Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536811031564/ff2023sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536811031564/ff2023Isup2.hkl |
CCDC reference: 845222
Key indicators
- Single-crystal X-ray study
- T = 173 K
- Mean (C-C) = 0.003 Å
- R factor = 0.033
- wR factor = 0.086
- Data-to-parameter ratio = 19.7
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT230_ALERT_2_C Hirshfeld Test Diff for C1 -- C2 .. 6.5 su PLAT910_ALERT_3_C Missing # of FCF Reflections Below Th(Min) ..... 1 PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L= 0.600 305
Alert level G PLAT005_ALERT_5_G No _iucr_refine_instructions_details in CIF .... ? PLAT128_ALERT_4_G Alternate Setting of Space-group P21/c ....... P21/n PLAT710_ALERT_4_G Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... # 6 O1 -CU1 -O1 -P1 -147.00 6.00 3.556 1.555 1.555 1.555 PLAT710_ALERT_4_G Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... # 10 O2 -CU1 -O2 -P2 -122.00 9.00 3.556 1.555 1.555 1.555 PLAT710_ALERT_4_G Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... # 25 P2 -C1 -C2 -N1 18.00 0.00 1.555 1.555 1.555 1.555 PLAT710_ALERT_4_G Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... # 26 P1 -C1 -C2 -N1 4.00 4.00 1.555 1.555 1.555 1.555
0 ALERT level A = Most likely a serious problem - resolve or explain 0 ALERT level B = A potentially serious problem, consider carefully 3 ALERT level C = Check. Ensure it is not caused by an omission or oversight 6 ALERT level G = General information/check it is not something unexpected 0 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 1 ALERT type 3 Indicator that the structure quality may be low 6 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check
Preparation and characterization of complex obtained pre-crystallization: A Schlenk flask equipped with a magnetic stirrer bar was charged with previously prepared [Au2{dppm-CN}2] complex (400 mg, 0.33 mmol) dissolved in dichloromethane (5 ml). A dichloromethane (8 ml) solution of [Cu(CH3CN)4][PF6] (123 mg, 0.33 mmol) was then added dropwise to the gold-containing solution at room temperature. The solution turned cloudy and was stirred for an hour, after which all dichloromethane solvent was removed under reduced pressure. Dry Et2O (2 x 2 ml) was added to wash the product which was further dried in vacuo for 2 hrs. The product was obtained as a free flowing off-white powder. Yield: (387 mg, 0.21 mmol) 65%; Mp: 155–160 oC (decompose); 1H NMR (400 MHz, CDCl3, 298 K) δH= 7.68–7.53 (m, 40H, Ph); 31P NMR (101 MHz, CDCl3, 298 K) δP = 22.8 (s, 2P). Green single crystals were obtained by slow evaporation of a dichloromethane solution of the complex.
All non-hydrogen atoms are refined anisotropically. H atoms were calculated by geometrical methods and refined as a riding model, with C—H distace 0.95 Å and Uiso(H) = 1.2Ueq(C). The crystal used for the diffraction study showed no decomposition during data collection.
The chemistry of the ligand bis(diphenylphosphane)acetonitrile, (dppm-CN), was recently revived when a facile preparation thereof was reported, starting with readily available acetonitrile (Braun et al., 2007). Development of its chemistry followed thereafter, including the observed sharp increase in acidity by the replacement of a proton with a cyano group on the bridging carbon atom (Spannhoff et al., 2009, and references therein). In continuing our interest in dinuclear gold(I) complexes (Van Zyl, 2010), we recently reported the first structural investigation of a chlorogold(I) complex with the ligand dppm-CN, (Sithole et al., 2011).
