Conformational control through co-operative nonconventional C—H...N hydro­gen bonds

We report the design, synthesis, and crystal structure of a conjugated aryl­ene­ethynyl mol­ecule, 2-(2-{4,5-dimeth­oxy-2-[2-(2,3,4-tri­fluoro­phen­yl)ethyn­yl]phen­yl}ethyn­yl)-6-[2-(pyri­din-2-yl)ethyn­yl]pyri­dine, C₃₀H₁₇F₃N₂O₂, that adopts a planar rhombus conformation in the solid state. The mol­ecule crystallizes in the space group P, with Z = 2, and features two intra­molecular sp²-C—H...N hydro­gen bonds that co-operatively hold the aryl­ethynyl mol­ecule in a rhombus conformation. The H atoms are activated towards hydro­gen bonding since they are situated on a tri­fluoro­phenyl ring and the H...N distances are 2.470 (16) and 2.646 (16) Å, with C—H...N angles of 161.7 (2) and 164.7 (2)°, respectively. Mol­ecular electrostatic potential calculations support the formation of C—H...N hydro­gen bonds to the tri­fluoro­phenyl moiety. Hirshfeld surface analysis identifies a self-com­plementary C—H...O dimeric inter­action between adjacent 1,2-di­meth­oxy­ben­zene segments that is shown to be common in structures containing that moiety.

Computing details

Data collection: APEX2 (Bruker, 2014); cell refinement: SAINT (Bruker, 2014); data reduction: SAINT (Bruker, 2014); 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).

2-(2-{4,5-Dimethoxy-2-[2-(2,3,4-trifluorophenyl)ethynyl]phenyl}ethynyl)-6-[2-(pyridin-2-yl)ethynyl]pyridine

Crystal data

C30H17F3N2O2	Z = 2
Mr = 494.45	F(000) = 508
Triclinic, P1	Dx = 1.428 Mg m^−3
a = 8.0037 (4) Å	Mo Kα radiation, λ = 0.71073 Å
b = 12.1365 (6) Å	Cell parameters from 4694 reflections
c = 13.4922 (6) Å	θ = 2.7–27.1°
α = 104.697 (1)°	µ = 0.11 mm^−1
β = 103.023 (1)°	T = 100 K
γ = 106.619 (1)°	Block, colorless
V = 1150.30 (10) Å^3	0.56 × 0.23 × 0.21 mm

Data collection

Bruker APEXI CCD diffractometer	5017 independent reflections
Radiation source: fine-focus sealed tube	3939 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.022
Detector resolution: 8.3660 pixels mm^-1	θmax = 27.2°, θmin = 1.7°
phi and ω scans	h = −10→10
Absorption correction: multi-scan (SADABS; Bruker, 2014)	k = −15→15
Tmin = 0.714, Tmax = 0.746	l = −17→17
14094 measured reflections

Refinement

Refinement on F^2	Primary atom site location: dual
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.050	Hydrogen site location: mixed
wR(F^2) = 0.137	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0588P)^2 + 0.8077P] where P = (Fo^2 + 2Fc^2)/3
5017 reflections	(Δ/σ)max < 0.001
342 parameters	Δρmax = 0.62 e Å^−3
2 restraints	Δρmin = −0.28 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. A single crystal of (1) was mounted on a Kryoloop using viscous hydrocarbon oil. Data were collected using a Bruker Apex1 CCD diffractometer equipped with Mo Kα radiation with λ = 0.71073 Å. Data collection at low temperature was facilitated by use of a Kryoflex system with an accuracy of ±1 K. Initial data processing was carried out using the Apex II software suite (Bruker, 2014). Structures were solved using the dual-space method SHELXT-2018 (Sheldrick, 2015a) and refined against F² using SHELXL-2018 (Sheldrick, 2015a). The program X-Seed was used as a graphical interface (Barbour, 2020).

