Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807051203/bt2543sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807051203/bt2543Isup2.hkl |
CCDC reference: 667189
Key indicators
- Single-crystal X-ray study
- T = 133 K
- Mean (C-C) = 0.004 Å
- R factor = 0.041
- wR factor = 0.098
- Data-to-parameter ratio = 19.6
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ? PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given ....... ? PLAT220_ALERT_2_C Large Non-Solvent C Ueq(max)/Ueq(min) ... 3.27 Ratio PLAT244_ALERT_4_C Low 'Solvent' Ueq as Compared to Neighbors for P PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd. # 2 F6 P
Alert level G PLAT794_ALERT_5_G Check Predicted Bond Valency for Cu (2) 2.28
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 5 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 1 ALERT type 2 Indicator that the structure model may be wrong or deficient 0 ALERT type 3 Indicator that the structure quality may be low 3 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check
The title compound was prepared according to the literature procedure (Petrovic et al., 2007). Crystals could be obtained selectively as clear yellow prisms by cooling the acetone solution. The compound exhibits dichroism (the previously reported acetone solvate, obtained by evaporation of an acetone solution, is deep green or red depending on the view direction), but we have not investigated this phenomenon further.
The bicarbonate hydrogen H1 was freely refined. Methyl H atoms were included on the basis of idealized rigid groups (C—H 0.98 Å, H—C—H 109.5°) allowed to rotate but not tip. Other hydrogen atoms were included using a riding model with C—H 0.95 (aromatic) or 0.99 (methylene) Å. U(H) values were fixed at 1.2Uiso(C) of the parent C atom.
As we have recently demonstrated (Petrovic et al., 2007), copper(I) complexes of the highly basic pincer ligand 2,6-bis[(1,3-di-tert-butylimidazolin-2-imino)methyl]pyridine, TLtBu, are extremely reactive and exhibit a pronounced tendency to form stable, square-planar copper(II) complexes. Exposure of an acetone solution of [(TLtBu)Cu]PF6 to the air readily leads to oxidation and trapping of atmospheric CO2 to form the square-planar complex [(TLtBu)Cu(HCO3-κO)]PF6 with the bicarbonate ligand adopting a rarely observed monodentate coordination mode. The compound was previously crystallized as an acetone solvate (Petrovic et al., 2007). Here we report the structure of the solvent-free material. All structural features of the cation [(TLtBu)Cu(HCO3-κO)]+ are very similar to those of the acetone solvate. The copper center displays a slightly distorted square-planar environment; the sum of the four cis angles is 359.38°. The copper atom lies 0.049 (2) Å out of the plane defined by the donor atoms N1, N2 and N3. The displacement of the metal-bound oxygen atom O1 of the bicarbonate ligand, 0.224 (5) Å in the opposite direction, is considerably greater, which is presumably a consequence of minimizing the steric interaction with the bulky di-tert-butylimidazolin-2-ylidene moieties. As a result, the N1—Cu—O1 angle of 170.38 (8)° deviates significantly from linearity. The Cu—O1 distance of 1.9205 (16) Å is very short in comparison to the other structurally characterized copper(II) bicarbonate complexes. The angles in the bicarbonate unit are close to 120°, and the C—O distances (Table 1), with a much longer C30—O3 bond, clearly indicate that the hydrogen atom of the HCO3 unit is bound to O3. This was in any case confirmed by free refinement of this hydrogen position. The packing involves inversion-symmetric cation dimers bridged via hydrogen bonding of the bicarbonate groups (analogous to the well known "carboxylic acid dimer" type; Table 2), as observed for the acetone solvate (with two crystallographically independent formula units, each associating over an inversion centre to a dimer) and in some other transition metal bicarbonate complexes (Hossain et al., 1981; Ito et al., 1994; Darensbourg et al., 1996; Jazzar et al., 2003; Kim et al., 2004).
