π-Complexation and C—H hydrogen bonding in the formation of colored cocrystals

Bosch, E.; Moreno, B.S.; Bowling, N.P.

doi:10.1107/S2053229623002231

π-Complexation and C—H hydrogen bonding in the formation of colored cocrystals

E. Bosch, B. S. Moreno and N. P. Bowling

The present study evaluates the potential combination of charge-transfer electron-donor–acceptor π–π complexation and C—H hydrogen bonding to form colored cocrystals. The crystal structures of the red 1:1 cocrystals formed from the isomeric pyridines 4- and 3-{2-[4-(dimethylamino)phenyl]ethynyl}pyridine with 1-[2-(3,5-dinitrophenyl)ethynyl]-2,3,5,6-tetrafluorobenzene, both C₁₄H₄F₄N₂O₄·C₁₅H₁₄N₂, are reported. Intermolecular interaction energy calculations confirm that π-stacking interactions dominate the intermolecular interactions within each crystal structure. The close contacts revealed by Hirshfeld surface calculations are predominantly C—H interactions with N, O, and F atoms.

Keywords: crystal structure; C—H

N hydrogen bond; C—H

O hydrogen bond; C—H

F hydrogen bond; π-stacking; cocrystal.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229623002231/ov3169sup1.cif Contains datablocks 1, 2, global
	Structure factor file (CIF format) https://doi.org/10.1107/S2053229623002231/ov31691sup2.hkl Contains datablock 1
	Structure factor file (CIF format) https://doi.org/10.1107/S2053229623002231/ov31692sup3.hkl Contains datablock 2
	Chemical Markup Language (CML) file https://doi.org/10.1107/S2053229623002231/ov31691sup4.cml Supplementary material
	Chemical Markup Language (CML) file https://doi.org/10.1107/S2053229623002231/ov31692sup5.cml Supplementary material

CCDC references: 2247037; 2247036

Computing details top

Data collection: CrysAlis PRO (Rigaku OD, 2022) for (1); SMART (Bruker, 2014) for (2). Cell refinement: CrysAlis PRO (Rigaku OD, 2022) for (1); SMART (Bruker, 2014) for (2). Data reduction: CrysAlis PRO (Rigaku OD, 2022) for (1); SAINT (Bruker, 2014) for (2). For both structures, program(s) used to solve structure: SHELXT2018 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015b); molecular graphics: X-SEED (Barbour, 2020); software used to prepare material for publication: X-SEED (Barbour, 2020).

4-{2-[4-(Dimethylamino)phenyl]ethynyl}pyridine; 1-[2-(3,5-dinitrophenyl)ethynyl]-2,3,5,6-tetrafluorobenzene (1) top

Crystal data top

C₁₄H₄F₄N₂O₄·C₁₅H₁₄N₂	F(000) = 1152
M_r = 562.47	D_x = 1.467 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 23.8353 (8) Å	Cell parameters from 4996 reflections
b = 6.8067 (2) Å	θ = 2.6–26.0°
c = 16.6103 (5) Å	µ = 0.12 mm⁻¹
β = 109.104 (3)°	T = 100 K
V = 2546.43 (14) Å³	Cut block, red
Z = 4	0.40 × 0.20 × 0.02 mm

Data collection top

Rigaku XtaLAB Synergy Dualflex HyPix diffractometer	6490 independent reflections
Radiation source: micro-focus sealed X-ray tube, PhotonJet (Mo) X-ray Source	4632 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.045
Detector resolution: 10.0000 pixels mm^-1	θ_max = 30.1°, θ_min = 2.5°
ω scans	h = −32→30
Absorption correction: gaussian (CrysAlis PRO; Rigaku OD, 2022)	k = −8→9
T_min = 0.734, T_max = 1.000	l = −21→22
50721 measured reflections