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

	x	y	z	Uiso*/Ueq
F1	0.93690 (15)	0.08813 (10)	0.37066 (9)	0.0311 (3)
O1	1.31660 (17)	0.88155 (10)	0.44776 (10)	0.0240 (3)
N1	−0.0723 (3)	−0.13168 (17)	0.13171 (14)	0.0378 (4)
C1	−0.1550 (3)	−0.2497 (2)	0.11907 (17)	0.0425 (5)
H1	−0.082583	−0.289952	0.149735	0.051*
F2	0.69008 (17)	−0.13974 (10)	0.31484 (10)	0.0363 (3)
O2	1.49544 (17)	0.74849 (11)	0.49921 (10)	0.0250 (3)
N2	0.2829 (2)	0.32816 (14)	0.18746 (12)	0.0252 (3)
C2	−0.3375 (3)	−0.3149 (2)	0.06455 (19)	0.0468 (6)
H2	−0.390915	−0.397588	0.059538	0.056*
F3	0.33172 (17)	−0.19383 (10)	0.20777 (11)	0.0415 (3)
C3	−0.4429 (3)	−0.2590 (2)	0.01701 (19)	0.0517 (7)
H3	−0.569694	−0.303159	−0.022653	0.062*
C4	−0.3609 (3)	−0.1355 (2)	0.02768 (18)	0.0433 (6)
H4	−0.430378	−0.094661	−0.004531	0.052*
C5	−0.1755 (3)	−0.0755 (2)	0.08671 (15)	0.0318 (4)
C6	−0.0797 (3)	0.0525 (2)	0.10419 (16)	0.0314 (4)
C7	0.0030 (3)	0.1584 (2)	0.12007 (16)	0.0315 (4)
C8	0.0992 (3)	0.28441 (18)	0.13770 (15)	0.0287 (4)
C9	0.0065 (3)	0.3576 (2)	0.10534 (17)	0.0357 (5)
H9	−0.122574	0.323411	0.069185	0.043*
C10	0.1020 (3)	0.4785 (2)	0.12585 (18)	0.0386 (5)
H10	0.039291	0.529035	0.105646	0.046*
C11	0.2900 (3)	0.5265 (2)	0.17605 (16)	0.0316 (4)
H11	0.359909	0.609952	0.190897	0.038*
C12	0.3745 (3)	0.44607 (17)	0.20460 (14)	0.0248 (4)
C13	0.5703 (3)	0.49169 (16)	0.25491 (15)	0.0247 (4)
C14	0.7342 (3)	0.53331 (15)	0.29700 (14)	0.0229 (4)
C15	0.9293 (2)	0.58423 (15)	0.34847 (14)	0.0208 (4)
C16	1.0247 (2)	0.71038 (15)	0.37281 (14)	0.0211 (4)
H16	0.958310	0.760191	0.355364	0.025*
C17	1.2128 (2)	0.76185 (15)	0.42156 (14)	0.0204 (4)
C18	1.3113 (2)	0.68818 (15)	0.44922 (13)	0.0203 (3)
C19	1.2188 (2)	0.56456 (15)	0.42579 (14)	0.0203 (3)
H19	1.285584	0.515388	0.444351	0.024*
