Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807047605/fj2041sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807047605/fj2041Isup2.hkl |
CCDC reference: 667112
Key indicators
- Single-crystal X-ray study
- T = 168 K
- Mean (C-C) = 0.003 Å
- R factor = 0.026
- wR factor = 0.073
- Data-to-parameter ratio = 12.7
checkCIF/PLATON results
No syntax errors found
Alert level B PLAT232_ALERT_2_B Hirshfeld Test Diff (M-X) Mn1 - C12 .. 10.51 su
Alert level C ABSTM02_ALERT_3_C The ratio of expected to reported Tmax/Tmin(RR) is > 1.10 Tmin and Tmax reported: 0.711 0.870 Tmin and Tmax expected: 0.525 0.871 RR = 1.356 Please check that your absorption correction is appropriate. PLAT060_ALERT_3_C Ratio Tmax/Tmin (Exp-to-Rep) (too) Large ....... 1.37 PLAT063_ALERT_3_C Crystal Probably too Large for Beam Size ....... 0.72 mm PLAT153_ALERT_1_C The su's on the Cell Axes are Equal (x 100000) 200 Ang. PLAT154_ALERT_1_C The su's on the Cell Angles are Equal (x 10000) 300 Deg. PLAT164_ALERT_4_C Nr. of Refined C-H H-Atoms in Heavy-At Struct... 9 PLAT230_ALERT_2_C Hirshfeld Test Diff for O12 - C12 .. 5.62 su PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Mn1 - C11 .. 7.38 su PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Mn1 - C13 .. 9.27 su PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Mn1 - C14 .. 9.31 su PLAT380_ALERT_4_C Check Incorrectly? Oriented X(sp2)-Methyl Moiety C10
0 ALERT level A = In general: serious problem 1 ALERT level B = Potentially serious problem 11 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 5 ALERT type 2 Indicator that the structure model may be wrong or deficient 3 ALERT type 3 Indicator that the structure quality may be low 2 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
The preparations and structures of related orthomanganated aryl ketones have been reviewed (Main & Nicholson, 1994). Preference in cyclometallation reactions for the more sterically crowded isomer for other 3'-substituted acetophenones has been observed (Cooney et al., 1988, 2001; Liebeskind et al., 1989).
The title compound was prepared by reaction of PhCH2Mn(CO)5 with 3'-acetoxyacetophenone in refluxing heptane, under the usual conditions (Main and Nicholson, 1994). The structure was determined to confirm that cyclometallation had occurred at the sterically crowded 2'-position, rather than the alternative 6'-position, and to detect any residual interactions with the adjacent acetoxy group which might have directed this preference.
All H-atoms were located as the highest peaks in a penultimate difference map and were refined with isotropic temperature factors.
(2-Acetyl-κO1-6-acetoxyphenyl- κC1)tetracarbonylmanganese(I) is formed by orthomanganation of 3'-acetoxyacetophenone at the sterically crowded ortho site. The atoms of the phenyl and the cyclometallated rings are coplanar to within <0.018 Å, and there are no significant intramolecular interactions between the Mn(CO)4 group and the adjacent acetoxy one. The Mn1—C12 distance trans to O1 (1.8046 (18) Å) is shorter than the Mn1—C11 distance trans to C1 (1.8367 (19) Å), while the two Mn—CO distances trans to each other are the longest (av. 1.857 (2) Å). The Mn1—C1 distance is significantly shorter than the Mn1—O1 distance (2.0445 (15) and 2.0548 (11) Å respectively) contrary to the trend expected purely on covalent radii. These conform to the pattern found for other orthomanganated arenes (Main and Nicholson, 1994).
The preparations and structures of related orthomanganated aryl ketones have been reviewed (Main & Nicholson, 1994). Preference in cyclometallation reactions for the more sterically crowded isomer for other 3'-substituted acetophenones has been observed (Cooney et al., 1988, 2001; Liebeskind et al., 1989).
Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
Fig. 1. Structure of (2-Acetyl-κO1-6-acetoxyphenyl- κC1)tetracarbonylmanganese(I), with ellipsoids drawn at the 30% probability level. |
[Mn(C10H9O3)(CO)4] | Z = 2 |
Mr = 344.15 | F(000) = 348 |
Triclinic, P1 | Dx = 1.543 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 9.306 (2) Å | Cell parameters from 3920 reflections |
b = 9.635 (2) Å | θ = 2–26° |
c = 9.954 (2) Å | µ = 0.92 mm−1 |
α = 68.594 (3)° | T = 168 K |
β = 67.663 (3)° | Block, yellow |
γ = 68.422 (3)° | 0.72 × 0.65 × 0.15 mm |
V = 740.9 (3) Å3 |
Bruker SMART CCD diffractometer | 2988 independent reflections |
Radiation source: fine-focus sealed tube | 2730 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.015 |
ω scans | θmax = 26.4°, θmin = 2.3° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1998) | h = −11→11 |
Tmin = 0.711, Tmax = 0.870 | k = −12→11 |
9684 measured reflections | l = −12→12 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.026 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.073 | All H-atom parameters refined |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0452P)2 + 0.1914P] where P = (Fo2 + 2Fc2)/3 |
2988 reflections | (Δ/σ)max = 0.004 |
235 parameters | Δρmax = 0.26 e Å−3 |
0 restraints | Δρmin = −0.41 e Å−3 |
[Mn(C10H9O3)(CO)4] | γ = 68.422 (3)° |
Mr = 344.15 | V = 740.9 (3) Å3 |
Triclinic, P1 | Z = 2 |
a = 9.306 (2) Å | Mo Kα radiation |
b = 9.635 (2) Å | µ = 0.92 mm−1 |
c = 9.954 (2) Å | T = 168 K |
α = 68.594 (3)° | 0.72 × 0.65 × 0.15 mm |
β = 67.663 (3)° |
Bruker SMART CCD diffractometer | 2988 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1998) | 2730 reflections with I > 2σ(I) |
Tmin = 0.711, Tmax = 0.870 | Rint = 0.015 |
9684 measured reflections |
R[F2 > 2σ(F2)] = 0.026 | 0 restraints |
wR(F2) = 0.073 | All H-atom parameters refined |
S = 1.02 | Δρmax = 0.26 e Å−3 |
2988 reflections | Δρmin = −0.41 e Å−3 |
235 parameters |
x | y | z | Uiso*/Ueq | ||
Mn1 | 0.15624 (3) | 0.30950 (3) | 0.24687 (2) | 0.03251 (9) | |
C1 | 0.37221 (17) | 0.14695 (17) | 0.24738 (15) | 0.0287 (3) | |
C2 | 0.46885 (18) | 0.18432 (17) | 0.30330 (16) | 0.0311 (3) | |
C3 | 0.6217 (2) | 0.09150 (19) | 0.31439 (19) | 0.0380 (3) | |
C4 | 0.6832 (2) | −0.0424 (2) | 0.2682 (2) | 0.0428 (4) | |
C5 | 0.5919 (2) | −0.08368 (19) | 0.21356 (19) | 0.0389 (3) | |
C6 | 0.44005 (18) | 0.00979 (17) | 0.20521 (16) | 0.0314 (3) | |
C7 | 0.3934 (2) | 0.32656 (18) | 0.35101 (16) | 0.0337 (3) | |
