Δ9-Tetra­hydro­cannabinolic acid A, the precursor to Δ9-tetra­hydro­cannabinol (THC)

Skell, J.M.; Kahn, M.; Foxman, B.M.

doi:10.1107/S2053229621000280

Δ⁹-Tetrahydrocannabinolic acid A, the precursor to Δ⁹-tetrahydrocannabinol (THC)

While Δ⁹-tetrahydrocannabinolic acid A (THCA-A) has been reported to be difficult to crystallize and/or amorphous, we have obtained THCA-A in a pure crystalline form by extraction of marijuana and selective fractionation with liquid CO₂. THCA-A (systematic name: 1-hydroxy-6,6,9-trimethyl-3-pentyl-6a,7,8,10a-tetrahydro-6H-benzo[c]isochromene-2-carboxylic acid, C₂₂H₃₀O₄) crystallizes in the orthorhombic space group P2₁2₁2₁, with Z = 8 and Z′ = 2. The two independent molecules are related by a pseudo-twofold axis centered between the two –CO₂H groups, but the conformations of the two –C₅H₁₁ chains are quite different (tgt and ttg; t is trans and g is gauche). The carboxylate groups form an intermolecular R₂²(8) hydrogen-bonded ring; the two C₂O₂ carboxylate planes are twisted out of the planes of the attached arene rings in opposite directions by 13.59 (8) and 18.92 (8)°, respectively, with a resultant interplanar angle of 28.89 (8)°. Each molecule also has an intramolecular S(6) hydrogen-bond motif between the ortho –OH group and the dihydropyran-ring O atom. Other conformational aspects of the two independent molecules are quite similar to those found in the previously determined structure of THCA-B. THCA-A has shown promise in a number of medical applications. Demonstration of the crystallinity and details of the crystal structure are expected to provide a standard point of departure for chemical and medical experiments.

Keywords: hashish; marijuana; cannabis; THC precursor; crystal structure; extract fractionation.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229621000280/cu3167sup1.cif Contains datablocks I, global
	Structure factor file (CIF format) https://doi.org/10.1107/S2053229621000280/cu3167Isup2.hkl Contains datablock I
	Text file https://doi.org/10.1107/S2053229621000280/cu3167sup3.txt Cif file for the full Friedel refinement, as described in text
	Text file https://doi.org/10.1107/S2053229621000280/cu3167sup4.txt fcf file for the full unaveraged Friedel data, as described in text

CCDC reference: 2054808

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: APEX2 (Bruker, 2005); data reduction: APEX2 (Bruker, 2005); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: CRYSTALS (Betteridge et al., 2003); molecular graphics: CAMERON (Watkin et al., 1996); software used to prepare material for publication: PLATON (Spek, 2020), enCIFer (Allen et al., 2004) and publCIF (Westrip, 2010).

1-Hydroxy-6,6,9-trimethyl-3-pentyl-6a,7,8,10a-tetrahydro-6H- benzo[c]isochromene-2-carboxylic acid top

Crystal data top

C₂₂H₃₀O₄	F(000) = 1551.985
M_r = 358.48	D_x = 1.212 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 9857 reflections
a = 11.4069 (4) Å	θ = 2.4–30.0°
b = 17.9819 (7) Å	µ = 0.08 mm⁻¹
c = 19.1565 (7) Å	T = 120 K
V = 3929.3 (3) Å³	Prism fragment, colourless
Z = 8	0.60 × 0.57 × 0.55 mm

Data collection top

Bruker-Nonius Kappa APEXII diffractometer	5129 reflections with I > 2.0σ(I)
Graphite monochromator	R_int = 0.025
φ & ω scans	θ_max = 28.3°, θ_min = 1.6°
Absorption correction: numerical APEX2 (Bruker, 2005)	h = −15→11
T_min = 0.95, T_max = 0.96	k = −23→23
27315 measured reflections	l = −25→25
5394 independent reflections

Refinement top

Refinement on F²	Primary atom site location: other
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F² > 2σ(F²)] = 0.032	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.084	Method = Modified Sheldrick w = 1/[σ²(F²) + ( 0.05P)² + 0.63P], where P = (max(F_o²,0) + 2F_c²)/3
S = 1.00	(Δ/σ)_max = 0.001
5394 reflections	Δρ_max = 0.28 e Å⁻³
485 parameters	Δρ_min = −0.23 e Å⁻³
0 restraints

