Syntheses and crystal structures of two piperine derivatives

The title compounds, 5-(2H-1,3-benzodioxol-5-yl)-N-cyclo­hexyl­penta-2,4-dienamide, (I), and 5-(2H-1,3-benzodioxol-5-yl)-1-(pyrrolidin-1-yl)penta-2,4-dien-1-one (II), are derivatives of piperine, which is known as a pungent component of pepper. Their geometrical parameters are similar to those of the three polymorphs of piperine, which indicate conjugation of electrons over the length of the mol­ecules. The extended structure of (I) features N—H...O amide hydrogen bonds, which generate C(4) [010] chains. The crystal of (II) features aromatic π–π stacking, as for two of three known piperine polymorphs.

Key indicators

Structure: I

• Single-crystal X-ray study
• T = 90 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.049
• wR factor = 0.121
• Data-to-parameter ratio = 24.1

Structure: II

• Single-crystal X-ray study
• T = 90 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.050
• wR factor = 0.143
• Data-to-parameter ratio = 19.3

checkCIF/PLATON results

No syntax errors found



Datablock: I


Alert level C
PLAT906_ALERT_3_C Large K Value in the Analysis of Variance ......      3.356 Check

Alert level G
PLAT398_ALERT_2_G Deviating  C-O-C    Angle From 120 for O2             105.9 Degree
PLAT398_ALERT_2_G Deviating  C-O-C    Angle From 120 for O3             106.1 Degree
PLAT720_ALERT_4_G Number of Unusual/Non-Standard Labels ..........          7 Note
PLAT910_ALERT_3_G Missing # of FCF Reflection(s) Below Theta(Min).          2 Note
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600          5 Note
PLAT913_ALERT_3_G Missing # of Very Strong Reflections in FCF ....          1 Note
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density.         18 Info

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   1 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   7 ALERT level G = General information/check it is not something unexpected

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   3 ALERT type 2 Indicator that the structure model may be wrong or deficient
   3 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check




Datablock: II


Alert level C
RINTA01_ALERT_3_C  The value of Rint is greater than 0.12
            Rint given   0.128
PLAT905_ALERT_3_C Negative K value in the Analysis of Variance ...     -6.690 Report
PLAT905_ALERT_3_C Negative K value in the Analysis of Variance ...     -0.368 Report

Alert level G
PLAT020_ALERT_3_G The Value of Rint is Greater Than 0.12 .........      0.128 Report
PLAT398_ALERT_2_G Deviating  C-O-C    Angle From 120 for O2             105.0 Degree
PLAT398_ALERT_2_G Deviating  C-O-C    Angle From 120 for O3             105.5 Degree
PLAT910_ALERT_3_G Missing # of FCF Reflection(s) Below Theta(Min).          2 Note
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density.          6 Info

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   3 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   5 ALERT level G = General information/check it is not something unexpected

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   3 ALERT type 2 Indicator that the structure model may be wrong or deficient
   5 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check


checkCIF publication errors

Alert level A
PUBL024_ALERT_1_A The number of authors is greater than 5.
              Please specify the role of each of the co-authors
              for your paper.

   1 ALERT level A = Data missing that is essential or data in wrong format
   0 ALERT level G = General alerts. Data that may be required is missing

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Computing details

For both structures, data collection: APEX3 (Bruker, 2018); cell refinement: SAINT (Bruker, 2018); data reduction: SAINT (Bruker, 2018); program(s) used to solve structure: SHELXT2014/5 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015b); molecular graphics: ShelXle (Hübschle et al., 2011); software used to prepare material for publication: Generate Report (Bruker, 2018).