C20	1.0280 (2)	0.51129 (15)	0.37507 (13)	0.0200 (3)
C21	0.9300 (2)	0.38337 (15)	0.35011 (14)	0.0212 (4)
C22	0.8351 (2)	0.27841 (15)	0.32648 (14)	0.0213 (4)
C23	0.7068 (2)	0.15664 (15)	0.29617 (14)	0.0211 (4)
C24	0.7605 (2)	0.06497 (16)	0.31951 (14)	0.0224 (4)
C25	0.6342 (3)	−0.05248 (16)	0.29105 (15)	0.0268 (4)
C26	0.4526 (3)	−0.07785 (16)	0.23721 (16)	0.0291 (4)
C27	0.3928 (3)	0.00974 (18)	0.21204 (17)	0.0311 (4)
H27	0.262 (2)	−0.024 (2)	0.1754 (17)	0.037*
C28	0.5200 (3)	0.12693 (17)	0.24219 (15)	0.0258 (4)
H28	0.478 (3)	0.1913 (17)	0.2256 (17)	0.031*
C29	1.2213 (3)	0.95978 (16)	0.42264 (16)	0.0257 (4)
H29A	1.156540	0.929730	0.344644	0.039*
H29B	1.310178	1.043171	0.444220	0.039*
H29C	1.132147	0.959855	0.461897	0.039*
C30	1.6007 (3)	0.68180 (17)	0.53796 (16)	0.0288 (4)
H30A	1.550389	0.647855	0.588165	0.043*
H30B	1.729176	0.736752	0.575521	0.043*
H30C	1.594664	0.615085	0.476743	0.043*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
F1	0.0262 (6)	0.0265 (6)	0.0392 (6)	0.0096 (5)	0.0059 (5)	0.0127 (5)
O1	0.0253 (6)	0.0133 (6)	0.0321 (7)	0.0059 (5)	0.0059 (5)	0.0099 (5)
N1	0.0381 (10)	0.0376 (10)	0.0318 (9)	0.0048 (8)	0.0098 (8)	0.0136 (8)
C1	0.0477 (13)	0.0429 (13)	0.0286 (11)	0.0050 (11)	0.0127 (10)	0.0113 (9)
F2	0.0454 (7)	0.0206 (6)	0.0502 (7)	0.0155 (5)	0.0194 (6)	0.0161 (5)
O2	0.0241 (6)	0.0157 (6)	0.0330 (7)	0.0061 (5)	0.0049 (5)	0.0100 (5)
N2	0.0243 (8)	0.0321 (8)	0.0230 (8)	0.0117 (7)	0.0105 (6)	0.0113 (7)
C2	0.0442 (13)	0.0459 (13)	0.0365 (12)	−0.0008 (11)	0.0220 (11)	0.0034 (10)
F3	0.0377 (7)	0.0186 (6)	0.0579 (8)	−0.0012 (5)	0.0197 (6)	0.0054 (5)
C3	0.0231 (10)	0.0602 (16)	0.0393 (13)	−0.0034 (11)	0.0093 (9)	−0.0140 (11)
C4	0.0262 (10)	0.0588 (15)	0.0310 (11)	0.0089 (10)	0.0087 (9)	0.0006 (10)
C5	0.0251 (9)	0.0409 (11)	0.0235 (9)	0.0031 (8)	0.0121 (8)	0.0078 (8)
