A cocrystal of L-ascorbic acid with picolinic acid: the role of O—H...O, N—H...O and C—H...O hydrogen bonds and L-ascorbic acid con­formation in structure stabilization

A new 1:1 cocrystal (L-Asc–Pic) of L-ascorbic acid (vitamin C) with picolinic acid was prepared as a powder and as single crystals. The crystal structure was solved and refined from single-crystal X-ray diffraction (SCXRD) data collected at 293 (2) and 100 (2) K. The samples of the L-Asc–Pic cocrystal were characterized by elemental (HCNS) analysis and titrimetric methods, TG/DTG/DSC, and IR and Raman spectroscopy. The asymmetric unit comprises a picolinic acid zwitterion and an L-ascorbic acid molecule. The stabilization energy of intermolecular interactions involving hydrogen bonds, the vibrational spectrum and the energies of the frontier molecular orbitals were calculated using the GAUSSIAN09 and the CrystalExplorer17 programs. The charge distribution on the atoms of the L-Asc–Pic cocrystal, L-ascorbic acid itself and its 12 known cocrystals (structures from Version 5.40 of the Cambridge Structural Database) were calculated by the methods of Mulliken, Voronoi and Hirshfeld charge analyses (ADF) at the bp86/TZ2P+ level of theory. The total effective charges and con­formations of the L-ascorbic acid molecules in the new and previously reported cocrystals were compared with those of the two symmetry-independent molecules in the crystals of L-ascorbic acid. A correlation between molecular con­formation and its effective charge is discussed.

Computing details

Data collection: CrysAlis PRO, Agilent Technologies, Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET) (compiled Aug 13 2014,18:06:01) for picasc_293; CrysAlis PRO 1.171.38.43d (Rigaku OD, 2015) for picasc_100. Cell refinement: CrysAlis PRO, Agilent Technologies, Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET) (compiled Aug 13 2014,18:06:01) for picasc_293; CrysAlis PRO 1.171.38.43d (Rigaku OD, 2015) for picasc_100. Data reduction: CrysAlis PRO, Agilent Technologies, Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET) (compiled Aug 13 2014,18:06:01) for picasc_293; CrysAlis PRO 1.171.38.43d (Rigaku OD, 2015) for picasc_100. For both structures, program(s) used to solve structure: ShelXT (Sheldrick, 2015); program(s) used to refine structure: SHELXL (Sheldrick, 2015); molecular graphics: Olex2 (Dolomanov et al., 2009); software used to prepare material for publication: Olex2 (Dolomanov et al., 2009).

L-ascorbic acid picolinic acid cocrystal (picasc_293)

Crystal data

C6H8O6·C6H5NO2	Dx = 1.562 Mg m^−3
Mr = 299.23	Melting point: 455.6 K
Orthorhombic, P21212	Mo Kα radiation, λ = 0.71073 Å
a = 29.1612 (4) Å	Cell parameters from 13377 reflections
b = 9.2070 (1) Å	θ = 2.1–31.5°
c = 4.7387 (1) Å	µ = 0.13 mm^−1
V = 1272.28 (3) Å^3	T = 293 K
Z = 4	Block, clear light yellow
F(000) = 624	0.45 × 0.34 × 0.28 mm

Data collection

Xcalibur, Ruby, Gemini ultra diffractometer	3979 reflections with I > 2σ(I)
Detector resolution: 10.3457 pixels mm^-1	Rint = 0.020
ω scans	θmax = 31.9°, θmin = 2.3°
Absorption correction: multi-scan CrysAlisPro, Agilent Technologies, Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET) (compiled Aug 13 2014,18:06:01) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm. Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	h = −42→41
Tmin = 0.933, Tmax = 1.000	k = −13→13
23240 measured reflections	l = −7→7
4223 independent reflections

