Crystal forms and phase transformation of 1,5-pentanedi­amine-terephthalate: a bio-based nylon 5T monomer

Nylon 5T is one of the bio-based nylons, its raw material 1,5-pentanedi­amine is derived from biomass resources and produced by biological methods. 1,5-pentanedi­amine-terephthalate (PDA-TPA) is the monomeric salt for nylon 5T polymerization, and its own product quality has a significant impact on the performance of nylon 5T. PDA-TPA was prepared by anti-solvent crystallization in this study. It exists in two solid forms, a monohydrate [form (I)] and an anhydrous phase [form (II)]. The transition temperature of the two phases was around 65°C in the given ethanol–water binary (7:1) mixture. The characterization of monohydrate and anhydrate phases regarding structures and stabilities was carefully carried out using powder X-ray diffraction, single crystal X-ray diffraction, differential scanning calorimetry, thermogravimetric analysis, hot-stage microscopy and Fourier transform infrared spectroscopy. The relationship between the molecular interactions of monohydrate and anhydrate phases under different packing architectures and their thermal behaviours was analysed and established. In addition, the relationships between the structures and thermal behaviours for the two solid forms were analysed and established. In addition, the effect of solvent on phase conversion, the relationships between the temperature and water activity, as well as the relative stability of monohydrate and anhydrate phases under different thermodynamic conditions, were investigated by solid–solid transformation and solvent-mediated transformation experiments. It was obvious that the transition temperature of monohydrate and anhydrate phases of PDA-TPA was significantly influenced by water activity, and the larger the value of water activity is, the higher is the transition temperature. These studies give insight into the transformation of nylon 5T monomer salt and contribute to the control of target crystal preparation.

Computing details

For both structures, program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2018).

(monohydrate)

Crystal data

C13H22N2O5	F(000) = 616
Mr = 286.32	Dx = 1.325 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 9.8441 (8) Å	Cell parameters from 2154 reflections
b = 10.8561 (9) Å	θ = 2.4–28.1°
c = 13.5205 (12) Å	µ = 0.10 mm^−1
β = 96.728 (2)°	T = 298 K
V = 1435.0 (2) Å^3	Rod-like, colorless
Z = 4	0.48 × 0.36 × 0.17 mm

Data collection

CCD area detector diffractometer	1801 reflections with I > 2σ(I)
phi and ω scans	Rint = 0.065
Absorption correction: multi-scan sadabs	θmax = 25.0°, θmin = 2.4°
Tmin = 0.953, Tmax = 0.983	h = −11→11
6997 measured reflections	k = −12→12
2515 independent reflections	l = −16→11

Refinement

Refinement on F^2	Hydrogen site location: mixed
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.046	w = 1/[σ^2(Fo^2) + (0.0646P)^2 + 0.0978P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.136	(Δ/σ)max < 0.001
S = 1.02	Δρmax = 0.21 e Å^−3
2515 reflections	Δρmin = −0.19 e Å^−3
184 parameters	Extinction correction: SHELXL-2018/3 (Sheldrick 2018), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.014 (2)