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.053	H-atom parameters constrained
wR(F²) = 0.147	w = 1/[σ²(F_o²) + (0.0582P)² + 1.7045P] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max < 0.001
6490 reflections	Δρ_max = 0.43 e Å⁻³
372 parameters	Δρ_min = −0.33 e Å⁻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
F1	0.28456 (5)	0.8952 (2)	0.56244 (9)	0.0523 (3)
O1	0.16990 (7)	0.8728 (3)	0.02012 (10)	0.0569 (4)
N1	0.56110 (8)	0.8842 (3)	0.77962 (11)	0.0479 (5)
C1	0.66347 (9)	0.9153 (3)	0.86474 (11)	0.0377 (4)
H1	0.703142	0.939993	0.866805	0.045*
F2	0.38279 (6)	0.8967 (2)	0.69917 (7)	0.0542 (3)
O2	0.07428 (7)	0.8889 (3)	−0.01819 (9)	0.0622 (5)
N2	0.87535 (7)	0.8433 (3)	1.43508 (9)	0.0374 (4)
C2	0.61747 (10)	0.9154 (3)	0.78774 (12)	0.0456 (5)
H2	0.627064	0.939357	0.737419	0.055*
F3	0.49846 (5)	0.7940 (2)	0.52233 (9)	0.0590 (4)
O3	−0.02267 (7)	0.8563 (4)	0.19380 (11)	0.0835 (8)
N3	0.12366 (8)	0.8794 (3)	0.03622 (10)	0.0446 (4)
C3	0.54875 (9)	0.8501 (3)	0.85129 (14)	0.0438 (5)
H3	0.508550	0.827434	0.847032	0.053*
F4	0.40060 (6)	0.8014 (2)	0.38489 (7)	0.0545 (3)
O4	0.02756 (8)	0.8887 (4)	0.32412 (11)	0.0803 (7)
N4	0.02398 (7)	0.8720 (3)	0.25021 (10)	0.0388 (4)
C4	0.59125 (8)	0.8459 (3)	0.93119 (12)	0.0364 (4)
H4	0.580164	0.821170	0.980224	0.044*
C5	0.65027 (8)	0.8782 (3)	0.93908 (11)	0.0302 (4)
C6	0.69531 (8)	0.8735 (3)	1.02069 (11)	0.0316 (4)
C7	0.73052 (8)	0.8709 (3)	1.09104 (11)	0.0311 (4)
C8	0.76868 (7)	0.8680 (2)	1.17791 (10)	0.0280 (3)
C9	0.74375 (8)	0.8652 (3)	1.24264 (11)	0.0319 (4)
H9	0.701761	0.866569	1.228328	0.038*
C10	0.77861 (8)	0.8605 (3)	1.32728 (11)	0.0325 (4)
H10	0.760409	0.859549	1.370321	0.039*
C11	0.84062 (7)	0.8572 (3)	1.35024 (10)	0.0270 (3)
C12	0.86623 (7)	0.8646 (2)	1.28534 (10)	0.0272 (3)
H12	0.908213	0.865951	1.299570	0.033*
C13	0.83073 (7)	0.8699 (3)	1.20077 (10)	0.0280 (3)
H13	0.848688	0.875039	1.157496	0.034*
C14	0.84830 (9)	0.8579 (3)	1.50130 (11)	0.0415 (5)
H14A	0.828751	0.985830	1.497565	0.062*
H14B	0.878988	0.844721	1.557196	0.062*
H14C	0.818879	0.753012	1.493936	0.062*
C15	0.93842 (8)	0.8670 (3)	1.45946 (12)	0.0404 (4)
H15A	0.954801	0.767690	1.430668	0.061*
H15B	0.956009	0.851147	1.521291	0.061*
H15C	0.947599	0.998385	1.443099	0.061*
C16	0.33747 (8)	0.8741 (3)	0.55145 (12)	0.0342 (4)
C17	0.38804 (9)	0.8729 (3)	0.62161 (11)	0.0351 (4)
C18	0.44282 (8)	0.8476 (3)	0.61351 (12)	0.0356 (4)
H18	0.477752	0.846873	0.661968	0.043*
C19	0.44556 (8)	0.8234 (3)	0.53314 (13)	0.0372 (4)
C20	0.39544 (8)	0.8263 (3)	0.46219 (11)	0.0354 (4)
C21	0.33970 (7)	0.8529 (3)	0.46970 (11)	0.0313 (4)
C22	0.28676 (8)	0.8556 (3)	0.39792 (12)	0.0363 (4)
C23	0.24107 (8)	0.8576 (3)	0.34014 (12)	0.0368 (4)
C24	0.18501 (8)	0.8612 (3)	0.27323 (11)	0.0313 (4)
C25	0.18202 (8)	0.8654 (3)	0.18809 (12)	0.0328 (4)
H25	0.217176	0.862299	0.173019	0.039*
C26	0.12667 (8)	0.8741 (3)	0.12585 (11)	0.0325 (4)
C27	0.07436 (8)	0.8779 (3)	0.14376 (10)	0.0307 (4)
H27	0.036964	0.885664	0.099941	0.037*
C28	0.07892 (7)	0.8700 (3)	0.22857 (11)	0.0292 (3)
C29	0.13262 (8)	0.8613 (3)	0.29382 (11)	0.0316 (4)