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O1	−0.28826 (10)	0.55121 (6)	0.64471 (5)	0.0228
O15	−0.05035 (11)	0.68684 (6)	0.80269 (6)	0.0221
O17	0.16067 (10)	0.71275 (7)	0.76716 (6)	0.0251
O18	0.20719 (11)	0.70768 (7)	0.65491 (6)	0.0285
O101	0.89691 (9)	0.87119 (6)	0.78699 (5)	0.0197
O115	0.56771 (10)	0.83424 (6)	0.64098 (5)	0.0191
O117	0.37570 (9)	0.79710 (6)	0.69720 (5)	0.0212
O118	0.37530 (11)	0.75361 (7)	0.80563 (6)	0.0253
C2	−0.18612 (13)	0.58341 (8)	0.66511 (7)	0.0183
C3	−0.09812 (13)	0.58235 (8)	0.61439 (7)	0.0193
C4	0.00986 (13)	0.61426 (8)	0.62523 (7)	0.0173
C5	0.02835 (13)	0.65202 (8)	0.68990 (7)	0.0165
C6	−0.06129 (13)	0.65073 (8)	0.74122 (7)	0.0166
C7	−0.16771 (13)	0.61310 (8)	0.73123 (7)	0.0166
C8	−0.25942 (13)	0.60371 (8)	0.78814 (7)	0.0178
C9	−0.21044 (14)	0.58081 (9)	0.85860 (7)	0.0213
C10	−0.26620 (14)	0.53594 (9)	0.90258 (8)	0.0240
C11	−0.38501 (16)	0.50359 (11)	0.88708 (9)	0.0327
C12	−0.44159 (14)	0.53521 (10)	0.82096 (9)	0.0277
C13	−0.34747 (13)	0.54400 (8)	0.76493 (8)	0.0191
C14	−0.39026 (13)	0.55734 (8)	0.69042 (8)	0.0210
C16	0.13587 (13)	0.69202 (8)	0.70678 (7)	0.0181
C19	−0.21365 (17)	0.51437 (10)	0.97178 (8)	0.0315
C20	−0.46924 (15)	0.49555 (10)	0.66424 (10)	0.0296
C21	−0.44607 (17)	0.63335 (10)	0.67883 (10)	0.0318
C22	0.10228 (13)	0.59999 (8)	0.56999 (7)	0.0198
C23	0.18865 (14)	0.53919 (9)	0.59334 (8)	0.0244
C24	0.26584 (14)	0.50943 (9)	0.53464 (8)	0.0243
C25	0.19819 (17)	0.46847 (11)	0.47818 (9)	0.0319
C26	0.2733 (2)	0.41759 (11)	0.43408 (10)	0.0420
C102	0.78449 (13)	0.85051 (8)	0.77527 (7)	0.0168
C103	0.71770 (13)	0.83850 (8)	0.83553 (7)	0.0184
C104	0.60106 (13)	0.81924 (8)	0.83237 (7)	0.0165
C105	0.54740 (13)	0.81357 (8)	0.76555 (7)	0.0156
C106	0.61546 (13)	0.83032 (7)	0.70533 (7)	0.0151
C107	0.73625 (12)	0.84333 (7)	0.70893 (7)	0.0150
C108	0.81054 (12)	0.85459 (8)	0.64427 (7)	0.0159
C109	0.79494 (13)	0.79704 (8)	0.58704 (7)	0.0184
C110	0.87958 (14)	0.78000 (9)	0.54231 (7)	0.0210
C111	1.00041 (14)	0.81374 (10)	0.54567 (8)	0.0264
C112	1.01288 (14)	0.87550 (9)	0.60037 (8)	0.0241
C113	0.94034 (13)	0.85610 (8)	0.66481 (7)	0.0171
C114	0.96037 (13)	0.90525 (8)	0.72853 (7)	0.0194
C116	0.42738 (13)	0.78905 (8)	0.75428 (7)	0.0172
C119	0.86211 (16)	0.72440 (10)	0.48467 (8)	0.0282
C120	1.08711 (14)	0.90462 (10)	0.75268 (8)	0.0266
C121	0.91637 (16)	0.98449 (9)	0.72018 (8)	0.0263
C122	0.53829 (14)	0.80968 (8)	0.90157 (7)	0.0194
C123	0.56377 (16)	0.73488 (9)	0.93581 (8)	0.0258
C124	0.50727 (16)	0.72753 (10)	1.00802 (8)	0.0294
C125	0.55761 (16)	0.66374 (11)	1.05117 (9)	0.0317
C126	0.68259 (17)	0.67740 (12)	1.07415 (9)	0.0361
H31	−0.1137	0.5571	0.5710	0.0229*
H81	−0.3008	0.6510	0.7944	0.0211*
H91	−0.1370	0.5995	0.8740	0.0256*
H111	−0.3775	0.4483	0.8814	0.0400*
H112	−0.4350	0.5126	0.9274	0.0405*
H121	−0.5026	0.5008	0.8047	0.0334*
H122	−0.4753	0.5834	0.8300	0.0330*
