Download citation
Download citation
link to html
The Mn and Br atoms as well as one of the carbonyl groups of the title compound, [MnBr(CO)5], are located on a crystallographic mirror plane. As a result, there is just half a mol­ecule in the asymmetric unit displaying Cs symmetry. However, the deviations from C4v symmetry are very small. BrMn(CO)5 is isomorphous with ClMn(CO)5 and CH3Mn(CO)5.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803017197/lh6098sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536803017197/lh6098Isup2.hkl
Contains datablock I

Key indicators

  • Single-crystal X-ray study
  • T = 100 K
  • Mean [sigma](O-C) = 0.005 Å
  • R factor = 0.032
  • wR factor = 0.076
  • Data-to-parameter ratio = 15.7

checkCIF/PLATON results

No syntax errors found



Alert level C PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low ..... 0.99 PLAT040_ALERT_1_C No H-atoms in this Carbon Containing Compound ? PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Mn1 - C2 = 5.80 su PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Mn1 - C3 = 7.39 su
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 4 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 2 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion

Comment top

The central Mn atom in BrMn(CO)5 is octahedrally coordinated. The molecule has Cs symmetry. Mn, Br and one of the carbonyl groups are located on a mirror plane perpendicular to the b axis. The deviations from C4v symmetry are very small. The Mn—C bond trans to the Mn—Br bond is significantly shorter than the equatorial Mn—C bonds. BrMn(CO)5 is isomorphous with ClMn(CO)5 (Greene & Bryan, 1971) and CH3Mn(CO)5 (Andrews et al., 1983). Unfortunately, the methyl group in the latter structure is statistically disordered over all six coordination sites about the Mn atom.

Experimental top

BrMn(CO)5 was dissolved in C6D6 and heated to 353 K for 24 h. When the solution was cooled down to room temperature BrMn(CO)5 precipitated as yellow crystals.

Computing details top

Data collection: X-AREA (Stoe & Cie, 2001); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP in SHELXTL-Plus (Sheldrick, 1991); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. Perspective view of the title compound with the atom-numbering scheme; displacement ellipsoids are at the 50% probability level. The symmetry operator for generating equivalent atoms is (i) x, −y + 1/2, z.
Bromopentacarbonylmanganese top
Crystal data top
[MnBr(CO)5]F(000) = 520
Mr = 274.90Dx = 2.295 Mg m3
Orthorhombic, PnmaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2nCell parameters from 11620 reflections
a = 11.6252 (16) Åθ = 3.8–27.6°
b = 11.3317 (18) ŵ = 6.66 mm1
c = 6.0403 (10) ÅT = 100 K
V = 795.7 (2) Å3Plate, yellow
Z = 40.22 × 0.14 × 0.12 mm
Data collection top
Stoe IPDS-II two-circle
diffractometer
958 independent reflections
Radiation source: fine-focus sealed tube772 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.074
ω scansθmax = 27.6°, θmin = 3.9°
Absorption correction: multi-scan
(MULABS; Spek, 1990; Blessing, 1995)
h = 1415
Tmin = 0.290, Tmax = 0.452k = 1414
9213 measured reflectionsl = 77
Refinement top
Refinement on F20 restraints
Least-squares matrix: fullPrimary atom site location: structure-invariant direct methods
R[F2 > 2σ(F2)] = 0.032Secondary atom site location: difference Fourier map
wR(F2) = 0.076 w = 1/[σ2(Fo2) + (0.0409P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.00(Δ/σ)max < 0.001
958 reflectionsΔρmax = 0.60 e Å3
61 parametersΔρmin = 1.25 e Å3
Crystal data top
[MnBr(CO)5]V = 795.7 (2) Å3
Mr = 274.90Z = 4
Orthorhombic, PnmaMo Kα radiation
a = 11.6252 (16) ŵ = 6.66 mm1
b = 11.3317 (18) ÅT = 100 K
c = 6.0403 (10) Å0.22 × 0.14 × 0.12 mm
Data collection top
Stoe IPDS-II two-circle
diffractometer
958 independent reflections
Absorption correction: multi-scan
(MULABS; Spek, 1990; Blessing, 1995)
772 reflections with I > 2σ(I)
Tmin = 0.290, Tmax = 0.452Rint = 0.074
9213 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.03261 parameters
wR(F2) = 0.0760 restraints
S = 1.00Δρmax = 0.60 e Å3
958 reflectionsΔρmin = 1.25 e Å3
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Mn10.37968 (7)0.25000.44786 (13)0.02054 (19)
Br10.25152 (5)0.25000.11225 (8)0.02419 (16)
O10.5319 (3)0.25000.8427 (7)0.0287 (8)
O20.2236 (2)0.4385 (2)0.6351 (5)0.0303 (6)
O30.5172 (2)0.44526 (19)0.2329 (4)0.0300 (6)
C10.4722 (5)0.25000.6912 (9)0.0232 (10)
C20.2825 (3)0.3671 (3)0.5684 (6)0.0236 (7)
C30.4675 (3)0.3701 (3)0.3111 (6)0.0238 (7)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Mn10.0245 (4)0.0151 (3)0.0220 (4)0.0000.0002 (3)0.000
Br10.0269 (3)0.0215 (2)0.0242 (3)0.0000.0019 (2)0.000
O10.0307 (19)0.0274 (15)0.0280 (19)0.0000.0032 (18)0.000
O20.0332 (15)0.0213 (10)0.0365 (15)0.0028 (10)0.0037 (13)0.0008 (10)
O30.0322 (15)0.0219 (10)0.0358 (14)0.0026 (10)0.0022 (13)0.0033 (10)
C10.024 (2)0.0162 (17)0.029 (3)0.0000.006 (2)0.000
C20.0283 (17)0.0177 (12)0.0249 (17)0.0050 (13)0.0018 (15)0.0020 (13)
C30.0255 (17)0.0228 (14)0.0232 (16)0.0041 (13)0.0019 (15)0.0050 (13)
Geometric parameters (Å, º) top
Mn1—C11.821 (6)Mn1—Br12.5158 (10)
Mn1—C2i1.889 (4)O1—C11.149 (7)
Mn1—C21.889 (4)O2—C21.134 (4)
Mn1—C3i1.892 (4)O3—C31.132 (4)
Mn1—C31.892 (4)
C1—Mn1—C2i92.41 (16)C3i—Mn1—C392.0 (2)
C1—Mn1—C292.41 (16)C1—Mn1—Br1179.88 (17)
C2i—Mn1—C289.3 (2)C2i—Mn1—Br187.51 (11)
C1—Mn1—C3i91.93 (16)C2—Mn1—Br187.51 (11)
C2i—Mn1—C3i89.16 (14)C3i—Mn1—Br188.16 (11)
C2—Mn1—C3i175.46 (16)C3—Mn1—Br188.16 (11)
C1—Mn1—C391.93 (16)O1—C1—Mn1179.0 (5)
C2i—Mn1—C3175.46 (16)O2—C2—Mn1178.1 (3)
C2—Mn1—C389.16 (14)O3—C3—Mn1177.2 (3)
Symmetry code: (i) x, y+1/2, z.

