Crystal structures and properties of derivatives of the alkaloid matrine: salts and hydrate forms

We report the crystal structures of three matrine derivatives, namely, the salts (1R,2R,9S,17S)-6-oxo-7,13-di­aza­tetra­cyclo­[7.7.1.0^2,7.0^13,17]hepta­decan-13-ium (2E)-3-(3,4-di­hydroxy­phen­yl)prop-2-enoate (matrine caffeinate) sesquihydrate, C₁₅H₂₅N₂O⁺·C₉H₇O₄⁻·1.5H₂O (Matrine–CA), and the 2-hy­droxy­benzoate (sali­cylate) monohydrate, C₁₅H₂₅N₂O⁺·C₇H₅O₃⁻·H₂O (Matrine–SA), as well as the 1.75-hydrate form, (1R,2R,9S,17S)-7,13-di­aza­tetra­cyclo­[7.7.1.0^2,7.0^13,17]hep­ta­decan-6-one 1.75-hydrate, C₁₅H₂₄N₂O·1.75H₂O (Matrine–H). Each derivative exhibited a consistent mol­ecular conformation for the matrine core, which is notably distinct from that of the anhydrous form. Notably, both salts crystallized in the ortho­rhom­bic space group P2₁2₁2₁, with an asymmetric unit featuring one cation and one anion. Within the two salt structures, inter­molecular proton transfer between matrine and the acid is observed, culminating in the formation of a matrine cation protonated at the tertiary amine N site. The Matrine–CA crystal packing is manifested as a three-dimensional (3D) network arising from one-dimensional (1D) supra­molecular helical chains, stabilized by N—H...O and O—H...O hy­dro­gen bonds. In the case of Matrine–SA, the matrine cation is inter­connected via hy­dro­gen bonds with salicylate anions and water mol­ecules, also forming a 1D helical motif. The structure of the hydrate form, Matrine–H, is reported again with the disordered solvent mol­ecules accurately located. To further elucidate the structural attributes, Hirshfeld surface analysis and fingerprint plots are employed, offering a nuanced perspective on the inter­molecular contacts and inter­actions within these crystalline forms.

Computing details

(1R,2R,9S,17S)-6-Oxo-7,13-diazatetracyclo[7.7.1.0^2,7.0^13,17]heptadecan-13-ium (2E)-3-(3,4-dihydroxyphenyl)prop-2-enoate sesquihydrate (matrine-ca)

Crystal data

C15H25N2O^+·C9H7O4^−·1.5H2O	Dx = 1.312 Mg m^−3
Mr = 455.54	Ga Kα radiation, λ = 1.34139 Å
Orthorhombic, P212121	Cell parameters from 9998 reflections
a = 8.1508 (4) Å	θ = 3.8–60.5°
b = 11.0066 (5) Å	µ = 0.50 mm^−1
c = 25.7084 (12) Å	T = 170 K
V = 2306.37 (19) Å^3	Block, colourless
Z = 4	0.05 × 0.04 × 0.03 mm
F(000) = 980

Data collection

Bruker D8 Venture diffractometer	4863 reflections with I > 2σ(I)
ω and φ scans	Rint = 0.059
Absorption correction: multi-scan (SADABS; Bruker, 2016)	θmax = 60.7°, θmin = 3.8°
Tmin = 0.699, Tmax = 0.752	h = −10→10
43143 measured reflections	k = −14→14
5269 independent reflections	l = −33→33

Refinement

Refinement on F^2	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.037	w = 1/[σ^2(Fo^2) + (0.0585P)^2 + 0.1825P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.097	(Δ/σ)max < 0.001
S = 1.08	Δρmax = 0.17 e Å^−3
5269 reflections	Δρmin = −0.26 e Å^−3
316 parameters	Absolute structure: Flack x determined using 1970 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
6 restraints	Absolute structure parameter: 0.07 (7)
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.

Refinement. Single-crystal X-ray diffraction (SCXRD) data were collected on a Bruker D8 Venture diffractometer (Bruker, Ettlingen, Germany) with Ga Kα (λ = 1.34139 Å) radiation. Using OLEX2, the crystal structure was solved using intrinsic phasing methods (SHELXT) and refined with full-matrix least-squares methods with anisotropic thermal parameters for all non-H atoms on F² using the SHELXL package. Crystal data, data collection and structure refinement details are summarized in Table 1 and hydrogen bonding parameters detailed in Tables 2–4.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
O1	0.5438 (3)	0.53361 (16)	0.49236 (6)	0.0520 (5)
N1	0.53019 (19)	0.92335 (13)	0.34514 (6)	0.0235 (3)
H1	0.438145	0.863396	0.346719	0.028*
C1	0.4718 (3)	1.04146 (18)	0.36834 (9)	0.0344 (5)
H1A	0.379672	1.073818	0.347434	0.041*
H1B	0.562011	1.101697	0.367518	0.041*
N2	0.5827 (2)	0.63595 (15)	0.41774 (6)	0.0270 (4)
C2	0.4164 (3)	1.0225 (2)	0.42375 (9)	0.0397 (5)
H2A	0.322513	0.965468	0.424327	0.048*
H2B	0.379183	1.100876	0.438515	0.048*
C3	0.5556 (3)	0.9716 (2)	0.45698 (9)	0.0395 (5)
H3A	0.513707	0.953659	0.492298	0.047*
H3B	0.643087	1.033512	0.460247	0.047*
C4	0.6281 (3)	0.8558 (2)	0.43348 (8)	0.0309 (4)
H4	0.731778	0.837676	0.452771	0.037*
C5	0.6738 (2)	0.87313 (17)	0.37614 (7)	0.0250 (4)
H5	0.764646	0.934034	0.374496	0.030*
C6	0.5756 (3)	0.94248 (18)	0.28915 (8)	0.0302 (4)
H6A	0.662769	1.004871	0.286806	0.036*
H6B	0.478781	0.972556	0.269787	0.036*
C7	0.6356 (3)	0.82540 (19)	0.26464 (7)	0.0295 (4)
H7A	0.669002	0.841091	0.228224	0.035*
H7B	0.545389	0.765222	0.264202	0.035*
C8	0.7805 (2)	0.77397 (18)	0.29480 (7)	0.0275 (4)
H8A	0.874499	0.830642	0.292171	0.033*
H8B	0.813962	0.695566	0.279187	0.033*
C9	0.7374 (2)	0.75436 (17)	0.35245 (7)	0.0242 (4)
H9	0.842413	0.734812	0.370713	0.029*
C10	0.6217 (2)	0.64554 (17)	0.36138 (7)	0.0229 (4)
H10	0.517228	0.661228	0.342128	0.028*
C11	0.5140 (3)	0.74717 (19)	0.44099 (8)	0.0317 (4)
H11A	0.495806	0.733855	0.478635	0.038*
H11B	0.406493	0.764998	0.424776	0.038*
C12	0.5834 (3)	0.5327 (2)	0.44574 (8)	0.0328 (5)
C13	0.6315 (3)	0.4153 (2)	0.42007 (9)	0.0377 (5)
H13A	0.564376	0.348670	0.434773	0.045*
H13B	0.747864	0.397825	0.428122	0.045*
C14	0.6092 (3)	0.41761 (18)	0.36135 (8)	0.0309 (4)
H14A	0.655963	0.343091	0.345694	0.037*
H14B	0.491032	0.421340	0.352546	0.037*
C15	0.6965 (2)	0.52851 (18)	0.34053 (8)	0.0287 (4)
H15A	0.690221	0.528596	0.302070	0.034*
H15B	0.813740	0.524829	0.350478	0.034*
O2	−0.11594 (18)	0.14923 (12)	0.32599 (5)	0.0266 (3)
O3	−0.0428 (2)	0.07081 (13)	0.42002 (6)	0.0364 (4)
H3	−0.016 (4)	0.055 (3)	0.4504 (6)	0.055*
O4	0.20784 (19)	0.75778 (12)	0.25842 (5)	0.0313 (3)
O5	0.25683 (17)	0.77954 (12)	0.34258 (5)	0.0268 (3)
C16	0.0296 (2)	0.33722 (15)	0.34039 (7)	0.0200 (3)
H16	0.005098	0.364277	0.306176	0.024*
C17	−0.0248 (2)	0.22420 (16)	0.35669 (7)	0.0203 (3)
C18	0.0132 (2)	0.18249 (16)	0.40686 (7)	0.0233 (4)
C19	0.1048 (2)	0.25604 (17)	0.44005 (7)	0.0255 (4)
H19	0.130957	0.228449	0.474074	0.031*
C20	0.1583 (2)	0.36992 (17)	0.42352 (7)	0.0228 (4)
H20	0.221194	0.419210	0.446392	0.027*
C21	0.1209 (2)	0.41239 (15)	0.37391 (7)	0.0200 (3)
C22	0.1730 (2)	0.53495 (16)	0.35921 (7)	0.0206 (3)
H22	0.228572	0.580354	0.385242	0.025*
C23	0.1516 (2)	0.59053 (16)	0.31343 (7)	0.0210 (4)
H23	0.098384	0.548120	0.286022	0.025*
C24	0.2090 (2)	0.71695 (16)	0.30435 (7)	0.0208 (4)
O6	0.1538 (2)	0.01337 (14)	0.28106 (7)	0.0414 (4)
H2	−0.140 (4)	0.183 (3)	0.2974 (7)	0.062*
H6C	0.159 (4)	−0.0640 (13)	0.2867 (12)	0.062*
H6D	0.075 (3)	0.030 (3)	0.3032 (10)	0.062*
O7	0.5728 (6)	0.7344 (4)	0.56539 (16)	0.0626 (11)	0.5
H7C	0.611 (10)	0.743 (7)	0.5976 (13)	0.094*	0.5
H7D	0.570 (12)	0.663 (4)	0.550 (3)	0.094*	0.5