Refinement

Refinement on F^2	Hydrogen site location: difference Fourier map
Least-squares matrix: full	Only H-atom coordinates refined
R[F^2 > 2σ(F^2)] = 0.032	w = 1/[σ^2(Fo^2) + (0.0502P)^2 + 0.1136P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.086	(Δ/σ)max = 0.001
S = 1.05	Δρmax = 0.28 e Å^−3
4223 reflections	Δρmin = −0.12 e Å^−3
229 parameters	Absolute structure: Flack x determined using 1551 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
0 restraints	Absolute structure parameter: −0.4 (2)
Primary atom site location: dual

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
O5	0.53551 (4)	0.85762 (11)	0.3122 (2)	0.0320 (2)
O1	0.57762 (3)	0.75676 (12)	−0.1822 (2)	0.0321 (2)
O4	0.57112 (3)	0.48770 (12)	0.3560 (3)	0.0367 (3)
O8	0.68675 (4)	0.40952 (13)	0.5803 (3)	0.0404 (3)
O6	0.44292 (3)	0.86978 (14)	0.1177 (3)	0.0417 (3)
O3	0.67107 (3)	0.61440 (14)	0.2135 (3)	0.0411 (3)
O7	0.61635 (4)	0.33680 (13)	0.7035 (3)	0.0418 (3)
O2	0.65114 (4)	0.82685 (14)	−0.2169 (3)	0.0463 (3)
N1	0.64974 (4)	0.15715 (13)	1.0929 (3)	0.0292 (2)
C3	0.58697 (4)	0.58642 (14)	0.1746 (3)	0.0266 (2)
C2	0.62859 (4)	0.64111 (15)	0.1163 (3)	0.0277 (2)
C7	0.67926 (4)	0.24026 (15)	0.9482 (3)	0.0273 (2)
C1	0.62330 (5)	0.74994 (16)	−0.1048 (3)	0.0299 (3)
C5	0.51530 (4)	0.74096 (15)	0.1585 (3)	0.0280 (2)
C12	0.65901 (5)	0.33915 (14)	0.7241 (3)	0.0286 (2)
C4	0.55173 (4)	0.65797 (15)	−0.0087 (3)	0.0274 (2)
C11	0.66330 (5)	0.06151 (16)	1.2900 (3)	0.0341 (3)
C6	0.47908 (5)	0.80321 (18)	−0.0355 (3)	0.0347 (3)
C8	0.72550 (5)	0.22899 (19)	1.0040 (4)	0.0370 (3)
C10	0.70921 (6)	0.04742 (18)	1.3512 (3)	0.0388 (3)
C9	0.74042 (5)	0.1324 (2)	1.2087 (4)	0.0428 (4)
H5A	0.5000 (8)	0.673 (3)	0.291 (4)	0.051*
H4A	0.5382 (7)	0.585 (3)	−0.136 (5)	0.051*
H11	0.6402 (8)	0.005 (2)	1.379 (5)	0.051*
H6	0.4519 (8)	0.948 (3)	0.190 (6)	0.064*
H8	0.7471 (7)	0.285 (3)	0.905 (5)	0.051*