C8 | 0.4716 (3) | 0.3870 (2) | 0.4155 (2) | 0.0425 (4) | |
C9 | 0.29739 (19) | −0.15989 (18) | 0.22594 (19) | 0.0378 (3) | |
C10 | 0.2255 (3) | −0.2011 (2) | 0.1395 (3) | 0.0512 (5) | |
C11 | −0.0262 (2) | 0.4716 (2) | 0.2641 (2) | 0.0509 (4) | |
C12 | 0.0719 (2) | 0.2290 (2) | 0.1657 (2) | 0.0415 (4) | |
C13 | 0.08616 (19) | 0.1809 (2) | 0.43689 (19) | 0.0395 (4) | |
C14 | 0.2643 (2) | 0.4043 (2) | 0.0558 (2) | 0.0470 (4) | |
O1 | 0.25602 (14) | 0.39925 (12) | 0.33756 (13) | 0.0383 (3) | |
O2 | 0.35525 (14) | −0.03417 (12) | 0.14249 (12) | 0.0359 (2) | |
O3 | 0.30441 (17) | −0.22465 (16) | 0.35196 (16) | 0.0559 (4) | |
O11 | −0.1391 (2) | 0.5708 (2) | 0.2727 (2) | 0.0809 (5) | |
O12 | 0.01425 (17) | 0.18291 (17) | 0.11287 (17) | 0.0599 (4) | |
O13 | 0.05411 (16) | 0.09520 (18) | 0.55063 (15) | 0.0572 (4) | |
O14 | 0.3357 (2) | 0.4562 (2) | −0.06173 (17) | 0.0813 (5) | |
H3 | 0.679 (2) | 0.117 (2) | 0.353 (2) | 0.046 (5)* | |
H4 | 0.788 (2) | −0.112 (2) | 0.276 (2) | 0.048 (5)* | |
H5 | 0.629 (2) | −0.178 (2) | 0.182 (2) | 0.044 (5)* | |
H81 | 0.574 (3) | 0.399 (3) | 0.353 (3) | 0.075 (8)* | |
H82 | 0.489 (3) | 0.321 (3) | 0.506 (3) | 0.063 (6)* | |
H83 | 0.406 (3) | 0.481 (3) | 0.435 (2) | 0.059 (6)* | |
H101 | 0.304 (3) | −0.215 (3) | 0.049 (3) | 0.081 (8)* | |
H102 | 0.143 (3) | −0.120 (3) | 0.113 (3) | 0.072 (7)* | |
H103 | 0.185 (3) | −0.288 (4) | 0.196 (3) | 0.093 (9)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Mn1 | 0.03310 (14) | 0.02938 (14) | 0.03785 (15) | −0.00427 (9) | −0.01615 (10) | −0.00960 (10) |
C1 | 0.0313 (7) | 0.0291 (7) | 0.0266 (7) | −0.0100 (6) | −0.0102 (6) | −0.0042 (5) |
C2 | 0.0357 (7) | 0.0310 (7) | 0.0297 (7) | −0.0133 (6) | −0.0121 (6) | −0.0039 (6) |
C3 | 0.0358 (8) | 0.0409 (9) | 0.0417 (8) | −0.0121 (7) | −0.0175 (7) | −0.0069 (7) |
C4 | 0.0341 (8) | 0.0444 (9) | 0.0480 (9) | −0.0038 (7) | −0.0168 (7) | −0.0115 (8) |
C5 | 0.0402 (8) | 0.0337 (8) | 0.0406 (8) | −0.0032 (7) | −0.0123 (7) | −0.0129 (7) |
C6 | 0.0374 (8) | 0.0307 (7) | 0.0289 (7) | −0.0109 (6) | −0.0115 (6) | −0.0068 (6) |
C7 | 0.0448 (8) | 0.0304 (7) | 0.0302 (7) | −0.0155 (6) | −0.0148 (6) | −0.0030 (6) |
C8 | 0.0582 (11) | 0.0383 (9) | 0.0444 (10) | −0.0193 (8) | −0.0241 (9) | −0.0089 (8) |
C9 | 0.0356 (8) | 0.0287 (7) | 0.0500 (10) | −0.0049 (6) | −0.0148 (7) | −0.0124 (7) |
C10 | 0.0623 (12) | 0.0427 (10) | 0.0631 (13) | −0.0209 (10) | −0.0232 (11) | −0.0170 (9) |
C11 | 0.0477 (10) | 0.0448 (10) | 0.0624 (12) | 0.0007 (8) | −0.0264 (9) | −0.0182 (9) |
