Hirshfeld atom refinement for modelling strong hydrogen bonds

High-resolution low-temperature synchrotron X-ray diffraction data of the salt L-phenylalaninium hydrogen maleate are used to test the new automated iterative Hirshfeld atom refinement (HAR) procedure for the modelling of strong hydrogen bonds. The HAR models used present the first examples of Z′ > 1 treatments in the framework of wavefunction-based refinement methods. L-Phenylalaninium hydrogen maleate exhibits several hydrogen bonds in its crystal structure, of which the shortest and the most challenging to model is the O—H...O intramolecular hydrogen bond present in the hydrogen maleate anion (O...O distance is about 2.41 Å). In particular, the reconstruction of the electron density in the hydrogen maleate moiety and the determination of hydrogen-atom properties [positions, bond distances and anisotropic displacement parameters (ADPs)] are the focus of the study. For comparison to the HAR results, different spherical (independent atom model, IAM) and aspherical (free multipole model, MM; transferable aspherical atom model, TAAM) X-ray refinement techniques as well as results from a low-temperature neutron-diffraction experiment are employed. Hydrogen-atom ADPs are furthermore compared to those derived from a TLS/rigid-body (SHADE) treatment of the X-ray structures. The reference neutron-diffraction experiment reveals a truly symmetric hydrogen bond in the hydrogen maleate anion. Only with HAR is it possible to freely refine hydrogen-atom positions and ADPs from the X-ray data, which leads to the best electron-density model and the closest agreement with the structural parameters derived from the neutron-diffraction experiment, e.g. the symmetric hydrogen position can be reproduced. The multipole-based refinement techniques (MM and TAAM) yield slightly asymmetric positions, whereas the IAM yields a significantly asymmetric position.

Computing details

Data collection: MAATEL/ANSTO control program for neutron. Data reduction: argonne_boxes (Wilkinson et al., 1988) & LaueG (Piltz, 2011) for neutron. Program(s) used to refine structure: CRYSTALS (Betteridge et al., 2003) for neutron.

(xray)

Crystal data

C9H12NO2·C4H3O4	F(000) = 296
Mr = 281.27	Dx = 1.459 Mg m^−3
Monoclinic, P21	Synchrotron radiation, λ = 0.3540 Å
Hall symbol: P 2yb	Cell parameters from 124185 reflections
a = 10.905 (2) Å	θ = 0.9–26.3°
b = 5.2338 (10) Å	µ = 0.04 mm^−1
c = 11.439 (2) Å	T = 25 K
β = 101.36 (3)°	Block, colorless
V = 640.1 (2) Å^3	0.20 × 0.10 × 0.03 mm
Z = 2

Data collection

SPring-8 BL02B1 Imaging plate camera diffractometer	Rint = 0.022
Radiation source: synchrotron	θmax = 23.2°, θmin = 0.9°
ω scans	h = −24→23
124185 measured reflections	k = −11→11
7820 independent reflections	l = −24→25
7370 reflections with I > 2σ(I)

Refinement

Refinement on F	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.020	H atoms treated by a mixture of independent and constrained refinement
S = 0.86	w = 1/σ(F)
7370 reflections	(Δ/σ)max < 0.001
105 parameters	Δρmax = 0.22 e Å^−3
0 restraints	Δρmin = −0.20 e Å^−3
211 constraints	Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.3 (3)

Special details

Refinement. . Hirshfeld atom refinement:. Uses aspherical atomic scattering factors obtained from Hirshfeld partitioning of a Gaussian quantum chemical wavefunction.. Hirshfeld weight functions obtained from spherically averaged unrestricted atomic densities.. Wavefunction type: rks becke88lyp using cluster charges, radius=8.0 angstrom. Gaussian basis set: cc-pVTZ. Refinement based on |F| with weight=1/σ(|F|). Negative |F|2 were pruned from the data. |F| < 4.0 σ(|F|) were pruned from the data. Eigenvalues < 0.1E-04 removed from normal equations. Reflection used in the refinement appear below. Refined using the Tonto program:. Version: 3.2 ($Rev: 4042 $). Platform: GNU-mpif90-on-LINUX. Build-date: Thu May 30 16:50:27 WST 2013