A relatively straightforward method for the preparation of complex (I) would entail the reaction between Li[N≡C—C(Ph2P=O)2], prepared as described (Braun et al., 2008), and CuCl2 or Cu(NO3)2 (molar ratio 2:1), leading to formation of complex (I) after removal of LiCl or LiNO3. However, in the present study, we report complex (I) was obtained in a surprisingly different manner. Formation of (I) occurred post-synthesis during the crystallization process. An initial reaction between the well characterized complexes [Au2{dppm-CN}2], and [Cu(CH3CN)4][PF6] (1:1 molar ratio) was performed in an attempt to coordinate the copper(I) center to the CN group. The Experimental section describes a complex formed and isolated from this reaction as a colorless, free-flowing powder and suggests no sign of metal oxidation (both Au(I) and Cu(I) are closed-shell d10 systems and are usually colorless or pale yellow compounds, hence any sign of oxidation leading to deep color changes for either metal is readily observed). However, during subsequent crystallization procedures obvious oxidation occurred, firstly at the metal center where the precursor colorless Cu(I) species oxidized to a green-colored Cu(II) complex. Secondly, the P atoms in the anionic [dppm-CN]¯ ligand did oxidize to the corresponding oxide analogue (not uncommon in the presence of air or moisture), and the ligand transferred also from the gold(I) center to the much more oxophillic Cu(II) center whilst retaining the negative anionic charge, i.e. it did not become protonated and thus neutral in the process. No attempt was made in this study to determine the concurrent reduced species, but presumably the Au(I) species reduced to Au(0) metal. Single crystal X-ray analysis subsequently revealed the green colored material to be identified as complex (I).
For recent work on bis(diphenylphosphane)acetonitrile, see: Braun et al. (2007); Spannhoff et al. (2009). For a bis(diphenylphosphane)acetonitrile complex of gold(I), see: Sithole et al. (2011) and for bis(diphenylphosphane)acetonitrile oxides and sulfides (and their lithiated structures), see: Braun et al. (2008). For background to our interest in dinuclear gold(I) complexes, see: Van Zyl (2010)
Data collection: COSMO (Bruker, 2009); cell refinement: APEX2 (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
Fig. 1. Molecular structure of the title complex. Ellipsoids are drawn at the 50% probability level. Unlabelled atoms are related to the reference ones by the (-x -y, 1-z) symmetry transformation. |
[Cu(C26H20NO2P2)2] | F(000) = 974 |
Mr = 944.28 | Dx = 1.405 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 9929 reflections |
a = 9.5917 (7) Å | θ = 2.4–28.7° |
b = 25.8793 (19) Å | µ = 0.68 mm−1 |
c = 9.6648 (7) Å | T = 173 K |
β = 111.526 (1)° | Block, green |
V = 2231.7 (3) Å3 | 0.33 × 0.23 × 0.12 mm |
Z = 2 |
Bruker APEXII CCD diffractometer | 5640 independent reflections |