5-(2H-1,3-Benzodioxol-5-yl)-N-cyclohexylpenta-2,4-dienamide (I)

Crystal data

C18H21NO3	F(000) = 640
Mr = 299.36	Dx = 1.304 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 11.4982 (7) Å	Cell parameters from 9948 reflections
b = 5.0086 (3) Å	θ = 2.5–33.5°
c = 26.7240 (16) Å	µ = 0.09 mm^−1
β = 97.683 (2)°	T = 90 K
V = 1525.22 (16) Å^3	Needle, light-yellow
Z = 4	0.58 × 0.07 × 0.07 mm

Data collection

Bruker D8 goniometer diffractometer	4862 independent reflections
Radiation source: microfocus X-ray tube	4204 reflections with I > 2σ(I)
Multilayered conforacal mirror monochromator	Rint = 0.066
Detector resolution: 7.391 pixels mm^-1	θmax = 31.0°, θmin = 2.2°
ω scans	h = −16→16
Absorption correction: multi-scan (SADABS; Bruker, 2018)	k = −7→7
Tmin = 0.580, Tmax = 0.747	l = −38→38
27741 measured reflections

Refinement

Refinement on F^2	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.049	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.121	w = 1/[σ^2(Fo^2) + (0.0455P)^2 + 0.7464P] where P = (Fo^2 + 2Fc^2)/3
S = 1.07	(Δ/σ)max = 0.001
4862 reflections	Δρmax = 0.42 e Å^−3
202 parameters	Δρmin = −0.26 e Å^−3
0 restraints