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

	x	y	z	Biso*/Beq
O1	0.09516 (2)	0.4786 (3)	−0.38078 (2)
O2	0.12318 (2)	0.5095 (3)	−0.58415 (2)
O3	0.13521 (2)	0.7084 (3)	−0.21652 (2)
O4	0.17832 (2)	0.8004 (3)	−0.70331 (2)
C1	0.13464 (2)	0.6824 (3)	−0.32530 (2)
C2	0.18015 (2)	0.9012 (3)	−0.38884 (2)
C3	0.18958 (2)	0.9238 (3)	−0.50385 (2)
C4	0.16122 (2)	0.7356 (3)	−0.60348 (2)
H1	0.108 (1)	0.490 (3)	−0.482 (1)
H2	0.205 (1)	1.067 (2)	−0.3353 (8)
H3	0.223 (1)	1.103 (2)	−0.5310 (8)
O5	0.22350 (2)	1.0886 (3)	−0.09277 (2)
O6	0.09514 (2)	0.9225 (3)	0.01777 (2)
N1	0.12387 (2)	1.2983 (3)	0.17420 (2)
C5	0.16349 (2)	1.0922 (3)	−0.00443 (2)
C6	0.18067 (2)	1.3373 (3)	0.06745 (2)
C7	0.31499 (2)	1.4370 (3)	0.10137 (2)
C8	0.40364 (2)	1.2627 (3)	0.18246 (2)
C9	0.41968 (2)	1.2878 (3)	0.30620 (2)
C10	0.49986 (3)	1.1253 (3)	0.38180 (2)
C11	0.56582 (2)	0.9369 (3)	0.33443 (2)
C12	0.55181 (2)	0.9116 (3)	0.21135 (2)
C13	0.47072 (2)	1.0735 (3)	0.13591 (2)
H41	0.137 (1)	1.462 (2)	0.2237 (9)
H42	0.1611 (9)	1.145 (2)	0.2191 (9)
H43	0.0284 (8)	1.259 (2)	0.1514 (9)
H5	0.191 (1)	0.936 (3)	−0.147 (1)
H6	0.1241 (8)	1.484 (2)	0.0128 (8)
H71	0.3113 (9)	1.624 (2)	0.1428 (8)
H72	0.3460 (9)	1.469 (2)	0.0183 (7)
H9	0.3685 (8)	1.440 (2)	0.3399 (8)
H10	0.5120 (9)	1.146 (2)	0.4803 (7)
H11	0.6284 (9)	0.811 (2)	0.3954 (8)
H12	0.6043 (9)	0.768 (2)	0.1718 (8)
H13	0.4605 (9)	1.056 (2)	0.0400 (8)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.01646 (7)	0.01068 (7)	0.00853 (7)	−0.00359 (6)	0.00372 (6)	−0.00249 (5)
O2	0.01926 (8)	0.01050 (7)	0.00815 (7)	−0.00152 (6)	0.00366 (6)	−0.00258 (6)
O3	0.01414 (7)	0.01251 (7)	0.00739 (7)	−0.00203 (5)	0.00355 (5)	−0.00217 (5)
O4	0.01598 (7)	0.01452 (8)	0.00723 (7)	0.00031 (6)	0.00405 (6)	−0.00077 (6)
C1	0.00959 (7)	0.00972 (8)	0.00675 (8)	−0.00052 (6)	0.00211 (6)	−0.00174 (6)
C2	0.01340 (8)	0.00952 (8)	0.00690 (8)	−0.00159 (6)	0.00205 (6)	−0.00159 (6)
C3	0.01380 (8)	0.01006 (8)	0.00713 (8)	−0.00141 (7)	0.00237 (6)	−0.00117 (6)
C4	0.01101 (7)	0.01069 (8)	0.00660 (8)	0.00068 (6)	0.00212 (6)	−0.00140 (6)
H1	0.032229	0.021593	0.014323	−0.004560	0.007500	−0.002937
H2	0.050908	0.020288	0.020426	−0.011301	0.008015	−0.008378
H3	0.049493	0.021023	0.023246	−0.012974	0.010398	0.000701
O5	0.01394 (7)	0.01418 (8)	0.00831 (7)	−0.00443 (6)	0.00508 (5)	−0.00296 (6)
O6	0.01046 (6)	0.00952 (6)	0.00873 (7)	−0.00194 (5)	0.00323 (5)	−0.00132 (5)
N1	0.00898 (6)	0.01308 (8)	0.00862 (7)	0.00013 (6)	0.00222 (5)	−0.00330 (6)
C5	0.00767 (6)	0.00881 (7)	0.00615 (7)	−0.00059 (6)	0.00126 (5)	−0.00076 (6)
C6	0.00766 (7)	0.00837 (7)	0.00778 (8)	0.00008 (6)	0.00032 (5)	−0.00099 (6)
C7	0.00835 (7)	0.00894 (8)	0.00954 (8)	−0.00074 (6)	0.00049 (6)	−0.00018 (6)
C8	0.00734 (6)	0.00977 (8)	0.00804 (8)	0.00020 (6)	0.00105 (5)	−0.00087 (6)
C9	0.01081 (8)	0.01369 (9)	0.00832 (8)	0.00277 (7)	0.00050 (6)	−0.00176 (7)
C10	0.01242 (8)	0.0170 (1)	0.00842 (9)	0.00363 (7)	0.00063 (7)	−0.00010 (7)
C11	0.01054 (8)	0.0147 (1)	0.01095 (9)	0.00310 (7)	0.00121 (6)	0.00161 (8)
C12	0.01130 (8)	0.0143 (1)	0.01159 (9)	0.00439 (7)	0.00238 (7)	−0.00025 (8)
C13	0.01035 (7)	0.01349 (9)	0.00875 (8)	0.00289 (7)	0.00215 (6)	−0.00074 (7)
H41	0.028772	0.019697	0.020108	−0.001366	0.006197	−0.008044
H42	0.024967	0.020437	0.019232	0.004187	0.004838	0.003742
H43	0.015442	0.030540	0.021418	−0.002431	0.002841	−0.001821
H5	0.027483	0.022141	0.018063	−0.005753	0.005664	−0.007252
H6	0.024663	0.020767	0.020108	0.003306	0.001461	0.002606
H71	0.029741	0.019137	0.027174	0.000570	0.002775	−0.008497
H72	0.027461	0.034190	0.015848	−0.001989	0.007720	0.001710
H9	0.029896	0.024316	0.020637	0.007224	0.006926	−0.005617
H10	0.031200	0.031722	0.011758	0.002231	0.004056	−0.002203
H11	0.026694	0.026469	0.020663	0.006578	0.001406	0.003709
H12	0.028694	0.026002	0.023556	0.007786	0.008678	−0.005035
H13	0.031482	0.030288	0.012221	0.002900	0.005585	−0.003120

