Polymorphic transition due to grinding: the case of 3-[1-(tert-but­oxy­carbonyl)­azetidin-3-yl]-1,2-oxaz­ole-4-carb­oxy­lic acid

A polymorphic transition as a result of grinding was found for 3-[1-(tert-but­oxy­carbonyl)­azetidin-3-yl]-1,2-oxazole-4-carb­oxy­lic acid. The thorough study of polymorphic structures before and after crystal structure transformation has revealed some pre-conditions for a polymorphic transition and regularities of changes in molecular and crystal structure. In metastable polymorph 1a, the conformationally flexible molecule adopts a conformation with the higher energy and forms a less preferable linear supramolecular synthon. Additional energy imparted to a crystal structure during the grinding process proved to be enough to overcome low energy barriers for the nitro­gen inversion and rotation of the oxazole ring around the sp³–sp² single bond. As a result, polymorph 1b with a molecule adopting conformation with lower energy and forming a more preferable centrosymmetric supramolecular synthon was obtained. The study of pairwise interaction energies in the two polymorphs has shown that metastable polymorph 1a is organized by molecular building units and has a columnar-layered structure. A centrosymmetric dimer should be recognized as a complex building unit in more stable polymorph 1b, which has a layered structure.

Computing details

For both structures, program(s) used to solve structure: SHELXT 2014/5 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2016/6 (Sheldrick, 2015b); molecular graphics: Mercury 3.1 (Macrae et al., 2008).

(1a)

Crystal data

C12H16N2O5	F(000) = 1136
Mr = 268.27	Dx = 1.350 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 16.0117 (9) Å	Cell parameters from 2536 reflections
b = 9.6657 (9) Å	θ = 3.2–30.1°
c = 17.4382 (9) Å	µ = 0.11 mm^−1
β = 101.948 (7)°	T = 100 K
V = 2640.3 (3) Å^3	Block, colorless
Z = 8	0.05 × 0.04 × 0.03 mm

Data collection

Xcalibur, Sapphire3 diffractometer	2322 independent reflections
Radiation source: Enhance (Mo) X-ray Source	1625 reflections with I > 2σ(I)
Detector resolution: 16.1827 pixels mm^-1	Rint = 0.039
ω scans	θmax = 25.0°, θmin = 2.9°
Absorption correction: multi-scan CrysAlis RED, Agilent Technologies, Version 1.171.36.24 (release 03-12-2012 CrysAlis171 .NET) (compiled Dec 3 2012,18:21:49) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	h = −18→18
Tmin = 0.815, Tmax = 1.000	k = −11→11
8636 measured reflections	l = −20→16

