Psilacetin derivatives: fumarate salts of the meth­yl–ethyl, meth­yl–allyl and diallyl variants of the psilocin prodrug

Pham, D.N.K.; Chadeayne, A.R.; Golen, J.A.; Manke, D.R.

doi:10.1107/S2056989021000116

research communications

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 77| Part 2| February 2021| Pages 101-106

https://doi.org/10.1107/S2056989021000116

Open

access

Psilacetin derivatives: fumarate salts of the methyl–ethyl, methyl–allyl and diallyl variants of the psilocin prodrug

Duyen N. K. Pham,^a Andrew R. Chadeayne,^b James A. Golen ^a and David R. Manke ^a ^*

^aUniversity of Massachusetts Dartmouth, 285 Old Westport Road, North Dartmouth, MA 02747, USA, and ^bCaaMTech, Inc., 58 East Sunset Way, Suite 209, Issaquah, WA 98027, USA
^*Correspondence e-mail: dmanke@umassd.edu

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 31 December 2020; accepted 4 January 2021; online 8 January 2021)

The solid-state structures of the salts of three psilacetin derivatives, namely, 4-acetoxy-N-ethyl-N-methyltryptammonium (4-AcO-MET) hydrofumarate {systematic name: [2-(4-acetyloxy-1H-indol-3-yl)ethyl](methyl)ethylazanium 3-carboxyprop-2-enoate}, C₁₅H₂₁N₂O₂⁺·C₄H₃O₄⁻, 4-acetoxy-N-allyl-N-methyltryptammonium (4-AcO-MALT) hydrofumarate {systematic name: [2-(4-acetyloxy-1H-indol-3-yl)ethyl](methyl)prop-2-enylazanium 3-carboxyprop-2-enoate}, C₁₆H₂₁N₂O₂⁺·C₄H₃O₄⁻, and 4-acetoxy-N,N-diallyltryptammonium (4-AcO-DALT) fumarate–fumaric acid (1/1) (systematic name: bis{[2-(4-acetyloxy-1H-indol-3-yl)ethyl]diprop-2-enylazanium} but-2-enedioate–(E)-butenedioic acid (1/1)), 2C₁₈H₂₃N₂O₂⁺·C₄H₂O₄²⁻·C₄H₄O₄, are reported. All three salts possess a protonated tryptammonium cation. The 4-AcO-MET and 4-AcO-MALT compounds are charge-balanced by 3-carboxyacrylate (hydrofumarate) anions. The 4-AcO-DALT complex crystallizes as a two-to-one tryptammonium-to-fumarate salt, which co-crystallizes with a fumaric acid molecule. Each structure is consolidated by N—H⋯O and O—H⋯O hydrogen bonds.

Keywords: crystal structure; tryptamines; indoles; fumarates; hydrogen bonding.

CCDC references: 2053845; 2053844; 2053843

1. Chemical context

Psychotropic tryptamines have emerged as leading candidates in the treatment of mood disorders, including anxiety, addiction, depression and post-traumatic stress disorder (Byock, 2018 ; Daniel & Haberman, 2017 ). Perhaps the best known of these tryptamines is psilocybin, N,N,N-trimethyl-4-phosphoryloxytryptamine (C₁₂H₁₇N₂O₄P), which has recently been cleared for a number of clinical trials after receiving the `breakthrough therapy' designation from the US Food and Drug Administration (Feltman, 2019 ). When psilocybin is consumed orally, it is hydrolysed to generate 4-hydroxy-N,N-dimethyltryptamine, C₁₂H₁₆N₂O (4-HO-DMT), or psilocin, which is the active metabolite. Psilocin is a potent serotonin 2a agonist, and is the primary origin of its psychoactive properties (Geiger et al., 2018 ).

Psilacetin, 4-acetoxy-N,N-dimethyltryptamine, C₁₄H₁₈N₂O₂ (4-AcO-DMT), is a synthetic alternative to psilocybin. It also acts as a prodrug of psilocin, with the acetyl group of psilacetin being hydrolysed as it is metabolized, converting 4-AcO-DMT to 4-HO-DMT. Psilacetin is easier to synthesize than psilocybin, and can also be produced at a lower cost, making it, perhaps, a better candidate for the delivery of psilocin (Nichols & Frescas, 1999 ). Presumably, all 4-acetoxy-substituted tryptamines would similarly function as prodrugs for their active metabolite psilocin analogues. Three such compounds are 4-acetoxy-N-ethyl-N-methyltryptamine, C₁₅H₂₀N₂O₂ (4-AcO-MET), 4-acetoxy-N-allyl-N-methyltryptamine, C₁₆H₂₀N₂O₂ (4-AcO-MALT), and 4-acetoxy-N,N-diallyltryptamine, C₁₈H₂₂N₂O₂ (4-AcO-DALT). These variations of psilacetin have garnered very little attention in the scientific literature, with only one reference made to 4-AcO-MET in a chromatographic screening article prior to this year (Lehmann et al., 2017 ). A recent report on the activity of psilacetin analogues and their metabolites included 4-AcO-MET (Klein et al., 2020 ). Herein, we report the first solid-state structures of the fumarate salts of 4-AcO-MET, 4-AcO-MALT and 4-AcO-DALT.

2. Structural commentary

The molecular structure of 4-AcO-MET hydrofumarate, (I), is shown in Fig. 1. The asymmetric unit contains one 4-acetoxy-N-ethyl-N-methyltryptammonium (C₁₅H₂₁N₂O₂⁺) cation and one hydrofumarate (C₄H₃O₄⁻) anion. The indole ring system of the cation is near planar with an r.m.s. deviation of 0.015 Å. The hydrofumarate anion is slightly twisted, demonstrating a deviation from planarity of 0.158 Å, and a C16/O3/O4 carboxylate to C19/O5/O6 carboxylic acid plane normal angle of 23.0 (3)°. The N-methyl-N-ethyl group of the cation is disordered over two orientations in a 0.76 (1):0.24 (7) ratio. The ethylammonium arm is turned slightly away from the plane of the indole, with C10—C9—C11—C12 and C10—C9—C11—C12A torsion angles of 39.7 (7) and 49.5 (2)°, respectively, for the two orientations.

Figure 1
The molecular structure of 4-AcO-MET hydrofumarate (I)

The molecular structure of 4-AcO-MALT hydrofumarate, (II), is shown in Fig. 2. The asymmetric unit contains one 4-acetoxy-N-allyl-N-methyltryptammonium (C₁₆H₂₁N₂O₂⁺) cation and one hydrofumarate (C₄H₃O₄⁻) anion. The indole ring system of the compound is almost planar with an r.m.s. deviation from planarity of 0.006 Å. The ethylammonium arm is turned slightly away from the plane of the indole ring, with a C10—C9—C11—C12 torsion angle of 39.8 (4)°. The hydrofumarate anion is slightly twisted, showing a deviation from planarity of 0.128 Å, and a C20/O5/O6 carboxylate to C17/O3/O4 carboxylic acid twist of 18.6 (2)°.

Figure 2
The molecular structure of 4-AcO-MALT hydrofumarate (II)

, showing the atomic labeling. Displacement ellipsoids are drawn at the 50% probability level. Hydrogen bonds are shown as dashed lines.

The molecular structure of 4-AcO-DALT fumarate–fumaric acid, (III), is shown in Fig. 3. The asymmetric unit contains one 4-acetoxy-N,N-diallyltryptammonium (C₁₈H₂₃N₂O₂⁺) cation, one half of a fumarate (C₂HO₂⁻) dianion, and one half of a fumaric acid (C₂H₄O₂) molecule. The indole ring system of the compound is near planar with a r.m.s. deviation from planarity of 0.016 Å. The ethylammonium arm is turned significantly away from the plane of the indole ring, with a C10—C9—C11—C12 torsion angle of 104.3 (2)°. The complete fumarate dianion is generated through crystallographic inversion symmetry, and is also near planar, with an r.m.s. deviation from planarity of 0.004 Å. The full disordered (vide infra) fumaric acid molecule is generated through inversion, and also demonstrates near planarity, with r.m.s. deviations from planarity of 0.082 and 0.083 Å for the two conformations. One of the allyl groups in the cation is disordered over two orientations with a 0.90 (1):0.10 (1) ratio. The fumaric acid molecule is also disordered over two components with a 0.52 (4):0.48 (4) ratio. The 4-acetoxy group also shows a disorder over two orientations with a 0.62 (4):0.38 (4) ratio. The carboxylate group of the fumarate anion is delocalized, with C—O distances of 1.251 (3) and 1.258 (2) Å.

Figure 3
The molecular structure of 4-AcO-DALT fumarate fumaric acid (III)

, showing the atomic labeling. Displacement ellipsoids are drawn at the 50% probability level. Dashed bonds indicate a disordered component in the structures. Hydrogen bonds are shown as dashed lines. Symmetry codes: (i) 1 − x, 2 − y, 1 − z; (ii) $[{3\over 2}]$ − x, $[{3\over 2}]$ − y, 1 − z.

3. Supramolecular features

In the extended structure of (I), the N-ethyl-N-methyltryptammonium cations and hydrofumarate anions are linked together in a two-dimensional network lying in the (010) plane through N—H⋯O and O—H⋯O hydrogen bonds (Table 1). The O—H group of the hydrofumarate hydrogen bonds with the carbonyl oxygen atom of the carboxylate unit of another hydrofumarate ion, the ammonium N—H hydrogen bonds to the negatively charged oxygen atom of the carboxylate group of a hydrofumarate ion, and the indole N—H hydrogen bonds to the carbonyl oxygen atom of the carboxylic acid unit of a hydrofumarate ion (Fig. 4, top). The packing of 4-AcO-MET hydrofumarate is shown at the top left of Fig. 5.

Table 1
Hydrogen-bond geometry (Å, °) for (I)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O6ⁱ	0.86 (1)	2.02 (2)	2.858 (4)	165 (5)
N2—H2⋯O4	0.88 (2)	1.85 (4)	2.644 (6)	150 (7)
N2A—H2A⋯O4	0.87 (2)	1.94 (6)	2.776 (14)	162 (17)
O5—H5A⋯O3ⁱⁱ	0.89 (2)	1.61 (2)	2.459 (4)	160 (6)
Symmetry codes: (i) ; (ii) .

Figure 4
The hydrogen bonding environments of the hydrofumarate ion in the structure of (I)

(top), the hydrofumarate ion in the structure of (II)

(middle), and the fumarate dianion in the structure of (III)

(bottom). Displacement ellipsoids are drawn at the 50% probability level. Hydrogen atoms not involved in hydrogen bonds are omitted for clarity. Only one component of disorders are shown. Symmetry codes: (i) 1 + x, y, z; (ii) −1 + x, y, 1 + z; (iii) −1 + x, y, z; (iv) 2 + x, y, 1 + z; (v) 1 − x, 2 − y, 1 − z; (vi) $[{1\over 2}]$ − x, $[{1\over 2}]$ + y, $[{1\over 2}]$ − z; (vii) $[{1\over 2}]$ + x, $[{3\over 2}]$ − y, $[{1\over 2}]$ + z.