For related literature, see: Darensbourg et al. (1996); Hossain et al. (1981); Ito et al. (1994); Jazzar et al. (2003); Kim et al. (2004); Petrovic et al. (2007); Steiner (2002).
Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP (Siemens, 1994); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).
Fig. 1. The formula unit of the title compound in the crystal. Ellipsoids represent 30% probability levels. Hydrogen atoms and butyl atom labels have been omitted for clarity. |
[Cu(CHO3)(C29H47N7)]PF6 | Z = 2 |
Mr = 763.26 | F(000) = 798 |
Triclinic, P1 | Dx = 1.423 Mg m−3 |
a = 9.0309 (12) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 13.824 (2) Å | Cell parameters from 8159 reflections |
c = 15.654 (2) Å | θ = 2–28° |
α = 109.619 (3)° | µ = 0.73 mm−1 |
β = 101.729 (4)° | T = 133 K |
γ = 94.164 (3)° | Prism, yellow |
V = 1781.2 (4) Å3 | 0.20 × 0.11 × 0.08 mm |
Bruker SMART 1000 CCD diffractometer | 8789 independent reflections |
Radiation source: fine-focus sealed tube | 6166 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.053 |
Detector resolution: 8.192 pixels mm-1 | θmax = 28.3°, θmin = 1.4° |
ω and φ scans | h = −11→12 |
Absorption correction: multi-scan (SADABS; Bruker, 1998) | k = −18→18 |
Tmin = 0.868, Tmax = 0.944 | l = −20→20 |
33075 measured reflections |
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)] = 0.042 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.098 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0337P)2 + 1.4465P] where P = (Fo2 + 2Fc2)3 |
8789 reflections | (Δ/σ)max < 0.001 |
449 parameters | Δρmax = 0.46 e Å−3 |
0 restraints | Δρmin = −0.41 e Å−3 |
[Cu(CHO3)(C29H47N7)]PF6 | γ = 94.164 (3)° |
Mr = 763.26 | V = 1781.2 (4) Å3 |
Triclinic, P1 | Z = 2 |
a = 9.0309 (12) Å | Mo Kα radiation |
b = 13.824 (2) Å | µ = 0.73 mm−1 |
c = 15.654 (2) Å | T = 133 K |
α = 109.619 (3)° | 0.20 × 0.11 × 0.08 mm |
β = 101.729 (4)° |
Bruker SMART 1000 CCD diffractometer | 8789 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 1998) | 6166 reflections with I > 2σ(I) |
Tmin = 0.868, Tmax = 0.944 | Rint = 0.053 |
33075 measured reflections |
R[F2 > 2σ(F2)] = 0.042 | 0 restraints |
wR(F2) = 0.098 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | Δρmax = 0.46 e Å−3 |
8789 reflections | Δρmin = −0.41 e Å−3 |
449 parameters |
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. Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane) - 6.3861 (0.0088) x + 7.5326 (0.0093) y + 6.7527 (0.0131) z = 1.9001 (0.0040) * 0.0000 (0.0000) N1 * 0.0000 (0.0000) N2 * 0.0000 (0.0000) N3 0.0486 (0.0017) Cu -0.2240 (0.0045) O1 Rms deviation of fitted atoms = 0.0000 3.0050 (0.0115) x + 11.4156 (0.0098) y - 11.5236 (0.0125) z = 1.4495 (0.0078) Angle to previous plane (with approximate e.s.d.) = 89.00 (0.08) * 0.0000 (0.0000) O1 * 0.0000 (0.0000) O2 * 0.0000 (0.0000) O3 0.0052 (0.0026) C30 Rms deviation of fitted atoms = 0.0000 |
Refinement. Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > σ(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
Cu | 0.23080 (3) | 0.25694 (2) | 0.220239 (18) | 0.01536 (8) | |
P | 0.18744 (8) | 0.18997 (5) | −0.23416 (4) | 0.02368 (15) | |
O1 | 0.43029 (19) | 0.31751 (13) | 0.30096 (11) | 0.0248 (4) | |
O2 | 0.3586 (2) | 0.44446 (16) | 0.40803 (13) | 0.0399 (5) | |
O3 | 0.5977 (2) | 0.40524 (17) | 0.43152 (14) | 0.0368 (5) | |