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.043	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.109	w = 1/[σ^2(Fo^2) + (0.043P)^2 + 1.7721P] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max < 0.001
2322 reflections	Δρmax = 0.19 e Å^−3
179 parameters	Δρmin = −0.17 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
O1	0.45741 (12)	0.44939 (16)	0.06163 (10)	0.0654 (6)
O2	0.65464 (10)	−0.05836 (14)	0.30980 (8)	0.0435 (4)
O3	0.66246 (9)	0.11553 (13)	0.39920 (7)	0.0342 (4)
O4	0.66508 (12)	0.61671 (17)	0.25829 (11)	0.0693 (6)
O5	0.57402 (11)	0.77584 (16)	0.19748 (9)	0.0474 (4)
H5O	0.6060 (19)	0.832 (3)	0.2375 (17)	0.081 (9)*
N1	0.51646 (13)	0.34353 (19)	0.09260 (11)	0.0509 (6)
N2	0.63376 (13)	0.16536 (17)	0.27403 (9)	0.0429 (5)
C1	0.57312 (14)	0.4043 (2)	0.14704 (12)	0.0392 (5)
C2	0.55512 (15)	0.5475 (2)	0.15364 (12)	0.0432 (6)
C3	0.48293 (17)	0.5669 (2)	0.09928 (15)	0.0578 (7)
H3	0.454053	0.652889	0.089148	0.069*
C4	0.64475 (14)	0.3225 (2)	0.19380 (12)	0.0410 (5)
H4	0.701220	0.353292	0.183937	0.049*
C5	0.63568 (15)	0.1632 (2)	0.19018 (12)	0.0412 (5)
H5A	0.582004	0.130369	0.156175	0.049*
H5B	0.685808	0.114773	0.177938	0.049*
C6	0.64507 (15)	0.3152 (2)	0.28293 (12)	0.0429 (6)
H6A	0.699911	0.343007	0.316999	0.051*
H6B	0.596392	0.363402	0.298137	0.051*
C7	0.65100 (13)	0.0643 (2)	0.32655 (11)	0.0340 (5)
C8	0.66530 (14)	0.0257 (2)	0.46809 (12)	0.0383 (5)
C9	0.5891 (2)	−0.0688 (3)	0.45437 (16)	0.0874 (11)
H9A	0.536740	−0.013625	0.441267	0.131*
H9B	0.588860	−0.122652	0.501948	0.131*
H9C	0.592030	−0.131782	0.410962	0.131*
C10	0.7494 (2)	−0.0512 (3)	0.48436 (16)	0.0736 (9)
H10A	0.749540	−0.119967	0.443102	0.110*
H10B	0.756825	−0.097921	0.535206	0.110*
H10C	0.796211	0.014457	0.485332	0.110*
C11	0.66054 (16)	0.1281 (2)	0.53251 (12)	0.0455 (6)
H11A	0.711527	0.186859	0.541758	0.068*
H11B	0.657450	0.078037	0.580712	0.068*
H11C	0.609553	0.185872	0.516851	0.068*
C12	0.60401 (15)	0.6484 (2)	0.20832 (13)	0.0426 (6)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0700 (12)	0.0450 (10)	0.0621 (11)	−0.0083 (9)	−0.0306 (9)	0.0108 (8)
O2	0.0584 (11)	0.0339 (8)	0.0378 (8)	0.0036 (7)	0.0091 (7)	−0.0056 (7)
O3	0.0428 (9)	0.0310 (7)	0.0274 (7)	−0.0021 (6)	0.0039 (6)	−0.0008 (6)
O4	0.0588 (12)	0.0436 (10)	0.0856 (13)	0.0009 (9)	−0.0314 (10)	−0.0088 (9)
O5	0.0569 (11)	0.0414 (9)	0.0399 (9)	0.0002 (8)	0.0008 (8)	0.0018 (7)
N1	0.0539 (13)	0.0421 (11)	0.0461 (11)	−0.0074 (9)	−0.0144 (10)	0.0119 (9)
N2	0.0637 (13)	0.0339 (10)	0.0296 (10)	0.0060 (9)	0.0065 (9)	−0.0010 (8)
C1	0.0389 (13)	0.0416 (12)	0.0339 (11)	−0.0124 (10)	0.0004 (10)	0.0091 (9)
C2	0.0453 (14)	0.0405 (13)	0.0385 (12)	−0.0095 (10)	−0.0040 (10)	0.0082 (10)
C3	0.0646 (18)	0.0373 (13)	0.0586 (15)	−0.0051 (12)	−0.0167 (13)	0.0098 (11)
C4	0.0361 (13)	0.0486 (13)	0.0352 (12)	−0.0058 (10)	0.0004 (10)	0.0042 (10)
C5	0.0450 (14)	0.0473 (13)	0.0303 (11)	0.0058 (11)	0.0058 (10)	−0.0003 (10)
C6	0.0509 (15)	0.0341 (12)	0.0369 (12)	0.0000 (10)	−0.0062 (10)	0.0018 (9)
C7	0.0331 (12)	0.0354 (12)	0.0330 (11)	0.0013 (9)	0.0060 (9)	−0.0036 (9)
C8	0.0512 (14)	0.0330 (11)	0.0315 (11)	−0.0073 (10)	0.0103 (10)	0.0013 (9)
C9	0.116 (3)	0.106 (2)	0.0464 (15)	−0.076 (2)	0.0316 (16)	−0.0180 (16)
C10	0.098 (2)	0.0728 (19)	0.0525 (16)	0.0421 (17)	0.0205 (15)	0.0233 (14)
C11	0.0562 (15)	0.0462 (13)	0.0327 (12)	−0.0053 (11)	0.0057 (10)	−0.0023 (10)
C12	0.0438 (14)	0.0384 (13)	0.0420 (13)	−0.0050 (10)	0.0009 (11)	0.0055 (10)

Geometric parameters (Å, º)