Figure 5
The crystal packing of (I)

(top left), viewed along the a-axis direction, the crystal packing of (II)

(top right), viewed along the a-axis direction and the crystal packing of (III)

(bottom), viewed along the b-axis direction. The hydrogen bonds (Tables 1

–3

) are shown as dashed lines. Displacement ellipsoids are drawn at the 50% probability level. Hydrogen atoms not involved in hydrogen bonds are omitted for clarity. Only one component of disorders are shown.

In the extended structure of (II), the N-allyl-N-methyltryptammonium cations and hydrofumarate anions are linked together in an infinite two-dimensional network parallel to (010) through N—H⋯O and O—H⋯O hydrogen bonds (Table 2). The O—H group of the hydrofumarate hydrogen bonds with the negatively charged oxygen atom of the carboxylate unit of another hydrofumarate ion, the indole N—H hydrogen bond to the carbonyl O atom of the carboxylate group of the hydrofumarate ion, and the ammonium N—H hydrogen bonds to the carbonyl oxygen atom of the carboxylic acid unit of the hydrofumarate ion (Fig. 4, center). The packing of 4-AcO-MALT hydrofumarate is shown at the top right of Fig. 5.

Table 2
Hydrogen-bond geometry (Å, °) for (II)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O5ⁱ	0.87 (1)	2.00 (2)	2.857 (3)	169 (4)
O4—H4A⋯O6ⁱⁱ	0.89 (1)	1.56 (2)	2.454 (3)	175 (6)
Symmetry codes: (i) ; (ii) .

In the extended structure of (III), the N,N-diallyltryptammonium cations, fumarate dianions and fumaric acid molecules are linked together in a three-dimensional network through N—H⋯O and O—H⋯O hydrogen bonds (Table 3). The O—H group of the fumaric acid, the ammonium N—H, and the indole N—H group all hydrogen bond to oxygen atoms of the fumarate dianion (Fig. 4, bottom). The packing of 4-AcO-DALT fumarate–fumaric acid is shown at the bottom of Fig. 5.

Table 3
Hydrogen-bond geometry (Å, °) for (III)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O3ⁱ	0.87 (1)	2.22 (2)	2.962 (2)	144 (2)
N2—H2⋯O3	0.88 (1)	1.87 (1)	2.7446 (19)	177 (2)
O6—H6A⋯O4	0.82	1.72	2.530 (17)	168
O6A—H6AA⋯O4	0.82	1.81	2.577 (16)	156
Symmetry code: (i) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

4. Database survey

The three structures reported here are closely related to psilacetin, which has been reported as both the hydrofumarate (HOCJUH: Chadeayne, Golen & Manke 2019b ) and fumarate (XOFDOO: Chadeayne et al., 2019a ) salts. 4-AcO-MET and 4-AcO-MALT both form hydrofumarate salts, though the hydrogen-bonding networks vary from that observed for psilacetin. 4-AcO-DALT crystallizes as the fumarate salt, but also co-crystallizes with a fumaric acid molecule in the structure. The structure of the acetoxy-protected version of the active metabolite of aeruginascin, 4-acetoxy-N,N,N-trimethyltryptamine, has been reported (XUXDUS: Chadeayne, Pham, Reid et al., 2020 ). The other reported structures of tryptammonium hydrofumarate monoanion salts are for 4-hydroxy-N-methyl-N-isopropyltryptamine and N-methyl-N-isopropyltryptamine (RONSUL and RONSOF: Chadeayne, Pham et al., 2019b) and N-ethyl-N-n-propyltryptamine and N-allyl-N-methyltryptamine (CCDC 2012495 and CCDC 2012494: Chadeayne et al., 2020c ). The other reported structures of tryptammonium fumarate dianion salts are for 4-hydroxy-N,N-dipropyltryptamine (CCDC 1962339: Chadeayne et al., 2019b ), 4-hydroxy-N-methyl-N-isopropyltryptamine (CCDC 1987588: Chadeayne et al., 2020a ) and 4-hydroxy-N-methyltryptamine (CCDC 1992278: Chadeayne et al., 2020b ).

5. Synthesis and crystallization

Single crystals of 4-acetoxy-N-ethyl-N-methyltryptammonium hydrofumarate suitable for X-ray analysis were obtained from the slow evaporation of an ethanolic solution of a commercial sample (The Indole Shop). A commercial sample of 4-acetoxy-N-allyl-N-methyltryptammonium hydrofumarate (The Indole Shop) was recrystallized by the slow evaporation of an aqueous solution to yield samples suitable for single crystal X-ray diffraction studies. Single crystals of bis(4-acetoxy-N,N-diallyltryptammonium) fumarate fumaric acid suitable for X-ray analysis were obtained from the slow evaporation of an acetone solution of a commercial sample (The Indole Shop).

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 4. O and N-bound H atoms were refined with the restraints O—H = 0.88±1 and N—H = 0.87±1 Å and with U_iso(H) = 1.2U_eq(N) or 1.5U_eq(O). C-bound H atoms were positioned geometrically and refined using a riding model: C—H = 0.95 Å with U_iso(H) = 1.2U_eq(C) or 1.5U_eq(C-methyl).

Table 4
Experimental details

	(I)	(II)	(III)
Crystal data
Chemical formula	C₁₅H₂₁N₂O₂⁺·C₄H₃O₄⁻	C₁₆H₂₁N₂O₂⁺·C₄H₃O₄⁻	2C₁₈H₂₃N₂O₂⁺·C₄H₂O₄²⁻·C₄H₄O₄
M_r	376.40	388.41	828.90
Crystal system, space group	Monoclinic, P2₁	Monoclinic, P2₁	Monoclinic, C2/c
Temperature (K)	200	297	297
a, b, c (Å)	7.9555 (4), 13.3696 (7), 9.9708 (5)	7.9702 (4), 14.1788 (7), 9.8035 (5)	23.6642 (19), 8.4204 (7), 23.4002 (18)
β (°)	112.874 (2)	113.394 (2)	111.614 (2)
V (Å³)	977.12 (9)	1016.80 (9)	4334.9 (6)
Z	2	2	4
Radiation type	Mo Kα	Mo Kα	Mo Kα
μ (mm⁻¹)	0.10	0.09	0.09
Crystal size (mm)	0.24 × 0.2 × 0.2	0.34 × 0.24 × 0.2	0.22 × 0.2 × 0.12

Data collection
Diffractometer	Bruker D8 Venture CMOS	Bruker D8 Venture CMOS	Bruker D8 Venture CMOS
Absorption correction	Multi-scan (SADABS; Bruker, 2018 )	Multi-scan (SADABS; Bruker, 2018)	Multi-scan (SADABS; Bruker, 2018)
T_min, T_max	0.708, 0.745	0.686, 0.745	0.715, 0.745
No. of measured, independent and observed [I > 2σ(I)] reflections	21973, 3536, 3232	26393, 3797, 3516	99597, 4126, 3441
R_int	0.036	0.039	0.040
(sin θ/λ)_max (Å⁻¹)	0.603	0.610	0.611

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.052, 0.146, 1.04	0.043, 0.113, 1.04	0.051, 0.140, 1.06
No. of reflections	3536	3797	4126
No. of parameters	271	264	354
No. of restraints	15	4	114
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement	H atoms treated by a mixture of independent and constrained refinement	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.39, −0.55	0.27, −0.16	0.50, −0.30
Absolute structure	Flack x determined using 1411 quotients [(I⁺)−(I⁻)]/[(I⁺)+(I⁻)] (Parsons et al., 2013 )	Flack x determined using 1577 quotients [(I⁺)−(I⁻)]/[(I⁺)+(I⁻)] (Parsons et al., 2013)	–
Absolute structure parameter	−0.3 (3)	0.4 (3)	–
Computer programs: APEX3 and SAINT (Bruker, 2018), SHELXT2014 (Sheldrick, 2015a ), SHELXL2018 (Sheldrick, 2015b ), OLEX2 (Dolomanov et al., 2009 ), and publCIF (Westrip, 2010 ).

Supporting information

CCDC references: 2053845; 2053844; 2053843

Crystal structure: contains datablocks I, II, III, global. DOI: https://doi.org/10.1107/S2056989021000116/hb7959sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989021000116/hb7959Isup2.hkl

Structure factors: contains datablock II. DOI: https://doi.org/10.1107/S2056989021000116/hb7959IIsup3.hkl

Structure factors: contains datablock III. DOI: https://doi.org/10.1107/S2056989021000116/hb7959IIIsup4.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989021000116/hb7959Isup5.cml

Supporting information file. DOI: https://doi.org/10.1107/S2056989021000116/hb7959IIsup6.cml

Supporting information file. DOI: https://doi.org/10.1107/S2056989021000116/hb7959IIIsup7.cml

checkCIF report

Computing details top

For all structures, data collection: APEX3 (Bruker, 2018); cell refinement: SAINT (Bruker, 2018); data reduction: SAINT (Bruker, 2018); program(s) used to solve structure: SHELXT2014 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: publCIF (Westrip, 2010).

[2-(4-Acetyloxy-1H-indol-3-yl)ethyl](methyl)ethylazanium 3-carboxyprop-2-enoate (I) top

Crystal data top

C₁₅H₂₁N₂O₂⁺·C₄H₃O₄⁻	F(000) = 400
M_r = 376.40	D_x = 1.279 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
a = 7.9555 (4) Å	Cell parameters from 9372 reflections
b = 13.3696 (7) Å	θ = 2.7–25.4°
c = 9.9708 (5) Å	µ = 0.10 mm⁻¹
β = 112.874 (2)°	T = 200 K
V = 977.12 (9) Å³	Block, colorless
Z = 2	0.24 × 0.2 × 0.2 mm

Data collection top

Bruker D8 Venture CMOS diffractometer	3232 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.036
Absorption correction: multi-scan (SADABS; Bruker, 2018)	θ_max = 25.4°, θ_min = 2.8°
T_min = 0.708, T_max = 0.745	h = −9→9
21973 measured reflections	k = −16→16
3536 independent reflections	l = −11→12

Refinement top

Refinement on F²	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.052	w = 1/[σ²(F_o²) + (0.0859P)² + 0.4056P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.146	(Δ/σ)_max < 0.001
S = 1.04	Δρ_max = 0.39 e Å⁻³
3536 reflections	Δρ_min = −0.55 e Å⁻³
271 parameters	Absolute structure: Flack x determined using 1411 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons et al., 2013)
15 restraints	Absolute structure parameter: −0.3 (3)

