Table 1.

B3LYP/6‐31G(d,p) fully optimized dihedral angles (φ₁ to φ₆ in degrees) and relative energies (ΔE _rel and ΔG _rel, in kcal mol⁻¹) for eight possible distinct configurations of the sugar moieties in the rutin molecule, with the CH₃–C5′′′ group in axial position, located on the PES. There are eight equivalent structures but with the CH₃–C5′′′ group in equatorial position having lower energy than axial forms (2, 6, 12, 16, 18, 22, 24 and 28). In the second part of the Table fully optimized geometries using as input combinations of φ_i's optimized torsion angles from structures 1 to 27 are given. There are three equivalent structures but with the CH₃–C5′′′ group in equatorial position having lower energy than axial forms (30, 32 and 34).

Rutin	Rotating	Optimized dihedral angles [°]						ΔE rel [a,c] [kcal mol−1]		ΔG rel [b]
molecule	dihedral angle [°]	φ1	φ 2	φ 3	φ 4	φ 5	φ 6	Vacuum	PCM (H2O)	PCM (H2O)
Fully optimized geometries using minimum energy input structures from the rigid 1D scan (Figure 1)
1	φ1: M1‐axial	162.3	−80.2	176.3	−169.3	−68.8	−44.3	19.7	17.6	15.9
5 [d]	φ2: M3‐axial	160.4	124.4	134.2	−169.2	−68.9	−43.3	13.5	13	11.6
11 [d]	φ3: M6‐axial	154.6	−97.2	−64.0	−170.0	−68.0	−46.4	14.9	15.8	14.1
15 [e]	φ4: M8‐axial	156.0	−75.5	170.7	68.9	−83.3	−35.7	14.6	15.2	16.7
17 [d]	φ4: M9‐axial	161.7	−79.7	175.0	−72.4	−102.9	−25.4	19.3	15.9	14.5
21 [f]	φ5: M11‐axial	162.2	−80.8	175.3	173.3	157.3	−83.6	14.1	10.8	9.6
23	φ5: M12‐axial	162.8	−81.0	176.1	162.7	−165.9	−59.9	20	16.8	13.9
27 [e]	φ6: M14‐axial	164.5	−85.1	177.1	116.2	−77.8	−156.6	16.4	17.3	15.3
Geometries optimized using input combinations of φ1, φ2, φ3, φ4, φ5 and φ6 from structures 1 to 27
29g	E‐ax (φ5: M11‐eq)	−145.4	106.8	−86.7	−170.0	−100.6	177.4	16.1	14.6	11.9
31g	E‐ax (φ5: M11‐eq)	−174.5	114.2	138.2	−168.7	−98.4	177.9	7.7	6.4	5.4
33g	H‐ax (φ5: M11‐eq)	−171.6	109.1	138.9	−60.9	−125.5	−168.8	0	0	0

[a] The PCM‐water relative energy values are evaluated as single‐point calculations using gas phase optimized geometries. [b] ΔG _rel (kcal mol⁻¹) in PCM‐water are evaluated with gas phase thermal corrections (p=1 atm., T=298.15 K). [c] The corresponding PCM‐DMSO relative energies are very similar to PCM–water values (the same energetic trend). [d] Unique spatial arrangement: 5/6; 11/12; 17/18 (axial and equivalent equatorial forms are separated by slash). [e] Group 2 structures (15/16=19/20; 27/28). [f] Group 1 structures (1/2=3/4=7/8=9/10=13/14=25/26; 21/22; 23/24). [g] Unique structures obtained through re‐optimization combining different dihedral angles: 29/30, 31/32, 33/34.