H131	−0.3034	0.4968	0.7636	0.0211*
H151	0.015 (2)	0.7022 (15)	0.8025 (13)	0.049 (7)*
H181	0.258 (2)	0.7353 (12)	0.6710 (11)	0.033 (6)*
H191	−0.1338	0.5346	0.9773	0.0458*
H192	−0.2105	0.4607	0.9769	0.0475*
H193	−0.2589	0.5339	1.0102	0.0461*
H201	−0.5445	0.4993	0.6869	0.0437*
H202	−0.4344	0.4485	0.6747	0.0431*
H203	−0.4832	0.4999	0.6144	0.0435*
H211	−0.5125	0.6398	0.7108	0.0480*
H212	−0.4746	0.6360	0.6305	0.0474*
H213	−0.3888	0.6728	0.6881	0.0464*
H221	0.1455	0.6450	0.5581	0.0245*
H222	0.0622	0.5837	0.5281	0.0240*
H231	0.2376	0.5605	0.6312	0.0295*
H232	0.1439	0.4979	0.6124	0.0288*
H241	0.3074	0.5510	0.5139	0.0304*
H242	0.3217	0.4745	0.5562	0.0302*
H251	0.1594	0.5054	0.4474	0.0397*
H252	0.1376	0.4388	0.5014	0.0383*
H261	0.3034	0.3768	0.4630	0.0623*
H262	0.3400	0.4458	0.4148	0.0641*
H263	0.2280	0.3966	0.3965	0.0624*
H1031	0.7540	0.8441	0.8795	0.0209*
H1081	0.7887	0.9030	0.6239	0.0199*
H1091	0.7201	0.7732	0.5826	0.0234*
H1111	1.0203	0.8332	0.4996	0.0333*
H1112	1.0533	0.7738	0.5583	0.0313*
H1121	0.9854	0.9225	0.5812	0.0285*
H1122	1.0961	0.8800	0.6123	0.0298*
H1131	0.9636	0.8058	0.6781	0.0203*
H1151	0.498 (2)	0.8265 (13)	0.6449 (12)	0.040 (6)*
H1181	0.307 (2)	0.7452 (13)	0.7919 (12)	0.040 (6)*
H1191	0.7866	0.7008	0.4874	0.0416*
H1192	0.8687	0.7494	0.4407	0.0413*
H1193	0.9223	0.6870	0.4862	0.0423*
H1201	1.1152	0.8529	0.7569	0.0390*
H1202	1.0935	0.9292	0.7976	0.0391*
H1203	1.1343	0.9315	0.7201	0.0396*
H1211	0.8334	0.9860	0.7105	0.0387*
H1212	0.9586	1.0084	0.6833	0.0376*
H1213	0.9304	1.0107	0.7629	0.0384*
H1221	0.4544	0.8151	0.8956	0.0231*
H1222	0.5670	0.8494	0.9332	0.0223*
H1231	0.5347	0.6965	0.9060	0.0308*
H1232	0.6497	0.7293	0.9403	0.0310*
H1241	0.4239	0.7206	1.0021	0.0350*
H1242	0.5216	0.7747	1.0341	0.0340*
H1251	0.5542	0.6173	1.0241	0.0369*
H1252	0.5075	0.6581	1.0928	0.0384*
H1261	0.7330	0.6804	1.0325	0.0526*
H1262	0.6885	0.7250	1.0994	0.0544*
H1263	0.7103	0.6365	1.1030	0.0537*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0162 (5)	0.0285 (5)	0.0236 (5)	−0.0059 (4)	−0.0014 (4)	−0.0051 (4)
O15	0.0198 (5)	0.0274 (5)	0.0192 (5)	−0.0088 (5)	0.0041 (4)	−0.0066 (4)
O17	0.0190 (5)	0.0378 (6)	0.0186 (5)	−0.0113 (5)	0.0016 (4)	−0.0038 (5)
O18	0.0221 (6)	0.0442 (7)	0.0191 (5)	−0.0163 (5)	0.0032 (5)	−0.0023 (5)
O101	0.0165 (5)	0.0265 (5)	0.0162 (4)	−0.0074 (4)	−0.0022 (4)	0.0018 (4)
O115	0.0135 (5)	0.0305 (6)	0.0132 (4)	−0.0020 (4)	−0.0016 (4)	0.0015 (4)
O117	0.0150 (5)	0.0306 (5)	0.0180 (5)	−0.0046 (4)	−0.0020 (4)	0.0018 (4)
O118	0.0170 (5)	0.0414 (7)	0.0176 (5)	−0.0101 (5)	0.0010 (4)	0.0026 (5)
C2	0.0157 (7)	0.0170 (6)	0.0222 (6)	−0.0016 (5)	−0.0029 (6)	0.0005 (5)
C3	0.0205 (7)	0.0206 (6)	0.0169 (6)	−0.0015 (6)	−0.0023 (5)	−0.0014 (5)
C4	0.0181 (7)	0.0184 (6)	0.0155 (6)	−0.0004 (5)	0.0004 (5)	0.0009 (5)
C5	0.0151 (6)	0.0177 (6)	0.0166 (6)	−0.0020 (5)	0.0000 (5)	0.0008 (5)
C6	0.0166 (7)	0.0162 (6)	0.0170 (6)	−0.0013 (5)	−0.0001 (5)	0.0009 (5)