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0879 (14)	0.0412 (9)	0.0267 (8)	0.0028 (9)	0.0087 (9)	0.0119 (7)
N1	0.0244 (7)	0.0178 (7)	0.0282 (8)	−0.0029 (6)	−0.0021 (6)	0.0008 (6)
C1	0.0350 (10)	0.0192 (9)	0.0490 (12)	0.0007 (8)	−0.0026 (9)	−0.0057 (9)
N2	0.0350 (9)	0.0245 (8)	0.0213 (7)	0.0049 (7)	0.0029 (6)	0.0041 (6)
C2	0.0413 (12)	0.0279 (10)	0.0497 (13)	0.0023 (9)	0.0032 (10)	−0.0133 (10)
C3	0.0469 (13)	0.0370 (11)	0.0346 (11)	−0.0029 (10)	−0.0003 (10)	−0.0141 (9)
C4	0.0347 (10)	0.0341 (10)	0.0239 (9)	0.0013 (9)	−0.0058 (8)	−0.0046 (8)
C5	0.0223 (8)	0.0257 (9)	0.0269 (9)	−0.0026 (7)	−0.0052 (7)	−0.0021 (7)
C6	0.0291 (10)	0.0296 (10)	0.0319 (10)	−0.0049 (8)	−0.0018 (8)	0.0098 (8)
C7	0.0314 (10)	0.0354 (10)	0.0215 (9)	−0.0073 (8)	0.0017 (8)	0.0038 (8)
C8	0.0255 (9)	0.0302 (10)	0.0269 (10)	−0.0022 (8)	0.0050 (8)	0.0022 (8)
C9	0.0210 (8)	0.0283 (9)	0.0234 (9)	0.0017 (7)	−0.0016 (7)	−0.0005 (7)
C10	0.0242 (8)	0.0247 (9)	0.0199 (8)	0.0038 (7)	0.0001 (7)	0.0024 (7)
C11	0.0420 (11)	0.0313 (10)	0.0216 (8)	0.0046 (9)	0.0049 (8)	0.0014 (8)
C12	0.0373 (11)	0.0328 (10)	0.0284 (10)	0.0008 (9)	−0.0009 (8)	0.0083 (8)
C13	0.0442 (12)	0.0271 (10)	0.0418 (12)	0.0051 (9)	−0.0012 (10)	0.0096 (9)
C14	0.0303 (10)	0.0245 (9)	0.0379 (11)	0.0027 (8)	0.0028 (9)	0.0002 (8)
C15	0.0292 (9)	0.0249 (9)	0.0319 (10)	0.0031 (8)	0.0052 (8)	−0.0015 (8)
O2	0.0328 (7)	0.0199 (6)	0.0271 (7)	−0.0060 (6)	−0.0074 (5)	−0.0001 (5)
O3	0.0473 (9)	0.0275 (7)	0.0345 (7)	−0.0141 (7)	−0.0135 (7)	0.0122 (6)
O4	0.0403 (8)	0.0267 (7)	0.0270 (7)	−0.0099 (6)	−0.0092 (6)	0.0077 (6)
O5	0.0289 (6)	0.0219 (6)	0.0295 (7)	−0.0073 (5)	0.0004 (5)	−0.0042 (5)
C16	0.0214 (8)	0.0201 (8)	0.0184 (8)	0.0010 (7)	−0.0012 (7)	0.0010 (6)
C17	0.0205 (8)	0.0184 (8)	0.0220 (8)	0.0004 (7)	−0.0015 (7)	−0.0033 (6)
C18	0.0259 (9)	0.0173 (8)	0.0266 (9)	−0.0008 (7)	−0.0007 (7)	0.0033 (7)
C19	0.0291 (9)	0.0267 (9)	0.0206 (8)	−0.0015 (8)	−0.0038 (7)	0.0028 (7)
C20	0.0250 (9)	0.0222 (8)	0.0212 (8)	−0.0015 (7)	−0.0020 (7)	−0.0026 (7)
C21	0.0202 (8)	0.0175 (8)	0.0223 (8)	0.0004 (7)	0.0014 (7)	−0.0009 (7)
C22	0.0200 (8)	0.0184 (8)	0.0235 (8)	−0.0014 (6)	−0.0012 (7)	−0.0024 (7)
C23	0.0225 (8)	0.0190 (8)	0.0215 (8)	−0.0022 (7)	−0.0020 (7)	−0.0033 (7)
C24	0.0163 (7)	0.0180 (8)	0.0281 (9)	0.0008 (6)	−0.0029 (7)	0.0011 (7)
O6	0.0502 (10)	0.0262 (7)	0.0478 (9)	0.0091 (7)	0.0063 (8)	0.0064 (7)
O7	0.066 (3)	0.067 (3)	0.055 (2)	0.013 (2)	−0.016 (2)	−0.013 (2)

Geometric parameters (Å, º)