C12 | 0.0398 (8) | 0.0392 (9) | 0.0482 (9) | −0.0061 (7) | −0.0203 (7) | −0.0105 (7) |
C13 | 0.0323 (8) | 0.0479 (10) | 0.0430 (9) | −0.0094 (7) | −0.0142 (7) | −0.0147 (8) |
C14 | 0.0565 (10) | 0.0435 (10) | 0.0458 (10) | −0.0138 (8) | −0.0259 (9) | −0.0045 (8) |
O1 | 0.0462 (6) | 0.0299 (5) | 0.0451 (6) | −0.0062 (5) | −0.0207 (5) | −0.0128 (5) |
O2 | 0.0471 (6) | 0.0323 (6) | 0.0362 (6) | −0.0136 (5) | −0.0170 (5) | −0.0091 (4) |
O3 | 0.0630 (8) | 0.0504 (8) | 0.0587 (8) | −0.0268 (7) | −0.0330 (7) | 0.0092 (6) |
O11 | 0.0606 (9) | 0.0622 (10) | 0.1086 (14) | 0.0228 (8) | −0.0392 (9) | −0.0332 (10) |
O12 | 0.0597 (8) | 0.0649 (9) | 0.0777 (10) | −0.0146 (7) | −0.0405 (8) | −0.0235 (8) |
O13 | 0.0491 (7) | 0.0742 (10) | 0.0447 (7) | −0.0256 (7) | −0.0133 (6) | −0.0023 (7) |
O14 | 0.0975 (13) | 0.0914 (13) | 0.0457 (9) | −0.0431 (11) | −0.0189 (8) | 0.0090 (8) |
Mn1—C12 | 1.8046 (18) | C6—O2 | 1.4161 (18) |
Mn1—C11 | 1.8367 (19) | C7—O1 | 1.243 (2) |
Mn1—C14 | 1.849 (2) | C7—C8 | 1.490 (2) |
Mn1—C13 | 1.8665 (18) | C8—H83 | 0.93 (2) |
Mn1—C1 | 2.0443 (15) | C8—H82 | 0.93 (2) |
Mn1—O1 | 2.0548 (11) | C8—H81 | 0.94 (3) |
C1—C6 | 1.382 (2) | C9—O3 | 1.195 (2) |
C1—C2 | 1.419 (2) | C9—O2 | 1.3611 (19) |
C2—C3 | 1.395 (2) | C9—C10 | 1.493 (2) |
C2—C7 | 1.453 (2) | C10—H101 | 0.94 (3) |
C3—C4 | 1.376 (2) | C10—H102 | 0.91 (3) |
C3—H3 | 0.90 (2) | C10—H103 | 0.94 (3) |
C4—C5 | 1.391 (2) | C11—O11 | 1.131 (2) |
C4—H4 | 0.97 (2) | C12—O12 | 1.150 (2) |
C5—C6 | 1.383 (2) | C13—O13 | 1.138 (2) |
C5—H5 | 0.97 (2) | C14—O14 | 1.133 (2) |
C12—Mn1—C11 | 90.40 (8) | C4—C5—H5 | 122.5 (11) |
C12—Mn1—C14 | 89.72 (8) | C1—C6—C5 | 123.10 (14) |
C11—Mn1—C14 | 95.64 (9) | C1—C6—O2 | 119.06 (13) |
C12—Mn1—C13 | 90.80 (8) | C5—C6—O2 | 117.74 (14) |
C11—Mn1—C13 | 96.13 (8) | O1—C7—C2 | 117.28 (13) |
C14—Mn1—C13 | 168.21 (8) | O1—C7—C8 | 119.36 (15) |
C12—Mn1—C1 | 100.08 (7) | C2—C7—C8 | 123.35 (15) |
C11—Mn1—C1 | 169.49 (7) | C7—C8—H83 | 110.0 (14) |
C14—Mn1—C1 | 85.22 (7) | C7—C8—H82 | 112.0 (14) |
C13—Mn1—C1 | 83.09 (6) | H83—C8—H82 | 106.7 (19) |
C12—Mn1—O1 | 179.05 (6) | C7—C8—H81 | 112.6 (15) |
C11—Mn1—O1 | 90.46 (7) | H83—C8—H81 | 110 (2) |
C14—Mn1—O1 | 89.80 (7) | H82—C8—H81 | 105 (2) |
C13—Mn1—O1 | 89.51 (6) | O3—C9—O2 | 122.64 (15) |
C1—Mn1—O1 | 79.06 (5) | O3—C9—C10 | 126.36 (16) |
C6—C1—C2 | 115.00 (13) | O2—C9—C10 | 111.00 (15) |
C6—C1—Mn1 | 132.64 (11) | C9—C10—H102 | 110.0 (16) |
C2—C1—Mn1 | 112.36 (11) | C9—C10—H103 | 111.9 (17) |