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

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

	x	y	z	Uiso*/Ueq
O1	0.96864 (7)	0.23821 (16)	0.65434 (3)	0.01577 (17)
O2	0.26072 (7)	0.95788 (18)	0.47532 (3)	0.01982 (18)
O3	0.09239 (7)	0.7586 (2)	0.49784 (4)	0.0246 (2)
N1	1.02983 (8)	0.66732 (19)	0.66764 (4)	0.01464 (18)
H1	1.0072 (13)	0.834 (3)	0.6656 (6)	0.018*
C1	1.35763 (10)	0.7868 (2)	0.69502 (4)	0.0179 (2)
H1A	1.387593	0.633931	0.677037	0.021*
H1AB	1.404140	0.946479	0.688562	0.021*
C2	1.37316 (10)	0.7289 (2)	0.75164 (4)	0.0177 (2)
H2A	1.456652	0.689410	0.763536	0.021*
H2AB	1.350298	0.887869	0.770054	0.021*
C3	1.29754 (11)	0.4914 (2)	0.76259 (4)	0.0184 (2)
H3A	1.306633	0.458942	0.799445	0.022*
H3AB	1.324548	0.329830	0.746168	0.022*
C4	1.16802 (10)	0.5412 (2)	0.74321 (4)	0.0174 (2)
H4A	1.121475	0.381401	0.749567	0.021*
H4AB	1.139004	0.693282	0.761708	0.021*
C5	1.15165 (9)	0.6024 (2)	0.68667 (4)	0.01204 (19)
H5	1.174757	0.440743	0.668389	0.014*
C6	1.22876 (10)	0.8346 (2)	0.67461 (4)	0.0156 (2)
H6A	1.201602	1.000303	0.689604	0.019*
H6AB	1.220984	0.859459	0.637563	0.019*
C7	0.13448 (10)	0.9561 (2)	0.46564 (4)	0.0178 (2)
H00F	0.103160	1.134167	0.472821	0.021*
H00G	0.108313	0.912274	0.429779	0.021*
C8	0.29070 (10)	0.7663 (2)	0.51139 (4)	0.0146 (2)
C9	0.19016 (9)	0.6451 (2)	0.52444 (4)	0.0157 (2)
C10	0.19552 (10)	0.4395 (2)	0.55871 (4)	0.0172 (2)
H10	0.126694	0.356487	0.567425	0.021*
C11	0.30804 (10)	0.3586 (2)	0.58014 (4)	0.0154 (2)
H11	0.315407	0.213891	0.603318	0.018*
C12	0.40980 (9)	0.4841 (2)	0.56850 (4)	0.0135 (2)
C13	0.40115 (9)	0.6936 (2)	0.53284 (4)	0.0142 (2)
H13	0.469038	0.780458	0.524074	0.017*
C14	0.52399 (9)	0.3949 (2)	0.59388 (4)	0.0151 (2)
H14	0.528504	0.219194	0.607404	0.018*
C15	0.62312 (9)	0.5413 (2)	0.59963 (4)	0.0153 (2)
H15	0.618873	0.720765	0.588024	0.018*
C16	0.73553 (9)	0.4407 (2)	0.62246 (4)	0.0144 (2)
H16	0.741526	0.256496	0.630909	0.017*
C17	0.83199 (9)	0.5927 (2)	0.63240 (4)	0.0147 (2)
H17	0.825437	0.779183	0.626212	0.018*
C18	0.94810 (9)	0.4819 (2)	0.65259 (4)	0.01252 (19)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0151 (4)	0.0087 (3)	0.0230 (4)	0.0010 (3)	0.0008 (3)	0.0012 (3)
O2	0.0130 (4)	0.0226 (4)	0.0237 (4)	0.0022 (3)	0.0019 (3)	0.0074 (3)
O3	0.0116 (4)	0.0333 (5)	0.0284 (5)	0.0015 (4)	0.0014 (3)	0.0109 (4)
N1	0.0124 (4)	0.0082 (4)	0.0228 (5)	0.0014 (3)	0.0006 (3)	0.0001 (3)
C1	0.0146 (5)	0.0186 (5)	0.0199 (5)	−0.0044 (4)	0.0007 (4)	0.0004 (4)
C2	0.0181 (5)	0.0134 (5)	0.0201 (5)	0.0006 (4)	−0.0034 (4)	−0.0003 (4)
C3	0.0222 (5)	0.0137 (5)	0.0181 (5)	0.0006 (4)	−0.0016 (4)	0.0024 (4)
C4	0.0191 (5)	0.0176 (5)	0.0160 (5)	−0.0002 (4)	0.0037 (4)	0.0016 (4)
C5	0.0112 (4)	0.0089 (4)	0.0158 (5)	0.0010 (3)	0.0012 (3)	0.0004 (3)
C6	0.0160 (5)	0.0119 (5)	0.0181 (5)	−0.0033 (4)	−0.0007 (4)	0.0031 (4)
C7	0.0140 (5)	0.0196 (5)	0.0195 (5)	0.0029 (4)	0.0010 (4)	0.0003 (4)
C8	0.0149 (5)	0.0148 (5)	0.0144 (5)	0.0007 (4)	0.0035 (4)	−0.0001 (4)
C9	0.0106 (4)	0.0198 (5)	0.0167 (5)	0.0007 (4)	0.0020 (4)	−0.0022 (4)
C10	0.0128 (5)	0.0208 (5)	0.0183 (5)	−0.0038 (4)	0.0035 (4)	−0.0010 (4)
C11	0.0148 (5)	0.0160 (5)	0.0156 (5)	−0.0028 (4)	0.0031 (4)	0.0003 (4)
C12	0.0121 (4)	0.0134 (5)	0.0153 (5)	−0.0005 (4)	0.0030 (3)	−0.0015 (4)
C13	0.0117 (4)	0.0145 (5)	0.0169 (5)	−0.0008 (4)	0.0037 (4)	0.0006 (4)
C14	0.0137 (5)	0.0148 (5)	0.0169 (5)	0.0016 (4)	0.0030 (4)	0.0016 (4)
C15	0.0138 (5)	0.0138 (5)	0.0183 (5)	0.0025 (4)	0.0027 (4)	0.0006 (4)
C16	0.0144 (5)	0.0129 (5)	0.0162 (5)	0.0023 (4)	0.0029 (4)	0.0011 (4)
C17	0.0138 (5)	0.0110 (4)	0.0194 (5)	0.0030 (4)	0.0023 (4)	0.0020 (4)
C18	0.0127 (4)	0.0108 (4)	0.0143 (5)	0.0006 (4)	0.0027 (3)	0.0010 (3)

Geometric parameters (Å, º)