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
N1	0.79690 (16)	0.54433 (14)	0.30729 (11)	0.0365 (4)
H1A	0.864554	0.598419	0.320381	0.055*
H1B	0.743799	0.567300	0.252578	0.055*
H1C	0.831739	0.470171	0.297886	0.055*
N2	0.81872 (17)	0.57151 (15)	0.85960 (11)	0.0399 (4)
H2A	0.875189	0.507294	0.867205	0.060*
H2B	0.768693	0.574422	0.910275	0.060*
H2C	0.867166	0.640567	0.858141	0.060*
O1	0.39717 (15)	0.35598 (14)	−0.17397 (9)	0.0518 (4)
O2	0.28756 (14)	0.37527 (13)	−0.03982 (10)	0.0458 (4)
O3	0.89483 (14)	0.29767 (13)	0.26860 (10)	0.0458 (4)
O4	0.99995 (13)	0.23208 (12)	0.14114 (10)	0.0430 (4)
O5	0.97146 (14)	0.89919 (13)	0.63201 (11)	0.0526 (4)
H5C	0.890775	0.883743	0.605282	0.063*
H5D	1.004525	0.834303	0.660662	0.063*
C1	0.3927 (2)	0.35649 (17)	−0.08193 (14)	0.0349 (5)
C2	0.8971 (2)	0.27269 (17)	0.17855 (15)	0.0343 (5)
C3	0.52488 (19)	0.33143 (16)	−0.01584 (13)	0.0302 (5)
C4	0.6468 (2)	0.31181 (16)	−0.05503 (14)	0.0345 (5)
H4	0.647926	0.311536	−0.123710	0.041*
C5	0.7668 (2)	0.29263 (17)	0.00693 (14)	0.0351 (5)
H5	0.848015	0.279676	−0.020475	0.042*
C6	0.76748 (19)	0.29249 (15)	0.10928 (13)	0.0298 (4)
C7	0.6460 (2)	0.30956 (19)	0.14847 (14)	0.0376 (5)
H7	0.644568	0.308502	0.217117	0.045*
C8	0.5260 (2)	0.32830 (19)	0.08613 (14)	0.0389 (5)
H8	0.444462	0.338983	0.113590	0.047*
C9	0.7148 (2)	0.53949 (19)	0.39211 (13)	0.0396 (5)
H9A	0.658865	0.465701	0.386524	0.048*
H9B	0.653886	0.609977	0.388674	0.048*
C10	0.8010 (2)	0.53936 (18)	0.49115 (13)	0.0386 (5)
H10A	0.858855	0.611978	0.495999	0.046*
H10B	0.860135	0.467597	0.495353	0.046*
C11	0.7166 (2)	0.53799 (18)	0.57810 (14)	0.0381 (5)
H11A	0.651659	0.605530	0.571052	0.046*
H11B	0.665278	0.461642	0.577250	0.046*
C12	0.8061 (2)	0.54981 (19)	0.67682 (14)	0.0407 (5)
H12A	0.866434	0.478988	0.685436	0.049*
H12B	0.862777	0.622696	0.674983	0.049*
C13	0.7269 (2)	0.5585 (2)	0.76455 (14)	0.0423 (5)
H13A	0.666025	0.628942	0.756225	0.051*
H13B	0.671347	0.485141	0.767556	0.051*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0375 (9)	0.0389 (9)	0.0316 (9)	0.0017 (8)	−0.0015 (7)	0.0006 (7)
N2	0.0418 (10)	0.0420 (10)	0.0362 (10)	0.0026 (8)	0.0049 (8)	0.0004 (8)
O1	0.0554 (10)	0.0666 (10)	0.0298 (8)	0.0121 (8)	−0.0095 (7)	0.0010 (7)
O2	0.0334 (8)	0.0625 (10)	0.0389 (8)	0.0047 (7)	−0.0073 (6)	−0.0074 (7)
O3	0.0443 (9)	0.0529 (9)	0.0365 (8)	0.0097 (7)	−0.0105 (6)	−0.0068 (7)
O4	0.0329 (8)	0.0435 (8)	0.0516 (9)	0.0082 (7)	0.0005 (7)	0.0001 (7)
O5	0.0385 (9)	0.0540 (9)	0.0610 (10)	−0.0073 (7)	−0.0119 (7)	0.0129 (8)
C1	0.0423 (12)	0.0290 (10)	0.0308 (11)	0.0007 (9)	−0.0071 (9)	−0.0022 (9)
C2	0.0351 (12)	0.0281 (10)	0.0381 (12)	−0.0001 (9)	−0.0019 (9)	0.0022 (9)
C3	0.0368 (11)	0.0255 (10)	0.0267 (10)	−0.0002 (8)	−0.0030 (8)	−0.0008 (8)
C4	0.0443 (12)	0.0346 (11)	0.0244 (10)	0.0010 (9)	0.0032 (8)	0.0013 (9)
C5	0.0341 (11)	0.0355 (11)	0.0366 (11)	0.0014 (9)	0.0074 (9)	0.0009 (9)
C6	0.0330 (11)	0.0245 (9)	0.0308 (11)	0.0008 (8)	−0.0012 (8)	0.0007 (8)
C7	0.0384 (12)	0.0493 (12)	0.0242 (10)	0.0037 (10)	0.0006 (8)	−0.0009 (9)
C8	0.0308 (11)	0.0543 (13)	0.0311 (11)	0.0051 (10)	0.0014 (8)	−0.0023 (10)
C9	0.0371 (11)	0.0449 (12)	0.0364 (11)	0.0042 (10)	0.0020 (9)	0.0039 (10)
C10	0.0405 (12)	0.0401 (12)	0.0346 (11)	−0.0010 (9)	0.0022 (9)	0.0010 (9)
C11	0.0413 (12)	0.0344 (11)	0.0384 (11)	0.0033 (9)	0.0034 (9)	0.0036 (9)
C12	0.0417 (12)	0.0432 (12)	0.0368 (12)	0.0026 (10)	0.0028 (9)	−0.0011 (10)
C13	0.0403 (12)	0.0515 (13)	0.0344 (11)	0.0022 (10)	0.0010 (9)	0.0051 (10)

