Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536813013470/gk2571sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536813013470/gk2571Isup2.hkl |
CCDC reference: 954396
Key indicators
- Single-crystal X-ray study
- T = 200 K
- Mean (C-C) = 0.009 Å
- Disorder in main residue
- R factor = 0.048
- wR factor = 0.083
- Data-to-parameter ratio = 19.4
checkCIF/PLATON results
No syntax errors found
Alert level B PLAT910_ALERT_3_B Missing # of FCF Reflections Below Th(Min) ..... 19 PLAT934_ALERT_3_B Number of (Iobs-Icalc)/SigmaW > 10 Outliers .... 3 PLAT973_ALERT_2_B Large Calcd. Positive Residual Density on Au2 1.68 eA-3 PLAT973_ALERT_2_B Large Calcd. Positive Residual Density on Au1 1.56 eA-3
Alert level C PLAT244_ALERT_4_C Low 'Solvent' Ueq as Compared to Neighbors of Ni1 PLAT244_ALERT_4_C Low 'Solvent' Ueq as Compared to Neighbors of O1 PLAT342_ALERT_3_C Low Bond Precision on C-C Bonds ............... 0.0087 Ang PLAT906_ALERT_3_C Large K value in the Analysis of Variance ...... 8.891 PLAT906_ALERT_3_C Large K value in the Analysis of Variance ...... 2.438 PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L= 0.600 6 PLAT972_ALERT_2_C Large Calcd. Non-Metal Negative Residual Density -1.58 eA-3
Alert level G PLAT002_ALERT_2_G Number of Distance or Angle Restraints on AtSite 12 PLAT003_ALERT_2_G Number of Uiso or Uij Restrained non-H Atoms ... 12 PLAT005_ALERT_5_G No _iucr_refine_instructions_details in the CIF ? PLAT083_ALERT_2_G SHELXL Second Parameter in WGHT Unusually Large. 5.06 PLAT128_ALERT_4_G Note: Alternate Setting of Space-group P21/c . P21/n PLAT301_ALERT_3_G Note: Main Residue Disorder ................... 10 % PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 78 PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L= 0.600 15
0 ALERT level A = Most likely a serious problem - resolve or explain 4 ALERT level B = A potentially serious problem, consider carefully 7 ALERT level C = Check. Ensure it is not caused by an omission or oversight 8 ALERT level G = General information/check it is not something unexpected 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 6 ALERT type 2 Indicator that the structure model may be wrong or deficient 8 ALERT type 3 Indicator that the structure quality may be low 4 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check
To a white suspension containing 0.15 g (0.17 mmol) of [Au2Cl2(dppp)] in 300 ml of EtOH was added 0.056 g (0.17 mmol) of N,N'-ethylene-bis-D-penicillamine dissolved in 3 ml of a 0.1 M KOH aqueous solution. The mixture was stirred at room temperature for 3 h. The resulting colorless solution was evaporated to dryness, and then the residue was washed with H2O to give a white powder (0.15 g). When 2.5 mg (0.01 mmol) of NiCl2.6H2O was added to a suspension of this white powder (10 mg) in 1 ml of EtOH, followed by stirring at room temperature for 3 h, a clear red orange solution was obtained. Vapor diffusion of diethylether into the resulting red orange solution afforded a small amount of blue needle crystals of [Au2(dppp)2][NiCl4].Et2O.
H atoms were placed at calculated positions [C–H = 0.99 (methylene) or 0.95 Å (phenyl)] and refined as riding with Uiso(H) = 1.2Ueq(C). One phenyl ring is disordered over two positions (C7–C12 and C13–C18) with site occupancies of 0.5. The FLAT and SIMU restraints were used to model the disordered phenyl ring.
Data collection: PROCESS-AUTO (Rigaku, 2000); cell refinement: PROCESS-AUTO (Rigaku, 2000); data reduction: PROCESS-AUTO (Rigaku, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Yadokari-XG 2009 (Kabuto et al., 2009); software used to prepare material for publication: Yadokari-XG 2009 (Kabuto et al., 2009).
