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The formation of a photoreactive cocrystal based upon 1,2-di­iodo­perchloro­benzene (1,2-C6I2Cl4) and trans-1,2-bis­(pyridin-4-yl)ethyl­ene (BPE) has been achieved. The resulting cocrystal, 2(1,2-C6I2Cl4)·(BPE) or C6Cl4I2·0.5C12H10N2, com­prises planar sheets of the com­ponents held together by the combination of I...N halogen bonds and halogen–halogen contacts. Notably, the 1,2-C6I2Cl4 mol­ecules π-stack in a homogeneous and face-to-face orientation that results in an infinite column of the halogen-bond donor. As a consequence of this stacking arrangement and I...N halogen bonds, mol­ecules of BPE also stack in this type of pattern. In particular, neighbouring ethyl­ene groups in BPE are found to be parallel and within the accepted distance for a photoreaction. Upon exposure to ultraviolet light, the cocrystal undergoes a solid-state [2 + 2] cyclo­addition reaction that produces rctt-tetra­kis­(pyridin-4-yl)cyclo­butane (TPCB) with an overall yield of 89%. A solvent-free approach utilizing dry vortex grinding of the com­ponents also resulted in a photoreactive material with a similar yield.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229620006233/ov3139sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2053229620006233/ov3139Isup2.hkl
Contains datablock I

CCDC reference: 1947990

Computing details top

Data collection: APEX2 (Bruker, 2016); cell refinement: SAINT (Bruker, 2016); data reduction: SAINT (Bruker, 2016); program(s) used to solve structure: SHELXT2018 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015b); molecular graphics: SHELXTL (Bruker, 2016) and X-SEED (Barbour, 2001); software used to prepare material for publication: SHELXTL (Bruker, 2016).

1,2-Diiodo-3,4,5,6-chlorobenzene–trans-1,2-bis(pyridin-4-yl)ethylene (2/1) top
Crystal data top
C6Cl4I2·0.5C12H10N2Z = 2
Mr = 558.77F(000) = 516
Triclinic, P1Dx = 2.419 Mg m3
a = 4.1177 (13) ÅMo Kα radiation, λ = 0.71073 Å
b = 13.502 (4) ÅCell parameters from 5904 reflections
c = 14.151 (4) Åθ = 2.3–27.5°
α = 78.864 (12)°µ = 4.78 mm1
β = 83.719 (12)°T = 290 K
γ = 87.935 (12)°Rod, yellow
V = 767.2 (4) Å30.15 × 0.08 × 0.05 mm
Data collection top
Bruker SMART APEX CCD area detector
diffractometer
3508 independent reflections
Radiation source: sealed tube2928 reflections with I > 2σ(I)
Detector resolution: 8 pixels mm-1Rint = 0.031
ω and φ scansθmax = 27.5°, θmin = 2.3°
Absorption correction: multi-scan
(SADABS; Bruker, 2016)
h = 55
Tmin = 0.783, Tmax = 1.000k = 1717
11912 measured reflectionsl = 1818
Refinement top
Refinement on F24 restraints
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.029H-atom parameters constrained
wR(F2) = 0.065 w = 1/[σ2(Fo2) + (0.0213P)2 + 0.601P]
where P = (Fo2 + 2Fc2)/3
S = 1.11(Δ/σ)max = 0.002
3508 reflectionsΔρmax = 0.72 e Å3
191 parametersΔρmin = 0.58 e Å3
Special details top

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 2(1,2-C6I2Cl4).(BPE) was mounted on a MiTeGen cryoloop in a random orientation for X-ray data collection. A Bruker Venture Duo Photon-II single-crystal X-ray diffractometer equipped with an Oxford Cryostream device was used for the data collection. APEXII and SAINT software packages (Bruker, 2016) were used for data collection and integration, respectively. The data were corrected for systematic errors using SADABS based on the Laue symmetry using equivalent reflections. The structure was solved by dual space methods using SHELXT-2018 (Sheldrick, 2015a) and refined against F2 using SHELXL-2018 (Sheldrick, 2015b). The program X-Seed was used as a graphical interface (Barbour, 2001).