Radiation source: fine-focus sealed tube | 4832 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.036 |
Detector resolution: 836.6 pixels mm-1 | θmax = 29.1°, θmin = 2.4° |
ω,and/f 0.5° scans | h = −12→12 |
Absorption correction: multi-scan (SADABS; Bruker, 2009) | k = −34→34 |
Tmin = 0.807, Tmax = 0.920 | l = −13→13 |
43689 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)] = 0.033 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.086 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0428P)2 + 1.1569P] where P = (Fo2 + 2Fc2)/3 |
5640 reflections | (Δ/σ)max = 0.001 |
286 parameters | Δρmax = 0.49 e Å−3 |
0 restraints | Δρmin = −0.32 e Å−3 |
[Cu(C26H20NO2P2)2] | V = 2231.7 (3) Å3 |
Mr = 944.28 | Z = 2 |
Monoclinic, P21/n | Mo Kα radiation |
a = 9.5917 (7) Å | µ = 0.68 mm−1 |
b = 25.8793 (19) Å | T = 173 K |
c = 9.6648 (7) Å | 0.33 × 0.23 × 0.12 mm |
β = 111.526 (1)° |
Bruker APEXII CCD diffractometer | 5640 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2009) | 4832 reflections with I > 2σ(I) |
Tmin = 0.807, Tmax = 0.920 | Rint = 0.036 |
43689 measured reflections |
R[F2 > 2σ(F2)] = 0.033 | 0 restraints |
wR(F2) = 0.086 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.49 e Å−3 |
5640 reflections | Δρmin = −0.32 e Å−3 |
286 parameters |
Experimental. Data was collected using a BRUKER CCD (charge coupled device) based diffractometer equipped with an Oxford low-temperature apparatus operating at 173 K. A suitable crystal was chosen and mounted on a glass fiber or nylon loop using Paratone oil for Mo radiation and Mineral oil for Copper radiation. Data were measured using omega and phi scans of 0.5° per frame for 20 s. The total number of images were based on results from the program COSMO where redundancy was expected to be 4 and completeness to 0.83Å to 100%. Cell parameters were retrieved using APEX II software and refined using SAINT on all observed reflections.Data reduction was performed using the SAINT software which corrects for Lp. Scaling and absorption corrections were applied using SADABS6 multi-scan technique, supplied by George Sheldrick. The structures are solved by the direct method using the SHELXS97 program and refined by least squares method on F2, SHELXL97, incorporated in SHELXTL-PC V 6.14. All H atoms were placed in calculated positions and refined using a riding model. C—H(aromatic) = 0.94 Å and Uiso(H) = 1.2Ueq(C) C—H (alaphatic) = 0.99 Å and Uiso(H) = 1.2Ueq(C) CH2 = 0.98 Å and Uiso(H) = 1.2Ueq(C) CH3 = 0.97Å and Uiso(H) = 1.5Ueq(C) N—H = 0.86 (0.92)Å and Uiso(H) = 1.2 Ueq(N) O—H(alcohol) = 0.85Åand Uiso(H) = 1.2Ueq(O) O—H(acid) = 0.82 Å and Uiso(H) = 1.5Ueq(O) |
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. |
x | y | z | Uiso*/Ueq | ||
Cu1 | 0.0000 | 0.0000 | 0.5000 | 0.01782 (8) | |
P1 | 0.11652 (4) | 0.085542 (15) | 0.73438 (4) | 0.02022 (9) | |
P2 | 0.19258 (4) | 0.090614 (15) | 0.46718 (4) | 0.01886 (9) | |
