Å^3	T = 150 K
Z = 4	Prism, colourless
F(000) = 984	0.36 × 0.35 × 0.20 mm

Data collection

KappaCCD diffractometer	1674 independent reflections
Radiation source: fine-focus sealed tube	1570 reflections with I > 2σ(I)
Horizontally mounted graphite crystal monochromator	Rint = 0.013
Detector resolution: 9 pixels mm^-1	θmax = 27.4°, θmin = 3.6°
ω scans at χ = 55 deg	h = −9→9
Absorption correction: multi-scan HKL DENZO and SCALEPACK (Otwinowski & Minor, 1997)	k = −6→6
Tmin = 0.967, Tmax = 0.981	l = −59→60
6431 measured reflections

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.035	w = 1/[σ^2(Fo^2) + (0.0431P)^2 + 0.7149P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.093	(Δ/σ)max < 0.001
S = 1.08	Δρmax = 0.20 e Å^−3
1674 reflections	Δρmin = −0.24 e Å^−3
151 parameters

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
N1	0.1604 (2)	0.1277 (2)	0.21825 (3)	0.0197 (3)
H1	0.1776	0.0112	0.2261	0.024*
C1	−0.1600 (2)	0.1749 (2)	0.19980 (4)	0.0207 (3)
O1	−0.2433 (2)	0.1105 (2)	0.21969 (3)	0.0345 (4)
C2	0.0465 (2)	0.1374 (2)	0.19275 (3)	0.0187 (3)
H2	0.0947	0.2421	0.1805	0.022*
O2	−0.23874 (17)	0.28341 (19)	0.17975 (3)	0.0240 (3)
C3	0.0583 (2)	−0.0493 (3)	0.17603 (4)	0.0214 (4)
H3A	0.0342	−0.1557	0.1891	0.026*
H3B	−0.0418	−0.0506	0.1614	0.026*
C4	0.2471 (2)	−0.0785 (2)	0.16184 (3)	0.0194 (3)
C5	0.2838 (3)	0.0066 (2)	0.13569 (4)	0.0229 (4)
H5	0.1891	0.0812	0.1269	0.027*
C6	0.3876 (2)	−0.1871 (2)	0.17435 (4)	0.0218 (4)
H6	0.3642	−0.2477	0.1920	0.026*
C7	0.4570 (3)	−0.0165 (3)	0.12240 (4)	0.0260 (4)
H7	0.4797	0.0411	0.1045	0.031*
C8	0.5621 (3)	−0.2076 (3)	0.16123 (4)	0.0247 (4)
H8	0.6581	−0.2796	0.1702	0.030*
C9	0.5973 (3)	−0.1238 (3)	0.13521 (4)	0.0260 (4)
H9	0.7161	−0.1396	0.1262	0.031*
C10	0.2145 (2)	0.2860 (2)	0.23166 (4)	0.0202 (3)
O10	0.1758 (2)	0.44422 (18)	0.22200 (3)	0.0271 (3)
C11	0.3291 (3)	0.2605 (3)	0.25812 (4)	0.0267 (4)
H11A	0.4634	0.2725	0.2536	0.032*
H11B	0.3048	0.1351	0.2661	0.032*
H11C	0.2938	0.3571	0.2720	0.032*
C12	−0.4397 (3)	0.3113 (3)	0.18263 (4)	0.0269 (4)
H12A	−0.4851	0.3918	0.1672	0.032*
H12B	−0.4665	0.3721	0.2009	0.032*
H12C	−0.5040	0.1891	0.1818	0.032*
O5	0.22252 (17)	−0.22252 (17)	0.2500	0.0221 (4)
H51	0.3404	−0.2120	0.2570	0.026*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0206 (7)	0.0178 (7)	0.0207 (7)	0.0015 (5)	−0.0020 (6)	−0.0008 (6)
C1	0.0213 (8)	0.0203 (8)	0.0205 (8)	0.0001 (6)	−0.0001 (7)	−0.0027 (7)
O1	0.0265 (7)	0.0487 (9)	0.0283 (7)	0.0045 (6)	0.0075 (6)	0.0121 (7)
C2	0.0188 (8)	0.0183 (8)	0.0188 (7)	−0.0004 (6)	−0.0001 (6)	−0.0022 (6)
O2	0.0180 (6)	0.0282 (7)	0.0259 (6)	0.0027 (5)	0.0003 (5)	0.0043 (5)
C3	0.0187 (8)	0.0227 (9)	0.0227 (8)	−0.0014 (6)	−0.0004 (7)	−0.0041 (7)
C4	0.0218 (8)	0.0177 (8)	0.0188 (7)	−0.0019 (6)	0.0003 (6)	−0.0052 (6)
C5	0.0258 (9)	0.0208 (9)	0.0221 (8)	0.0017 (7)	−0.0028 (7)	−0.0012 (7)
C6	0.0242 (9)	0.0230 (9)	0.0180 (7)	−0.0010 (7)	−0.0004 (7)	−0.0002 (6)
C7	0.0307 (10)	0.0268 (10)	0.0205 (8)	−0.0031 (7)	0.0025 (7)	0.0010 (7)
C8	0.0213 (9)	0.0269 (9)	0.0259 (8)	0.0022 (7)	−0.0038 (7)	−0.0023 (7)
C9	0.0213 (9)	0.0302 (10)	0.0264 (9)	−0.0015 (8)	0.0038 (7)	−0.0058 (7)
C10	0.0175 (8)	0.0220 (8)	0.0212 (8)	−0.0016 (7)	0.0027 (6)	−0.0047 (7)
O10	0.0342 (7)	0.0187 (6)	0.0285 (6)	0.0012 (5)	−0.0030 (6)	−0.0034 (5)
C11	0.0296 (9)	0.0274 (9)	0.0232 (8)	−0.0014 (7)	−0.0037 (7)	−0.0039 (7)
C12	0.0188 (8)	0.0268 (9)	0.0350 (10)	0.0024 (7)	−0.0012 (7)	−0.0002 (8)
O5	0.0201 (5)	0.0201 (5)	0.0259 (8)	0.0015 (7)	−0.0030 (5)	−0.0030 (5)