Experimental details

Crystal data
Chemical formula[MnBr(CO)5]
Mr274.90
Crystal system, space groupOrthorhombic, Pnma
Temperature (K)100
a, b, c (Å)11.6252 (16), 11.3317 (18), 6.0403 (10)
V3)795.7 (2)
Z4
Radiation typeMo Kα
µ (mm1)6.66
Crystal size (mm)0.22 × 0.14 × 0.12
Data collection
DiffractometerStoe IPDS-II two-circle
diffractometer
Absorption correctionMulti-scan
(MULABS; Spek, 1990; Blessing, 1995)
Tmin, Tmax0.290, 0.452
No. of measured, independent and
observed [I > 2σ(I)] reflections
9213, 958, 772
Rint0.074
(sin θ/λ)max1)0.651
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.032, 0.076, 1.00
No. of reflections958
No. of parameters61
Δρmax, Δρmin (e Å3)0.60, 1.25

Computer programs: X-AREA (Stoe & Cie, 2001), X-AREA, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), XP in SHELXTL-Plus (Sheldrick, 1991), SHELXL97.

Selected geometric parameters (Å, º) top
Mn1—C11.821 (6)O1—C11.149 (7)
Mn1—C21.889 (4)O2—C21.134 (4)
Mn1—C31.892 (4)O3—C31.132 (4)
Mn1—Br12.5158 (10)
C1—Mn1—C292.41 (16)C2—Mn1—Br187.51 (11)
C2i—Mn1—C289.3 (2)C3—Mn1—Br188.16 (11)
C2—Mn1—C3i175.46 (16)O1—C1—Mn1179.0 (5)
C1—Mn1—C391.93 (16)O2—C2—Mn1178.1 (3)
C2—Mn1—C389.16 (14)O3—C3—Mn1177.2 (3)
C1—Mn1—Br1179.88 (17)
Symmetry code: (i) x, y+1/2, z.
 

Follow Acta Cryst. E
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds