Bis(4-hy­droxy-N-isopropyl-N-methyl­trypt­ammo­nium) fumarate: a new crystalline form of miprocin

A new form of the synthetic psychedelic miprocin, a psilocin derivative, is reported. The title compound has a single protonated tryptammonium cation and one half of a fumarate in the asymmetric unit. The ions are held together in an elaborate set of rings and chains along (110).

Key indicators

• Single-crystal X-ray study
• T = 200 K
• Mean [sigma](C-C) = 0.003 Å
• Disorder in main residue
• R factor = 0.047
• wR factor = 0.105
• Data-to-parameter ratio = 10.9

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT420_ALERT_2_C D-H Without Acceptor       N1       --H1A      .     Please Check
PLAT906_ALERT_3_C Large K Value in the Analysis of Variance ......      6.341 Check
PLAT911_ALERT_3_C Missing FCF Refl Between Thmin & STh/L=    0.600         11 Report

Alert level G
PLAT002_ALERT_2_G Number of Distance or Angle Restraints on AtSite         16 Note
PLAT042_ALERT_1_G Calc. and Reported MoietyFormula Strings  Differ     Please Check
PLAT172_ALERT_4_G The CIF-Embedded .res File Contains DFIX Records          3 Report
PLAT176_ALERT_4_G The CIF-Embedded .res File Contains SADI Records          2 Report
PLAT301_ALERT_3_G Main Residue  Disorder ..............(Resd  1  )        29% Note
PLAT302_ALERT_4_G Anion/Solvent/Minor-Residue Disorder (Resd  2  )        25% Note
PLAT793_ALERT_4_G Model has Chirality at N2          (Centro SPGR)          S Verify
PLAT811_ALERT_5_G No ADDSYM Analysis: Too Many Excluded Atoms ....          ! Info
PLAT860_ALERT_3_G Number of Least-Squares Restraints .............         11 Note
PLAT910_ALERT_3_G Missing # of FCF Reflection(s) Below Theta(Min).          3 Note
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600         58 Note
PLAT913_ALERT_3_G Missing # of Very Strong Reflections in FCF ....          2 Note
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density.          3 Info

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   3 ALERT level C = Check. Ensure it is not caused by an omission or oversight
  13 ALERT level G = General information/check it is not something unexpected

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   3 ALERT type 2 Indicator that the structure model may be wrong or deficient
   6 ALERT type 3 Indicator that the structure quality may be low
   5 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

---

Computing details

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).

Bis{[2-(4-hydroxy-1H-indol-3-yl)ethyl](methyl)propan-2-ylazanium} but-2-enedioate

Crystal data

C14H21N2O^+·C2HO2^−	F(000) = 1248
Mr = 290.35	Dx = 1.214 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 19.770 (13) Å	Cell parameters from 5659 reflections
b = 9.477 (6) Å	θ = 2.6–23.3°
c = 17.620 (12) Å	µ = 0.08 mm^−1
β = 105.78 (2)°	T = 200 K
V = 3177 (4) Å^3	Block, colourless
Z = 8	0.25 × 0.2 × 0.1 mm

Data collection

Bruker D8 Venture CMOS diffractometer	2007 reflections with I > 2σ(I)
φ and ω scans	Rint = 0.086
Absorption correction: multi-scan (SADABS; Bruker, 2018)	θmax = 25.5°, θmin = 2.6°
Tmin = 0.692, Tmax = 0.745	h = −23→23
39417 measured reflections	k = −11→11
2890 independent reflections	l = −21→21

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.047	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.105	w = 1/[σ^2(Fo^2) + (0.0307P)^2 + 2.6574P] where P = (Fo^2 + 2Fc^2)/3
S = 1.06	(Δ/σ)max < 0.001
2890 reflections	Δρmax = 0.15 e Å^−3
265 parameters	Δρmin = −0.13 e Å^−3
11 restraints	Extinction correction: SHELXL2018 (Sheldrick, 2015b), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: iterative	Extinction coefficient: 0.0036 (5)

