Pentacarbonyl{tris[4-(methylsulfonyl)phenyl]stannyl}manganese(I): an unexpected tetragonal structure
Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270102004377/fg1638sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270102004377/fg1638Isup2.hkl |
CCDC reference: 187911
Compound (I) was prepared earlier by Christendat et al. (2002). Suitable crystals were obtained by slow evaporation of a CH2Cl2/benzene solution of (I).
Data collection: SMART (Bruker, 1999); cell refinement: SMART; data reduction: SHELXTL (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
[MnSn(C7H7O2S)3(CO)5] | Dx = 1.720 Mg m−3 |
Mr = 779.24 | Cu Kα radiation, λ = 1.54178 Å |
Tetragonal, I4 | Cell parameters from 28577 reflections |
a = 22.4188 (1) Å | θ = 2.7–73.3° |
c = 11.9764 (1) Å | µ = 12.47 mm−1 |
V = 6019.37 (6) Å3 | T = 279 K |
Z = 8 | Needle, colourless |
F(000) = 3104 | 0.70 × 0.08 × 0.05 mm |
Bruker SMART 2K/Platform diffractometer | 5976 independent reflections |
Radiation source: normal-focus sealed tube | 5643 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.072 |
Detector resolution: 5.5 pixels mm-1 | θmax = 73.3°, θmin = 2.8° |
ω scans | h = −27→27 |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | k = −27→27 |
Tmin = 0.037, Tmax = 0.536 | l = −14→13 |
34825 measured reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.033 | H-atom parameters constrained |
wR(F2) = 0.082 | w = 1/[σ2(Fo2) + (0.0544P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.99 | (Δ/σ)max = 0.002 |
5976 reflections | Δρmax = 0.69 e Å−3 |
382 parameters | Δρmin = −0.37 e Å−3 |
0 restraints | Absolute structure: Flack (1983), 2802 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.009 (5) |
[MnSn(C7H7O2S)3(CO)5] | Z = 8 |
Mr = 779.24 | Cu Kα radiation |
Tetragonal, I4 | µ = 12.47 mm−1 |
a = 22.4188 (1) Å | T = 279 K |
c = 11.9764 (1) Å | 0.70 × 0.08 × 0.05 mm |
V = 6019.37 (6) Å3 |
Bruker SMART 2K/Platform diffractometer | 5976 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 5643 reflections with I > 2σ(I) |
Tmin = 0.037, Tmax = 0.536 | Rint = 0.072 |
34825 measured reflections |
R[F2 > 2σ(F2)] = 0.033 | H-atom parameters constrained |
wR(F2) = 0.082 | Δρmax = 0.69 e Å−3 |
S = 0.99 | Δρmin = −0.37 e Å−3 |
5976 reflections | Absolute structure: Flack (1983), 2802 Friedel pairs |
382 parameters | Absolute structure parameter: 0.009 (5) |
0 restraints |
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. |
x | y | z | Uiso*/Ueq | ||
Sn1 | 0.696106 (11) | 0.899651 (11) | 0.95549 (2) | 0.03475 (7) | |
Mn1 | 0.62486 (3) | 0.98948 (3) | 1.01148 (6) | 0.03932 (16) | |
S1 | 0.55226 (5) | 0.65385 (5) | 1.13441 (10) | 0.0458 (2) | |
