fac-Bromidotricarbonyl[2-(diisopropylphosphanyl)benzaldehyde-κ²O,P]rhenium(I)

The structure of the title complex, [ReBr(C₁₃H₁₉OP)(CO)₃], displays a facial coordination of the three CO ligands and a κ²O,P coordination mode of the 2-diisopropyl­phosphino­benzaldehyde ligands. The Re—C bond distance for the CO ligand trans to the P atom is, due to its trans influence, elongated to 1.943 (3) Å, showing that this CO ligand is more weakly bound to the Re centre than the other two.

Key indicators

• Single-crystal X-ray study
• T = 200 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.018
• wR factor = 0.045
• Data-to-parameter ratio = 20.1

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT919_ALERT_3_B Reflection # Likely Affected by the Beamstop ...          1
PLAT934_ALERT_3_B Number of (Iobs-Icalc)/SigmaW .gt. 10 Outliers .          1

Alert level C
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low .......      0.975
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600          2

Alert level G
PLAT005_ALERT_5_G No _iucr_refine_instructions_details in CIF ....          ?
PLAT164_ALERT_4_G Nr. of Refined C-H H-Atoms in Heavy-Atom Struct.          1
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X)  Re1    --  Br1     ..        6.3 su
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X)  Re1    --  C14     ..        6.0 su
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X)  Re1    --  C15     ..        6.5 su
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X)  Re1    --  C16     ..        5.8 su
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600         90

   0 ALERT level A = Most likely a serious problem - resolve or explain
   2 ALERT level B = A potentially serious problem, consider carefully
   2 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   7 ALERT level G = General information/check it is not something unexpected

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   4 ALERT type 2 Indicator that the structure model may be wrong or deficient
   4 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

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Related literature

For the structures of halo-fac-tricarbonyl-[η²-P,O-(ligand)]rhenium(I) complexes with ligands based on 2-diphenylphosphinobenzaldehyde or 2-diphenylphosphinobenzoic acid derivatives, see: Correia et al. (2001); Chen et al. (2001); Palma et al. (2004).

S1. Experimental

The title compound was obtained from the reaction of 371.0 mg (1.38 mmol) 2-diisopropylphosphinobenzaldehydedimethylacetale and 561.5 mg (1.38 mmol) bromo-pentacarbonyl-rhenium(I) in refluxing thf (30 ml) after recrystallization from diethylether in 93% yield (736 mg). Single crystals of the title compound were grown in an NMR tube with CDCl₃ as the solvant.

S2. Refinement

The position of the H atom located at the aldehyde carbon atom was localized and refined together with its isotropic displacement parameter. The positions of all other H atoms were calculated at geometrical positions according to the hybridization of the atoms they are bound to. The isotropic U values of the hydrogen atoms were refined group-wisely.

Computing details

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XPMA (Zsolnai, 1996), ORTEP (Farrugia, 1997); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures

Fig. 1. Molecular structure of the title compound with displacement ellipsoids at the 50% probability level.

fac-Bromidotricarbonyl[2-(diisopropylphosphanyl)benzaldehyde- κ²O,P]rhenium(I)

Crystal data

[ReBr(C13H19OP)(CO)3]	F(000) = 1088
Mr = 572.39	Dx = 2.082 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 165 reflections
a = 10.750 (2) Å	θ = 2.3–28.3°
b = 15.194 (3) Å	µ = 8.94 mm^−1
c = 13.699 (3) Å	T = 200 K
β = 125.29 (3)°	Cube, orange
V = 1826.4 (9) Å^3	0.43 × 0.33 × 0.31 mm
Z = 4

Data collection

Siemens SMART 1000 CCD diffractometer	4436 independent reflections
Radiation source: fine-focus sealed tube	4095 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.027
Detector resolution: 8 pixels mm^-1	θmax = 28.3°, θmin = 2.3°
ω scans	h = −14→14
Absorption correction: numerical SADABS (Bruker, 1997)	k = −19→19
Tmin = 0.631, Tmax = 1	l = −17→17
18487 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.018	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.045	H atoms treated by a mixture of independent and constrained refinement
S = 1.11	w = 1/[σ^2(Fo^2) + (0.0228P)^2 + 0.987P] where P = (Fo^2 + 2Fc^2)/3
4436 reflections	(Δ/σ)max = 0.002
221 parameters	Δρmax = 0.51 e Å^−3
0 restraints	Δρmin = −1.04 e Å^−3