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	0.31856 (7)	0.49585 (15)	0.58406 (9)	0.0493 (4)
H1	0.3549 (9)	0.553 (2)	0.5887 (14)	0.074*
N1	0.21977 (11)	0.1682 (2)	0.71648 (12)	0.0605 (5)
H1A	0.2128 (12)	0.107 (2)	0.7503 (11)	0.073*
C1	0.27162 (10)	0.33085 (19)	0.65757 (11)	0.0381 (5)
C2	0.32760 (11)	0.42144 (19)	0.65257 (12)	0.0400 (5)
C3	0.38761 (11)	0.4290 (2)	0.71573 (13)	0.0505 (6)
H3	0.425086	0.489562	0.712691	0.061*
C4	0.39340 (13)	0.3476 (3)	0.78447 (14)	0.0609 (6)
H4	0.434890	0.354722	0.826879	0.073*
C5	0.34054 (14)	0.2583 (3)	0.79158 (14)	0.0620 (7)
H5	0.344946	0.203862	0.837966	0.074*
C6	0.27957 (12)	0.2504 (2)	0.72753 (13)	0.0487 (6)
C7	0.17506 (12)	0.1943 (2)	0.64280 (13)	0.0522 (6)
H7	0.130641	0.150538	0.622100	0.063*
C8	0.20396 (10)	0.29280 (19)	0.60364 (12)	0.0400 (5)
C9	0.17292 (11)	0.33949 (19)	0.51916 (12)	0.0431 (5)
H9A	0.133346	0.276143	0.494062	0.052*
H9B	0.209080	0.329163	0.490173	0.052*
C10	0.14642 (10)	0.49194 (19)	0.51102 (11)	0.0392 (5)
H10A	0.112079	0.503834	0.542269	0.047*	0.753 (7)
H10B	0.186480	0.555914	0.533343	0.047*	0.753 (7)
H10C	0.098438	0.494556	0.518071	0.047*	0.247 (7)
H10D	0.177245	0.549775	0.553315	0.047*	0.247 (7)
N2	0.1120 (2)	0.5345 (4)	0.4263 (3)	0.0424 (10)	0.753 (7)
H2	0.1020 (16)	0.6251 (14)	0.427 (2)	0.064*	0.753 (7)
C11	0.16090 (17)	0.5281 (3)	0.37193 (17)	0.0460 (11)	0.753 (7)
H11	0.174245	0.427448	0.366898	0.055*	0.753 (7)
C12	0.1208 (6)	0.5835 (11)	0.2891 (5)	0.075 (2)	0.753 (7)
H12A	0.081724	0.519686	0.265521	0.113*	0.753 (7)
H12B	0.152896	0.587641	0.255495	0.113*	0.753 (7)
H12C	0.102418	0.678046	0.294075	0.113*	0.753 (7)
C13	0.2280 (5)	0.6136 (11)	0.4063 (5)	0.0550 (16)	0.753 (7)
H13A	0.254848	0.570569	0.455889	0.082*	0.753 (7)
H13B	0.215425	0.710610	0.416231	0.082*	0.753 (7)
H13C	0.256526	0.614481	0.368717	0.082*	0.753 (7)
C14	0.0444 (4)	0.4557 (8)	0.3919 (4)	0.0602 (16)	0.753 (7)
H14A	0.012269	0.515034	0.352607	0.090*	0.753 (7)
H14B	0.022643	0.432096	0.434091	0.090*	0.753 (7)
H14C	0.054337	0.368833	0.366817	0.090*	0.753 (7)
N2A	0.1450 (7)	0.5560 (14)	0.4311 (9)	0.050 (3)	0.247 (7)
H2A	0.134 (5)	0.643 (4)	0.439 (7)	0.075*	0.247 (7)
C11A	0.1027 (5)	0.4723 (9)	0.3612 (6)	0.056 (4)	0.247 (7)
H11A	0.129490	0.383119	0.360557	0.067*	0.247 (7)
C12A	0.1043 (18)	0.553 (3)	0.2865 (15)	0.072 (9)	0.247 (7)
H12D	0.152027	0.587736	0.291618	0.108*	0.247 (7)
H12E	0.071726	0.632858	0.279034	0.108*	0.247 (7)
H12F	0.090242	0.489724	0.240840	0.108*	0.247 (7)
C13A	0.0317 (13)	0.428 (3)	0.3716 (17)	0.083 (7)	0.247 (7)
H13D	0.038819	0.359379	0.414764	0.124*	0.247 (7)