S2 | 0.96855 (5) | 0.85146 (6) | 1.16909 (12) | 0.0556 (3) | |
S3 | 0.71662 (5) | 0.84524 (5) | 0.40473 (10) | 0.0459 (2) | |
O1 | 0.54612 (19) | 0.9335 (2) | 0.8409 (4) | 0.0760 (12) | |
O2 | 0.6762 (2) | 1.0679 (2) | 0.8360 (4) | 0.0859 (15) | |
O3 | 0.7141 (2) | 1.0378 (2) | 1.1712 (5) | 0.0992 (19) | |
O5 | 0.53476 (17) | 1.08178 (19) | 1.0643 (5) | 0.0816 (14) | |
O4 | 0.57984 (19) | 0.9088 (2) | 1.1907 (4) | 0.0754 (12) | |
O11 | 0.49105 (16) | 0.65891 (19) | 1.1004 (4) | 0.0687 (11) | |
O12 | 0.56475 (19) | 0.64656 (17) | 1.2524 (3) | 0.0632 (10) | |
O21 | 0.9674 (2) | 0.8630 (3) | 1.2852 (4) | 0.0939 (17) | |
O22 | 0.98832 (19) | 0.79457 (19) | 1.1302 (5) | 0.0892 (16) | |
O31 | 0.69427 (19) | 0.89423 (19) | 0.3427 (3) | 0.0695 (10) | |
O32 | 0.6924 (2) | 0.78726 (19) | 0.3861 (3) | 0.0767 (12) | |
C1 | 0.5765 (2) | 0.9542 (2) | 0.9056 (5) | 0.0505 (11) | |
C2 | 0.6585 (2) | 1.0371 (2) | 0.9006 (5) | 0.0550 (12) | |
C3 | 0.6819 (2) | 1.0192 (3) | 1.1118 (5) | 0.0587 (14) | |
C5 | 0.5702 (2) | 1.0473 (2) | 1.0479 (5) | 0.0533 (11) | |
C4 | 0.5971 (2) | 0.9386 (2) | 1.1226 (4) | 0.0509 (11) | |
C11 | 0.65176 (18) | 0.81769 (18) | 1.0075 (3) | 0.0354 (8) | |
C12 | 0.60592 (19) | 0.79180 (19) | 0.9451 (4) | 0.0429 (9) | |
H12 | 0.5954 | 0.8085 | 0.8768 | 0.051* | |
C13 | 0.57572 (19) | 0.74158 (19) | 0.9828 (4) | 0.0424 (10) | |
H13 | 0.5456 | 0.7245 | 0.9399 | 0.051* | |
C14 | 0.59103 (17) | 0.71748 (18) | 1.0847 (4) | 0.0360 (8) | |
C15 | 0.6365 (2) | 0.7416 (2) | 1.1483 (4) | 0.0424 (9) | |
H15 | 0.6468 | 0.7248 | 1.2167 | 0.051* | |
C16 | 0.66639 (19) | 0.7912 (2) | 1.1084 (4) | 0.0420 (9) | |
H16 | 0.6973 | 0.8073 | 1.1507 | 0.050* | |
C17 | 0.5850 (3) | 0.5939 (2) | 1.0630 (6) | 0.0761 (19) | |
H17A | 0.5662 | 0.5573 | 1.0856 | 0.114* | |
H17B | 0.6268 | 0.5922 | 1.0803 | 0.114* | |
H17C | 0.5799 | 0.5993 | 0.9841 | 0.114* | |
C21 | 0.78469 (17) | 0.88860 (18) | 1.0269 (3) | 0.0363 (8) | |
C22 | 0.8055 (2) | 0.9197 (3) | 1.1172 (4) | 0.0539 (12) | |
H22 | 0.7814 | 0.9486 | 1.1498 | 0.065* | |
C23 | 0.8622 (2) | 0.9091 (3) | 1.1612 (4) | 0.0551 (12) | |
H23 | 0.8761 | 0.9306 | 1.2224 | 0.066* | |
C24 | 0.89676 (18) | 0.8660 (2) | 1.1118 (4) | 0.0417 (9) | |
C25 | 0.8774 (2) | 0.8346 (2) | 1.0219 (5) | 0.0611 (14) | |
H25 | 0.9015 | 0.8057 | 0.9893 | 0.073* | |
C26 | 0.8218 (2) | 0.8462 (2) | 0.9801 (5) | 0.0554 (13) | |
H26 | 0.8085 | 0.8250 | 0.9182 | 0.066* | |
C27 | 1.0145 (2) | 0.9051 (3) | 1.1055 (6) | 0.0698 (16) | |
H27A | 0.9994 | 0.9442 | 1.1213 | 0.105* | |
H27B | 1.0149 | 0.8988 | 1.0262 | 0.105* | |
H27C | 1.0543 | 0.9015 | 1.1342 | 0.105* | |
C31 | 0.70613 (19) | 0.8848 (2) | 0.7775 (4) | 0.0402 (9) | |
