Conformational disorder in 4-(5,5′-di­bromo-2′-chloro-4,4′-bipyridyl-2-yl)benzaldehyde: role of π–π and halogen inter­actions

Abboud, M.; Kadimi, A.; Mamane, V.; Aubert, E.

doi:10.1107/S0108270110024261

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Conformational disorder in 4-(5,5′-dibromo-2′-chloro-4,4′-bipyridyl-2-yl)benzaldehyde: role of π–π and halogen interactions

M. Abboud, A. Kadimi, V. Mamane and E. Aubert

The crystal packing of the title compound, C₁₇H₉Br₂ClN₂O, is governed by strong π–π stacking, where molecules are tightly bound within infinite (100) planes; these planes interact mainly through non-optimal π–π stacking where arene rings are noticeably displaced from perfect overlap, and also through halogen–halogen interactions. The aldehyde group shows conformational disorder, with a significant population difference between the two conformers; this difference is rationalized by the energetic analysis of the crystal packing using the PIXEL method, which also allows a decomposition of intermolecular interaction energy into Coulombic, polarization, dispersion and repulsion contributions. Using such an analysis, it is found that the main reason for this unequal population of the two conformers in the crystal is two hydrogen bonds that are present only for the major conformer.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270110024261/ku3026sup1.cif Contains datablocks I, global
	Structure factor file (CIF format) https://doi.org/10.1107/S0108270110024261/ku3026Isup2.hkl Contains datablock I

CCDC reference: 786830

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: 'SIR2004 (Burla et al., 2005)'; program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2008); software used to prepare material for publication: PLATON (Spek, 2009).

4-(5,5'-dibromo-2'-chloro-4,4'-bipyridyl-2-yl)benzaldehyde top

Crystal data top

C₁₇H₉Br₂ClN₂O	Z = 2
M_r = 452.53	F(000) = 440
Triclinic, P1	D_x = 1.908 Mg m⁻³
Hall symbol: -P 1	Melting point: 170 K
a = 7.5759 (2) Å	Mo Kα radiation, λ = 0.71069 Å
b = 8.4629 (2) Å	Cell parameters from 19163 reflections
c = 13.1534 (2) Å	θ = 3.2–37.7°
α = 103.082 (2)°	µ = 5.32 mm⁻¹
β = 94.473 (2)°	T = 110 K
γ = 104.401 (2)°	Prism, light yellow
V = 787.52 (3) Å³	0.22 × 0.15 × 0.07 mm

Data collection top

Oxford Diffraction SuperNova, Dual, Cu at zero, Atlas diffractometer	5351 independent reflections
Radiation source: Enhance (Mo) X-ray Source	4767 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.028
Detector resolution: 10.4508 pixels mm^-1	θ_max = 31.7°, θ_min = 3.2°
φ and ω scans	h = −11→11
Absorption correction: analytical [CrysAlis Pro (Oxford Diffraction, 2009), based on expressions derived by Clark & Reid (1995)]	k = −12→12
T_min = 0.444, T_max = 0.758	l = −19→19
35546 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.028	Hydrogen site location: difference Fourier map
wR(F²) = 0.073	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.0371P)² + 0.6279P] where P = (F_o² + 2F_c²)/3
5351 reflections	(Δ/σ)_max = 0.001
218 parameters	Δρ_max = 2.08 e Å⁻³
0 restraints	Δρ_min = −1.25 e Å⁻³

Special details top

Experimental. CrysAlisPro, Oxford Diffraction Ltd, Version 1.171.33.41 Analytical numeric absorption correction using a multifaceted crystal model based on expressions derived by Clark & Reid (Clark & Reid, 1995)