C7	0.0149 (6)	0.0160 (6)	0.0190 (6)	−0.0009 (5)	0.0001 (5)	0.0000 (5)
C8	0.0137 (6)	0.0182 (6)	0.0215 (6)	−0.0019 (5)	0.0031 (5)	−0.0021 (5)
C9	0.0180 (7)	0.0259 (7)	0.0199 (6)	−0.0018 (6)	0.0030 (6)	−0.0012 (6)
C10	0.0225 (7)	0.0264 (7)	0.0231 (7)	−0.0006 (6)	0.0073 (6)	−0.0013 (6)
C11	0.0266 (8)	0.0418 (10)	0.0298 (8)	−0.0112 (8)	0.0102 (7)	0.0025 (7)
C12	0.0159 (7)	0.0331 (8)	0.0341 (8)	−0.0068 (6)	0.0068 (6)	−0.0033 (7)
C13	0.0137 (6)	0.0180 (6)	0.0257 (7)	−0.0031 (5)	0.0020 (6)	−0.0004 (5)
C14	0.0137 (7)	0.0201 (7)	0.0292 (7)	−0.0006 (5)	−0.0006 (6)	−0.0011 (6)
C16	0.0157 (7)	0.0210 (6)	0.0176 (6)	−0.0023 (5)	0.0006 (5)	0.0015 (5)
C19	0.0343 (9)	0.0372 (9)	0.0229 (7)	0.0005 (8)	0.0096 (7)	0.0052 (6)
C20	0.0205 (8)	0.0309 (8)	0.0373 (8)	−0.0088 (7)	−0.0035 (7)	−0.0044 (7)
C21	0.0288 (9)	0.0267 (8)	0.0398 (9)	0.0071 (7)	−0.0070 (8)	0.0003 (7)
C22	0.0189 (7)	0.0251 (7)	0.0154 (6)	−0.0003 (6)	0.0018 (5)	−0.0003 (5)
C23	0.0233 (8)	0.0310 (8)	0.0190 (6)	0.0049 (7)	0.0000 (6)	0.0016 (6)
C24	0.0186 (7)	0.0301 (8)	0.0241 (7)	0.0016 (6)	0.0031 (6)	0.0006 (6)
C25	0.0280 (9)	0.0379 (9)	0.0297 (8)	0.0009 (8)	0.0024 (7)	−0.0057 (7)
C26	0.0554 (13)	0.0403 (10)	0.0304 (8)	0.0111 (10)	0.0019 (9)	−0.0064 (8)
C102	0.0156 (7)	0.0180 (6)	0.0169 (6)	−0.0028 (5)	−0.0010 (5)	0.0000 (5)
C103	0.0193 (7)	0.0229 (7)	0.0130 (5)	−0.0032 (6)	−0.0021 (5)	−0.0008 (5)
C104	0.0183 (7)	0.0179 (6)	0.0133 (5)	−0.0007 (5)	0.0005 (5)	−0.0004 (5)
C105	0.0140 (6)	0.0176 (6)	0.0151 (6)	−0.0009 (5)	0.0009 (5)	−0.0011 (5)
C106	0.0160 (6)	0.0161 (6)	0.0133 (5)	−0.0003 (5)	−0.0014 (5)	−0.0004 (5)
C107	0.0154 (6)	0.0161 (6)	0.0136 (5)	−0.0011 (5)	0.0013 (5)	−0.0005 (5)
C108	0.0148 (6)	0.0191 (6)	0.0138 (5)	−0.0012 (5)	0.0004 (5)	0.0010 (5)
C109	0.0168 (7)	0.0236 (7)	0.0150 (6)	0.0001 (6)	−0.0026 (5)	−0.0005 (5)
C110	0.0208 (7)	0.0277 (7)	0.0144 (6)	0.0030 (6)	−0.0015 (6)	0.0014 (5)
C111	0.0205 (7)	0.0397 (9)	0.0190 (6)	0.0013 (7)	0.0053 (6)	0.0007 (6)
C112	0.0174 (7)	0.0325 (8)	0.0224 (7)	−0.0040 (6)	0.0036 (6)	0.0046 (6)
C113	0.0142 (6)	0.0198 (6)	0.0173 (6)	−0.0027 (5)	0.0006 (5)	0.0023 (5)
C114	0.0176 (7)	0.0231 (7)	0.0176 (6)	−0.0068 (6)	0.0001 (5)	0.0010 (5)
C116	0.0146 (6)	0.0203 (6)	0.0168 (6)	−0.0007 (5)	0.0019 (5)	−0.0022 (5)
C119	0.0266 (8)	0.0403 (9)	0.0176 (6)	0.0096 (7)	−0.0020 (6)	−0.0065 (6)
C120	0.0180 (7)	0.0357 (9)	0.0261 (7)	−0.0107 (7)	−0.0030 (6)	0.0007 (6)
C121	0.0338 (9)	0.0198 (7)	0.0253 (7)	−0.0056 (6)	0.0007 (7)	−0.0009 (6)
C122	0.0201 (7)	0.0251 (7)	0.0131 (6)	−0.0028 (6)	0.0023 (5)	−0.0011 (5)
C123	0.0299 (8)	0.0284 (8)	0.0191 (6)	0.0008 (7)	0.0047 (6)	0.0036 (6)
C124	0.0261 (8)	0.0413 (10)	0.0208 (7)	−0.0008 (7)	0.0048 (6)	0.0077 (7)
C125	0.0282 (9)	0.0437 (9)	0.0233 (7)	−0.0062 (8)	−0.0001 (7)	0.0114 (7)
C126	0.0323 (10)	0.0509 (11)	0.0251 (7)	−0.0054 (8)	−0.0058 (7)	0.0026 (8)