H1	0.6205 (8)	0.170 (2)	1.059 (5)	0.051*
H6A	0.4651 (8)	0.727 (3)	−0.146 (5)	0.051*
H6B	0.4928 (7)	0.871 (3)	−0.170 (5)	0.051*
H9	0.7729 (7)	0.123 (2)	1.248 (5)	0.051*
H3	0.6717 (9)	0.541 (3)	0.343 (6)	0.064*
H10	0.7197 (8)	−0.023 (2)	1.486 (5)	0.051*
H4	0.5921 (9)	0.446 (3)	0.470 (6)	0.064*
H5	0.5506 (8)	0.830 (3)	0.447 (6)	0.064*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O5	0.0367 (5)	0.0309 (5)	0.0283 (5)	0.0016 (4)	−0.0080 (4)	0.0016 (4)
O1	0.0312 (4)	0.0383 (5)	0.0267 (4)	0.0021 (4)	−0.0004 (4)	0.0084 (4)
O4	0.0273 (4)	0.0347 (5)	0.0479 (6)	−0.0022 (4)	−0.0028 (4)	0.0175 (5)
O8	0.0349 (5)	0.0431 (6)	0.0433 (6)	−0.0048 (5)	−0.0034 (5)	0.0170 (5)
O6	0.0227 (4)	0.0391 (6)	0.0633 (8)	0.0007 (4)	−0.0017 (5)	−0.0121 (6)
O3	0.0238 (4)	0.0512 (6)	0.0482 (6)	−0.0003 (4)	−0.0009 (4)	0.0194 (6)
O7	0.0286 (5)	0.0495 (6)	0.0475 (6)	0.0034 (4)	−0.0028 (4)	0.0201 (6)
O2	0.0408 (6)	0.0527 (7)	0.0456 (6)	−0.0049 (5)	0.0069 (5)	0.0200 (6)
N1	0.0261 (5)	0.0307 (5)	0.0309 (5)	0.0012 (4)	−0.0001 (4)	0.0050 (4)
C3	0.0257 (5)	0.0244 (5)	0.0299 (6)	0.0006 (4)	−0.0005 (5)	0.0028 (5)
C2	0.0263 (5)	0.0295 (6)	0.0274 (5)	0.0016 (5)	0.0004 (4)	0.0034 (5)
C7	0.0266 (5)	0.0282 (6)	0.0269 (5)	0.0024 (4)	−0.0003 (4)	0.0030 (5)
C1	0.0308 (6)	0.0333 (6)	0.0257 (5)	0.0016 (5)	0.0024 (5)	0.0040 (5)
C5	0.0248 (5)	0.0276 (5)	0.0315 (6)	−0.0008 (4)	−0.0003 (4)	0.0041 (5)
C12	0.0319 (6)	0.0261 (5)	0.0279 (6)	0.0023 (5)	−0.0024 (5)	0.0026 (5)
C4	0.0263 (5)	0.0278 (6)	0.0283 (6)	−0.0003 (4)	−0.0035 (4)	0.0028 (5)
C11	0.0375 (7)	0.0326 (6)	0.0323 (6)	0.0010 (5)	0.0023 (6)	0.0071 (6)
C6	0.0254 (6)	0.0389 (7)	0.0397 (7)	0.0053 (5)	−0.0081 (5)	−0.0040 (6)
C8	0.0269 (6)	0.0453 (8)	0.0388 (7)	0.0026 (6)	0.0013 (5)	0.0110 (7)
C10	0.0405 (7)	0.0411 (8)	0.0349 (7)	0.0117 (6)	−0.0014 (6)	0.0098 (6)
C9	0.0292 (6)	0.0565 (9)	0.0427 (8)	0.0102 (6)	−0.0023 (6)	0.0133 (8)

Geometric parameters (Å, º)

O5—C5	1.4252 (17)	C3—C4	1.4980 (18)
O5—H5	0.82 (3)	C2—C1	1.4580 (19)
O1—C1	1.3831 (16)	C7—C12	1.5186 (18)
O1—C4	1.4399 (16)	C7—C8	1.3779 (19)
O4—C3	1.3338 (16)	C5—C4	1.5298 (19)
O4—H4	0.90 (3)	C5—C6	1.5130 (18)
O8—C12	1.2402 (17)	C5—H5A	0.99 (2)
O6—C6	1.4193 (18)	C4—H4A	0.99 (3)
O6—H6	0.84 (3)	C11—C10	1.376 (2)
O3—C2	1.3443 (16)	C11—H11	0.95 (2)
O3—H3	0.91 (3)	C6—H6A	0.96 (2)
O7—C12	1.2478 (16)	C6—H6B	0.98 (2)
O2—C1	1.2011 (18)	C8—C9	1.386 (2)
N1—C7	1.3404 (17)	C8—H8	0.94 (2)
N1—C11	1.3432 (18)	C10—C9	1.377 (2)
N1—H1	0.88 (2)	C10—H10	0.96 (2)
C3—C2	1.3426 (18)	C9—H9	0.97 (2)
C5—O5—H5	112.5 (19)	O8—C12—C7	116.35 (12)
C1—O1—C4	108.95 (10)	O7—C12—C7	115.59 (12)
C3—O4—H4	116.1 (16)	O1—C4—C3	104.43 (10)
C6—O6—H6	110.3 (17)	O1—C4—C5	110.14 (11)
C2—O3—H3	112.6 (16)	O1—C4—H4A	106.9 (14)
C7—N1—C11	122.74 (12)	C3—C4—C5	113.31 (11)
C7—N1—H1	116.8 (16)	C3—C4—H4A	109.1 (14)
C11—N1—H1	120.4 (16)	C5—C4—H4A	112.4 (13)
O4—C3—C2	134.53 (12)	N1—C11—C10	119.65 (13)
O4—C3—C4	115.83 (11)	N1—C11—H11	117.4 (14)
C2—C3—C4	109.63 (12)	C10—C11—H11	122.9 (14)
O3—C2—C1	117.99 (12)	O6—C6—C5	111.82 (13)
C3—C2—O3	133.95 (13)	O6—C6—H6A	106.0 (14)
C3—C2—C1	108.05 (11)	O6—C6—H6B	111.3 (13)
N1—C7—C12	116.76 (11)	C5—C6—H6A	110.5 (14)
N1—C7—C8	119.17 (13)	C5—C6—H6B	110.6 (12)
C8—C7—C12	124.04 (13)	H6A—C6—H6B	106.4 (19)
O1—C1—C2	108.88 (11)	C7—C8—C9	119.33 (14)
O2—C1—O1	120.46 (13)	C7—C8—H8	121.3 (14)
O2—C1—C2	130.66 (13)	C9—C8—H8	119.4 (14)
O5—C5—C4	110.73 (10)	C11—C10—C9	119.08 (14)
O5—C5—C6	108.27 (11)	C11—C10—H10	121.0 (14)
O5—C5—H5A	109.8 (13)	C9—C10—H10	119.9 (14)
C4—C5—H5A	108.9 (13)	C8—C9—H9	119.9 (14)
C6—C5—C4	111.06 (11)	C10—C9—C8	120.02 (14)
C6—C5—H5A	108.0 (13)	C10—C9—H9	120.1 (14)
O8—C12—O7	128.04 (13)
O5—C5—C4—O1	−53.45 (14)	C7—N1—C11—C10	0.6 (2)
O5—C5—C4—C3	63.11 (14)	C7—C8—C9—C10	0.9 (3)
O5—C5—C6—O6	−63.31 (15)	C1—O1—C4—C3	−2.11 (14)
O4—C3—C2—O3	2.3 (3)	C1—O1—C4—C5	119.87 (11)
O4—C3—C2—C1	−178.90 (15)	C12—C7—C8—C9	−178.37 (15)
O4—C3—C4—O1	−179.59 (11)	C4—O1—C1—O2	−177.83 (14)
O4—C3—C4—C5	60.53 (16)	C4—O1—C1—C2	2.19 (15)
O3—C2—C1—O1	177.64 (12)	C4—C3—C2—O3	−178.77 (16)
O3—C2—C1—O2	−2.3 (3)	C4—C3—C2—C1	0.00 (16)
N1—C7—C12—O8	−176.05 (13)	C4—C5—C6—O6	174.92 (12)
N1—C7—C12—O7	2.40 (19)	C11—N1—C7—C12	177.71 (13)
N1—C7—C8—C9	−0.2 (2)	C11—N1—C7—C8	−0.6 (2)
N1—C11—C10—C9	0.2 (2)	C11—C10—C9—C8	−0.9 (3)
C3—C2—C1—O1	−1.36 (16)	C6—C5—C4—O1	66.88 (14)
C3—C2—C1—O2	178.66 (16)	C6—C5—C4—C3	−176.56 (12)
C2—C3—C4—O1	1.28 (15)	C8—C7—C12—O8	2.2 (2)
C2—C3—C4—C5	−118.59 (13)	C8—C7—C12—O7	−179.38 (15)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5A···O4^i	0.99 (2)	2.57 (2)	3.4146 (17)	143 (2)
C11—H11···O2^ii	0.95 (2)	2.54 (2)	3.2020 (19)	127 (2)
O6—H6···O5^iii	0.84 (3)	1.92 (3)	2.7468 (16)	170 (3)
N1—H1···O6^iv	0.88 (2)	1.91 (2)	2.7158 (15)	153 (2)
C6—H6A···O7^v	0.96 (2)	2.55 (2)	3.3072 (18)	136 (2)
C9—H9···O8^vi	0.97 (2)	2.43 (2)	3.1182 (19)	128 (2)
O3—H3···O8	0.91 (3)	1.71 (3)	2.6055 (16)	166 (2)
O4—H4···O7	0.90 (3)	1.65 (3)	2.5261 (15)	162 (2)
O5—H5···O1^vii	0.82 (3)	2.04 (3)	2.8480 (14)	170 (2)