Geometric parameters (Å, º)

N1—C9	1.479 (2)	C5—C6	1.383 (2)
N1—H1A	0.8900	C5—H5	0.9300
N1—H1B	0.8900	C6—C7	1.376 (3)
N1—H1C	0.8900	C7—C8	1.384 (3)
N2—C13	1.488 (2)	C7—H7	0.9300
N2—H2A	0.8900	C8—H8	0.9300
N2—H2B	0.8900	C9—C10	1.499 (3)
N2—H2C	0.8900	C9—H9A	0.9700
O1—C1	1.250 (2)	C9—H9B	0.9700
O2—C1	1.255 (2)	C10—C11	1.517 (3)
O3—C2	1.250 (2)	C10—H10A	0.9700
O4—C2	1.263 (2)	C10—H10B	0.9700
O5—H5C	0.8500	C11—C12	1.516 (3)
O5—H5D	0.8501	C11—H11A	0.9700
C1—C3	1.514 (3)	C11—H11B	0.9700
C2—C6	1.507 (3)	C12—C13	1.497 (3)
C3—C8	1.378 (3)	C12—H12A	0.9700
C3—C4	1.384 (2)	C12—H12B	0.9700
C4—C5	1.382 (3)	C13—H13A	0.9700
C4—H4	0.9300	C13—H13B	0.9700
C9—N1—H1A	109.5	C3—C8—C7	121.27 (18)
C9—N1—H1B	109.5	C3—C8—H8	119.4
H1A—N1—H1B	109.5	C7—C8—H8	119.4
C9—N1—H1C	109.5	N1—C9—C10	112.89 (16)
H1A—N1—H1C	109.5	N1—C9—H9A	109.0
H1B—N1—H1C	109.5	C10—C9—H9A	109.0
C13—N2—H2A	109.5	N1—C9—H9B	109.0
C13—N2—H2B	109.5	C10—C9—H9B	109.0
H2A—N2—H2B	109.5	H9A—C9—H9B	107.8
C13—N2—H2C	109.5	C9—C10—C11	112.82 (17)
H2A—N2—H2C	109.5	C9—C10—H10A	109.0
H2B—N2—H2C	109.5	C11—C10—H10A	109.0
H5C—O5—H5D	108.6	C9—C10—H10B	109.0
O1—C1—O2	125.40 (18)	C11—C10—H10B	109.0
O1—C1—C3	117.29 (18)	H10A—C10—H10B	107.8
O2—C1—C3	117.31 (17)	C12—C11—C10	111.49 (17)
O3—C2—O4	124.92 (18)	C12—C11—H11A	109.3
O3—C2—C6	117.62 (17)	C10—C11—H11A	109.3
O4—C2—C6	117.45 (17)	C12—C11—H11B	109.3
C8—C3—C4	118.28 (17)	C10—C11—H11B	109.3
C8—C3—C1	120.02 (17)	H11A—C11—H11B	108.0
C4—C3—C1	121.69 (17)	C13—C12—C11	113.57 (17)
C5—C4—C3	120.63 (17)	C13—C12—H12A	108.9
C5—C4—H4	119.7	C11—C12—H12A	108.9
C3—C4—H4	119.7	C13—C12—H12B	108.9
C4—C5—C6	120.66 (17)	C11—C12—H12B	108.9
C4—C5—H5	119.7	H12A—C12—H12B	107.7
C6—C5—H5	119.7	N2—C13—C12	111.74 (17)
C7—C6—C5	118.87 (18)	N2—C13—H13A	109.3
C7—C6—C2	119.38 (17)	C12—C13—H13A	109.3
C5—C6—C2	121.74 (17)	N2—C13—H13B	109.3
C6—C7—C8	120.26 (18)	C12—C13—H13B	109.3
C6—C7—H7	119.9	H13A—C13—H13B	107.9
C8—C7—H7	119.9
O1—C1—C3—C8	−178.70 (18)	O3—C2—C6—C5	166.22 (17)
O2—C1—C3—C8	0.9 (3)	O4—C2—C6—C5	−13.8 (3)
O1—C1—C3—C4	1.6 (3)	C5—C6—C7—C8	−0.9 (3)
O2—C1—C3—C4	−178.82 (17)	C2—C6—C7—C8	179.78 (18)
C8—C3—C4—C5	−1.6 (3)	C4—C3—C8—C7	1.8 (3)
C1—C3—C4—C5	178.13 (17)	C1—C3—C8—C7	−177.89 (18)
C3—C4—C5—C6	0.1 (3)	C6—C7—C8—C3	−0.6 (3)
C4—C5—C6—C7	1.2 (3)	N1—C9—C10—C11	178.40 (16)
C4—C5—C6—C2	−179.56 (17)	C9—C10—C11—C12	−174.74 (17)
O3—C2—C6—C7	−14.5 (3)	C10—C11—C12—C13	175.64 (17)
O4—C2—C6—C7	165.48 (17)	C11—C12—C13—N2	−179.31 (16)