O1—C12	1.241 (3)	C11—H11A	0.9900
N1—H1	1.0000	C11—H11B	0.9900
N1—C1	1.507 (2)	C12—C13	1.503 (3)
N1—C5	1.520 (2)	C13—H13A	0.9900
N1—C6	1.501 (2)	C13—H13B	0.9900
C1—H1A	0.9900	C13—C14	1.521 (3)
C1—H1B	0.9900	C14—H14A	0.9900
C1—C2	1.509 (3)	C14—H14B	0.9900
N2—C10	1.487 (2)	C14—C15	1.511 (3)
N2—C11	1.473 (3)	C15—H15A	0.9900
N2—C12	1.345 (3)	C15—H15B	0.9900
C2—H2A	0.9900	O2—C17	1.362 (2)
C2—H2B	0.9900	O2—H2	0.850 (13)
C2—C3	1.527 (4)	O3—H3	0.831 (13)
C3—H3A	0.9900	O3—C18	1.354 (2)
C3—H3B	0.9900	O4—C24	1.263 (2)
C3—C4	1.529 (3)	O5—C24	1.262 (2)
C4—H4	1.0000	C16—H16	0.9500
C4—C5	1.532 (3)	C16—C17	1.386 (2)
C4—C11	1.526 (3)	C16—C21	1.407 (2)
C5—H5	1.0000	C17—C18	1.404 (2)
C5—C9	1.533 (3)	C18—C19	1.393 (3)
C6—H6A	0.9900	C19—H19	0.9500
C6—H6B	0.9900	C19—C20	1.394 (3)
C6—C7	1.516 (3)	C20—H20	0.9500
C7—H7A	0.9900	C20—C21	1.392 (2)
C7—H7B	0.9900	C21—C22	1.464 (2)
C7—C8	1.522 (3)	C22—H22	0.9500
C8—H8A	0.9900	C22—C23	1.338 (2)
C8—H8B	0.9900	C23—H23	0.9500
C8—C9	1.539 (3)	C23—C24	1.486 (2)
C9—H9	1.0000	O6—H6C	0.865 (13)
C9—C10	1.541 (3)	O6—H6D	0.879 (13)
C10—H10	1.0000	O7—H7C	0.890 (14)
C10—C15	1.523 (3)	O7—H7D	0.881 (14)
C1—N1—H1	108.4	N2—C10—H10	108.2
C1—N1—C5	110.43 (15)	N2—C10—C15	111.63 (15)
C5—N1—H1	108.4	C9—C10—H10	108.2
C6—N1—H1	108.4	C15—C10—C9	111.10 (15)
C6—N1—C1	109.65 (15)	C15—C10—H10	108.2
C6—N1—C5	111.35 (15)	N2—C11—C4	111.57 (17)
N1—C1—H1A	109.6	N2—C11—H11A	109.3
N1—C1—H1B	109.6	N2—C11—H11B	109.3
N1—C1—C2	110.41 (17)	C4—C11—H11A	109.3
H1A—C1—H1B	108.1	C4—C11—H11B	109.3
C2—C1—H1A	109.6	H11A—C11—H11B	108.0
C2—C1—H1B	109.6	O1—C12—N2	120.6 (2)
C11—N2—C10	114.68 (14)	O1—C12—C13	119.92 (19)
C12—N2—C10	125.48 (17)	N2—C12—C13	119.50 (17)
C12—N2—C11	119.11 (16)	C12—C13—H13A	109.0
C1—C2—H2A	109.5	C12—C13—H13B	109.0
C1—C2—H2B	109.5	C12—C13—C14	112.99 (17)
C1—C2—C3	110.9 (2)	H13A—C13—H13B	107.8
H2A—C2—H2B	108.1	C14—C13—H13A	109.0
C3—C2—H2A	109.5	C14—C13—H13B	109.0
C3—C2—H2B	109.5	C13—C14—H14A	110.1
C2—C3—H3A	109.2	C13—C14—H14B	110.1
C2—C3—H3B	109.2	H14A—C14—H14B	108.4
C2—C3—C4	111.84 (17)	C15—C14—C13	107.98 (17)
H3A—C3—H3B	107.9	C15—C14—H14A	110.1
C4—C3—H3A	109.2	C15—C14—H14B	110.1
C4—C3—H3B	109.2	C10—C15—H15A	109.3
C3—C4—H4	107.2	C10—C15—H15B	109.3
C3—C4—C5	111.70 (18)	C14—C15—C10	111.71 (16)
C5—C4—H4	107.2	C14—C15—H15A	109.3
C11—C4—C3	111.57 (18)	C14—C15—H15B	109.3
C11—C4—H4	107.2	H15A—C15—H15B	107.9
C11—C4—C5	111.55 (16)	C17—O2—H2	111 (2)
N1—C5—C4	111.27 (16)	C18—O3—H3	110 (2)
N1—C5—H5	107.7	C17—C16—H16	119.6
N1—C5—C9	111.24 (14)	C17—C16—C21	120.79 (16)
C4—C5—H5	107.7	C21—C16—H16	119.6
C4—C5—C9	110.98 (16)	O2—C17—C16	122.90 (16)
C9—C5—H5	107.7	O2—C17—C18	117.04 (15)
N1—C6—H6A	109.4	C16—C17—C18	120.06 (16)
N1—C6—H6B	109.4	O3—C18—C17	116.88 (16)
N1—C6—C7	111.04 (15)	O3—C18—C19	123.71 (17)
H6A—C6—H6B	108.0	C19—C18—C17	119.40 (16)
C7—C6—H6A	109.4	C18—C19—H19	119.9
C7—C6—H6B	109.4	C18—C19—C20	120.23 (17)
C6—C7—H7A	109.5	C20—C19—H19	119.9
C6—C7—H7B	109.5	C19—C20—H20	119.6
C6—C7—C8	110.79 (16)	C21—C20—C19	120.84 (17)
H7A—C7—H7B	108.1	C21—C20—H20	119.6
C8—C7—H7A	109.5	C16—C21—C22	122.49 (16)
C8—C7—H7B	109.5	C20—C21—C16	118.66 (16)
C7—C8—H8A	109.3	C20—C21—C22	118.82 (16)
C7—C8—H8B	109.3	C21—C22—H22	116.2
C7—C8—C9	111.44 (15)	C23—C22—C21	127.62 (16)
H8A—C8—H8B	108.0	C23—C22—H22	116.2
C9—C8—H8A	109.3	C22—C23—H23	119.2
C9—C8—H8B	109.3	C22—C23—C24	121.68 (16)
C5—C9—C8	109.91 (16)	C24—C23—H23	119.2
C5—C9—H9	106.7	O4—C24—C23	118.52 (16)
C5—C9—C10	113.37 (15)	O5—C24—O4	122.41 (17)
C8—C9—H9	106.7	O5—C24—C23	119.07 (16)
C8—C9—C10	113.11 (15)	H6C—O6—H6D	98 (3)
C10—C9—H9	106.7	H7C—O7—H7D	122 (8)
N2—C10—C9	109.32 (15)
O1—C12—C13—C14	156.6 (2)	C10—N2—C11—C4	−56.8 (2)
N1—C1—C2—C3	58.8 (2)	C10—N2—C12—O1	−177.6 (2)
N1—C5—C9—C8	54.9 (2)	C10—N2—C12—C13	1.9 (3)
N1—C5—C9—C10	−72.74 (19)	C11—N2—C10—C9	55.1 (2)
N1—C6—C7—C8	−56.9 (2)	C11—N2—C10—C15	178.40 (16)
C1—N1—C5—C4	56.9 (2)	C11—N2—C12—O1	−8.0 (3)
C1—N1—C5—C9	−178.75 (15)	C11—N2—C12—C13	171.6 (2)
C1—N1—C6—C7	179.75 (16)	C11—C4—C5—N1	73.2 (2)
C1—C2—C3—C4	−54.3 (2)	C11—C4—C5—C9	−51.3 (2)
N2—C10—C15—C14	42.2 (2)	C12—N2—C10—C9	−134.8 (2)
N2—C12—C13—C14	−22.9 (3)	C12—N2—C10—C15	−11.5 (3)
C2—C3—C4—C5	51.2 (3)	C12—N2—C11—C4	132.40 (19)
C2—C3—C4—C11	−74.5 (2)	C12—C13—C14—C15	52.2 (2)
C3—C4—C5—N1	−52.5 (2)	C13—C14—C15—C10	−62.9 (2)
C3—C4—C5—C9	−176.91 (17)	O2—C17—C18—O3	0.7 (3)
C3—C4—C11—N2	179.23 (16)	O2—C17—C18—C19	−179.43 (17)
C4—C5—C9—C8	179.40 (15)	O3—C18—C19—C20	179.83 (19)
C4—C5—C9—C10	51.7 (2)	C16—C17—C18—O3	−179.44 (17)
C5—N1—C1—C2	−60.2 (2)	C16—C17—C18—C19	0.4 (3)
C5—N1—C6—C7	57.2 (2)	C16—C21—C22—C23	−3.5 (3)
C5—C4—C11—N2	53.5 (2)	C17—C16—C21—C20	1.3 (3)
C5—C9—C10—N2	−52.3 (2)	C17—C16—C21—C22	−176.61 (16)
C5—C9—C10—C15	−175.90 (15)	C17—C18—C19—C20	0.0 (3)
C6—N1—C1—C2	176.75 (17)	C18—C19—C20—C21	0.3 (3)
C6—N1—C5—C4	179.01 (15)	C19—C20—C21—C16	−0.9 (3)
C6—N1—C5—C9	−56.69 (19)	C19—C20—C21—C22	177.09 (17)
C6—C7—C8—C9	56.1 (2)	C20—C21—C22—C23	178.56 (18)
C7—C8—C9—C5	−55.0 (2)	C21—C16—C17—O2	178.77 (16)
C7—C8—C9—C10	72.8 (2)	C21—C16—C17—C18	−1.1 (3)
C8—C9—C10—N2	−178.26 (15)	C21—C22—C23—C24	178.90 (16)
C8—C9—C10—C15	58.1 (2)	C22—C23—C24—O4	169.44 (18)
C9—C10—C15—C14	164.55 (16)	C22—C23—C24—O5	−10.6 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O5	1.00	1.75	2.734 (2)	169
O3—H3···O1^i	0.83 (1)	1.83 (2)	2.626 (2)	160 (3)
O2—H2···O4^ii	0.85 (1)	1.74 (1)	2.5879 (19)	174 (3)
O6—H6C···O4^iii	0.87 (1)	2.13 (2)	2.906 (2)	149 (3)
O6—H6D···O2	0.88 (1)	2.12 (2)	2.899 (2)	148 (3)
O7—H7C···O5^iv	0.89 (1)	1.96 (3)	2.806 (4)	158 (8)
O7—H7D···O1	0.88 (1)	2.06 (3)	2.910 (5)	161 (8)