Geometric parameters (Å, º)

O1—C1	1.2721 (19)	C5—C6	1.5153 (19)
O1—H1	1.192 (8)	C6—C7	1.5312 (9)
O2—C4	1.287 (2)	C6—H6	1.100 (5)
O2—H1	1.219 (8)	C7—C8	1.5080 (14)
O3—C1	1.2506 (5)	C7—H71	1.089 (5)
O4—C4	1.2401 (7)	C7—H72	1.082 (4)
C1—C2	1.4927 (17)	C8—C9	1.3978 (5)
C2—C3	1.3449 (5)	C8—C13	1.3974 (16)
C2—H2	1.065 (5)	C9—C10	1.3921 (14)
C3—C4	1.4919 (15)	C9—H9	1.085 (5)
C3—H3	1.074 (11)	C10—C11	1.3917 (16)
O5—C5	1.3078 (2)	C10—H10	1.114 (4)
O5—H5	1.026 (7)	C11—C12	1.3923 (5)
O6—C5	1.2180 (17)	C11—H11	1.096 (5)
N1—H41	1.022 (10)	C12—C13	1.3943 (14)
N1—H42	0.996 (10)	C12—H12	1.095 (5)
N1—H43	1.044 (9)	C13—H13	1.085 (9)
O1—C1—O3	121.50 (12)	C4—C3—H3	112.7 (5)
O2—C4—O4	121.44 (11)	C5—C6—H6	106.7 (5)
O5—C5—O6	124.79 (13)	C6—C7—H71	107.5 (5)
O1—C1—C2	120.84 (6)	C6—C7—H72	106.2 (5)
O2—C4—C3	120.07 (6)	C7—C6—H6	107.9 (5)
O3—C1—C2	117.65 (13)	C8—C7—H71	110.4 (5)
O4—C4—C3	118.47 (13)	C8—C7—H72	111.1 (5)
O5—C5—C6	113.85 (11)	C8—C9—H9	117.3 (5)
O6—C5—C6	121.30 (6)	C8—C13—H13	119.1 (5)
O1—H1—O2	178 (1)	C9—C10—H10	120.4 (6)
C1—O1—H1	110.4 (7)	C10—C9—H9	122.1 (5)
C4—O2—H1	110.5 (7)	C10—C11—H11	119.0 (5)
C5—O5—H5	108.1 (6)	C11—C10—H10	119.6 (6)
C1—C2—C3	129.84 (12)	C11—C12—H12	121.4 (5)
C2—C3—C4	130.16 (13)	C12—C11—H11	121.1 (5)
C5—C6—C7	115.84 (7)	C12—C13—H13	120.2 (5)
C6—C7—C8	114.53 (11)	C13—C12—H12	118.7 (5)
C7—C8—C9	120.21 (10)	C6—N1—H41	107.8 (6)
C7—C8—C13	120.97 (5)	C6—N1—H42	109.9 (5)
C8—C9—C10	120.64 (10)	C6—N1—H43	112.3 (5)
C8—C13—C12	120.70 (5)	H71—C7—H72	106.7 (8)
C9—C8—C13	118.82 (9)	H41—N1—H42	113.2 (8)
C9—C10—C11	120.04 (5)	H41—N1—H43	109.1 (9)
C10—C11—C12	119.93 (9)	H42—N1—H43	104.7 (9)
C11—C12—C13	119.87 (10)	N1—C6—C5	107.59 (11)
C1—C2—H2	114.5 (5)	N1—C6—C7	111.77 (2)