Geometric parameters (Å, º) top

O1—C2	1.3584 (17)	C24—H242	0.985
O1—C14	1.4603 (18)	C25—C26	1.512 (3)
O15—C6	1.3506 (17)	C25—H251	0.991
O15—H151	0.79 (3)	C25—H252	0.980
O17—C16	1.2478 (18)	C26—H261	0.981
O18—C16	1.3146 (17)	C26—H262	0.986
O18—H181	0.82 (2)	C26—H263	0.964
O101—C102	1.3540 (18)	C102—C103	1.3998 (19)
O101—C114	1.4674 (17)	C102—C107	1.3907 (18)
O115—C106	1.3495 (16)	C103—C104	1.376 (2)
O115—H1151	0.81 (2)	C103—H1031	0.943
O117—C116	1.2507 (17)	C104—C105	1.4225 (18)
O118—C116	1.3138 (18)	C104—C122	1.5163 (18)
O118—H1181	0.83 (3)	C105—C106	1.4227 (19)
C2—C3	1.397 (2)	C105—C116	1.454 (2)
C2—C7	1.3905 (19)	C106—C107	1.399 (2)
C3—C4	1.375 (2)	C107—C108	1.5145 (18)
C3—H31	0.964	C108—C109	1.5180 (19)
C4—C5	1.4283 (19)	C108—C113	1.5323 (19)
C4—C22	1.5157 (19)	C108—H1081	0.985
C5—C6	1.4187 (19)	C109—C110	1.327 (2)
C5—C16	1.4581 (19)	C109—H1091	0.959
C6—C7	1.403 (2)	C110—C111	1.507 (2)
C7—C8	1.5203 (19)	C110—C119	1.503 (2)
C8—C9	1.518 (2)	C111—C112	1.534 (2)
C8—C13	1.536 (2)	C111—H1111	0.977
C8—H81	0.980	C111—H1112	0.968
C9—C10	1.329 (2)	C112—C113	1.5266 (19)
C9—H91	0.950	C112—H1121	0.974
C10—C11	1.504 (2)	C112—H1122	0.979
C10—C19	1.506 (2)	C113—C114	1.524 (2)
C11—C12	1.531 (2)	C113—H1131	0.976
C11—H111	1.004	C114—C120	1.518 (2)
C11—H112	0.975	C114—C121	1.519 (2)
C12—C13	1.526 (2)	C119—H1191	0.961
C12—H121	0.983	C119—H1192	0.959
C12—H122	0.964	C119—H1193	0.961
C13—C14	1.528 (2)	C120—H1201	0.987
C13—H131	0.987	C120—H1202	0.970
C14—C20	1.516 (2)	C120—H1203	0.956
C14—C21	1.524 (2)	C121—H1211	0.965
C19—H191	0.986	C121—H1212	0.957
C19—H192	0.971	C121—H1213	0.958
C19—H193	0.965	C122—C123	1.524 (2)
C20—H201	0.965	C122—H1221	0.968
C20—H202	0.955	C122—H1222	0.992
C20—H203	0.972	C123—C124	1.532 (2)
C21—H211	0.981	C123—H1231	0.955
C21—H212	0.983	C123—H1232	0.989
C21—H213	0.980	C124—C125	1.526 (2)
C22—C23	1.538 (2)	C124—H1241	0.966
C22—H221	0.974	C124—H1242	0.997
C22—H222	0.968	C125—C126	1.512 (3)
C23—C24	1.525 (2)	C125—H1251	0.985
C23—H231	0.993	C125—H1252	0.986
C23—H232	0.973	C126—H1261	0.985
C24—C25	1.519 (2)	C126—H1262	0.986
C24—H241	0.971	C126—H1263	0.973

