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The title compound, [Re(C12H8N2)(CO)3Cl], contains isolated molecular units. Rhenium(I) is six-coordinated by the two N atoms of 1,10-phenanthroline, three carbonyls and one chloride anion. The coordination sphere is a distorted octahedron, with the chloride anion trans to one of the carbonyls. There is a significant trans influence, which lengthens one of the Re—C bonds by ca. 0.05 Å. The bidentate 1,10-phenanthroline deviates slightly from planarity, with a dihedral angle between its two heterocyclic rings of 5.5 (3)°, and is folded away from the chloride anion. The Re(I) atom lies 0.192 (3) Å from the least-squares plane of 1,10-phenanthroline. There are no π ring interactions between adjacent 1,10-phenanthroline rings.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802016379/wn6111sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536802016379/wn6111Isup2.hkl
Contains datablock I

CCDC reference: 198307

Key indicators

  • Single-crystal X-ray study
  • T = 203 K
  • Mean [sigma](C-C) = 0.009 Å
  • R factor = 0.027
  • wR factor = 0.067
  • Data-to-parameter ratio = 12.5

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry








Comment top

Charge-transfer excited states of rhenium(I) diimine complexes result in properties which make these molecules useful as photosensitizers in photochemical and photo-electron transfer reactions (Luong et al., 1978; Richter et al., 1996; Stufkens & Vlcek, 1998), as well as in situ chemical probes (Lees, 1998; Tran et al., 1997). The existence of a Frank-Condon-type barrier between close-lying metal-to-ligand charge transfer (MLCT) and ligand-centered (LC) states for both the singlet states and for the triplet manifolds has been suggested (Striplin & Crosby, 1994; Striplin & Crosby, 2001); also the possibility of preferential loading of the triplet manifolds that is dependent on the nature of the singlet state to which the molecule is excited or of the singlet state to which the excited state initially deactivates through internal conversion (IC). The title compound, (I), is one molecule in a series of rhenium(I) complexes which have been synthesized to examine the validity of the barrier proposal.

The asymmetric unit is shown in Fig. 1. The Re—N distances are 2.181 (5) and 2.186 (5) Å, and the bidentate bite angle N—Re—N is 75.8 (2)°. The Cl—Re—N bond angles are 83.40 (12) and 85.43 (12)°, significantly less than expected for octahedral geometry. There is a noticeable trans influence induced by the Cl atom on the carbonyl Re—C distance. The Re—C17 distance is ca 0.05 Å longer than the Re—C15 and Re—C16 distances. The bidentate 1,10-phenanthroline deviates slightly from planarity, with a dihedral angle between its two heterocyclic rings of 5.48(0.34)°, and is folded away from the chloride anion. The Re(I) atom lies 0.192 (3) Å from the least-squares plane of 1,10-phenanthroline (Fig. 2).

Some C—H···Cl interactions exist (Neve & Crispini, 2001; Freytag et al., 1999), also C—H···O interactions, as shown in Fig. 3: Cl···C2i 3.584 (6), Cl···C3ii 3.704 (6), O15···C9iii 3.498 (7), O16···C7iv 3.393 (8), O16···C14v 3.473, O17···C7vi 3.460 (8), O17···C9vii 3.378 (7) Å [symmetry codes: (i) −1 + x, y, z; (ii) 1 − x, 1 − y, −z; (iii) −x, 2 − y, 1 − z; (iv) 1 + x, 1 + y, z; (v) 1 + x, 1 + y, z; (vi) −x, 1 − y, 1 − z; (vii) 1 + x, 1 + y, z. These long H contacts with electronegative Cl and O may account for the folding in the 1,10-phenanthroline moiety. There are no stacking effects between adjacent 1,10-phenanthroline moieties; the closest atomic contact of 3.285 (11) Å is between C2 and C3viii [symmetry code: (viii) 1 − x, 1 − y, z].

Experimental top

Rhenium pentacarbonyl chloride (0.1 mmol, 37 mg) and 1,10-phenanthroline (0.11 mmol, 20 mg) were refluxed in toluene for 1 h under N2. The resulting yellow precipitate was collected by vacuum filtration and chromatographed on a column of silica gel (60–200 mesh), first with CH2Cl2 to elute unreacted starting materials, and then with 5% methanol in CH2Cl2 to elute the desired product. Slow evaporation of the solvent yielded the product as yellow crystals.

Refinement top

H atoms were placed geometrically and refined using a riding model, with Uiso values constrained to be 1.2Ueq of the carrier atom. The largest residual electron density peak is 1.91 e.Å −3 and lies at 1.06 Å from the Re atom.