H13E	0.003480	0.384461	0.322671	0.124*	0.247 (7)
H13F	0.007061	0.510726	0.383946	0.124*	0.247 (7)
C14A	0.2162 (13)	0.601 (3)	0.4231 (16)	0.048 (5)	0.247 (7)
H14D	0.210287	0.677296	0.384573	0.072*	0.247 (7)
H14E	0.238906	0.520050	0.405164	0.072*	0.247 (7)
H14F	0.245452	0.633016	0.474299	0.072*	0.247 (7)
O2	0.41362 (7)	0.68230 (14)	0.57453 (9)	0.0518 (4)
C15	0.45985 (11)	0.6662 (2)	0.53625 (14)	0.0489 (5)
C16	0.47710 (10)	0.5170 (2)	0.51944 (13)	0.0438 (5)
H16	0.453512	0.442783	0.538017	0.053*
O3	0.4846 (16)	0.7662 (12)	0.5058 (18)	0.079 (4)	0.73 (8)
O3A	0.5040 (17)	0.762 (4)	0.537 (4)	0.066 (7)	0.27 (8)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0463 (9)	0.0440 (8)	0.0593 (9)	−0.0065 (7)	0.0175 (7)	0.0114 (7)
N1	0.0821 (14)	0.0515 (12)	0.0562 (13)	−0.0066 (11)	0.0332 (11)	0.0146 (10)
C1	0.0498 (12)	0.0287 (10)	0.0412 (11)	0.0039 (9)	0.0215 (10)	−0.0007 (8)
C2	0.0464 (12)	0.0298 (10)	0.0474 (12)	0.0064 (9)	0.0189 (10)	−0.0015 (9)
C3	0.0466 (13)	0.0467 (12)	0.0581 (14)	0.0043 (10)	0.0145 (12)	−0.0041 (11)
C4	0.0633 (15)	0.0632 (15)	0.0520 (14)	0.0116 (13)	0.0085 (12)	−0.0056 (12)
C5	0.0827 (18)	0.0618 (15)	0.0435 (14)	0.0132 (14)	0.0206 (14)	0.0069 (11)
C6	0.0628 (15)	0.0419 (12)	0.0475 (13)	0.0043 (11)	0.0251 (12)	0.0032 (10)
C7	0.0583 (14)	0.0436 (12)	0.0600 (15)	−0.0069 (10)	0.0253 (12)	0.0032 (11)
C8	0.0485 (12)	0.0290 (10)	0.0485 (12)	0.0010 (8)	0.0234 (10)	0.0018 (9)
C9	0.0504 (12)	0.0305 (10)	0.0503 (12)	−0.0006 (9)	0.0168 (10)	−0.0035 (9)
C10	0.0436 (11)	0.0336 (10)	0.0454 (12)	0.0016 (9)	0.0204 (10)	−0.0011 (9)
N2	0.048 (2)	0.0347 (16)	0.0467 (19)	0.0054 (18)	0.016 (2)	0.0011 (13)
C11	0.063 (3)	0.0365 (16)	0.0449 (19)	0.0035 (15)	0.0246 (17)	−0.0003 (13)
C12	0.102 (4)	0.074 (6)	0.049 (3)	−0.009 (4)	0.019 (3)	0.009 (3)
C13	0.051 (4)	0.063 (3)	0.059 (3)	0.001 (3)	0.028 (2)	0.010 (3)
C14	0.056 (4)	0.044 (3)	0.074 (3)	−0.016 (2)	0.007 (3)	0.003 (3)
N2A	0.060 (8)	0.034 (6)	0.056 (6)	0.022 (6)	0.017 (7)	−0.001 (5)
C11A	0.059 (8)	0.034 (5)	0.064 (7)	0.004 (5)	0.000 (5)	−0.007 (5)
C12A	0.13 (2)	0.032 (8)	0.054 (10)	0.029 (12)	0.032 (12)	0.011 (6)
C13A	0.048 (10)	0.061 (11)	0.130 (18)	−0.024 (7)	0.007 (11)	−0.035 (10)
C14A	0.049 (9)	0.039 (7)	0.074 (12)	0.011 (6)	0.046 (7)	0.010 (7)
O2	0.0507 (9)	0.0341 (7)	0.0808 (11)	0.0017 (6)	0.0353 (8)	0.0008 (7)
C15	0.0470 (12)	0.0326 (11)	0.0739 (16)	0.0036 (10)	0.0278 (12)	0.0051 (11)
C16	0.0402 (11)	0.0306 (10)	0.0651 (14)	−0.0004 (9)	0.0221 (10)	0.0069 (9)
O3	0.100 (8)	0.0310 (18)	0.137 (9)	0.008 (3)	0.083 (7)	0.017 (4)
O3A	0.057 (10)	0.031 (6)	0.124 (19)	−0.012 (6)	0.048 (11)	0.001 (9)