O1 | −0.01591 (12) | 0.05965 (4) | 0.61444 (12) | 0.0222 (2) | |
O2 | 0.12911 (12) | 0.03636 (4) | 0.42218 (12) | 0.0230 (2) | |
N1 | 0.49225 (17) | 0.14605 (6) | 0.81575 (19) | 0.0374 (4) | |
C1 | 0.24792 (17) | 0.10182 (6) | 0.65683 (17) | 0.0217 (3) | |
C2 | 0.38298 (18) | 0.12620 (6) | 0.74163 (18) | 0.0243 (3) | |
C3 | 0.04936 (19) | 0.14124 (6) | 0.80190 (19) | 0.0259 (3) | |
C4 | −0.1033 (2) | 0.15090 (8) | 0.7557 (2) | 0.0349 (4) | |
H4 | −0.1730 | 0.1273 | 0.6911 | 0.042* | |
C5 | −0.1545 (3) | 0.19521 (8) | 0.8038 (3) | 0.0474 (5) | |
H5 | −0.2590 | 0.2017 | 0.7729 | 0.057* | |
C6 | −0.0534 (3) | 0.22945 (8) | 0.8963 (3) | 0.0525 (6) | |
H6 | −0.0884 | 0.2598 | 0.9284 | 0.063* | |
C7 | 0.0989 (3) | 0.22001 (9) | 0.9432 (3) | 0.0571 (7) | |
H7 | 0.1680 | 0.2438 | 1.0074 | 0.069* | |
C8 | 0.1504 (2) | 0.17605 (8) | 0.8966 (3) | 0.0442 (5) | |
H8 | 0.2550 | 0.1695 | 0.9291 | 0.053* | |
C9 | 0.19949 (18) | 0.04236 (6) | 0.88816 (18) | 0.0241 (3) | |
C10 | 0.2915 (2) | 0.00309 (7) | 0.87194 (19) | 0.0289 (4) | |
H10 | 0.3206 | 0.0028 | 0.7880 | 0.035* | |
C11 | 0.3408 (2) | −0.03571 (7) | 0.9783 (2) | 0.0336 (4) | |
H11 | 0.4036 | −0.0625 | 0.9670 | 0.040* | |
C12 | 0.2983 (2) | −0.03529 (8) | 1.1009 (2) | 0.0356 (4) | |
H12 | 0.3309 | −0.0621 | 1.1729 | 0.043* | |
C13 | 0.2088 (3) | 0.00393 (8) | 1.1186 (2) | 0.0389 (4) | |
H13 | 0.1812 | 0.0044 | 1.2035 | 0.047* | |
C14 | 0.1591 (2) | 0.04268 (7) | 1.0126 (2) | 0.0335 (4) | |
H14 | 0.0972 | 0.0696 | 1.0249 | 0.040* | |
C15 | 0.05405 (18) | 0.13679 (6) | 0.36258 (18) | 0.0248 (3) | |
C16 | 0.0541 (2) | 0.18605 (7) | 0.4181 (3) | 0.0440 (5) | |
H16 | 0.1279 | 0.1955 | 0.5112 | 0.053* | |
C17 | −0.0536 (3) | 0.22178 (9) | 0.3379 (3) | 0.0625 (7) | |
H17 | −0.0526 | 0.2558 | 0.3750 | 0.075* | |
C18 | −0.1616 (3) | 0.20742 (10) | 0.2045 (3) | 0.0596 (7) | |
H18 | −0.2361 | 0.2316 | 0.1505 | 0.072* | |
C19 | −0.1631 (2) | 0.15861 (10) | 0.1484 (2) | 0.0463 (5) | |
H19 | −0.2383 | 0.1493 | 0.0561 | 0.056* | |
C20 | −0.05537 (19) | 0.12307 (8) | 0.22608 (19) | 0.0316 (4) | |
H20 | −0.0557 | 0.0894 | 0.1868 | 0.038* | |
C21 | 0.35557 (17) | 0.09861 (6) | 0.42016 (17) | 0.0226 (3) | |
C22 | 0.3618 (2) | 0.13313 (7) | 0.3125 (2) | 0.0322 (4) | |
H22 | 0.2780 | 0.1543 | 0.2610 | 0.039* | |
C23 | 0.4920 (2) | 0.13646 (9) | 0.2805 (2) | 0.0445 (5) | |
H23 | 0.4968 | 0.1599 | 0.2069 | 0.053* | |
C24 | 0.6140 (2) | 0.10571 (8) | 0.3557 (2) | 0.0406 (5) | |
H24 | 0.7030 | 0.1085 | 0.3347 | 0.049* | |
C25 | 0.6072 (2) | 0.07084 (8) | 0.4614 (2) | 0.0344 (4) | |
H25 | 0.6909 | 0.0494 | 0.5118 | 0.041* | |
C26 | 0.47879 (18) | 0.06714 (7) | 0.49360 (19) | 0.0272 (3) | |
H26 | 0.4743 | 0.0431 | 0.5661 | 0.033* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.01623 (13) | 0.01786 (13) | 0.01979 (13) | −0.00193 (9) | 0.00712 (10) | −0.00220 (9) |
P1 | 0.02000 (19) | 0.02058 (19) | 0.02087 (19) | −0.00208 (14) | 0.00841 (15) | −0.00352 (14) |
