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The title compound, [Mn(C10H9O3)(CO)4], is formed by orthomanganation of 3′-acetoxy­acetophenone at the sterically crowded ortho site. The atoms of the benzene 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 group.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807047605/fj2041sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807047605/fj2041Isup2.hkl
Contains datablock I

CCDC reference: 667112

Key indicators

  • Single-crystal X-ray study
  • T = 168 K
  • Mean [sigma](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

Comment top

(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).

Related literature top

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).

Experimental top

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.

Refinement top

All H-atoms were located as the highest peaks in a penultimate difference map and were refined with isotropic temperature factors.

Structure description top

(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).

Computing details top

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).

Figures top
[Figure 1] Fig. 1. Structure of (2-Acetyl-κO1-6-acetoxyphenyl- κC1)tetracarbonylmanganese(I), with ellipsoids drawn at the 30% probability level.
(6-Acetoxy-2-acetylphenyl-κ2C1,O1)tetracarbonylmanganese(I) top
Crystal data top
[Mn(C10H9O3)(CO)4]Z = 2
Mr = 344.15F(000) = 348
Triclinic, P1Dx = 1.543 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 9.306 (2) ÅCell parameters from 3920 reflections
b = 9.635 (2) Åθ = 2–26°
c = 9.954 (2) ŵ = 0.92 mm1
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
Data collection top
Bruker SMART CCD
diffractometer
2988 independent reflections
Radiation source: fine-focus sealed tube2730 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.015
ω scansθmax = 26.4°, θmin = 2.3°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1998)
h = 1111
Tmin = 0.711, Tmax = 0.870k = 1211
9684 measured reflectionsl = 1212
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.026Hydrogen site location: difference Fourier map
wR(F2) = 0.073All 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 parametersΔρmax = 0.26 e Å3
0 restraintsΔρmin = 0.41 e Å3
Crystal data top
[Mn(C10H9O3)(CO)4]γ = 68.422 (3)°
Mr = 344.15V = 740.9 (3) Å3
Triclinic, P1Z = 2
a = 9.306 (2) ÅMo Kα radiation
b = 9.635 (2) ŵ = 0.92 mm1
c = 9.954 (2) ÅT = 168 K
α = 68.594 (3)°0.72 × 0.65 × 0.15 mm
β = 67.663 (3)°
Data collection top
Bruker SMART CCD
diffractometer
2988 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1998)
2730 reflections with I > 2σ(I)
Tmin = 0.711, Tmax = 0.870Rint = 0.015
9684 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0260 restraints