Symmetry codes: (i) −x+1, −y+1, z; (ii) x, y−1, z+2; (iii) −x+1, −y+2, z; (iv) −x+1, −y+1, z+1; (v) −x+1, −y+1, z−1; (vi) −x+3/2, y−1/2, −z+2; (vii) x, y, z+1.

L-ascorbic acid picolinic acid cocrystal (picasc_100)

Crystal data

C6H8O6·C6H5NO2	Dx = 1.589 Mg m^−3
Mr = 299.23	Melting point: 455.6 K
Orthorhombic, P21212	Mo Kα radiation, λ = 0.71073 Å
a = 29.0583 (2) Å	Cell parameters from 31071 reflections
b = 9.15479 (8) Å	θ = 2.3–37.1°
c = 4.70223 (4) Å	µ = 0.14 mm^−1
V = 1250.90 (2) Å^3	T = 100 K
Z = 4	Block, clear light colourless
F(000) = 624	0.45 × 0.34 × 0.28 mm

Data collection

Xcalibur, Ruby, Gemini ultra diffractometer	6109 reflections with I > 2σ(I)
Detector resolution: 10.3457 pixels mm^-1	Rint = 0.026
ω scans	θmax = 37.2°, θmin = 2.3°
Absorption correction: multi-scan CrysAlisPro 1.171.38.43d (Rigaku Oxford Diffraction, 2015) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	h = −48→48
Tmin = 0.940, Tmax = 1.000	k = −15→15
43507 measured reflections	l = −7→7
6327 independent reflections

Refinement

Refinement on F^2	Hydrogen site location: difference Fourier map
Least-squares matrix: full	Only H-atom coordinates refined
R[F^2 > 2σ(F^2)] = 0.028	w = 1/[σ^2(Fo^2) + (0.0532P)^2 + 0.0676P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.078	(Δ/σ)max = 0.001
S = 1.07	Δρmax = 0.48 e Å^−3
6327 reflections	Δρmin = −0.21 e Å^−3
229 parameters	Absolute structure: Flack x determined using 2532 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
0 restraints	Absolute structure parameter: −0.06 (11)
Primary atom site location: dual