C2—C3—H3	117.1 (5)	N1—C6—H6	106.5 (5)
C3—C2—H2	115.6 (5)
O3—C1—O1—H1	−176.8 (7)	C7—C8—C9—H9	−1.9 (6)
O4—C4—O2—H1	−177.5 (7)	C7—C8—C13—H13	1.8 (6)
O6—C5—O5—H5	9.5 (8)	C8—C7—C6—H6	176.9 (5)
O1—C1—C2—C3	−1.09 (4)	C8—C9—C10—H10	−180.0 (6)
O2—C4—C3—C2	−1.36 (4)	C8—C13—C12—H12	−178.7 (7)
O3—C1—C2—C3	179.88 (8)	C9—C8—C7—H71	31.2 (6)
O4—C4—C3—C2	−179.50 (3)	C9—C8—C7—H72	149.4 (6)
O5—C5—C6—C7	−45.70 (3)	C9—C8—C13—H13	−178.4 (6)
O6—C5—C6—C7	137.11 (2)	C9—C10—C11—H11	−180.0 (6)
O1—C1—C2—H2	175.7 (7)	C10—C11—C12—H12	178.5 (7)
O2—C4—C3—H3	178.1 (7)	C11—C10—C9—H9	−178.5 (6)
O3—C1—C2—H2	−3.3 (7)	C11—C12—C13—H13	179.1 (6)
O4—C4—C3—H3	−0.0 (7)	C12—C11—C10—H10	−179.5 (6)
O5—C5—C6—H6	74.4 (5)	C13—C8—C7—H71	−148.9 (6)
O6—C5—C6—H6	−102.8 (5)	C13—C8—C7—H72	−30.7 (6)
O5—C5—C6—N1	−171.56 (2)	C13—C8—C9—H9	178.3 (6)
O6—C5—C6—N1	11.24 (3)	C13—C12—C11—H11	179.5 (7)
C2—C1—O1—H1	4.1 (7)	C5—C6—N1—H41	179.0 (6)
C3—C4—O2—H1	4.5 (7)	C5—C6—N1—H42	55.2 (7)
C6—C5—O5—H5	−167.6 (8)	C5—C6—N1—H43	−60.9 (7)
C1—C2—C3—C4	−1.99 (5)	C7—C6—N1—H41	50.7 (6)
C5—C6—C7—C8	−63.64 (3)	C7—C6—N1—H42	−73.0 (7)
C6—C7—C8—C9	−90.20 (3)	C7—C6—N1—H43	170.9 (7)
C6—C7—C8—C13	89.62 (3)	H2—C2—C3—H3	2 (1)
C7—C8—C9—C10	179.03 (3)	H6—C6—C7—H71	53.8 (8)
C7—C8—C13—C12	−179.49 (10)	H6—C6—C7—H72	−60.1 (8)
C8—C9—C10—C11	0.53 (4)	H9—C9—C10—H10	1.2 (9)
C8—C13—C12—C11	0.41 (4)	H10—C10—C11—H11	0.4 (9)
C9—C8—C13—C12	0.32 (4)	H11—C11—C12—H12	−1 (1)
C9—C10—C11—C12	0.19 (16)	H12—C12—C13—H13	−0.0 (9)
C10—C9—C8—C13	−0.79 (4)	H41—N1—C6—H6	−66.8 (9)
C10—C11—C12—C13	−0.68 (4)	H42—N1—C6—H6	169.4 (9)
C1—C2—C3—H3	178.6 (7)	H43—N1—C6—H6	53.3 (9)
C4—C3—C2—H2	−178.8 (7)	N1—C6—C7—C8	60.06 (14)
C5—C6—C7—H71	173.3 (6)	N1—C6—C7—H71	−63.0 (6)
C5—C6—C7—H72	59.4 (6)	N1—C6—C7—H72	−176.9 (6)