Geometric parameters (Å, º)

N1—C10	1.344 (2)	C6—C8	1.391 (2)
N1—C2	1.450 (2)	C6—H6	0.9500
N1—H1	0.9131	C7—C9	1.390 (3)
C1—O1	1.198 (2)	C7—H7	0.9500
C1—O2	1.340 (2)	C8—C9	1.385 (3)
C1—C2	1.525 (2)	C8—H8	0.9500
C2—C3	1.543 (2)	C9—H9	0.9500
C2—H2	1.0000	C10—O10	1.241 (2)
O2—C12	1.445 (2)	C10—C11	1.500 (2)
C3—C4	1.511 (2)	C11—H11A	0.9800
C3—H3A	0.9900	C11—H11B	0.9800
C3—H3B	0.9900	C11—H11C	0.9800
C4—C6	1.390 (2)	C12—H12A	0.9800
C4—C5	1.397 (2)	C12—H12B	0.9800
C5—C7	1.388 (3)	C12—H12C	0.9800
C5—H5	0.9500	O5—H51	0.9024
C10—N1—C2	120.6 (1)	C4—C6—H6	119.8
C10—N1—H1	121.8	C8—C6—H6	119.8
C2—N1—H1	117.0	C5—C7—C9	120.1 (2)
O1—C1—O2	124.4 (2)	C5—C7—H7	120.0
O1—C1—C2	125.2 (2)	C9—C7—H7	120.0
O2—C1—C2	110.3 (1)	C9—C8—C6	120.6 (2)
N1—C2—C1	111.2 (1)	C9—C8—H8	119.7
N1—C2—C3	110.7 (1)	C6—C8—H8	119.7
C1—C2—C3	108.2 (1)	C8—C9—C7	119.4 (2)
N1—C2—H2	108.9	C8—C9—H9	120.3
C1—C2—H2	108.9	C7—C9—H9	120.3
C3—C2—H2	108.9	O10—C10—N1	121.3 (2)
C1—O2—C12	115.0 (1)	O10—C10—C11	122.3 (2)
C4—C3—C2	113.0 (1)	N1—C10—C11	116.4 (2)
C4—C3—H3A	109.0	C10—C11—H11A	109.5
C2—C3—H3A	109.0	C10—C11—H11B	109.5
C4—C3—H3B	109.0	H11A—C11—H11B	109.5
C2—C3—H3B	109.0	C10—C11—H11C	109.5
H3A—C3—H3B	107.8	H11A—C11—H11C	109.5
C6—C4—C5	118.7 (2)	H11B—C11—H11C	109.5
C6—C4—C3	121.5 (2)	O2—C12—H12A	109.5
C5—C4—C3	119.8 (2)	O2—C12—H12B	109.5
C7—C5—C4	120.8 (2)	H12A—C12—H12B	109.5
C7—C5—H5	119.6	O2—C12—H12C	109.5
C4—C5—H5	119.6	H12A—C12—H12C	109.5
C4—C6—C8	120.4 (2)	H12B—C12—H12C	109.5
C10—N1—C2—C1	−78.6 (2)	C2—C3—C4—C5	−82.5 (2)
C10—N1—C2—C3	161.0 (2)	C6—C4—C5—C7	0.0 (3)
O1—C1—C2—N1	−37.8 (2)	C3—C4—C5—C7	179.3 (2)
O2—C1—C2—N1	145.3 (1)	C5—C4—C6—C8	1.1 (3)
O1—C1—C2—C3	84.0 (2)	C3—C4—C6—C8	−178.2 (2)
O2—C1—C2—C3	−93.0 (2)	C4—C5—C7—C9	−0.6 (3)
O1—C1—O2—C12	−3.4 (3)	C4—C6—C8—C9	−1.5 (3)
C2—C1—O2—C12	173.6 (1)	C6—C8—C9—C7	0.9 (3)
N1—C2—C3—C4	−71.7 (2)	C5—C7—C9—C8	0.2 (3)
C1—C2—C3—C4	166.2 (1)	C2—N1—C10—O10	−3.1 (2)
C2—C3—C4—C6	96.8 (2)	C2—N1—C10—C11	179.0 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O5	0.91	2.03	2.932 (2)	170
O5—H51···O10^i	0.90	1.84	2.727 (2)	168
C11—H11B···O10^i	0.98	2.89	3.609 (2)	131
C12—H12B···O10^ii	0.98	2.77	3.430 (2)	125
C11—H11A···O1^iii	0.98	2.86	3.689 (2)	143
C5—H5···CG1^iv	0.95	2.80	3.66 (4)	152
C12—H12C···CG1^ii	0.98	2.53	3.35 (4)	142

Symmetry codes: (i) −y+1, −x, −z+1/2; (ii) x−1, y, z; (iii) x+1, y, z; (iv) −x+1/2, y+1/2, −z+1/4.