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.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Br2	−0.21454 (3)	0.40481 (2)	0.630746 (15)	0.02574 (5)
Br1	0.46231 (2)	0.61723 (2)	0.730990 (15)	0.02387 (5)
Cl1	0.35160 (7)	0.07488 (6)	0.39575 (4)	0.02768 (10)
N7	0.0487 (2)	0.1677 (2)	0.40743 (13)	0.0261 (3)
C10	0.1154 (2)	0.2939 (2)	0.62769 (13)	0.0183 (3)
C13	−0.0391 (2)	0.2168 (2)	0.97970 (12)	0.0174 (3)
C4	0.1519 (2)	0.3497 (2)	0.74460 (13)	0.0174 (3)
C16	−0.2482 (3)	0.0428 (2)	1.10670 (14)	0.0226 (3)
C8	0.1966 (3)	0.1631 (2)	0.46446 (14)	0.0221 (3)
C11	−0.0409 (3)	0.3032 (2)	0.56814 (14)	0.0207 (3)
O19A	−0.3632 (3)	−0.0180 (3)	1.26193 (15)	0.0269 (5)	0.740 (5)
C14	−0.0037 (3)	0.2754 (2)	1.08992 (14)	0.0238 (3)
H14	0.0925	0.3747	1.1220	0.029*
C2	0.0770 (2)	0.3074 (2)	0.91377 (13)	0.0173 (3)
C9	0.2390 (3)	0.2212 (2)	0.57369 (13)	0.0205 (3)
H9	0.3477	0.2118	0.6101	0.025*
C5	0.3030 (2)	0.4799 (2)	0.79958 (14)	0.0193 (3)
C3	0.0369 (2)	0.2644 (2)	0.80388 (13)	0.0185 (3)
H3	−0.0696	0.1764	0.7694	0.022*
C17	−0.2832 (3)	−0.0164 (2)	0.99754 (15)	0.0242 (3)
H17	−0.3781	−0.1170	0.9660	0.029*
N1	0.2267 (2)	0.4316 (2)	0.96527 (12)	0.0226 (3)
C15	−0.1085 (3)	0.1889 (3)	1.15240 (14)	0.0259 (4)
H15	−0.0843	0.2300	1.2270	0.031*
C18	−0.1811 (3)	0.0699 (2)	0.93426 (13)	0.0213 (3)
H18	−0.2075	0.0292	0.8597	0.026*
C19A	−0.3621 (3)	−0.0542 (3)	1.17076 (18)	0.0324 (5)	0.740 (5)
H19A	−0.4447	−0.1591	1.1329	0.039*	0.740 (5)
C6	0.3346 (3)	0.5154 (2)	0.90908 (15)	0.0245 (3)
H6	0.4390	0.6043	0.9455	0.029*
C12	−0.0700 (3)	0.2376 (3)	0.45934 (15)	0.0260 (4)
H12	−0.1784	0.2424	0.4201	0.031*
O19B	−0.4572 (8)	−0.1575 (8)	1.1563 (6)	0.0346 (17)	0.260 (5)
C19B	−0.3621 (3)	−0.0542 (3)	1.17076 (18)	0.0324 (5)	0.260 (5)
H19B	−0.3333	−0.0004	1.2440	0.039*	0.260 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br2	0.02583 (9)	0.02767 (10)	0.02527 (9)	0.00982 (7)	0.00302 (7)	0.00732 (7)
Br1	0.02309 (9)	0.02083 (9)	0.02600 (9)	0.00072 (6)	0.00706 (6)	0.00729 (7)
Cl1	0.0324 (2)	0.0258 (2)	0.0224 (2)	0.00374 (17)	0.01280 (17)	0.00305 (16)
N7	0.0324 (8)	0.0269 (8)	0.0167 (7)	0.0027 (6)	0.0047 (6)	0.0065 (6)
C10	0.0219 (7)	0.0170 (7)	0.0145 (7)	0.0011 (6)	0.0036 (5)	0.0053 (5)
C13	0.0221 (7)	0.0197 (7)	0.0126 (6)	0.0084 (6)	0.0036 (5)	0.0050 (5)
C4	0.0201 (7)	0.0181 (7)	0.0142 (6)	0.0047 (6)	0.0031 (5)	0.0046 (5)
C16	0.0303 (9)	0.0279 (8)	0.0185 (7)	0.0164 (7)	0.0109 (6)	0.0117 (6)
C8	0.0291 (9)	0.0183 (7)	0.0173 (7)	0.0014 (6)	0.0090 (6)	0.0051 (6)
C11	0.0242 (8)	0.0202 (7)	0.0177 (7)	0.0043 (6)	0.0033 (6)	0.0067 (6)
O19A	0.0316 (10)	0.0352 (11)	0.0189 (9)	0.0115 (8)	0.0112 (7)	0.0119 (7)
C14	0.0334 (9)	0.0246 (8)	0.0131 (7)	0.0080 (7)	0.0036 (6)	0.0038 (6)
C2	0.0208 (7)	0.0183 (7)	0.0131 (6)	0.0059 (6)	0.0016 (5)	0.0043 (5)
C9	0.0242 (8)	0.0204 (7)	0.0158 (7)	0.0023 (6)	0.0051 (6)	0.0057 (6)
C5	0.0193 (7)	0.0192 (7)	0.0196 (7)	0.0033 (6)	0.0036 (6)	0.0072 (6)
C3	0.0208 (7)	0.0198 (7)	0.0130 (6)	0.0026 (6)	0.0021 (5)	0.0036 (5)
C17	0.0260 (8)	0.0269 (8)	0.0199 (8)	0.0041 (7)	0.0062 (6)	0.0089 (7)
N1	0.0253 (7)	0.0218 (7)	0.0171 (6)	0.0011 (6)	−0.0020 (5)	0.0051 (5)
C15	0.0399 (10)	0.0301 (9)	0.0129 (7)	0.0166 (8)	0.0085 (7)	0.0063 (6)
C18	0.0241 (8)	0.0255 (8)	0.0144 (7)	0.0053 (6)	0.0036 (6)	0.0065 (6)
C19A	0.0443 (12)	0.0388 (12)	0.0309 (10)	0.0249 (10)	0.0219 (9)	0.0216 (9)
C6	0.0242 (8)	0.0234 (8)	0.0205 (8)	−0.0012 (6)	−0.0035 (6)	0.0057 (6)
C12	0.0292 (9)	0.0288 (9)	0.0186 (8)	0.0038 (7)	0.0005 (6)	0.0085 (7)
O19B	0.028 (3)	0.030 (3)	0.047 (4)	0.000 (2)	0.011 (3)	0.018 (3)
C19B	0.0443 (12)	0.0388 (12)	0.0309 (10)	0.0249 (10)	0.0219 (9)	0.0216 (9)