[Au2(C27H26P2)2][NiCl4]·C4H10O | F(000) = 2928 |
Mr = 1493.40 | Dx = 1.709 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71075 Å |
Hall symbol: -P 2yn | Cell parameters from 2299 reflections |
a = 18.9290 (5) Å | θ = 4.1–27.6° |
b = 16.1945 (7) Å | µ = 5.70 mm−1 |
c = 19.0895 (17) Å | T = 200 K |
β = 97.368 (7)° | Needle, blue |
V = 5803.5 (6) Å3 | 0.28 × 0.05 × 0.03 mm |
Z = 4 |
Rigaku R-AXIS VII diffractometer | 13273 independent reflections |
Radiation source: fine-focus sealed tube | 10666 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.042 |
Detector resolution: 10.000 pixels mm-1 | θmax = 27.5°, θmin = 3.0° |
ω scans | h = −22→24 |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | k = −20→21 |
Tmin = 0.580, Tmax = 0.773 | l = −24→24 |
45449 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)] = 0.048 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.083 | H-atom parameters constrained |
S = 1.14 | w = 1/[σ2(Fo2) + (0.0332P)2 + 5.0632P] where P = (Fo2 + 2Fc2)/3 |
13273 reflections | (Δ/σ)max = 0.001 |
685 parameters | Δρmax = 1.16 e Å−3 |
78 restraints | Δρmin = −0.88 e Å−3 |
[Au2(C27H26P2)2][NiCl4]·C4H10O | V = 5803.5 (6) Å3 |
Mr = 1493.40 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 18.9290 (5) Å | µ = 5.70 mm−1 |
b = 16.1945 (7) Å | T = 200 K |
c = 19.0895 (17) Å | 0.28 × 0.05 × 0.03 mm |
β = 97.368 (7)° |
Rigaku R-AXIS VII diffractometer | 13273 independent reflections |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | 10666 reflections with I > 2σ(I) |
Tmin = 0.580, Tmax = 0.773 | Rint = 0.042 |
45449 measured reflections |
R[F2 > 2σ(F2)] = 0.048 | 78 restraints |
wR(F2) = 0.083 | H-atom parameters constrained |
S = 1.14 | Δρmax = 1.16 e Å−3 |
13273 reflections | Δρmin = −0.88 e Å−3 |
685 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. |
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 | Occ. (<1) | |
Au1 | 0.779915 (10) | 0.834674 (12) | 0.074536 (10) | 0.03063 (6) | |
Au2 | 0.549659 (10) | 0.900739 (12) | 0.218117 (10) | 0.02907 (6) | |
P1 | 0.73666 (7) | 0.70192 (8) | 0.05633 (7) | 0.0304 (3) | |
P2 | 0.53747 (7) | 0.76109 (8) | 0.23538 (7) | 0.0285 (3) | |
P3 | 0.81787 (6) | 0.96902 (8) | 0.09657 (7) | 0.0271 (3) | |
P4 | 0.56077 (6) | 1.03989 (8) | 0.19661 (7) | 0.0266 (3) | |
C1 | 0.7040 (3) | 0.6692 (3) | 0.1377 (3) | 0.0324 (12) | |
H1 | 0.6837 | 0.6129 | 0.1313 | 0.039* | |
H2 | 0.7443 | 0.6670 | 0.1762 | 0.039* | |
C2 | 0.6472 (2) | 0.7282 (3) | 0.1583 (3) | 0.0306 (11) | |
H3 | 0.6057 | 0.7270 | 0.1210 | 0.037* | |