H1 | 0.607 (4) | 0.458 (3) | 0.484 (3) | 0.066 (12)* | |
N1 | 0.0481 (2) | 0.18007 (14) | 0.12599 (12) | 0.0153 (4) | |
N2 | 0.2354 (2) | 0.33105 (14) | 0.13469 (12) | 0.0163 (4) | |
N3 | 0.1781 (2) | 0.15538 (15) | 0.27650 (13) | 0.0203 (4) | |
N4 | 0.3319 (2) | 0.51640 (14) | 0.19051 (13) | 0.0195 (4) | |
N5 | 0.4858 (2) | 0.40802 (16) | 0.13604 (14) | 0.0221 (4) | |
N6 | 0.1977 (2) | 0.23238 (15) | 0.44538 (13) | 0.0235 (5) | |
N7 | 0.3711 (2) | 0.13706 (15) | 0.39765 (13) | 0.0224 (4) | |
F1 | 0.2607 (2) | 0.28868 (12) | −0.14117 (11) | 0.0438 (4) | |
F2 | 0.1146 (2) | 0.09254 (13) | −0.32614 (12) | 0.0504 (5) | |
F3 | 0.34247 (18) | 0.19827 (12) | −0.26827 (12) | 0.0408 (4) | |
F4 | 0.2523 (2) | 0.11459 (14) | −0.18277 (13) | 0.0522 (5) | |
F5 | 0.03368 (19) | 0.18281 (13) | −0.19943 (12) | 0.0427 (4) | |
F6 | 0.1247 (2) | 0.26685 (15) | −0.28479 (13) | 0.0512 (5) | |
C1 | 0.0126 (3) | 0.20213 (17) | 0.04791 (15) | 0.0161 (4) | |
C2 | −0.1082 (3) | 0.14157 (18) | −0.02528 (16) | 0.0196 (5) | |
H2 | −0.1332 | 0.1554 | −0.0815 | 0.024* | |
C3 | −0.1921 (3) | 0.05982 (18) | −0.01428 (17) | 0.0234 (5) | |
H3 | −0.2762 | 0.0179 | −0.0634 | 0.028* | |
C4 | −0.1544 (3) | 0.03885 (18) | 0.06722 (16) | 0.0218 (5) | |
H4 | −0.2121 | −0.0167 | 0.0747 | 0.026* | |
C5 | −0.0304 (2) | 0.10082 (17) | 0.13787 (15) | 0.0166 (5) | |
C6 | 0.1133 (3) | 0.29510 (18) | 0.04916 (15) | 0.0192 (5) | |
H6A | 0.1575 | 0.2755 | −0.0061 | 0.023* | |
H6B | 0.0522 | 0.3512 | 0.0471 | 0.023* | |
C7 | 0.0292 (3) | 0.08814 (18) | 0.22988 (16) | 0.0214 (5) | |
H7A | −0.0440 | 0.1077 | 0.2698 | 0.026* | |
H7B | 0.0412 | 0.0147 | 0.2194 | 0.026* | |
C8 | 0.3419 (3) | 0.41321 (17) | 0.15052 (15) | 0.0172 (5) | |
C9 | 0.4700 (3) | 0.5742 (2) | 0.19914 (19) | 0.0297 (6) | |
H9 | 0.4936 | 0.6479 | 0.2236 | 0.036* | |
C10 | 0.5630 (3) | 0.5087 (2) | 0.16724 (19) | 0.0305 (6) | |
H10 | 0.6656 | 0.5275 | 0.1659 | 0.037* | |
C11 | 0.2396 (3) | 0.17239 (17) | 0.36715 (16) | 0.0189 (5) | |
C12 | 0.3025 (3) | 0.2319 (2) | 0.52342 (17) | 0.0315 (6) | |
H12 | 0.2992 | 0.2660 | 0.5866 | 0.038* | |
C13 | 0.4083 (3) | 0.1757 (2) | 0.49465 (17) | 0.0303 (6) | |
H13 | 0.4947 | 0.1640 | 0.5339 | 0.036* | |
C14 | 0.1976 (3) | 0.56795 (18) | 0.21563 (16) | 0.0225 (5) | |
C15 | 0.0870 (3) | 0.5000 (2) | 0.2413 (2) | 0.0322 (6) | |
H15A | 0.0386 | 0.4385 | 0.1861 | 0.039* | |
H15B | 0.0082 | 0.5396 | 0.2639 | 0.039* | |
H15C | 0.1432 | 0.4783 | 0.2905 | 0.039* | |
C16 | 0.1178 (4) | 0.5944 (2) | 0.1323 (2) | 0.0388 (7) | |
H16A | 0.1886 | 0.6431 | 0.1208 | 0.047* | |
H16B | 0.0277 | 0.6264 | 0.1458 | 0.047* | |
H16C | 0.0858 | 0.5307 | 0.0768 | 0.047* | |
C17 | 0.2579 (4) | 0.6672 (2) | 0.3017 (2) | 0.0426 (7) | |
H17A | 0.3211 | 0.6501 | 0.3519 | 0.051* | |
H17B | 0.1715 | 0.6983 | 0.3227 | 0.051* | |
H17C | 0.3198 | 0.7166 | 0.2855 | 0.051* | |
C18 | 0.5652 (3) | 0.3173 (2) | 0.09667 (18) | 0.0261 (6) | |
C19 | 0.6273 (4) | 0.3355 (3) | 0.0180 (2) | 0.0405 (7) | |
H19A | 0.5428 | 0.3431 | −0.0286 | 0.049* | |
H19B | 0.6757 | 0.2761 | −0.0119 | 0.049* | |
H19C | 0.7029 | 0.3989 | 0.0442 | 0.049* | |
C20 | 0.6955 (3) | 0.3160 (2) | 0.1756 (2) | 0.0344 (6) | |
H20A | 0.7660 | 0.3818 | 0.1998 | 0.041* | |
H20B | 0.7508 | 0.2583 | 0.1516 | 0.041* | |
H20C | 0.6534 | 0.3073 | 0.2260 | 0.041* | |
C21 | 0.4611 (3) | 0.2128 (2) | 0.0560 (2) | 0.0334 (6) | |
H21A | 0.4231 | 0.1988 | 0.1057 | 0.040* | |
H21B | 0.5187 | 0.1579 | 0.0285 | 0.040* | |
H21C | 0.3744 | 0.2144 | 0.0076 | 0.040* | |
C22 | 0.0600 (3) | 0.2867 (2) | 0.45535 (17) | 0.0274 (6) | |
C23 | −0.0643 (3) | 0.2122 (2) | 0.4646 (2) | 0.0367 (7) | |
H23A | −0.0925 | 0.1497 | 0.4079 | 0.044* | |