Special details

Experimental. Spectroscopic data: ¹H{³¹P} NMR (CDCl₃): δ = 9.71, s, 1H, CHO; 7.99, dd, ³J_HH = 7.5 Hz, ⁴J_HH = 1.2 Hz, 1H, CH(arom); 7.89, dt, ³J_HH = 7.5 Hz, ⁴J_HH = 1.2 Hz, 1H, CH(arom); 7.78, dt, ³J_HH = 7.5 Hz, ⁴J_HH = 1.2 Hz, 1H, CH(arom); 7.72, dd, ³J_HH = 7.5 Hz, ⁴J_HH = 1.2 Hz, 1H, CH(arom); 2.94, hept, ³J_HH = 7.0 Hz, 1H, CH(Me)₂; 2.55, hept, ³J_HH = 6.9 Hz, 1H, CH(Me)₂; 1.38, d, ³J_HH = 7.0 Hz, 3H, CH₃; 1.31, d, ³J_HH = 7.0 Hz, 3H, CH₃; 1.03, d, ³J_HH = 7.0 Hz, 3H, CH₃; 0.97, d, ³J_HH = 6.9 Hz, 3H, CH₃; ³¹P{¹H} NMR (CDCl₃): δ = 19.7, s; ¹³C{³¹P}{¹H} NMR (CDCl₃): δ = 200.6; 196.2; 190.3; 141.0; 136.0; 132.5; 131.6; 27.9; 23.3; 18.9; 18.2; 17.2; 16.2; IR ν_CO [cm^-1]: 2041, 1949, 1905, 1634; UV vis (CHCl₃): 414 nm (ε 2142); 261 nm (ε 9780); UV vis (MeCN): 391 nm (ε 1794); 312 nm (sh); 257 nm (ε 7952); 214 nm (ε 27000)

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. The data of the structure have been deposited at the CCDC with the reference number 894003 (Allen, 2002).

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Re1	0.096757 (10)	0.651316 (6)	0.822326 (9)	0.01984 (4)
Br1	0.09257 (4)	0.70831 (2)	1.00026 (3)	0.03331 (7)
P1	−0.17759 (7)	0.68270 (4)	0.68063 (6)	0.01901 (13)
O1	0.0136 (2)	0.53062 (12)	0.85118 (17)	0.0246 (4)
O2	0.2119 (2)	0.83034 (14)	0.8052 (2)	0.0381 (5)
O3	0.4316 (2)	0.59455 (16)	1.0029 (2)	0.0446 (6)
O4	0.1170 (3)	0.57547 (15)	0.6249 (2)	0.0387 (5)
C1	−0.2889 (3)	0.63407 (17)	0.7300 (2)	0.0217 (5)
C2	−0.4274 (3)	0.6705 (2)	0.6956 (3)	0.0294 (6)
H2	−0.4596	0.7228	0.6525	0.035 (4)*
C3	−0.5192 (3)	0.6307 (2)	0.7243 (3)	0.0343 (7)
H3	−0.6104	0.6571	0.7013	0.035 (4)*
C4	−0.4759 (3)	0.5528 (2)	0.7861 (3)	0.0320 (6)
H4	−0.5383	0.5258	0.8038	0.035 (4)*
C5	−0.3387 (3)	0.51476 (19)	0.8221 (2)	0.0275 (6)
H5	−0.3092	0.4618	0.8638	0.035 (4)*
C6	−0.2436 (3)	0.55548 (17)	0.7962 (2)	0.0220 (5)
C7	−0.1008 (3)	0.50735 (17)	0.8444 (2)	0.0231 (5)
C8	−0.2409 (3)	0.79816 (17)	0.6455 (3)	0.0273 (6)
H8	−0.3526	0.7981	0.5939	0.038 (9)*
C9	−0.1909 (4)	0.8520 (2)	0.7555 (3)	0.0427 (8)
H9A	−0.0820	0.8576	0.8046	0.049 (4)*
H9B	−0.2227	0.8231	0.8000	0.049 (4)*
H9C	−0.2365	0.9093	0.7316	0.049 (4)*
C10	−0.1865 (4)	0.8395 (2)	0.5746 (3)	0.0390 (8)
H10A	−0.2189	0.8998	0.5572	0.049 (4)*
H10B	−0.2292	0.8077	0.5011	0.049 (4)*
H10C	−0.0773	0.8368	0.6209	0.049 (4)*
C11	−0.2622 (3)	0.6290 (2)	0.5325 (3)	0.0288 (6)
H11	−0.2026	0.6485	0.5029	0.030 (9)*
C12	−0.4282 (4)	0.6553 (2)	0.4382 (3)	0.0429 (8)
H12A	−0.4655	0.6244	0.3650	0.048 (4)*
H12B	−0.4338	0.7176	0.4242	0.048 (4)*
H12C	−0.4892	0.6404	0.4663	0.048 (4)*
C13	−0.2484 (4)	0.5296 (2)	0.5436 (3)	0.0357 (7)
H13A	−0.3162	0.5073	0.5620	0.048 (4)*
H13B	−0.1455	0.5138	0.6063	0.048 (4)*
H13C	−0.2749	0.5047	0.4694	0.048 (4)*
C14	0.1677 (3)	0.76221 (19)	0.8091 (2)	0.0262 (6)
C15	0.3070 (3)	0.6152 (2)	0.9370 (3)	0.0296 (6)
C16	0.1055 (3)	0.60419 (18)	0.6968 (3)	0.0256 (6)
H7	−0.101 (3)	0.4472 (19)	0.876 (2)	0.015 (7)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Re1	0.01570 (6)	0.01934 (6)	0.02291 (6)	−0.00064 (3)	0.01024 (4)	0.00179 (4)
Br1	0.04358 (17)	0.02932 (15)	0.02861 (14)	−0.00256 (12)	0.02177 (13)	−0.00259 (12)
P1	0.0162 (3)	0.0179 (3)	0.0219 (3)	−0.0005 (2)	0.0105 (2)	0.0015 (3)
O1	0.0244 (9)	0.0195 (9)	0.0297 (10)	0.0009 (7)	0.0155 (8)	0.0024 (8)
O2	0.0290 (11)	0.0302 (11)	0.0431 (13)	−0.0090 (9)	0.0139 (10)	0.0058 (10)
O3	0.0185 (10)	0.0465 (14)	0.0523 (14)	0.0029 (9)	0.0110 (10)	0.0147 (11)
O4	0.0445 (13)	0.0394 (13)	0.0460 (13)	−0.0008 (10)	0.0342 (11)	−0.0043 (10)
C1	0.0184 (12)	0.0227 (13)	0.0240 (13)	−0.0042 (10)	0.0122 (10)	−0.0025 (10)
C2	0.0242 (14)	0.0278 (15)	0.0385 (16)	−0.0006 (11)	0.0194 (12)	0.0019 (12)
C3	0.0220 (14)	0.0438 (18)	0.0406 (17)	−0.0017 (12)	0.0201 (13)	−0.0037 (14)
C4	0.0296 (15)	0.0386 (17)	0.0346 (15)	−0.0143 (13)	0.0225 (13)	−0.0074 (13)
C5	0.0296 (14)	0.0285 (14)	0.0261 (13)	−0.0083 (11)	0.0172 (11)	−0.0033 (11)
C6	0.0238 (12)	0.0200 (13)	0.0227 (12)	−0.0051 (10)	0.0136 (10)	−0.0037 (10)
C7	0.0265 (13)	0.0186 (13)	0.0242 (13)	−0.0033 (10)	0.0147 (11)	−0.0013 (10)
C8	0.0219 (13)	0.0190 (13)	0.0375 (15)	0.0028 (10)	0.0151 (12)	0.0069 (11)
C9	0.0440 (19)	0.0245 (16)	0.054 (2)	0.0056 (13)	0.0251 (17)	−0.0042 (14)
C10	0.0322 (16)	0.0329 (17)	0.0437 (19)	−0.0016 (12)	0.0171 (14)	0.0165 (14)
C11	0.0243 (13)	0.0342 (15)	0.0253 (14)	0.0002 (11)	0.0127 (11)	−0.0040 (12)
C12	0.0294 (16)	0.053 (2)	0.0275 (16)	−0.0033 (14)	0.0055 (13)	−0.0007 (14)
C13	0.0361 (16)	0.0339 (17)	0.0338 (16)	−0.0083 (13)	0.0184 (13)	−0.0114 (13)
C14	0.0182 (12)	0.0294 (15)	0.0268 (14)	0.0000 (10)	0.0106 (10)	0.0037 (11)
C15	0.0241 (14)	0.0283 (15)	0.0338 (15)	−0.0038 (11)	0.0152 (12)	0.0044 (12)
C16	0.0210 (12)	0.0241 (14)	0.0316 (14)	0.0002 (10)	0.0151 (11)	0.0033 (11)

Geometric parameters (Å, º)