C32 | 0.7059 (3) | 0.9303 (2) | 0.7001 (4) | 0.0613 (14) | |
H32 | 0.7040 | 0.9696 | 0.7251 | 0.074* | |
C33 | 0.7084 (3) | 0.9193 (2) | 0.5851 (4) | 0.0581 (14) | |
H33 | 0.7075 | 0.9506 | 0.5341 | 0.070* | |
C34 | 0.71215 (19) | 0.8611 (2) | 0.5494 (4) | 0.0419 (9) | |
C35 | 0.7127 (2) | 0.8144 (2) | 0.6253 (4) | 0.0478 (10) | |
H35 | 0.7152 | 0.7752 | 0.6005 | 0.057* | |
C36 | 0.7094 (2) | 0.8268 (2) | 0.7381 (4) | 0.0469 (10) | |
H36 | 0.7095 | 0.7954 | 0.7888 | 0.056* | |
C37 | 0.7932 (3) | 0.8400 (3) | 0.3795 (5) | 0.0689 (15) | |
H37A | 0.7998 | 0.8305 | 0.3023 | 0.103* | |
H37B | 0.8100 | 0.8092 | 0.4255 | 0.103* | |
H37C | 0.8119 | 0.8774 | 0.3967 | 0.103* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Sn1 | 0.03491 (14) | 0.03749 (14) | 0.03186 (13) | −0.00159 (11) | −0.00251 (10) | −0.00022 (10) |
Mn1 | 0.0336 (3) | 0.0415 (4) | 0.0428 (4) | −0.0004 (3) | −0.0022 (3) | −0.0028 (3) |
S1 | 0.0491 (6) | 0.0412 (5) | 0.0470 (6) | −0.0056 (4) | 0.0092 (5) | 0.0001 (4) |
S2 | 0.0388 (6) | 0.0645 (8) | 0.0634 (8) | 0.0030 (5) | −0.0038 (5) | 0.0197 (6) |
S3 | 0.0528 (6) | 0.0519 (6) | 0.0331 (5) | −0.0029 (5) | −0.0062 (4) | −0.0030 (4) |
O1 | 0.066 (2) | 0.083 (3) | 0.079 (3) | −0.002 (2) | −0.032 (2) | −0.013 (2) |
O2 | 0.103 (4) | 0.066 (3) | 0.089 (4) | 0.005 (2) | 0.029 (3) | 0.024 (3) |
O3 | 0.076 (3) | 0.091 (3) | 0.130 (5) | 0.010 (2) | −0.047 (3) | −0.051 (3) |
O5 | 0.051 (2) | 0.075 (3) | 0.119 (4) | 0.0193 (19) | −0.009 (2) | −0.026 (3) |
O4 | 0.069 (3) | 0.093 (3) | 0.064 (3) | −0.002 (2) | 0.018 (2) | 0.017 (2) |
O11 | 0.0460 (19) | 0.079 (3) | 0.081 (3) | −0.0213 (18) | 0.0044 (18) | 0.005 (2) |
O12 | 0.084 (3) | 0.056 (2) | 0.049 (2) | −0.0108 (19) | 0.0065 (18) | 0.0074 (16) |
O21 | 0.056 (3) | 0.163 (5) | 0.062 (3) | 0.011 (3) | −0.011 (2) | 0.018 (3) |
O22 | 0.063 (3) | 0.060 (2) | 0.144 (5) | 0.020 (2) | −0.013 (3) | 0.019 (3) |
O31 | 0.077 (3) | 0.089 (3) | 0.0420 (19) | 0.027 (3) | −0.0104 (19) | 0.0060 (19) |
O32 | 0.110 (3) | 0.073 (3) | 0.047 (2) | −0.037 (2) | −0.006 (2) | −0.0091 (18) |
C1 | 0.044 (2) | 0.051 (3) | 0.056 (3) | 0.002 (2) | −0.009 (2) | −0.002 (2) |
C2 | 0.058 (3) | 0.046 (3) | 0.061 (3) | 0.004 (2) | 0.005 (2) | 0.004 (2) |
C3 | 0.046 (3) | 0.060 (3) | 0.071 (4) | 0.005 (2) | −0.013 (2) | −0.018 (3) |
C5 | 0.040 (2) | 0.059 (3) | 0.061 (3) | −0.002 (2) | −0.003 (2) | −0.001 (2) |
C4 | 0.046 (3) | 0.063 (3) | 0.043 (3) | −0.002 (2) | 0.003 (2) | 0.002 (2) |
C11 | 0.036 (2) | 0.034 (2) | 0.036 (2) | −0.0021 (16) | 0.0021 (15) | 0.0013 (15) |
C12 | 0.043 (2) | 0.045 (2) | 0.040 (2) | 0.0015 (17) | −0.0096 (18) | 0.0034 (19) |
C13 | 0.035 (2) | 0.045 (2) | 0.048 (3) | −0.0019 (16) | −0.0085 (17) | −0.0021 (18) |