(anhydrate)

Crystal data

C13H20N2O4	Z = 2
Mr = 268.31	F(000) = 288
Triclinic, P1	Dx = 1.259 Mg m^−3
a = 8.2881 (9) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.5302 (8) Å	Cell parameters from 893 reflections
c = 10.6708 (11) Å	θ = 2.4–26.6°
α = 113.460 (4)°	µ = 0.09 mm^−1
β = 105.990 (3)°	T = 298 K
γ = 99.162 (2)°	Block-like, colorless
V = 707.87 (12) Å^3	0.46 × 0.40 × 0.37 mm

Data collection

CCD area detector diffractometer	1412 reflections with I > 2σ(I)
phi and ω scans	Rint = 0.026
Absorption correction: multi-scan sadabs	θmax = 25.0°, θmin = 2.4°
Tmin = 0.958, Tmax = 0.966	h = −9→5
3533 measured reflections	k = −11→11
2449 independent reflections	l = −11→12

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.055	H-atom parameters constrained
wR(F^2) = 0.139	w = 1/[σ^2(Fo^2) + (0.057P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max < 0.001
2449 reflections	Δρmax = 0.18 e Å^−3
174 parameters	Δρmin = −0.30 e Å^−3

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
N1	0.9161 (3)	0.7792 (2)	0.0280 (2)	0.0432 (6)
H1A	0.934186	0.879831	0.093272	0.065*
H1B	0.870883	0.767700	−0.062732	0.065*
H1C	1.018076	0.757182	0.041312	0.065*
N2	0.7035 (3)	0.1756 (2)	0.1711 (2)	0.0436 (6)
H2A	0.655432	0.179147	0.087265	0.065*
H2B	0.635242	0.093212	0.170770	0.065*
H2C	0.809660	0.163537	0.179738	0.065*
O1	0.0156 (2)	0.1062 (2)	0.2303 (2)	0.0524 (5)
O2	0.2469 (3)	0.2868 (3)	0.2601 (2)	0.0795 (7)
O3	0.7572 (2)	0.2511 (2)	0.8799 (2)	0.0563 (6)
O4	0.5216 (3)	0.0999 (2)	0.87532 (19)	0.0562 (6)
C1	0.1755 (4)	0.1933 (3)	0.2973 (3)	0.0442 (7)
C2	0.5984 (4)	0.1717 (3)	0.8210 (3)	0.0371 (6)
C3	0.2849 (3)	0.1845 (3)	0.4310 (3)	0.0352 (6)
C4	0.2153 (4)	0.0800 (3)	0.4766 (3)	0.0433 (7)
H4	0.099521	0.013363	0.423189	0.052*
C5	0.3146 (3)	0.0731 (3)	0.5997 (3)	0.0410 (7)
H5	0.264729	0.002298	0.628333	0.049*
C6	0.4879 (3)	0.1703 (3)	0.6816 (2)	0.0326 (6)
C7	0.5580 (3)	0.2742 (3)	0.6351 (3)	0.0398 (6)
H7	0.674662	0.338923	0.686939	0.048*
C8	0.4569 (3)	0.2826 (3)	0.5129 (3)	0.0404 (7)
H8	0.505374	0.355333	0.485448	0.049*
C9	0.7922 (4)	0.6680 (3)	0.0481 (3)	0.0468 (7)