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

(1R,2R,9S,17S)-6-Oxo-7,13-diazatetracyclo[7.7.1.0^2,7.0^13,17]heptadecan-13-ium 2-hydroxybenzoate monohydrate (matrine-sa)

Crystal data

C15H25N2O^+·C7H5O3^−·H2O	Dx = 1.294 Mg m^−3
Mr = 404.49	Ga Kα radiation, λ = 1.34139 Å
Orthorhombic, P212121	Cell parameters from 9983 reflections
a = 9.2999 (4) Å	θ = 3.7–60.7°
b = 12.7329 (5) Å	µ = 0.47 mm^−1
c = 17.5349 (8) Å	T = 170 K
V = 2076.39 (15) Å^3	Block, colourless
Z = 4	0.09 × 0.07 × 0.06 mm
F(000) = 872

Data collection

Bruker D8 Venture diffractometer	4568 reflections with I > 2σ(I)
ω and φ scans	Rint = 0.038
Absorption correction: multi-scan (SADABS; Bruker, 2016)	θmax = 60.8°, θmin = 3.7°
Tmin = 0.704, Tmax = 0.752	h = −12→12
33326 measured reflections	k = −16→16
4679 independent reflections	l = −22→22

Refinement

Refinement on F^2	Hydrogen site location: mixed
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.031	w = 1/[σ^2(Fo^2) + (0.0405P)^2 + 0.2725P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.081	(Δ/σ)max < 0.001
S = 1.06	Δρmax = 0.17 e Å^−3
4679 reflections	Δρmin = −0.19 e Å^−3
266 parameters	Absolute structure: Flack x determined using 1920 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
0 restraints	Absolute structure parameter: 0.04 (4)