H29	0.133930	0.855430	0.351555	0.038*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
F1	0.0337 (6)	0.0577 (8)	0.0685 (8)	0.0075 (6)	0.0209 (6)	−0.0085 (6)
O1	0.0573 (10)	0.0682 (11)	0.0561 (9)	0.0014 (8)	0.0333 (8)	0.0001 (8)
N1	0.0459 (10)	0.0446 (10)	0.0386 (9)	0.0085 (8)	−0.0062 (7)	−0.0064 (8)
C1	0.0350 (9)	0.0434 (11)	0.0330 (9)	0.0064 (8)	0.0088 (7)	0.0028 (8)
F2	0.0701 (9)	0.0547 (8)	0.0378 (6)	0.0059 (7)	0.0175 (6)	−0.0106 (6)
O2	0.0533 (9)	0.0982 (15)	0.0290 (7)	−0.0181 (9)	0.0053 (7)	−0.0041 (8)
N2	0.0308 (8)	0.0565 (11)	0.0235 (7)	0.0034 (7)	0.0071 (6)	0.0009 (7)
C2	0.0516 (12)	0.0526 (13)	0.0274 (9)	0.0136 (10)	0.0061 (8)	0.0017 (8)
F3	0.0284 (6)	0.0817 (10)	0.0686 (9)	0.0057 (6)	0.0183 (6)	0.0109 (7)
O3	0.0274 (8)	0.173 (2)	0.0483 (9)	−0.0018 (11)	0.0095 (7)	−0.0078 (12)
N3	0.0466 (10)	0.0540 (11)	0.0359 (9)	−0.0075 (8)	0.0171 (7)	−0.0036 (8)
C3	0.0333 (10)	0.0366 (11)	0.0523 (12)	−0.0003 (8)	0.0016 (8)	−0.0037 (9)
F4	0.0568 (8)	0.0738 (9)	0.0346 (6)	0.0064 (7)	0.0175 (5)	0.0087 (6)
O4	0.0555 (10)	0.148 (2)	0.0449 (9)	−0.0032 (12)	0.0271 (8)	0.0004 (11)
N4	0.0359 (8)	0.0431 (10)	0.0388 (8)	0.0022 (7)	0.0142 (7)	0.0031 (7)
C4	0.0351 (9)	0.0316 (10)	0.0401 (10)	0.0002 (8)	0.0092 (8)	0.0019 (8)
C5	0.0339 (9)	0.0225 (8)	0.0291 (8)	0.0013 (7)	0.0035 (7)	0.0003 (6)
C6	0.0336 (9)	0.0257 (9)	0.0325 (9)	0.0008 (7)	0.0069 (7)	0.0009 (7)
C7	0.0341 (9)	0.0239 (8)	0.0313 (8)	0.0008 (7)	0.0054 (7)	−0.0008 (7)
C8	0.0314 (8)	0.0219 (8)	0.0263 (8)	0.0010 (7)	0.0034 (6)	−0.0001 (6)
C9	0.0265 (8)	0.0333 (9)	0.0340 (9)	0.0006 (7)	0.0073 (7)	−0.0007 (7)
C10	0.0304 (8)	0.0399 (10)	0.0293 (8)	0.0011 (8)	0.0125 (7)	−0.0002 (7)
C11	0.0284 (8)	0.0269 (8)	0.0243 (7)	0.0018 (7)	0.0070 (6)	−0.0010 (6)
C12	0.0262 (8)	0.0274 (8)	0.0274 (8)	0.0010 (7)	0.0079 (6)	0.0005 (6)
C13	0.0315 (8)	0.0271 (8)	0.0258 (8)	0.0002 (7)	0.0102 (6)	−0.0006 (6)
C14	0.0427 (10)	0.0547 (13)	0.0267 (9)	0.0001 (9)	0.0109 (8)	0.0008 (8)
C15	0.0310 (9)	0.0517 (12)	0.0334 (9)	0.0010 (9)	0.0034 (7)	0.0007 (8)
C16	0.0268 (8)	0.0279 (9)	0.0471 (10)	0.0020 (7)	0.0110 (7)	−0.0039 (8)
C17	0.0422 (10)	0.0286 (9)	0.0315 (9)	−0.0002 (8)	0.0077 (7)	−0.0037 (7)
C18	0.0307 (9)	0.0296 (9)	0.0367 (9)	−0.0012 (7)	−0.0023 (7)	0.0005 (7)
C19	0.0231 (8)	0.0405 (11)	0.0453 (10)	0.0005 (7)	0.0078 (7)	0.0066 (8)
C20	0.0351 (9)	0.0379 (10)	0.0313 (9)	0.0007 (8)	0.0080 (7)	0.0054 (7)
C21	0.0264 (8)	0.0230 (8)	0.0368 (9)	−0.0009 (7)	−0.0002 (7)	0.0004 (7)
C22	0.0331 (9)	0.0234 (9)	0.0430 (10)	−0.0008 (7)	−0.0004 (8)	0.0004 (7)
C23	0.0337 (9)	0.0230 (9)	0.0439 (10)	−0.0005 (7)	−0.0007 (8)	0.0005 (7)
C24	0.0301 (8)	0.0204 (8)	0.0352 (9)	−0.0014 (7)	−0.0006 (7)	−0.0010 (7)
C25	0.0271 (8)	0.0279 (9)	0.0414 (10)	−0.0033 (7)	0.0084 (7)	−0.0009 (7)
C26	0.0347 (9)	0.0336 (10)	0.0274 (8)	−0.0049 (8)	0.0076 (7)	−0.0015 (7)
C27	0.0270 (8)	0.0334 (9)	0.0274 (8)	−0.0037 (7)	0.0030 (6)	0.0003 (7)
C28	0.0282 (8)	0.0269 (8)	0.0309 (8)	−0.0008 (7)	0.0075 (6)	−0.0009 (7)
C29	0.0368 (9)	0.0259 (9)	0.0270 (8)	0.0008 (7)	0.0034 (7)	−0.0010 (7)