Geometric parameters (Å, º) top

Br2—C11	1.8864 (19)	C11—C12	1.391 (3)
Br1—C5	1.8886 (17)	O19A—C19A	1.170 (3)
Cl1—C8	1.7461 (19)	C14—C15	1.388 (3)
N7—C8	1.313 (3)	C14—H14	0.9500
N7—C12	1.342 (3)	C2—N1	1.348 (2)
C10—C11	1.397 (2)	C2—C3	1.397 (2)
C10—C9	1.397 (2)	C9—H9	0.9500
C10—C4	1.485 (2)	C5—C6	1.392 (2)
C13—C18	1.399 (2)	C3—H3	0.9500
C13—C14	1.403 (2)	C17—C18	1.386 (2)
C13—C2	1.483 (2)	C17—H17	0.9500
C4—C5	1.390 (2)	N1—C6	1.326 (2)
C4—C3	1.391 (2)	C15—H15	0.9500
C16—C15	1.387 (3)	C18—H18	0.9500
C16—C17	1.390 (3)	C19A—H19A	0.9500
C16—C19A	1.484 (3)	C6—H6	0.9500
C8—C9	1.392 (2)	C12—H12	0.9500

C8—N7—C12	116.76 (16)	C10—C9—H9	121.3
C11—C10—C9	117.62 (16)	C4—C5—C6	119.23 (16)
C11—C10—C4	123.55 (16)	C4—C5—Br1	122.13 (13)
C9—C10—C4	118.77 (15)	C6—C5—Br1	118.59 (13)
C18—C13—C14	118.85 (16)	C4—C3—C2	120.43 (16)
C18—C13—C2	121.24 (14)	C4—C3—H3	119.8
C14—C13—C2	119.89 (16)	C2—C3—H3	119.8
C5—C4—C3	117.14 (15)	C18—C17—C16	120.63 (18)
C5—C4—C10	123.03 (15)	C18—C17—H17	119.7
C3—C4—C10	119.75 (15)	C16—C17—H17	119.7
C15—C16—C17	119.49 (17)	C6—N1—C2	118.30 (16)
C15—C16—C19A	122.10 (18)	C16—C15—C14	120.45 (17)
C17—C16—C19A	118.41 (19)	C16—C15—H15	119.8
N7—C8—C9	125.78 (18)	C14—C15—H15	119.8
N7—C8—Cl1	116.29 (14)	C17—C18—C13	120.27 (16)
C9—C8—Cl1	117.93 (15)	C17—C18—H18	119.9
C12—C11—C10	119.61 (17)	C13—C18—H18	119.9
C12—C11—Br2	118.48 (14)	O19A—C19A—C16	128.3 (3)
C10—C11—Br2	121.90 (13)	O19A—C19A—H19A	115.9
C15—C14—C13	120.31 (18)	C16—C19A—H19A	115.9
C15—C14—H14	119.8	N1—C6—C5	123.49 (16)
C13—C14—H14	119.8	N1—C6—H6	118.3
N1—C2—C3	121.39 (16)	C5—C6—H6	118.3
N1—C2—C13	116.43 (15)	N7—C12—C11	122.76 (18)
C3—C2—C13	122.17 (15)	N7—C12—H12	118.6
C8—C9—C10	117.43 (17)	C11—C12—H12	118.6
C8—C9—H9	121.3

C11—C10—C4—C5	−117.6 (2)	C10—C4—C5—Br1	7.6 (2)
C9—C10—C4—C5	65.3 (2)	C5—C4—C3—C2	−1.5 (3)
C11—C10—C4—C3	65.7 (2)	C10—C4—C3—C2	175.32 (16)
C9—C10—C4—C3	−111.39 (19)	N1—C2—C3—C4	0.0 (3)
C12—N7—C8—C9	1.3 (3)	C13—C2—C3—C4	−178.32 (16)
C12—N7—C8—Cl1	−179.03 (14)	C15—C16—C17—C18	−0.6 (3)
C9—C10—C11—C12	1.4 (3)	C19B—C16—C17—C18	179.83 (18)
C4—C10—C11—C12	−175.67 (17)	C3—C2—N1—C6	1.3 (3)
C9—C10—C11—Br2	−177.95 (12)	C13—C2—N1—C6	179.75 (16)
C4—C10—C11—Br2	4.9 (2)	C17—C16—C15—C14	−0.2 (3)
C18—C13—C14—C15	−0.2 (3)	C19B—C16—C15—C14	179.37 (18)
C2—C13—C14—C15	−178.30 (17)	C13—C14—C15—C16	0.6 (3)
C18—C13—C2—N1	−170.15 (17)	C16—C17—C18—C13	1.0 (3)
C14—C13—C2—N1	7.9 (2)	C14—C13—C18—C17	−0.6 (3)
C18—C13—C2—C3	8.3 (3)	C2—C13—C18—C17	177.49 (17)
C14—C13—C2—C3	−173.66 (17)	C15—C16—C19A—O19A	7.0 (3)
N7—C8—C9—C10	−1.3 (3)	C17—C16—C19A—O19A	−173.5 (2)
Cl1—C8—C9—C10	179.02 (13)	C2—N1—C6—C5	−1.1 (3)
C11—C10—C9—C8	−0.2 (2)	C4—C5—C6—N1	−0.4 (3)
C4—C10—C9—C8	177.10 (15)	Br1—C5—C6—N1	177.02 (15)
C3—C4—C5—C6	1.7 (3)	C8—N7—C12—C11	0.2 (3)
C10—C4—C5—C6	−175.03 (17)	C10—C11—C12—N7	−1.5 (3)
C3—C4—C5—Br1	−175.63 (13)	Br2—C11—C12—N7	177.89 (15)

Intermolecular interaction energies within pairs of molecules [the reference molecule is (x, y, z)]. d is the distance between molecular mass centres (Å); Coul., Pol., Disp. and Rep. are Coulombic, polarization, dispersion and repulsion contributions to total interaction energy for conformer A (Tot. A). For each molecular pair, the corresponding interaction energies obtained for the B conformer are also reported (tot. B). Energies are in kJ mol^-1. top