O1—C3	1.333 (3)	C4—C6	1.555 (3)
O1—N1	1.422 (2)	C4—H4	1.0000
O2—C7	1.225 (2)	C5—H5A	0.9900
O3—C7	1.337 (2)	C5—H5B	0.9900
O3—C8	1.475 (2)	C6—H6A	0.9900
O4—C12	1.207 (3)	C6—H6B	0.9900
O5—C12	1.322 (3)	C8—C9	1.503 (3)
O5—H5O	0.95 (3)	C8—C11	1.511 (3)
N1—C1	1.309 (3)	C8—C10	1.512 (3)
N2—C7	1.329 (3)	C9—H9A	0.9800
N2—C6	1.464 (3)	C9—H9B	0.9800
N2—C5	1.469 (3)	C9—H9C	0.9800
C1—C2	1.423 (3)	C10—H10A	0.9800
C1—C4	1.489 (3)	C10—H10B	0.9800
C2—C3	1.348 (3)	C10—H10C	0.9800
C2—C12	1.471 (3)	C11—H11A	0.9800
C3—H3	0.9500	C11—H11B	0.9800
C4—C5	1.547 (3)	C11—H11C	0.9800
C3—O1—N1	108.31 (16)	C4—C6—H6B	114.0
C7—O3—C8	121.90 (15)	H6A—C6—H6B	111.2
C12—O5—H5O	107.9 (16)	O2—C7—N2	124.10 (18)
C1—N1—O1	105.04 (17)	O2—C7—O3	125.49 (18)
C7—N2—C6	130.64 (17)	N2—C7—O3	110.40 (17)
C7—N2—C5	129.16 (17)	O3—C8—C9	109.93 (18)
C6—N2—C5	95.26 (16)	O3—C8—C11	102.83 (15)
N1—C1—C2	111.91 (19)	C9—C8—C11	110.6 (2)
N1—C1—C4	119.9 (2)	O3—C8—C10	108.56 (18)
C2—C1—C4	128.13 (19)	C9—C8—C10	113.1 (2)
C3—C2—C1	103.72 (19)	C11—C8—C10	111.25 (19)
C3—C2—C12	128.9 (2)	C8—C9—H9A	109.5
C1—C2—C12	127.41 (19)	C8—C9—H9B	109.5
O1—C3—C2	111.0 (2)	H9A—C9—H9B	109.5
O1—C3—H3	124.5	C8—C9—H9C	109.5
C2—C3—H3	124.5	H9A—C9—H9C	109.5
C1—C4—C5	116.78 (18)	H9B—C9—H9C	109.5
C1—C4—C6	114.48 (19)	C8—C10—H10A	109.5
C5—C4—C6	88.65 (15)	C8—C10—H10B	109.5
C1—C4—H4	111.7	H10A—C10—H10B	109.5
C5—C4—H4	111.7	C8—C10—H10C	109.5
C6—C4—H4	111.7	H10A—C10—H10C	109.5
N2—C5—C4	88.08 (15)	H10B—C10—H10C	109.5
N2—C5—H5A	114.0	C8—C11—H11A	109.5
C4—C5—H5A	114.0	C8—C11—H11B	109.5
N2—C5—H5B	114.0	H11A—C11—H11B	109.5
C4—C5—H5B	114.0	C8—C11—H11C	109.5
H5A—C5—H5B	111.2	H11A—C11—H11C	109.5
N2—C6—C4	87.95 (15)	H11B—C11—H11C	109.5
N2—C6—H6A	114.0	O4—C12—O5	123.8 (2)
C4—C6—H6A	114.0	O4—C12—C2	122.9 (2)
N2—C6—H6B	114.0	O5—C12—C2	113.36 (19)
C3—O1—N1—C1	0.4 (3)	C7—N2—C6—C4	157.9 (2)
O1—N1—C1—C2	−0.5 (3)	C5—N2—C6—C4	1.77 (18)
O1—N1—C1—C4	178.69 (19)	C1—C4—C6—N2	117.31 (19)
N1—C1—C2—C3	0.5 (3)	C5—C4—C6—N2	−1.67 (17)
C4—C1—C2—C3	−178.7 (2)	C6—N2—C7—O2	−164.8 (2)
N1—C1—C2—C12	179.6 (2)	C5—N2—C7—O2	−16.1 (4)
C4—C1—C2—C12	0.5 (4)	C6—N2—C7—O3	16.0 (3)
N1—O1—C3—C2	−0.1 (3)	C5—N2—C7—O3	164.7 (2)
C1—C2—C3—O1	−0.2 (3)	C8—O3—C7—O2	−11.7 (3)
C12—C2—C3—O1	−179.3 (2)	C8—O3—C7—N2	167.52 (18)
N1—C1—C4—C5	−15.3 (3)	C7—O3—C8—C9	−50.9 (3)
C2—C1—C4—C5	163.8 (2)	C7—O3—C8—C11	−168.69 (18)
N1—C1—C4—C6	−116.9 (2)	C7—O3—C8—C10	73.4 (2)
C2—C1—C4—C6	62.2 (3)	C3—C2—C12—O4	174.9 (3)
C7—N2—C5—C4	−158.5 (2)	C1—C2—C12—O4	−4.0 (4)
C6—N2—C5—C4	−1.78 (18)	C3—C2—C12—O5	−4.6 (4)
C1—C4—C5—N2	−115.2 (2)	C1—C2—C12—O5	176.4 (2)
C6—C4—C5—N2	1.67 (17)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5O···O2^i	0.95 (3)	1.70 (3)	2.650 (2)	175 (3)