Geometric parameters (Å, º) top

F1—C16	1.340 (2)	C10—H10	0.9500
O1—N3	1.217 (2)	C11—C12	1.403 (2)
N1—C2	1.323 (3)	C12—C13	1.383 (2)
N1—C3	1.337 (3)	C12—H12	0.9500
C1—C2	1.386 (3)	C13—H13	0.9500
C1—C5	1.393 (3)	C14—H14A	0.9800
C1—H1	0.9500	C14—H14B	0.9800
F2—C17	1.344 (2)	C14—H14C	0.9800
O2—N3	1.229 (2)	C15—H15A	0.9800
N2—C11	1.384 (2)	C15—H15B	0.9800
N2—C15	1.432 (2)	C15—H15C	0.9800
N2—C14	1.449 (2)	C16—C17	1.375 (3)
C2—H2	0.9500	C16—C21	1.384 (3)
F3—C19	1.345 (2)	C17—C18	1.367 (3)
O3—N4	1.202 (2)	C18—C19	1.368 (3)
N3—C26	1.467 (2)	C18—H18	0.9500
C3—C4	1.381 (3)	C19—C20	1.377 (3)
C3—H3	0.9500	C20—C21	1.386 (3)
F4—C20	1.340 (2)	C21—C22	1.425 (2)
O4—N4	1.208 (2)	C22—C23	1.193 (3)
N4—C28	1.467 (2)	C23—C24	1.431 (2)
C4—C5	1.387 (3)	C24—C25	1.393 (3)
C4—H4	0.9500	C24—C29	1.399 (3)
C5—C6	1.428 (2)	C25—C26	1.386 (2)
C6—C7	1.195 (2)	C25—H25	0.9500
C7—C8	1.432 (2)	C26—C27	1.374 (2)
C8—C9	1.388 (2)	C27—C28	1.378 (2)
C8—C13	1.402 (2)	C27—H27	0.9500
C9—C10	1.380 (2)	C28—C29	1.381 (2)
C9—H9	0.9500	C29—H29	0.9500
C10—C11	1.400 (2)

C2—N1—C3	116.71 (17)	N2—C14—H14C	109.5
C2—C1—C5	118.57 (18)	H14A—C14—H14C	109.5
C2—C1—H1	120.7	H14B—C14—H14C	109.5
C5—C1—H1	120.7	N2—C15—H15A	109.5
C11—N2—C15	120.18 (15)	N2—C15—H15B	109.5
C11—N2—C14	120.10 (15)	H15A—C15—H15B	109.5
C15—N2—C14	117.66 (15)	N2—C15—H15C	109.5
N1—C2—C1	124.36 (19)	H15A—C15—H15C	109.5
N1—C2—H2	117.8	H15B—C15—H15C	109.5
C1—C2—H2	117.8	F1—C16—C17	119.21 (17)
O1—N3—O2	123.95 (17)	F1—C16—C21	119.01 (16)
O1—N3—C26	118.36 (17)	C17—C16—C21	121.77 (17)
O2—N3—C26	117.68 (16)	F2—C17—C18	120.07 (17)
N1—C3—C4	123.58 (19)	F2—C17—C16	118.74 (17)
N1—C3—H3	118.2	C18—C17—C16	121.18 (17)
C4—C3—H3	118.2	C17—C18—C19	117.63 (16)
O3—N4—O4	122.72 (18)	C17—C18—H18	121.2
O3—N4—C28	118.72 (16)	C19—C18—H18	121.2
O4—N4—C28	118.56 (17)	F3—C19—C18	119.63 (16)
C3—C4—C5	119.32 (19)	F3—C19—C20	118.46 (18)
C3—C4—H4	120.3	C18—C19—C20	121.91 (17)
C5—C4—H4	120.3	F4—C20—C19	119.49 (17)
C4—C5—C1	117.46 (16)	F4—C20—C21	119.60 (16)
C4—C5—C6	120.69 (17)	C19—C20—C21	120.90 (17)
C1—C5—C6	121.85 (17)	C16—C21—C20	116.60 (15)
C7—C6—C5	176.3 (2)	C16—C21—C22	120.80 (17)
C6—C7—C8	175.3 (2)	C20—C21—C22	122.60 (17)
C9—C8—C13	118.13 (15)	C23—C22—C21	177.2 (2)
C9—C8—C7	119.27 (16)	C22—C23—C24	177.7 (2)
C13—C8—C7	122.60 (16)	C25—C24—C29	119.69 (15)
C10—C9—C8	121.45 (16)	C25—C24—C23	120.88 (17)
C10—C9—H9	119.3	C29—C24—C23	119.43 (17)
C8—C9—H9	119.3	C26—C25—C24	118.57 (17)
C9—C10—C11	120.53 (16)	C26—C25—H25	120.7
C9—C10—H10	119.7	C24—C25—H25	120.7
C11—C10—H10	119.7	C27—C26—C25	123.32 (16)
N2—C11—C10	120.31 (15)	C27—C26—N3	118.22 (16)
N2—C11—C12	121.26 (15)	C25—C26—N3	118.46 (17)
C10—C11—C12	118.42 (15)	C26—C27—C28	116.56 (16)
C13—C12—C11	120.40 (15)	C26—C27—H27	121.7
C13—C12—H12	119.8	C28—C27—H27	121.7
C11—C12—H12	119.8	C27—C28—C29	123.14 (17)
C12—C13—C8	121.03 (15)	C27—C28—N4	118.16 (15)
C12—C13—H13	119.5	C29—C28—N4	118.70 (15)
C8—C13—H13	119.5	C28—C29—C24	118.69 (16)
N2—C14—H14A	109.5	C28—C29—H29	120.7
N2—C14—H14B	109.5	C24—C29—H29	120.7
H14A—C14—H14B	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···F4ⁱ	0.95	2.61	3.364 (2)	137
C4—H4···F3ⁱⁱ	0.95	2.41	3.207 (2)	142
C10—H10···F1ⁱⁱⁱ	0.95	2.44	3.193 (2)	136
C14—H14A···O1^iv	0.98	2.65	3.535 (3)	150
C14—H14C···O1^v	0.98	2.62	3.334 (3)	130
C18—H18···N1	0.95	2.30	3.245 (2)	173

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

3-{2-[4-(Dimethylamino)phenyl]ethynyl}pyridine; 1-[2-(3,5-dinitrophenyl)ethynyl]-2,3,5,6-tetrafluorobenzene (2) top