(neutron)

Crystal data

C9H12NO2·C4H3O4	F(000) = 152
Mr = 281.27	Dx = 1.459 Mg m^−3
Monoclinic, P21	Neutron radiation, λ = 0.85 Å
Hall symbol: P 2yb	Cell parameters from 124185 reflections
a = 10.905 (2) Å	θ = 0.9–26.3°
b = 5.2338 (10) Å	µ = 0.0 mm^−1
c = 11.439 (2) Å	T = 25 K
β = 101.36 (3)°	Block, colorless
V = 640.1 (2) Å^3	1.8 × 1.6 × 0.7 mm
Z = 2

Data collection

KOALA diffractometer	Rint = 0.064
Radiation source: nuclear reactor, OPAL reactor, ANSTO, Lucas Heights, Australia	θmax = 71.0°
Laue scans	h = −18→18
31922 measured reflections	k = −18→18
2487 independent reflections	l = −18→18
2231 reflections with > 3σ(F)

Refinement

Refinement on F	Hydrogen site location: difference Fourier map
Least-squares matrix: full	All H-atom parameters refined
R[F^2 > 2σ(F^2)] = 0.029	Method, part 1, Chebychev polynomial, (Watkin, 1994, Prince, 1982) [weight] = 1.0/[A0*T0(x) + A1*T1(x) ··· + An-1]*Tn-1(x)] where Ai are the Chebychev coefficients listed below and x = F /Fmax Method = Robust Weighting (Prince, 1982) W = [weight] * [1-(deltaF/6*sigmaF)^2]^2 Ai are: 4.39 -0.947 1.73 1.80
wR(F^2) = 0.029	(Δ/σ)max = 0.0002806
S = 1.00	Δρmax = 0.96 e Å^−3
2231 reflections	Δρmin = −1.00 e Å^−3
317 parameters	Extinction correction: Larson (1970), Equation 22
1 restraint	Extinction coefficient: 5.6 (10)
Primary atom site location: isomorphous structure methods