Re1—C14	1.901 (3)	C5—H5	0.9300
Re1—C15	1.943 (3)	C6—C7	1.468 (4)
Re1—C16	1.915 (3)	C7—H7	1.01 (3)
Re1—O1	2.1739 (18)	C8—C9	1.514 (5)
Re1—P1	2.4655 (13)	C8—C10	1.528 (4)
Re1—Br1	2.6116 (6)	C8—H8	0.9800
P1—C1	1.835 (3)	C9—H9A	0.9600
P1—C8	1.842 (3)	C9—H9B	0.9600
P1—C11	1.865 (3)	C9—H9C	0.9600
O1—C7	1.231 (3)	C10—H10A	0.9600
O2—C14	1.153 (3)	C10—H10B	0.9600
O3—C15	1.144 (3)	C10—H10C	0.9600
O4—C16	1.148 (3)	C11—C13	1.517 (4)
C1—C2	1.392 (4)	C11—C12	1.533 (4)
C1—C6	1.406 (4)	C11—H11	0.9800
C2—C3	1.393 (4)	C12—H12A	0.9600
C2—H2	0.9300	C12—H12B	0.9600
C3—C4	1.371 (5)	C12—H12C	0.9600
C3—H3	0.9300	C13—H13A	0.9600
C4—C5	1.383 (4)	C13—H13B	0.9600
C4—H4	0.9300	C13—H13C	0.9600
C5—C6	1.405 (3)
C14—Re1—C16	90.87 (12)	O1—C7—H7	118.4 (15)
C14—Re1—C15	89.06 (12)	C6—C7—H7	112.5 (15)
C16—Re1—C15	89.00 (12)	C9—C8—C10	111.4 (3)
C14—Re1—O1	174.15 (10)	C9—C8—P1	112.9 (2)
C16—Re1—O1	94.97 (9)	C10—C8—P1	109.7 (2)
C15—Re1—O1	91.35 (10)	C9—C8—H8	107.5
C14—Re1—P1	96.71 (8)	C10—C8—H8	107.5
C16—Re1—P1	91.28 (8)	P1—C8—H8	107.5
C15—Re1—P1	174.22 (8)	C8—C9—H9A	109.5
O1—Re1—P1	82.87 (5)	C8—C9—H9B	109.5
C14—Re1—Br1	91.10 (9)	H9A—C9—H9B	109.5
C16—Re1—Br1	177.00 (8)	C8—C9—H9C	109.5
C15—Re1—Br1	88.77 (10)	H9A—C9—H9C	109.5
O1—Re1—Br1	83.07 (5)	H9B—C9—H9C	109.5
P1—Re1—Br1	90.74 (3)	C8—C10—H10A	109.5
C1—P1—C8	104.98 (12)	C8—C10—H10B	109.5
C1—P1—C11	102.31 (13)	H10A—C10—H10B	109.5
C8—P1—C11	104.94 (14)	C8—C10—H10C	109.5
C1—P1—Re1	111.71 (9)	H10A—C10—H10C	109.5
C8—P1—Re1	118.89 (9)	H10B—C10—H10C	109.5
C11—P1—Re1	112.42 (10)	C13—C11—C12	110.0 (3)
C7—O1—Re1	136.60 (18)	C13—C11—P1	111.6 (2)
C2—C1—C6	117.4 (2)	C12—C11—P1	113.6 (2)
C2—C1—P1	120.9 (2)	C13—C11—H11	107.1
C6—C1—P1	121.56 (19)	C12—C11—H11	107.1
C1—C2—C3	121.7 (3)	P1—C11—H11	107.1
C1—C2—H2	119.1	C11—C12—H12A	109.5
C3—C2—H2	119.1	C11—C12—H12B	109.5
C4—C3—C2	120.4 (3)	H12A—C12—H12B	109.5
C4—C3—H3	119.8	C11—C12—H12C	109.5
C2—C3—H3	119.8	H12A—C12—H12C	109.5
C3—C4—C5	119.6 (3)	H12B—C12—H12C	109.5
C3—C4—H4	120.2	C11—C13—H13A	109.5
C5—C4—H4	120.2	C11—C13—H13B	109.5
C4—C5—C6	120.5 (3)	H13A—C13—H13B	109.5
C4—C5—H5	119.7	C11—C13—H13C	109.5
C6—C5—H5	119.7	H13A—C13—H13C	109.5
C5—C6—C1	120.4 (2)	H13B—C13—H13C	109.5
C5—C6—C7	113.0 (2)	O2—C14—Re1	177.4 (3)
C1—C6—C7	126.6 (2)	O3—C15—Re1	178.6 (3)
O1—C7—C6	129.1 (2)	O4—C16—Re1	177.2 (2)