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
O1	0.8969 (4)	0.6685 (2)	0.3476 (3)	0.0419 (7)
O2	0.6590 (4)	0.7649 (2)	0.2143 (3)	0.0527 (8)
O3	0.6091 (4)	0.4634 (4)	0.5977 (3)	0.0643 (11)
O4	0.3948 (4)	0.4494 (4)	0.3791 (3)	0.0726 (12)
O5	−0.1636 (4)	0.4458 (3)	0.4883 (3)	0.0464 (7)
H5A	−0.228 (7)	0.461 (5)	0.541 (5)	0.070*
O6	0.0341 (4)	0.5232 (3)	0.6851 (3)	0.0530 (8)
N1	0.8829 (5)	0.5556 (3)	−0.1012 (4)	0.0445 (8)
H1	0.909 (7)	0.546 (4)	−0.177 (3)	0.053*
C1	0.6770 (8)	0.7029 (4)	0.4462 (5)	0.0609 (13)
H1A	0.771261	0.727703	0.536780	0.091*
H1B	0.656163	0.631605	0.456386	0.091*
H1C	0.563452	0.739969	0.425935	0.091*
C2	0.7388 (6)	0.7176 (3)	0.3229 (4)	0.0398 (9)
C3	0.9685 (5)	0.6723 (3)	0.2378 (4)	0.0377 (9)
C4	1.1178 (6)	0.7317 (3)	0.2611 (5)	0.0505 (11)
H4	1.165836	0.772222	0.345887	0.061*
C5	1.1983 (7)	0.7322 (4)	0.1596 (6)	0.0581 (13)
H5	1.303718	0.772121	0.177668	0.070*
C6	1.1292 (7)	0.6765 (4)	0.0340 (6)	0.0547 (12)
H6	1.183090	0.678752	−0.035920	0.066*
C7	0.9784 (6)	0.6171 (3)	0.0127 (5)	0.0399 (9)
C8	0.8952 (5)	0.6117 (3)	0.1155 (4)	0.0344 (8)
C9	0.7462 (5)	0.5416 (3)	0.0580 (4)	0.0347 (8)
C10	0.7465 (6)	0.5098 (3)	−0.0720 (4)	0.0413 (9)
H10	0.663545	0.462369	−0.133842	0.050*
C11	0.6170 (6)	0.5075 (3)	0.1251 (5)	0.0462 (10)
H11A	0.500209	0.544176	0.080710	0.055*	0.760 (7)
H11B	0.669365	0.522179	0.230754	0.055*	0.760 (7)
H11C	0.493724	0.534844	0.069534	0.055*	0.240 (7)
H11D	0.658515	0.532211	0.226482	0.055*	0.240 (7)
N2	0.4319 (8)	0.3670 (4)	0.1512 (6)	0.0478 (14)	0.760 (7)
H2	0.460 (10)	0.389 (6)	0.240 (4)	0.057*	0.760 (7)
C12	0.583 (2)	0.3971 (6)	0.1019 (15)	0.0747 (14)	0.760 (7)
H12A	0.695565	0.359695	0.158198	0.090*	0.760 (7)
H12B	0.546626	0.380879	−0.002452	0.090*	0.760 (7)
C13	0.4415 (12)	0.2578 (5)	0.1741 (9)	0.0747 (14)	0.760 (7)
H13A	0.434068	0.222514	0.084645	0.090*	0.760 (7)
H13B	0.339870	0.234739	0.200220	0.090*	0.760 (7)
C14	0.6257 (12)	0.2371 (6)	0.2991 (9)	0.0747 (14)	0.760 (7)
H14A	0.609720	0.186452	0.364171	0.112*	0.760 (7)
H14B	0.671948	0.299017	0.353700	0.112*	0.760 (7)
H14C	0.712937	0.212798	0.259233	0.112*	0.760 (7)
C15	0.2372 (8)	0.3878 (5)	0.0459 (7)	0.0518 (14)	0.760 (7)
H15A	0.222136	0.459583	0.024871	0.078*	0.760 (7)
H15B	0.152161	0.366435	0.089854	0.078*	0.760 (7)
H15C	0.211710	0.350719	−0.044649	0.078*	0.760 (7)
N2A	0.5331 (17)	0.3315 (9)	0.2166 (13)	0.024 (3)	0.240 (7)
H2A	0.51 (2)	0.371 (11)	0.278 (13)	0.029*	0.240 (7)
C12A	0.609 (7)	0.3915 (11)	0.124 (5)	0.0747 (14)	0.240 (7)
H12C	0.539526	0.371383	0.021726	0.090*	0.240 (7)
H12D	0.736058	0.367924	0.149239	0.090*	0.240 (7)
C13A	0.555 (4)	0.2363 (15)	0.305 (2)	0.0747 (14)	0.240 (7)
H13C	0.640638	0.192254	0.282152	0.090*	0.240 (7)
H13D	0.435712	0.202054	0.269481	0.090*	0.240 (7)
C14A	0.623 (4)	0.242 (2)	0.471 (2)	0.0747 (14)	0.240 (7)
H14D	0.724365	0.195394	0.515462	0.112*	0.240 (7)
H14E	0.523313	0.224946	0.501539	0.112*	0.240 (7)
H14F	0.664930	0.310475	0.503391	0.112*	0.240 (7)
C15A	0.335 (2)	0.3065 (18)	0.116 (2)	0.0518 (14)	0.240 (7)
H15D	0.277454	0.268541	0.170713	0.078*	0.240 (7)
H15E	0.334919	0.266491	0.033717	0.078*	0.240 (7)
H15F	0.267400	0.368689	0.079997	0.078*	0.240 (7)
C16	0.4441 (5)	0.4620 (3)	0.5089 (4)	0.0363 (8)
C17	0.3065 (5)	0.4772 (3)	0.5751 (4)	0.0384 (9)
H17	0.348389	0.491198	0.676267	0.046*
C18	0.1302 (5)	0.4720 (3)	0.4987 (4)	0.0375 (8)
H18	0.087892	0.460653	0.396827	0.045*
C19	−0.0063 (5)	0.4833 (3)	0.5668 (4)	0.0366 (9)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0513 (17)	0.0443 (15)	0.0315 (13)	0.0013 (13)	0.0174 (12)	−0.0005 (12)
O2	0.0541 (18)	0.060 (2)	0.0505 (18)	0.0116 (16)	0.0277 (15)	0.0128 (16)
O3	0.0266 (14)	0.130 (3)	0.0416 (16)	0.0008 (18)	0.0187 (12)	−0.0061 (19)
O4	0.0403 (16)	0.144 (4)	0.0440 (18)	0.002 (2)	0.0277 (14)	−0.027 (2)
O5	0.0324 (14)	0.069 (2)	0.0456 (16)	−0.0014 (13)	0.0234 (12)	−0.0050 (14)
O6	0.0393 (15)	0.087 (2)	0.0433 (16)	−0.0022 (15)	0.0274 (13)	−0.0111 (16)
N1	0.057 (2)	0.051 (2)	0.0400 (18)	0.0093 (17)	0.0352 (17)	0.0022 (15)
C1	0.089 (4)	0.057 (3)	0.059 (3)	0.012 (3)	0.054 (3)	0.006 (2)
C2	0.052 (2)	0.036 (2)	0.039 (2)	−0.0023 (17)	0.0260 (18)	−0.0033 (17)
C3	0.038 (2)	0.0386 (19)	0.039 (2)	0.0028 (16)	0.0168 (17)	0.0023 (16)
C4	0.043 (2)	0.051 (3)	0.051 (2)	−0.0071 (19)	0.0112 (19)	0.000 (2)
C5	0.043 (2)	0.063 (3)	0.073 (3)	−0.009 (2)	0.028 (2)	0.005 (3)
C6	0.049 (3)	0.056 (3)	0.077 (3)	0.003 (2)	0.045 (2)	0.012 (2)
C7	0.040 (2)	0.042 (2)	0.046 (2)	0.0097 (17)	0.0263 (18)	0.0063 (17)
C8	0.0338 (19)	0.0388 (19)	0.0367 (19)	0.0029 (15)	0.0201 (16)	0.0036 (15)
C9	0.0394 (19)	0.0374 (19)	0.0324 (18)	0.0029 (15)	0.0194 (16)	−0.0015 (15)
C10	0.045 (2)	0.047 (2)	0.0367 (19)	0.0011 (18)	0.0205 (17)	−0.0045 (17)
C11	0.052 (2)	0.053 (2)	0.048 (2)	−0.0120 (19)	0.035 (2)	−0.0122 (19)
N2	0.055 (3)	0.046 (3)	0.054 (3)	−0.016 (3)	0.034 (3)	−0.018 (3)
C12	0.100 (4)	0.061 (2)	0.084 (3)	−0.020 (2)	0.060 (3)	−0.009 (2)
C13	0.100 (4)	0.061 (2)	0.084 (3)	−0.020 (2)	0.060 (3)	−0.009 (2)
C14	0.100 (4)	0.061 (2)	0.084 (3)	−0.020 (2)	0.060 (3)	−0.009 (2)
C15	0.043 (3)	0.064 (4)	0.046 (3)	0.000 (3)	0.014 (2)	−0.016 (3)
N2A	0.024 (6)	0.025 (6)	0.021 (6)	−0.009 (5)	0.007 (5)	0.004 (5)
C12A	0.100 (4)	0.061 (2)	0.084 (3)	−0.020 (2)	0.060 (3)	−0.009 (2)
C13A	0.100 (4)	0.061 (2)	0.084 (3)	−0.020 (2)	0.060 (3)	−0.009 (2)
C14A	0.100 (4)	0.061 (2)	0.084 (3)	−0.020 (2)	0.060 (3)	−0.009 (2)
C15A	0.043 (3)	0.064 (4)	0.046 (3)	0.000 (3)	0.014 (2)	−0.016 (3)
C16	0.0355 (18)	0.045 (2)	0.0360 (19)	−0.0002 (17)	0.0220 (15)	−0.0020 (16)
C17	0.0327 (18)	0.056 (2)	0.0319 (17)	0.0024 (17)	0.0184 (15)	0.0001 (17)
C18	0.0340 (18)	0.051 (2)	0.0343 (18)	0.0040 (17)	0.0209 (15)	0.0009 (17)
C19	0.0316 (18)	0.048 (2)	0.0373 (19)	0.0052 (16)	0.0209 (15)	0.0039 (17)