Crystal data top

C₁₄H₄F₄N₂O₄·C₁₅H₁₄N₂	D_x = 1.488 Mg m⁻³
M_r = 562.47	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbcn	Cell parameters from 6048 reflections
a = 13.131 (4) Å	θ = 2.2–24.9°
b = 14.423 (4) Å	µ = 0.12 mm⁻¹
c = 26.523 (7) Å	T = 100 K
V = 5023 (2) Å³	Cut block, red
Z = 8	0.30 × 0.20 × 0.15 mm
F(000) = 2304

Data collection top

Bruker APEXI CCD diffractometer	5554 independent reflections
Radiation source: fine-focus sealed tube	3976 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.077
Detector resolution: 8.3660 pixels mm^-1	θ_max = 27.1°, θ_min = 2.1°
phi and ω scans	h = −16→16
Absorption correction: multi-scan (SADABS; Bruker, 2014)	k = −18→18
T_min = 0.598, T_max = 0.746	l = −33→33
60342 measured reflections

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.056	H-atom parameters constrained
wR(F²) = 0.154	w = 1/[σ²(F_o²) + (0.0771P)² + 2.8101P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max < 0.001
5554 reflections	Δρ_max = 0.34 e Å⁻³
372 parameters	Δρ_min = −0.27 e Å⁻³
0 restraints