Computing details top

Data collection: SMART (Bruker, 1997-98); cell refinement: SAINT-Plus (Bruker, 1999); data reduction: SHELXTL (Sheldrick, 1998); program(s) used to solve structure: XS in SHELXTL; program(s) used to refine structure: XL in SHELXTL; molecular graphics: XP in SHELXTL; software used to prepare material for publication: XCIF in SHELXTL.

Figures top
[Figure 1] Fig. 1. A view of (I). Displacement ellipsoids are drawn at the 25% probability level.
[Figure 2] Fig. 2. Equatorial view of the 1,10-phenanthroline moiety in (I).
[Figure 3] Fig. 3. Intermolecular hydrogen contacts involving Cl and carbonyl O atoms. Only one complete molecule of (I) is shown. Contacts to the 1,10-phenanthroline units of other molecules are represented by dashed lines.
Fac-tricarbonylchloro(1,10-phenanthroline)rhenium(I) top
Crystal data top
[Re(C12H8N2)(CO)3Cl]Z = 2
Mr = 485.88F(000) = 456
Triclinic, P1Dx = 2.262 Mg m3
a = 6.4536 (14) ÅMo Kα radiation, λ = 0.71073 Å
b = 9.132 (2) ÅCell parameters from 950 reflections
c = 12.841 (3) Åθ = 2.4–27.4°
α = 108.264 (3)°µ = 8.72 mm1
β = 95.935 (3)°T = 203 K
γ = 91.440 (3)°Plate, yellow
V = 713.5 (3) Å30.13 × 0.08 × 0.03 mm
Data collection top
Siemens SMART 1K CCD
diffractometer
2509 independent reflections
Radiation source: normal-focus sealed tube2286 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.031
Detector resolution: 8.3 pixels mm-1θmax = 25.0°, θmin = 2.4°
ω scansh = 77
Absorption correction: multi-scan
(SADABS; Sheldrick, 1999)
k = 1010
Tmin = 0.397, Tmax = 0.780l = 1515
7351 measured reflections
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)] = 0.027Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.067H-atom parameters constrained
S = 1.04 w = 1/[σ2(Fo2) + (0.0427P)2]
where P = (Fo2 + 2Fc2)/3
2509 reflections(Δ/σ)max < 0.001
200 parametersΔρmax = 1.91 e Å3
0 restraintsΔρmin = 1.38 e Å3
Crystal data top
[Re(C12H8N2)(CO)3Cl]γ = 91.440 (3)°
Mr = 485.88V = 713.5 (3) Å3
Triclinic, P1Z = 2
a = 6.4536 (14) ÅMo Kα radiation
b = 9.132 (2) ŵ = 8.72 mm1
c = 12.841 (3) ÅT = 203 K
α = 108.264 (3)°0.13 × 0.08 × 0.03 mm
β = 95.935 (3)°
Data collection top
Siemens SMART 1K CCD
diffractometer
2509 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1999)
2286 reflections with I > 2σ(I)
Tmin = 0.397, Tmax = 0.780Rint = 0.031
7351 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0270 restraints
wR(F2) = 0.067H-atom parameters constrained
S = 1.04Δρmax = 1.91 e Å3
2509 reflectionsΔρmin = 1.38 e Å3
200 parameters
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
Re0.24818 (3)0.76085 (2)0.293721 (18)0.02225 (10)
Cl0.0123 (2)0.71967 (18)0.11861 (13)0.0311 (3)
N10.3725 (7)0.5433 (5)0.2014 (4)0.0230 (10)
C20.5408 (9)0.5258 (7)0.1457 (5)0.0267 (13)
H20.62620.61390.15210.032*
C30.5935 (9)0.3819 (8)0.0785 (5)0.0299 (14)
H30.71150.37440.04040.036*
C40.4726 (10)0.2527 (7)0.0689 (5)0.0333 (14)
H40.50580.15570.02320.040*