H4 | 0.6666 | 0.7850 | 0.1605 | 0.037* | |
C3 | 0.6218 (2) | 0.7075 (3) | 0.2294 (2) | 0.0296 (11) | |
H5 | 0.6580 | 0.7251 | 0.2686 | 0.036* | |
H6 | 0.6149 | 0.6471 | 0.2333 | 0.036* | |
C4 | 0.7729 (2) | 1.0247 (3) | 0.1619 (3) | 0.0289 (11) | |
H7 | 0.7878 | 1.0008 | 0.2092 | 0.035* | |
H8 | 0.7881 | 1.0832 | 0.1630 | 0.035* | |
C5 | 0.6909 (2) | 1.0206 (3) | 0.1457 (3) | 0.0348 (12) | |
H9 | 0.6760 | 1.0424 | 0.0976 | 0.042* | |
H10 | 0.6754 | 0.9622 | 0.1466 | 0.042* | |
C6 | 0.6541 (2) | 1.0700 (3) | 0.1987 (3) | 0.0304 (11) | |
H11 | 0.6568 | 1.1296 | 0.1877 | 0.036* | |
H12 | 0.6794 | 1.0610 | 0.2468 | 0.036* | |
C7 | 0.802 (2) | 0.623 (3) | 0.0354 (17) | 0.055 (4) | 0.50 |
C8 | 0.7861 (11) | 0.5432 (14) | 0.0384 (9) | 0.064 (4) | 0.50 |
H13 | 0.7424 | 0.5264 | 0.0537 | 0.077* | 0.50 |
C9 | 0.8353 (12) | 0.4825 (17) | 0.0181 (13) | 0.070 (4) | 0.50 |
H14 | 0.8255 | 0.4253 | 0.0218 | 0.085* | 0.50 |
C10 | 0.8946 (13) | 0.5076 (15) | −0.0057 (11) | 0.075 (4) | 0.50 |
H15 | 0.9253 | 0.4681 | −0.0228 | 0.090* | 0.50 |
C11 | 0.9112 (9) | 0.5852 (10) | −0.0060 (10) | 0.078 (3) | 0.50 |
H16 | 0.9559 | 0.6015 | −0.0191 | 0.094* | 0.50 |
C12 | 0.8637 (8) | 0.6454 (10) | 0.0129 (9) | 0.067 (3) | 0.50 |
H17 | 0.8751 | 0.7023 | 0.0097 | 0.081* | 0.50 |
C13 | 0.7966 (16) | 0.622 (3) | 0.0378 (12) | 0.030 (3) | 0.50 |
C14 | 0.7708 (9) | 0.5416 (12) | 0.0162 (8) | 0.042 (3) | 0.50 |
H18 | 0.7210 | 0.5317 | 0.0094 | 0.051* | 0.50 |
C15 | 0.8156 (8) | 0.4794 (15) | 0.0055 (11) | 0.049 (3) | 0.50 |
H19 | 0.7983 | 0.4265 | −0.0099 | 0.059* | 0.50 |
C16 | 0.8907 (12) | 0.4968 (14) | 0.0186 (9) | 0.056 (3) | 0.50 |
H20 | 0.9236 | 0.4548 | 0.0101 | 0.067* | 0.50 |
C17 | 0.9153 (7) | 0.5694 (9) | 0.0421 (8) | 0.056 (3) | 0.50 |
H21 | 0.9652 | 0.5785 | 0.0516 | 0.068* | 0.50 |
C18 | 0.8683 (7) | 0.6319 (9) | 0.0526 (7) | 0.045 (3) | 0.50 |
H22 | 0.8866 | 0.6833 | 0.0708 | 0.054* | 0.50 |
C19 | 0.6622 (3) | 0.6947 (3) | −0.0140 (3) | 0.0304 (11) | |
C20 | 0.6632 (3) | 0.7447 (3) | −0.0737 (3) | 0.0430 (14) | |
H23 | 0.7014 | 0.7821 | −0.0764 | 0.052* | |
C21 | 0.6076 (3) | 0.7395 (4) | −0.1294 (3) | 0.0500 (16) | |
H24 | 0.6087 | 0.7727 | −0.1703 | 0.060* | |
C22 | 0.5512 (3) | 0.6863 (4) | −0.1253 (3) | 0.0525 (17) | |
H25 | 0.5130 | 0.6839 | −0.1627 | 0.063* | |
C23 | 0.5506 (3) | 0.6369 (3) | −0.0668 (3) | 0.0469 (15) | |
H26 | 0.5123 | 0.5996 | −0.0647 | 0.056* | |
C24 | 0.6050 (3) | 0.6407 (3) | −0.0109 (3) | 0.0404 (13) | |
H27 | 0.6034 | 0.6067 | 0.0294 | 0.048* | |