Geometric parameters (Å, º) top

O1—C2	1.354 (5)	N2—C12	1.517 (10)
O1—C3	1.418 (5)	N2—C13	1.476 (8)
O2—C2	1.200 (5)	N2—C15	1.521 (8)
O3—C16	1.267 (5)	C12—H12A	0.9900
O4—C16	1.209 (5)	C12—H12B	0.9900
O5—H5A	0.886 (15)	C13—H13A	0.9900
O5—C19	1.292 (5)	C13—H13B	0.9900
O6—C19	1.218 (5)	C13—C14	1.535 (10)
N1—H1	0.862 (14)	C14—H14A	0.9800
N1—C7	1.368 (6)	C14—H14B	0.9800
N1—C10	1.372 (6)	C14—H14C	0.9800
C1—H1A	0.9800	C15—H15A	0.9800
C1—H1B	0.9800	C15—H15B	0.9800
C1—H1C	0.9800	C15—H15C	0.9800
C1—C2	1.504 (6)	N2A—H2A	0.870 (15)
C3—C4	1.371 (6)	N2A—C12A	1.518 (14)
C3—C8	1.390 (6)	N2A—C13A	1.521 (13)
C4—H4	0.9500	N2A—C15A	1.538 (12)
C4—C5	1.392 (7)	C12A—H12C	0.9900
C5—H5	0.9500	C12A—H12D	0.9900
C5—C6	1.376 (8)	C13A—H13C	0.9900
C6—H6	0.9500	C13A—H13D	0.9900
C6—C7	1.385 (7)	C13A—C14A	1.532 (14)
C7—C8	1.422 (5)	C14A—H14D	0.9800
C8—C9	1.443 (6)	C14A—H14E	0.9800
C9—C10	1.365 (5)	C14A—H14F	0.9800
C9—C11	1.500 (5)	C15A—H15D	0.9800
C10—H10	0.9500	C15A—H15E	0.9800
C11—H11A	0.9900	C15A—H15F	0.9800
C11—H11B	0.9900	C16—C17	1.495 (5)
C11—H11C	0.9900	C17—H17	0.9500
C11—H11D	0.9900	C17—C18	1.312 (5)
C11—C12	1.501 (9)	C18—H18	0.9500
C11—C12A	1.551 (14)	C18—C19	1.496 (5)
N2—H2	0.875 (15)

C2—O1—C3	117.8 (3)	H12A—C12—H12B	108.3
C19—O5—H5A	101 (4)	N2—C13—H13A	110.5
C7—N1—H1	125 (3)	N2—C13—H13B	110.5
C7—N1—C10	108.7 (3)	N2—C13—C14	106.2 (6)
C10—N1—H1	126 (3)	H13A—C13—H13B	108.7
H1A—C1—H1B	109.5	C14—C13—H13A	110.5
H1A—C1—H1C	109.5	C14—C13—H13B	110.5
H1B—C1—H1C	109.5	C13—C14—H14A	109.5
C2—C1—H1A	109.5	C13—C14—H14B	109.5
C2—C1—H1B	109.5	C13—C14—H14C	109.5
C2—C1—H1C	109.5	H14A—C14—H14B	109.5
O1—C2—C1	111.3 (4)	H14A—C14—H14C	109.5
O2—C2—O1	123.2 (4)	H14B—C14—H14C	109.5
O2—C2—C1	125.4 (4)	N2—C15—H15A	109.5
C4—C3—O1	118.1 (4)	N2—C15—H15B	109.5
C4—C3—C8	121.8 (4)	N2—C15—H15C	109.5
C8—C3—O1	119.9 (3)	H15A—C15—H15B	109.5
C3—C4—H4	120.2	H15A—C15—H15C	109.5
C3—C4—C5	119.5 (4)	H15B—C15—H15C	109.5
C5—C4—H4	120.2	C12A—N2A—H2A	109 (10)
C4—C5—H5	119.2	C12A—N2A—C13A	144 (2)
C6—C5—C4	121.7 (4)	C12A—N2A—C15A	106 (2)
C6—C5—H5	119.2	C13A—N2A—H2A	97 (10)
C5—C6—H6	121.1	C13A—N2A—C15A	93.2 (16)
C5—C6—C7	117.8 (4)	C15A—N2A—H2A	101 (10)
C7—C6—H6	121.1	C11—C12A—H12C	106.5
N1—C7—C6	129.8 (4)	C11—C12A—H12D	106.5
N1—C7—C8	107.7 (3)	N2A—C12A—C11	123.2 (16)
C6—C7—C8	122.5 (4)	N2A—C12A—H12C	106.5
C3—C8—C7	116.7 (4)	N2A—C12A—H12D	106.5
C3—C8—C9	136.6 (4)	H12C—C12A—H12D	106.5
C7—C8—C9	106.7 (3)	N2A—C13A—H13C	107.4
C8—C9—C11	128.3 (3)	N2A—C13A—H13D	107.4
C10—C9—C8	105.9 (3)	N2A—C13A—C14A	119.8 (18)
C10—C9—C11	125.7 (4)	H13C—C13A—H13D	106.9
N1—C10—H10	124.6	C14A—C13A—H13C	107.4
C9—C10—N1	110.9 (4)	C14A—C13A—H13D	107.4
C9—C10—H10	124.6	C13A—C14A—H14D	109.5
C9—C11—H11A	109.6	C13A—C14A—H14E	109.5
C9—C11—H11B	109.6	C13A—C14A—H14F	109.5
C9—C11—H11C	109.8	H14D—C14A—H14E	109.5
C9—C11—H11D	109.8	H14D—C14A—H14F	109.5
C9—C11—C12	110.2 (5)	H14E—C14A—H14F	109.5
C9—C11—C12A	109.4 (10)	N2A—C15A—H15D	109.5
H11A—C11—H11B	108.1	N2A—C15A—H15E	109.5
H11C—C11—H11D	108.2	N2A—C15A—H15F	109.5
C12—C11—H11A	109.6	H15D—C15A—H15E	109.5
C12—C11—H11B	109.6	H15D—C15A—H15F	109.5
C12A—C11—H11C	109.8	H15E—C15A—H15F	109.5
C12A—C11—H11D	109.8	O3—C16—C17	115.3 (3)
C12—N2—H2	108 (6)	O4—C16—O3	124.5 (3)
C12—N2—C15	116.7 (8)	O4—C16—C17	120.2 (3)
C13—N2—H2	101 (6)	C16—C17—H17	118.7
C13—N2—C12	108.3 (6)	C18—C17—C16	122.5 (3)
C13—N2—C15	105.4 (5)	C18—C17—H17	118.7
C15—N2—H2	115 (5)	C17—C18—H18	118.9
C11—C12—N2	109.3 (6)	C17—C18—C19	122.2 (3)
C11—C12—H12A	109.8	C19—C18—H18	118.9
C11—C12—H12B	109.8	O5—C19—C18	112.9 (3)
N2—C12—H12A	109.8	O6—C19—O5	125.9 (3)
N2—C12—H12B	109.8	O6—C19—C18	121.2 (3)

O1—C3—C4—C5	176.0 (4)	C7—C8—C9—C11	178.7 (4)
O1—C3—C8—C7	−177.9 (3)	C8—C3—C4—C5	0.4 (6)
O1—C3—C8—C9	3.9 (7)	C8—C9—C10—N1	−0.8 (5)
O3—C16—C17—C18	−175.9 (4)	C8—C9—C11—C12	−139.1 (7)
O4—C16—C17—C18	3.9 (7)	C8—C9—C11—C12A	−129 (2)
N1—C7—C8—C3	−177.6 (3)	C9—C11—C12—N2	−172.0 (7)
N1—C7—C8—C9	1.1 (4)	C9—C11—C12A—N2A	164 (3)
C2—O1—C3—C4	105.8 (4)	C10—N1—C7—C6	178.4 (4)
C2—O1—C3—C8	−78.5 (5)	C10—N1—C7—C8	−1.6 (5)
C3—O1—C2—O2	−1.2 (6)	C10—C9—C11—C12	39.6 (9)
C3—O1—C2—C1	177.7 (4)	C10—C9—C11—C12A	49 (2)
C3—C4—C5—C6	1.8 (7)	C11—C9—C10—N1	−179.8 (4)
C3—C8—C9—C10	178.2 (5)	C12—N2—C13—C14	63.8 (9)
C3—C8—C9—C11	−2.9 (7)	C13—N2—C12—C11	−161.4 (8)
C4—C3—C8—C7	−2.3 (6)	C15—N2—C12—C11	80.0 (10)
C4—C3—C8—C9	179.4 (4)	C15—N2—C13—C14	−170.6 (5)
C4—C5—C6—C7	−1.7 (8)	C12A—N2A—C13A—C14A	110 (4)
C5—C6—C7—N1	179.6 (4)	C13A—N2A—C12A—C11	−144 (3)
C5—C6—C7—C8	−0.4 (7)	C15A—N2A—C12A—C11	97 (4)
C6—C7—C8—C3	2.4 (6)	C15A—N2A—C13A—C14A	−128 (2)
C6—C7—C8—C9	−178.9 (4)	C16—C17—C18—C19	177.5 (4)
C7—N1—C10—C9	1.6 (5)	C17—C18—C19—O5	−159.5 (4)
C7—C8—C9—C10	−0.2 (4)	C17—C18—C19—O6	19.7 (6)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O6ⁱ	0.86 (1)	2.02 (2)	2.858 (4)	165 (5)
N2—H2···O4	0.88 (2)	1.85 (4)	2.644 (6)	150 (7)
N2A—H2A···O4	0.87 (2)	1.94 (6)	2.776 (14)	162 (17)
O5—H5A···O3ⁱⁱ	0.89 (2)	1.61 (2)	2.459 (4)	160 (6)

Symmetry codes: (i) x+1, y, z−1; (ii) x−1, y, z.

[2-(4-Acetyloxy-1H-indol-3-yl)ethyl](methyl)prop-2-enylazanium 3-carboxyprop-2-enoate (II) top

Crystal data top

C₁₆H₂₁N₂O₂⁺·C₄H₃O₄⁻	F(000) = 412
M_r = 388.41	D_x = 1.269 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
a = 7.9702 (4) Å	Cell parameters from 9882 reflections
b = 14.1788 (7) Å	θ = 2.7–25.6°
c = 9.8035 (5) Å	µ = 0.09 mm⁻¹
β = 113.394 (2)°	T = 297 K
V = 1016.80 (9) Å³	BLOCK, colourless
Z = 2	0.34 × 0.24 × 0.2 mm

Data collection top

Bruker D8 Venture CMOS diffractometer	3516 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.039
Absorption correction: multi-scan (SADABS; Bruker, 2018)	θ_max = 25.7°, θ_min = 2.8°
T_min = 0.686, T_max = 0.745	h = −9→9
26393 measured reflections	k = −17→17
3797 independent reflections	l = −11→11

Refinement top

Refinement on F²	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.043	w = 1/[σ²(F_o²) + (0.0592P)² + 0.2448P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.113	(Δ/σ)_max < 0.001
S = 1.04	Δρ_max = 0.27 e Å⁻³
3797 reflections	Δρ_min = −0.16 e Å⁻³
264 parameters	Absolute structure: Flack x determined using 1577 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons et al., 2013)
4 restraints	Absolute structure parameter: 0.4 (3)