Special details top

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

	x	y	z	U_iso*/U_eq
F1	0.38474 (11)	0.41632 (9)	0.43737 (5)	0.0380 (4)
O1	0.31801 (13)	0.97332 (11)	0.54808 (6)	0.0346 (4)
N1	0.39262 (14)	0.40849 (12)	0.60892 (7)	0.0277 (4)
C1	0.40199 (16)	0.35428 (14)	0.56857 (8)	0.0249 (4)
H1	0.404321	0.383090	0.536381	0.030*
F2	0.40359 (11)	0.36309 (8)	0.34049 (5)	0.0370 (3)
O2	0.34149 (13)	0.98327 (10)	0.62884 (6)	0.0332 (4)
N2	0.37851 (17)	−0.01111 (13)	0.29567 (7)	0.0367 (5)
C2	0.39061 (16)	0.36700 (15)	0.65390 (9)	0.0282 (5)
H2	0.384300	0.404670	0.683118	0.034*
F3	0.35870 (10)	0.67142 (9)	0.28711 (5)	0.0351 (3)
O3	0.36752 (18)	0.70936 (13)	0.72859 (7)	0.0568 (6)
N3	0.33430 (14)	0.93901 (12)	0.58941 (7)	0.0259 (4)
C3	0.39728 (17)	0.27162 (16)	0.66019 (9)	0.0296 (5)
H3	0.396045	0.245202	0.692996	0.036*
F4	0.33985 (10)	0.72583 (8)	0.38375 (5)	0.0312 (3)
O4	0.37845 (15)	0.57505 (11)	0.69379 (6)	0.0419 (5)
N4	0.37037 (15)	0.65946 (13)	0.69135 (7)	0.0300 (4)
C4	0.40574 (16)	0.21554 (15)	0.61807 (9)	0.0279 (5)
H4	0.409481	0.150057	0.621452	0.034*
C5	0.40866 (16)	0.25686 (14)	0.57060 (8)	0.0245 (4)
C6	0.41423 (16)	0.20425 (14)	0.52504 (9)	0.0266 (5)
C7	0.41224 (16)	0.16104 (14)	0.48619 (9)	0.0266 (5)
C8	0.40680 (15)	0.11544 (14)	0.43836 (8)	0.0247 (4)
C9	0.40617 (16)	0.01862 (14)	0.43342 (8)	0.0256 (5)
H9	0.412462	−0.019045	0.462633	0.031*
C10	0.39657 (16)	−0.02264 (14)	0.38683 (8)	0.0265 (5)
H10	0.395229	−0.088382	0.384679	0.032*
C11	0.38867 (16)	0.03017 (15)	0.34216 (8)	0.0253 (5)
C12	0.39060 (16)	0.12726 (15)	0.34730 (9)	0.0275 (5)
H12	0.385972	0.165304	0.318150	0.033*
C13	0.39914 (16)	0.16776 (14)	0.39422 (8)	0.0269 (5)
H13	0.399829	0.233486	0.396587	0.032*
C14	0.3687 (2)	−0.11100 (16)	0.29177 (9)	0.0383 (6)
H14A	0.308064	−0.131321	0.310226	0.057*
H14B	0.429238	−0.140616	0.306219	0.057*
H14C	0.362319	−0.128576	0.256217	0.057*
C15	0.3625 (2)	0.04253 (18)	0.25039 (9)	0.0384 (6)
H15A	0.416917	0.088593	0.246992	0.058*
H15B	0.296569	0.074181	0.252385	0.058*
H15C	0.363092	0.001212	0.221055	0.058*
C16	0.37692 (17)	0.48011 (15)	0.40039 (8)	0.0257 (5)
C17	0.38694 (17)	0.45312 (14)	0.35105 (8)	0.0259 (5)
C18	0.38115 (16)	0.51602 (15)	0.31196 (8)	0.0260 (5)
H18	0.388326	0.496944	0.277863	0.031*
C19	0.36461 (16)	0.60723 (14)	0.32426 (8)	0.0247 (5)
C20	0.35458 (15)	0.63559 (14)	0.37361 (8)	0.0243 (4)
C21	0.36105 (15)	0.57272 (15)	0.41342 (8)	0.0230 (4)
C22	0.35608 (16)	0.60451 (15)	0.46421 (8)	0.0246 (5)
C23	0.35522 (15)	0.63854 (14)	0.50532 (8)	0.0241 (4)
C24	0.35445 (15)	0.68955 (14)	0.55165 (8)	0.0230 (4)
C25	0.34476 (15)	0.78594 (14)	0.54866 (8)	0.0222 (4)
H25	0.337937	0.815635	0.516863	0.027*
C26	0.34526 (15)	0.83733 (14)	0.59255 (8)	0.0219 (4)
C27	0.35444 (15)	0.79785 (14)	0.63971 (8)	0.0227 (4)
H27	0.354911	0.834366	0.669514	0.027*
C28	0.36292 (16)	0.70242 (14)	0.64131 (8)	0.0230 (4)
C29	0.36315 (15)	0.64641 (15)	0.59890 (8)	0.0237 (4)
H29	0.368998	0.580953	0.601686	0.028*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
F1	0.0628 (9)	0.0243 (7)	0.0268 (7)	0.0032 (6)	−0.0021 (6)	0.0041 (5)
O1	0.0487 (10)	0.0253 (8)	0.0298 (9)	0.0004 (7)	0.0012 (7)	0.0056 (7)
N1	0.0263 (10)	0.0220 (9)	0.0347 (11)	−0.0017 (7)	−0.0006 (8)	−0.0041 (8)
C1	0.0241 (10)	0.0233 (10)	0.0272 (11)	−0.0025 (8)	0.0012 (9)	0.0003 (9)
F2	0.0609 (9)	0.0185 (6)	0.0316 (7)	0.0055 (6)	−0.0031 (6)	−0.0035 (5)
O2	0.0483 (10)	0.0183 (7)	0.0331 (9)	−0.0033 (7)	−0.0010 (7)	−0.0034 (7)
N2	0.0605 (14)	0.0261 (10)	0.0234 (10)	0.0054 (9)	0.0015 (9)	−0.0002 (8)
C2	0.0262 (11)	0.0269 (11)	0.0315 (12)	−0.0023 (9)	−0.0021 (9)	−0.0045 (9)
F3	0.0536 (9)	0.0235 (7)	0.0284 (7)	0.0001 (6)	−0.0021 (6)	0.0048 (5)
O3	0.1175 (19)	0.0299 (9)	0.0229 (9)	0.0151 (10)	−0.0008 (10)	−0.0027 (7)
N3	0.0301 (10)	0.0204 (9)	0.0272 (10)	−0.0038 (7)	0.0008 (8)	0.0010 (8)
C3	0.0274 (11)	0.0332 (12)	0.0283 (12)	−0.0010 (9)	−0.0011 (9)	0.0027 (9)
F4	0.0406 (8)	0.0183 (6)	0.0347 (7)	0.0013 (5)	0.0000 (6)	−0.0034 (5)
O4	0.0763 (13)	0.0191 (8)	0.0304 (9)	0.0048 (8)	−0.0007 (9)	0.0040 (7)
N4	0.0433 (12)	0.0224 (9)	0.0242 (10)	0.0052 (8)	0.0021 (8)	0.0009 (8)
C4	0.0252 (11)	0.0214 (10)	0.0372 (13)	0.0007 (8)	−0.0004 (9)	0.0000 (9)
C5	0.0195 (10)	0.0237 (10)	0.0303 (12)	−0.0010 (8)	−0.0005 (9)	−0.0043 (9)
C6	0.0234 (11)	0.0213 (10)	0.0353 (13)	−0.0011 (8)	0.0000 (9)	−0.0012 (9)
C7	0.0219 (11)	0.0215 (10)	0.0363 (13)	−0.0017 (8)	0.0005 (9)	−0.0002 (9)
C8	0.0213 (10)	0.0221 (10)	0.0307 (12)	0.0003 (8)	0.0021 (9)	−0.0025 (9)
C9	0.0287 (11)	0.0227 (10)	0.0254 (11)	0.0014 (9)	0.0029 (9)	0.0030 (9)
C10	0.0327 (12)	0.0179 (10)	0.0289 (12)	0.0032 (9)	0.0024 (9)	0.0020 (9)
C11	0.0257 (11)	0.0257 (11)	0.0245 (11)	0.0025 (8)	0.0045 (9)	−0.0004 (9)
C12	0.0284 (11)	0.0225 (10)	0.0314 (12)	−0.0002 (9)	−0.0005 (9)	0.0067 (9)
C13	0.0259 (11)	0.0174 (10)	0.0373 (13)	−0.0013 (8)	−0.0003 (9)	0.0007 (9)
C14	0.0584 (17)	0.0290 (12)	0.0274 (12)	0.0103 (11)	−0.0044 (11)	−0.0066 (10)
C15	0.0481 (15)	0.0419 (14)	0.0253 (12)	0.0069 (11)	0.0016 (11)	0.0038 (11)
C16	0.0314 (11)	0.0224 (10)	0.0233 (11)	−0.0005 (9)	−0.0023 (9)	0.0030 (9)
C17	0.0311 (12)	0.0178 (10)	0.0288 (12)	0.0020 (8)	−0.0024 (9)	−0.0025 (9)
C18	0.0320 (12)	0.0252 (11)	0.0209 (10)	−0.0020 (9)	−0.0017 (9)	−0.0033 (9)
C19	0.0272 (11)	0.0218 (10)	0.0251 (11)	−0.0009 (8)	−0.0032 (9)	0.0032 (9)
C20	0.0239 (11)	0.0193 (10)	0.0299 (11)	−0.0007 (8)	−0.0008 (9)	−0.0032 (9)
C21	0.0209 (10)	0.0254 (11)	0.0226 (11)	−0.0006 (8)	−0.0021 (8)	−0.0023 (8)
C22	0.0235 (11)	0.0246 (10)	0.0258 (12)	−0.0007 (8)	0.0003 (8)	−0.0001 (9)
C23	0.0224 (10)	0.0237 (10)	0.0263 (11)	−0.0010 (8)	0.0016 (8)	0.0016 (9)
C24	0.0217 (10)	0.0247 (10)	0.0227 (11)	−0.0005 (8)	0.0017 (8)	−0.0024 (8)
C25	0.0200 (10)	0.0254 (10)	0.0213 (10)	−0.0017 (8)	0.0006 (8)	0.0019 (8)
C26	0.0204 (10)	0.0188 (10)	0.0264 (11)	−0.0025 (8)	0.0020 (8)	0.0005 (8)
C27	0.0223 (10)	0.0229 (10)	0.0229 (11)	−0.0008 (8)	0.0014 (8)	−0.0027 (8)
C28	0.0264 (10)	0.0216 (10)	0.0212 (11)	0.0007 (8)	0.0020 (8)	0.0009 (8)
C29	0.0246 (10)	0.0207 (10)	0.0258 (11)	0.0013 (8)	0.0014 (8)	−0.0024 (8)

