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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.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270110024261/ku3026sup1.cif
Contains datablocks I, global

hkl

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
C17H9Br2ClN2OZ = 2
Mr = 452.53F(000) = 440
Triclinic, P1Dx = 1.908 Mg m3
Hall symbol: -P 1Melting point: 170 K
a = 7.5759 (2) ÅMo Kα radiation, λ = 0.71069 Å
b = 8.4629 (2) ÅCell parameters from 19163 reflections
c = 13.1534 (2) Åθ = 3.2–37.7°
α = 103.082 (2)°µ = 5.32 mm1
β = 94.473 (2)°T = 110 K
γ = 104.401 (2)°Prism, light yellow
V = 787.52 (3) Å30.22 × 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 Source4767 reflections with I > 2σ(I)
Mirror monochromatorRint = 0.028
Detector resolution: 10.4508 pixels mm-1θmax = 31.7°, θmin = 3.2°
φ and ω scansh = 1111
Absorption correction: analytical
[CrysAlis Pro (Oxford Diffraction, 2009), based on expressions derived by Clark & Reid (1995)]
k = 1212
Tmin = 0.444, Tmax = 0.758l = 1919
35546 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.028Hydrogen site location: difference Fourier map
wR(F2) = 0.073H-atom parameters constrained
S = 1.07 w = 1/[σ2(Fo2) + (0.0371P)2 + 0.6279P]
where P = (Fo2 + 2Fc2)/3
5351 reflections(Δ/σ)max = 0.001
218 parametersΔρmax = 2.08 e Å3
0 restraintsΔρmin = 1.25 e Å3
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
xyzUiso*/UeqOcc. (<1)
Br20.21454 (3)0.40481 (2)0.630746 (15)0.02574 (5)
Br10.46231 (2)0.61723 (2)0.730990 (15)0.02387 (5)
Cl10.35160 (7)0.07488 (6)0.39575 (4)0.02768 (10)
N70.0487 (2)0.1677 (2)0.40743 (13)0.0261 (3)
C100.1154 (2)0.2939 (2)0.62769 (13)0.0183 (3)
C130.0391 (2)0.2168 (2)0.97970 (12)0.0174 (3)
C40.1519 (2)0.3497 (2)0.74460 (13)0.0174 (3)
C160.2482 (3)0.0428 (2)1.10670 (14)0.0226 (3)
C80.1966 (3)0.1631 (2)0.46446 (14)0.0221 (3)
C110.0409 (3)0.3032 (2)0.56814 (14)0.0207 (3)
O19A0.3632 (3)0.0180 (3)1.26193 (15)0.0269 (5)0.740 (5)
C140.0037 (3)0.2754 (2)1.08992 (14)0.0238 (3)
H140.09250.37471.12200.029*
C20.0770 (2)0.3074 (2)0.91377 (13)0.0173 (3)
C90.2390 (3)0.2212 (2)0.57369 (13)0.0205 (3)
H90.34770.21180.61010.025*
C50.3030 (2)0.4799 (2)0.79958 (14)0.0193 (3)
C30.0369 (2)0.2644 (2)0.80388 (13)0.0185 (3)
H30.06960.17640.76940.022*
C170.2832 (3)0.0164 (2)0.99754 (15)0.0242 (3)
H170.37810.11700.96600.029*
N10.2267 (2)0.4316 (2)0.96527 (12)0.0226 (3)
C150.1085 (3)0.1889 (3)1.15240 (14)0.0259 (4)
H150.08430.23001.22700.031*
C180.1811 (3)0.0699 (2)0.93426 (13)0.0213 (3)
H180.20750.02920.85970.026*
C19A0.3621 (3)0.0542 (3)1.17076 (18)0.0324 (5)0.740 (5)
H19A0.44470.15911.13290.039*0.740 (5)
C60.3346 (3)0.5154 (2)0.90908 (15)0.0245 (3)
H60.43900.60430.94550.029*
C120.0700 (3)0.2376 (3)0.45934 (15)0.0260 (4)
H120.17840.24240.42010.031*
O19B0.4572 (8)0.1575 (8)1.1563 (6)0.0346 (17)0.260 (5)
C19B0.3621 (3)0.0542 (3)1.17076 (18)0.0324 (5)0.260 (5)
H19B0.33330.00041.24400.039*0.260 (5)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br20.02583 (9)0.02767 (10)0.02527 (9)0.00982 (7)0.00302 (7)0.00732 (7)