Geometric parameters (Å, º)

O1—H1	0.885 (10)	C11—C13	1.531 (10)
O1—C2	1.367 (2)	C12—H12A	0.9800
N1—H1A	0.870 (10)	C12—H12B	0.9800
N1—C6	1.385 (3)	C12—H12C	0.9800
N1—C7	1.380 (3)	C13—H13A	0.9800
C1—C2	1.422 (3)	C13—H13B	0.9800
C1—C6	1.421 (3)	C13—H13C	0.9800
C1—C8	1.460 (3)	C14—H14A	0.9800
C2—C3	1.390 (3)	C14—H14B	0.9800
C3—H3	0.9500	C14—H14C	0.9800
C3—C4	1.414 (3)	N2A—H2A	0.874 (11)
C4—H4	0.9500	N2A—C11A	1.511 (18)
C4—C5	1.377 (3)	N2A—C14A	1.51 (2)
C5—H5	0.9500	C11A—H11A	1.0000
C5—C6	1.412 (3)	C11A—C12A	1.53 (2)
C7—H7	0.9500	C11A—C13A	1.52 (2)
C7—C8	1.374 (3)	C12A—H12D	0.9800
C8—C9	1.514 (3)	C12A—H12E	0.9800
C9—H9A	0.9900	C12A—H12F	0.9800
C9—H9B	0.9900	C13A—H13D	0.9800
C9—C10	1.530 (3)	C13A—H13E	0.9800
C10—H10A	0.9900	C13A—H13F	0.9800
C10—H10B	0.9900	C14A—H14D	0.9800
C10—H10C	0.9900	C14A—H14E	0.9800
C10—H10D	0.9900	C14A—H14F	0.9800
C10—N2	1.518 (5)	O2—C15	1.284 (2)
C10—N2A	1.527 (15)	C15—C16	1.503 (3)
N2—H2	0.882 (10)	C15—O3	1.251 (10)
N2—C11	1.536 (5)	C15—O3A	1.26 (3)
N2—C14	1.506 (7)	C16—C16^i	1.315 (4)
C11—H11	1.0000	C16—H16	0.9500
C11—C12	1.550 (9)
C2—O1—H1	109.0 (16)	C13—C11—C12	111.0 (5)
C6—N1—H1A	124.6 (17)	C11—C12—H12A	109.5
C7—N1—H1A	125.8 (17)	C11—C12—H12B	109.5
C7—N1—C6	109.58 (18)	C11—C12—H12C	109.5
C2—C1—C8	134.38 (18)	H12A—C12—H12B	109.5
C6—C1—C2	118.24 (19)	H12A—C12—H12C	109.5
C6—C1—C8	107.32 (18)	H12B—C12—H12C	109.5
O1—C2—C1	116.68 (18)	C11—C13—H13A	109.5
O1—C2—C3	123.93 (19)	C11—C13—H13B	109.5
C3—C2—C1	119.38 (19)	C11—C13—H13C	109.5
C2—C3—H3	119.7	H13A—C13—H13B	109.5
C2—C3—C4	120.7 (2)	H13A—C13—H13C	109.5
C4—C3—H3	119.7	H13B—C13—H13C	109.5
C3—C4—H4	119.1	N2—C14—H14A	109.5
C5—C4—C3	121.8 (2)	N2—C14—H14B	109.5
C5—C4—H4	119.1	N2—C14—H14C	109.5
C4—C5—H5	121.2	H14A—C14—H14B	109.5
C4—C5—C6	117.6 (2)	H14A—C14—H14C	109.5
C6—C5—H5	121.2	H14B—C14—H14C	109.5
N1—C6—C1	106.9 (2)	C10—N2A—H2A	100 (8)
N1—C6—C5	130.8 (2)	C11A—N2A—C10	114.2 (10)
C5—C6—C1	122.3 (2)	C11A—N2A—H2A	122 (8)
N1—C7—H7	124.8	C11A—N2A—C14A	113.2 (16)
C8—C7—N1	110.3 (2)	C14A—N2A—C10	114.4 (13)
C8—C7—H7	124.8	C14A—N2A—H2A	92 (7)
C1—C8—C9	128.51 (17)	N2A—C11A—H11A	106.0
C7—C8—C1	105.86 (18)	N2A—C11A—C12A	107.6 (15)
C7—C8—C9	125.42 (19)	N2A—C11A—C13A	111.8 (12)
C8—C9—H9A	108.8	C12A—C11A—H11A	106.0
C8—C9—H9B	108.8	C13A—C11A—H11A	106.0
C8—C9—C10	113.90 (16)	C13A—C11A—C12A	118.5 (19)
H9A—C9—H9B	107.7	C11A—C12A—H12D	109.5
C10—C9—H9A	108.8	C11A—C12A—H12E	109.5
