Structural and theoretical characterization of a new twisted 4′-substituted terpyridine compound: 4′-(isoquinolin-4-yl)-2,2′:6′,2′′-terpyridine

Granifo, J.; Arévalo, B.; Gaviño, R.; Suárez, S.; Baggio, R.

doi:10.1107/S2053229616016533

Structural and theoretical characterization of a new twisted 4′-substituted terpyridine compound: 4′-(isoquinolin-4-yl)-2,2′:6′,2′′-terpyridine

J. Granifo, B. Arévalo, R. Gaviño, S. Suárez and R. Baggio

4′-Substituted derivatives of 2,2′:6′,2′′-terpyridine with N-containing heteroaromatic substituents, such as pyridyl groups, might be able to coordinate metal centres through the extra N-donor atom, in addition to the chelating terpyridine N atoms. The incorporation of these peripheral N-donor sites would also allow for the diversification of the types of noncovalent interactions present, such as hydrogen bonding and π–π stacking. The title compound, C₂₄H₁₆N₄, consists of a 2,2′:6′,2′′-terpyridine nucleus (tpy), with a pendant isoquinoline group (isq) bound at the central pyridine (py) ring. The tpy nucleus deviates slightly from planarity, with interplanar angles between the lateral and central py rings in the range 2.24 (7)–7.90 (7)°, while the isq group is rotated significantly [by 46.57 (6)°] out of this planar scheme, associated with a short H_tpy

H_isq contact of 2.32 Å. There are no strong noncovalent interactions in the structure, the main ones being of the π–π and C—H

π types, giving rise to columnar arrays along [001], further linked by C—H

N hydrogen bonds into a three-dimensional supramolecular structure. An Atoms In Molecules (AIM) analysis of the noncovalent interactions provided illuminating results, and while confirming the bonding character for all those interactions unquestionable from a geometrical point of view, it also provided answers for some cases where geometric parameters are not informative, in particular, the short H_tpy

H_isq contact of 2.32 Å to which AIM ascribed an attractive character.

Keywords: atoms-in-molecules; AIM; 4′-substituted 2,2′:6′,2′′-terpyridine; attractive H

H interaction; crystal structure; Bader's theory; theoretical characterization.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229616016533/wq3124sup1.cif Contains datablocks I, global
	Structure factor file (CIF format) https://doi.org/10.1107/S2053229616016533/wq3124Isup2.hkl Contains datablock I
	Chemical Markup Language (CML) file https://doi.org/10.1107/S2053229616016533/wq3124Isup4.cml Supplementary material
	Portable Document Format (PDF) file https://doi.org/10.1107/S2053229616016533/wq3124sup4.pdf Supplementary material

CCDC reference: 1510131

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2009); cell refinement: CrysAlis PRO (Oxford Diffraction, 2009); data reduction: CrysAlis PRO (Oxford Diffraction, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015) and PLATON (Spek, 2009).

4'-(Isoquinolin-4-yl)-2,2':6',2''-terpyridine top

Crystal data top

C₂₄H₁₆N₄	F(000) = 752
M_r = 360.41	D_x = 1.348 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 12.3897 (3) Å	Cell parameters from 6249 reflections
b = 8.7940 (3) Å	θ = 3.9–27.7°
c = 17.1791 (6) Å	µ = 0.08 mm⁻¹
β = 108.369 (3)°	T = 170 K
V = 1776.38 (10) Å³	Prism, colourless
Z = 4	0.34 × 0.22 × 0.12 mm

Data collection top

Oxford Diffraction Xcalibur CCD (Eos, Gemini) diffractometer	3138 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.038
ω scans	θ_max = 28.9°, θ_min = 3.6°
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	h = −16→16
T_min = 0.97, T_max = 1.00	k = −9→11
18351 measured reflections	l = −22→23
4225 independent reflections

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.044	w = 1/[σ²(F_o²) + (0.0527P)² + 0.4471P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.123	(Δ/σ)_max < 0.001
S = 1.02	Δρ_max = 0.26 e Å⁻³
4225 reflections	Δρ_min = −0.20 e Å⁻³
254 parameters	Extinction correction: SHELXL2014 (Sheldrick, 2015), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0124 (13)