O1—C18	1.2429 (13)	C6—H6A	0.9900
O2—C8	1.3710 (14)	C6—H6AB	0.9900
O2—C7	1.4400 (14)	C7—H00F	0.9900
O3—C9	1.3705 (14)	C7—H00G	0.9900
O3—C7	1.4372 (15)	C8—C13	1.3710 (15)
N1—C18	1.3440 (14)	C8—C9	1.3909 (15)
N1—C5	1.4614 (13)	C9—C10	1.3741 (16)
N1—H1	0.874 (16)	C10—C11	1.4028 (15)
C1—C2	1.5275 (16)	C10—H10	0.9500
C1—C6	1.5279 (16)	C11—C12	1.3991 (15)
C1—H1A	0.9900	C11—H11	0.9500
C1—H1AB	0.9900	C12—C13	1.4120 (15)
C2—C3	1.5246 (17)	C12—C14	1.4648 (15)
C2—H2A	0.9900	C13—H13	0.9500
C2—H2AB	0.9900	C14—C15	1.3468 (15)
C3—C4	1.5305 (16)	C14—H14	0.9500
C3—H3A	0.9900	C15—C16	1.4442 (15)
C3—H3AB	0.9900	C15—H15	0.9500
C4—C5	1.5284 (15)	C16—C17	1.3423 (15)
C4—H4A	0.9900	C16—H16	0.9500
C4—H4AB	0.9900	C17—C18	1.4793 (15)
C5—C6	1.5228 (15)	C17—H17	0.9500
C5—H5	1.0000
C8—O2—C7	105.94 (9)	H6A—C6—H6AB	107.9
C9—O3—C7	106.11 (9)	O3—C7—O2	107.98 (9)
C18—N1—C5	123.36 (9)	O3—C7—H00F	110.1
C18—N1—H1	116.8 (10)	O2—C7—H00F	110.1
C5—N1—H1	119.9 (10)	O3—C7—H00G	110.1
C2—C1—C6	111.27 (9)	O2—C7—H00G	110.1
C2—C1—H1A	109.4	H00F—C7—H00G	108.4
C6—C1—H1A	109.4	C13—C8—O2	127.72 (10)
C2—C1—H1AB	109.4	C13—C8—C9	122.25 (10)
C6—C1—H1AB	109.4	O2—C8—C9	110.03 (10)
H1A—C1—H1AB	108.0	O3—C9—C10	128.10 (10)
C3—C2—C1	110.13 (9)	O3—C9—C8	109.91 (10)
C3—C2—H2A	109.6	C10—C9—C8	121.98 (10)
C1—C2—H2A	109.6	C9—C10—C11	116.43 (10)
C3—C2—H2AB	109.6	C9—C10—H10	121.8
C1—C2—H2AB	109.6	C11—C10—H10	121.8
H2A—C2—H2AB	108.1	C12—C11—C10	122.19 (11)
C2—C3—C4	111.23 (9)	C12—C11—H11	118.9
C2—C3—H3A	109.4	C10—C11—H11	118.9
C4—C3—H3A	109.4	C11—C12—C13	119.88 (10)
C2—C3—H3AB	109.4	C11—C12—C14	118.98 (10)
C4—C3—H3AB	109.4	C13—C12—C14	121.13 (10)
H3A—C3—H3AB	108.0	C8—C13—C12	117.22 (10)
C5—C4—C3	110.66 (9)	C8—C13—H13	121.4
C5—C4—H4A	109.5	C12—C13—H13	121.4
C3—C4—H4A	109.5	C15—C14—C12	125.40 (10)
C5—C4—H4AB	109.5	C15—C14—H14	117.3
C3—C4—H4AB	109.5	C12—C14—H14	117.3
H4A—C4—H4AB	108.1	C14—C15—C16	123.65 (11)
N1—C5—C6	108.34 (9)	C14—C15—H15	118.2
N1—C5—C4	111.98 (9)	C16—C15—H15	118.2
C6—C5—C4	111.37 (9)	C17—C16—C15	123.70 (10)
N1—C5—H5	108.3	C17—C16—H16	118.1
C6—C5—H5	108.3	C15—C16—H16	118.1
C4—C5—H5	108.3	C16—C17—C18	122.76 (10)
C5—C6—C1	111.66 (9)	C16—C17—H17	118.6
C5—C6—H6A	109.3	C18—C17—H17	118.6
C1—C6—H6A	109.3	O1—C18—N1	123.06 (10)
C5—C6—H6AB	109.3	O1—C18—C17	122.66 (10)
C1—C6—H6AB	109.3	N1—C18—C17	114.26 (9)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1^i	0.874 (16)	2.086 (16)	2.9547 (12)	172.8 (14)