H23B | −0.1544 | 0.2464 | 0.4729 | 0.044* | |
H23C | −0.0255 | 0.1929 | 0.5188 | 0.044* | |
C24 | 0.0022 (3) | 0.3225 (2) | 0.37383 (18) | 0.0309 (6) | |
H24A | 0.0861 | 0.3662 | 0.3669 | 0.037* | |
H24B | −0.0813 | 0.3626 | 0.3861 | 0.037* | |
H24C | −0.0352 | 0.2618 | 0.3162 | 0.037* | |
C25 | 0.1057 (4) | 0.3842 (2) | 0.54454 (18) | 0.0353 (7) | |
H25A | 0.1336 | 0.3637 | 0.5991 | 0.042* | |
H25B | 0.0193 | 0.4230 | 0.5498 | 0.042* | |
H25C | 0.1933 | 0.4281 | 0.5416 | 0.042* | |
C26 | 0.4527 (3) | 0.05894 (19) | 0.33900 (18) | 0.0271 (6) | |
C27 | 0.5864 (3) | 0.0373 (2) | 0.4033 (2) | 0.0367 (7) | |
H27A | 0.6544 | 0.1025 | 0.4420 | 0.044* | |
H27B | 0.6432 | −0.0107 | 0.3656 | 0.044* | |
H27C | 0.5475 | 0.0060 | 0.4436 | 0.044* | |
C28 | 0.5182 (4) | 0.1009 (2) | 0.2734 (2) | 0.0413 (7) | |
H28A | 0.4342 | 0.1107 | 0.2279 | 0.050* | |
H28B | 0.5780 | 0.0512 | 0.2403 | 0.050* | |
H28C | 0.5843 | 0.1676 | 0.3098 | 0.050* | |
C29 | 0.3417 (4) | −0.0418 (2) | 0.2847 (3) | 0.0529 (9) | |
H29A | 0.3010 | −0.0664 | 0.3285 | 0.063* | |
H29B | 0.3954 | −0.0945 | 0.2495 | 0.063* | |
H29C | 0.2573 | −0.0293 | 0.2413 | 0.063* | |
C30 | 0.4539 (3) | 0.39054 (19) | 0.37901 (17) | 0.0235 (5) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu | 0.01664 (14) | 0.01417 (14) | 0.01280 (13) | −0.00348 (11) | 0.00252 (10) | 0.00351 (10) |
P | 0.0280 (3) | 0.0187 (3) | 0.0246 (3) | −0.0005 (3) | 0.0085 (3) | 0.0079 (3) |
O1 | 0.0226 (9) | 0.0255 (9) | 0.0184 (8) | −0.0075 (8) | −0.0006 (7) | 0.0033 (7) |
O2 | 0.0253 (10) | 0.0459 (12) | 0.0284 (10) | 0.0048 (9) | −0.0034 (8) | −0.0062 (9) |
O3 | 0.0237 (10) | 0.0412 (12) | 0.0266 (10) | 0.0006 (9) | −0.0050 (8) | −0.0042 (9) |
N1 | 0.0147 (9) | 0.0141 (9) | 0.0154 (9) | 0.0002 (8) | 0.0049 (7) | 0.0026 (7) |
N2 | 0.0164 (9) | 0.0152 (9) | 0.0160 (9) | −0.0029 (8) | 0.0020 (8) | 0.0061 (8) |
N3 | 0.0241 (10) | 0.0185 (10) | 0.0158 (9) | −0.0056 (9) | 0.0024 (8) | 0.0063 (8) |
N4 | 0.0203 (10) | 0.0148 (9) | 0.0224 (10) | −0.0011 (8) | 0.0052 (8) | 0.0062 (8) |
N5 | 0.0171 (10) | 0.0221 (10) | 0.0297 (11) | 0.0017 (9) | 0.0076 (8) | 0.0120 (9) |
N6 | 0.0318 (12) | 0.0220 (11) | 0.0184 (10) | 0.0032 (9) | 0.0075 (9) | 0.0090 (8) |
N7 | 0.0283 (11) | 0.0188 (10) | 0.0194 (10) | 0.0002 (9) | 0.0040 (9) | 0.0077 (8) |
F1 | 0.0565 (11) | 0.0339 (9) | 0.0293 (8) | −0.0152 (8) | 0.0116 (8) | 0.0004 (7) |
F2 | 0.0455 (10) | 0.0424 (10) | 0.0413 (10) | −0.0112 (9) | 0.0121 (8) | −0.0101 (8) |
F3 | 0.0379 (9) | 0.0306 (9) | 0.0543 (10) | −0.0012 (7) | 0.0242 (8) | 0.0096 (8) |
F4 | 0.0572 (12) | 0.0454 (11) | 0.0690 (13) | 0.0096 (9) | 0.0119 (10) | 0.0413 (10) |
F5 | 0.0389 (9) | 0.0346 (9) | 0.0542 (11) | −0.0020 (8) | 0.0263 (8) | 0.0083 (8) |
F6 | 0.0643 (12) | 0.0567 (12) | 0.0515 (11) | 0.0241 (10) | 0.0203 (10) | 0.0370 (10) |
C1 | 0.0168 (11) | 0.0146 (11) | 0.0159 (11) | 0.0049 (9) | 0.0067 (9) | 0.0021 (9) |
C2 | 0.0181 (11) | 0.0196 (12) | 0.0170 (11) | 0.0038 (10) | 0.0022 (9) | 0.0023 (9) |
C3 | 0.0171 (11) | 0.0202 (12) | 0.0235 (12) | −0.0017 (10) | −0.0011 (10) | 0.0004 (10) |
C4 | 0.0186 (12) | 0.0155 (11) | 0.0274 (13) | −0.0008 (10) | 0.0064 (10) | 0.0030 (10) |
C5 | 0.0149 (11) | 0.0147 (11) | 0.0194 (11) | 0.0025 (9) | 0.0074 (9) | 0.0031 (9) |
C6 | 0.0203 (11) | 0.0190 (11) | 0.0175 (11) | −0.0018 (10) | 0.0030 (9) | 0.0076 (9) |
C7 | 0.0210 (12) | 0.0194 (12) | 0.0218 (12) | −0.0050 (10) | 0.0032 (10) | 0.0078 (10) |
C8 | 0.0193 (11) | 0.0171 (11) | 0.0165 (11) | 0.0011 (9) | 0.0043 (9) | 0.0080 (9) |
C9 | 0.0272 (13) | 0.0205 (13) | 0.0383 (15) | −0.0078 (11) | 0.0033 (12) | 0.0116 (11) |
C10 | 0.0193 (12) | 0.0277 (14) | 0.0461 (16) | −0.0062 (11) | 0.0080 (12) | 0.0171 (13) |