P2 | 0.01714 (18) | 0.01878 (18) | 0.02072 (19) | −0.00176 (14) | 0.00704 (15) | −0.00045 (14) |
O1 | 0.0191 (5) | 0.0225 (5) | 0.0259 (6) | −0.0019 (4) | 0.0093 (4) | −0.0054 (4) |
O2 | 0.0263 (6) | 0.0213 (5) | 0.0259 (6) | −0.0055 (4) | 0.0148 (5) | −0.0042 (4) |
N1 | 0.0250 (8) | 0.0389 (9) | 0.0417 (9) | −0.0058 (6) | 0.0046 (7) | −0.0069 (7) |
C1 | 0.0187 (7) | 0.0261 (7) | 0.0206 (7) | −0.0035 (6) | 0.0075 (6) | −0.0018 (6) |
C2 | 0.0233 (8) | 0.0237 (7) | 0.0255 (8) | 0.0009 (6) | 0.0086 (6) | 0.0004 (6) |
C3 | 0.0324 (9) | 0.0210 (7) | 0.0281 (8) | 0.0001 (6) | 0.0157 (7) | −0.0031 (6) |
C4 | 0.0348 (10) | 0.0355 (10) | 0.0347 (10) | 0.0061 (8) | 0.0130 (8) | −0.0032 (8) |
C5 | 0.0535 (13) | 0.0428 (11) | 0.0518 (13) | 0.0210 (10) | 0.0262 (11) | 0.0052 (10) |
C6 | 0.0843 (18) | 0.0255 (9) | 0.0676 (15) | 0.0096 (10) | 0.0512 (14) | −0.0018 (10) |
C7 | 0.0759 (17) | 0.0362 (11) | 0.0741 (17) | −0.0183 (11) | 0.0450 (14) | −0.0285 (11) |
C8 | 0.0405 (11) | 0.0404 (11) | 0.0563 (13) | −0.0104 (9) | 0.0231 (10) | −0.0226 (10) |
C9 | 0.0243 (8) | 0.0250 (8) | 0.0229 (7) | −0.0035 (6) | 0.0084 (6) | −0.0024 (6) |
C10 | 0.0286 (9) | 0.0334 (9) | 0.0257 (8) | 0.0013 (7) | 0.0113 (7) | 0.0007 (7) |
C11 | 0.0298 (9) | 0.0327 (9) | 0.0353 (9) | 0.0039 (7) | 0.0085 (7) | 0.0027 (7) |
C12 | 0.0378 (10) | 0.0360 (9) | 0.0263 (9) | −0.0029 (8) | 0.0039 (7) | 0.0057 (7) |
C13 | 0.0523 (12) | 0.0420 (11) | 0.0253 (9) | −0.0019 (9) | 0.0177 (8) | 0.0005 (8) |
C14 | 0.0424 (10) | 0.0330 (9) | 0.0298 (9) | 0.0018 (8) | 0.0187 (8) | −0.0023 (7) |
C15 | 0.0210 (7) | 0.0271 (8) | 0.0262 (8) | 0.0006 (6) | 0.0085 (6) | 0.0041 (6) |
C16 | 0.0452 (11) | 0.0274 (9) | 0.0499 (12) | 0.0070 (8) | 0.0062 (10) | 0.0019 (8) |
C17 | 0.0715 (17) | 0.0327 (11) | 0.0784 (18) | 0.0211 (11) | 0.0216 (14) | 0.0119 (11) |
C18 | 0.0472 (13) | 0.0583 (15) | 0.0683 (16) | 0.0239 (11) | 0.0151 (12) | 0.0355 (13) |
C19 | 0.0283 (10) | 0.0674 (15) | 0.0378 (11) | 0.0030 (9) | 0.0055 (8) | 0.0239 (10) |
C20 | 0.0244 (8) | 0.0437 (10) | 0.0256 (8) | −0.0016 (7) | 0.0077 (7) | 0.0058 (7) |
C21 | 0.0211 (7) | 0.0237 (7) | 0.0236 (7) | −0.0037 (6) | 0.0090 (6) | −0.0034 (6) |
C22 | 0.0300 (9) | 0.0331 (9) | 0.0369 (10) | −0.0013 (7) | 0.0162 (8) | 0.0069 (7) |
C23 | 0.0454 (12) | 0.0495 (12) | 0.0491 (12) | −0.0050 (9) | 0.0299 (10) | 0.0114 (10) |
C24 | 0.0314 (10) | 0.0491 (11) | 0.0514 (12) | −0.0077 (8) | 0.0269 (9) | −0.0045 (9) |
C25 | 0.0231 (8) | 0.0397 (10) | 0.0422 (10) | 0.0016 (7) | 0.0141 (8) | −0.0061 (8) |
C26 | 0.0239 (8) | 0.0287 (8) | 0.0293 (8) | −0.0006 (6) | 0.0102 (7) | −0.0001 (7) |
Cu1—O2 | 1.9153 (10) | C11—C12 | 1.388 (3) |
Cu1—O2i | 1.9153 (10) | C11—H11 | 0.9500 |
Cu1—O1i | 1.9373 (10) | C12—C13 | 1.380 (3) |
Cu1—O1 | 1.9373 (10) | C12—H12 | 0.9500 |
P1—O1 | 1.5250 (11) | C13—C14 | 1.387 (3) |
P1—C1 | 1.7381 (16) | C13—H13 | 0.9500 |
P1—C9 | 1.7953 (17) | C14—H14 | 0.9500 |
P1—C3 | 1.7963 (16) | C15—C16 | 1.383 (3) |