H9A	0.739685	0.566695	−0.041858	0.056*
H9B	0.698223	0.712467	0.065036	0.056*
C10	0.8777 (4)	0.6370 (3)	0.1738 (3)	0.0440 (7)
H10A	0.925988	0.737611	0.264412	0.053*
H10B	0.974688	0.596493	0.158899	0.053*
C11	0.7520 (4)	0.5184 (3)	0.1897 (3)	0.0447 (7)
H11A	0.693594	0.422582	0.095315	0.054*
H11B	0.662239	0.564559	0.215203	0.054*
C12	0.8387 (4)	0.4705 (3)	0.3050 (3)	0.0471 (7)
H12A	0.944331	0.446484	0.292490	0.057*
H12B	0.873929	0.560670	0.401991	0.057*
C13	0.7204 (4)	0.3270 (3)	0.2968 (3)	0.0509 (8)
H13A	0.767988	0.320896	0.387680	0.061*
H13B	0.604595	0.340185	0.286722	0.061*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0411 (14)	0.0446 (12)	0.0450 (13)	0.0108 (11)	0.0105 (11)	0.0263 (10)
N2	0.0383 (14)	0.0464 (12)	0.0465 (13)	0.0049 (11)	0.0071 (11)	0.0308 (11)
O1	0.0426 (13)	0.0513 (11)	0.0515 (12)	0.0130 (10)	0.0002 (10)	0.0248 (9)
O2	0.0694 (16)	0.0987 (16)	0.0679 (14)	−0.0034 (13)	−0.0019 (12)	0.0654 (14)
O3	0.0345 (12)	0.0813 (14)	0.0550 (13)	0.0154 (11)	0.0093 (10)	0.0394 (11)
O4	0.0586 (14)	0.0570 (11)	0.0477 (12)	−0.0006 (10)	0.0046 (10)	0.0363 (10)
C1	0.0453 (19)	0.0464 (16)	0.0365 (16)	0.0135 (15)	0.0043 (14)	0.0226 (14)
C2	0.0416 (18)	0.0378 (14)	0.0344 (15)	0.0140 (13)	0.0108 (14)	0.0208 (12)
C3	0.0376 (16)	0.0344 (13)	0.0323 (14)	0.0120 (12)	0.0101 (13)	0.0160 (11)
C4	0.0357 (16)	0.0401 (14)	0.0435 (16)	0.0010 (12)	0.0029 (13)	0.0212 (13)
C5	0.0434 (17)	0.0360 (13)	0.0397 (15)	0.0023 (13)	0.0067 (13)	0.0233 (12)
C6	0.0345 (15)	0.0332 (13)	0.0298 (13)	0.0121 (12)	0.0100 (12)	0.0149 (11)
C7	0.0285 (15)	0.0529 (15)	0.0360 (14)	0.0059 (12)	0.0075 (12)	0.0242 (12)
C8	0.0383 (17)	0.0480 (15)	0.0405 (15)	0.0096 (13)	0.0129 (14)	0.0283 (13)
C9	0.0410 (17)	0.0484 (15)	0.0542 (18)	0.0119 (13)	0.0152 (14)	0.0293 (14)
C10	0.0440 (17)	0.0420 (14)	0.0435 (16)	0.0088 (13)	0.0120 (14)	0.0222 (13)
C11	0.0464 (18)	0.0423 (14)	0.0522 (17)	0.0165 (13)	0.0207 (14)	0.0257 (13)
C12	0.0549 (19)	0.0428 (15)	0.0419 (16)	0.0122 (14)	0.0162 (14)	0.0204 (13)
C13	0.057 (2)	0.0579 (17)	0.0464 (17)	0.0168 (15)	0.0233 (15)	0.0298 (15)

Geometric parameters (Å, º)

