A second polymorph of phenylselenium trichloride, PhSeCl
3 or C
6H
5Cl
3Se, is disclosed, which is comprised of asymmetric chlorine-bridged noncovalent dimer units rather than polymeric chains. These dimers are each weakly bound to an adjacent dimer through noncovalent Se
Cl bonding interactions. Phenyl rings within each dimer are oriented in a
syn fashion. Density functional theory (DFT) calculations reveal that the putative
anti isomer is within 5 kJ mol
−1 of the experimentally observed form. This structure represents the first additional polymorph discovered for an organoselenium trihalide compound.
Supporting information
CCDC reference: 1954913
Data collection: APEX3 (Bruker, 2016; cell refinement: SAINT (Bruker, 2016); data reduction: SAINT (Bruker, 2016; program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).
Phenylselenium trichloride
top
Crystal data top
C6H5Cl3Se | Z = 4 |
Mr = 262.41 | F(000) = 504 |
Triclinic, P1 | Dx = 2.037 Mg m−3 |
a = 8.6245 (3) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 9.5342 (4) Å | Cell parameters from 8248 reflections |
c = 11.7229 (5) Å | θ = 2.6–32.6° |
α = 78.332 (2)° | µ = 5.24 mm−1 |
β = 77.789 (2)° | T = 150 K |
γ = 66.341 (2)° | Prism, clear colourless |
V = 855.50 (6) Å3 | 0.53 × 0.52 × 0.35 mm |
Data collection top
Bruker APEXII CCD diffractometer | 3470 reflections with I > 2σ(I) |
φ and ω scans | Rint = 0.037 |
Absorption correction: numerical (SADABS; Bruker, 2016) | θmax = 28.7°, θmin = 2.6° |
Tmin = 0.456, Tmax = 0.747 | h = −11→11 |
15455 measured reflections | k = −12→12 |
4426 independent reflections | l = −15→15 |
Refinement top
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.029 | w = 1/[σ2(Fo2) + (0.0095P)2 + 0.5686P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.051 | (Δ/σ)max = 0.001 |
S = 1.05 | Δρmax = 0.46 e Å−3 |
4426 reflections | Δρmin = −0.57 e Å−3 |
182 parameters | Extinction correction: SHELXL2018 (Sheldrick, 2015b), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction coefficient: 0.0114 (3) |
Primary atom site location: dual | |
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Se1 | 0.46873 (3) | 0.37174 (3) | 0.37701 (2) | 0.01526 (7) | |
Se2 | 0.33135 (3) | 0.82730 (3) | 0.29123 (2) | 0.01719 (7) | |
Cl4 | 0.23956 (8) | 0.64558 (7) | 0.46326 (5) | 0.02005 (13) | |
Cl1 | 0.57258 (8) | 0.55087 (8) | 0.21325 (5) | 0.02304 (14) | |
Cl3 | 0.37555 (9) | 0.22740 (8) | 0.53285 (6) | 0.02807 (16) | |
Cl2 | 0.67527 (8) | 0.17097 (8) | 0.30719 (6) | 0.02984 (16) | |
Cl5 | 0.15514 (9) | 1.02879 (8) | 0.37443 (6) | 0.03339 (17) | |
Cl6 | 0.44520 (9) | 0.96373 (8) | 0.14372 (6) | 0.03359 (17) | |
C1 | 0.3008 (3) | 0.3840 (3) | 0.2832 (2) | 0.0155 (5) | |