P2—O2 | 1.5287 (11) | C15—C20 | 1.397 (2) |
P2—C1 | 1.7353 (16) | C16—C17 | 1.391 (3) |
P2—C21 | 1.7929 (16) | C16—H16 | 0.9500 |
P2—C15 | 1.7972 (16) | C17—C18 | 1.376 (4) |
N1—C2 | 1.151 (2) | C17—H17 | 0.9500 |
C1—C2 | 1.403 (2) | C18—C19 | 1.373 (4) |
C3—C4 | 1.388 (2) | C18—H18 | 0.9500 |
C3—C8 | 1.392 (3) | C19—C20 | 1.381 (3) |
C4—C5 | 1.393 (3) | C19—H19 | 0.9500 |
C4—H4 | 0.9500 | C20—H20 | 0.9500 |
C5—C6 | 1.374 (3) | C21—C22 | 1.389 (2) |
C5—H5 | 0.9500 | C21—C26 | 1.396 (2) |
C6—C7 | 1.383 (4) | C22—C23 | 1.395 (3) |
C6—H6 | 0.9500 | C22—H22 | 0.9500 |
C7—C8 | 1.380 (3) | C23—C24 | 1.381 (3) |
C7—H7 | 0.9500 | C23—H23 | 0.9500 |
C8—H8 | 0.9500 | C24—C25 | 1.382 (3) |
C9—C14 | 1.392 (2) | C24—H24 | 0.9500 |
C9—C10 | 1.392 (2) | C25—C26 | 1.380 (2) |
C10—C11 | 1.390 (2) | C25—H25 | 0.9500 |
C10—H10 | 0.9500 | C26—H26 | 0.9500 |
O2—Cu1—O2i | 180.0 | C12—C11—C10 | 119.92 (17) |
O2—Cu1—O1i | 88.26 (5) | C12—C11—H11 | 120.0 |
O2i—Cu1—O1i | 91.74 (5) | C10—C11—H11 | 120.0 |
O2—Cu1—O1 | 91.74 (5) | C13—C12—C11 | 120.17 (17) |
O2i—Cu1—O1 | 88.26 (5) | C13—C12—H12 | 119.9 |
O1i—Cu1—O1 | 180.0 | C11—C12—H12 | 119.9 |
O1—P1—C1 | 108.19 (7) | C12—C13—C14 | 120.08 (18) |
O1—P1—C9 | 110.39 (7) | C12—C13—H13 | 120.0 |
C1—P1—C9 | 109.66 (8) | C14—C13—H13 | 120.0 |
O1—P1—C3 | 108.61 (7) | C13—C14—C9 | 120.30 (18) |
C1—P1—C3 | 112.06 (8) | C13—C14—H14 | 119.9 |
C9—P1—C3 | 107.93 (8) | C9—C14—H14 | 119.9 |
O2—P2—C1 | 112.92 (7) | C16—C15—C20 | 119.59 (17) |
O2—P2—C21 | 109.10 (7) | C16—C15—P2 | 119.98 (14) |
C1—P2—C21 | 106.93 (7) | C20—C15—P2 | 120.42 (13) |
O2—P2—C15 | 108.40 (7) | C15—C16—C17 | 120.1 (2) |
C1—P2—C15 | 111.07 (8) | C15—C16—H16 | 119.9 |
C21—P2—C15 | 108.31 (8) | C17—C16—H16 | 119.9 |
P1—O1—Cu1 | 124.47 (6) | C18—C17—C16 | 119.5 (2) |
P2—O2—Cu1 | 125.94 (6) | C18—C17—H17 | 120.3 |
C2—C1—P2 | 123.44 (12) | C16—C17—H17 | 120.3 |
C2—C1—P1 | 121.15 (12) | C19—C18—C17 | 120.9 (2) |
P2—C1—P1 | 115.20 (9) | C19—C18—H18 | 119.5 |
N1—C2—C1 | 177.44 (19) | C17—C18—H18 | 119.5 |
C4—C3—C8 | 119.55 (16) | C18—C19—C20 | 120.0 (2) |
C4—C3—P1 | 120.28 (13) | C18—C19—H19 | 120.0 |
C8—C3—P1 | 120.13 (14) | C20—C19—H19 | 120.0 |
C3—C4—C5 | 120.01 (19) | C19—C20—C15 | 119.80 (19) |
C3—C4—H4 | 120.0 | C19—C20—H20 | 120.1 |
C5—C4—H4 | 120.0 | C15—C20—H20 | 120.1 |
C6—C5—C4 | 119.8 (2) | C22—C21—C26 | 119.65 (15) |
C6—C5—H5 | 120.1 | C22—C21—P2 | 123.05 (13) |
C4—C5—H5 | 120.1 | C26—C21—P2 | 117.27 (12) |
C5—C6—C7 | 120.49 (19) | C21—C22—C23 | 119.59 (17) |
C5—C6—H6 | 119.8 | C21—C22—H22 | 120.2 |
C7—C6—H6 | 119.8 | C23—C22—H22 | 120.2 |
C8—C7—C6 | 120.0 (2) | C24—C23—C22 | 120.19 (18) |
C8—C7—H7 | 120.0 | C24—C23—H23 | 119.9 |
C6—C7—H7 | 120.0 | C22—C23—H23 | 119.9 |
C7—C8—C3 | 120.1 (2) | C23—C24—C25 | 120.25 (17) |
C7—C8—H8 | 120.0 | C23—C24—H24 | 119.9 |
C3—C8—H8 | 120.0 | C25—C24—H24 | 119.9 |
C14—C9—C10 | 119.37 (16) | C26—C25—C24 | 120.03 (18) |
C14—C9—P1 | 122.14 (13) | C26—C25—H25 | 120.0 |