Special details top

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

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

	x	y	z	U_iso*/U_eq
N1	0.73444 (9)	0.54800 (14)	0.11880 (7)	0.0274 (3)
N2	0.51893 (9)	0.27644 (13)	0.01691 (7)	0.0237 (3)
N3	0.27126 (10)	0.03477 (14)	−0.03023 (7)	0.0296 (3)
N4	0.36475 (11)	0.24792 (17)	0.34177 (8)	0.0412 (4)
C1	0.82661 (12)	0.61388 (17)	0.10901 (9)	0.0308 (3)
H1	0.8632	0.6888	0.1462	0.037*
C2	0.87058 (12)	0.57697 (17)	0.04677 (9)	0.0319 (3)
H2	0.9351	0.6257	0.0424	0.038*
C3	0.81662 (12)	0.46642 (17)	−0.00855 (9)	0.0324 (3)
H3	0.8442	0.4389	−0.0510	0.039*
C4	0.72084 (12)	0.39693 (16)	−0.00006 (9)	0.0273 (3)
H4	0.6830	0.3220	−0.0367	0.033*
C5	0.68206 (10)	0.44116 (15)	0.06438 (8)	0.0221 (3)
C6	0.57955 (10)	0.36965 (15)	0.07620 (8)	0.0224 (3)
C7	0.55043 (11)	0.39990 (15)	0.14679 (8)	0.0238 (3)
H7	0.5952	0.4644	0.1870	0.029*
C8	0.45389 (11)	0.33261 (16)	0.15643 (8)	0.0244 (3)
C9	0.39205 (11)	0.23408 (15)	0.09548 (8)	0.0247 (3)
H9	0.3279	0.1854	0.1004	0.030*
C10	0.42695 (10)	0.20867 (15)	0.02681 (8)	0.0231 (3)
C11	0.36231 (11)	0.10557 (15)	−0.04007 (8)	0.0241 (3)
C12	0.39502 (12)	0.08606 (17)	−0.10971 (9)	0.0305 (3)
H12	0.4582	0.1370	−0.1148	0.037*
C13	0.33292 (14)	−0.00957 (18)	−0.17121 (9)	0.0363 (4)
H13	0.3535	−0.0240	−0.2183	0.044*
C14	0.23981 (13)	−0.08322 (18)	−0.16149 (9)	0.0344 (4)
H14	0.1965	−0.1489	−0.2016	0.041*
C15	0.21250 (12)	−0.05715 (17)	−0.09083 (10)	0.0338 (3)
H15	0.1492	−0.1066	−0.0849	0.041*
C16	0.41990 (11)	0.36066 (16)	0.23095 (8)	0.0250 (3)
C17	0.39188 (12)	0.23932 (18)	0.27095 (9)	0.0326 (3)
H17	0.3914	0.1435	0.2479	0.039*
C18	0.36569 (13)	0.3839 (2)	0.37317 (10)	0.0412 (4)
H18	0.3484	0.3917	0.4219	0.049*
C19	0.39101 (11)	0.51904 (19)	0.33848 (9)	0.0344 (4)
C20	0.39052 (13)	0.6628 (2)	0.37540 (11)	0.0473 (5)
H20	0.3746	0.6693	0.4247	0.057*
C21	0.41314 (15)	0.7914 (2)	0.33940 (13)	0.0550 (5)
H21	0.4132	0.8854	0.3643	0.066*
C22	0.43630 (14)	0.7822 (2)	0.26487 (12)	0.0469 (5)
H22	0.4506	0.8709	0.2403	0.056*
C23	0.43836 (12)	0.64552 (17)	0.22752 (10)	0.0335 (3)
H23	0.4534	0.6423	0.1778	0.040*
C24	0.41772 (11)	0.50872 (17)	0.26402 (9)	0.0277 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0266 (6)	0.0296 (7)	0.0254 (6)	−0.0031 (5)	0.0073 (5)	−0.0006 (5)
N2	0.0244 (5)	0.0236 (6)	0.0231 (6)	0.0003 (4)	0.0077 (5)	0.0011 (5)
N3	0.0265 (6)	0.0282 (7)	0.0328 (7)	−0.0027 (5)	0.0074 (5)	−0.0008 (5)
N4	0.0406 (7)	0.0548 (9)	0.0337 (8)	0.0024 (6)	0.0197 (6)	0.0091 (7)
C1	0.0277 (7)	0.0324 (8)	0.0300 (8)	−0.0057 (6)	0.0056 (6)	0.0008 (6)
C2	0.0240 (7)	0.0357 (8)	0.0372 (8)	−0.0016 (6)	0.0114 (6)	0.0093 (7)
C3	0.0331 (7)	0.0365 (9)	0.0324 (8)	0.0029 (6)	0.0171 (6)	0.0050 (7)
C4	0.0296 (7)	0.0280 (7)	0.0256 (7)	0.0003 (6)	0.0108 (6)	0.0004 (6)
C5	0.0225 (6)	0.0221 (7)	0.0211 (7)	0.0014 (5)	0.0059 (5)	0.0033 (5)
C6	0.0224 (6)	0.0215 (7)	0.0230 (7)	0.0025 (5)	0.0065 (5)	0.0018 (5)
C7	0.0244 (6)	0.0236 (7)	0.0237 (7)	−0.0001 (5)	0.0079 (5)	−0.0030 (5)
C8	0.0240 (6)	0.0248 (7)	0.0252 (7)	0.0038 (5)	0.0089 (5)	0.0012 (6)
C9	0.0229 (6)	0.0254 (7)	0.0274 (7)	0.0005 (5)	0.0104 (5)	0.0015 (6)
C10	0.0229 (6)	0.0218 (7)	0.0237 (7)	0.0024 (5)	0.0059 (5)	0.0016 (5)
C11	0.0247 (6)	0.0203 (7)	0.0251 (7)	0.0023 (5)	0.0050 (5)	0.0026 (5)
C12	0.0339 (7)	0.0312 (8)	0.0252 (7)	−0.0035 (6)	0.0078 (6)	−0.0014 (6)
C13	0.0456 (9)	0.0366 (9)	0.0241 (8)	0.0000 (7)	0.0072 (6)	−0.0034 (7)
C14	0.0361 (8)	0.0286 (8)	0.0286 (8)	−0.0002 (6)	−0.0039 (6)	−0.0021 (6)
C15	0.0274 (7)	0.0291 (8)	0.0390 (9)	−0.0022 (6)	0.0020 (6)	0.0003 (7)
C16	0.0209 (6)	0.0311 (8)	0.0235 (7)	0.0017 (5)	0.0076 (5)	−0.0017 (6)
C17	0.0328 (7)	0.0360 (9)	0.0322 (8)	0.0024 (6)	0.0149 (6)	0.0045 (7)
C18	0.0349 (8)	0.0669 (12)	0.0260 (8)	0.0018 (8)	0.0158 (7)	−0.0007 (8)
C19	0.0220 (7)	0.0529 (10)	0.0298 (8)	−0.0003 (6)	0.0105 (6)	−0.0108 (7)
C20	0.0297 (8)	0.0707 (13)	0.0457 (10)	−0.0051 (8)	0.0182 (7)	−0.0284 (9)
C21	0.0431 (9)	0.0526 (12)	0.0773 (14)	−0.0085 (8)	0.0302 (10)	−0.0377 (11)
C22	0.0444 (9)	0.0365 (9)	0.0677 (12)	−0.0018 (7)	0.0287 (9)	−0.0128 (9)
C23	0.0305 (7)	0.0330 (8)	0.0406 (9)	0.0007 (6)	0.0164 (7)	−0.0066 (7)
C24	0.0193 (6)	0.0367 (8)	0.0280 (7)	0.0011 (6)	0.0086 (5)	−0.0049 (6)

Geometric parameters (Å, º) top

N1—C1	1.3376 (17)	C10—C11	1.4845 (19)
N1—C5	1.3400 (17)	C11—C12	1.3894 (19)
N2—C6	1.3384 (17)	C12—C13	1.380 (2)
N2—C10	1.3435 (16)	C12—H12	0.9300
N3—C15	1.3377 (19)	C13—C14	1.378 (2)
N3—C11	1.3450 (17)	C13—H13	0.9300
N4—C18	1.310 (2)	C14—C15	1.378 (2)
N4—C17	1.3626 (18)	C14—H14	0.9300
C1—C2	1.383 (2)	C15—H15	0.9300
C1—H1	0.9300	C16—C17	1.372 (2)
C2—C3	1.377 (2)	C16—C24	1.4243 (19)
C2—H2	0.9300	C17—H17	0.9300
C3—C4	1.3829 (19)	C18—C19	1.409 (2)
C3—H3	0.9300	C18—H18	0.9300
C4—C5	1.3938 (18)	C19—C20	1.415 (2)
C4—H4	0.9300	C19—C24	1.4216 (19)
C5—C6	1.4873 (17)	C20—C21	1.360 (3)
C6—C7	1.3955 (18)	C20—H20	0.9300
C7—C8	1.3903 (18)	C21—C22	1.400 (3)
C7—H7	0.9300	C21—H21	0.9300
C8—C9	1.3887 (19)	C22—C23	1.366 (2)
C8—C16	1.4888 (18)	C22—H22	0.9300
C9—C10	1.3965 (18)	C23—C24	1.417 (2)
C9—H9	0.9300	C23—H23	0.9300