C14 | 0.0333 (19) | 0.0351 (19) | 0.040 (2) | 0.0002 (15) | 0.0027 (15) | −0.0034 (16) |
C15 | 0.047 (2) | 0.049 (2) | 0.030 (2) | −0.0001 (18) | −0.0058 (17) | 0.0048 (17) |
C16 | 0.039 (2) | 0.049 (2) | 0.038 (2) | −0.0090 (18) | −0.0074 (17) | −0.0049 (18) |
C17 | 0.111 (5) | 0.041 (3) | 0.076 (4) | 0.000 (3) | 0.036 (4) | −0.003 (3) |
C21 | 0.0310 (18) | 0.042 (2) | 0.036 (2) | 0.0002 (15) | −0.0020 (15) | 0.0047 (16) |
C22 | 0.047 (3) | 0.074 (3) | 0.041 (3) | 0.018 (2) | −0.0035 (19) | −0.019 (2) |
C23 | 0.042 (2) | 0.077 (4) | 0.046 (3) | 0.008 (2) | −0.006 (2) | −0.016 (2) |
C24 | 0.034 (2) | 0.048 (2) | 0.043 (2) | 0.0010 (17) | 0.0000 (17) | 0.0126 (18) |
C25 | 0.054 (3) | 0.052 (3) | 0.078 (4) | 0.012 (2) | −0.002 (3) | −0.019 (3) |
C26 | 0.056 (3) | 0.046 (3) | 0.064 (3) | 0.006 (2) | −0.011 (2) | −0.019 (2) |
C27 | 0.038 (3) | 0.078 (4) | 0.094 (5) | −0.008 (2) | 0.007 (3) | 0.007 (3) |
C31 | 0.037 (2) | 0.047 (2) | 0.036 (2) | −0.0047 (16) | −0.0035 (17) | −0.0015 (17) |
C32 | 0.099 (4) | 0.038 (2) | 0.048 (3) | −0.013 (3) | −0.002 (3) | −0.006 (2) |
C33 | 0.095 (4) | 0.042 (3) | 0.037 (2) | −0.012 (2) | −0.008 (3) | 0.0070 (19) |
C34 | 0.042 (2) | 0.049 (2) | 0.034 (2) | −0.0031 (17) | −0.0063 (18) | −0.0037 (19) |
C35 | 0.060 (3) | 0.038 (2) | 0.045 (3) | 0.002 (2) | 0.002 (2) | −0.0038 (19) |
C36 | 0.058 (3) | 0.036 (2) | 0.047 (3) | 0.0106 (19) | 0.002 (2) | 0.0046 (18) |
C37 | 0.064 (3) | 0.089 (4) | 0.053 (4) | 0.010 (3) | 0.005 (3) | −0.001 (3) |
Sn1—C31 | 2.169 (4) | C15—C16 | 1.383 (6) |
Sn1—C21 | 2.177 (4) | C15—H15 | 0.9300 |
Sn1—C11 | 2.180 (4) | C16—H16 | 0.9300 |
Sn1—Mn1 | 2.6564 (7) | C17—H17A | 0.9600 |
Mn1—C5 | 1.836 (5) | C17—H17B | 0.9600 |
Mn1—C1 | 1.847 (5) | C17—H17C | 0.9600 |
Mn1—C4 | 1.860 (5) | C21—C22 | 1.368 (6) |
Mn1—C2 | 1.863 (6) | C21—C26 | 1.381 (6) |
Mn1—C3 | 1.877 (5) | C22—C23 | 1.396 (7) |
S1—O11 | 1.436 (4) | C22—H22 | 0.9300 |
S1—O12 | 1.450 (4) | C23—C24 | 1.373 (7) |
S1—C17 | 1.754 (5) | C23—H23 | 0.9300 |
S1—C14 | 1.774 (4) | C24—C25 | 1.358 (7) |
S2—O21 | 1.414 (5) | C25—C26 | 1.370 (7) |
S2—O22 | 1.428 (5) | C25—H25 | 0.9300 |
S2—C27 | 1.757 (6) | C26—H26 | 0.9300 |
S2—C24 | 1.780 (4) | C27—H27A | 0.9600 |
S3—O31 | 1.417 (4) | C27—H27B | 0.9600 |
S3—O32 | 1.426 (4) | C27—H27C | 0.9600 |
S3—C37 | 1.747 (6) | C31—C32 | 1.379 (7) |
S3—C34 | 1.771 (5) | C31—C36 | 1.384 (6) |
O1—C1 | 1.130 (6) | C32—C33 | 1.401 (7) |
O2—C2 | 1.110 (7) | C32—H32 | 0.9300 |
O3—C3 | 1.096 (7) | C33—C34 | 1.376 (7) |
O5—C5 | 1.126 (6) | C33—H33 | 0.9300 |
O4—C4 | 1.123 (7) | C34—C35 | 1.386 (6) |
C11—C16 | 1.386 (6) | C35—C36 | 1.381 (7) |