C6	0.0245 (10)	0.0405 (12)	0.0269 (10)	0.0081 (9)	0.0108 (8)	0.0099 (9)
C7	0.0254 (10)	0.0443 (12)	0.0264 (10)	0.0123 (9)	0.0106 (8)	0.0127 (9)
C8	0.0284 (10)	0.0362 (11)	0.0245 (9)	0.0120 (8)	0.0124 (8)	0.0114 (8)
C9	0.0268 (10)	0.0575 (14)	0.0339 (11)	0.0236 (10)	0.0121 (9)	0.0220 (10)
C10	0.0435 (12)	0.0529 (14)	0.0395 (12)	0.0337 (11)	0.0181 (10)	0.0259 (11)
C11	0.0346 (11)	0.0410 (11)	0.0290 (10)	0.0199 (9)	0.0150 (8)	0.0166 (9)
C12	0.0266 (9)	0.0320 (10)	0.0203 (8)	0.0135 (8)	0.0110 (7)	0.0098 (7)
C13	0.0302 (10)	0.0209 (9)	0.0255 (9)	0.0105 (8)	0.0099 (8)	0.0100 (7)
C14	0.0305 (10)	0.0161 (8)	0.0245 (9)	0.0083 (7)	0.0111 (8)	0.0088 (7)
C15	0.0258 (9)	0.0169 (8)	0.0194 (8)	0.0063 (7)	0.0087 (7)	0.0063 (7)
C16	0.0262 (9)	0.0167 (8)	0.0234 (9)	0.0090 (7)	0.0092 (7)	0.0092 (7)
C17	0.0273 (9)	0.0117 (7)	0.0212 (8)	0.0045 (7)	0.0093 (7)	0.0058 (6)
C18	0.0236 (9)	0.0177 (8)	0.0199 (8)	0.0066 (7)	0.0078 (7)	0.0069 (7)
C19	0.0269 (9)	0.0155 (8)	0.0216 (8)	0.0096 (7)	0.0092 (7)	0.0081 (7)
C20	0.0278 (9)	0.0148 (8)	0.0180 (8)	0.0066 (7)	0.0095 (7)	0.0059 (6)
C21	0.0254 (9)	0.0191 (8)	0.0215 (8)	0.0086 (7)	0.0100 (7)	0.0080 (7)
C22	0.0248 (9)	0.0188 (8)	0.0215 (8)	0.0082 (7)	0.0089 (7)	0.0070 (7)
C23	0.0257 (9)	0.0169 (8)	0.0201 (8)	0.0056 (7)	0.0109 (7)	0.0049 (7)
C24	0.0239 (9)	0.0200 (8)	0.0233 (9)	0.0068 (7)	0.0100 (7)	0.0063 (7)
C25	0.0391 (11)	0.0165 (8)	0.0302 (10)	0.0125 (8)	0.0171 (8)	0.0086 (7)
C26	0.0276 (10)	0.0182 (9)	0.0333 (10)	−0.0014 (7)	0.0150 (8)	0.0021 (8)
C27	0.0235 (9)	0.0271 (10)	0.0358 (11)	0.0036 (8)	0.0105 (8)	0.0050 (8)
C28	0.0268 (9)	0.0221 (9)	0.0284 (9)	0.0079 (8)	0.0119 (8)	0.0071 (7)
C29	0.0293 (9)	0.0157 (8)	0.0343 (10)	0.0089 (7)	0.0087 (8)	0.0125 (7)
C30	0.0272 (10)	0.0231 (9)	0.0351 (10)	0.0103 (8)	0.0038 (8)	0.0126 (8)