C7 | 0.1696 (3) | 0.8222 (3) | 0.1993 (2) | 0.0170 (5) | |
C8 | 0.0049 (3) | 0.8412 (3) | 0.2539 (2) | 0.0199 (5) | |
H8 | −0.029076 | 0.855370 | 0.334641 | 0.024* | |
C2 | 0.1329 (3) | 0.4140 (3) | 0.3366 (2) | 0.0185 (5) | |
H2 | 0.100984 | 0.424952 | 0.417965 | 0.022* | |
C6 | 0.3511 (3) | 0.3669 (3) | 0.1649 (2) | 0.0213 (5) | |
H6 | 0.466331 | 0.347356 | 0.129613 | 0.026* | |
C9 | −0.1095 (3) | 0.8390 (3) | 0.1870 (2) | 0.0235 (6) | |
H9 | −0.223387 | 0.852156 | 0.222208 | 0.028* | |
C4 | 0.0613 (3) | 0.4096 (3) | 0.1506 (2) | 0.0218 (6) | |
H4 | −0.021439 | 0.418381 | 0.104667 | 0.026* | |
C3 | 0.0130 (3) | 0.4276 (3) | 0.2690 (2) | 0.0215 (6) | |
H3 | −0.102844 | 0.449365 | 0.303758 | 0.026* | |
C12 | 0.2236 (3) | 0.7984 (3) | 0.0828 (2) | 0.0229 (6) | |
H12 | 0.337873 | 0.784085 | 0.047616 | 0.027* | |
C10 | −0.0587 (3) | 0.8180 (3) | 0.0700 (2) | 0.0253 (6) | |
H10 | −0.138341 | 0.818728 | 0.024752 | 0.030* | |
C5 | 0.2290 (3) | 0.3791 (3) | 0.0991 (2) | 0.0248 (6) | |
H5 | 0.261162 | 0.366247 | 0.018056 | 0.030* | |
C11 | 0.1075 (4) | 0.7958 (3) | 0.0183 (2) | 0.0281 (6) | |
H11 | 0.142480 | 0.778644 | −0.061869 | 0.034* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Se1 | 0.01433 (13) | 0.01787 (13) | 0.01336 (13) | −0.00551 (10) | −0.00342 (10) | −0.00121 (10) |
Se2 | 0.01727 (13) | 0.01849 (14) | 0.01750 (14) | −0.00836 (11) | −0.00562 (10) | 0.00074 (10) |
Cl4 | 0.0202 (3) | 0.0267 (3) | 0.0139 (3) | −0.0100 (3) | −0.0013 (2) | −0.0028 (2) |
Cl1 | 0.0160 (3) | 0.0320 (4) | 0.0201 (3) | −0.0105 (3) | 0.0004 (2) | −0.0012 (3) |
Cl3 | 0.0340 (4) | 0.0354 (4) | 0.0197 (3) | −0.0209 (3) | −0.0104 (3) | 0.0092 (3) |
Cl2 | 0.0234 (3) | 0.0235 (3) | 0.0337 (4) | 0.0028 (3) | −0.0049 (3) | −0.0083 (3) |
Cl5 | 0.0405 (4) | 0.0216 (3) | 0.0387 (4) | −0.0062 (3) | −0.0105 (3) | −0.0118 (3) |
Cl6 | 0.0313 (4) | 0.0375 (4) | 0.0365 (4) | −0.0235 (3) | −0.0116 (3) | 0.0146 (3) |
C1 | 0.0184 (12) | 0.0160 (12) | 0.0148 (12) | −0.0078 (10) | −0.0057 (10) | −0.0016 (10) |
C7 | 0.0180 (12) | 0.0139 (12) | 0.0189 (13) | −0.0043 (10) | −0.0083 (10) | 0.0002 (10) |
C8 | 0.0166 (12) | 0.0199 (13) | 0.0199 (13) | −0.0030 (10) | −0.0034 (10) | −0.0028 (11) |
C2 | 0.0199 (13) | 0.0221 (13) | 0.0132 (12) | −0.0075 (11) | −0.0009 (10) | −0.0041 (10) |
C6 | 0.0192 (13) | 0.0285 (14) | 0.0160 (13) | −0.0094 (11) | 0.0012 (10) | −0.0056 (11) |
C9 | 0.0156 (13) | 0.0227 (14) | 0.0313 (15) | −0.0049 (11) | −0.0084 (11) | −0.0011 (12) |
C4 | 0.0279 (15) | 0.0236 (14) | 0.0198 (13) | −0.0138 (12) | −0.0111 (11) | 0.0012 (11) |
C3 | 0.0182 (13) | 0.0258 (14) | 0.0223 (14) | −0.0105 (11) | −0.0036 (11) | −0.0018 (11) |
C12 | 0.0192 (13) | 0.0277 (14) | 0.0203 (13) | −0.0070 (11) | −0.0022 (11) | −0.0046 (11) |