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

(1b)

Crystal data

C12H16N2O5	F(000) = 568
Mr = 268.27	Dx = 1.347 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 14.3254 (10) Å	Cell parameters from 1931 reflections
b = 8.7613 (7) Å	θ = 3.7–25.9°
c = 11.4085 (8) Å	µ = 0.11 mm^−1
β = 112.480 (8)°	T = 293 K
V = 1323.07 (18) Å^3	Stick, colorless
Z = 4	0.13 × 0.04 × 0.03 mm

Data collection

Xcalibur, Sapphire3 diffractometer	2319 independent reflections
Radiation source: Enhance (Mo) X-ray Source	1858 reflections with I > 2σ(I)
Detector resolution: 16.1827 pixels mm^-1	Rint = 0.080
ω scans	θmax = 25.0°, θmin = 3.0°
Absorption correction: multi-scan CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	h = −17→14
Tmin = 0.138, Tmax = 1.000	k = −10→10
8684 measured reflections	l = −13→12

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.059	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.175	w = 1/[σ^2(Fo^2) + (0.0893P)^2 + 0.1233P] where P = (Fo^2 + 2Fc^2)/3
S = 1.10	(Δ/σ)max < 0.001
2319 reflections	Δρmax = 0.23 e Å^−3
179 parameters	Δρmin = −0.21 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
O1	0.58603 (13)	0.1651 (2)	0.49364 (15)	0.0548 (5)
O3	0.15089 (15)	0.4655 (2)	0.28431 (17)	0.0613 (6)
O2	0.17671 (13)	0.5037 (2)	0.10179 (17)	0.0604 (6)
O4	0.42575 (12)	0.0185 (2)	0.08450 (14)	0.0494 (5)
O5	0.59410 (12)	0.0321 (2)	0.15129 (16)	0.0546 (5)
H5O	0.583 (3)	0.004 (6)	0.067 (5)	0.132 (16)*
N1	0.47972 (15)	0.1700 (3)	0.45717 (18)	0.0505 (6)
N2	0.21608 (15)	0.2805 (3)	0.20963 (18)	0.0497 (6)
C1	0.44202 (16)	0.1259 (3)	0.3393 (2)	0.0408 (6)
C2	0.51935 (17)	0.0938 (3)	0.2937 (2)	0.0418 (6)
C3	0.60665 (19)	0.1204 (3)	0.3950 (2)	0.0481 (6)
H3	0.671241	0.108916	0.395143	0.058*
C4	0.33062 (17)	0.1138 (3)	0.2701 (2)	0.0457 (6)
H4	0.309389	0.007350	0.250555	0.055*
C5	0.26412 (18)	0.1983 (3)	0.3291 (2)	0.0493 (6)
H5A	0.218550	0.131943	0.350088	0.059*
H5B	0.301980	0.263352	0.400262	0.059*
C6	0.28316 (18)	0.2174 (3)	0.1519 (2)	0.0490 (6)
H6A	0.329775	0.291338	0.141387	0.059*
H6B	0.248183	0.161794	0.073857	0.059*
C7	0.18101 (17)	0.4258 (3)	0.1912 (2)	0.0475 (6)
C8	0.1041 (2)	0.6151 (3)	0.2851 (3)	0.0648 (8)
C9	0.1772 (3)	0.7421 (5)	0.2865 (5)	0.1055 (14)
H9A	0.240525	0.726552	0.356099	0.158*
H9B	0.149405	0.838871	0.296086	0.158*
H9C	0.187626	0.741054	0.208263	0.158*
C10	0.0072 (2)	0.6298 (5)	0.1700 (4)	0.0887 (11)
H10A	0.021749	0.625379	0.094620	0.133*
H10B	−0.024331	0.725669	0.172955	0.133*
H10C	−0.037547	0.547885	0.169143	0.133*
C11	0.0829 (5)	0.6075 (6)	0.4037 (4)	0.138 (2)
H11A	0.038906	0.522938	0.398474	0.208*
H11B	0.051109	0.700545	0.413167	0.208*
H11C	0.145207	0.594210	0.475480	0.208*
C12	0.50979 (17)	0.0449 (3)	0.1675 (2)	0.0423 (6)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0518 (10)	0.0595 (13)	0.0495 (9)	0.0018 (8)	0.0156 (7)	−0.0084 (8)
O3	0.0734 (12)	0.0526 (13)	0.0672 (11)	0.0152 (9)	0.0372 (9)	−0.0005 (9)
O2	0.0519 (11)	0.0652 (14)	0.0633 (11)	0.0056 (9)	0.0212 (8)	0.0129 (10)
O4	0.0439 (9)	0.0581 (12)	0.0490 (9)	−0.0008 (8)	0.0210 (7)	−0.0085 (8)
O5	0.0444 (10)	0.0752 (14)	0.0497 (10)	0.0057 (8)	0.0241 (7)	−0.0034 (8)
N1	0.0514 (12)	0.0524 (14)	0.0492 (12)	0.0042 (10)	0.0210 (9)	−0.0034 (9)
N2	0.0499 (12)	0.0534 (14)	0.0505 (11)	0.0066 (10)	0.0244 (9)	0.0006 (9)
C1	0.0476 (13)	0.0336 (13)	0.0445 (12)	0.0022 (9)	0.0213 (10)	0.0029 (9)
C2	0.0455 (12)	0.0385 (14)	0.0439 (12)	0.0029 (10)	0.0199 (9)	0.0008 (10)
C3	0.0478 (13)	0.0503 (16)	0.0504 (13)	0.0005 (11)	0.0236 (11)	−0.0035 (11)
C4	0.0484 (13)	0.0422 (14)	0.0529 (13)	−0.0020 (10)	0.0265 (10)	−0.0027 (11)
C5	0.0478 (13)	0.0526 (16)	0.0568 (14)	0.0032 (11)	0.0305 (11)	0.0046 (12)
C6	0.0443 (13)	0.0605 (18)	0.0451 (13)	0.0038 (11)	0.0200 (10)	−0.0041 (11)
C7	0.0370 (12)	0.0558 (17)	0.0492 (13)	0.0011 (11)	0.0159 (10)	−0.0018 (12)
C8	0.0613 (17)	0.0492 (18)	0.0863 (19)	0.0073 (13)	0.0310 (14)	−0.0119 (15)
C9	0.064 (2)	0.067 (3)	0.169 (4)	−0.0049 (17)	0.026 (2)	−0.035 (2)
C10	0.0488 (17)	0.077 (3)	0.134 (3)	0.0099 (15)	0.0283 (17)	−0.006 (2)
C11	0.218 (6)	0.116 (4)	0.123 (3)	0.073 (4)	0.113 (4)	0.006 (3)
C12	0.0438 (13)	0.0396 (14)	0.0467 (12)	0.0038 (10)	0.0210 (10)	0.0005 (10)

Geometric parameters (Å, º)

O1—C3	1.327 (3)	C4—C6	1.550 (3)
O1—N1	1.418 (3)	C4—H4	0.9800
O3—C7	1.336 (3)	C5—H5A	0.9700
O3—C8	1.473 (3)	C5—H5B	0.9700
O2—C7	1.209 (3)	C6—H6A	0.9700
O4—C12	1.236 (3)	C6—H6B	0.9700
O5—C12	1.295 (3)	C8—C11	1.497 (5)
O5—H5O	0.94 (5)	C8—C10	1.508 (5)
N1—C1	1.302 (3)	C8—C9	1.524 (5)
N2—C7	1.355 (4)	C9—H9A	0.9600
N2—C5	1.461 (3)	C9—H9B	0.9600
N2—C6	1.465 (3)	C9—H9C	0.9600
C1—C2	1.421 (3)	C10—H10A	0.9600
C1—C4	1.489 (3)	C10—H10B	0.9600
C2—C3	1.360 (3)	C10—H10C	0.9600
C2—C12	1.457 (3)	C11—H11A	0.9600
C3—H3	0.9300	C11—H11B	0.9600
C4—C5	1.549 (3)	C11—H11C	0.9600
C3—O1—N1	108.82 (17)	C4—C6—H6B	113.9
C7—O3—C8	121.5 (2)	H6A—C6—H6B	111.1
C12—O5—H5O	111 (3)	O2—C7—O3	126.6 (3)
C1—N1—O1	105.59 (18)	O2—C7—N2	123.8 (2)
C7—N2—C5	128.5 (2)	O3—C7—N2	109.5 (2)
C7—N2—C6	123.6 (2)	O3—C8—C11	102.5 (3)
C5—N2—C6	94.44 (18)	O3—C8—C10	109.9 (2)
N1—C1—C2	111.33 (19)	C11—C8—C10	110.7 (3)
N1—C1—C4	120.4 (2)	O3—C8—C9	109.7 (2)
C2—C1—C4	128.28 (19)	C11—C8—C9	113.5 (3)
C3—C2—C1	104.31 (19)	C10—C8—C9	110.3 (3)
C3—C2—C12	126.8 (2)	C8—C9—H9A	109.5
C1—C2—C12	128.9 (2)	C8—C9—H9B	109.5
O1—C3—C2	109.9 (2)	H9A—C9—H9B	109.5
O1—C3—H3	125.0	C8—C9—H9C	109.5
C2—C3—H3	125.0	H9A—C9—H9C	109.5
C1—C4—C5	116.6 (2)	H9B—C9—H9C	109.5
C1—C4—C6	116.4 (2)	C8—C10—H10A	109.5
C5—C4—C6	87.71 (18)	C8—C10—H10B	109.5
C1—C4—H4	111.4	H10A—C10—H10B	109.5
C5—C4—H4	111.4	C8—C10—H10C	109.5
C6—C4—H4	111.4	H10A—C10—H10C	109.5
N2—C5—C4	88.77 (17)	H10B—C10—H10C	109.5
N2—C5—H5A	113.9	C8—C11—H11A	109.5
C4—C5—H5A	113.9	C8—C11—H11B	109.5
N2—C5—H5B	113.9	H11A—C11—H11B	109.5
C4—C5—H5B	113.9	C8—C11—H11C	109.5
H5A—C5—H5B	111.1	H11A—C11—H11C	109.5
N2—C6—C4	88.57 (16)	H11B—C11—H11C	109.5
N2—C6—H6A	113.9	O4—C12—O5	124.2 (2)
C4—C6—H6A	113.9	O4—C12—C2	120.5 (2)
N2—C6—H6B	113.9	O5—C12—C2	115.2 (2)
C3—O1—N1—C1	0.9 (3)	C7—N2—C6—C4	148.7 (2)
O1—N1—C1—C2	−1.1 (3)	C5—N2—C6—C4	5.55 (19)
O1—N1—C1—C4	178.6 (2)	C1—C4—C6—N2	−123.9 (2)
N1—C1—C2—C3	0.8 (3)	C5—C4—C6—N2	−5.22 (18)
C4—C1—C2—C3	−178.8 (2)	C8—O3—C7—O2	1.9 (4)
N1—C1—C2—C12	−178.5 (2)	C8—O3—C7—N2	−176.7 (2)
C4—C1—C2—C12	1.8 (4)	C5—N2—C7—O2	151.8 (2)
N1—O1—C3—C2	−0.4 (3)	C6—N2—C7—O2	21.6 (4)
C1—C2—C3—O1	−0.2 (3)	C5—N2—C7—O3	−29.6 (3)
C12—C2—C3—O1	179.2 (2)	C6—N2—C7—O3	−159.8 (2)
N1—C1—C4—C5	17.2 (4)	C7—O3—C8—C11	179.6 (3)
C2—C1—C4—C5	−163.2 (2)	C7—O3—C8—C10	61.9 (3)
N1—C1—C4—C6	118.7 (2)	C7—O3—C8—C9	−59.6 (4)
C2—C1—C4—C6	−61.7 (3)	C3—C2—C12—O4	177.0 (2)
C7—N2—C5—C4	−145.9 (2)	C1—C2—C12—O4	−3.7 (4)
C6—N2—C5—C4	−5.6 (2)	C3—C2—C12—O5	−2.9 (4)
C1—C4—C5—N2	123.7 (2)	C1—C2—C12—O5	176.4 (2)
C6—C4—C5—N2	5.23 (18)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5O···O4^i	0.94 (5)	1.70 (5)	2.632 (2)	170 (5)

Symmetry code: (i) −x+1, −y, −z.