C3—C2—C1 | 123.14 (14) | H102—C10—H103 | 108 (2) |
C3—C2—C7 | 122.76 (14) | C9—C10—H101 | 108.0 (16) |
C1—C2—C7 | 114.09 (13) | H102—C10—H101 | 106 (2) |
C4—C3—C2 | 118.92 (15) | H103—C10—H101 | 113 (2) |
C4—C3—H3 | 120.1 (13) | O11—C11—Mn1 | 178.71 (19) |
C2—C3—H3 | 120.9 (13) | O12—C12—Mn1 | 177.51 (16) |
C3—C4—C5 | 119.73 (15) | O13—C13—Mn1 | 175.05 (15) |
C3—C4—H4 | 122.1 (12) | O14—C14—Mn1 | 176.86 (19) |
C5—C4—H4 | 118.1 (12) | C7—O1—Mn1 | 117.18 (10) |
C6—C5—C4 | 120.10 (15) | C9—O2—C6 | 117.20 (12) |
C6—C5—H5 | 117.4 (11) |
Experimental details
Crystal data | |
Chemical formula | [Mn(C10H9O3)(CO)4] |
Mr | 344.15 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 168 |
a, b, c (Å) | 9.306 (2), 9.635 (2), 9.954 (2) |
α, β, γ (°) | 68.594 (3), 67.663 (3), 68.422 (3) |
V (Å3) | 740.9 (3) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.92 |
Crystal size (mm) | 0.72 × 0.65 × 0.15 |
Data collection | |
Diffractometer | Bruker SMART CCD |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1998) |
Tmin, Tmax | 0.711, 0.870 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9684, 2988, 2730 |
Rint | 0.015 |
(sin θ/λ)max (Å−1) | 0.625 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.026, 0.073, 1.02 |
No. of reflections | 2988 |
No. of parameters | 235 |
H-atom treatment | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 0.26, −0.41 |
Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).
Subscribe to Acta Crystallographica Section E: Crystallographic Communications
The full text of this article is available to subscribers to the journal.
- Information on subscribing
- Sample issue
- If you have already subscribed, you may need to register
(2-Acetyl-κO1-6-acetoxyphenyl- κC1)tetracarbonylmanganese(I) is formed by orthomanganation of 3'-acetoxyacetophenone at the sterically crowded ortho site. The atoms of the phenyl and the cyclometallated rings are coplanar to within <0.018 Å, and there are no significant intramolecular interactions between the Mn(CO)4 group and the adjacent acetoxy one. The Mn1—C12 distance trans to O1 (1.8046 (18) Å) is shorter than the Mn1—C11 distance trans to C1 (1.8367 (19) Å), while the two Mn—CO distances trans to each other are the longest (av. 1.857 (2) Å). The Mn1—C1 distance is significantly shorter than the Mn1—O1 distance (2.0445 (15) and 2.0548 (11) Å respectively) contrary to the trend expected purely on covalent radii. These conform to the pattern found for other orthomanganated arenes (Main and Nicholson, 1994).