wR(F2) = 0.073All H-atom parameters refined
S = 1.02Δρmax = 0.26 e Å3
2988 reflectionsΔρmin = 0.41 e Å3
235 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Mn10.15624 (3)0.30950 (3)0.24687 (2)0.03251 (9)
C10.37221 (17)0.14695 (17)0.24738 (15)0.0287 (3)
C20.46885 (18)0.18432 (17)0.30330 (16)0.0311 (3)
C30.6217 (2)0.09150 (19)0.31439 (19)0.0380 (3)
C40.6832 (2)0.0424 (2)0.2682 (2)0.0428 (4)
C50.5919 (2)0.08368 (19)0.21356 (19)0.0389 (3)
C60.44005 (18)0.00979 (17)0.20521 (16)0.0314 (3)
C70.3934 (2)0.32656 (18)0.35101 (16)0.0337 (3)
C80.4716 (3)0.3870 (2)0.4155 (2)0.0425 (4)
C90.29739 (19)0.15989 (18)0.22594 (19)0.0378 (3)
C100.2255 (3)0.2011 (2)0.1395 (3)0.0512 (5)
C110.0262 (2)0.4716 (2)0.2641 (2)0.0509 (4)
C120.0719 (2)0.2290 (2)0.1657 (2)0.0415 (4)
C130.08616 (19)0.1809 (2)0.43689 (19)0.0395 (4)
C140.2643 (2)0.4043 (2)0.0558 (2)0.0470 (4)
O10.25602 (14)0.39925 (12)0.33756 (13)0.0383 (3)
O20.35525 (14)0.03417 (12)0.14249 (12)0.0359 (2)
O30.30441 (17)0.22465 (16)0.35196 (16)0.0559 (4)
O110.1391 (2)0.5708 (2)0.2727 (2)0.0809 (5)
O120.01425 (17)0.18291 (17)0.11287 (17)0.0599 (4)
O130.05411 (16)0.09520 (18)0.55063 (15)0.0572 (4)
O140.3357 (2)0.4562 (2)0.06173 (17)0.0813 (5)
H30.679 (2)0.117 (2)0.353 (2)0.046 (5)*
H40.788 (2)0.112 (2)0.276 (2)0.048 (5)*
H50.629 (2)0.178 (2)0.182 (2)0.044 (5)*
H810.574 (3)0.399 (3)0.353 (3)0.075 (8)*
H820.489 (3)0.321 (3)0.506 (3)0.063 (6)*
H830.406 (3)0.481 (3)0.435 (2)0.059 (6)*
H1010.304 (3)0.215 (3)0.049 (3)0.081 (8)*
H1020.143 (3)0.120 (3)0.113 (3)0.072 (7)*
H1030.185 (3)0.288 (4)0.196 (3)0.093 (9)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Mn10.03310 (14)0.02938 (14)0.03785 (15)0.00427 (9)0.01615 (10)0.00960 (10)
C10.0313 (7)0.0291 (7)0.0266 (7)0.0100 (6)0.0102 (6)0.0042 (5)
C20.0357 (7)0.0310 (7)0.0297 (7)0.0133 (6)0.0121 (6)0.0039 (6)
C30.0358 (8)0.0409 (9)0.0417 (8)0.0121 (7)0.0175 (7)0.0069 (7)
C40.0341 (8)0.0444 (9)0.0480 (9)0.0038 (7)0.0168 (7)0.0115 (8)
C50.0402 (8)0.0337 (8)0.0406 (8)0.0032 (7)0.0123 (7)0.0129 (7)
C60.0374 (8)0.0307 (7)0.0289 (7)0.0109 (6)0.0115 (6)0.0068 (6)
C70.0448 (8)0.0304 (7)0.0302 (7)0.0155 (6)0.0148 (6)0.0030 (6)
C80.0582 (11)0.0383 (9)0.0444 (10)0.0193 (8)0.0241 (9)0.0089 (8)
C90.0356 (8)0.0287 (7)0.0500 (10)0.0049 (6)0.0148 (7)0.0124 (7)
C100.0623 (12)0.0427 (10)0.0631 (13)0.0209 (10)0.0232 (11)0.0170 (9)
C110.0477 (10)0.0448 (10)0.0624 (12)0.0007 (8)0.0264 (9)0.0182 (9)
C120.0398 (8)0.0392 (9)0.0482 (9)0.0061 (7)0.0203 (7)0.0105 (7)
C130.0323 (8)0.0479 (10)0.0430 (9)0.0094 (7)0.0142 (7)0.0147 (8)
C140.0565 (10)0.0435 (10)0.0458 (10)0.0138 (8)0.0259 (9)0.0045 (8)
O10.0462 (6)0.0299 (5)0.0451 (6)0.0062 (5)0.0207 (5)0.0128 (5)
O20.0471 (6)0.0323 (6)0.0362 (6)0.0136 (5)0.0170 (5)0.0091 (4)
O30.0630 (8)0.0504 (8)0.0587 (8)0.0268 (7)0.0330 (7)0.0092 (6)