Number	d	Symmetry	Coul.	Pol.	Disp.	Rep.	Tot. A	Tot. B
1	7.358	-x,-y,1-z	-21	-8.1	-53.3	36.3	-46.2	-45.9
2	9.136	-x,-y,2-z	-23.2	-8.6	-64.5	56.8	-39.5	-31.6
3	6.785	-x,1-y,2-z	-12	-4.1	-66.9	43.6	-39.5	-40.1
4	8.191	-x,1-y,1-z	-4	-1.3	-28.3	13.3	-20.3	-20.6
5	12.021	-1-x,-y,2-z	-7.7	-2.6	-22.7	15	-18	-13.7
6	8.239	1-x,1-y,2-z	-6	-2.1	-20.3	12	-16.4	-16.3
7	13.153	x,y,-1+z	-8.3	-3.7	-13.3	11.9	-13.5	-9.1
8	13.153	x,y,1+z	-8.3	-3.7	-13.3	11.9	-13.5	-9.1
9	7.576	-1+x,y,z	-5.7	-2.2	-19.2	16.5	-10.6	-11.4
10	7.576	1+x,y,z	-5.7	-2.2	-19.2	16.5	-10.6	-11.4
11	10.222	1-x,1-y,1-z	-9.4	-3.8	-18.5	22.4	-9.2	-9
12	9.855	-1+x,-1+y,z	0.3	-2.8	-14	9.7	-6.9	-8.3
13	9.855	1+x,1+y,z	0.3	-2.8	-14	9.7	-6.9	-8.3
14	11.11	1-x,-y,1-z	-0.6	-0.3	-6.1	1.7	-5.3	-5.4
15	8.463	x,-1+y,z	0.6	-0.1	-2.3	0	-1.9	-2.2
16	8.463	x,1+y,z	0.6	-0.1	-2.3	0	-1.9	-2.2
17	15.683	-1+x,y,1+z	-3.4	-1.5	-5.2	8.6	-1.5	-2.7
18	15.683	1+x,y,-1+z	-3.4	-1.5	-5.2	8.6	-1.5	-2.7

π–π interactions. Cg1, Cg2 and Cg3 are the centroids of the N1/C2–C6, N7/C8–C12 and C13–C18 rings, respectively. CCD is the distance between ring centroids, SA is the angle subtended by the intercentroid vector to the plane normal (i.e. slippage angle), IPD is the distance from one plane to the neighbouring centroid (mean interplanar distance) top

Group 1/Group 2	CCD (Å)	SA (°)	IPD (Å)
Cg2/Cg2ⁱ	3.708 (2)	18.1	3.5240 (8)
Cg3/Cg3ⁱⁱ	3.537 (2)	19.9	3.3255 (9)
Cg1/Cg3ⁱⁱⁱ	4.076 (1)	29.9	3.2023 (7)
Cg3/Cg1ⁱⁱⁱ	4.076 (1)	38.2	3.5340 (8)
Cg2/Cg2^iv	5.104 (2)	43.8	3.6865 (8)

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

Hydrogen-bond geometry (Å,°) top

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9···O19Aⁱ	0.95	2.62	3.269 (3)	126
C12—H12···O19Aⁱⁱ	0.95	2.66	3.244 (2)	120
C15—H15···N7ⁱⁱⁱ	0.95	2.72	3.530 (3)	144
C6—H6···N1^iv	0.95	2.82	3.470 (3)	126
C3—H3···Cl1^v	0.95	2.95	3.870 (1)	162

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

C—X···X'—C' interactions (Å, °) where X/X' = Br/Cl top

C—X···X'—C'	C—X	X'—C'	X···X'	C—X···X'	X···X'—C'
C5—Br1···(Br2-C11)ⁱ	1.889 (2)	1.886 (2)	3.5473 (3)	108.83 (5)	174.79 (5)
C5—Br1···(Cl1-C8)ⁱⁱ	1.889 (2)	1.746 (2)	3.4730 (5)	162.92 (5)	101.62 (6)

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

C—Cl···O═C' interaction (Å, °) top

C—Cl···O═C'	C—Cl	O═C	Cl···O	C—Cl···O	Cl···O═C
C8-Cl1···(O19A═C19A)ⁱ	1.889 (2)	1.170 (3)	3.033 (2)	169.16 (7)	132.6 (2)

Symmetry code: (i) 1+x, y, -1+z.

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Conformational disorder in 4-(5,5′-di­bromo-2′-chloro-4,4′-bipyridyl-2-yl)benzaldehyde: role of π–π and halogen inter­actions

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Conformational disorder in 4-(5,5′-dibromo-2′-chloro-4,4′-bipyridyl-2-yl)benzaldehyde: role of π–π and halogen interactions