C11 | 0.0231 (12) | 0.0136 (11) | 0.0194 (11) | −0.0044 (10) | 0.0051 (10) | 0.0068 (9) |
C12 | 0.0472 (17) | 0.0291 (14) | 0.0159 (12) | 0.0080 (13) | 0.0027 (12) | 0.0075 (11) |
C13 | 0.0400 (16) | 0.0268 (14) | 0.0206 (13) | 0.0052 (12) | −0.0020 (11) | 0.0095 (11) |
C14 | 0.0270 (13) | 0.0180 (12) | 0.0226 (12) | 0.0056 (10) | 0.0076 (10) | 0.0063 (10) |
C15 | 0.0300 (14) | 0.0318 (15) | 0.0403 (16) | 0.0102 (12) | 0.0203 (12) | 0.0120 (13) |
C16 | 0.0461 (18) | 0.0456 (18) | 0.0350 (16) | 0.0259 (15) | 0.0150 (14) | 0.0207 (14) |
C17 | 0.0467 (18) | 0.0300 (15) | 0.0390 (17) | 0.0025 (14) | 0.0121 (14) | −0.0032 (13) |
C18 | 0.0234 (12) | 0.0337 (14) | 0.0296 (13) | 0.0111 (11) | 0.0135 (11) | 0.0166 (12) |
C19 | 0.0439 (17) | 0.0520 (19) | 0.0454 (17) | 0.0229 (15) | 0.0285 (15) | 0.0289 (16) |
C20 | 0.0236 (13) | 0.0438 (17) | 0.0433 (16) | 0.0109 (13) | 0.0106 (12) | 0.0226 (14) |
C21 | 0.0311 (15) | 0.0272 (14) | 0.0388 (16) | 0.0127 (12) | 0.0119 (12) | 0.0044 (12) |
C22 | 0.0360 (15) | 0.0257 (13) | 0.0226 (13) | 0.0042 (12) | 0.0132 (11) | 0.0077 (11) |
C23 | 0.0405 (16) | 0.0358 (16) | 0.0383 (16) | 0.0017 (13) | 0.0216 (13) | 0.0126 (13) |
C24 | 0.0352 (15) | 0.0304 (14) | 0.0317 (14) | 0.0107 (12) | 0.0117 (12) | 0.0138 (12) |
C25 | 0.0501 (18) | 0.0285 (15) | 0.0279 (14) | 0.0092 (14) | 0.0170 (13) | 0.0060 (12) |
C26 | 0.0323 (14) | 0.0202 (12) | 0.0277 (13) | 0.0062 (11) | 0.0071 (11) | 0.0069 (11) |
C27 | 0.0353 (15) | 0.0422 (17) | 0.0435 (17) | 0.0148 (14) | 0.0155 (13) | 0.0237 (14) |
C28 | 0.0520 (19) | 0.0480 (19) | 0.0382 (16) | 0.0233 (16) | 0.0230 (15) | 0.0232 (15) |
C29 | 0.0393 (18) | 0.0242 (15) | 0.073 (2) | 0.0037 (14) | 0.0066 (17) | −0.0056 (15) |
C30 | 0.0229 (12) | 0.0238 (13) | 0.0218 (12) | −0.0032 (11) | 0.0040 (10) | 0.0079 (10) |
Cu—O1 | 1.9205 (16) | C13—H13 | 0.9500 |
Cu—N1 | 1.9318 (17) | C14—C15 | 1.523 (3) |
Cu—N2 | 1.9449 (17) | C14—C16 | 1.527 (3) |
Cu—N3 | 1.9689 (18) | C14—C17 | 1.531 (4) |
P—F2 | 1.5824 (17) | C15—H15A | 0.9800 |
P—F4 | 1.5925 (17) | C15—H15B | 0.9800 |
P—F6 | 1.5967 (17) | C15—H15C | 0.9800 |
P—F5 | 1.5989 (17) | C16—H16A | 0.9800 |
P—F1 | 1.6007 (16) | C16—H16B | 0.9800 |
P—F3 | 1.6063 (17) | C16—H16C | 0.9800 |
O1—C30 | 1.262 (3) | C17—H17A | 0.9800 |
O2—C30 | 1.236 (3) | C17—H17B | 0.9800 |
O3—C30 | 1.349 (3) | C17—H17C | 0.9800 |
O3—H1 | 0.88 (4) | C18—C21 | 1.522 (4) |
N1—C1 | 1.340 (3) | C18—C20 | 1.530 (3) |
N1—C5 | 1.347 (3) | C18—C19 | 1.538 (3) |
N2—C8 | 1.353 (3) | C19—H19A | 0.9800 |
N2—C6 | 1.459 (3) | C19—H19B | 0.9800 |
N3—C11 | 1.347 (3) | C19—H19C | 0.9800 |
N3—C7 | 1.473 (3) | C20—H20A | 0.9800 |
N4—C8 | 1.370 (3) | C20—H20B | 0.9800 |
N4—C9 | 1.388 (3) | C20—H20C | 0.9800 |
N4—C14 | 1.505 (3) | C21—H21A | 0.9800 |
N5—C8 | 1.367 (3) | C21—H21B | 0.9800 |
N5—C10 | 1.388 (3) | C21—H21C | 0.9800 |
N5—C18 | 1.503 (3) | C22—C24 | 1.529 (3) |
N6—C11 | 1.372 (3) | C22—C23 | 1.529 (3) |
N6—C12 | 1.387 (3) | C22—C25 | 1.535 (4) |
N6—C22 | 1.507 (3) | C23—H23A | 0.9800 |
N7—C11 | 1.373 (3) | C23—H23B | 0.9800 |
N7—C13 | 1.388 (3) | C23—H23C | 0.9800 |
N7—C26 | 1.509 (3) | C24—H24A | 0.9800 |
C1—C2 | 1.385 (3) | C24—H24B | 0.9800 |
C1—C6 | 1.512 (3) | C24—H24C | 0.9800 |
C2—C3 | 1.393 (3) | C25—H25A | 0.9800 |
C2—H2 | 0.9500 | C25—H25B | 0.9800 |
C3—C4 | 1.383 (3) | C25—H25C | 0.9800 |
C3—H3 | 0.9500 | C26—C27 | 1.524 (4) |
C4—C5 | 1.390 (3) | C26—C29 | 1.524 (4) |
C4—H4 | 0.9500 | C26—C28 | 1.529 (4) |
C5—C7 | 1.504 (3) | C27—H27A | 0.9800 |
C6—H6A | 0.9900 | C27—H27B | 0.9800 |
C6—H6B | 0.9900 | C27—H27C | 0.9800 |
C7—H7A | 0.9900 | C28—H28A | 0.9800 |
C7—H7B | 0.9900 | C28—H28B | 0.9800 |
C9—C10 | 1.324 (4) | C28—H28C | 0.9800 |
C9—H9 | 0.9500 | C29—H29A | 0.9800 |