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

	x	y	z	Uiso*/Ueq
O1	0.09398 (11)	0.4797 (3)	−0.38042 (10)	0.0062
C1	0.13435 (9)	0.6832 (2)	−0.32466 (9)	0.0049
O3	0.13502 (11)	0.7093 (3)	−0.21586 (10)	0.0070
C2	0.18056 (9)	0.9027 (2)	−0.38813 (9)	0.0061
C3	0.18958 (9)	0.9259 (2)	−0.50303 (8)	0.0062
C4	0.16080 (9)	0.7375 (2)	−0.60262 (8)	0.0051
O2	0.12246 (11)	0.5108 (3)	−0.58414 (10)	0.0074
O4	0.17820 (12)	0.8024 (3)	−0.70279 (10)	0.0077
H3	0.2224 (3)	1.1068 (5)	−0.5314 (2)	0.0220
H2	0.2053 (3)	1.0688 (5)	−0.3314 (2)	0.0218
H1	0.1053 (3)	0.4899 (5)	−0.4834 (3)	0.0200
O5	0.22401 (11)	1.0900 (3)	−0.09239 (10)	0.0075
C5	0.16363 (9)	1.0948 (2)	−0.00459 (8)	0.0043
O6	0.09486 (10)	0.9256 (3)	0.01774 (10)	0.0066
C6	0.18084 (8)	1.3412 (2)	0.06700 (8)	0.0041
N1	0.12404 (6)	1.3033 (2)	0.17391 (6)	0.0060
H41	0.1348 (3)	1.4678 (6)	0.2256 (2)	0.0206
H42	0.1613 (3)	1.1467 (6)	0.2250 (2)	0.0214
H43	0.0294 (2)	1.2663 (6)	0.1498 (2)	0.0200
C7	0.31497 (9)	1.4413 (2)	0.10135 (8)	0.0053
C8	0.40380 (9)	1.2666 (2)	0.18219 (8)	0.0048
C9	0.41924 (9)	1.2907 (2)	0.30587 (8)	0.0064
C10	0.49976 (10)	1.1277 (3)	0.38181 (9)	0.0071
C11	0.56617 (9)	0.9395 (3)	0.33456 (8)	0.0068
C12	0.55255 (9)	0.9154 (3)	0.21131 (9)	0.0074
C13	0.47136 (9)	1.0775 (2)	0.13570 (9)	0.0062
H13	0.4592 (3)	1.0570 (6)	0.0392 (2)	0.0217
H12	0.6056 (3)	0.7704 (6)	0.1741 (3)	0.0242
H11	0.6289 (3)	0.8129 (7)	0.3939 (2)	0.0250
H10	0.5115 (3)	1.1508 (7)	0.4775 (2)	0.0255
H9	0.3696 (3)	1.4408 (6)	0.3429 (2)	0.0225
H71	0.3114 (3)	1.6287 (5)	0.1434 (2)	0.0199
H72	0.3472 (2)	1.4738 (6)	0.0173 (2)	0.0192
H6	0.1255 (2)	1.4865 (5)	0.0116 (2)	0.0158
H5	0.1928 (2)	0.9300 (6)	−0.1457 (2)	0.0185