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	0.78504 (13)	0.83322 (8)	0.79102 (7)	0.0378 (3)
O2	0.42780 (16)	0.37680 (11)	0.42017 (7)	0.0486 (3)
H2	0.498189	0.359280	0.447368	0.073*
O3	0.61198 (13)	0.39053 (9)	0.52537 (7)	0.0370 (3)
O4	0.59618 (11)	0.51857 (9)	0.61152 (6)	0.0330 (2)
O5	0.63164 (13)	1.02448 (11)	0.77714 (7)	0.0417 (3)
H5A	0.572343	1.023439	0.815493	0.063*
H5B	0.681952	0.967285	0.782106	0.063*
N1	0.84031 (13)	0.42023 (9)	0.66386 (7)	0.0242 (2)
H1	0.751522	0.461616	0.652381	0.029*
N2	0.76049 (12)	0.65766 (9)	0.77737 (6)	0.0227 (2)
C1	0.93159 (17)	0.41605 (12)	0.59299 (8)	0.0299 (3)
H1A	0.879508	0.377843	0.552310	0.036*
H1B	1.021873	0.377689	0.603890	0.036*
C2	0.96626 (17)	0.52600 (13)	0.56625 (8)	0.0314 (3)
H2A	0.876041	0.563138	0.553168	0.038*
H2B	1.026419	0.522431	0.519743	0.038*
C3	1.04610 (17)	0.58705 (13)	0.62809 (9)	0.0330 (3)
H3A	1.058403	0.660759	0.611350	0.040*
H3B	1.142961	0.556245	0.635040	0.040*
C4	0.96595 (15)	0.58541 (11)	0.70476 (8)	0.0261 (3)
H4	1.034485	0.611460	0.744427	0.031*
C5	0.92096 (15)	0.47438 (11)	0.72809 (8)	0.0249 (3)
H5	1.010510	0.433186	0.738159	0.030*
C6	0.7968 (2)	0.31069 (11)	0.68560 (9)	0.0350 (3)
H6A	0.883973	0.267487	0.693605	0.042*
H6B	0.740929	0.278935	0.643423	0.042*
C7	0.7068 (2)	0.31005 (12)	0.75768 (10)	0.0380 (4)
H7A	0.683779	0.236714	0.771940	0.046*
H7B	0.615191	0.347556	0.748373	0.046*
C8	0.7879 (2)	0.36310 (12)	0.82286 (9)	0.0351 (3)
H8A	0.874846	0.321623	0.835212	0.042*
H8B	0.725979	0.364788	0.868785	0.042*
C9	0.83204 (15)	0.47536 (11)	0.80185 (8)	0.0250 (3)
H9	0.897536	0.500410	0.843259	0.030*
C10	0.70531 (15)	0.55288 (10)	0.79893 (7)	0.0218 (2)
H10	0.637152	0.528916	0.758400	0.026*
C11	0.83793 (15)	0.65995 (11)	0.70437 (8)	0.0249 (3)
H11A	0.871964	0.732299	0.694289	0.030*
H11B	0.771432	0.639869	0.662763	0.030*
C12	0.73395 (15)	0.74889 (11)	0.81362 (8)	0.0272 (3)
C13	0.63792 (19)	0.74690 (13)	0.88284 (10)	0.0355 (3)
H13A	0.581027	0.812575	0.884501	0.043*
H13B	0.698400	0.744472	0.929269	0.043*
C14	0.53621 (17)	0.65391 (12)	0.88326 (9)	0.0307 (3)
H14A	0.481426	0.652144	0.931651	0.037*
H14B	0.467049	0.659752	0.840548	0.037*
C15	0.62470 (17)	0.55474 (12)	0.87496 (8)	0.0278 (3)
H15A	0.560623	0.492804	0.878144	0.033*
H15B	0.694694	0.550399	0.917384	0.033*
C16	0.38377 (17)	0.47386 (14)	0.44007 (8)	0.0352 (3)
C17	0.27822 (19)	0.52336 (19)	0.39600 (9)	0.0466 (5)
H17	0.238162	0.488063	0.353260	0.056*
C18	0.2324 (2)	0.62246 (19)	0.41420 (11)	0.0501 (5)
H18	0.160580	0.655142	0.383852	0.060*
C19	0.2893 (2)	0.67601 (16)	0.47634 (12)	0.0463 (4)
H19	0.256764	0.744686	0.488617	0.056*
C20	0.39450 (19)	0.62748 (13)	0.52024 (9)	0.0358 (3)
H20	0.433763	0.663655	0.562799	0.043*
C21	0.44349 (16)	0.52690 (13)	0.50307 (8)	0.0293 (3)
C22	0.55864 (15)	0.47501 (12)	0.54960 (8)	0.0279 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0386 (6)	0.0233 (5)	0.0516 (7)	−0.0050 (4)	0.0145 (5)	−0.0070 (5)
O2	0.0569 (8)	0.0531 (8)	0.0358 (6)	−0.0184 (6)	−0.0005 (6)	−0.0132 (6)
O3	0.0369 (6)	0.0372 (6)	0.0367 (6)	−0.0018 (5)	0.0031 (5)	−0.0040 (5)
O4	0.0288 (5)	0.0440 (6)	0.0260 (5)	−0.0014 (5)	−0.0042 (4)	−0.0041 (4)
O5	0.0391 (6)	0.0493 (7)	0.0367 (6)	0.0085 (6)	0.0071 (5)	0.0098 (5)
N1	0.0278 (6)	0.0217 (5)	0.0230 (5)	0.0014 (4)	−0.0010 (5)	−0.0040 (4)
N2	0.0251 (5)	0.0213 (5)	0.0216 (5)	0.0004 (4)	0.0017 (4)	−0.0015 (4)
C1	0.0318 (7)	0.0318 (7)	0.0260 (7)	0.0022 (6)	0.0032 (6)	−0.0088 (5)
C2	0.0321 (7)	0.0365 (7)	0.0257 (6)	−0.0035 (6)	0.0060 (6)	−0.0061 (6)
C3	0.0268 (7)	0.0390 (8)	0.0331 (7)	−0.0067 (6)	0.0076 (6)	−0.0099 (6)
C4	0.0218 (6)	0.0305 (7)	0.0259 (6)	−0.0026 (5)	0.0001 (5)	−0.0067 (5)
C5	0.0244 (6)	0.0267 (6)	0.0237 (6)	0.0053 (5)	−0.0043 (5)	−0.0048 (5)
C6	0.0507 (9)	0.0200 (6)	0.0341 (8)	−0.0005 (6)	0.0018 (7)	−0.0035 (5)
C7	0.0569 (10)	0.0217 (6)	0.0352 (8)	−0.0046 (7)	0.0041 (8)	0.0017 (6)
C8	0.0520 (9)	0.0248 (7)	0.0286 (7)	0.0084 (7)	0.0007 (7)	0.0051 (5)
C9	0.0294 (6)	0.0248 (6)	0.0208 (6)	0.0059 (5)	−0.0042 (5)	−0.0006 (5)
C10	0.0243 (6)	0.0205 (5)	0.0205 (6)	0.0006 (5)	−0.0012 (5)	−0.0002 (4)
C11	0.0288 (6)	0.0225 (6)	0.0236 (6)	−0.0018 (5)	0.0034 (5)	−0.0011 (5)
C12	0.0238 (6)	0.0251 (6)	0.0326 (7)	0.0013 (5)	0.0014 (5)	−0.0049 (6)
C13	0.0397 (8)	0.0312 (7)	0.0356 (8)	−0.0004 (7)	0.0112 (7)	−0.0106 (6)
C14	0.0291 (7)	0.0342 (7)	0.0287 (7)	0.0020 (6)	0.0072 (6)	−0.0005 (6)
C15	0.0304 (7)	0.0295 (6)	0.0233 (6)	0.0007 (6)	0.0026 (5)	0.0014 (5)
C16	0.0340 (7)	0.0491 (9)	0.0224 (6)	−0.0189 (7)	0.0026 (6)	−0.0011 (6)
C17	0.0383 (9)	0.0761 (13)	0.0254 (7)	−0.0255 (9)	−0.0070 (7)	0.0102 (8)
C18	0.0362 (9)	0.0725 (13)	0.0415 (9)	−0.0119 (9)	−0.0087 (7)	0.0262 (9)
C19	0.0418 (9)	0.0493 (10)	0.0479 (10)	−0.0006 (8)	−0.0019 (8)	0.0152 (8)
C20	0.0357 (8)	0.0404 (8)	0.0314 (7)	−0.0056 (7)	−0.0030 (6)	0.0032 (6)
C21	0.0277 (6)	0.0388 (8)	0.0212 (6)	−0.0101 (6)	0.0008 (5)	0.0026 (5)
C22	0.0255 (6)	0.0350 (7)	0.0231 (6)	−0.0086 (6)	0.0032 (5)	0.0006 (6)

Geometric parameters (Å, º)