Geometric parameters (Å, º) top

F1—C16	1.349 (2)	C10—H10	0.9500
O1—N3	1.222 (2)	C11—C12	1.407 (3)
N1—C1	1.331 (3)	C12—C13	1.379 (3)
N1—C2	1.335 (3)	C12—H12	0.9500
C1—C5	1.409 (3)	C13—H13	0.9500
C1—H1	0.9500	C14—H14A	0.9800
F2—C17	1.346 (2)	C14—H14B	0.9800
O2—N3	1.229 (2)	C14—H14C	0.9800
N2—C11	1.376 (3)	C15—H15A	0.9800
N2—C15	1.444 (3)	C15—H15B	0.9800
N2—C14	1.450 (3)	C15—H15C	0.9800
C2—C3	1.388 (3)	C16—C17	1.372 (3)
C2—H2	0.9500	C16—C21	1.395 (3)
F3—C19	1.354 (2)	C17—C18	1.380 (3)
O3—N4	1.223 (2)	C18—C19	1.373 (3)
N3—C26	1.476 (3)	C18—H18	0.9500
C3—C4	1.384 (3)	C19—C20	1.378 (3)
C3—H3	0.9500	C20—C21	1.394 (3)
F4—C20	1.343 (2)	C21—C22	1.424 (3)
O4—N4	1.224 (2)	C22—C23	1.196 (3)
N4—C28	1.468 (3)	C23—C24	1.432 (3)
C4—C5	1.393 (3)	C24—C25	1.398 (3)
C4—H4	0.9500	C24—C29	1.404 (3)
C5—C6	1.429 (3)	C25—C26	1.380 (3)
C6—C7	1.204 (3)	C25—H25	0.9500
C7—C8	1.431 (3)	C26—C27	1.380 (3)
C8—C13	1.396 (3)	C27—C28	1.381 (3)
C8—C9	1.403 (3)	C27—H27	0.9500
C9—C10	1.377 (3)	C28—C29	1.385 (3)
C9—H9	0.9500	C29—H29	0.9500
C10—C11	1.412 (3)