C1—N1—C5	117.44 (12)	C13—C12—H12	120.3
C6—N2—C10	118.06 (11)	C11—C12—H12	120.3
C15—N3—C11	117.01 (12)	C14—C13—C12	118.68 (14)
C18—N4—C17	116.46 (14)	C14—C13—H13	120.7
N1—C1—C2	123.75 (14)	C12—C13—H13	120.7
N1—C1—H1	118.1	C15—C14—C13	118.40 (14)
C2—C1—H1	118.1	C15—C14—H14	120.8
C3—C2—C1	118.40 (13)	C13—C14—H14	120.8
C3—C2—H2	120.8	N3—C15—C14	124.16 (14)
C1—C2—H2	120.8	N3—C15—H15	117.9
C2—C3—C4	119.05 (13)	C14—C15—H15	117.9
C2—C3—H3	120.5	C17—C16—C24	118.15 (13)
C4—C3—H3	120.5	C17—C16—C8	119.12 (13)
C3—C4—C5	118.85 (13)	C24—C16—C8	122.72 (12)
C3—C4—H4	120.6	N4—C17—C16	125.22 (15)
C5—C4—H4	120.6	N4—C17—H17	117.4
N1—C5—C4	122.51 (12)	C16—C17—H17	117.4
N1—C5—C6	116.60 (11)	N4—C18—C19	124.76 (14)
C4—C5—C6	120.89 (12)	N4—C18—H18	117.6
N2—C6—C7	122.77 (12)	C19—C18—H18	117.6
N2—C6—C5	116.97 (11)	C18—C19—C20	122.09 (15)
C7—C6—C5	120.25 (12)	C18—C19—C24	118.22 (14)
C8—C7—C6	119.35 (12)	C20—C19—C24	119.70 (15)
C8—C7—H7	120.3	C21—C20—C19	120.57 (15)
C6—C7—H7	120.3	C21—C20—H20	119.7
C9—C8—C7	117.82 (12)	C19—C20—H20	119.7
C9—C8—C16	120.88 (12)	C20—C21—C22	119.91 (16)
C7—C8—C16	121.26 (12)	C20—C21—H21	120.0
C8—C9—C10	119.51 (12)	C22—C21—H21	120.0
C8—C9—H9	120.2	C23—C22—C21	121.34 (17)
C10—C9—H9	120.2	C23—C22—H22	119.3
N2—C10—C9	122.47 (12)	C21—C22—H22	119.3
N2—C10—C11	116.44 (11)	C22—C23—C24	120.42 (15)
C9—C10—C11	121.09 (12)	C22—C23—H23	119.8
N3—C11—C12	122.34 (13)	C24—C23—H23	119.8
N3—C11—C10	117.05 (12)	C23—C24—C19	118.02 (13)
C12—C11—C10	120.61 (12)	C23—C24—C16	124.82 (13)
C13—C12—C11	119.41 (14)	C19—C24—C16	117.15 (13)

Relevant dihedral angles between aromatic rings (°) top

<Cg2–Cg1>	7.90 (7)
<Cg2–Cg3>	2.24 (7)
<Cg4–Cg5>	1.91 (8)
<Cg2–isq>	46.57 (6)

Ring codes are as in Fig. 1.

Hydrogen-bond geometry top

Interaction code	D—H···A	D—H (Å)	H···A (Å)	D···A (Å)	D—H···A (°)	100ρ(r) (a.u)	100\nabla²ρ(r) (a.u)
#1	C3—H3···N4ⁱ	0.93	2.54	3.389 (2)	152	1.26	0.36
#1*	C13—H13···N1ⁱⁱ	0.93	2.73	3.441 (2)	134	0.80	0.24
#2	C15—H15···Cg5ⁱⁱ	0.93	2.97	3.665 (2)	132	0.48	0.13

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

π–π contacts top

Interaction code	Cg···Cg	ccd (Å)	da (°)	sa (°)	ipd (Å)	100ρ(r) (a.u)	100\nabla²ρ(r)(a.u)
#3	Cg2···Cg1ⁱⁱⁱ	3.7750 (8)	7.90 (7)	22.2 (18)	3.48 (5)	0.52	0.15
#4	Cg3···Cg2ⁱⁱⁱ	3.7700 (8)	2.24 (7)	26.1 (11)	3.38 (3)	0.55	0.16
#5	Cg4···Cg5^iv	4.1539 (9)	11.43 (8)	29 (5)	3.6 (2)	0.30	0.10

Symmetry codes: (iii) -x+1, -y+1, -z; (iv) -x+1/2, y-1/2, -z+1/2.

Ring codes are as in Fig. 1. Notes : ccd is the center-to-center distance; da is the dihedral angle between rings; sa is the slippage angle; ipd is the interplanar distance, or (mean) distance from one plane to the neighbouring centroid. For details, see Janiak (2000).

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