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
O5	0.53512 (2)	0.85824 (7)	0.30684 (14)	0.01359 (10)
O1	0.57740 (2)	0.75786 (7)	−0.19051 (13)	0.01356 (10)
O4	0.57101 (2)	0.48652 (7)	0.35082 (15)	0.01548 (11)
O6	0.44216 (2)	0.87053 (8)	0.11308 (16)	0.01735 (12)
O3	0.67143 (2)	0.61520 (7)	0.20889 (16)	0.01722 (12)
O7	0.61659 (2)	0.33718 (7)	0.70252 (15)	0.01718 (11)
O2	0.65132 (2)	0.82976 (8)	−0.22328 (16)	0.01889 (12)
N1	0.65040 (2)	0.15662 (7)	1.09411 (15)	0.01225 (11)
C3	0.58680 (2)	0.58599 (8)	0.16891 (16)	0.01144 (11)
C2	0.62876 (2)	0.64171 (8)	0.11053 (16)	0.01192 (11)
C7	0.68004 (2)	0.24041 (8)	0.94740 (16)	0.01155 (11)
C1	0.62320 (3)	0.75137 (8)	−0.11130 (16)	0.01272 (12)
C5	0.51482 (2)	0.74076 (8)	0.15229 (17)	0.01210 (11)
C12	0.65971 (3)	0.33865 (8)	0.72107 (17)	0.01203 (11)
C4	0.55152 (2)	0.65769 (8)	−0.01596 (16)	0.01175 (11)
C11	0.66405 (3)	0.06107 (8)	1.29354 (18)	0.01417 (12)
C6	0.47830 (3)	0.80348 (9)	−0.04281 (18)	0.01481 (13)
C8	0.72665 (3)	0.23090 (10)	1.00474 (18)	0.01525 (13)
C10	0.71033 (3)	0.04775 (9)	1.35706 (18)	0.01561 (13)
C9	0.74185 (3)	0.13455 (10)	1.2133 (2)	0.01716 (14)
H5A	0.4994 (6)	0.6696 (17)	0.282 (3)	0.021*
H6	0.4491 (6)	0.949 (2)	0.184 (4)	0.026*
H4A	0.5380 (5)	0.5807 (18)	−0.146 (4)	0.021*
H11	0.6407 (5)	0.0027 (17)	1.385 (4)	0.021*
H8	0.7473 (5)	0.2898 (19)	0.900 (3)	0.021*
H6A	0.4653 (5)	0.7282 (18)	−0.153 (4)	0.021*
H1	0.6213 (5)	0.1675 (17)	1.067 (4)	0.021*
H6B	0.4918 (5)	0.8700 (18)	−0.173 (4)	0.021*
H10	0.7216 (6)	−0.0198 (18)	1.488 (4)	0.021*
H9	0.7742 (5)	0.1280 (18)	1.261 (3)	0.021*
H5	0.5499 (5)	0.8266 (19)	0.436 (4)	0.026*
H3	0.6736 (6)	0.539 (2)	0.335 (4)	0.026*
H4	0.5910 (6)	0.449 (2)	0.460 (4)	0.026*
O8	0.68761 (2)	0.40848 (7)	0.57260 (14)	0.01609 (11)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O5	0.0154 (2)	0.0132 (2)	0.0121 (2)	0.00011 (18)	−0.00343 (18)	0.00037 (18)
O1	0.0120 (2)	0.0164 (2)	0.0123 (2)	0.00059 (18)	−0.00023 (17)	0.00387 (19)
O4	0.0119 (2)	0.0148 (2)	0.0198 (3)	−0.00118 (17)	−0.00109 (19)	0.0076 (2)
O6	0.0099 (2)	0.0166 (2)	0.0255 (3)	0.00057 (18)	−0.0002 (2)	−0.0053 (2)
O3	0.0101 (2)	0.0211 (3)	0.0205 (3)	0.00022 (18)	−0.0012 (2)	0.0085 (2)
O7	0.0112 (2)	0.0208 (3)	0.0196 (3)	0.00122 (18)	−0.0005 (2)	0.0078 (2)
O2	0.0163 (2)	0.0214 (3)	0.0190 (3)	−0.0019 (2)	0.0028 (2)	0.0078 (2)
N1	0.0111 (2)	0.0127 (2)	0.0130 (3)	0.00030 (18)	0.00018 (19)	0.0023 (2)
C3	0.0109 (2)	0.0111 (2)	0.0123 (3)	0.0001 (2)	−0.0004 (2)	0.0017 (2)
C2	0.0107 (2)	0.0127 (3)	0.0125 (3)	0.0004 (2)	0.0000 (2)	0.0022 (2)
C7	0.0111 (2)	0.0121 (3)	0.0114 (3)	0.0006 (2)	0.0001 (2)	0.0016 (2)
C1	0.0123 (3)	0.0140 (3)	0.0118 (3)	0.0008 (2)	0.0007 (2)	0.0017 (2)
C5	0.0108 (2)	0.0122 (2)	0.0133 (3)	−0.0002 (2)	−0.0004 (2)	0.0012 (2)
C12	0.0127 (3)	0.0116 (2)	0.0118 (3)	0.0008 (2)	−0.0008 (2)	0.0014 (2)
C4	0.0110 (3)	0.0122 (3)	0.0121 (3)	−0.0001 (2)	−0.0011 (2)	0.0012 (2)
C11	0.0150 (3)	0.0140 (3)	0.0135 (3)	0.0005 (2)	0.0005 (2)	0.0035 (2)
C6	0.0110 (3)	0.0165 (3)	0.0169 (3)	0.0020 (2)	−0.0026 (2)	−0.0019 (2)
C8	0.0115 (3)	0.0183 (3)	0.0160 (3)	0.0010 (2)	0.0002 (2)	0.0042 (3)
C10	0.0153 (3)	0.0169 (3)	0.0147 (3)	0.0038 (2)	−0.0002 (2)	0.0036 (2)
C9	0.0126 (3)	0.0217 (3)	0.0172 (3)	0.0034 (2)	−0.0002 (2)	0.0053 (3)
O8	0.0139 (2)	0.0174 (2)	0.0170 (2)	−0.00192 (19)	−0.0004 (2)	0.0064 (2)