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

5-(2H-1,3-Benzodioxol-5-yl)-1-(pyrrolidin-1-yl)penta-2,4-dien-1-one (II)

Crystal data

C16H17NO3	Dx = 1.378 Mg m^−3
Mr = 271.30	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbca	Cell parameters from 3874 reflections
a = 11.8747 (10) Å	θ = 2.7–25.8°
b = 7.2485 (6) Å	µ = 0.10 mm^−1
c = 30.392 (2) Å	T = 90 K
V = 2616.0 (4) Å^3	Needle, colorless
Z = 8	0.28 × 0.06 × 0.06 mm
F(000) = 1152

Data collection

Bruker D8 goniometer diffractometer	3506 independent reflections
Radiation source: microfocus X-ray tube	2193 reflections with I > 2σ(I)
Multilayered conforacal mirror monochromator	Rint = 0.128
Detector resolution: 7.391 pixels mm^-1	θmax = 29.1°, θmin = 2.7°
ω scans	h = −16→16
Absorption correction: multi-scan (SADABS; Bruker, 2018)	k = −9→9
Tmin = 0.666, Tmax = 0.746	l = −41→41
41504 measured reflections

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.050	w = 1/[σ^2(Fo^2) + (0.0492P)^2 + 1.9223P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.143	(Δ/σ)max = 0.001
S = 1.05	Δρmax = 0.28 e Å^−3
3506 reflections	Δρmin = −0.26 e Å^−3
182 parameters	Extinction correction: SHELXL-2018/3 (Sheldrick 2015b), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0038 (6)