O1—C12	1.2392 (19)	C7—H7B	0.9900
O2—H2	0.8400	C7—C8	1.527 (2)
O2—C16	1.348 (2)	C8—H8A	0.9900
O3—C22	1.2584 (19)	C8—H8B	0.9900
O4—C22	1.2683 (18)	C8—C9	1.532 (2)
O5—H5A	0.8698	C9—H9	1.0000
O5—H5B	0.8701	C9—C10	1.5381 (18)
N1—H1	1.0000	C10—H10	1.0000
N1—C1	1.5060 (18)	C10—C15	1.5297 (18)
N1—C5	1.5186 (17)	C11—H11A	0.9900
N1—C6	1.5016 (18)	C11—H11B	0.9900
N2—C10	1.4787 (17)	C12—C13	1.507 (2)
N2—C11	1.4689 (17)	C13—H13A	0.9900
N2—C12	1.3470 (18)	C13—H13B	0.9900
C1—H1A	0.9900	C13—C14	1.516 (2)
C1—H1B	0.9900	C14—H14A	0.9900
C1—C2	1.511 (2)	C14—H14B	0.9900
C2—H2A	0.9900	C14—C15	1.514 (2)
C2—H2B	0.9900	C15—H15A	0.9900
C2—C3	1.527 (2)	C15—H15B	0.9900
C3—H3A	0.9900	C16—C17	1.399 (3)
C3—H3B	0.9900	C16—C21	1.409 (2)
C3—C4	1.537 (2)	C17—H17	0.9500
C4—H4	1.0000	C17—C18	1.370 (3)
C4—C5	1.530 (2)	C18—H18	0.9500
C4—C11	1.5226 (19)	C18—C19	1.390 (3)
C5—H5	1.0000	C19—H19	0.9500
C5—C9	1.5352 (18)	C19—C20	1.390 (3)
C6—H6A	0.9900	C20—H20	0.9500
C6—H6B	0.9900	C20—C21	1.392 (2)
C6—C7	1.516 (2)	C21—C22	1.500 (2)
C7—H7A	0.9900
C16—O2—H2	109.5	C5—C9—C10	112.95 (11)
H5A—O5—H5B	104.5	C8—C9—C5	109.84 (12)
C1—N1—H1	108.5	C8—C9—H9	106.6
C1—N1—C5	110.46 (11)	C8—C9—C10	113.65 (12)
C5—N1—H1	108.5	C10—C9—H9	106.6
C6—N1—H1	108.5	N2—C10—C9	108.76 (11)
C6—N1—C1	109.19 (11)	N2—C10—H10	108.3
C6—N1—C5	111.51 (11)	N2—C10—C15	112.27 (11)
C11—N2—C10	114.26 (10)	C9—C10—H10	108.3
C12—N2—C10	126.43 (11)	C15—C10—C9	110.88 (11)
C12—N2—C11	118.94 (12)	C15—C10—H10	108.3
N1—C1—H1A	109.6	N2—C11—C4	111.54 (11)
N1—C1—H1B	109.6	N2—C11—H11A	109.3
N1—C1—C2	110.09 (11)	N2—C11—H11B	109.3
H1A—C1—H1B	108.2	C4—C11—H11A	109.3
C2—C1—H1A	109.6	C4—C11—H11B	109.3
C2—C1—H1B	109.6	H11A—C11—H11B	108.0
C1—C2—H2A	109.5	O1—C12—N2	121.74 (13)
C1—C2—H2B	109.5	O1—C12—C13	119.95 (13)
C1—C2—C3	110.79 (13)	N2—C12—C13	118.30 (13)
H2A—C2—H2B	108.1	C12—C13—H13A	109.0
C3—C2—H2A	109.5	C12—C13—H13B	109.0
C3—C2—H2B	109.5	C12—C13—C14	112.76 (12)
C2—C3—H3A	109.2	H13A—C13—H13B	107.8
C2—C3—H3B	109.2	C14—C13—H13A	109.0
C2—C3—C4	112.23 (12)	C14—C13—H13B	109.0
H3A—C3—H3B	107.9	C13—C14—H14A	110.1
C4—C3—H3A	109.2	C13—C14—H14B	110.1
C4—C3—H3B	109.2	H14A—C14—H14B	108.4
C3—C4—H4	107.1	C15—C14—C13	108.17 (13)
C5—C4—C3	112.27 (12)	C15—C14—H14A	110.1
C5—C4—H4	107.1	C15—C14—H14B	110.1
C11—C4—C3	111.52 (12)	C10—C15—H15A	109.4
C11—C4—H4	107.1	C10—C15—H15B	109.4
C11—C4—C5	111.30 (11)	C14—C15—C10	111.28 (11)
N1—C5—C4	110.87 (11)	C14—C15—H15A	109.4
N1—C5—H5	107.7	C14—C15—H15B	109.4
N1—C5—C9	111.25 (11)	H15A—C15—H15B	108.0
C4—C5—H5	107.7	O2—C16—C17	118.89 (16)
C4—C5—C9	111.41 (11)	O2—C16—C21	121.51 (16)
C9—C5—H5	107.7	C17—C16—C21	119.59 (18)
N1—C6—H6A	109.3	C16—C17—H17	119.8
N1—C6—H6B	109.3	C18—C17—C16	120.30 (17)
N1—C6—C7	111.44 (11)	C18—C17—H17	119.8
H6A—C6—H6B	108.0	C17—C18—H18	119.5
C7—C6—H6A	109.3	C17—C18—C19	121.08 (17)
C7—C6—H6B	109.3	C19—C18—H18	119.5
C6—C7—H7A	109.6	C18—C19—H19	120.5
C6—C7—H7B	109.6	C20—C19—C18	118.9 (2)
C6—C7—C8	110.43 (16)	C20—C19—H19	120.5
H7A—C7—H7B	108.1	C19—C20—H20	119.3
C8—C7—H7A	109.6	C19—C20—C21	121.31 (16)
C8—C7—H7B	109.6	C21—C20—H20	119.3
C7—C8—H8A	109.3	C16—C21—C22	119.80 (16)
C7—C8—H8B	109.3	C20—C21—C16	118.78 (15)
C7—C8—C9	111.41 (12)	C20—C21—C22	121.42 (13)
H8A—C8—H8B	108.0	O3—C22—O4	123.67 (15)
C9—C8—H8A	109.3	O3—C22—C21	118.32 (13)
C9—C8—H8B	109.3	O4—C22—C21	118.01 (14)
C5—C9—H9	106.6
O1—C12—C13—C14	155.09 (15)	C7—C8—C9—C10	71.83 (17)
O2—C16—C17—C18	−179.23 (15)	C8—C9—C10—N2	−179.36 (11)
O2—C16—C21—C20	179.33 (14)	C8—C9—C10—C15	56.72 (15)
O2—C16—C21—C22	−0.1 (2)	C9—C10—C15—C14	160.17 (12)
N1—C1—C2—C3	59.02 (16)	C10—N2—C11—C4	−58.51 (14)
N1—C5—C9—C8	55.17 (15)	C10—N2—C12—O1	−179.83 (13)
N1—C5—C9—C10	−72.85 (14)	C10—N2—C12—C13	−0.6 (2)
N1—C6—C7—C8	−56.48 (19)	C11—N2—C10—C9	57.32 (14)
N2—C10—C15—C14	38.29 (16)	C11—N2—C10—C15	−179.59 (11)
N2—C12—C13—C14	−24.2 (2)	C11—N2—C12—O1	−7.2 (2)
C1—N1—C5—C4	57.78 (14)	C11—N2—C12—C13	172.08 (13)
C1—N1—C5—C9	−177.64 (10)	C11—C4—C5—N1	74.28 (14)
C1—N1—C6—C7	178.91 (14)	C11—C4—C5—C9	−50.21 (15)
C1—C2—C3—C4	−52.93 (18)	C12—N2—C10—C9	−129.75 (14)
C2—C3—C4—C5	49.45 (18)	C12—N2—C10—C15	−6.66 (19)
C2—C3—C4—C11	−76.23 (16)	C12—N2—C11—C4	127.99 (13)
C3—C4—C5—N1	−51.53 (15)	C12—C13—C14—C15	54.72 (17)
C3—C4—C5—C9	−176.02 (11)	C13—C14—C15—C10	−62.32 (16)
C3—C4—C11—N2	179.46 (11)	C16—C17—C18—C19	0.1 (3)
C4—C5—C9—C8	179.45 (12)	C16—C21—C22—O3	8.9 (2)
C4—C5—C9—C10	51.42 (15)	C16—C21—C22—O4	−170.70 (13)
C5—N1—C1—C2	−61.78 (15)	C17—C16—C21—C20	0.6 (2)
C5—N1—C6—C7	56.56 (18)	C17—C16—C21—C22	−178.83 (13)
C5—C4—C11—N2	53.23 (15)	C17—C18—C19—C20	0.1 (3)
C5—C9—C10—N2	−53.35 (14)	C18—C19—C20—C21	0.0 (3)
C5—C9—C10—C15	−177.27 (11)	C19—C20—C21—C16	−0.4 (2)
C6—N1—C1—C2	175.24 (13)	C19—C20—C21—C22	179.03 (15)
C6—N1—C5—C4	179.39 (11)	C20—C21—C22—O3	−170.51 (14)
C6—N1—C5—C9	−56.03 (15)	C20—C21—C22—O4	9.9 (2)
C6—C7—C8—C9	56.54 (18)	C21—C16—C17—C18	−0.4 (2)
C7—C8—C9—C5	−55.81 (18)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O3	0.84	1.77	2.5233 (19)	147
O5—H5A···O4^i	0.87	2.02	2.8820 (16)	169
O5—H5B···O1	0.87	1.96	2.8329 (17)	176
N1—H1···O4	1.00	1.77	2.7505 (17)	167

Symmetry code: (i) −x+1, y+1/2, −z+3/2.

(1R,2R,9S,17S)-7,13-Diazatetracyclo[7.7.1.0^{2,7}.0{13,17}]heptadecan-6-one 1.75-hydrate (matrine-h)

Crystal data

C15H24N2O·1.75H2O	Dx = 1.231 Mg m^−3
Mr = 279.89	Ga Kα radiation, λ = 1.34139 Å
Tetragonal, P43212	Cell parameters from 9770 reflections
a = 11.7364 (3) Å	θ = 3.7–60.5°
c = 21.9295 (9) Å	µ = 0.43 mm^−1
V = 3020.6 (2) Å^3	T = 170 K
Z = 8	Block, colourless
F(000) = 1228	0.09 × 0.08 × 0.06 mm

Data collection

Bruker D8 Venture diffractometer	3335 reflections with I > 2σ(I)
ω and φ scans	Rint = 0.042
Absorption correction: multi-scan (SADABS; Bruker, 2016)	θmax = 60.8°, θmin = 3.7°
Tmin = 0.698, Tmax = 0.752	h = −15→15
49632 measured reflections	k = −14→15
3473 independent reflections	l = −28→28