C10 | 0.0280 (14) | 0.0209 (14) | 0.0310 (15) | −0.0082 (12) | −0.0154 (12) | −0.0026 (12) |
C5 | 0.0301 (15) | 0.0333 (16) | 0.0150 (13) | −0.0154 (13) | −0.0019 (11) | −0.0062 (11) |
C11 | 0.0339 (16) | 0.0312 (16) | 0.0195 (14) | −0.0100 (13) | −0.0074 (12) | −0.0052 (12) |
Geometric parameters (Å, º) top
Se1—Cl4i | 3.3760 (6) | C8—C9 | 1.393 (3) |
Se1—Cl4 | 2.7975 (7) | C2—H2 | 0.9500 |
Se1—Cl1 | 2.5648 (7) | C2—C3 | 1.382 (3) |
Se1—Cl3 | 2.2643 (7) | C6—H6 | 0.9500 |
Se1—Cl2 | 2.1881 (7) | C6—C5 | 1.388 (3) |
Se1—C1 | 1.951 (2) | C9—H9 | 0.9500 |
Se2—Cl4 | 2.5900 (6) | C9—C10 | 1.378 (4) |
Se2—Cl1 | 2.8070 (7) | C4—H4 | 0.9500 |
Se2—Cl3i | 3.4099 (7) | C4—C3 | 1.388 (3) |
Se2—Cl5 | 2.1769 (7) | C4—C5 | 1.380 (4) |
Se2—Cl6 | 2.2458 (7) | C3—H3 | 0.9500 |
Se2—C7 | 1.955 (2) | C12—H12 | 0.9500 |
C1—C2 | 1.389 (3) | C12—C11 | 1.387 (3) |
C1—C6 | 1.385 (3) | C10—H10 | 0.9500 |
C7—C8 | 1.384 (3) | C10—C11 | 1.381 (4) |
C7—C12 | 1.380 (3) | C5—H5 | 0.9500 |
C8—H8 | 0.9500 | C11—H11 | 0.9500 |
| | | |
Cl4—Se1—Cl4i | 90.204 (17) | C6—C1—C2 | 121.9 (2) |
Cl1—Se1—Cl4 | 84.71 (2) | C8—C7—Se2 | 118.66 (18) |
Cl1—Se1—Cl4i | 89.433 (18) | C12—C7—Se2 | 119.06 (18) |
Cl3—Se1—Cl4i | 87.29 (2) | C12—C7—C8 | 122.3 (2) |
Cl3—Se1—Cl4 | 91.45 (2) | C7—C8—H8 | 121.0 |
Cl3—Se1—Cl1 | 174.95 (2) | C7—C8—C9 | 118.0 (2) |
Cl2—Se1—Cl4i | 83.89 (2) | C9—C8—H8 | 121.0 |
Cl2—Se1—Cl4 | 172.03 (2) | C1—C2—H2 | 120.7 |
Cl2—Se1—Cl1 | 89.87 (3) | C3—C2—C1 | 118.7 (2) |
Cl2—Se1—Cl3 | 93.60 (3) | C3—C2—H2 | 120.7 |
C1—Se1—Cl4 | 89.59 (7) | C1—C6—H6 | 120.8 |
C1—Se1—Cl4i | 179.21 (7) | C1—C6—C5 | 118.4 (2) |
C1—Se1—Cl1 | 89.78 (7) | C5—C6—H6 | 120.8 |
C1—Se1—Cl3 | 93.48 (7) | C8—C9—H9 | 119.7 |
C1—Se1—Cl2 | 96.25 (7) | C10—C9—C8 | 120.5 (2) |
Cl4—Se2—Cl1 | 84.06 (2) | C10—C9—H9 | 119.7 |
Cl4—Se2—Cl3i | 81.751 (18) | C3—C4—H4 | 119.8 |
Cl1—Se2—Cl3i | 83.668 (19) | C5—C4—H4 | 119.8 |
Cl5—Se2—Cl4 | 90.83 (3) | C5—C4—C3 | 120.3 (2) |
Cl5—Se2—Cl1 | 172.41 (3) | C2—C3—C4 | 120.2 (2) |
Cl5—Se2—Cl3i | 90.06 (2) | C2—C3—H3 | 119.9 |
Cl5—Se2—Cl6 | 94.38 (3) | C4—C3—H3 | 119.9 |
Cl6—Se2—Cl4 | 172.72 (3) | C7—C12—H12 | 120.7 |
Cl6—Se2—Cl1 | 90.24 (3) | C7—C12—C11 | 118.6 (2) |
Cl6—Se2—Cl3i | 93.14 (2) | C11—C12—H12 | 120.7 |
C7—Se2—Cl4 | 90.64 (7) | C9—C10—H10 | 119.8 |
C7—Se2—Cl1 | 89.74 (7) | C9—C10—C11 | 120.3 (2) |
C7—Se2—Cl3i | 170.39 (7) | C11—C10—H10 | 119.8 |
C7—Se2—Cl5 | 95.94 (7) | C6—C5—H5 | 119.8 |
C7—Se2—Cl6 | 93.87 (7) | C4—C5—C6 | 120.5 (2) |
Se2—Cl4—Se1 | 95.36 (2) | C4—C5—H5 | 119.8 |
Se1—Cl1—Se2 | 95.70 (2) | C12—C11—H11 | 119.9 |
C2—C1—Se1 | 118.78 (17) | C10—C11—C12 | 120.3 (2) |
C6—C1—Se1 | 119.29 (18) | C10—C11—H11 | 119.9 |
Symmetry code: (i) −x+1, −y+1, −z+1. |