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
CCDC reference: 786830
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 |
Mr = 452.53 | F(000) = 440 |
Triclinic, P1 | Dx = 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 | Rint = 0.028 |
Detector resolution: 10.4508 pixels mm-1 | θmax = 31.7°, θmin = 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 |
Tmin = 0.444, Tmax = 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(Fo2) + (0.0371P)2 + 0.6279P] where P = (Fo2 + 2Fc2)/3 |
5351 reflections | (Δ/σ)max = 0.001 |
218 parameters | Δρmax = 2.08 e Å−3 |
0 restraints | Δρmin = −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 | Uiso*/Ueq | 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. topNumber | 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) topGroup 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/Cg2iv | 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,°) topD—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···N1iv | 0.95 | 2.82 | 3.470 (3) | 126 |
C3—H3···Cl1v | 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 topC—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, °) topC—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. |