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

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

	x	y	z	Uiso*/Ueq
O1	0.90586 (12)	0.3421 (2)	0.67241 (5)	0.0219 (3)
O2	0.77314 (12)	0.9757 (2)	0.35830 (4)	0.0239 (4)
O3	0.62806 (12)	0.8589 (2)	0.40118 (5)	0.0238 (3)
N1	0.72232 (13)	0.3304 (2)	0.69173 (5)	0.0178 (4)
C1	0.80525 (16)	0.3650 (3)	0.66249 (6)	0.0179 (4)
C2	0.77084 (17)	0.4355 (3)	0.61881 (6)	0.0200 (4)
H2	0.693195	0.435608	0.611273	0.024*
C3	0.84580 (17)	0.4994 (3)	0.58954 (6)	0.0195 (4)
H3	0.923497	0.493700	0.596862	0.023*
C4	0.81458 (18)	0.5762 (3)	0.54755 (6)	0.0202 (4)
H4	0.737486	0.571321	0.539278	0.024*
C5	0.88758 (17)	0.6543 (3)	0.51932 (6)	0.0204 (4)
H5	0.964674	0.654787	0.527665	0.024*
C6	0.85964 (17)	0.7386 (3)	0.47701 (6)	0.0189 (4)
C7	0.94619 (18)	0.8085 (3)	0.45072 (7)	0.0233 (5)
H7	1.021461	0.801352	0.461170	0.028*
C8	0.92613 (18)	0.8889 (3)	0.40946 (7)	0.0238 (5)
H8	0.985763	0.934891	0.391755	0.029*
C9	0.81622 (17)	0.8975 (3)	0.39603 (6)	0.0197 (4)
C10	0.65583 (18)	0.9250 (3)	0.35806 (7)	0.0243 (5)
H10A	0.608744	1.033210	0.350559	0.029*
H10B	0.642106	0.827357	0.335911	0.029*
C11	0.72958 (17)	0.8288 (3)	0.42176 (6)	0.0192 (4)
C12	0.74749 (17)	0.7485 (3)	0.46174 (6)	0.0194 (4)
H12	0.686800	0.701056	0.478668	0.023*
C13	0.74989 (17)	0.2759 (3)	0.73696 (6)	0.0191 (4)
H13A	0.803365	0.364049	0.750477	0.023*
H13B	0.783182	0.150743	0.737737	0.023*
C14	0.63666 (17)	0.2799 (3)	0.76059 (7)	0.0214 (4)
H14A	0.633146	0.183869	0.783722	0.026*
H14B	0.622901	0.401963	0.774158	0.026*
C15	0.55179 (17)	0.2411 (3)	0.72417 (7)	0.0229 (5)
H15A	0.476464	0.289608	0.731974	0.028*
H15B	0.545712	0.107030	0.718398	0.028*
C16	0.59994 (16)	0.3421 (3)	0.68437 (7)	0.0202 (4)
H16A	0.578131	0.280454	0.656583	0.024*
H16B	0.574336	0.472052	0.683550	0.024*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0160 (7)	0.0250 (8)	0.0247 (7)	0.0012 (6)	−0.0006 (6)	0.0005 (6)
O2	0.0236 (8)	0.0286 (8)	0.0195 (7)	−0.0012 (6)	−0.0007 (6)	0.0050 (6)
O3	0.0196 (8)	0.0307 (8)	0.0209 (7)	0.0019 (6)	−0.0009 (6)	0.0048 (6)
N1	0.0134 (8)	0.0218 (9)	0.0181 (8)	−0.0001 (7)	−0.0008 (6)	0.0024 (7)
C1	0.0177 (10)	0.0158 (9)	0.0204 (10)	−0.0005 (8)	−0.0011 (8)	−0.0021 (8)
C2	0.0186 (10)	0.0206 (10)	0.0208 (10)	0.0005 (8)	−0.0025 (8)	−0.0014 (8)
C3	0.0199 (10)	0.0194 (10)	0.0191 (10)	0.0002 (8)	−0.0009 (8)	−0.0017 (8)
C4	0.0201 (10)	0.0201 (10)	0.0203 (10)	0.0012 (8)	−0.0022 (8)	−0.0017 (8)
C5	0.0181 (10)	0.0214 (10)	0.0216 (10)	0.0014 (8)	−0.0003 (8)	−0.0002 (8)
C6	0.0187 (10)	0.0197 (10)	0.0184 (10)	0.0013 (8)	0.0002 (8)	−0.0022 (8)
C7	0.0185 (10)	0.0283 (11)	0.0230 (10)	−0.0001 (9)	0.0006 (8)	0.0003 (9)
C8	0.0214 (11)	0.0265 (11)	0.0236 (10)	−0.0015 (9)	0.0048 (8)	0.0028 (9)
C9	0.0232 (11)	0.0204 (10)	0.0156 (9)	−0.0011 (8)	0.0008 (8)	0.0006 (8)
C10	0.0218 (11)	0.0308 (12)	0.0204 (10)	0.0001 (9)	−0.0006 (8)	0.0026 (9)
C11	0.0180 (10)	0.0197 (10)	0.0200 (10)	0.0009 (8)	−0.0011 (8)	−0.0004 (8)
C12	0.0182 (10)	0.0202 (10)	0.0197 (9)	−0.0001 (8)	0.0025 (8)	−0.0001 (8)
C13	0.0198 (10)	0.0196 (10)	0.0180 (9)	0.0017 (8)	−0.0007 (8)	0.0008 (8)
C14	0.0206 (10)	0.0218 (10)	0.0218 (10)	0.0007 (9)	0.0021 (8)	0.0008 (8)
C15	0.0171 (10)	0.0266 (11)	0.0251 (10)	−0.0011 (9)	0.0018 (8)	−0.0016 (9)
C16	0.0144 (9)	0.0241 (11)	0.0221 (10)	0.0011 (8)	−0.0007 (8)	0.0000 (8)