Refinement

Refinement on F^2	Hydrogen site location: mixed
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.037	w = 1/[σ^2(Fo^2) + (0.0507P)^2 + 0.5768P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.095	(Δ/σ)max < 0.001
S = 1.08	Δρmax = 0.35 e Å^−3
3473 reflections	Δρmin = −0.23 e Å^−3
192 parameters	Absolute structure: Flack x determined using 1323 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
0 restraints	Absolute structure parameter: −0.01 (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	Occ. (<1)
O1	0.63861 (10)	0.70536 (11)	0.64097 (5)	0.0310 (3)
O2	0.25063 (14)	0.96006 (12)	0.53692 (7)	0.0412 (3)
H2C	0.214514	0.905173	0.557856	0.062*
H2D	0.287433	0.918759	0.509271	0.062*
O3	0.1771 (4)	1.1412 (5)	0.4712 (2)	0.0987 (17)	0.5
H3C	0.105070	1.162701	0.465220	0.148*	0.5
H3D	0.186460	1.088110	0.498270	0.148*	0.5
O4	0.3131 (5)	1.3131 (5)	0.500000	0.117 (3)	0.5
H4A	0.289350	1.350300	0.468121	0.176*	0.25
H4B	0.253201	1.280849	0.515650	0.176*	0.25
N1	0.35870 (12)	0.84195 (12)	0.44148 (6)	0.0254 (3)
N2	0.49194 (11)	0.71006 (11)	0.57406 (5)	0.0208 (3)
C1	0.40419 (16)	0.94079 (16)	0.40753 (8)	0.0336 (4)
H1A	0.344535	1.000163	0.404530	0.040*
H1B	0.424411	0.916764	0.365634	0.040*
C2	0.50831 (17)	0.99034 (16)	0.43835 (8)	0.0342 (4)
H2A	0.487252	1.019445	0.479195	0.041*
H2B	0.537723	1.054976	0.413985	0.041*
C3	0.60086 (15)	0.89975 (16)	0.44473 (8)	0.0305 (4)
H3A	0.630356	0.879702	0.403818	0.037*
H3B	0.664846	0.930947	0.468948	0.037*
C4	0.55521 (13)	0.79272 (14)	0.47577 (7)	0.0234 (3)
H4	0.614007	0.731703	0.470997	0.028*
C5	0.44555 (14)	0.75018 (14)	0.44537 (6)	0.0238 (3)
H5	0.464608	0.725312	0.402969	0.029*
C6	0.25572 (16)	0.80021 (18)	0.40986 (8)	0.0355 (4)
H6A	0.276142	0.777110	0.367844	0.043*
H6B	0.199362	0.862766	0.407092	0.043*
C7	0.20234 (16)	0.69976 (17)	0.44275 (9)	0.0358 (4)
H7A	0.135245	0.672375	0.419651	0.043*
H7B	0.176392	0.723771	0.483740	0.043*
C8	0.28963 (16)	0.60356 (16)	0.44880 (9)	0.0337 (4)
H8A	0.308776	0.573702	0.407839	0.040*
H8B	0.256455	0.540519	0.472975	0.040*
C9	0.39828 (13)	0.64686 (14)	0.48012 (7)	0.0244 (3)
H9	0.456334	0.584830	0.476626	0.029*
C10	0.38189 (13)	0.67060 (13)	0.54886 (7)	0.0222 (3)
H10	0.325463	0.733922	0.553222	0.027*
C11	0.53762 (13)	0.81170 (13)	0.54397 (7)	0.0227 (3)
H11A	0.611311	0.832346	0.562950	0.027*
H11B	0.484356	0.876102	0.550080	0.027*
C12	0.54387 (13)	0.66987 (13)	0.62436 (7)	0.0223 (3)
C13	0.48330 (15)	0.58008 (15)	0.66176 (8)	0.0294 (4)
H13A	0.497952	0.594392	0.705554	0.035*
H13B	0.515119	0.504308	0.651576	0.035*
C14	0.35597 (15)	0.57851 (15)	0.65091 (8)	0.0314 (4)
H14A	0.321211	0.649850	0.666214	0.038*
H14B	0.320937	0.513558	0.672782	0.038*
C15	0.33563 (15)	0.56709 (15)	0.58279 (8)	0.0307 (4)
H15A	0.252904	0.559686	0.574898	0.037*
H15B	0.373619	0.497351	0.567567	0.037*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0276 (6)	0.0382 (7)	0.0273 (5)	−0.0056 (5)	−0.0083 (5)	0.0061 (5)
O2	0.0506 (9)	0.0319 (7)	0.0412 (7)	0.0041 (6)	0.0191 (6)	−0.0013 (6)
O3	0.065 (3)	0.125 (4)	0.107 (3)	0.045 (3)	0.030 (2)	0.076 (3)
O4	0.139 (5)	0.139 (5)	0.073 (4)	−0.069 (6)	−0.030 (4)	0.030 (4)
N1	0.0248 (7)	0.0290 (7)	0.0223 (6)	0.0074 (5)	−0.0017 (5)	0.0026 (5)
N2	0.0197 (6)	0.0219 (6)	0.0210 (5)	−0.0021 (4)	−0.0012 (5)	0.0022 (5)
C1	0.0375 (9)	0.0371 (10)	0.0262 (8)	0.0103 (7)	0.0024 (7)	0.0100 (7)
C2	0.0415 (10)	0.0296 (9)	0.0316 (8)	0.0019 (8)	0.0068 (7)	0.0094 (7)
C3	0.0286 (8)	0.0355 (9)	0.0272 (8)	−0.0009 (7)	0.0060 (6)	0.0070 (7)
C4	0.0205 (7)	0.0272 (8)	0.0223 (7)	0.0039 (6)	0.0018 (6)	0.0024 (6)
C5	0.0243 (8)	0.0277 (8)	0.0194 (6)	0.0073 (6)	−0.0001 (6)	−0.0026 (6)
C6	0.0304 (9)	0.0446 (10)	0.0313 (8)	0.0097 (8)	−0.0107 (7)	−0.0027 (8)
C7	0.0248 (8)	0.0411 (10)	0.0415 (9)	0.0034 (8)	−0.0130 (7)	−0.0070 (8)
C8	0.0310 (9)	0.0329 (9)	0.0371 (9)	0.0015 (7)	−0.0112 (7)	−0.0086 (7)
C9	0.0222 (7)	0.0234 (7)	0.0276 (7)	0.0035 (6)	−0.0044 (6)	−0.0045 (6)
C10	0.0177 (7)	0.0219 (7)	0.0271 (7)	−0.0004 (5)	−0.0025 (6)	0.0002 (6)
C11	0.0233 (7)	0.0236 (7)	0.0212 (7)	−0.0041 (6)	−0.0012 (5)	0.0025 (6)
C12	0.0226 (7)	0.0247 (7)	0.0195 (6)	0.0016 (6)	0.0007 (6)	0.0004 (6)
C13	0.0300 (8)	0.0317 (8)	0.0265 (7)	0.0000 (7)	0.0022 (6)	0.0083 (7)
C14	0.0271 (8)	0.0311 (9)	0.0360 (9)	−0.0039 (7)	0.0078 (7)	0.0076 (7)
C15	0.0261 (8)	0.0280 (8)	0.0382 (9)	−0.0071 (6)	−0.0002 (7)	0.0042 (7)

Geometric parameters (Å, º)