C2—O1—C14	118.61 (11)	C25—C26—H263	110.5
C6—O15—H151	104.5 (18)	H261—C26—H263	108.5
C16—O18—H181	106.3 (15)	H262—C26—H263	109.6
C102—O101—C114	117.08 (11)	O101—C102—C103	114.90 (12)
C106—O115—H1151	107.7 (16)	O101—C102—C107	123.49 (12)
C116—O118—H1181	105.9 (16)	C103—C102—C107	121.59 (13)
O1—C2—C3	114.23 (12)	C102—C103—C104	121.93 (13)
O1—C2—C7	123.72 (13)	C102—C103—H1031	118.7
C3—C2—C7	122.02 (13)	C104—C103—H1031	119.3
C2—C3—C4	122.21 (13)	C103—C104—C105	118.26 (12)
C2—C3—H31	118.3	C103—C104—C122	116.53 (12)
C4—C3—H31	119.5	C105—C104—C122	125.12 (12)
C3—C4—C5	117.50 (13)	C104—C105—C106	118.66 (12)
C3—C4—C22	116.56 (12)	C104—C105—C116	124.07 (12)
C5—C4—C22	125.69 (13)	C106—C105—C116	117.23 (12)
C4—C5—C6	119.13 (13)	C105—C106—O115	122.11 (12)
C4—C5—C16	123.44 (13)	C105—C106—C107	122.19 (13)
C6—C5—C16	117.43 (12)	O115—C106—C107	115.70 (12)
C5—C6—O15	121.99 (13)	C106—C107—C102	116.76 (12)
C5—C6—C7	122.48 (12)	C106—C107—C108	122.20 (12)
O15—C6—C7	115.52 (12)	C102—C107—C108	120.91 (12)
C6—C7—C2	116.11 (13)	C107—C108—C109	115.73 (12)
C6—C7—C8	123.44 (12)	C107—C108—C113	109.44 (11)
C2—C7—C8	120.44 (12)	C109—C108—C113	108.11 (12)
C7—C8—C9	114.50 (12)	C107—C108—H1081	107.5
C7—C8—C13	108.66 (11)	C109—C108—H1081	106.6
C9—C8—C13	107.97 (12)	C113—C108—H1081	109.3
C7—C8—H81	108.8	C108—C109—C110	122.58 (14)
C9—C8—H81	107.7	C108—C109—H1091	118.3
C13—C8—H81	109.1	C110—C109—H1091	119.1
C8—C9—C10	123.54 (14)	C109—C110—C111	123.02 (14)
C8—C9—H91	120.4	C109—C110—C119	122.11 (15)
C10—C9—H91	116.1	C111—C110—C119	114.86 (14)
C9—C10—C11	122.74 (15)	C110—C111—C112	113.92 (13)
C9—C10—C19	121.61 (15)	C110—C111—H1111	108.6
C11—C10—C19	115.64 (14)	C112—C111—H1111	109.7
C10—C11—C12	113.54 (14)	C110—C111—H1112	106.4
C10—C11—H111	109.2	C112—C111—H1112	108.0
C12—C11—H111	108.3	H1111—C111—H1112	110.3
C10—C11—H112	107.8	C111—C112—C113	109.68 (13)
C12—C11—H112	110.3	C111—C112—H1121	109.9
H111—C11—H112	107.5	C113—C112—H1121	109.3
C11—C12—C13	108.89 (13)	C111—C112—H1122	108.0
C11—C12—H121	109.1	C113—C112—H1122	110.8
C13—C12—H121	109.9	H1121—C112—H1122	109.1
C11—C12—H122	110.7	C108—C113—C112	108.67 (11)
C13—C12—H122	108.3	C108—C113—C114	111.15 (12)
H121—C12—H122	109.9	C112—C113—C114	115.71 (12)
C8—C13—C12	109.19 (12)	C108—C113—H1131	108.3
C8—C13—C14	111.70 (12)	C112—C113—H1131	106.0
C12—C13—C14	116.65 (13)	C114—C113—H1131	106.7
C8—C13—H131	106.0	C113—C114—O101	107.17 (11)
C12—C13—H131	106.7	C113—C114—C120	112.49 (13)