N1—C9	1.477 (3)	C5—H5	0.9300
N1—H1A	0.8900	C6—C7	1.389 (3)
N1—H1B	0.8900	C7—C8	1.383 (3)
N1—H1C	0.8900	C7—H7	0.9300
N2—C13	1.480 (3)	C8—H8	0.9300
N2—H2A	0.8900	C9—C10	1.499 (3)
N2—H2B	0.8900	C9—H9A	0.9700
N2—H2C	0.8900	C9—H9B	0.9700
O1—C1	1.269 (3)	C10—C11	1.506 (3)
O2—C1	1.243 (3)	C10—H10A	0.9700
O3—C2	1.244 (3)	C10—H10B	0.9700
O4—C2	1.261 (3)	C11—C12	1.517 (3)
C1—C3	1.508 (3)	C11—H11A	0.9700
C2—C6	1.511 (3)	C11—H11B	0.9700
C3—C8	1.382 (3)	C12—C13	1.507 (3)
C3—C4	1.385 (3)	C12—H12A	0.9700
C4—C5	1.377 (4)	C12—H12B	0.9700
C4—H4	0.9300	C13—H13A	0.9700
C5—C6	1.388 (3)	C13—H13B	0.9700
C9—N1—H1A	109.5	C3—C8—C7	120.9 (2)
C9—N1—H1B	109.5	C3—C8—H8	119.6
H1A—N1—H1B	109.5	C7—C8—H8	119.6
C9—N1—H1C	109.5	N1—C9—C10	113.2 (2)
H1A—N1—H1C	109.5	N1—C9—H9A	108.9
H1B—N1—H1C	109.5	C10—C9—H9A	108.9
C13—N2—H2A	109.5	N1—C9—H9B	108.9
C13—N2—H2B	109.5	C10—C9—H9B	108.9
H2A—N2—H2B	109.5	H9A—C9—H9B	107.7
C13—N2—H2C	109.5	C9—C10—C11	112.9 (2)
H2A—N2—H2C	109.5	C9—C10—H10A	109.0
H2B—N2—H2C	109.5	C11—C10—H10A	109.0
O2—C1—O1	123.9 (2)	C9—C10—H10B	109.0
O2—C1—C3	118.0 (2)	C11—C10—H10B	109.0
O1—C1—C3	118.1 (2)	H10A—C10—H10B	107.8
O3—C2—O4	123.9 (2)	C10—C11—C12	114.1 (2)
O3—C2—C6	118.2 (2)	C10—C11—H11A	108.7
O4—C2—C6	117.8 (2)	C12—C11—H11A	108.7
C8—C3—C4	118.2 (2)	C10—C11—H11B	108.7
C8—C3—C1	120.7 (2)	C12—C11—H11B	108.7
C4—C3—C1	121.1 (2)	H11A—C11—H11B	107.6
C5—C4—C3	121.1 (2)	C13—C12—C11	113.2 (2)
C5—C4—H4	119.4	C13—C12—H12A	108.9
C3—C4—H4	119.4	C11—C12—H12A	108.9
C4—C5—C6	121.0 (2)	C13—C12—H12B	108.9
C4—C5—H5	119.5	C11—C12—H12B	108.9
C6—C5—H5	119.5	H12A—C12—H12B	107.7
C5—C6—C7	117.9 (2)	N2—C13—C12	111.7 (2)
C5—C6—C2	122.6 (2)	N2—C13—H13A	109.3
C7—C6—C2	119.5 (2)	C12—C13—H13A	109.3
C8—C7—C6	121.0 (2)	N2—C13—H13B	109.3
C8—C7—H7	119.5	C12—C13—H13B	109.3
C6—C7—H7	119.5	H13A—C13—H13B	107.9
O2—C1—C3—C8	2.7 (4)	O3—C2—C6—C7	−9.3 (3)
O1—C1—C3—C8	−176.6 (2)	O4—C2—C6—C7	166.7 (2)
O2—C1—C3—C4	−178.3 (3)	C5—C6—C7—C8	1.3 (4)
O1—C1—C3—C4	2.4 (4)	C2—C6—C7—C8	−176.2 (2)
C8—C3—C4—C5	−0.3 (4)	C4—C3—C8—C7	1.4 (4)
C1—C3—C4—C5	−179.3 (2)	C1—C3—C8—C7	−179.6 (2)
C3—C4—C5—C6	−0.3 (4)	C6—C7—C8—C3	−2.0 (4)
C4—C5—C6—C7	−0.2 (4)	N1—C9—C10—C11	−177.7 (2)
C4—C5—C6—C2	177.2 (2)	C9—C10—C11—C12	173.6 (2)
O3—C2—C6—C5	173.4 (2)	C10—C11—C12—C13	−167.5 (2)
O4—C2—C6—C5	−10.7 (3)	C11—C12—C13—N2	75.2 (3)