Geometric parameters (Å, º)

O5—C5	1.4258 (10)	C2—C1	1.4567 (11)
O5—H5	0.797 (18)	C7—C12	1.5135 (10)
O1—C1	1.3832 (9)	C7—C8	1.3836 (10)
O1—C4	1.4423 (9)	C5—C4	1.5303 (10)
O4—C3	1.3309 (9)	C5—C6	1.5157 (11)
O4—H4	0.846 (18)	C5—H5A	0.999 (16)
O6—C6	1.4202 (10)	C12—O8	1.2463 (10)
O6—H6	0.818 (18)	C4—H4A	1.012 (17)
O3—C2	1.3456 (9)	C11—C10	1.3828 (11)
O3—H3	0.922 (18)	C11—H11	0.963 (16)
O7—C12	1.2560 (9)	C6—H6A	0.942 (16)
O2—C1	1.2083 (10)	C6—H6B	0.947 (17)
N1—C7	1.3439 (10)	C8—C9	1.3912 (12)
N1—C11	1.3424 (10)	C8—H8	0.946 (16)
N1—H1	0.861 (15)	C10—C9	1.3882 (12)
C3—C2	1.3500 (10)	C10—H10	0.933 (16)
C3—C4	1.4956 (10)	C9—H9	0.969 (15)
C5—O5—H5	109.6 (12)	O8—C12—O7	127.99 (7)
C1—O1—C4	108.73 (6)	O8—C12—C7	116.41 (7)
C3—O4—H4	115.4 (12)	O1—C4—C3	104.63 (6)
C6—O6—H6	114.2 (12)	O1—C4—C5	109.98 (6)
C2—O3—H3	114.9 (10)	O1—C4—H4A	107.5 (10)
C7—N1—H1	119.1 (11)	C3—C4—C5	113.28 (6)
C11—N1—C7	122.76 (7)	C3—C4—H4A	108.2 (9)
C11—N1—H1	118.1 (12)	C5—C4—H4A	112.8 (9)
O4—C3—C2	134.47 (7)	N1—C11—C10	119.72 (7)
O4—C3—C4	115.96 (6)	N1—C11—H11	117.6 (10)
C2—C3—C4	109.57 (6)	C10—C11—H11	122.6 (10)
O3—C2—C3	133.98 (7)	O6—C6—C5	111.66 (7)
O3—C2—C1	118.21 (6)	O6—C6—H6A	107.7 (10)
C3—C2—C1	107.81 (6)	O6—C6—H6B	111.1 (10)
N1—C7—C12	116.74 (6)	C5—C6—H6A	109.7 (10)
N1—C7—C8	119.43 (7)	C5—C6—H6B	110.1 (9)
C8—C7—C12	123.82 (7)	H6A—C6—H6B	106.3 (14)
O1—C1—C2	109.22 (6)	C7—C8—C9	119.21 (7)
O2—C1—O1	120.52 (7)	C7—C8—H8	118.8 (9)
O2—C1—C2	130.27 (7)	C9—C8—H8	121.9 (9)
O5—C5—C4	110.49 (6)	C11—C10—C9	119.08 (7)
O5—C5—C6	108.21 (6)	C11—C10—H10	122.9 (10)
O5—C5—H5A	111.5 (9)	C9—C10—H10	118.0 (10)