C50.2984 (9)0.2654 (7)0.1274 (5)0.0280 (13)
C60.0411 (8)0.3041 (7)0.2579 (5)0.0247 (12)
C70.1987 (9)0.3299 (7)0.3287 (5)0.0300 (14)
H70.28120.24630.33320.036*
C80.2308 (9)0.4775 (7)0.3907 (5)0.0296 (14)
H80.33650.49590.43760.036*
C90.1063 (9)0.6005 (7)0.3842 (5)0.0264 (13)
H90.13090.70110.42730.032*
N100.0472 (7)0.5814 (5)0.3190 (4)0.0209 (10)
C110.0824 (8)0.4331 (6)0.2582 (4)0.0207 (12)
C120.2551 (8)0.4143 (6)0.1940 (5)0.0212 (12)
C130.1625 (10)0.1372 (7)0.1248 (5)0.0311 (14)
H130.18540.03830.07800.037*
C140.0037 (9)0.1530 (7)0.1867 (5)0.0295 (13)
H140.07920.06530.18380.035*
O150.0104 (7)1.0478 (5)0.4025 (4)0.0393 (11)
C150.1007 (9)0.9398 (7)0.3634 (5)0.0283 (13)
C160.4410 (10)0.8945 (7)0.2562 (5)0.0297 (14)
O160.5550 (7)0.9725 (5)0.2296 (4)0.0440 (12)
C170.4213 (9)0.7847 (6)0.4354 (5)0.0249 (13)
O170.5122 (8)0.8039 (6)0.5134 (4)0.0449 (12)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Re0.01975 (13)0.02004 (14)0.02647 (15)0.00248 (9)0.00854 (9)0.00513 (10)
Cl0.0276 (7)0.0327 (8)0.0341 (8)0.0004 (6)0.0087 (6)0.0107 (7)
N10.020 (2)0.026 (3)0.024 (3)0.003 (2)0.0076 (19)0.008 (2)
C20.020 (3)0.032 (3)0.029 (3)0.001 (2)0.007 (2)0.010 (3)
C30.021 (3)0.042 (4)0.030 (3)0.005 (3)0.009 (2)0.016 (3)
C40.036 (3)0.031 (4)0.035 (4)0.011 (3)0.008 (3)0.011 (3)
C50.031 (3)0.026 (3)0.028 (3)0.006 (3)0.006 (2)0.007 (3)
C60.022 (3)0.026 (3)0.028 (3)0.004 (2)0.005 (2)0.010 (3)
C70.027 (3)0.031 (3)0.037 (4)0.007 (3)0.005 (3)0.018 (3)
C80.023 (3)0.037 (4)0.034 (3)0.003 (3)0.012 (2)0.016 (3)
C90.022 (3)0.026 (3)0.029 (3)0.001 (2)0.009 (2)0.004 (3)
N100.019 (2)0.020 (2)0.022 (3)0.0005 (19)0.0049 (19)0.005 (2)
C110.021 (3)0.018 (3)0.023 (3)0.000 (2)0.004 (2)0.007 (2)
C120.021 (3)0.020 (3)0.023 (3)0.001 (2)0.004 (2)0.007 (2)
C130.038 (3)0.022 (3)0.032 (4)0.006 (3)0.007 (3)0.006 (3)
C140.034 (3)0.021 (3)0.035 (4)0.004 (3)0.002 (3)0.012 (3)
O150.050 (3)0.029 (3)0.042 (3)0.012 (2)0.017 (2)0.011 (2)
C150.029 (3)0.027 (3)0.030 (3)0.002 (3)0.006 (3)0.011 (3)
C160.033 (3)0.024 (3)0.027 (3)0.001 (3)0.001 (3)0.002 (3)
O160.042 (3)0.035 (3)0.058 (3)0.014 (2)0.020 (2)0.016 (2)
C170.020 (3)0.017 (3)0.029 (3)0.004 (2)0.016 (3)0.008 (2)
O170.040 (3)0.047 (3)0.046 (3)0.005 (2)0.008 (2)0.011 (2)
Geometric parameters (Å, º) top
Re—C161.921 (7)C6—C71.409 (8)
Re—C151.927 (6)C6—C141.452 (8)
Re—C171.981 (7)C7—C81.367 (9)
Re—N102.188 (5)C7—H70.9400
Re—N12.191 (5)C8—C91.393 (8)
Re—Cl2.4996 (16)C8—H80.9400
N1—C21.347 (7)C9—N101.342 (7)
N1—C121.356 (7)C9—H90.9400
C2—C31.400 (8)N10—C111.373 (7)
C2—H20.9400C11—C121.436 (7)
C3—C41.363 (9)C13—C141.344 (9)
C3—H30.9400C13—H130.9400
C4—C51.403 (9)C14—H140.9400
C4—H40.9400O15—C151.160 (7)
C5—C121.414 (8)C16—O161.158 (8)
C5—C131.435 (9)C17—O171.069 (7)
C6—C111.404 (8)
C16—Re—C1588.5 (3)C11—C6—C7117.6 (5)
C16—Re—C1791.6 (2)C11—C6—C14118.3 (5)
C15—Re—C1790.6 (2)C7—C6—C14124.2 (5)
C16—Re—N10171.8 (2)C8—C7—C6119.5 (5)
C15—Re—N1099.5 (2)C8—C7—H7120.3
C17—Re—N1090.6 (2)C6—C7—H7120.3