C14—C13—H131	105.8	O101—C114—C120	103.54 (11)
C13—C14—O1	107.08 (12)	C113—C114—C121	114.21 (12)
C13—C14—C20	112.58 (13)	O101—C114—C121	107.99 (12)
O1—C14—C20	102.70 (12)	C120—C114—C121	110.71 (13)
C13—C14—C21	114.23 (13)	C105—C116—O118	117.49 (12)
O1—C14—C21	108.25 (13)	C105—C116—O117	122.57 (13)
C20—C14—C21	111.16 (14)	O118—C116—O117	119.84 (13)
C5—C16—O18	117.29 (13)	C110—C119—H1191	111.9
C5—C16—O17	122.93 (13)	C110—C119—H1192	108.9
O18—C16—O17	119.76 (13)	H1191—C119—H1192	109.0
C10—C19—H191	111.5	C110—C119—H1193	110.3
C10—C19—H192	111.0	H1191—C119—H1193	109.3
H191—C19—H192	108.7	H1192—C119—H1193	107.4
C10—C19—H193	111.4	C114—C120—H1201	109.9
H191—C19—H193	106.2	C114—C120—H1202	109.8
H192—C19—H193	107.8	H1201—C120—H1202	109.4
C14—C20—H201	109.2	C114—C120—H1203	109.5
C14—C20—H202	109.4	H1201—C120—H1203	110.3
H201—C20—H202	109.7	H1202—C120—H1203	107.9
C14—C20—H203	111.4	C114—C121—H1211	111.7
H201—C20—H203	106.9	C114—C121—H1212	109.5
H202—C20—H203	110.2	H1211—C121—H1212	109.8
C14—C21—H211	109.7	C114—C121—H1213	108.4
C14—C21—H212	108.6	H1211—C121—H1213	108.3
H211—C21—H212	109.1	H1212—C121—H1213	109.0
C14—C21—H213	110.1	C104—C122—C123	112.71 (12)
H211—C21—H213	108.4	C104—C122—H1221	110.6
H212—C21—H213	110.8	C123—C122—H1221	109.1
C4—C22—C23	111.27 (11)	C104—C122—H1222	107.3
C4—C22—H221	112.0	C123—C122—H1222	108.0
C23—C22—H221	109.5	H1221—C122—H1222	109.0
C4—C22—H222	107.5	C122—C123—C124	112.61 (13)
C23—C22—H222	109.2	C122—C123—H1231	108.3
H221—C22—H222	107.2	C124—C123—H1231	109.4
C22—C23—C24	113.87 (12)	C122—C123—H1232	108.4
C22—C23—H231	107.3	C124—C123—H1232	109.2
C24—C23—H231	110.5	H1231—C123—H1232	108.9
C22—C23—H232	108.4	C123—C124—C125	113.31 (15)
C24—C23—H232	108.1	C123—C124—H1241	108.6
H231—C23—H232	108.5	C125—C124—H1241	109.7
C23—C24—C25	113.69 (14)	C123—C124—H1242	108.0
C23—C24—H241	108.3	C125—C124—H1242	107.9
C25—C24—H241	109.2	H1241—C124—H1242	109.3
C23—C24—H242	106.8	C124—C125—C126	112.97 (16)
C25—C24—H242	108.5	C124—C125—H1251	109.8
H241—C24—H242	110.3	C126—C125—H1251	109.1
C24—C25—C26	113.79 (16)	C124—C125—H1252	107.2
C24—C25—H251	109.0	C126—C125—H1252	109.2
C26—C25—H251	109.0	H1251—C125—H1252	108.4
C24—C25—H252	107.4	C125—C126—H1261	108.9
C26—C25—H252	109.0	C125—C126—H1262	110.4
H251—C25—H252	108.6	H1261—C126—H1262	108.0
C25—C26—H261	109.6	C125—C126—H1263	110.4
C25—C26—H262	109.6	H1261—C126—H1263	108.2
H261—C26—H262	109.0	H1262—C126—H1263	110.9