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
I10.24195 (6)0.26852 (2)0.51627 (2)0.04165 (9)
Cl10.5409 (3)0.54003 (8)0.15189 (8)0.0619 (3)
Cl20.9278 (3)0.37431 (9)0.06306 (7)0.0645 (3)
I20.2089 (4)0.51541 (16)0.37413 (14)0.0477 (2)0.5895 (13)
Cl30.9897 (3)0.15892 (8)0.18345 (8)0.0581 (3)
Cl40.658 (2)0.1062 (4)0.3924 (6)0.0592 (14)0.5895 (13)
N10.0686 (8)0.2054 (2)0.7094 (2)0.0477 (8)
C70.4609 (8)0.3024 (2)0.3720 (2)0.0333 (7)
C80.4379 (8)0.3997 (2)0.3175 (2)0.0347 (7)
C120.6292 (8)0.2279 (2)0.3300 (2)0.0358 (7)
C110.7737 (8)0.2506 (3)0.2351 (3)0.0385 (8)
C90.5790 (9)0.4211 (3)0.2214 (3)0.0403 (8)
C100.7492 (9)0.3466 (3)0.1810 (3)0.0416 (8)
C20.2387 (9)0.1216 (3)0.7194 (3)0.0457 (9)
H20.2756180.0987700.6636010.055*
C10.3637 (9)0.0665 (3)0.8074 (3)0.0415 (8)
H10.4846200.0089610.8102710.050*
C40.1303 (10)0.1856 (3)0.8812 (3)0.0484 (9)
H40.0876020.2104420.9353760.058*
C50.3065 (9)0.0981 (3)0.8920 (3)0.0400 (8)
C30.0176 (10)0.2361 (3)0.7893 (3)0.0510 (10)
H30.1003200.2947300.7837420.061*
C60.4232 (9)0.0435 (3)0.9892 (3)0.0450 (9)
H60.3849530.0731431.0409950.054*
Cl4A0.244 (3)0.4982 (9)0.3684 (9)0.075 (3)0.4105 (13)
I2A0.6649 (7)0.08069 (16)0.4059 (2)0.0485 (4)0.4105 (13)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
I10.04061 (14)0.05105 (15)0.03022 (13)0.00472 (10)0.00041 (9)0.00170 (10)
Cl10.0889 (8)0.0433 (5)0.0455 (6)0.0013 (5)0.0026 (5)0.0088 (4)
Cl20.0877 (8)0.0682 (7)0.0331 (5)0.0121 (6)0.0149 (5)0.0081 (5)
I20.0535 (5)0.0474 (5)0.0425 (4)0.0125 (5)0.0025 (4)0.0128 (3)
Cl30.0621 (6)0.0582 (6)0.0582 (6)0.0053 (5)0.0033 (5)0.0277 (5)
Cl40.0847 (19)0.029 (2)0.057 (2)0.0114 (19)0.0050 (15)0.0052 (17)
N10.0558 (19)0.0425 (17)0.0384 (18)0.0010 (14)0.0027 (15)0.0038 (14)
C70.0318 (16)0.0427 (18)0.0249 (16)0.0064 (13)0.0022 (13)0.0046 (13)
C80.0361 (17)0.0366 (17)0.0329 (18)0.0028 (13)0.0070 (14)0.0082 (14)
C120.0363 (17)0.0356 (17)0.0349 (18)0.0038 (13)0.0067 (14)0.0033 (14)
C110.0363 (18)0.0428 (19)0.039 (2)0.0047 (14)0.0026 (15)0.0153 (15)
C90.047 (2)0.0399 (19)0.0316 (18)0.0083 (15)0.0061 (16)0.0005 (14)
C100.044 (2)0.049 (2)0.0317 (19)0.0094 (16)0.0006 (16)0.0082 (16)
C20.059 (2)0.050 (2)0.0276 (18)0.0062 (18)0.0047 (17)0.0057 (15)
C10.048 (2)0.0381 (18)0.036 (2)0.0018 (15)0.0018 (16)0.0031 (15)
C40.065 (2)0.045 (2)0.036 (2)0.0046 (18)0.0043 (18)0.0091 (16)
C50.0452 (19)0.0411 (19)0.0314 (18)0.0047 (15)0.0022 (15)0.0034 (15)
C30.062 (3)0.041 (2)0.047 (2)0.0095 (18)0.002 (2)0.0026 (17)
C60.056 (2)0.046 (2)0.0309 (19)0.0017 (16)0.0017 (17)0.0039 (16)
Cl4A0.083 (4)0.070 (5)0.061 (4)0.035 (3)0.015 (2)0.007 (3)
I2A0.0628 (6)0.0329 (10)0.0472 (8)0.0021 (7)0.0074 (5)0.0007 (7)
Geometric parameters (Å, º) top
I1—C72.110 (3)C11—C101.378 (5)
Cl1—C91.726 (4)C9—C101.384 (5)
Cl2—C101.725 (4)C2—C11.379 (5)
I2—C82.046 (4)C2—H20.9300
Cl3—C111.728 (4)C1—C51.391 (5)
Cl4—C121.716 (6)C1—H10.9300
N1—C31.316 (5)C4—C51.383 (5)
N1—C21.328 (5)C4—C31.385 (5)
C7—C121.392 (5)C4—H40.9300
C7—C81.395 (5)C5—C61.469 (5)
C8—C91.398 (5)C3—H30.9300
C8—Cl4A1.758 (11)C6—C6i1.320 (7)
C12—C111.390 (5)C6—H60.9300
C12—I2A2.077 (4)
C3—N1—C2117.0 (3)C11—C10—Cl2120.5 (3)
C12—C7—C8119.1 (3)C9—C10—Cl2119.8 (3)
C12—C7—I1120.5 (2)N1—C2—C1123.9 (4)
C8—C7—I1120.4 (2)N1—C2—H2118.0
C7—C8—C9120.0 (3)C1—C2—H2118.0
C7—C8—Cl4A121.1 (5)C2—C1—C5119.1 (3)
C9—C8—Cl4A118.8 (5)C2—C1—H1120.4
C7—C8—I2122.1 (3)C5—C1—H1120.4
C9—C8—I2117.9 (3)C5—C4—C3119.7 (4)
C11—C12—C7120.2 (3)C5—C4—H4120.1
C11—C12—Cl4118.4 (4)C3—C4—H4120.1
C7—C12—Cl4121.3 (4)C4—C5—C1116.7 (3)
C11—C12—I2A118.5 (3)C4—C5—C6120.1 (3)
C7—C12—I2A121.2 (3)C1—C5—C6123.3 (3)
C10—C11—C12120.6 (3)N1—C3—C4123.5 (4)
C10—C11—Cl3119.0 (3)N1—C3—H3118.3
C12—C11—Cl3120.3 (3)C4—C3—H3118.3
C10—C9—C8120.2 (3)C6i—C6—C5126.7 (5)
C10—C9—Cl1119.3 (3)C6i—C6—H6116.6
C8—C9—Cl1120.5 (3)C5—C6—H6116.6
C11—C10—C9119.7 (3)
Symmetry code: (i) x1, y, z+2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C2—H2···I2Aii0.933.314.072 (5)141
Symmetry code: (ii) x, y, z+1.
 

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