C11—C12 | 1.397 (6) | C35—H35 | 0.9300 |
C12—C13 | 1.389 (6) | C36—H36 | 0.9300 |
C12—H12 | 0.9300 | C37—H37A | 0.9600 |
C13—C14 | 1.378 (6) | C37—H37B | 0.9600 |
C13—H13 | 0.9300 | C37—H37C | 0.9600 |
C14—C15 | 1.383 (6) | Sn1—O22i | 3.498 (4) |
C31—Sn1—C21 | 105.92 (16) | C15—C16—H16 | 119.0 |
C31—Sn1—C11 | 101.44 (16) | C11—C16—H16 | 119.0 |
C21—Sn1—C11 | 101.99 (15) | S1—C17—H17A | 109.5 |
C31—Sn1—Mn1 | 115.28 (12) | S1—C17—H17B | 109.5 |
C21—Sn1—Mn1 | 122.39 (11) | H17A—C17—H17B | 109.5 |
C11—Sn1—Mn1 | 107.01 (11) | S1—C17—H17C | 109.5 |
C5—Mn1—C1 | 94.3 (2) | H17A—C17—H17C | 109.5 |
C5—Mn1—C4 | 92.3 (2) | H17B—C17—H17C | 109.5 |
C1—Mn1—C4 | 91.8 (2) | C22—C21—C26 | 117.8 (4) |
C5—Mn1—C2 | 92.0 (2) | C22—C21—Sn1 | 124.3 (3) |
C1—Mn1—C2 | 89.6 (3) | C26—C21—Sn1 | 117.9 (3) |
C4—Mn1—C2 | 175.4 (2) | C21—C22—C23 | 121.4 (4) |
C5—Mn1—C3 | 92.9 (2) | C21—C22—H22 | 119.3 |
C1—Mn1—C3 | 172.7 (2) | C23—C22—H22 | 119.3 |
C4—Mn1—C3 | 89.3 (3) | C24—C23—C22 | 118.1 (5) |
C2—Mn1—C3 | 88.7 (3) | C24—C23—H23 | 120.9 |
C5—Mn1—Sn1 | 175.13 (15) | C22—C23—H23 | 120.9 |
C1—Mn1—Sn1 | 81.65 (16) | C25—C24—C23 | 121.8 (4) |
C4—Mn1—Sn1 | 85.23 (16) | C25—C24—S2 | 119.9 (4) |
C2—Mn1—Sn1 | 90.64 (16) | C23—C24—S2 | 118.3 (4) |
C3—Mn1—Sn1 | 91.22 (16) | C24—C25—C26 | 118.8 (5) |
O11—S1—O12 | 118.0 (3) | C24—C25—H25 | 120.6 |
O11—S1—C17 | 108.8 (3) | C26—C25—H25 | 120.6 |
O12—S1—C17 | 107.9 (3) | C25—C26—C21 | 122.1 (5) |
O11—S1—C14 | 108.0 (2) | C25—C26—H26 | 119.0 |
O12—S1—C14 | 108.9 (2) | C21—C26—H26 | 119.0 |
C17—S1—C14 | 104.3 (2) | S2—C27—H27A | 109.5 |
O21—S2—O22 | 119.3 (3) | S2—C27—H27B | 109.5 |
O21—S2—C27 | 108.2 (3) | H27A—C27—H27B | 109.5 |
O22—S2—C27 | 106.7 (3) | S2—C27—H27C | 109.5 |
O21—S2—C24 | 109.2 (3) | H27A—C27—H27C | 109.5 |
O22—S2—C24 | 108.6 (3) | H27B—C27—H27C | 109.5 |
C27—S2—C24 | 103.7 (2) | C32—C31—C36 | 117.8 (4) |
O31—S3—O32 | 119.3 (3) | C32—C31—Sn1 | 123.1 (3) |
O31—S3—C37 | 108.0 (3) | C36—C31—Sn1 | 119.0 (3) |
O32—S3—C37 | 106.6 (3) | C31—C32—C33 | 122.0 (5) |
O31—S3—C34 | 109.7 (2) | C31—C32—H32 | 119.0 |
O32—S3—C34 | 108.4 (2) | C33—C32—H32 | 119.0 |
C37—S3—C34 | 103.8 (3) | C34—C33—C32 | 118.4 (5) |
O1—C1—Mn1 | 178.6 (5) | C34—C33—H33 | 120.8 |
O2—C2—Mn1 | 176.0 (5) | C32—C33—H33 | 120.8 |
O3—C3—Mn1 | 178.0 (5) | C33—C34—C35 | 120.8 (5) |
O5—C5—Mn1 | 175.6 (5) | C33—C34—S3 | 119.9 (4) |
O4—C4—Mn1 | 178.6 (5) | C35—C34—S3 | 119.3 (3) |
C16—C11—C12 | 117.6 (4) | C36—C35—C34 | 119.3 (4) |
C16—C11—Sn1 | 120.2 (3) | C36—C35—H35 | 120.4 |
C12—C11—Sn1 | 122.2 (3) | C34—C35—H35 | 120.4 |
C13—C12—C11 | 121.4 (4) | C35—C36—C31 | 121.7 (4) |
C13—C12—H12 | 119.3 | C35—C36—H36 | 119.2 |
C11—C12—H12 | 119.3 | C31—C36—H36 | 119.2 |
