Development of a scalar-based geometric parameterization approach for the crystal structure landscape of dithienylethene-based crystalline solids

The crystal structure landscape of (Z)-1,2-bis[2-methyl-5-(pyridin-4-yl)thiophen-3-yl]-1,2-diphenylethene (DTE) was determined using a combination of computational and experimental molecular geometries. A novel D–D analysis was developed which provides a rapid, effective and intuitive means of visualizing the crystal landscape and assessing the conformer type present in and photoactivity of the resulting crystalline solids.


S3.1. Synchrotron Source Data Collection
A single crystal suitable for X-ray diffraction was mounted on the tip of a glass fibre with oil and placed on a Huber three-circle diffractometer at the National Science Foundation's (NSF) ChemMatCARS beamline 15ID-D at Argonne National Laboratory (λ = 0.41328 Å).Using a Dectris IUCrJ (2023).10, https://doi.org/10.1107/S2052252523008060Supporting information, sup-8 Pilatus3X 1M (CdTe) shutterless detector at 130 mm from the crystal, frames were collected with ω = -180° and a 2θ-angle of 0°.During the data collection, the crystal was cooled to 100 K using an Oxford cryojet nitrogen-gas flow apparatus.A total of 1440 frames were collected during two 360° φscans (0.5° image width) at κ = 45° and κ = 30°, nominally covering complete reciprocal space.Dectris frames (.cbf) were converted to Bruker format (.sfrm) using custom software developed by NSF's ChemMatCARS.Following frame conversion, indexing was performed using the Bruker APEX3 software suite.(Bruker,2013)

S3.2. Home Source Data Collection
A single crystal suitable for X-ray diffraction was mounted on the tip of a glass fibre with oil and placed on a Bruker SMART APEX II CCD diffractometer installed at a rotating anode source (Mo-Kα radiation, λ = 0.71073 Å) with a detector distance of 40.00 mm from the crystal and a 2θ-angle of -30°.During the data collection, the crystal was cooled to 90(1) K using an Oxford cryostream nitrogen gas-flow apparatus.A total of 1800 frames were collected using five 180° ω-scans (0.5° scan width) at different φ-angles (φ = 0° to 288° in 72° increments), nominally covering complete reciprocal space.

S3.3. Data Reduction and Analysis
Data reduction was completed using SAINT version 8.40A, and a multi-scan absorption correction was applied using SADABS version 2016 included in the Bruker APEX3 software suite.Space-group determination was performed using the XPREP utility included in the SHELXTL software package.(Sheldrick,2008) Using Olex2, (Dolomanov et al., 2009) the structure was solved with ShelXT(Sheldrick, 2015a) using intrinsic phasing and refined with ShelXL(Sheldrick, 2015b) using least squares minimization (full-matrix least-squares on F 2 ).Hydrogen atoms bonded to oxygen and nitrogen atoms were located in the Fourier difference map.Their distances were restrained using the DFIX command with the recommended O-H distance of 0.84 Å and N-H distance of 0.88 Å found in the .lstfile with UISO(H) = 1.2Ueq (O or N).(Müller et al., 2006)

Figure S3
Figure S3 Difference in planarity of Pyridyl 1 and Pyridyl 2 for DTE-P4 in each scan direction (positive, blue; negative, green).

Table S1
Selected geometric parameters for each crystallographically unique DTE.

Table S2
Relative energy (ΔE) and selected structural parameters for BMeDTS.

Table S12
Crystal data and structure refinement for DTE-[19].