Special details top

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

	x	y	z	U_iso*/U_eq
O1	0.0798 (3)	0.7896 (2)	0.2116 (3)	0.0688 (8)
O2	−0.0241 (3)	0.69624 (16)	0.3445 (2)	0.0496 (5)
O3	0.5149 (3)	0.4747 (3)	0.3619 (3)	0.0834 (11)
O4	0.5188 (3)	0.4841 (3)	0.5856 (3)	0.0701 (8)
H4A	0.397 (2)	0.484 (4)	0.543 (5)	0.105*
O5	1.1781 (3)	0.53485 (19)	0.6822 (2)	0.0559 (6)
O6	1.1837 (2)	0.47635 (18)	0.4735 (2)	0.0493 (5)
N1	−0.4734 (4)	0.5921 (2)	−0.1031 (3)	0.0585 (8)
H1	−0.577 (3)	0.580 (3)	−0.176 (3)	0.070*
N2	0.2259 (4)	0.4086 (2)	0.1361 (3)	0.0499 (6)
H2	0.297 (4)	0.436 (3)	0.221 (3)	0.060*
C1	0.2902 (5)	0.7280 (3)	0.4444 (5)	0.0754 (12)
H1A	0.377223	0.771990	0.436158	0.113*
H1B	0.330726	0.664822	0.439678	0.113*
H1C	0.279217	0.737271	0.537570	0.113*
C2	0.1079 (5)	0.7436 (2)	0.3193 (4)	0.0506 (8)
C3	−0.2038 (4)	0.7039 (2)	0.2363 (3)	0.0464 (7)
C4	−0.3218 (6)	0.7650 (3)	0.2617 (5)	0.0642 (9)
H4	−0.281087	0.803090	0.345811	0.077*
C5	−0.5046 (6)	0.7694 (3)	0.1595 (6)	0.0776 (12)
H5	−0.584090	0.810842	0.177293	0.093*
C6	−0.5689 (5)	0.7147 (3)	0.0352 (5)	0.0685 (11)
H6	−0.690394	0.718337	−0.031497	0.082*
C7	−0.4473 (4)	0.6531 (2)	0.0109 (4)	0.0494 (8)
C8	−0.2618 (4)	0.6455 (2)	0.1114 (3)	0.0401 (6)
C9	−0.1793 (4)	0.5762 (2)	0.0515 (3)	0.0418 (6)
C10	−0.3140 (5)	0.5459 (3)	−0.0778 (3)	0.0531 (8)
H10	−0.299037	0.500150	−0.139982	0.064*
C11	0.0171 (4)	0.5439 (2)	0.1121 (4)	0.0491 (7)
H11A	0.082400	0.578146	0.062769	0.059*
H11B	0.074142	0.558138	0.217389	0.059*
C12	0.0315 (4)	0.4409 (2)	0.0897 (4)	0.0554 (8)
H12A	−0.036085	0.425881	−0.014403	0.066*
H12B	−0.024264	0.406630	0.146635	0.066*
C13	0.2451 (6)	0.3047 (3)	0.1669 (5)	0.0656 (10)
H13A	0.165728	0.271014	0.078805	0.079*
H13B	0.369974	0.285978	0.188000	0.079*
C14	0.1994 (6)	0.2777 (3)	0.2918 (5)	0.0745 (11)
H14	0.260747	0.308976	0.381312	0.089*
C15	0.0818 (9)	0.2144 (4)	0.2897 (8)	0.1105 (19)
H15A	0.017104	0.181308	0.202624	0.133*
H15B	0.061757	0.201983	0.375131	0.133*
C16	0.3019 (6)	0.4354 (4)	0.0257 (4)	0.0741 (12)
H16A	0.425726	0.413518	0.058781	0.111*
H16B	0.299241	0.502755	0.015387	0.111*
H16C	0.229752	0.407199	−0.068548	0.111*
C17	0.5946 (3)	0.4843 (2)	0.4951 (3)	0.0412 (6)
C18	0.7971 (3)	0.4950 (2)	0.5624 (3)	0.0418 (6)
H18	0.853754	0.504450	0.664454	0.050*
C19	0.8996 (3)	0.4919 (2)	0.4870 (3)	0.0406 (6)
H19	0.844150	0.482380	0.384840	0.049*
C20	1.1021 (3)	0.5030 (2)	0.5574 (3)	0.0372 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0517 (14)	0.0828 (19)	0.0643 (16)	−0.0064 (13)	0.0149 (12)	0.0250 (14)
O2	0.0521 (12)	0.0543 (12)	0.0358 (10)	−0.0098 (10)	0.0102 (9)	−0.0002 (9)
O3	0.0276 (10)	0.176 (3)	0.0441 (13)	−0.0232 (16)	0.0119 (9)	−0.0257 (17)
O4	0.0255 (10)	0.142 (3)	0.0462 (12)	−0.0035 (14)	0.0177 (9)	−0.0141 (15)
O5	0.0243 (9)	0.0955 (18)	0.0443 (12)	−0.0058 (10)	0.0098 (9)	−0.0179 (11)
O6	0.0274 (9)	0.0772 (15)	0.0464 (11)	−0.0007 (10)	0.0177 (8)	−0.0114 (10)
N1	0.0341 (14)	0.076 (2)	0.0502 (15)	−0.0136 (13)	0.0009 (12)	0.0058 (14)
N2	0.0438 (14)	0.0591 (16)	0.0439 (14)	−0.0010 (12)	0.0144 (11)	−0.0097 (12)
C1	0.053 (2)	0.077 (3)	0.071 (2)	−0.0121 (19)	−0.0019 (18)	0.006 (2)
C2	0.0490 (17)	0.0470 (17)	0.0483 (18)	−0.0062 (14)	0.0113 (14)	−0.0035 (14)
C3	0.0439 (16)	0.0499 (17)	0.0452 (16)	−0.0041 (13)	0.0176 (13)	0.0034 (14)
C4	0.071 (2)	0.063 (2)	0.069 (2)	0.0029 (18)	0.039 (2)	−0.0023 (18)
C5	0.064 (2)	0.076 (3)	0.110 (4)	0.019 (2)	0.052 (3)	0.016 (3)
C6	0.0366 (17)	0.080 (3)	0.089 (3)	0.0054 (17)	0.0247 (18)	0.019 (2)
C7	0.0334 (14)	0.0576 (18)	0.0536 (18)	−0.0082 (13)	0.0134 (13)	0.0112 (15)
C8	0.0327 (13)	0.0462 (15)	0.0385 (14)	−0.0042 (11)	0.0110 (11)	0.0070 (12)
C9	0.0397 (14)	0.0479 (15)	0.0325 (13)	−0.0044 (12)	0.0087 (11)	0.0030 (12)
C10	0.0490 (17)	0.064 (2)	0.0374 (15)	−0.0099 (16)	0.0078 (13)	−0.0025 (14)
C11	0.0408 (15)	0.0561 (18)	0.0430 (15)	0.0002 (14)	0.0087 (13)	−0.0020 (14)
C12	0.0429 (17)	0.0551 (19)	0.063 (2)	−0.0037 (14)	0.0151 (16)	−0.0039 (15)
C13	0.062 (2)	0.062 (2)	0.065 (2)	0.0093 (17)	0.0170 (18)	−0.0060 (17)
C14	0.089 (3)	0.056 (2)	0.078 (3)	0.006 (2)	0.033 (2)	0.003 (2)
C15	0.117 (5)	0.094 (4)	0.118 (4)	−0.012 (3)	0.044 (4)	0.018 (4)
C16	0.071 (2)	0.105 (3)	0.058 (2)	−0.005 (2)	0.039 (2)	−0.006 (2)
C17	0.0252 (12)	0.0562 (17)	0.0398 (15)	−0.0030 (13)	0.0104 (11)	−0.0064 (13)
C18	0.0264 (12)	0.0607 (18)	0.0370 (14)	−0.0035 (12)	0.0113 (11)	−0.0052 (13)
C19	0.0233 (12)	0.0588 (17)	0.0370 (13)	−0.0041 (12)	0.0091 (10)	−0.0037 (12)
C20	0.0232 (11)	0.0485 (15)	0.0384 (14)	−0.0016 (11)	0.0107 (10)	−0.0002 (12)

Geometric parameters (Å, º) top

O1—C2	1.185 (4)	C6—C7	1.394 (6)
O2—C2	1.351 (4)	C7—C8	1.419 (4)
O2—C3	1.408 (4)	C8—C9	1.431 (5)
O3—C17	1.212 (3)	C9—C10	1.365 (4)
O4—H4A	0.894 (14)	C9—C11	1.508 (4)
O4—C17	1.256 (3)	C10—H10	0.9300
O5—C20	1.216 (3)	C11—H11A	0.9700
O6—C20	1.290 (3)	C11—H11B	0.9700
N1—H1	0.867 (14)	C11—C12	1.488 (5)
N1—C7	1.362 (5)	C12—H12A	0.9700
N1—C10	1.362 (5)	C12—H12B	0.9700
N2—H2	0.890 (14)	C13—H13A	0.9700
N2—C12	1.502 (4)	C13—H13B	0.9700
N2—C13	1.499 (5)	C13—C14	1.460 (6)
N2—C16	1.484 (4)	C14—H14	0.9300
C1—H1A	0.9600	C14—C15	1.292 (7)
C1—H1B	0.9600	C15—H15A	0.9300
C1—H1C	0.9600	C15—H15B	0.9300
C1—C2	1.499 (5)	C16—H16A	0.9600
C3—C4	1.372 (5)	C16—H16B	0.9600
C3—C8	1.396 (4)	C16—H16C	0.9600
C4—H4	0.9300	C17—C18	1.489 (3)
C4—C5	1.404 (6)	C18—H18	0.9300
C5—H5	0.9300	C18—C19	1.302 (4)
C5—C6	1.361 (7)	C19—H19	0.9300
C6—H6	0.9300	C19—C20	1.491 (3)