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0087 (4)	0.0063 (4)	0.0040 (4)	−0.0018 (3)	0.0020 (3)	−0.0013 (3)
C1	0.0059 (3)	0.0047 (3)	0.0043 (3)	−0.0003 (2)	0.0017 (3)	−0.0008 (2)
O3	0.0090 (4)	0.0078 (4)	0.0042 (4)	−0.0015 (3)	0.0014 (4)	−0.0015 (3)
C2	0.0077 (3)	0.0054 (3)	0.0054 (3)	−0.0010 (3)	0.0020 (3)	−0.0006 (3)
C3	0.0093 (4)	0.0048 (3)	0.0047 (3)	−0.0018 (3)	0.0017 (3)	−0.0006 (3)
C4	0.0060 (3)	0.0062 (3)	0.0036 (3)	0.0002 (3)	0.0018 (3)	−0.0004 (3)
O2	0.0114 (4)	0.0057 (3)	0.0053 (4)	−0.0017 (3)	0.0020 (4)	−0.0016 (3)
O4	0.0111 (4)	0.0072 (4)	0.0048 (4)	−0.0007 (3)	0.0019 (3)	−0.0001 (3)
H3	0.0347 (13)	0.0136 (8)	0.0181 (9)	−0.0091 (8)	0.0061 (10)	0.0017 (7)
H2	0.0375 (14)	0.0145 (8)	0.0142 (8)	−0.0080 (9)	0.0070 (9)	−0.0063 (7)
H1	0.0220 (10)	0.0150 (8)	0.0229 (10)	−0.0033 (7)	0.0043 (9)	−0.0007 (7)
O5	0.0090 (4)	0.0086 (4)	0.0054 (4)	−0.0031 (3)	0.0022 (4)	−0.0015 (3)
C5	0.0049 (3)	0.0044 (3)	0.0038 (3)	−0.0005 (2)	0.0012 (3)	−0.0002 (2)
O6	0.0070 (4)	0.0063 (3)	0.0065 (4)	−0.0025 (3)	0.0015 (3)	−0.0014 (3)
C6	0.0040 (3)	0.0044 (3)	0.0036 (3)	−0.0002 (2)	0.0002 (3)	0.0004 (2)
N1	0.0050 (2)	0.0079 (2)	0.0052 (2)	−0.00027 (19)	0.0013 (2)	−0.00171 (19)
H41	0.0233 (11)	0.0191 (9)	0.0201 (9)	−0.0018 (8)	0.0058 (9)	−0.0107 (8)
H42	0.0258 (11)	0.0214 (9)	0.0172 (9)	0.0057 (8)	0.0048 (9)	0.0057 (8)
H43	0.0108 (8)	0.0277 (11)	0.0226 (10)	−0.0031 (7)	0.0061 (8)	−0.0034 (8)
C7	0.0041 (3)	0.0052 (3)	0.0065 (3)	−0.0001 (2)	0.0006 (3)	0.0003 (3)
C8	0.0046 (3)	0.0056 (3)	0.0043 (3)	0.0004 (2)	0.0011 (3)	−0.0003 (2)
C9	0.0068 (4)	0.0075 (3)	0.0047 (3)	0.0017 (3)	0.0005 (3)	−0.0006 (3)
C10	0.0072 (3)	0.0089 (3)	0.0050 (3)	0.0025 (3)	0.0010 (3)	0.0005 (3)
C11	0.0058 (3)	0.0085 (3)	0.0060 (3)	0.0025 (3)	0.0013 (3)	0.0009 (3)
C12	0.0075 (3)	0.0083 (3)	0.0062 (3)	0.0028 (3)	0.0011 (3)	0.0000 (3)
C13	0.0067 (3)	0.0076 (3)	0.0050 (3)	0.0019 (3)	0.0024 (3)	−0.0002 (2)
H13	0.0258 (12)	0.0322 (12)	0.0070 (7)	0.0086 (9)	0.0027 (8)	0.0007 (7)
H12	0.0284 (12)	0.0248 (11)	0.0201 (10)	0.0122 (9)	0.0066 (10)	−0.0036 (8)
H11	0.0253 (11)	0.0282 (11)	0.0206 (10)	0.0140 (10)	0.0021 (9)	0.0055 (9)
H10	0.0320 (13)	0.0326 (13)	0.0111 (8)	0.0103 (10)	0.0022 (9)	−0.0010 (8)
H9	0.0259 (11)	0.0241 (10)	0.0181 (9)	0.0104 (9)	0.0058 (9)	−0.0040 (8)
H71	0.0206 (10)	0.0124 (8)	0.0248 (10)	0.0006 (7)	−0.0002 (9)	−0.0037 (8)
H72	0.0178 (9)	0.0256 (11)	0.0158 (9)	−0.0006 (8)	0.0072 (8)	0.0055 (8)
H6	0.0146 (8)	0.0139 (8)	0.0180 (9)	0.0039 (6)	0.0009 (8)	0.0035 (7)
H5	0.0199 (9)	0.0188 (9)	0.0185 (9)	−0.0025 (8)	0.0081 (8)	−0.0045 (8)

Geometric parameters (Å, º)