O110.0606 (9)0.0622 (10)0.1086 (14)0.0228 (8)0.0392 (9)0.0332 (10)
O120.0597 (8)0.0649 (9)0.0777 (10)0.0146 (7)0.0405 (8)0.0235 (8)
O130.0491 (7)0.0742 (10)0.0447 (7)0.0256 (7)0.0133 (6)0.0023 (7)
O140.0975 (13)0.0914 (13)0.0457 (9)0.0431 (11)0.0189 (8)0.0090 (8)
Geometric parameters (Å, º) top
Mn1—C121.8046 (18)C6—O21.4161 (18)
Mn1—C111.8367 (19)C7—O11.243 (2)
Mn1—C141.849 (2)C7—C81.490 (2)
Mn1—C131.8665 (18)C8—H830.93 (2)
Mn1—C12.0443 (15)C8—H820.93 (2)
Mn1—O12.0548 (11)C8—H810.94 (3)
C1—C61.382 (2)C9—O31.195 (2)
C1—C21.419 (2)C9—O21.3611 (19)
C2—C31.395 (2)C9—C101.493 (2)
C2—C71.453 (2)C10—H1010.94 (3)
C3—C41.376 (2)C10—H1020.91 (3)
C3—H30.90 (2)C10—H1030.94 (3)
C4—C51.391 (2)C11—O111.131 (2)
C4—H40.97 (2)C12—O121.150 (2)
C5—C61.383 (2)C13—O131.138 (2)
C5—H50.97 (2)C14—O141.133 (2)
C12—Mn1—C1190.40 (8)C4—C5—H5122.5 (11)
C12—Mn1—C1489.72 (8)C1—C6—C5123.10 (14)
C11—Mn1—C1495.64 (9)C1—C6—O2119.06 (13)
C12—Mn1—C1390.80 (8)C5—C6—O2117.74 (14)
C11—Mn1—C1396.13 (8)O1—C7—C2117.28 (13)
C14—Mn1—C13168.21 (8)O1—C7—C8119.36 (15)
C12—Mn1—C1100.08 (7)C2—C7—C8123.35 (15)
C11—Mn1—C1169.49 (7)C7—C8—H83110.0 (14)
C14—Mn1—C185.22 (7)C7—C8—H82112.0 (14)
C13—Mn1—C183.09 (6)H83—C8—H82106.7 (19)
C12—Mn1—O1179.05 (6)C7—C8—H81112.6 (15)
C11—Mn1—O190.46 (7)H83—C8—H81110 (2)
C14—Mn1—O189.80 (7)H82—C8—H81105 (2)
C13—Mn1—O189.51 (6)O3—C9—O2122.64 (15)
C1—Mn1—O179.06 (5)O3—C9—C10126.36 (16)
C6—C1—C2115.00 (13)O2—C9—C10111.00 (15)
C6—C1—Mn1132.64 (11)C9—C10—H102110.0 (16)
C2—C1—Mn1112.36 (11)C9—C10—H103111.9 (17)
C3—C2—C1123.14 (14)H102—C10—H103108 (2)
C3—C2—C7122.76 (14)C9—C10—H101108.0 (16)
C1—C2—C7114.09 (13)H102—C10—H101106 (2)
C4—C3—C2118.92 (15)H103—C10—H101113 (2)
C4—C3—H3120.1 (13)O11—C11—Mn1178.71 (19)
C2—C3—H3120.9 (13)O12—C12—Mn1177.51 (16)
C3—C4—C5119.73 (15)O13—C13—Mn1175.05 (15)
C3—C4—H4122.1 (12)O14—C14—Mn1176.86 (19)
C5—C4—H4118.1 (12)C7—O1—Mn1117.18 (10)
C6—C5—C4120.10 (15)C9—O2—C6117.20 (12)
C6—C5—H5117.4 (11)

Experimental details

Crystal data
Chemical formula[Mn(C10H9O3)(CO)4]
Mr344.15
Crystal system, space groupTriclinic, 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)
V3)740.9 (3)
Z2
Radiation typeMo Kα
µ (mm1)0.92
Crystal size (mm)0.72 × 0.65 × 0.15
Data collection
DiffractometerBruker SMART CCD
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1998)
Tmin, Tmax0.711, 0.870
No. of measured, independent and
observed [I > 2σ(I)] reflections
9684, 2988, 2730
Rint0.015
(sin θ/λ)max1)0.625
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.026, 0.073, 1.02
No. of reflections2988
No. of parameters235
H-atom treatmentAll H-atom parameters refined
Δρmax, Δρmin (e Å3)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).

 

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