C2—O2—C3	117.2 (2)	C9—C10—H10	124.7
C17—O4—H4A	114 (3)	C9—C11—H11A	109.3
C7—N1—H1	126 (3)	C9—C11—H11B	109.3
C7—N1—C10	109.2 (3)	H11A—C11—H11B	107.9
C10—N1—H1	124 (3)	C12—C11—C9	111.7 (3)
C12—N2—H2	110 (3)	C12—C11—H11A	109.3
C13—N2—H2	105 (3)	C12—C11—H11B	109.3
C13—N2—C12	111.8 (3)	N2—C12—H12A	109.1
C16—N2—H2	106 (3)	N2—C12—H12B	109.1
C16—N2—C12	111.8 (3)	C11—C12—N2	112.7 (3)
C16—N2—C13	111.1 (3)	C11—C12—H12A	109.1
H1A—C1—H1B	109.5	C11—C12—H12B	109.1
H1A—C1—H1C	109.5	H12A—C12—H12B	107.8
H1B—C1—H1C	109.5	N2—C13—H13A	109.0
C2—C1—H1A	109.5	N2—C13—H13B	109.0
C2—C1—H1B	109.5	H13A—C13—H13B	107.8
C2—C1—H1C	109.5	C14—C13—N2	112.8 (3)
O1—C2—O2	123.5 (3)	C14—C13—H13A	109.0
O1—C2—C1	126.1 (3)	C14—C13—H13B	109.0
O2—C2—C1	110.4 (3)	C13—C14—H14	116.9
C4—C3—O2	118.5 (3)	C15—C14—C13	126.1 (5)
C4—C3—C8	121.4 (3)	C15—C14—H14	116.9
C8—C3—O2	119.9 (3)	C14—C15—H15A	120.0
C3—C4—H4	120.3	C14—C15—H15B	120.0
C3—C4—C5	119.4 (4)	H15A—C15—H15B	120.0
C5—C4—H4	120.3	N2—C16—H16A	109.5
C4—C5—H5	119.0	N2—C16—H16B	109.5
C6—C5—C4	121.9 (4)	N2—C16—H16C	109.5
C6—C5—H5	119.0	H16A—C16—H16B	109.5
C5—C6—H6	121.0	H16A—C16—H16C	109.5
C5—C6—C7	118.0 (3)	H16B—C16—H16C	109.5
C7—C6—H6	121.0	O3—C17—O4	124.6 (2)
N1—C7—C6	130.4 (3)	O3—C17—C18	120.1 (2)
N1—C7—C8	107.4 (3)	O4—C17—C18	115.3 (2)
C6—C7—C8	122.2 (3)	C17—C18—H18	118.0
C3—C8—C7	117.0 (3)	C19—C18—C17	124.0 (2)
C3—C8—C9	136.1 (3)	C19—C18—H18	118.0
C7—C8—C9	106.8 (3)	C18—C19—H19	118.6
C8—C9—C11	128.4 (3)	C18—C19—C20	122.8 (2)
C10—C9—C8	106.1 (3)	C20—C19—H19	118.6
C10—C9—C11	125.5 (3)	O5—C20—O6	125.1 (2)
N1—C10—C9	110.5 (3)	O5—C20—C19	121.3 (2)
N1—C10—H10	124.7	O6—C20—C19	113.6 (2)

O2—C3—C4—C5	−176.1 (3)	C6—C7—C8—C3	−1.0 (4)
O2—C3—C8—C7	176.5 (2)	C6—C7—C8—C9	179.9 (3)
O2—C3—C8—C9	−4.7 (5)	C7—N1—C10—C9	−0.9 (4)
O3—C17—C18—C19	−2.3 (6)	C7—C8—C9—C10	−0.1 (3)
O4—C17—C18—C19	176.4 (4)	C7—C8—C9—C11	177.7 (3)
N1—C7—C8—C3	178.7 (3)	C8—C3—C4—C5	−0.4 (5)
N1—C7—C8—C9	−0.4 (3)	C8—C9—C10—N1	0.6 (4)
N2—C13—C14—C15	125.8 (5)	C8—C9—C11—C12	142.7 (3)
C2—O2—C3—C4	−100.4 (3)	C9—C11—C12—N2	174.6 (3)
C2—O2—C3—C8	83.9 (4)	C10—N1—C7—C6	−179.6 (4)
C3—O2—C2—O1	−0.7 (5)	C10—N1—C7—C8	0.8 (4)
C3—O2—C2—C1	−180.0 (3)	C10—C9—C11—C12	−39.8 (4)
C3—C4—C5—C6	−0.1 (6)	C11—C9—C10—N1	−177.3 (3)
C3—C8—C9—C10	−179.0 (3)	C12—N2—C13—C14	−63.6 (4)
C3—C8—C9—C11	−1.1 (6)	C13—N2—C12—C11	158.9 (3)
C4—C3—C8—C7	0.9 (5)	C16—N2—C12—C11	−75.8 (4)
C4—C3—C8—C9	179.7 (3)	C16—N2—C13—C14	170.7 (3)
C4—C5—C6—C7	0.0 (6)	C17—C18—C19—C20	179.9 (3)
C5—C6—C7—N1	−179.0 (4)	C18—C19—C20—O5	−15.6 (5)
C5—C6—C7—C8	0.5 (5)	C18—C19—C20—O6	164.6 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O5ⁱ	0.87 (1)	2.00 (2)	2.857 (3)	169 (4)
O4—H4A···O6ⁱⁱ	0.89 (1)	1.56 (2)	2.454 (3)	175 (6)

Symmetry codes: (i) x−2, y, z−1; (ii) x−1, y, z.

Bis{[2-(4-acetyloxy-1H-indol-3-yl)ethyl]diprop-2-enylazanium} but-2-enedioate–(E)-butenedioic acid (1/1) (III) top

Crystal data top

2C₁₈H₂₃N₂O₂⁺·C₄H₂O₄²⁻·C₄H₄O₄	F(000) = 1760
M_r = 828.90	D_x = 1.270 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 23.6642 (19) Å	Cell parameters from 9906 reflections
b = 8.4204 (7) Å	θ = 2.6–24.9°
c = 23.4002 (18) Å	µ = 0.09 mm⁻¹
β = 111.614 (2)°	T = 297 K
V = 4334.9 (6) Å³	Block, colorless
Z = 4	0.22 × 0.2 × 0.12 mm

Data collection top

Bruker D8 Venture CMOS diffractometer	3441 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.040
Absorption correction: multi-scan (SADABS; Bruker, 2018)	θ_max = 25.8°, θ_min = 2.6°
T_min = 0.715, T_max = 0.745	h = −28→28
99597 measured reflections	k = −10→10
4126 independent reflections	l = −28→28

Refinement top

Refinement on F²	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.051	w = 1/[σ²(F_o²) + (0.0623P)² + 3.3312P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.140	(Δ/σ)_max = 0.001
S = 1.06	Δρ_max = 0.50 e Å⁻³
4126 reflections	Δρ_min = −0.29 e Å⁻³
354 parameters	Extinction correction: SHELXL2018 (Sheldrick, 2015b), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
114 restraints	Extinction coefficient: 0.0057 (13)