C14—C13—C12 | 118.9 (4) | S3—C37—H37A | 109.5 |
C14—C13—H13 | 120.5 | S3—C37—H37B | 109.5 |
C12—C13—H13 | 120.5 | H37A—C37—H37B | 109.5 |
C13—C14—C15 | 121.2 (4) | S3—C37—H37C | 109.5 |
C13—C14—S1 | 119.4 (3) | H37A—C37—H37C | 109.5 |
C15—C14—S1 | 119.4 (3) | H37B—C37—H37C | 109.5 |
C14—C15—C16 | 118.7 (4) | C31—Sn1—O22i | 75.93 (15) |
C14—C15—H15 | 120.6 | C21—Sn1—O22i | 67.74 (13) |
C16—C15—H15 | 120.6 | C11—Sn1—O22i | 167.65 (13) |
C15—C16—C11 | 122.1 (4) | Mn1—Sn1—O22i | 84.79 (8) |
C31—Sn1—Mn1—C1 | 46.3 (2) | Mn1—Sn1—C21—C26 | −170.0 (3) |
C21—Sn1—Mn1—C1 | 177.6 (2) | C26—C21—C22—C23 | −0.3 (8) |
C11—Sn1—Mn1—C1 | −65.6 (2) | Sn1—C21—C22—C23 | 177.8 (4) |
C31—Sn1—Mn1—C4 | 138.9 (2) | C21—C22—C23—C24 | −0.3 (9) |
C21—Sn1—Mn1—C4 | −89.9 (2) | C22—C23—C24—C25 | 0.6 (8) |
C11—Sn1—Mn1—C4 | 26.9 (2) | C22—C23—C24—S2 | −179.0 (4) |
C31—Sn1—Mn1—C2 | −43.2 (2) | O21—S2—C24—C25 | −149.4 (5) |
C21—Sn1—Mn1—C2 | 88.0 (2) | O22—S2—C24—C25 | −17.8 (5) |
C11—Sn1—Mn1—C2 | −155.2 (2) | C27—S2—C24—C25 | 95.4 (5) |
C31—Sn1—Mn1—C3 | −131.9 (2) | O21—S2—C24—C23 | 30.2 (5) |
C21—Sn1—Mn1—C3 | −0.7 (2) | O22—S2—C24—C23 | 161.8 (4) |
C11—Sn1—Mn1—C3 | 116.1 (2) | C27—S2—C24—C23 | −85.0 (5) |
C31—Sn1—C11—C16 | 141.9 (3) | C23—C24—C25—C26 | −0.3 (8) |
C21—Sn1—C11—C16 | 32.7 (4) | S2—C24—C25—C26 | 179.3 (4) |
Mn1—Sn1—C11—C16 | −96.9 (3) | C24—C25—C26—C21 | −0.4 (9) |
C31—Sn1—C11—C12 | −41.7 (4) | C22—C21—C26—C25 | 0.7 (8) |
C21—Sn1—C11—C12 | −150.9 (4) | Sn1—C21—C26—C25 | −177.6 (5) |
Mn1—Sn1—C11—C12 | 79.5 (4) | C21—Sn1—C31—C32 | −104.5 (5) |
C16—C11—C12—C13 | 0.4 (7) | C11—Sn1—C31—C32 | 149.3 (4) |
Sn1—C11—C12—C13 | −176.1 (3) | Mn1—Sn1—C31—C32 | 34.1 (5) |
C11—C12—C13—C14 | 0.8 (7) | C21—Sn1—C31—C36 | 79.4 (4) |
C12—C13—C14—C15 | −1.4 (7) | C11—Sn1—C31—C36 | −26.8 (4) |
C12—C13—C14—S1 | 179.3 (3) | Mn1—Sn1—C31—C36 | −142.0 (3) |
O11—S1—C14—C13 | −35.8 (4) | C36—C31—C32—C33 | 0.5 (9) |
O12—S1—C14—C13 | −165.1 (4) | Sn1—C31—C32—C33 | −175.6 (5) |
C17—S1—C14—C13 | 79.9 (4) | C31—C32—C33—C34 | −1.1 (10) |
O11—S1—C14—C15 | 144.9 (4) | C32—C33—C34—C35 | 0.8 (9) |
O12—S1—C14—C15 | 15.6 (4) | C32—C33—C34—S3 | −179.0 (5) |
C17—S1—C14—C15 | −99.5 (4) | O31—S3—C34—C33 | −21.2 (5) |
C13—C14—C15—C16 | 0.6 (7) | O32—S3—C34—C33 | −152.9 (5) |
S1—C14—C15—C16 | 179.9 (3) | C37—S3—C34—C33 | 94.0 (5) |
C14—C15—C16—C11 | 0.7 (7) | O31—S3—C34—C35 | 159.0 (4) |
C12—C11—C16—C15 | −1.2 (7) | O32—S3—C34—C35 | 27.2 (5) |
Sn1—C11—C16—C15 | 175.4 (4) | C37—S3—C34—C35 | −85.8 (4) |
C31—Sn1—C21—C22 | 146.8 (4) | C33—C34—C35—C36 | −0.1 (8) |
C11—Sn1—C21—C22 | −107.5 (4) | S3—C34—C35—C36 | 179.7 (4) |
Mn1—Sn1—C21—C22 | 11.8 (5) | C34—C35—C36—C31 | −0.5 (8) |