O1—C1	1.2748 (13)	N1—H41	1.038 (2)
O1—H1	1.209 (3)	N1—H42	1.041 (3)
C1—O3	1.2507 (14)	N1—H43	1.032 (2)
C1—C2	1.4981 (14)	C7—C8	1.5089 (13)
C2—C3	1.3427 (14)	C7—H71	1.096 (3)
C2—H2	1.087 (2)	C7—H72	1.100 (3)
C3—C4	1.4926 (13)	C8—C9	1.3971 (13)
C3—H3	1.084 (3)	C8—C13	1.3999 (14)
C4—O2	1.2891 (14)	C9—C10	1.3973 (13)
C4—O4	1.2450 (15)	C9—H9	1.087 (3)
O2—H1	1.208 (3)	C10—C11	1.3933 (15)
O5—C5	1.3051 (17)	C10—H10	1.084 (3)
O5—H5	1.053 (3)	C11—C12	1.3940 (14)
C5—O6	1.2195 (15)	C11—H11	1.088 (3)
C5—C6	1.5195 (13)	C12—C13	1.3962 (13)
C6—N1	1.4890 (12)	C12—H12	1.090 (3)
C6—C7	1.5304 (13)	C13—H13	1.091 (3)
C6—H6	1.092 (2)
C1—O1—H1	111.03 (16)	C6—N1—H43	111.13 (17)
O1—C1—O3	121.54 (11)	H41—N1—H43	107.6 (2)
O1—C1—C2	120.94 (10)	H42—N1—H43	105.1 (2)
O3—C1—C2	117.51 (9)	C6—C7—C8	114.56 (8)
C1—C2—C3	129.82 (8)	C6—C7—H71	107.72 (16)
C1—C2—H2	113.08 (17)	C8—C7—H71	110.31 (15)
C3—C2—H2	117.02 (16)	C6—C7—H72	106.39 (16)
C2—C3—C4	129.96 (9)	C8—C7—H72	110.64 (16)
C2—C3—H3	117.65 (16)	H71—C7—H72	106.9 (2)
C4—C3—H3	112.39 (16)	C7—C8—C9	120.05 (8)
C3—C4—O2	120.60 (10)	C7—C8—C13	121.20 (8)
C3—C4—O4	118.35 (10)	C9—C8—C13	118.75 (8)
O2—C4—O4	121.02 (10)	C8—C9—C10	120.67 (9)
C4—O2—H1	110.85 (15)	C8—C9—H9	119.36 (16)
O2—H1—O1	176.0 (3)	C10—C9—H9	119.95 (16)
C5—O5—H5	107.88 (17)	C9—C10—C11	120.09 (9)
O5—C5—O6	124.86 (10)	C9—C10—H10	119.66 (19)
O5—C5—C6	113.79 (9)	C11—C10—H10	120.25 (18)
O6—C5—C6	121.28 (10)	C10—C11—C12	119.76 (8)
C5—C6—N1	107.60 (7)	C10—C11—H11	119.97 (18)
C5—C6—C7	116.06 (8)	C12—C11—H11	120.27 (18)
N1—C6—C7	111.47 (7)	C11—C12—C13	119.99 (9)
C5—C6—H6	106.44 (15)	C11—C12—H12	119.90 (17)
N1—C6—H6	107.28 (17)	C13—C12—H12	120.11 (17)
C7—C6—H6	107.56 (15)	C8—C13—C12	120.74 (9)
C6—N1—H41	109.83 (18)	C8—C13—H13	119.05 (16)
C6—N1—H42	112.73 (18)	C12—C13—H13	120.21 (17)
H41—N1—H42	110.2 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···O2^i	1.084	2.401	3.2404 (15)	133.1 (2)
C2—H2···O1^i	1.087	2.478	3.1705 (15)	120.4 (2)
N1—H41···C4^ii	1.038	2.390	3.3846 (15)	160.0 (2)
N1—H41···O2^ii	1.038	2.218	2.9763 (15)	128.4 (2)
N1—H41···O4^ii	1.038	1.952	2.9723 (15)	166.9 (3)
N1—H42···O4^iii	1.041	1.976	2.9803 (15)	161.2 (3)
N1—H43···O3^iv	1.032	2.100	2.9978 (15)	144.0 (2)
N1—H43···O6^iv	1.032	2.276	2.9753 (15)	123.7 (2)
C12—H12···O5^v	1.090	2.429	3.4633 (15)	157.8 (3)
C6—H6···O6^i	1.092	2.325	3.2161 (15)	137.46 (18)
O5—H5···C1	1.053	2.398	3.3949 (15)	157.6 (2)
O5—H5···O3	1.053	1.475	2.5231 (15)	173.3 (3)

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