Br10.02309 (9)0.02083 (9)0.02600 (9)0.00072 (6)0.00706 (6)0.00729 (7)
Cl10.0324 (2)0.0258 (2)0.0224 (2)0.00374 (17)0.01280 (17)0.00305 (16)
N70.0324 (8)0.0269 (8)0.0167 (7)0.0027 (6)0.0047 (6)0.0065 (6)
C100.0219 (7)0.0170 (7)0.0145 (7)0.0011 (6)0.0036 (5)0.0053 (5)
C130.0221 (7)0.0197 (7)0.0126 (6)0.0084 (6)0.0036 (5)0.0050 (5)
C40.0201 (7)0.0181 (7)0.0142 (6)0.0047 (6)0.0031 (5)0.0046 (5)
C160.0303 (9)0.0279 (8)0.0185 (7)0.0164 (7)0.0109 (6)0.0117 (6)
C80.0291 (9)0.0183 (7)0.0173 (7)0.0014 (6)0.0090 (6)0.0051 (6)
C110.0242 (8)0.0202 (7)0.0177 (7)0.0043 (6)0.0033 (6)0.0067 (6)
O19A0.0316 (10)0.0352 (11)0.0189 (9)0.0115 (8)0.0112 (7)0.0119 (7)
C140.0334 (9)0.0246 (8)0.0131 (7)0.0080 (7)0.0036 (6)0.0038 (6)
C20.0208 (7)0.0183 (7)0.0131 (6)0.0059 (6)0.0016 (5)0.0043 (5)
C90.0242 (8)0.0204 (7)0.0158 (7)0.0023 (6)0.0051 (6)0.0057 (6)
C50.0193 (7)0.0192 (7)0.0196 (7)0.0033 (6)0.0036 (6)0.0072 (6)
C30.0208 (7)0.0198 (7)0.0130 (6)0.0026 (6)0.0021 (5)0.0036 (5)
C170.0260 (8)0.0269 (8)0.0199 (8)0.0041 (7)0.0062 (6)0.0089 (7)
N10.0253 (7)0.0218 (7)0.0171 (6)0.0011 (6)0.0020 (5)0.0051 (5)
C150.0399 (10)0.0301 (9)0.0129 (7)0.0166 (8)0.0085 (7)0.0063 (6)
C180.0241 (8)0.0255 (8)0.0144 (7)0.0053 (6)0.0036 (6)0.0065 (6)
C19A0.0443 (12)0.0388 (12)0.0309 (10)0.0249 (10)0.0219 (9)0.0216 (9)
C60.0242 (8)0.0234 (8)0.0205 (8)0.0012 (6)0.0035 (6)0.0057 (6)
C120.0292 (9)0.0288 (9)0.0186 (8)0.0038 (7)0.0005 (6)0.0085 (7)
O19B0.028 (3)0.030 (3)0.047 (4)0.000 (2)0.011 (3)0.018 (3)
C19B0.0443 (12)0.0388 (12)0.0309 (10)0.0249 (10)0.0219 (9)0.0216 (9)
Geometric parameters (Å, º) top
Br2—C111.8864 (19)C11—C121.391 (3)
Br1—C51.8886 (17)O19A—C19A1.170 (3)
Cl1—C81.7461 (19)C14—C151.388 (3)
N7—C81.313 (3)C14—H140.9500
N7—C121.342 (3)C2—N11.348 (2)
C10—C111.397 (2)C2—C31.397 (2)
C10—C91.397 (2)C9—H90.9500
C10—C41.485 (2)C5—C61.392 (2)
C13—C181.399 (2)C3—H30.9500
C13—C141.403 (2)C17—C181.386 (2)
C13—C21.483 (2)C17—H170.9500
C4—C51.390 (2)N1—C61.326 (2)
C4—C31.391 (2)C15—H150.9500
C16—C151.387 (3)C18—H180.9500
C16—C171.390 (3)C19A—H19A0.9500
C16—C19A1.484 (3)C6—H60.9500
C8—C91.392 (2)C12—H120.9500
C8—N7—C12116.76 (16)C10—C9—H9121.3
C11—C10—C9117.62 (16)C4—C5—C6119.23 (16)
C11—C10—C4123.55 (16)C4—C5—Br1122.13 (13)
C9—C10—C4118.77 (15)C6—C5—Br1118.59 (13)
C18—C13—C14118.85 (16)C4—C3—C2120.43 (16)
C18—C13—C2121.24 (14)C4—C3—H3119.8
C14—C13—C2119.89 (16)C2—C3—H3119.8
C5—C4—C3117.14 (15)C18—C17—C16120.63 (18)
C5—C4—C10123.03 (15)C18—C17—H17119.7
C3—C4—C10119.75 (15)C16—C17—H17119.7
C15—C16—C17119.49 (17)C6—N1—C2118.30 (16)
C15—C16—C19A122.10 (18)C16—C15—C14120.45 (17)
C17—C16—C19A118.41 (19)C16—C15—H15119.8
N7—C8—C9125.78 (18)C14—C15—H15119.8
N7—C8—Cl1116.29 (14)C17—C18—C13120.27 (16)
C9—C8—Cl1117.93 (15)C17—C18—H18119.9
C12—C11—C10119.61 (17)C13—C18—H18119.9
C12—C11—Br2118.48 (14)O19A—C19A—C16128.3 (3)
C10—C11—Br2121.90 (13)O19A—C19A—H19A115.9
C15—C14—C13120.31 (18)C16—C19A—H19A115.9
C15—C14—H14119.8N1—C6—C5123.49 (16)