C10—C9—H9B	108.8	C11A—C12A—H12F	109.5
C9—C10—H10A	108.9	H12D—C12A—H12E	109.5
C9—C10—H10B	108.9	H12D—C12A—H12F	109.5
C9—C10—H10C	109.1	H12E—C12A—H12F	109.5
C9—C10—H10D	109.1	C11A—C13A—H13D	109.5
H10A—C10—H10B	107.8	C11A—C13A—H13E	109.5
H10C—C10—H10D	107.8	C11A—C13A—H13F	109.5
N2—C10—C9	113.2 (2)	H13D—C13A—H13E	109.5
N2—C10—H10A	108.9	H13D—C13A—H13F	109.5
N2—C10—H10B	108.9	H13E—C13A—H13F	109.5
N2A—C10—C9	112.5 (5)	N2A—C14A—H14D	109.5
N2A—C10—H10C	109.1	N2A—C14A—H14E	109.5
N2A—C10—H10D	109.1	N2A—C14A—H14F	109.5
C10—N2—H2	106 (2)	H14D—C14A—H14E	109.5
C10—N2—C11	114.3 (3)	H14D—C14A—H14F	109.5
C11—N2—H2	104 (2)	H14E—C14A—H14F	109.5
C14—N2—C10	112.0 (4)	O2—C15—C16	116.58 (17)
C14—N2—H2	108 (2)	O3—C15—O2	123.5 (5)
C14—N2—C11	111.7 (4)	O3—C15—C16	119.5 (5)
N2—C11—H11	108.6	O3A—C15—O2	120.2 (17)
N2—C11—C12	109.0 (5)	O3A—C15—C16	119.1 (14)
C12—C11—H11	108.6	C15—C16—H16	118.0
C13—C11—N2	110.9 (4)	C16^i—C16—C15	123.9 (2)
C13—C11—H11	108.6	C16^i—C16—H16	118.0
O1—C2—C3—C4	−179.34 (19)	C8—C1—C2—O1	2.2 (3)
N1—C7—C8—C1	−0.3 (2)	C8—C1—C2—C3	−177.32 (19)
N1—C7—C8—C9	174.91 (18)	C8—C1—C6—N1	−0.1 (2)
C1—C2—C3—C4	0.1 (3)	C8—C1—C6—C5	178.10 (19)
C1—C8—C9—C10	−74.2 (2)	C8—C9—C10—N2	−176.9 (2)
C2—C1—C6—N1	−177.84 (17)	C8—C9—C10—N2A	155.6 (6)
C2—C1—C6—C5	0.4 (3)	C9—C10—N2—C11	−61.5 (3)
C2—C1—C8—C7	177.5 (2)	C9—C10—N2—C14	66.9 (5)
C2—C1—C8—C9	2.4 (3)	C9—C10—N2A—C11A	55.6 (9)
C2—C3—C4—C5	0.1 (3)	C9—C10—N2A—C14A	−77.0 (14)
C3—C4—C5—C6	−0.1 (3)	C10—N2—C11—C12	−176.2 (5)
C4—C5—C6—N1	177.6 (2)	C10—N2—C11—C13	−53.7 (5)
C4—C5—C6—C1	−0.1 (3)	C10—N2A—C11A—C12A	178.0 (14)
C6—N1—C7—C8	0.3 (3)	C10—N2A—C11A—C13A	46.2 (17)
C6—C1—C2—O1	179.16 (17)	C14—N2—C11—C12	55.2 (6)
C6—C1—C2—C3	−0.4 (3)	C14—N2—C11—C13	177.7 (6)
C6—C1—C8—C7	0.3 (2)	C14A—N2A—C11A—C12A	−49 (2)
C6—C1—C8—C9	−174.77 (18)	C14A—N2A—C11A—C13A	179.3 (19)
C7—N1—C6—C1	−0.1 (2)	O2—C15—C16—C16^i	179.6 (3)
C7—N1—C6—C5	−178.1 (2)	O3—C15—C16—C16^i	7 (2)
C7—C8—C9—C10	111.7 (2)	O3A—C15—C16—C16^i	−23 (4)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

Cg2 is the centroid of the C1–C6 ring.

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2	0.89 (1)	1.75 (1)	2.618 (2)	165 (2)
N2—H2···O2^ii	0.88 (1)	1.85 (1)	2.730 (5)	175 (3)
N2A—H2A···O2^ii	0.87 (1)	1.89 (4)	2.727 (12)	160 (11)
N1—H1A···Cg2^iii	0.87 (1)	2.78 (2)	3.552 (3)	148 (2)

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