Special details top

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
O3	0.43377 (5)	0.84230 (16)	0.40787 (6)	0.0547 (4)
O4	0.52519 (5)	0.82545 (19)	0.40300 (6)	0.0650 (4)
N1	0.15205 (7)	0.5819 (2)	0.16972 (7)	0.0540 (4)
H1	0.1284 (8)	0.542 (2)	0.1349 (6)	0.065*
N2	0.40861 (6)	0.56750 (17)	0.34003 (6)	0.0444 (4)
H2	0.4151 (9)	0.6559 (16)	0.3614 (8)	0.053*
C3	0.19478 (8)	0.6147 (2)	0.33073 (8)	0.0533 (5)
C4	0.14362 (9)	0.5733 (3)	0.34114 (10)	0.0683 (6)
H4	0.144072	0.571251	0.381042	0.082*
C5	0.09055 (9)	0.5341 (3)	0.29169 (12)	0.0705 (6)
H5	0.055901	0.506800	0.299318	0.085*
C6	0.08822 (8)	0.5348 (2)	0.23271 (10)	0.0590 (5)
H6	0.052601	0.509456	0.200080	0.071*
C7	0.14110 (7)	0.5749 (2)	0.22293 (8)	0.0467 (4)
C8	0.19553 (7)	0.61618 (19)	0.27159 (8)	0.0432 (4)
C9	0.24029 (7)	0.6461 (2)	0.24481 (8)	0.0450 (4)
C10	0.21169 (8)	0.6216 (2)	0.18357 (9)	0.0537 (5)
H10	0.230151	0.630485	0.154837	0.064*
C11	0.30631 (7)	0.6867 (2)	0.27697 (9)	0.0496 (4)
H11A	0.310383	0.771998	0.306092	0.060*
H11B	0.323061	0.722895	0.247150	0.060*
C12	0.34109 (7)	0.5424 (2)	0.31047 (9)	0.0480 (4)
H12A	0.325670	0.511823	0.341969	0.058*
H12B	0.333443	0.455047	0.281562	0.058*
C16	0.43581 (9)	0.4308 (3)	0.38317 (11)	0.0664 (6)
H16A	0.417335	0.427499	0.413909	0.080*
H16B	0.425604	0.332482	0.360012	0.080*
C17	0.50234 (11)	0.4390 (3)	0.41471 (13)	0.0871 (8)
H17	0.519123	0.527455	0.438803	0.105*
C18	0.53850 (14)	0.3276 (5)	0.41018 (19)	0.1316 (14)
H18A	0.522600	0.238260	0.386311	0.158*
H18B	0.580261	0.337274	0.430818	0.158*
C19	0.48981 (7)	0.8722 (2)	0.42812 (8)	0.0467 (4)
C20	0.51576 (7)	0.9709 (2)	0.48471 (8)	0.0479 (4)
H20	0.557205	0.992472	0.499179	0.057*
O5	0.6457 (5)	0.730 (3)	0.5379 (4)	0.097 (5)	0.48 (4)
O6	0.6402 (8)	0.822 (2)	0.4447 (8)	0.062 (2)	0.48 (4)
H6A	0.603390	0.828442	0.436178	0.094*	0.48 (4)
C21	0.6647 (8)	0.748 (3)	0.4963 (7)	0.060 (3)	0.48 (4)
O5A	0.6392 (3)	0.645 (2)	0.5186 (10)	0.103 (4)	0.52 (4)
O6A	0.6418 (7)	0.800 (3)	0.4512 (8)	0.084 (4)	0.52 (4)
H6AA	0.605462	0.793944	0.444863	0.126*	0.52 (4)
C21A	0.6724 (9)	0.727 (3)	0.5011 (8)	0.070 (4)	0.52 (4)
C22	0.73480 (9)	0.7230 (3)	0.51577 (9)	0.0637 (6)
H22	0.755398	0.666681	0.551626	0.076*	0.48 (4)
H22A	0.757554	0.675587	0.553077	0.076*	0.52 (4)
C13	0.43825 (8)	0.5987 (3)	0.29456 (9)	0.0579 (5)
H13A	0.470397	0.672837	0.316182	0.069*	0.099 (4)
H13B	0.458837	0.499336	0.294117	0.069*	0.099 (4)
H13C	0.427809	0.705354	0.278487	0.069*	0.901 (4)
H13D	0.481992	0.594839	0.315899	0.069*	0.901 (4)
C14	0.4188 (10)	0.652 (3)	0.2307 (5)	0.0769 (8)	0.099 (4)
H14	0.423405	0.761671	0.228839	0.092*	0.099 (4)
C15	0.397 (3)	0.592 (7)	0.1760 (14)	0.1028 (15)	0.099 (4)
H15A	0.390253	0.483222	0.170924	0.123*	0.099 (4)
H15B	0.388512	0.657311	0.141789	0.123*	0.099 (4)
C14A	0.42144 (12)	0.4880 (3)	0.24310 (12)	0.0769 (8)	0.901 (4)
H14A	0.428767	0.380233	0.251180	0.092*	0.901 (4)
C15A	0.3967 (3)	0.5342 (6)	0.18674 (15)	0.1028 (15)	0.901 (4)
H15C	0.389088	0.641456	0.177808	0.123*	0.901 (4)
H15D	0.386609	0.460156	0.155046	0.123*	0.901 (4)
O1	0.2254 (8)	0.8833 (10)	0.3924 (13)	0.099 (6)	0.38 (4)
O2	0.2527 (6)	0.645 (2)	0.3753 (9)	0.071 (5)	0.38 (4)
C1	0.3155 (7)	0.789 (2)	0.4602 (7)	0.066 (4)	0.38 (4)
H1A	0.333536	0.689257	0.477037	0.098*	0.38 (4)
H1B	0.313766	0.856311	0.492675	0.098*	0.38 (4)
H1C	0.339598	0.839519	0.440153	0.098*	0.38 (4)
C2	0.2529 (8)	0.7621 (19)	0.4148 (8)	0.064 (6)	0.38 (4)
O1A	0.2133 (4)	0.848 (2)	0.4172 (7)	0.102 (4)	0.62 (4)
O2A	0.2484 (4)	0.6422 (12)	0.3825 (6)	0.063 (2)	0.62 (4)
C1A	0.3206 (6)	0.772 (2)	0.4660 (6)	0.113 (5)	0.62 (4)
H1AA	0.350811	0.753864	0.448371	0.170*	0.62 (4)
H1AB	0.321755	0.687720	0.493898	0.170*	0.62 (4)
H1AC	0.328772	0.871404	0.487805	0.170*	0.62 (4)
C2A	0.2590 (5)	0.7784 (14)	0.4159 (6)	0.071 (4)	0.62 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O3	0.0303 (6)	0.0649 (8)	0.0582 (7)	−0.0035 (5)	0.0039 (5)	−0.0155 (6)
O4	0.0370 (7)	0.0920 (11)	0.0605 (8)	−0.0001 (6)	0.0115 (6)	−0.0220 (7)
N1	0.0411 (8)	0.0576 (9)	0.0510 (9)	0.0042 (7)	0.0024 (6)	−0.0055 (7)
N2	0.0326 (7)	0.0479 (8)	0.0502 (8)	−0.0044 (6)	0.0122 (6)	−0.0050 (6)
C3	0.0375 (9)	0.0627 (11)	0.0553 (10)	0.0019 (8)	0.0119 (8)	−0.0016 (9)
C4	0.0538 (11)	0.0892 (16)	0.0675 (13)	−0.0008 (11)	0.0288 (10)	0.0034 (11)
C5	0.0405 (10)	0.0807 (15)	0.0945 (16)	−0.0076 (10)	0.0299 (11)	−0.0024 (12)
C6	0.0314 (8)	0.0566 (11)	0.0806 (14)	−0.0009 (8)	0.0108 (8)	−0.0072 (10)
C7	0.0343 (8)	0.0396 (9)	0.0584 (10)	0.0039 (6)	0.0079 (7)	−0.0025 (7)
C8	0.0313 (8)	0.0403 (8)	0.0528 (9)	0.0026 (6)	0.0095 (7)	−0.0019 (7)
C9	0.0348 (8)	0.0417 (9)	0.0553 (10)	0.0021 (7)	0.0128 (7)	−0.0009 (7)
C10	0.0468 (10)	0.0573 (11)	0.0553 (10)	0.0048 (8)	0.0170 (8)	0.0018 (8)
C11	0.0353 (8)	0.0457 (9)	0.0664 (11)	−0.0047 (7)	0.0170 (8)	−0.0052 (8)
C12	0.0307 (8)	0.0488 (9)	0.0624 (10)	−0.0065 (7)	0.0147 (7)	−0.0048 (8)
C16	0.0520 (11)	0.0612 (12)	0.0793 (14)	−0.0024 (9)	0.0163 (10)	0.0168 (10)
C17	0.0572 (13)	0.0821 (16)	0.0994 (18)	−0.0041 (12)	0.0022 (12)	0.0325 (14)
C18	0.0713 (18)	0.136 (3)	0.169 (4)	0.0369 (19)	0.021 (2)	0.068 (3)
C19	0.0323 (8)	0.0518 (10)	0.0467 (9)	0.0012 (7)	0.0035 (7)	−0.0023 (7)
C20	0.0288 (7)	0.0548 (10)	0.0505 (9)	−0.0047 (7)	0.0033 (6)	−0.0049 (8)
O5	0.053 (3)	0.178 (11)	0.073 (3)	0.018 (5)	0.037 (2)	0.035 (4)
O6	0.039 (4)	0.086 (4)	0.055 (4)	0.004 (3)	0.009 (3)	0.024 (3)
C21	0.021 (3)	0.104 (9)	0.054 (4)	0.014 (4)	0.014 (3)	0.030 (5)
O5A	0.055 (2)	0.139 (8)	0.120 (7)	−0.005 (3)	0.039 (3)	0.053 (6)
O6A	0.033 (4)	0.140 (11)	0.079 (6)	0.007 (4)	0.021 (4)	0.032 (5)
C21A	0.051 (8)	0.085 (5)	0.073 (6)	0.012 (5)	0.021 (5)	0.019 (5)
C22	0.0401 (10)	0.0906 (15)	0.0582 (11)	0.0058 (10)	0.0156 (8)	0.0138 (11)
C13	0.0387 (9)	0.0753 (13)	0.0602 (11)	−0.0093 (9)	0.0190 (8)	−0.0079 (10)
C14	0.0792 (17)	0.0819 (17)	0.0850 (19)	−0.0242 (14)	0.0481 (15)	−0.0265 (14)
C15	0.0831 (18)	0.165 (4)	0.0664 (19)	−0.026 (3)	0.0341 (17)	−0.027 (2)
C14A	0.0792 (17)	0.0819 (17)	0.0850 (19)	−0.0242 (14)	0.0481 (15)	−0.0265 (14)
C15A	0.0831 (18)	0.165 (4)	0.0664 (19)	−0.026 (3)	0.0341 (17)	−0.027 (2)
O1	0.087 (5)	0.069 (4)	0.116 (10)	−0.002 (3)	0.006 (6)	−0.008 (4)
O2	0.043 (4)	0.126 (10)	0.045 (4)	−0.007 (5)	0.015 (3)	−0.025 (5)
C1	0.052 (7)	0.099 (8)	0.046 (5)	−0.009 (6)	0.018 (6)	−0.016 (5)
C2	0.040 (6)	0.086 (11)	0.048 (7)	−0.005 (6)	−0.005 (5)	0.004 (6)
O1A	0.076 (3)	0.111 (6)	0.101 (5)	0.016 (3)	0.013 (3)	−0.032 (4)
O2A	0.040 (2)	0.090 (4)	0.052 (4)	0.012 (3)	0.009 (2)	−0.005 (3)
C1A	0.067 (5)	0.168 (12)	0.075 (5)	−0.018 (6)	−0.009 (4)	−0.013 (6)
C2A	0.066 (6)	0.079 (6)	0.070 (6)	−0.022 (4)	0.027 (5)	−0.014 (4)

Geometric parameters (Å, º) top

O3—C19	1.2583 (19)	C20—H20	0.9300
O4—C19	1.251 (2)	O5—C21	1.223 (9)
N1—H1	0.868 (10)	O6—H6A	0.8200
N1—C7	1.363 (2)	O6—C21	1.289 (8)
N1—C10	1.368 (2)	C21—C22	1.564 (18)
N2—H2	0.878 (9)	O5A—C21A	1.221 (10)
N2—C12	1.5038 (19)	O6A—H6AA	0.8200
N2—C16	1.510 (2)	O6A—C21A	1.285 (8)
N2—C13	1.498 (2)	C21A—C22	1.388 (19)
C3—C4	1.365 (3)	C22—C22ⁱⁱ	1.288 (4)
C3—C8	1.391 (3)	C22—H22	0.9300
C3—O2	1.407 (9)	C22—H22A	0.9300
C3—O2A	1.413 (6)	C13—H13A	0.9700
C4—H4	0.9300	C13—H13B	0.9700
C4—C5	1.398 (3)	C13—H13C	0.9700
C5—H5	0.9300	C13—H13D	0.9700
C5—C6	1.361 (3)	C13—C14	1.465 (10)
C6—H6	0.9300	C13—C14A	1.458 (3)
C6—C7	1.394 (3)	C14—H14	0.9300
C7—C8	1.413 (2)	C14—C15	1.294 (10)
C8—C9	1.438 (2)	C15—H15A	0.9300
C9—C10	1.357 (3)	C15—H15B	0.9300
C9—C11	1.503 (2)	C14A—H14A	0.9300
C10—H10	0.9300	C14A—C15A	1.290 (4)
C11—H11A	0.9700	C15A—H15C	0.9300
C11—H11B	0.9700	C15A—H15D	0.9300
C11—C12	1.514 (2)	O1—C2	1.220 (10)
C12—H12A	0.9700	O2—C2	1.348 (9)
C12—H12B	0.9700	C1—H1A	0.9600
C16—H16A	0.9700	C1—H1B	0.9600
C16—H16B	0.9700	C1—H1C	0.9600
C16—C17	1.474 (3)	C1—C2	1.489 (9)
C17—H17	0.9300	O1A—C2A	1.239 (9)
C17—C18	1.300 (4)	O2A—C2A	1.359 (7)
C18—H18A	0.9300	C1A—H1AA	0.9600
C18—H18B	0.9300	C1A—H1AB	0.9600
C19—C20	1.491 (2)	C1A—H1AC	0.9600
C20—C20ⁱ	1.304 (3)	C1A—C2A	1.498 (8)