C25 | 0.5129 (3) | 0.7377 (3) | 0.3220 (3) | 0.0354 (12) | |
C26 | 0.4619 (3) | 0.6787 (3) | 0.3322 (3) | 0.0456 (15) | |
H28 | 0.4399 | 0.6472 | 0.2934 | 0.055* | |
C27 | 0.4431 (4) | 0.6658 (4) | 0.3999 (4) | 0.0574 (18) | |
H29 | 0.4071 | 0.6269 | 0.4069 | 0.069* | |
C28 | 0.4769 (4) | 0.7097 (4) | 0.4565 (4) | 0.072 (2) | |
H30 | 0.4649 | 0.7002 | 0.5026 | 0.086* | |
C29 | 0.5281 (5) | 0.7671 (4) | 0.4462 (3) | 0.078 (2) | |
H31 | 0.5512 | 0.7973 | 0.4852 | 0.093* | |
C30 | 0.5462 (4) | 0.7811 (4) | 0.3794 (3) | 0.0577 (18) | |
H32 | 0.5816 | 0.8209 | 0.3728 | 0.069* | |
C31 | 0.4727 (2) | 0.7128 (3) | 0.1696 (3) | 0.0279 (11) | |
C32 | 0.4813 (3) | 0.6337 (3) | 0.1438 (3) | 0.0432 (14) | |
H33 | 0.5202 | 0.6007 | 0.1638 | 0.052* | |
C33 | 0.4338 (3) | 0.6028 (4) | 0.0894 (3) | 0.0498 (15) | |
H34 | 0.4401 | 0.5483 | 0.0728 | 0.060* | |
C34 | 0.3779 (3) | 0.6490 (4) | 0.0588 (3) | 0.0518 (16) | |
H35 | 0.3464 | 0.6274 | 0.0204 | 0.062* | |
C35 | 0.3675 (3) | 0.7272 (4) | 0.0841 (3) | 0.0485 (15) | |
H36 | 0.3277 | 0.7591 | 0.0644 | 0.058* | |
C36 | 0.4150 (3) | 0.7590 (3) | 0.1381 (3) | 0.0366 (12) | |
H37 | 0.4083 | 0.8135 | 0.1542 | 0.044* | |
C37 | 0.8062 (2) | 1.0336 (3) | 0.0176 (3) | 0.0303 (11) | |
C38 | 0.7747 (3) | 1.0013 (4) | −0.0457 (3) | 0.0444 (14) | |
H38 | 0.7611 | 0.9448 | −0.0481 | 0.053* | |
C39 | 0.7627 (3) | 1.0501 (5) | −0.1058 (3) | 0.0565 (18) | |
H39 | 0.7405 | 1.0277 | −0.1491 | 0.068* | |
C40 | 0.7836 (3) | 1.1317 (5) | −0.1014 (4) | 0.0618 (19) | |
H40 | 0.7763 | 1.1655 | −0.1423 | 0.074* | |
C41 | 0.8145 (3) | 1.1645 (4) | −0.0391 (4) | 0.0562 (18) | |
H41 | 0.8276 | 1.2211 | −0.0367 | 0.067* | |
C42 | 0.8268 (3) | 1.1151 (3) | 0.0208 (3) | 0.0422 (14) | |
H42 | 0.8495 | 1.1377 | 0.0639 | 0.051* | |
C43 | 0.9125 (2) | 0.9708 (3) | 0.1293 (3) | 0.0269 (11) | |
C44 | 0.9617 (3) | 0.9585 (3) | 0.0813 (3) | 0.0345 (12) | |
H43 | 0.9457 | 0.9566 | 0.0320 | 0.041* | |
C45 | 1.0339 (3) | 0.9489 (3) | 0.1052 (3) | 0.0396 (13) | |
H44 | 1.0666 | 0.9401 | 0.0721 | 0.048* | |
C46 | 1.0583 (3) | 0.9520 (3) | 0.1762 (3) | 0.0377 (13) | |
H45 | 1.1076 | 0.9455 | 0.1920 | 0.045* | |
C47 | 1.0108 (3) | 0.9648 (3) | 0.2241 (3) | 0.0363 (12) | |
H46 | 1.0276 | 0.9679 | 0.2731 | 0.044* | |
C48 | 0.9377 (3) | 0.9733 (3) | 0.2010 (3) | 0.0318 (11) | |
H47 | 0.9052 | 0.9809 | 0.2345 | 0.038* | |
C49 | 0.5141 (2) | 1.0717 (3) | 0.1118 (2) | 0.0265 (10) | |
C50 | 0.5378 (3) | 1.1376 (3) | 0.0733 (3) | 0.0341 (12) | |
H48 | 0.5804 | 1.1664 | 0.0900 | 0.041* | |