C14—O1—C2—C3	−172.61 (12)	C114—O101—C102—C103	−162.57 (12)
C14—O1—C2—C7	9.3 (2)	C114—O101—C102—C107	15.77 (19)
C2—O1—C14—C13	−42.72 (16)	C102—O101—C114—C113	−48.07 (15)
C2—O1—C14—C20	−161.47 (13)	C102—O101—C114—C120	−167.16 (12)
C2—O1—C14—C21	80.89 (16)	C102—O101—C114—C121	75.40 (15)
O1—C2—C3—C4	178.13 (13)	O101—C102—C103—C104	178.17 (13)
C7—C2—C3—C4	−3.8 (2)	C107—C102—C103—C104	−0.2 (2)
O1—C2—C7—C6	−173.90 (13)	O101—C102—C107—C106	−172.50 (13)
O1—C2—C7—C8	6.5 (2)	O101—C102—C107—C108	3.4 (2)
C3—C2—C7—C6	8.2 (2)	C103—C102—C107—C106	5.7 (2)
C3—C2—C7—C8	−171.47 (13)	C103—C102—C107—C108	−178.42 (13)
C2—C3—C4—C5	−2.6 (2)	C102—C103—C104—C105	−1.7 (2)
C2—C3—C4—C22	171.92 (13)	C102—C103—C104—C122	−178.59 (13)
C3—C4—C5—C6	4.1 (2)	C103—C104—C105—C106	−2.0 (2)
C3—C4—C5—C16	−176.33 (14)	C103—C104—C105—C116	175.79 (14)
C22—C4—C5—C6	−169.88 (13)	C122—C104—C105—C106	174.59 (13)
C22—C4—C5—C16	9.7 (2)	C122—C104—C105—C116	−7.6 (2)
C3—C4—C22—C23	−100.99 (15)	C103—C104—C122—C123	−79.27 (17)
C5—C4—C22—C23	73.06 (18)	C105—C104—C122—C123	104.10 (17)
C4—C5—C6—O15	−178.35 (13)	C104—C105—C106—O115	−172.52 (13)
C4—C5—C6—C7	0.6 (2)	C104—C105—C106—C107	7.9 (2)
C16—C5—C6—O15	2.1 (2)	C116—C105—C106—O115	9.6 (2)
C16—C5—C6—C7	−179.03 (13)	C116—C105—C106—C107	−170.04 (13)
C4—C5—C16—O17	−166.12 (14)	C104—C105—C116—O117	166.82 (14)
C4—C5—C16—O18	15.4 (2)	C104—C105—C116—O118	−16.9 (2)
C6—C5—C16—O17	13.5 (2)	C106—C105—C116—O117	−15.4 (2)
C6—C5—C16—O18	−165.04 (13)	C106—C105—C116—O118	160.85 (13)
O15—C6—C7—C2	172.40 (13)	O115—C106—C107—C102	170.78 (12)
O15—C6—C7—C8	−8.0 (2)	O115—C106—C107—C108	−5.01 (18)
C5—C6—C7—C2	−6.6 (2)	C105—C106—C107—C102	−9.60 (19)
C5—C6—C7—C8	173.05 (13)	C105—C106—C107—C108	174.61 (13)
C2—C7—C8—C9	134.66 (14)	C102—C107—C108—C109	135.00 (13)
C2—C7—C8—C13	13.89 (18)	C102—C107—C108—C113	12.59 (18)
C6—C7—C8—C9	−44.94 (19)	C106—C107—C108—C109	−49.38 (18)
C6—C7—C8—C13	−165.72 (13)	C106—C107—C108—C113	−171.79 (12)
C7—C8—C9—C10	−145.15 (15)	C107—C108—C109—C110	−152.10 (14)
C13—C8—C9—C10	−24.0 (2)	C113—C108—C109—C110	−28.97 (19)
C7—C8—C13—C12	−178.79 (12)	C107—C108—C113—C112	−174.18 (11)
C7—C8—C13—C14	−48.27 (16)	C107—C108—C113—C114	−45.74 (15)
C9—C8—C13—C12	56.49 (15)	C109—C108—C113—C112	58.97 (15)
C9—C8—C13—C14	−172.99 (12)	C109—C108—C113—C114	−172.59 (11)
C8—C9—C10—C11	−0.6 (3)	C108—C109—C110—C111	2.5 (2)
C8—C9—C10—C19	179.59 (14)	C108—C109—C110—C119	−178.34 (14)
C9—C10—C11—C12	−7.6 (2)	C109—C110—C111—C112	−6.2 (2)
C19—C10—C11—C12	172.28 (15)	C119—C110—C111—C112	174.57 (13)
C10—C11—C12—C13	40.0 (2)	C110—C111—C112—C113	36.74 (18)
C11—C12—C13—C8	−66.11 (17)	C111—C112—C113—C108	−64.38 (15)
C11—C12—C13—C14	166.11 (13)	C111—C112—C113—C114	169.79 (13)
C8—C13—C14—O1	63.00 (15)	C108—C113—C114—O101	63.72 (14)
C8—C13—C14—C20	175.14 (13)	C108—C113—C114—C120	176.86 (12)
C8—C13—C14—C21	−56.85 (17)	C108—C113—C114—C121	−55.85 (16)
C12—C13—C14—O1	−170.45 (12)	C112—C113—C114—O101	−171.72 (12)
C12—C13—C14—C20	−58.31 (18)	C112—C113—C114—C120	−58.58 (17)
C12—C13—C14—C21	69.71 (18)	C112—C113—C114—C121	68.72 (17)
C4—C22—C23—C24	166.60 (13)	C104—C122—C123—C124	175.97 (13)
C22—C23—C24—C25	−65.26 (18)	C122—C123—C124—C125	−164.23 (14)
C23—C24—C25—C26	−160.45 (15)	C123—C124—C125—C126	69.06 (19)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O115—H1151···O117	0.81 (2)	1.80 (2)	2.5304 (15)	150 (2)
O118—H1181···O17	0.84 (2)	1.83 (2)	2.6603 (17)	171 (2)
O15—H151···O17	0.80 (2)	1.80 (2)	2.5445 (17)	154 (3)
O18—H181···O117	0.82 (2)	1.81 (2)	2.6337 (16)	174 (2)

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Δ9-Tetra­hydro­cannabinolic acid A, the precursor to Δ9-tetra­hydro­cannabinol (THC)

Supporting information

Δ⁹-Tetrahydrocannabinolic acid A, the precursor to Δ⁹-tetrahydrocannabinol (THC)