C10—C9—P1 | 117.91 (13) | C24—C25—H25 | 120.0 |
C11—C10—C9 | 120.14 (17) | C25—C26—C21 | 120.27 (17) |
C11—C10—H10 | 119.9 | C25—C26—H26 | 119.9 |
C9—C10—H10 | 119.9 | C21—C26—H26 | 119.9 |
C1—P1—O1—Cu1 | 54.82 (10) | C1—P1—C9—C14 | 146.86 (15) |
C9—P1—O1—Cu1 | −65.18 (10) | C3—P1—C9—C14 | 24.52 (17) |
C3—P1—O1—Cu1 | 176.68 (8) | O1—P1—C9—C10 | 77.18 (14) |
O2—Cu1—O1—P1 | −59.93 (8) | C1—P1—C9—C10 | −41.93 (15) |
O2i—Cu1—O1—P1 | 120.07 (8) | C3—P1—C9—C10 | −164.26 (13) |
O1i—Cu1—O1—P1 | −147 (6) | C14—C9—C10—C11 | 0.8 (3) |
C1—P2—O2—Cu1 | 40.14 (11) | P1—C9—C10—C11 | −170.67 (14) |
C21—P2—O2—Cu1 | 158.90 (8) | C9—C10—C11—C12 | 0.0 (3) |
C15—P2—O2—Cu1 | −83.36 (10) | C10—C11—C12—C13 | −0.9 (3) |
O2i—Cu1—O2—P2 | −122 (9) | C11—C12—C13—C14 | 1.0 (3) |
O1i—Cu1—O2—P2 | −174.51 (9) | C12—C13—C14—C9 | −0.2 (3) |
O1—Cu1—O2—P2 | 5.49 (9) | C10—C9—C14—C13 | −0.7 (3) |
O2—P2—C1—C2 | 135.75 (13) | P1—C9—C14—C13 | 170.41 (15) |
C21—P2—C1—C2 | 15.74 (16) | O2—P2—C15—C16 | 154.64 (15) |
C15—P2—C1—C2 | −102.24 (15) | C1—P2—C15—C16 | 30.03 (18) |
O2—P2—C1—P1 | −49.44 (11) | C21—P2—C15—C16 | −87.11 (17) |
C21—P2—C1—P1 | −169.45 (9) | O2—P2—C15—C20 | −24.48 (16) |
C15—P2—C1—P1 | 72.57 (11) | C1—P2—C15—C20 | −149.10 (14) |
O1—P1—C1—C2 | −179.75 (13) | C21—P2—C15—C20 | 93.76 (15) |
C9—P1—C1—C2 | −59.30 (15) | C20—C15—C16—C17 | −0.4 (3) |
C3—P1—C1—C2 | 60.54 (16) | P2—C15—C16—C17 | −179.55 (19) |
O1—P1—C1—P2 | 5.31 (11) | C15—C16—C17—C18 | 1.2 (4) |
C9—P1—C1—P2 | 125.76 (9) | C16—C17—C18—C19 | −1.0 (4) |
C3—P1—C1—P2 | −114.40 (10) | C17—C18—C19—C20 | 0.1 (4) |
P2—C1—C2—N1 | 178 (100) | C18—C19—C20—C15 | 0.7 (3) |
P1—C1—C2—N1 | 4 (4) | C16—C15—C20—C19 | −0.5 (3) |
O1—P1—C3—C4 | 6.89 (17) | P2—C15—C20—C19 | 178.61 (14) |
C1—P1—C3—C4 | 126.36 (15) | O2—P2—C21—C22 | 113.92 (15) |
C9—P1—C3—C4 | −112.80 (15) | C1—P2—C21—C22 | −123.65 (15) |
O1—P1—C3—C8 | −170.65 (15) | C15—P2—C21—C22 | −3.87 (17) |
C1—P1—C3—C8 | −51.19 (18) | O2—P2—C21—C26 | −64.13 (14) |
C9—P1—C3—C8 | 69.66 (17) | C1—P2—C21—C26 | 58.30 (14) |
C8—C3—C4—C5 | 0.1 (3) | C15—P2—C21—C26 | 178.08 (13) |
P1—C3—C4—C5 | −177.50 (15) | C26—C21—C22—C23 | −0.9 (3) |
C3—C4—C5—C6 | 0.5 (3) | P2—C21—C22—C23 | −178.91 (15) |
C4—C5—C6—C7 | −0.6 (3) | C21—C22—C23—C24 | −0.1 (3) |
C5—C6—C7—C8 | 0.3 (4) | C22—C23—C24—C25 | 1.0 (3) |
C6—C7—C8—C3 | 0.3 (4) | C23—C24—C25—C26 | −0.9 (3) |
C4—C3—C8—C7 | −0.4 (3) | C24—C25—C26—C21 | −0.2 (3) |
P1—C3—C8—C7 | 177.14 (18) | C22—C21—C26—C25 | 1.1 (3) |
O1—P1—C9—C14 | −94.03 (15) | P2—C21—C26—C25 | 179.18 (14) |
Symmetry code: (i) −x, −y, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [Cu(C26H20NO2P2)2] |
Mr | 944.28 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 173 |
a, b, c (Å) | 9.5917 (7), 25.8793 (19), 9.6648 (7) |
β (°) | 111.526 (1) |
V (Å3) | 2231.7 (3) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.68 |
Crystal size (mm) | 0.33 × 0.23 × 0.12 |
Data collection | |
Diffractometer | Bruker APEXII CCD |