C51 | 0.4972 (3) | 1.1601 (3) | 0.0095 (3) | 0.0434 (14) | |
H49 | 0.5123 | 1.2050 | −0.0170 | 0.052* | |
C52 | 0.4360 (3) | 1.1183 (4) | −0.0153 (3) | 0.0420 (14) | |
H50 | 0.4093 | 1.1340 | −0.0588 | 0.050* | |
C53 | 0.4130 (3) | 1.0534 (3) | 0.0231 (3) | 0.0409 (14) | |
H51 | 0.3702 | 1.0251 | 0.0064 | 0.049* | |
C54 | 0.4522 (3) | 1.0298 (3) | 0.0853 (3) | 0.0343 (12) | |
H52 | 0.4368 | 0.9842 | 0.1108 | 0.041* | |
C55 | 0.5201 (3) | 1.1036 (3) | 0.2596 (3) | 0.0320 (12) | |
C56 | 0.5434 (3) | 1.1835 (3) | 0.2746 (3) | 0.0463 (15) | |
H53 | 0.5833 | 1.2046 | 0.2549 | 0.056* | |
C57 | 0.5084 (4) | 1.2322 (4) | 0.3184 (3) | 0.0583 (18) | |
H54 | 0.5246 | 1.2869 | 0.3289 | 0.070* | |
C58 | 0.4510 (4) | 1.2029 (5) | 0.3467 (4) | 0.067 (2) | |
H55 | 0.4272 | 1.2376 | 0.3763 | 0.081* | |
C59 | 0.4271 (4) | 1.1241 (5) | 0.3329 (4) | 0.069 (2) | |
H56 | 0.3869 | 1.1040 | 0.3528 | 0.083* | |
C60 | 0.4624 (3) | 1.0732 (4) | 0.2892 (3) | 0.0530 (16) | |
H57 | 0.4468 | 1.0181 | 0.2800 | 0.064* | |
Ni1 | 0.79494 (3) | 0.85982 (4) | 0.34081 (3) | 0.03311 (16) | |
Cl1 | 0.81798 (9) | 0.81747 (9) | 0.23347 (7) | 0.0496 (4) | |
Cl2 | 0.68553 (8) | 0.91672 (11) | 0.32021 (9) | 0.0624 (5) | |
Cl3 | 0.87604 (7) | 0.96027 (8) | 0.37596 (7) | 0.0377 (3) | |
Cl4 | 0.77899 (8) | 0.74535 (9) | 0.40236 (8) | 0.0508 (4) | |
O1 | 0.2306 (3) | 0.4928 (4) | 0.2151 (3) | 0.0986 (18) | |
C61 | 0.2757 (5) | 0.5546 (8) | 0.2001 (6) | 0.125 (4) | |
H58 | 0.2643 | 0.5702 | 0.1498 | 0.150* | |
H59 | 0.3252 | 0.5337 | 0.2072 | 0.150* | |
C62 | 0.2710 (6) | 0.6288 (8) | 0.2443 (8) | 0.171 (6) | |
H60 | 0.3041 | 0.6709 | 0.2312 | 0.257* | |
H61 | 0.2835 | 0.6142 | 0.2942 | 0.257* | |
H62 | 0.2223 | 0.6505 | 0.2369 | 0.257* | |
C63 | 0.2334 (7) | 0.4189 (7) | 0.1756 (5) | 0.125 (4) | |
H63 | 0.2798 | 0.3912 | 0.1889 | 0.151* | |
H64 | 0.2286 | 0.4319 | 0.1246 | 0.151* | |
C64 | 0.1743 (8) | 0.3632 (7) | 0.1905 (7) | 0.174 (6) | |
H65 | 0.1764 | 0.3118 | 0.1637 | 0.260* | |
H66 | 0.1285 | 0.3905 | 0.1764 | 0.260* | |
H67 | 0.1793 | 0.3507 | 0.2411 | 0.260* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Au1 | 0.02931 (11) | 0.03070 (12) | 0.03187 (11) | −0.00375 (8) | 0.00394 (8) | −0.00447 (8) |
Au2 | 0.03258 (11) | 0.02486 (11) | 0.02932 (11) | 0.00187 (8) | 0.00220 (8) | 0.00207 (8) |
P1 | 0.0302 (7) | 0.0293 (7) | 0.0310 (7) | −0.0001 (6) | 0.0014 (6) | −0.0036 (6) |
P2 | 0.0322 (7) | 0.0262 (7) | 0.0271 (7) | 0.0005 (6) | 0.0038 (5) | 0.0034 (5) |
P3 | 0.0232 (7) | 0.0300 (7) | 0.0283 (7) | −0.0020 (5) | 0.0043 (5) | −0.0013 (5) |