C10—H10 | 0.9500 | C29—H29B | 0.9800 |
C12—C13 | 1.329 (4) | C29—H29C | 0.9800 |
C12—H12 | 0.9500 | ||
O1—Cu—N1 | 170.38 (8) | C16—C14—C17 | 110.4 (2) |
O1—Cu—N2 | 97.30 (7) | C14—C15—H15A | 109.5 |
N1—Cu—N2 | 81.77 (7) | C14—C15—H15B | 109.5 |
O1—Cu—N3 | 98.51 (7) | H15A—C15—H15B | 109.5 |
N1—Cu—N3 | 81.77 (8) | C14—C15—H15C | 109.5 |
N2—Cu—N3 | 163.36 (7) | H15A—C15—H15C | 109.5 |
F2—P—F4 | 89.86 (11) | H15B—C15—H15C | 109.5 |
F2—P—F6 | 90.87 (11) | C14—C16—H16A | 109.5 |
F4—P—F6 | 179.11 (11) | C14—C16—H16B | 109.5 |
F2—P—F5 | 90.27 (9) | H16A—C16—H16B | 109.5 |
F4—P—F5 | 89.88 (10) | C14—C16—H16C | 109.5 |
F6—P—F5 | 90.62 (10) | H16A—C16—H16C | 109.5 |
F2—P—F1 | 179.82 (13) | H16B—C16—H16C | 109.5 |
F4—P—F1 | 90.27 (10) | C14—C17—H17A | 109.5 |
F6—P—F1 | 89.00 (10) | C14—C17—H17B | 109.5 |
F5—P—F1 | 89.62 (9) | H17A—C17—H17B | 109.5 |
F2—P—F3 | 90.28 (9) | C14—C17—H17C | 109.5 |
F4—P—F3 | 90.25 (10) | H17A—C17—H17C | 109.5 |
F6—P—F3 | 89.25 (10) | H17B—C17—H17C | 109.5 |
F5—P—F3 | 179.44 (10) | N5—C18—C21 | 113.9 (2) |
F1—P—F3 | 89.83 (9) | N5—C18—C20 | 107.6 (2) |
C30—O1—Cu | 123.98 (17) | C21—C18—C20 | 109.1 (2) |
C30—O3—H1 | 108 (2) | N5—C18—C19 | 106.8 (2) |
C1—N1—C5 | 122.78 (18) | C21—C18—C19 | 108.3 (2) |
C1—N1—Cu | 118.34 (14) | C20—C18—C19 | 111.1 (2) |
C5—N1—Cu | 118.62 (15) | C18—C19—H19A | 109.5 |
C8—N2—C6 | 119.15 (17) | C18—C19—H19B | 109.5 |
C8—N2—Cu | 124.25 (14) | H19A—C19—H19B | 109.5 |
C6—N2—Cu | 116.59 (13) | C18—C19—H19C | 109.5 |
C11—N3—C7 | 119.26 (18) | H19A—C19—H19C | 109.5 |
C11—N3—Cu | 120.79 (14) | H19B—C19—H19C | 109.5 |
C7—N3—Cu | 115.19 (14) | C18—C20—H20A | 109.5 |
C8—N4—C9 | 108.4 (2) | C18—C20—H20B | 109.5 |
C8—N4—C14 | 130.01 (18) | H20A—C20—H20B | 109.5 |
C9—N4—C14 | 121.4 (2) | C18—C20—H20C | 109.5 |
C8—N5—C10 | 108.1 (2) | H20A—C20—H20C | 109.5 |
C8—N5—C18 | 131.80 (19) | H20B—C20—H20C | 109.5 |
C10—N5—C18 | 120.1 (2) | C18—C21—H21A | 109.5 |
C11—N6—C12 | 108.3 (2) | C18—C21—H21B | 109.5 |
C11—N6—C22 | 130.7 (2) | H21A—C21—H21B | 109.5 |
C12—N6—C22 | 120.9 (2) | C18—C21—H21C | 109.5 |
C11—N7—C13 | 108.1 (2) | H21A—C21—H21C | 109.5 |
C11—N7—C26 | 127.30 (19) | H21B—C21—H21C | 109.5 |
C13—N7—C26 | 124.1 (2) | N6—C22—C24 | 112.6 (2) |
N1—C1—C2 | 120.0 (2) | N6—C22—C23 | 107.7 (2) |
N1—C1—C6 | 114.48 (18) | C24—C22—C23 | 111.3 (2) |
C2—C1—C6 | 125.5 (2) | N6—C22—C25 | 108.5 (2) |
C1—C2—C3 | 118.3 (2) | C24—C22—C25 | 107.2 (2) |
C1—C2—H2 | 120.8 | C23—C22—C25 | 109.5 (2) |
C3—C2—H2 | 120.8 | C22—C23—H23A | 109.5 |
C4—C3—C2 | 120.8 (2) | C22—C23—H23B | 109.5 |
C4—C3—H3 | 119.6 | H23A—C23—H23B | 109.5 |
C2—C3—H3 | 119.6 | C22—C23—H23C | 109.5 |
C3—C4—C5 | 118.6 (2) | H23A—C23—H23C | 109.5 |
C3—C4—H4 | 120.7 | H23B—C23—H23C | 109.5 |
C5—C4—H4 | 120.7 | C22—C24—H24A | 109.5 |
N1—C5—C4 | 119.5 (2) | C22—C24—H24B | 109.5 |
N1—C5—C7 | 114.50 (18) | H24A—C24—H24B | 109.5 |
C4—C5—C7 | 126.0 (2) | C22—C24—H24C | 109.5 |
N2—C6—C1 | 108.48 (17) | H24A—C24—H24C | 109.5 |
N2—C6—H6A | 110.0 | H24B—C24—H24C | 109.5 |
C1—C6—H6A | 110.0 | C22—C25—H25A | 109.5 |
N2—C6—H6B | 110.0 | C22—C25—H25B | 109.5 |
C1—C6—H6B | 110.0 | H25A—C25—H25B | 109.5 |
H6A—C6—H6B | 108.4 | C22—C25—H25C | 109.5 |
N3—C7—C5 | 108.76 (17) | H25A—C25—H25C | 109.5 |
N3—C7—H7A | 109.9 | H25B—C25—H25C | 109.5 |
C5—C7—H7A | 109.9 | N7—C26—C27 | 109.0 (2) |
N3—C7—H7B | 109.9 | N7—C26—C29 | 108.9 (2) |
C5—C7—H7B | 109.9 | C27—C26—C29 | 108.8 (2) |
H7A—C7—H7B | 108.3 | N7—C26—C28 | 111.3 (2) |
N2—C8—N5 | 125.8 (2) | C27—C26—C28 | 107.5 (2) |
N2—C8—N4 | 127.2 (2) | C29—C26—C28 | 111.3 (2) |
N5—C8—N4 | 106.83 (18) | C26—C27—H27A | 109.5 |
C10—C9—N4 | 108.0 (2) | C26—C27—H27B | 109.5 |
C10—C9—H9 | 126.0 | H27A—C27—H27B | 109.5 |