C7—N1—H1	124.6 (14)	C19—C20—H20	117.8
C7—N1—C10	108.71 (15)	C20ⁱ—C20—C19	124.40 (19)
C10—N1—H1	124.6 (14)	C20ⁱ—C20—H20	117.8
C12—N2—H2	108.3 (13)	C21—O6—H6A	109.5
C12—N2—C16	108.62 (13)	O5—C21—O6	129.4 (19)
C16—N2—H2	108.9 (13)	O5—C21—C22	114.3 (14)
C13—N2—H2	103.1 (13)	O6—C21—C22	113.7 (10)
C13—N2—C12	113.22 (14)	C21A—O6A—H6AA	109.5
C13—N2—C16	114.38 (15)	O5A—C21A—O6A	111 (2)
C4—C3—C8	121.14 (17)	O5A—C21A—C22	131.5 (18)
C4—C3—O2	126.9 (12)	O6A—C21A—C22	115.3 (11)
C4—C3—O2A	117.6 (8)	C21—C22—H22	118.6
C8—C3—O2	111.7 (12)	C21A—C22—H22A	115.9
C8—C3—O2A	121.0 (8)	C22ⁱⁱ—C22—C21	122.7 (5)
C3—C4—H4	120.1	C22ⁱⁱ—C22—C21A	128.2 (7)
C3—C4—C5	119.9 (2)	C22ⁱⁱ—C22—H22	118.6
C5—C4—H4	120.1	C22ⁱⁱ—C22—H22A	115.9
C4—C5—H5	119.1	N2—C13—H13A	103.0
C6—C5—C4	121.79 (18)	N2—C13—H13B	103.0
C6—C5—H5	119.1	N2—C13—H13C	108.6
C5—C6—H6	121.2	N2—C13—H13D	108.6
C5—C6—C7	117.65 (18)	H13A—C13—H13B	105.1
C7—C6—H6	121.2	H13C—C13—H13D	107.6
N1—C7—C6	130.13 (17)	C14—C13—N2	136.6 (9)
N1—C7—C8	107.57 (15)	C14—C13—H13A	103.0
C6—C7—C8	122.29 (18)	C14—C13—H13B	103.0
C3—C8—C7	117.24 (15)	C14A—C13—N2	114.71 (17)
C3—C8—C9	135.79 (15)	C14A—C13—H13C	108.6
C7—C8—C9	106.93 (15)	C14A—C13—H13D	108.6
C8—C9—C11	128.22 (16)	C13—C14—H14	110.7
C10—C9—C8	105.82 (15)	C15—C14—C13	139 (3)
C10—C9—C11	125.87 (16)	C15—C14—H14	110.7
N1—C10—H10	124.5	C14—C15—H15A	120.0
C9—C10—N1	110.92 (16)	C14—C15—H15B	120.0
C9—C10—H10	124.5	H15A—C15—H15B	120.0
C9—C11—H11A	109.6	C13—C14A—H14A	118.8
C9—C11—H11B	109.6	C15A—C14A—C13	122.3 (3)
C9—C11—C12	110.08 (14)	C15A—C14A—H14A	118.8
H11A—C11—H11B	108.2	C14A—C15A—H15C	120.0
C12—C11—H11A	109.6	C14A—C15A—H15D	120.0
C12—C11—H11B	109.6	H15C—C15A—H15D	120.0
N2—C12—C11	114.08 (14)	C2—O2—C3	113.5 (14)
N2—C12—H12A	108.7	H1A—C1—H1B	109.5
N2—C12—H12B	108.7	H1A—C1—H1C	109.5
C11—C12—H12A	108.7	H1B—C1—H1C	109.5
C11—C12—H12B	108.7	C2—C1—H1A	109.5
H12A—C12—H12B	107.6	C2—C1—H1B	109.5
N2—C16—H16A	108.7	C2—C1—H1C	109.5
N2—C16—H16B	108.7	O1—C2—O2	117 (2)
H16A—C16—H16B	107.6	O1—C2—C1	114.3 (18)
C17—C16—N2	114.37 (17)	O2—C2—C1	110.6 (12)
C17—C16—H16A	108.7	C2A—O2A—C3	123.3 (8)
C17—C16—H16B	108.7	H1AA—C1A—H1AB	109.5
C16—C17—H17	118.7	H1AA—C1A—H1AC	109.5
C18—C17—C16	122.6 (3)	H1AB—C1A—H1AC	109.5
C18—C17—H17	118.7	C2A—C1A—H1AA	109.5
C17—C18—H18A	120.0	C2A—C1A—H1AB	109.5
C17—C18—H18B	120.0	C2A—C1A—H1AC	109.5
H18A—C18—H18B	120.0	O1A—C2A—O2A	115.7 (14)
O3—C19—C20	118.57 (15)	O1A—C2A—C1A	127.1 (11)
O4—C19—O3	123.72 (16)	O2A—C2A—C1A	110.0 (9)
O4—C19—C20	117.70 (14)

O3—C19—C20—C20ⁱ	0.2 (3)	C8—C3—O2—C2	128.5 (19)
O4—C19—C20—C20ⁱ	179.3 (2)	C8—C3—O2A—C2A	107.5 (16)
N1—C7—C8—C3	−179.21 (16)	C8—C9—C10—N1	1.3 (2)
N1—C7—C8—C9	−0.90 (18)	C8—C9—C11—C12	71.7 (2)
N2—C16—C17—C18	−121.8 (3)	C9—C11—C12—N2	175.40 (14)
N2—C13—C14—C15	−86 (5)	C10—N1—C7—C6	−177.82 (19)
N2—C13—C14A—C15A	121.5 (3)	C10—N1—C7—C8	1.7 (2)
C3—C4—C5—C6	0.4 (4)	C10—C9—C11—C12	−104.3 (2)
C3—C8—C9—C10	177.6 (2)	C11—C9—C10—N1	178.07 (16)
C3—C8—C9—C11	1.0 (3)	C12—N2—C16—C17	179.1 (2)
C3—O2—C2—O1	−47 (4)	C12—N2—C13—C14	20.0 (14)
C3—O2—C2—C1	−179.5 (18)	C12—N2—C13—C14A	−48.3 (2)
C3—O2A—C2A—O1A	29 (3)	C16—N2—C12—C11	167.33 (16)
C3—O2A—C2A—C1A	−177.9 (14)	C16—N2—C13—C14	145.2 (14)
C4—C3—C8—C7	0.7 (3)	C16—N2—C13—C14A	76.8 (2)
C4—C3—C8—C9	−177.0 (2)	O5—C21—C22—C22ⁱⁱ	−160.9 (18)
C4—C3—O2—C2	−57 (3)	O6—C21—C22—C22ⁱⁱ	3 (2)
C4—C3—O2A—C2A	−78.0 (17)	O5A—C21A—C22—C22ⁱⁱ	158 (2)
C4—C5—C6—C7	0.6 (3)	O6A—C21A—C22—C22ⁱⁱ	−4 (3)
C5—C6—C7—N1	178.49 (19)	C13—N2—C12—C11	−64.5 (2)
C5—C6—C7—C8	−1.0 (3)	C13—N2—C16—C17	51.5 (3)
C6—C7—C8—C3	0.4 (3)	O2—C3—C4—C5	−174.8 (10)
C6—C7—C8—C9	178.68 (16)	O2—C3—C8—C7	175.3 (9)
C7—N1—C10—C9	−2.0 (2)	O2—C3—C8—C9	−2.4 (9)
C7—C8—C9—C10	−0.25 (19)	O2A—C3—C4—C5	−175.5 (5)
C7—C8—C9—C11	−176.89 (16)	O2A—C3—C8—C7	175.0 (5)
C8—C3—C4—C5	−1.1 (3)	O2A—C3—C8—C9	−2.7 (6)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O3ⁱⁱⁱ	0.87 (1)	2.22 (2)	2.962 (2)	144 (2)
N2—H2···O3	0.88 (1)	1.87 (1)	2.7446 (19)	177 (2)
O6—H6A···O4	0.82	1.72	2.530 (17)	168
O6A—H6AA···O4	0.82	1.81	2.577 (16)	156

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

Acknowledgements

Financial statements and conflict of interest: This study was funded by CaaMTech, Inc. ARC reports an ownership interest in CaaMTech, Inc., which owns US and worldwide patent applications covering new tryptamine compounds, compositions, formulations, novel crystalline forms, and methods of making and using the same.

References

Bruker (2018). APEX3, SAINT, and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Byock, I. (2018). J. Palliat. Med. 21, 417–421. Web of Science CrossRef PubMed Google Scholar
Chadeayne, A. R., Golen, J. A. & Manke, D. R. (2019a). Acta Cryst. E75, 900–902. Web of Science CSD CrossRef IUCr Journals Google Scholar
Chadeayne, A. R., Golen, J. A. & Manke, D. R. (2019b). Psychedelic Science Review. https://psychedelicreview.com/the-crystal-structure-of-4-aco-dmt-fumarate/. Google Scholar
Chadeayne, A. R., Pham, D. N. K., Golen, J. A. & Manke, D. R. (2019). IUCrData, 4, x190962. Google Scholar
Chadeayne, A. R., Pham, D. N. K., Golen, J. A. & Manke, D. R. (2020a). Acta Cryst. E76, 514–517. Web of Science CSD CrossRef IUCr Journals Google Scholar
Chadeayne, A. R., Pham, D. N. K., Golen, J. A. & Manke, D. R. (2020b). Acta Cryst. E76, 589–593. Web of Science CSD CrossRef IUCr Journals Google Scholar
Chadeayne, A. R., Pham, D. N. K., Golen, J. A. & Manke, D. R. (2020c). Acta Cryst. E76, 1201–1205. Web of Science CSD CrossRef IUCr Journals Google Scholar
Chadeayne, A. R., Pham, D. N. K., Reid, B. G., Golen, J. A. & Manke, D. R. (2020). ACS Omega, 5, 16940–16943. Web of Science CSD CrossRef CAS PubMed Google Scholar
Daniel, J. & Haberman, M. (2017). Mental Health Clinician, 7, 24–28. CrossRef Google Scholar
Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339–341. Web of Science CrossRef CAS IUCr Journals Google Scholar
Feltman, R. (2019). Popular Science. https://popsci.com/story/health/psilocybin-magic-mushroom-fda-breakthrough-depression/ Google Scholar
Geiger, H. A., Wurst, M. G. & Daniels, R. N. (2018). ACS Chem. Neurosci. 9, 2438–2447. Web of Science CrossRef CAS PubMed Google Scholar
Klein, A. K., Chatha, M., Laskowski, L. J., Anderson, E. I., Brandt, S. D., Chapman, S. J., McCorvy, J. D. & Halberstadt, A. L. (2020). ACS Pharmacol. Transl. Sci. 3. https://dx.doi.org/10/1021/acsptsci.0c00176 Google Scholar
Lehmann, S., Kieliba, T., Beike, J., Thevis, M. & Mercer-Chalmers-Bender, K. (2017). J. Chromatogr. B, 1064, 124–138. CrossRef CAS Google Scholar
Nichols, D. E. & Frescas, S. (1999). Synthesis, pp. 935–938. CrossRef Google Scholar
Parsons, S., Flack, H. D. & Wagner, T. (2013). Acta Cryst. B69, 249–259. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2015a). Acta Cryst. A71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2015b). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 77| Part 2| February 2021| Pages 101-106

https://doi.org/10.1107/S2056989021000116

Open

access

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text
		Text

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text
		Text

Search IUCr Journals		doi		Advanced search
Author		volume	page

research communications\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Psilacetin derivatives: fumarate salts of the meth­yl–ethyl, meth­yl–allyl and di­allyl variants of the psilocin prodrug

1. Chemical context

2. Structural commentary

3. Supra­molecular features

4. Database survey

5. Synthesis and crystallization

6. Refinement

Supporting information

Acknowledgements

References

research communications

Psilacetin derivatives: fumarate salts of the methyl–ethyl, methyl–allyl and diallyl variants of the psilocin prodrug

3. Supramolecular features