C1—N1—C2	117.19 (19)	N2—C14—H14C	109.5
N1—C1—C5	124.1 (2)	H14A—C14—H14C	109.5
N1—C1—H1	117.9	H14B—C14—H14C	109.5
C5—C1—H1	117.9	N2—C15—H15A	109.5
C11—N2—C15	121.85 (19)	N2—C15—H15B	109.5
C11—N2—C14	120.17 (19)	H15A—C15—H15B	109.5
C15—N2—C14	117.4 (2)	N2—C15—H15C	109.5
N1—C2—C3	123.4 (2)	H15A—C15—H15C	109.5
N1—C2—H2	118.3	H15B—C15—H15C	109.5
C3—C2—H2	118.3	F1—C16—C17	119.53 (19)
O1—N3—O2	124.52 (18)	F1—C16—C21	118.96 (19)
O1—N3—C26	118.06 (17)	C17—C16—C21	121.49 (19)
O2—N3—C26	117.42 (17)	F2—C17—C16	119.19 (19)
C4—C3—C2	119.2 (2)	F2—C17—C18	119.14 (19)
C4—C3—H3	120.4	C16—C17—C18	121.7 (2)
C2—C3—H3	120.4	C19—C18—C17	117.4 (2)
O3—N4—O4	123.07 (19)	C19—C18—H18	121.3
O3—N4—C28	118.66 (18)	C17—C18—H18	121.3
O4—N4—C28	118.26 (18)	F3—C19—C18	119.44 (19)
C3—C4—C5	118.8 (2)	F3—C19—C20	118.86 (18)
C3—C4—H4	120.6	C18—C19—C20	121.7 (2)
C5—C4—H4	120.6	F4—C20—C19	119.46 (19)
C4—C5—C1	117.34 (19)	F4—C20—C21	119.16 (19)
C4—C5—C6	122.59 (19)	C19—C20—C21	121.37 (19)
C1—C5—C6	120.0 (2)	C20—C21—C16	116.36 (19)
C7—C6—C5	175.7 (2)	C20—C21—C22	120.27 (19)
C6—C7—C8	175.9 (2)	C16—C21—C22	123.3 (2)
C13—C8—C9	117.3 (2)	C23—C22—C21	174.2 (2)
C13—C8—C7	119.91 (19)	C22—C23—C24	173.3 (2)
C9—C8—C7	122.7 (2)	C25—C24—C29	119.92 (19)
C10—C9—C8	121.0 (2)	C25—C24—C23	117.56 (19)
C10—C9—H9	119.5	C29—C24—C23	122.52 (19)
C8—C9—H9	119.5	C26—C25—C24	119.05 (19)
C9—C10—C11	121.75 (19)	C26—C25—H25	120.5
C9—C10—H10	119.1	C24—C25—H25	120.5
C11—C10—H10	119.1	C27—C26—C25	122.92 (19)
N2—C11—C12	121.3 (2)	C27—C26—N3	118.03 (18)
N2—C11—C10	121.70 (19)	C25—C26—N3	119.05 (19)
C12—C11—C10	117.0 (2)	C26—C27—C28	116.51 (19)
C13—C12—C11	120.7 (2)	C26—C27—H27	121.7
C13—C12—H12	119.7	C28—C27—H27	121.7
C11—C12—H12	119.7	C27—C28—C29	123.8 (2)
C12—C13—C8	122.23 (19)	C27—C28—N4	116.99 (18)
C12—C13—H13	118.9	C29—C28—N4	119.20 (18)
C8—C13—H13	118.9	C28—C29—C24	117.79 (19)
N2—C14—H14A	109.5	C28—C29—H29	121.1
N2—C14—H14B	109.5	C24—C29—H29	121.1
H14A—C14—H14B	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C29—H29···N1	0.95	2.51	3.463 (3)	178
C2—H2···O4	0.95	2.47	3.186 (3)	132
C15—H15C···O2ⁱ	0.98	2.47	3.257 (3)	137
C18—H18···O4ⁱ	0.95	2.46	3.398 (3)	168

Symmetry code: (i) x, −y+1, z−1/2.

Intermolecular interaction energies between 4DMAPP and molecules closer than 3.8 Å in cocrystal (1) (kJ mol^-1); colors and labels are from Fig. 7. top

Scale factors for total energy of interaction: k_ele = 1.057, k_pol = 0.740, k_dis = 0.871 and k_rep = 0.618.

Color, label	E_ele	E_pol	E_dis	E_rep	E_tot
Red, R	-20.2	-4.3	-83.0	55.7	-62.5
Orange, O	-20.8	-4.3	-86.7	65.3	-60.4
Chartreuse, C	-18.4	-5.7	-8.5	0.0	-31.0
Blue, B	-5.6	-1.1	-22.9	18.7	-15.1
Pink, P	-4.8	-1.2	-21.2	16.1	-14.6
Turquoise, T	-3.9	-0.8	-9.9	0.0	-13.4
Green, G	-5.8	-1.5	-9.3	7.6	-10.7

Selected hydrogen-bond and close-contact parameters (Å, °) for cocrystal (2) top

D—H···A	Label^a	D—H	H···A	D···A	D—H···A
C29—H29···N1	A	0.95	2.51	3.463 (3)	177.5
C2—H2···O4	B	0.95	2.47	3.186 (3)	131.6
C13—H13···F2	C	0.95	2.39	3.158 (3)	137.7
C18—H18···O4ⁱ	D	0.95	2.46	3.398 (3)	168.1
C4—H4···O2ⁱⁱ	E	0.95	2.46	3.398 (3)	168.1
C9—H9···O1ⁱⁱ	F	0.95	2.59	3.319 (3)	134.2
C15—H15C···O2ⁱⁱⁱ	G	0.98	2.47	3.257 (3)	136.8
C27—H27···C15ⁱⁱⁱ	H	0.95	2.79	3.398 (3)	173.8

Note: (a) labels in Figs. 8 and 9. Symmetry codes: (i) x, -y+1, z-1/2; (ii) x, y-1, z; (iii) x, -y+1, z-1/2.

Intermolecular energies of interaction of 4DMAPP with molecules within 3.8 Å in cocrystal (2) in kJ mol^-1; colors and labels are from Fig. 10 top

Scale factors for total energy of interaction: k_ele = 1.057, k_pol = 0.740, k_dis = 0.871 and k_rep = 0.618.

Color/label	E_ele	E_pol	E_dis	E_rep	E_tot
Blue, B	-18.9	-5.3	-92.7	71.3	-60.6
Purple, P	-19.3	-4.1	-70.0	49.5	-53.9
Chartreuse, C	-23.4	-4.5	-24.1	32.1	-29.2
Green, G	-6.6	-1.1	-13.6	0.0	-19.6
Red, R	-4.4	-1.8	-23.1	19.4	-14.1

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