Absorption correction | Multi-scan (SADABS; Bruker, 2009) |
Tmin, Tmax | 0.807, 0.920 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 43689, 5640, 4832 |
Rint | 0.036 |
(sin θ/λ)max (Å−1) | 0.683 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.033, 0.086, 1.03 |
No. of reflections | 5640 |
No. of parameters | 286 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.49, −0.32 |
Computer programs: COSMO (Bruker, 2009), APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
The chemistry of the ligand bis(diphenylphosphane)acetonitrile, (dppm-CN), was recently revived when a facile preparation thereof was reported, starting with readily available acetonitrile (Braun et al., 2007). Development of its chemistry followed thereafter, including the observed sharp increase in acidity by the replacement of a proton with a cyano group on the bridging carbon atom (Spannhoff et al., 2009, and references therein). In continuing our interest in dinuclear gold(I) complexes (Van Zyl, 2010), we recently reported the first structural investigation of a chlorogold(I) complex with the ligand dppm-CN, (Sithole et al., 2011).
A relatively straightforward method for the preparation of complex (I) would entail the reaction between Li[N≡C—C(Ph2P=O)2], prepared as described (Braun et al., 2008), and CuCl2 or Cu(NO3)2 (molar ratio 2:1), leading to formation of complex (I) after removal of LiCl or LiNO3. However, in the present study, we report complex (I) was obtained in a surprisingly different manner. Formation of (I) occurred post-synthesis during the crystallization process. An initial reaction between the well characterized complexes [Au2{dppm-CN}2], and [Cu(CH3CN)4][PF6] (1:1 molar ratio) was performed in an attempt to coordinate the copper(I) center to the CN group. The Experimental section describes a complex formed and isolated from this reaction as a colorless, free-flowing powder and suggests no sign of metal oxidation (both Au(I) and Cu(I) are closed-shell d10 systems and are usually colorless or pale yellow compounds, hence any sign of oxidation leading to deep color changes for either metal is readily observed). However, during subsequent crystallization procedures obvious oxidation occurred, firstly at the metal center where the precursor colorless Cu(I) species oxidized to a green-colored Cu(II) complex. Secondly, the P atoms in the anionic [dppm-CN]¯ ligand did oxidize to the corresponding oxide analogue (not uncommon in the presence of air or moisture), and the ligand transferred also from the gold(I) center to the much more oxophillic Cu(II) center whilst retaining the negative anionic charge, i.e. it did not become protonated and thus neutral in the process. No attempt was made in this study to determine the concurrent reduced species, but presumably the Au(I) species reduced to Au(0) metal. Single crystal X-ray analysis subsequently revealed the green colored material to be identified as complex (I).