N4—C9—H9 | 126.0 | C26—C27—H27C | 109.5 |
C9—C10—N5 | 108.7 (2) | H27A—C27—H27C | 109.5 |
C9—C10—H10 | 125.7 | H27B—C27—H27C | 109.5 |
N5—C10—H10 | 125.7 | C26—C28—H28A | 109.5 |
N3—C11—N6 | 129.5 (2) | C26—C28—H28B | 109.5 |
N3—C11—N7 | 123.5 (2) | H28A—C28—H28B | 109.5 |
N6—C11—N7 | 106.83 (19) | C26—C28—H28C | 109.5 |
C13—C12—N6 | 108.3 (2) | H28A—C28—H28C | 109.5 |
C13—C12—H12 | 125.8 | H28B—C28—H28C | 109.5 |
N6—C12—H12 | 125.8 | C26—C29—H29A | 109.5 |
C12—C13—N7 | 108.4 (2) | C26—C29—H29B | 109.5 |
C12—C13—H13 | 125.8 | H29A—C29—H29B | 109.5 |
N7—C13—H13 | 125.8 | C26—C29—H29C | 109.5 |
N4—C14—C15 | 112.5 (2) | H29A—C29—H29C | 109.5 |
N4—C14—C16 | 107.5 (2) | H29B—C29—H29C | 109.5 |
C15—C14—C16 | 111.1 (2) | O2—C30—O1 | 125.7 (2) |
N4—C14—C17 | 108.3 (2) | O2—C30—O3 | 121.2 (2) |
C15—C14—C17 | 107.1 (2) | O1—C30—O3 | 113.1 (2) |
N2—Cu—O1—C30 | 100.16 (19) | C9—N4—C8—N5 | 0.8 (2) |
N3—Cu—O1—C30 | −85.02 (19) | C14—N4—C8—N5 | 175.5 (2) |
N2—Cu—N1—C1 | 4.54 (17) | C8—N4—C9—C10 | −1.2 (3) |
N3—Cu—N1—C1 | −173.00 (18) | C14—N4—C9—C10 | −176.4 (2) |
N2—Cu—N1—C5 | 178.79 (18) | N4—C9—C10—N5 | 1.1 (3) |
N3—Cu—N1—C5 | 1.25 (17) | C8—N5—C10—C9 | −0.6 (3) |
O1—Cu—N2—C8 | −11.7 (2) | C18—N5—C10—C9 | −179.5 (2) |
N1—Cu—N2—C8 | 177.9 (2) | C7—N3—C11—N6 | −73.3 (3) |
N3—Cu—N2—C8 | −173.5 (3) | Cu—N3—C11—N6 | 81.1 (3) |
O1—Cu—N2—C6 | 169.28 (16) | C7—N3—C11—N7 | 113.1 (3) |
N1—Cu—N2—C6 | −1.06 (16) | Cu—N3—C11—N7 | −92.5 (2) |
N3—Cu—N2—C6 | 7.5 (4) | C12—N6—C11—N3 | −175.5 (2) |
O1—Cu—N3—C11 | 26.8 (2) | C22—N6—C11—N3 | 8.9 (4) |
N1—Cu—N3—C11 | −162.9 (2) | C12—N6—C11—N7 | −1.0 (2) |
N2—Cu—N3—C11 | −171.4 (3) | C22—N6—C11—N7 | −176.6 (2) |
O1—Cu—N3—C7 | −177.78 (16) | C13—N7—C11—N3 | 175.0 (2) |
N1—Cu—N3—C7 | −7.50 (17) | C26—N7—C11—N3 | −12.3 (3) |
N2—Cu—N3—C7 | −16.0 (4) | C13—N7—C11—N6 | 0.1 (2) |
C5—N1—C1—C2 | −0.7 (3) | C26—N7—C11—N6 | 172.8 (2) |
Cu—N1—C1—C2 | 173.27 (17) | C11—N6—C12—C13 | 1.6 (3) |
C5—N1—C1—C6 | 179.1 (2) | C22—N6—C12—C13 | 177.7 (2) |
Cu—N1—C1—C6 | −6.9 (3) | N6—C12—C13—N7 | −1.5 (3) |
N1—C1—C2—C3 | 1.3 (3) | C11—N7—C13—C12 | 0.8 (3) |
C6—C1—C2—C3 | −178.5 (2) | C26—N7—C13—C12 | −172.1 (2) |
C1—C2—C3—C4 | −0.8 (4) | C8—N4—C14—C15 | 30.4 (3) |
C2—C3—C4—C5 | −0.3 (4) | C9—N4—C14—C15 | −155.5 (2) |
C1—N1—C5—C4 | −0.5 (3) | C8—N4—C14—C16 | −92.2 (3) |
Cu—N1—C5—C4 | −174.45 (17) | C9—N4—C14—C16 | 81.9 (3) |
C1—N1—C5—C7 | 179.1 (2) | C8—N4—C14—C17 | 148.5 (2) |
Cu—N1—C5—C7 | 5.1 (3) | C9—N4—C14—C17 | −37.3 (3) |
C3—C4—C5—N1 | 1.0 (3) | C8—N5—C18—C21 | 7.6 (4) |
C3—C4—C5—C7 | −178.5 (2) | C10—N5—C18—C21 | −173.8 (2) |
C8—N2—C6—C1 | 179.0 (2) | C8—N5—C18—C20 | −113.5 (3) |
Cu—N2—C6—C1 | −2.0 (2) | C10—N5—C18—C20 | 65.0 (3) |
N1—C1—C6—N2 | 5.5 (3) | C8—N5—C18—C19 | 127.2 (3) |
C2—C1—C6—N2 | −174.7 (2) | C10—N5—C18—C19 | −54.3 (3) |
C11—N3—C7—C5 | 167.3 (2) | C11—N6—C22—C24 | −31.5 (3) |
Cu—N3—C7—C5 | 11.6 (2) | C12—N6—C22—C24 | 153.4 (2) |
N1—C5—C7—N3 | −10.5 (3) | C11—N6—C22—C23 | 91.6 (3) |
C4—C5—C7—N3 | 169.0 (2) | C12—N6—C22—C23 | −83.5 (3) |
C6—N2—C8—N5 | −100.3 (3) | C11—N6—C22—C25 | −149.9 (2) |
Cu—N2—C8—N5 | 80.8 (3) | C12—N6—C22—C25 | 35.0 (3) |
C6—N2—C8—N4 | 85.3 (3) | C11—N7—C26—C27 | −175.7 (2) |
Cu—N2—C8—N4 | −93.7 (3) | C13—N7—C26—C27 | −4.1 (3) |
C10—N5—C8—N2 | −175.5 (2) | C11—N7—C26—C29 | −57.1 (3) |
C18—N5—C8—N2 | 3.2 (4) | C13—N7—C26—C29 | 114.4 (3) |
C10—N5—C8—N4 | −0.2 (2) | C11—N7—C26—C28 | 66.0 (3) |
C18—N5—C8—N4 | 178.5 (2) | C13—N7—C26—C28 | −122.5 (3) |
C9—N4—C8—N2 | 176.1 (2) | Cu—O1—C30—O2 | −12.5 (3) |
C14—N4—C8—N2 | −9.2 (4) | Cu—O1—C30—O3 | 166.73 (15) |
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H1···O2i | 0.88 (4) | 1.73 (4) | 2.599 (3) | 173 (4) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [Cu(CHO3)(C29H47N7)]PF6 |