O1—C12	1.242 (2)	C5—H5	1.0000
O2—H2C	0.90 (3)	C5—C9	1.536 (2)
O2—H2D	0.8882	C6—H6A	0.9900
O3—H3C	0.892 (4)	C6—H6B	0.9900
O3—H3D	0.868 (4)	C6—C7	1.517 (3)
O4—H4A	0.8701 (10)	C7—H7A	0.9900
O4—H4A^i	0.8700 (10)	C7—H7B	0.9900
O4—H4B	0.869 (7)	C7—C8	1.530 (3)
O4—H4B^i	0.869 (7)	C8—H8A	0.9900
N1—C1	1.478 (2)	C8—H8B	0.9900
N1—C5	1.485 (2)	C8—C9	1.535 (2)
N1—C6	1.477 (2)	C9—H9	1.0000
N2—C10	1.4793 (19)	C9—C10	1.545 (2)
N2—C11	1.4648 (19)	C10—H10	1.0000
N2—C12	1.3456 (19)	C10—C15	1.525 (2)
C1—H1A	0.9900	C11—H11A	0.9900
C1—H1B	0.9900	C11—H11B	0.9900
C1—C2	1.513 (3)	C12—C13	1.513 (2)
C2—H2A	0.9900	C13—H13A	0.9900
C2—H2B	0.9900	C13—H13B	0.9900
C2—C3	1.526 (3)	C13—C14	1.513 (2)
C3—H3A	0.9900	C14—H14A	0.9900
C3—H3B	0.9900	C14—H14B	0.9900
C3—C4	1.526 (2)	C14—C15	1.519 (3)
C4—H4	1.0000	C15—H15A	0.9900
C4—C5	1.533 (2)	C15—H15B	0.9900
C4—C11	1.526 (2)
H2C—O2—H2D	100.8	C6—C7—H7B	109.7
H3C—O3—H3D	115.1 (5)	C6—C7—C8	109.76 (16)
H4A—O4—H4A^i	165.2 (10)	H7A—C7—H7B	108.2
H4A^i—O4—H4B^i	106.1 (5)	C8—C7—H7A	109.7
H4A—O4—H4B^i	87.1 (4)	C8—C7—H7B	109.7
H4A—O4—H4B	106.1 (5)	C7—C8—H8A	109.5
H4B—O4—H4A^i	87.1 (4)	C7—C8—H8B	109.5
H4B—O4—H4B^i	56.7 (5)	C7—C8—C9	110.53 (14)
C1—N1—C5	110.50 (13)	H8A—C8—H8B	108.1
C6—N1—C1	108.64 (13)	C9—C8—H8A	109.5
C6—N1—C5	110.37 (14)	C9—C8—H8B	109.5
C11—N2—C10	113.97 (11)	C5—C9—H9	106.9
C12—N2—C10	126.29 (13)	C5—C9—C10	112.74 (13)
C12—N2—C11	119.28 (13)	C8—C9—C5	109.85 (14)
N1—C1—H1A	109.3	C8—C9—H9	106.9
N1—C1—H1B	109.3	C8—C9—C10	113.13 (14)
N1—C1—C2	111.63 (14)	C10—C9—H9	106.9
H1A—C1—H1B	108.0	N2—C10—C9	108.19 (12)
C2—C1—H1A	109.3	N2—C10—H10	108.0
C2—C1—H1B	109.3	N2—C10—C15	112.22 (13)
C1—C2—H2A	109.6	C9—C10—H10	108.0
C1—C2—H2B	109.6	C15—C10—C9	112.14 (13)
C1—C2—C3	110.37 (15)	C15—C10—H10	108.0
H2A—C2—H2B	108.1	N2—C11—C4	111.85 (13)
C3—C2—H2A	109.6	N2—C11—H11A	109.2
C3—C2—H2B	109.6	N2—C11—H11B	109.2
C2—C3—H3A	109.4	C4—C11—H11A	109.2
C2—C3—H3B	109.4	C4—C11—H11B	109.2
H3A—C3—H3B	108.0	H11A—C11—H11B	107.9
C4—C3—C2	111.38 (14)	O1—C12—N2	121.90 (14)
C4—C3—H3A	109.4	O1—C12—C13	119.69 (14)
C4—C3—H3B	109.4	N2—C12—C13	118.41 (14)
C3—C4—H4	107.5	C12—C13—H13A	109.0
C3—C4—C5	111.64 (13)	C12—C13—H13B	109.0
C3—C4—C11	111.38 (13)	C12—C13—C14	112.78 (14)
C5—C4—H4	107.5	H13A—C13—H13B	107.8
C11—C4—H4	107.5	C14—C13—H13A	109.0
C11—C4—C5	111.10 (12)	C14—C13—H13B	109.0
N1—C5—C4	111.41 (13)	C13—C14—H14A	110.1
N1—C5—H5	108.2	C13—C14—H14B	110.1
N1—C5—C9	110.69 (13)	C13—C14—C15	108.12 (14)
C4—C5—H5	108.2	H14A—C14—H14B	108.4
C4—C5—C9	110.16 (12)	C15—C14—H14A	110.1
C9—C5—H5	108.2	C15—C14—H14B	110.1
N1—C6—H6A	109.2	C10—C15—H15A	109.5
N1—C6—H6B	109.2	C10—C15—H15B	109.5
N1—C6—C7	111.87 (14)	C14—C15—C10	110.72 (14)
H6A—C6—H6B	107.9	C14—C15—H15A	109.5
C7—C6—H6A	109.2	C14—C15—H15B	109.5
C7—C6—H6B	109.2	H15A—C15—H15B	108.1
C6—C7—H7A	109.7
O1—C12—C13—C14	157.96 (15)	C6—N1—C1—C2	178.41 (14)
N1—C1—C2—C3	57.83 (18)	C6—N1—C5—C4	177.75 (12)
N1—C5—C9—C8	57.27 (16)	C6—N1—C5—C9	−59.31 (16)
N1—C5—C9—C10	−69.89 (16)	C6—C7—C8—C9	55.0 (2)
N1—C6—C7—C8	−57.47 (19)	C7—C8—C9—C5	−55.19 (19)
N2—C10—C15—C14	39.71 (19)	C7—C8—C9—C10	71.76 (19)
N2—C12—C13—C14	−21.2 (2)	C8—C9—C10—N2	179.23 (13)
C1—N1—C5—C4	57.57 (16)	C8—C9—C10—C15	54.94 (18)
C1—N1—C5—C9	−179.49 (12)	C9—C10—C15—C14	161.74 (14)
C1—N1—C6—C7	−178.87 (15)	C10—N2—C11—C4	−58.37 (16)
C1—C2—C3—C4	−52.81 (19)	C10—N2—C12—O1	177.29 (14)
C2—C3—C4—C5	50.99 (18)	C10—N2—C12—C13	−3.6 (2)
C2—C3—C4—C11	−73.86 (18)	C11—N2—C10—C9	57.60 (16)
C3—C4—C5—N1	−53.37 (17)	C11—N2—C10—C15	−178.16 (13)
C3—C4—C5—C9	−176.61 (13)	C11—N2—C12—O1	−11.0 (2)
C3—C4—C11—N2	179.02 (13)	C11—N2—C12—C13	168.13 (14)
C4—C5—C9—C8	−179.07 (13)	C11—C4—C5—N1	71.63 (16)
C4—C5—C9—C10	53.77 (16)	C11—C4—C5—C9	−51.61 (16)
C5—N1—C1—C2	−60.38 (18)	C12—N2—C10—C9	−130.31 (15)
C5—N1—C6—C7	59.84 (18)	C12—N2—C10—C15	−6.1 (2)
C5—C4—C11—N2	53.87 (16)	C12—N2—C11—C4	128.94 (14)
C5—C9—C10—N2	−55.36 (16)	C12—C13—C14—C15	53.73 (19)
C5—C9—C10—C15	−179.65 (13)	C13—C14—C15—C10	−63.65 (18)

Symmetry code: (i) y−1, x+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2C···O1^ii	0.90 (3)	1.93 (3)	2.8282 (19)	175 (3)
O2—H2D···N1	0.89	1.93	2.8125 (19)	173
O3—H3C···O2^i	0.892 (4)	1.9909 (14)	2.858 (4)	163.8 (4)
O3—H3D···O2	0.868 (4)	1.8826 (15)	2.710 (4)	158.8 (3)
O4—H4B···O3^i	0.869 (7)	1.815 (6)	2.648 (9)	160.2 (3)

Symmetry codes: (i) y−1, x+1, −z+1; (ii) x−1/2, −y+3/2, −z+5/4.