Geometric parameters (Å, º)

F1—C24	1.336 (2)	C12—C13	1.434 (3)
O1—C17	1.3573 (19)	C13—C14	1.199 (3)
O1—C29	1.435 (2)	C14—C15	1.430 (3)
N1—C1	1.342 (3)	C15—C20	1.404 (2)
N1—C5	1.350 (3)	C15—C16	1.413 (2)
C1—C2	1.364 (3)	C16—C17	1.377 (2)
C1—H1	0.9500	C16—H16	0.9500
F2—C25	1.343 (2)	C17—C18	1.415 (2)
O2—C18	1.359 (2)	C18—C19	1.385 (2)
O2—C30	1.430 (2)	C19—C20	1.399 (2)
N2—C12	1.340 (2)	C19—H19	0.9500
N2—C8	1.350 (2)	C20—C21	1.435 (2)
C2—C3	1.374 (4)	C21—C22	1.197 (2)
C2—H2	0.9500	C22—C23	1.429 (2)
F3—C26	1.356 (2)	C23—C24	1.383 (2)
C3—C4	1.408 (4)	C23—C28	1.401 (3)
C3—H3	0.9500	C24—C25	1.387 (2)
C4—C5	1.386 (3)	C25—C26	1.375 (3)
C4—H4	0.9500	C26—C27	1.369 (3)
C5—C6	1.452 (3)	C27—C28	1.384 (3)
C6—C7	1.202 (3)	C27—H27	0.966 (16)
C7—C8	1.431 (3)	C28—H28	0.991 (15)
C8—C9	1.400 (3)	C29—H29A	0.9800
C9—C10	1.367 (3)	C29—H29B	0.9800
C9—H9	0.9500	C29—H29C	0.9800
C10—C11	1.378 (3)	C30—H30A	0.9800
C10—H10	0.9500	C30—H30B	0.9800
C11—C12	1.417 (3)	C30—H30C	0.9800
C11—H11	0.9500
C17—O1—C29	116.89 (14)	O1—C17—C16	125.12 (15)
C1—N1—C5	117.94 (19)	O1—C17—C18	115.18 (15)
N1—C1—C2	123.5 (2)	C16—C17—C18	119.70 (15)
N1—C1—H1	118.3	O2—C18—C19	125.11 (15)
C2—C1—H1	118.3	O2—C18—C17	114.96 (14)
C18—O2—C30	117.80 (13)	C19—C18—C17	119.92 (16)
C12—N2—C8	116.88 (16)	C18—C19—C20	120.71 (16)
C1—C2—C3	118.9 (2)	C18—C19—H19	119.6
C1—C2—H2	120.5	C20—C19—H19	119.6
C3—C2—H2	120.5	C19—C20—C15	119.59 (15)
C2—C3—C4	119.3 (2)	C19—C20—C21	121.44 (15)
C2—C3—H3	120.4	C15—C20—C21	118.97 (16)
C4—C3—H3	120.4	C22—C21—C20	174.56 (19)
C5—C4—C3	117.9 (2)	C21—C22—C23	174.48 (19)
C5—C4—H4	121.1	C24—C23—C28	117.76 (16)
C3—C4—H4	121.1	C24—C23—C22	121.90 (16)
N1—C5—C4	122.4 (2)	C28—C23—C22	120.33 (16)
N1—C5—C6	115.63 (17)	F1—C24—C23	120.29 (15)
C4—C5—C6	121.9 (2)	F1—C24—C25	118.35 (16)
C7—C6—C5	178.6 (2)	C23—C24—C25	121.35 (17)
C6—C7—C8	179.1 (2)	F2—C25—C26	120.96 (16)
N2—C8—C9	122.28 (18)	F2—C25—C24	120.12 (18)
N2—C8—C7	116.30 (17)	C26—C25—C24	118.91 (17)
C9—C8—C7	121.42 (18)	F3—C26—C27	119.98 (18)
C10—C9—C8	119.89 (19)	F3—C26—C25	118.14 (17)
C10—C9—H9	120.1	C27—C26—C25	121.88 (17)
C8—C9—H9	120.1	C26—C27—C28	118.57 (19)
C9—C10—C11	119.56 (19)	C26—C27—H27	110.7 (14)
C9—C10—H10	120.2	C28—C27—H27	130.7 (14)
C11—C10—H10	120.2	C27—C28—C23	121.51 (18)
C10—C11—C12	117.26 (19)	C27—C28—H28	119.1 (13)
C10—C11—H11	121.4	C23—C28—H28	119.4 (13)
C12—C11—H11	121.4	O1—C29—H29A	109.5
N2—C12—C11	124.10 (17)	O1—C29—H29B	109.5
N2—C12—C13	116.87 (16)	H29A—C29—H29B	109.5
C11—C12—C13	119.04 (17)	O1—C29—H29C	109.5
C14—C13—C12	178.00 (18)	H29A—C29—H29C	109.5
C13—C14—C15	179.1 (2)	H29B—C29—H29C	109.5
C20—C15—C16	119.37 (16)	O2—C30—H30A	109.5
C20—C15—C14	121.26 (15)	O2—C30—H30B	109.5
C16—C15—C14	119.37 (15)	H30A—C30—H30B	109.5
C17—C16—C15	120.70 (16)	O2—C30—H30C	109.5
C17—C16—H16	119.6	H30A—C30—H30C	109.5
C15—C16—H16	119.6	H30B—C30—H30C	109.5

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C11—H11···F3^i	0.95	2.41	3.220 (2)	143
C27—H27···N1	0.97 (2)	2.47 (2)	3.400 (3)	162 (2)
C28—H28···N2	0.99 (2)	2.65 (2)	3.612 (2)	165 (2)
C29—H29B···O2^ii	0.98	2.37	3.350 (2)	175

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