Mr | 763.26 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 133 |
a, b, c (Å) | 9.0309 (12), 13.824 (2), 15.654 (2) |
α, β, γ (°) | 109.619 (3), 101.729 (4), 94.164 (3) |
V (Å3) | 1781.2 (4) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.73 |
Crystal size (mm) | 0.20 × 0.11 × 0.08 |
Data collection | |
Diffractometer | Bruker SMART 1000 CCD |
Absorption correction | Multi-scan (SADABS; Bruker, 1998) |
Tmin, Tmax | 0.868, 0.944 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 33075, 8789, 6166 |
Rint | 0.053 |
(sin θ/λ)max (Å−1) | 0.667 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.042, 0.098, 1.02 |
No. of reflections | 8789 |
No. of parameters | 449 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.46, −0.41 |
Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), XP (Siemens, 1994).
Cu—O1 | 1.9205 (16) | O1—C30 | 1.262 (3) |
Cu—N1 | 1.9318 (17) | O2—C30 | 1.236 (3) |
Cu—N2 | 1.9449 (17) | O3—C30 | 1.349 (3) |
Cu—N3 | 1.9689 (18) | ||
O1—Cu—N1 | 170.38 (8) | N2—Cu—N3 | 163.36 (7) |
O1—Cu—N2 | 97.30 (7) | C30—O1—Cu | 123.98 (17) |
N1—Cu—N2 | 81.77 (7) | O2—C30—O1 | 125.7 (2) |
O1—Cu—N3 | 98.51 (7) | O2—C30—O3 | 121.2 (2) |
N1—Cu—N3 | 81.77 (8) | O1—C30—O3 | 113.1 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H1···O2i | 0.88 (4) | 1.73 (4) | 2.599 (3) | 173 (4) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
As we have recently demonstrated (Petrovic et al., 2007), copper(I) complexes of the highly basic pincer ligand 2,6-bis[(1,3-di-tert-butylimidazolin-2-imino)methyl]pyridine, TLtBu, are extremely reactive and exhibit a pronounced tendency to form stable, square-planar copper(II) complexes. Exposure of an acetone solution of [(TLtBu)Cu]PF6 to the air readily leads to oxidation and trapping of atmospheric CO2 to form the square-planar complex [(TLtBu)Cu(HCO3-κO)]PF6 with the bicarbonate ligand adopting a rarely observed monodentate coordination mode. The compound was previously crystallized as an acetone solvate (Petrovic et al., 2007). Here we report the structure of the solvent-free material. All structural features of the cation [(TLtBu)Cu(HCO3-κO)]+ are very similar to those of the acetone solvate. The copper center displays a slightly distorted square-planar environment; the sum of the four cis angles is 359.38°. The copper atom lies 0.049 (2) Å out of the plane defined by the donor atoms N1, N2 and N3. The displacement of the metal-bound oxygen atom O1 of the bicarbonate ligand, 0.224 (5) Å in the opposite direction, is considerably greater, which is presumably a consequence of minimizing the steric interaction with the bulky di-tert-butylimidazolin-2-ylidene moieties. As a result, the N1—Cu—O1 angle of 170.38 (8)° deviates significantly from linearity. The Cu—O1 distance of 1.9205 (16) Å is very short in comparison to the other structurally characterized copper(II) bicarbonate complexes. The angles in the bicarbonate unit are close to 120°, and the C—O distances (Table 1), with a much longer C30—O3 bond, clearly indicate that the hydrogen atom of the HCO3 unit is bound to O3. This was in any case confirmed by free refinement of this hydrogen position. The packing involves inversion-symmetric cation dimers bridged via hydrogen bonding of the bicarbonate groups (analogous to the well known "carboxylic acid dimer" type; Table 2), as observed for the acetone solvate (with two crystallographically independent formula units, each associating over an inversion centre to a dimer) and in some other transition metal bicarbonate complexes (Hossain et al., 1981; Ito et al., 1994; Darensbourg et al., 1996; Jazzar et al., 2003; Kim et al., 2004).