C13—C14—H14119.8N1—C6—H6118.3
N1—C2—C3121.39 (16)C5—C6—H6118.3
N1—C2—C13116.43 (15)N7—C12—C11122.76 (18)
C3—C2—C13122.17 (15)N7—C12—H12118.6
C8—C9—C10117.43 (17)C11—C12—H12118.6
C8—C9—H9121.3
C11—C10—C4—C5117.6 (2)C10—C4—C5—Br17.6 (2)
C9—C10—C4—C565.3 (2)C5—C4—C3—C21.5 (3)
C11—C10—C4—C365.7 (2)C10—C4—C3—C2175.32 (16)
C9—C10—C4—C3111.39 (19)N1—C2—C3—C40.0 (3)
C12—N7—C8—C91.3 (3)C13—C2—C3—C4178.32 (16)
C12—N7—C8—Cl1179.03 (14)C15—C16—C17—C180.6 (3)
C9—C10—C11—C121.4 (3)C19B—C16—C17—C18179.83 (18)
C4—C10—C11—C12175.67 (17)C3—C2—N1—C61.3 (3)
C9—C10—C11—Br2177.95 (12)C13—C2—N1—C6179.75 (16)
C4—C10—C11—Br24.9 (2)C17—C16—C15—C140.2 (3)
C18—C13—C14—C150.2 (3)C19B—C16—C15—C14179.37 (18)
C2—C13—C14—C15178.30 (17)C13—C14—C15—C160.6 (3)
C18—C13—C2—N1170.15 (17)C16—C17—C18—C131.0 (3)
C14—C13—C2—N17.9 (2)C14—C13—C18—C170.6 (3)
C18—C13—C2—C38.3 (3)C2—C13—C18—C17177.49 (17)
C14—C13—C2—C3173.66 (17)C15—C16—C19A—O19A7.0 (3)
N7—C8—C9—C101.3 (3)C17—C16—C19A—O19A173.5 (2)
Cl1—C8—C9—C10179.02 (13)C2—N1—C6—C51.1 (3)
C11—C10—C9—C80.2 (2)C4—C5—C6—N10.4 (3)
C4—C10—C9—C8177.10 (15)Br1—C5—C6—N1177.02 (15)
C3—C4—C5—C61.7 (3)C8—N7—C12—C110.2 (3)
C10—C4—C5—C6175.03 (17)C10—C11—C12—N71.5 (3)
C3—C4—C5—Br1175.63 (13)Br2—C11—C12—N7177.89 (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
NumberdSymmetryCoul.Pol.Disp.Rep.Tot. ATot. B
17.358-x,-y,1-z-21-8.1-53.336.3-46.2-45.9
29.136-x,-y,2-z-23.2-8.6-64.556.8-39.5-31.6
36.785-x,1-y,2-z-12-4.1-66.943.6-39.5-40.1
48.191-x,1-y,1-z-4-1.3-28.313.3-20.3-20.6
512.021-1-x,-y,2-z-7.7-2.6-22.715-18-13.7
68.2391-x,1-y,2-z-6-2.1-20.312-16.4-16.3
713.153x,y,-1+z-8.3-3.7-13.311.9-13.5-9.1
813.153x,y,1+z-8.3-3.7-13.311.9-13.5-9.1
97.576-1+x,y,z-5.7-2.2-19.216.5-10.6-11.4
107.5761+x,y,z-5.7-2.2-19.216.5-10.6-11.4
1110.2221-x,1-y,1-z-9.4-3.8-18.522.4-9.2-9
129.855-1+x,-1+y,z0.3-2.8-149.7-6.9-8.3
139.8551+x,1+y,z0.3-2.8-149.7-6.9-8.3
1411.111-x,-y,1-z-0.6-0.3-6.11.7-5.3-5.4
158.463x,-1+y,z0.6-0.1-2.30-1.9-2.2
168.463x,1+y,z0.6-0.1-2.30-1.9-2.2
1715.683-1+x,y,1+z-3.4-1.5-5.28.6-1.5-2.7
1815.6831+x,y,-1+z-3.4-1.5-5.28.6-1.5-2.7
ππ 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 2CCD (Å)SA (°)IPD (Å)
Cg2/Cg2i3.708 (2)18.13.5240 (8)
Cg3/Cg3ii3.537 (2)19.93.3255 (9)
Cg1/Cg3iii4.076 (1)29.93.2023 (7)
Cg3/Cg1iii4.076 (1)38.23.5340 (8)
Cg2/Cg2iv5.104 (2)43.83.6865 (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···AD—HH···AD···AD—H···A
C9—H9···O19Ai0.952.623.269 (3)126
C12—H12···O19Aii0.952.663.244 (2)120
C15—H15···N7iii0.952.723.530 (3)144
C6—H6···N1iv0.952.823.470 (3)126
C3—H3···Cl1v0.952.953.870 (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—XX'—C'X···X'C—X···X'X···X'—C'
C5—Br1···(Br2-C11)i1.889 (2)1.886 (2)3.5473 (3)108.83 (5)174.79 (5)
C5—Br1···(Cl1-C8)ii1.889 (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···OC' interaction (Å, °) top
C—Cl···OC'C—ClOCCl···OC—Cl···OCl···OC
C8-Cl1···(O19AC19A)i1.889 (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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