C31—Sn1—C21—C26 | −35.1 (4) | C32—C31—C36—C35 | 0.3 (8) |
C11—Sn1—C21—C26 | 70.7 (4) | Sn1—C31—C36—C35 | 176.5 (4) |
Symmetry code: (i) y, −x+2, −z+2. |
Experimental details
Crystal data | |
Chemical formula | [MnSn(C7H7O2S)3(CO)5] |
Mr | 779.24 |
Crystal system, space group | Tetragonal, I4 |
Temperature (K) | 279 |
a, c (Å) | 22.4188 (1), 11.9764 (1) |
V (Å3) | 6019.37 (6) |
Z | 8 |
Radiation type | Cu Kα |
µ (mm−1) | 12.47 |
Crystal size (mm) | 0.70 × 0.08 × 0.05 |
Data collection | |
Diffractometer | Bruker SMART 2K/Platform diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.037, 0.536 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 34825, 5976, 5643 |
Rint | 0.072 |
(sin θ/λ)max (Å−1) | 0.621 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.033, 0.082, 0.99 |
No. of reflections | 5976 |
No. of parameters | 382 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.69, −0.37 |
Absolute structure | Flack (1983), 2802 Friedel pairs |
Absolute structure parameter | 0.009 (5) |
Computer programs: SMART (Bruker, 1999), SMART, SHELXTL (Bruker, 1997), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL.
Sn1—C31 | 2.169 (4) | Mn1—C1 | 1.847 (5) |
Sn1—C21 | 2.177 (4) | Mn1—C4 | 1.860 (5) |
Sn1—C11 | 2.180 (4) | Mn1—C2 | 1.863 (6) |
Sn1—Mn1 | 2.6564 (7) | Mn1—C3 | 1.877 (5) |
Mn1—C5 | 1.836 (5) | Sn1—O22i | 3.498 (4) |
C31—Sn1—C21 | 105.92 (16) | C4—Mn1—Sn1 | 85.23 (16) |
C31—Sn1—C11 | 101.44 (16) | C2—Mn1—Sn1 | 90.64 (16) |
C21—Sn1—C11 | 101.99 (15) | C3—Mn1—Sn1 | 91.22 (16) |
C31—Sn1—Mn1 | 115.28 (12) | C31—Sn1—O22i | 75.93 (15) |
C21—Sn1—Mn1 | 122.39 (11) | C21—Sn1—O22i | 67.74 (13) |
C11—Sn1—Mn1 | 107.01 (11) | C11—Sn1—O22i | 167.65 (13) |
C5—Mn1—Sn1 | 175.13 (15) | Mn1—Sn1—O22i | 84.79 (8) |
C1—Mn1—Sn1 | 81.65 (16) | ||
C31—Sn1—Mn1—C3 | −131.9 (2) | Mn1—Sn1—C11—C12 | 79.5 (4) |
C21—Sn1—Mn1—C3 | −0.7 (2) | Mn1—Sn1—C21—C22 | 11.8 (5) |
C11—Sn1—Mn1—C3 | 116.1 (2) | Mn1—Sn1—C31—C32 | 34.1 (5) |
Symmetry code: (i) y, −x+2, −z+2. |
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Group 14 tetraaryl molecules, MAr4, have been used extensively as model systems to test various paradigms for describing molecular packing and assessing the likelihood of a particular choice of space group (Lloyd & Brock, 1997). Often, as was predicted earlier by Kitaigorodskii (1961), such molecules crystallize in tetragonal space groups retaining molecular 4 (S4) symmetry, which is in fact the lowest energy configuration for these molecules (Hutchings et al., 1975a,b). However, it is generally found that asymmetric molecules pack more effectively using only a few low symmetry space groups, such as P21/c, P1, P212121, P21 or C2/c (Kitaigorodskii, 1961).