C16—Re—N196.4 (2)C7—C8—C9119.8 (5)
C15—Re—N1171.8 (2)C7—C8—H8120.1
C17—Re—N195.86 (19)C9—C8—H8120.1
N10—Re—N175.42 (17)N10—C9—C8122.8 (5)
C16—Re—Cl92.32 (18)N10—C9—H9118.6
C15—Re—Cl89.37 (18)C8—C9—H9118.6
C17—Re—Cl176.12 (17)C9—N10—C11117.5 (5)
N10—Re—Cl85.61 (12)C9—N10—Re127.6 (4)
N1—Re—Cl83.88 (12)C11—N10—Re114.8 (3)
C2—N1—C12117.8 (5)N10—C11—C6122.7 (5)
C2—N1—Re127.1 (4)N10—C11—C12116.7 (5)
C12—N1—Re114.8 (3)C6—C11—C12120.6 (5)
N1—C2—C3122.6 (6)N1—C12—C5122.6 (5)
N1—C2—H2118.7N1—C12—C11117.5 (5)
C3—C2—H2118.7C5—C12—C11119.9 (5)
C4—C3—C2119.6 (5)C14—C13—C5122.6 (5)
C4—C3—H3120.2C14—C13—H13118.7
C2—C3—H3120.2C5—C13—H13118.7
C3—C4—C5119.6 (6)C13—C14—C6120.6 (5)
C3—C4—H4120.2C13—C14—H14119.7
C5—C4—H4120.2C6—C14—H14119.7
C4—C5—C12117.7 (6)O15—C15—Re178.1 (5)
C4—C5—C13124.4 (5)O16—C16—Re177.6 (5)
C12—C5—C13117.9 (5)O17—C17—Re176.9 (5)
C16—Re—N1—C23.8 (5)Cl—Re—N10—C1178.0 (4)
C17—Re—N1—C288.4 (5)C9—N10—C11—C63.1 (8)
N10—Re—N1—C2177.5 (5)Re—N10—C11—C6175.5 (4)
Cl—Re—N1—C295.5 (5)C9—N10—C11—C12176.5 (5)
C16—Re—N1—C12170.9 (4)Re—N10—C11—C125.0 (6)
C17—Re—N1—C1296.9 (4)C7—C6—C11—N103.9 (8)
N10—Re—N1—C127.8 (4)C14—C6—C11—N10177.2 (5)
Cl—Re—N1—C1279.2 (4)C7—C6—C11—C12175.7 (5)
C12—N1—C2—C32.2 (8)C14—C6—C11—C123.3 (8)
Re—N1—C2—C3172.3 (4)C2—N1—C12—C52.5 (8)
N1—C2—C3—C40.6 (9)Re—N1—C12—C5172.7 (4)
C2—C3—C4—C50.8 (9)C2—N1—C12—C11176.8 (5)
C3—C4—C5—C120.5 (9)Re—N1—C12—C118.0 (6)
C3—C4—C5—C13179.0 (6)C4—C5—C12—N11.2 (9)
C11—C6—C7—C82.5 (8)C13—C5—C12—N1179.3 (5)
C14—C6—C7—C8178.6 (6)C4—C5—C12—C11178.1 (5)
C6—C7—C8—C90.6 (9)C13—C5—C12—C111.4 (8)
C7—C8—C9—N100.2 (9)N10—C11—C12—N12.0 (7)
C8—C9—N10—C111.0 (8)C6—C11—C12—N1177.5 (5)
C8—C9—N10—Re177.3 (4)N10—C11—C12—C5178.7 (5)
C15—Re—N10—C911.7 (5)C6—C11—C12—C51.8 (8)
C17—Re—N10—C979.0 (5)C4—C5—C13—C14176.3 (6)
N1—Re—N10—C9174.9 (5)C12—C5—C13—C143.2 (9)
Cl—Re—N10—C9100.3 (5)C5—C13—C14—C61.7 (9)
C15—Re—N10—C11166.7 (4)C11—C6—C14—C131.6 (8)
C17—Re—N10—C11102.7 (4)C7—C6—C14—C13177.3 (6)
N1—Re—N10—C116.8 (4)

Experimental details

Crystal data
Chemical formula[Re(C12H8N2)(CO)3Cl]
Mr485.88
Crystal system, space groupTriclinic, P1
Temperature (K)203
a, b, c (Å)6.4536 (14), 9.132 (2), 12.841 (3)
α, β, γ (°)108.264 (3), 95.935 (3), 91.440 (3)
V3)713.5 (3)
Z2
Radiation typeMo Kα
µ (mm1)8.72
Crystal size (mm)0.13 × 0.08 × 0.03
Data collection
DiffractometerSiemens SMART 1K CCD
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1999)
Tmin, Tmax0.397, 0.780
No. of measured, independent and
observed [I > 2σ(I)] reflections
7351, 2509, 2286
Rint0.031
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.027, 0.067, 1.04
No. of reflections2509
No. of parameters200
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)1.91, 1.38

Computer programs: SMART (Bruker, 1997-98), SAINT-Plus (Bruker, 1999), SHELXTL (Sheldrick, 1998), XS in SHELXTL, XL in SHELXTL, XP in SHELXTL, XCIF in SHELXTL.

 

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