C4—C5—H5A	107.7 (9)	C8—C9—H9	120.7 (10)
C6—C5—C4	111.30 (6)	C10—C9—C8	119.78 (7)
C6—C5—H5A	107.7 (9)	C10—C9—H9	119.5 (10)
O7—C12—C7	115.59 (7)
O5—C5—C4—O1	−53.40 (8)	C7—N1—C11—C10	0.89 (12)
O5—C5—C4—C3	63.27 (8)	C7—C8—C9—C10	1.14 (14)
O5—C5—C6—O6	−63.17 (8)	C1—O1—C4—C3	−2.12 (8)
O4—C3—C2—O3	2.23 (17)	C1—O1—C4—C5	119.85 (6)
O4—C3—C2—C1	−178.82 (9)	C12—C7—C8—C9	−178.57 (8)
O4—C3—C4—O1	−179.62 (6)	C4—O1—C1—O2	−177.68 (8)
O4—C3—C4—C5	60.60 (9)	C4—O1—C1—C2	2.32 (8)
O3—C2—C1—O1	177.57 (7)	C4—C3—C2—O3	−178.75 (9)
O3—C2—C1—O2	−2.42 (14)	C4—C3—C2—C1	0.19 (9)
N1—C7—C12—O7	3.36 (10)	C4—C5—C6—O6	175.25 (6)
N1—C7—C12—O8	−175.20 (7)	C11—N1—C7—C12	177.63 (7)
N1—C7—C8—C9	0.03 (12)	C11—N1—C7—C8	−1.07 (12)
N1—C11—C10—C9	0.33 (13)	C11—C10—C9—C8	−1.32 (13)
C3—C2—C1—O1	−1.57 (9)	C6—C5—C4—O1	66.84 (8)
C3—C2—C1—O2	178.44 (9)	C6—C5—C4—C3	−176.49 (6)
C2—C3—C4—O1	1.16 (8)	C8—C7—C12—O7	−178.01 (8)
C2—C3—C4—C5	−118.61 (7)	C8—C7—C12—O8	3.44 (11)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5A···O4^i	1.00 (2)	2.52 (2)	3.3796 (10)	144 (1)
O6—H6···O5^ii	0.82 (2)	1.91 (2)	2.7260 (9)	173 (2)
C11—H11···O2^iii	0.96 (2)	2.45 (2)	3.1278 (10)	127 (1)
C6—H6A···O7^iv	0.94 (2)	2.55 (2)	3.2704 (10)	134 (1)
N1—H1···O6^v	0.86 (2)	1.89 (2)	2.7026 (9)	157 (2)
C9—H9···O8^vi	0.97 (2)	2.42 (2)	3.0820 (10)	125 (1)
O5—H5···O1^vii	0.80 (2)	2.03 (2)	2.8179 (9)	169 (2)
O3—H3···O8	0.92 (2)	1.68 (2)	2.5937 (9)	170 (2)
O4—H4···O7	0.85 (2)	1.71 (2)	2.5216 (9)	161 (2)

Symmetry codes: (i) −x+1, −y+1, z; (ii) −x+1, −y+2, z; (iii) x, y−1, z+2; (iv) −x+1, −y+1, z−1; (v) −x+1, −y+1, z+1; (vi) −x+3/2, y−1/2, −z+2; (vii) x, y, z+1.