Recently, we have reported the crystal structures of the series of compounds [(p-XC6H4)3SnMn(CO)5], with X = CH3, CH3O, CH3S, F and Cl (Christendat et al., 2002). These molecules are inherently asymmetric and, like [Ph3SnMn(CO)5] (Weber & Bryan, 1967), crystallize in one of the most frequently used space groups, P21/c (P21/n) or P1. We now report the structure of a sixth member of this set of bimetallic Sn—Mn compounds, {[p-CH3S(O2)C6H4]3SnMn(CO)5}, (I). Although in these compounds, the Sn and Mn atoms represent the two poles of spectroscopic and chemical interest, in fact the Mn(CO)5 moiety is of similar size to an aryl group, so structurally, the Sn is the central atom in these molecules. Therefore, the structure of (I) will be compared with those of some related tetraaryltin compounds (Wharf & Lebuis, 2000) as well as with that of [p-CH3S(O2)C6H4]4Sn (Wharf et al., 1990). \sch
The molecular structure and atomic numbering scheme for (I) are shown in Fig. 1. The overall geometry is the same as for the other members of the series, although the phenyl ring torsion angle values cover a much wider range (79.5, 11.8 and 34.1°) in (I) than in the compounds studied previously. Around Sn, the average Sn—C distance of 2.175 (5) Å is clearly longer than found in analogous compounds (2.145–2.157 Å; Reference?), but the Sn—Mn distance of 2.6564 (7) Å is not significantly less than that found in the structures of other members of this group of compounds. Like all other Ar3SnMn(CO)5 compounds, there is a quasi-mirror plane of symmetry in the central C4MnSnC3 skeleton of (I) [C3—Mn1—Sn1—C21 - 0.7 (2)°]. Phenyl ring 2 (C21—C26?) is almost coplanar with this quasi-mirror plane.
By far the most novel aspect of the crystal structure of (I) is its high symmetry (tetragonal), which is achieved without the need for disorder, notwithstanding the low molecular symmetry. However, the resulting space group (I4), while acentric, is achiral (Jones, 1986), and no absolute chemical configuration is assigned to (I). Thus, the structure is not derived from that of [p-CH3S(O2)C6H4]4Sn (C2/c, local symmetry 2), with one p-CH3S(O2)C6H4 moiety replaced by Mn(CO)5 and subsequent disorder giving a molecule with pseudo 4 symmetry. Indeed, it is noteworthy that the high crystal symmetry is achieved without the need for disordered CH3S(O2)- groups. Instead, molecules of (I) are assembled in columns parallel to the c axis, with one p-CH3S(O2)C6H4– (ring 3, C31—C36?) acting as a spacer (Fig. 2). In each quadrant of the cell, two neighbouring columns of (I) related by a 21 axis are held together by a double embrace of CH3S(O2)- units taken from p-CH3S(O2)C6H4– ring 1 (C11—C16?) and ring 2 at (1/2 - x, 1/2 - y, z + 1/2), and ring 2 and ring 1 at (1/2 - x, 1/2 - y, z + 1/2). These double chains are then parallel to the 4 axes, leaving Mn(CO)5 groups from four adjacent double chains to pack around the other 4 axes in the unit cell. Please check the last part of this paragraph carefully. It was not particularly clear what (1), [1], etc. were intended to refer to.
The structure of (I) contradicts the general trend that unsymmetric molecules prefer to pack in lower symmetry space groups with the molecules packed in the most efficient way possible, the intermolecular interactions being much weaker than the colvalent bonds of the molecule. With this model, Kitaigorodskii (1961) predicted that, as more obtrusive para-substituents rendered an Ar4Sn moiety less spherical, this molecule would distort from 4 symmetry so as to pack more efficiently in low symmetry space groups. Examples of this are (p-C2H5OC6H4)4Sn (P21/c; Wharf & Simard, 1991) and [p-CH3S(O2)C6H4]4Sn (C2/c; Wharf et al., 1990). However, [p-(CH3)3C6H4]4Sn (Wharf & Lebuis, 2000) is tetragonal, the molecules having 4 symmetry.
The more recent approach of Desiraju (1996) considers a crystal as a supramolecular entity formed by the mutual recognition of molecules. These networks may then be dissected into supramolecular synthons and molecular synthons, the former being the structural units which yield the supermolecular network of the crystal. In the case of (I), the crystal is constructed from two such quasi-tetrahedral supramolecular synthons, the first being the [–Mn(CO)5]4 cluster surrounding one 4 symmetry element, and the second being the two overlapping clusters formed by the coming together of four [phenyl(1)-S(O2)CH3] and four [phenyl(2)-S(O2)CH3] units from neighbouring molecules which surround the parallel 4 symmetry element. The four double chains which run through the unit cell are then pulled together by weak but significant Sn1···O22i interactions [3.498 (4) Å; symmetry code: (i) y, 2 - x, 2 - z]. The geometry at Sn (Fig. 1) may then be considered as highly distorted trigonal-bipyramidal, with the axial angle [O22i···Sn1—C11] being 167.7 (1)°. Other intermolecular interactions that may be significant are O12···H27Cii 2.59 Å and O32···H16iii 2.86 Å [symmetry codes: (ii) 3/2 - y, x - 1/2, 5/2 - z; (iii) x, y, z - 1].