Geometric parameters (Å, º)

O1—C1	1.243 (2)	C7—H7	0.9500
O2—C9	1.377 (2)	C8—C9	1.369 (3)
O2—C10	1.441 (2)	C8—H8	0.9500
O3—C11	1.376 (2)	C9—C11	1.385 (3)
O3—C10	1.434 (2)	C10—H10A	0.9900
N1—C1	1.350 (2)	C10—H10B	0.9900
N1—C13	1.467 (2)	C11—C12	1.364 (3)
N1—C16	1.473 (2)	C12—H12	0.9500
C1—C2	1.480 (3)	C13—C14	1.525 (3)
C2—C3	1.341 (3)	C13—H13A	0.9900
C2—H2	0.9500	C13—H13B	0.9900
C3—C4	1.441 (3)	C14—C15	1.523 (3)
C3—H3	0.9500	C14—H14A	0.9900
C4—C5	1.345 (3)	C14—H14B	0.9900
C4—H4	0.9500	C15—C16	1.525 (3)
C5—C6	1.462 (3)	C15—H15A	0.9900
C5—H5	0.9500	C15—H15B	0.9900
C6—C7	1.397 (3)	C16—H16A	0.9900
C6—C12	1.412 (3)	C16—H16B	0.9900
C7—C8	1.403 (3)
C9—O2—C10	104.98 (15)	O2—C10—H10A	110.2
C11—O3—C10	105.50 (15)	O3—C10—H10B	110.2
C1—N1—C13	120.26 (16)	O2—C10—H10B	110.2
C1—N1—C16	127.52 (16)	H10A—C10—H10B	108.5
C13—N1—C16	112.21 (15)	C12—C11—O3	127.55 (19)
O1—C1—N1	121.10 (18)	C12—C11—C9	122.74 (19)
O1—C1—C2	121.93 (18)	O3—C11—C9	109.69 (17)
N1—C1—C2	116.95 (17)	C11—C12—C6	117.50 (19)
C3—C2—C1	122.08 (19)	C11—C12—H12	121.3
C3—C2—H2	119.0	C6—C12—H12	121.3
C1—C2—H2	119.0	N1—C13—C14	103.86 (16)
C2—C3—C4	123.4 (2)	N1—C13—H13A	111.0
C2—C3—H3	118.3	C14—C13—H13A	111.0
C4—C3—H3	118.3	N1—C13—H13B	111.0
C5—C4—C3	124.2 (2)	C14—C13—H13B	111.0
C5—C4—H4	117.9	H13A—C13—H13B	109.0
C3—C4—H4	117.9	C15—C14—C13	103.75 (16)
C4—C5—C6	126.23 (19)	C15—C14—H14A	111.0
C4—C5—H5	116.9	C13—C14—H14A	111.0
C6—C5—H5	116.9	C15—C14—H14B	111.0
C7—C6—C12	119.16 (18)	C13—C14—H14B	111.0
C7—C6—C5	119.19 (18)	H14A—C14—H14B	109.0
C12—C6—C5	121.64 (18)	C14—C15—C16	103.87 (16)
C6—C7—C8	122.5 (2)	C14—C15—H15A	111.0
C6—C7—H7	118.8	C16—C15—H15A	111.0
C8—C7—H7	118.8	C14—C15—H15B	111.0
C9—C8—C7	116.59 (19)	C16—C15—H15B	111.0
C9—C8—H8	121.7	H15A—C15—H15B	109.0
C7—C8—H8	121.7	N1—C16—C15	102.81 (16)
C8—C9—O2	128.41 (18)	N1—C16—H16A	111.2
C8—C9—C11	121.54 (19)	C15—C16—H16A	111.2
O2—C9—C11	110.01 (18)	N1—C16—H16B	111.2
O3—C10—O2	107.62 (16)	C15—C16—H16B	111.2
O3—C10—H10A	110.2	H16A—C16—H16B	109.1