P4 | 0.0250 (7) | 0.0248 (7) | 0.0297 (7) | 0.0018 (5) | 0.0029 (5) | −0.0008 (5) |
C1 | 0.038 (3) | 0.023 (3) | 0.034 (3) | 0.003 (2) | −0.004 (2) | 0.002 (2) |
C2 | 0.026 (3) | 0.029 (3) | 0.036 (3) | 0.000 (2) | 0.003 (2) | 0.002 (2) |
C3 | 0.031 (3) | 0.026 (3) | 0.031 (3) | 0.004 (2) | 0.000 (2) | 0.004 (2) |
C4 | 0.029 (3) | 0.028 (3) | 0.029 (3) | −0.005 (2) | 0.004 (2) | −0.003 (2) |
C5 | 0.027 (3) | 0.038 (3) | 0.039 (3) | −0.001 (2) | 0.002 (2) | −0.009 (2) |
C6 | 0.032 (3) | 0.027 (3) | 0.031 (3) | 0.007 (2) | 0.000 (2) | −0.007 (2) |
C7 | 0.046 (8) | 0.048 (7) | 0.077 (8) | 0.005 (6) | 0.026 (6) | −0.011 (7) |
C8 | 0.057 (8) | 0.055 (7) | 0.084 (8) | 0.013 (6) | 0.019 (6) | −0.008 (7) |
C9 | 0.063 (8) | 0.054 (7) | 0.098 (9) | 0.015 (7) | 0.020 (7) | −0.007 (7) |
C10 | 0.065 (7) | 0.061 (7) | 0.104 (9) | 0.019 (6) | 0.026 (7) | −0.011 (7) |
C11 | 0.063 (7) | 0.064 (7) | 0.111 (8) | 0.004 (6) | 0.023 (7) | −0.009 (7) |
C12 | 0.051 (7) | 0.055 (7) | 0.100 (8) | −0.002 (5) | 0.026 (6) | −0.012 (6) |
C13 | 0.023 (6) | 0.036 (6) | 0.030 (5) | 0.003 (5) | −0.005 (5) | −0.006 (5) |
C14 | 0.030 (6) | 0.042 (6) | 0.053 (6) | 0.001 (5) | −0.001 (5) | −0.010 (5) |
C15 | 0.035 (6) | 0.044 (6) | 0.067 (7) | 0.006 (5) | 0.005 (5) | −0.003 (5) |
C16 | 0.040 (6) | 0.057 (7) | 0.072 (7) | 0.014 (5) | 0.012 (6) | 0.005 (6) |
C17 | 0.034 (5) | 0.067 (6) | 0.068 (6) | 0.009 (5) | 0.006 (5) | −0.002 (5) |
C18 | 0.030 (5) | 0.052 (6) | 0.052 (5) | 0.010 (4) | −0.003 (5) | −0.008 (5) |
C19 | 0.030 (3) | 0.030 (3) | 0.029 (3) | 0.007 (2) | −0.003 (2) | −0.005 (2) |
C20 | 0.047 (3) | 0.040 (3) | 0.043 (3) | 0.002 (3) | 0.008 (3) | −0.002 (3) |
C21 | 0.064 (4) | 0.056 (4) | 0.028 (3) | 0.014 (3) | −0.003 (3) | 0.001 (3) |
C22 | 0.058 (4) | 0.050 (4) | 0.043 (4) | 0.017 (3) | −0.021 (3) | −0.015 (3) |
C23 | 0.039 (3) | 0.034 (3) | 0.063 (4) | −0.003 (3) | −0.010 (3) | −0.013 (3) |
C24 | 0.045 (3) | 0.026 (3) | 0.047 (3) | −0.005 (2) | −0.007 (3) | −0.002 (2) |
C25 | 0.048 (3) | 0.029 (3) | 0.031 (3) | 0.007 (2) | 0.010 (2) | 0.007 (2) |
C26 | 0.054 (4) | 0.042 (4) | 0.043 (3) | −0.001 (3) | 0.015 (3) | 0.004 (3) |
C27 | 0.078 (5) | 0.043 (4) | 0.059 (4) | −0.001 (3) | 0.036 (4) | 0.010 (3) |
C28 | 0.129 (7) | 0.053 (4) | 0.040 (4) | 0.007 (5) | 0.038 (4) | 0.005 (3) |
C29 | 0.138 (7) | 0.066 (5) | 0.029 (4) | −0.020 (5) | 0.009 (4) | −0.004 (3) |
C30 | 0.087 (5) | 0.051 (4) | 0.035 (3) | −0.019 (4) | 0.006 (3) | 0.003 (3) |
C31 | 0.026 (3) | 0.027 (3) | 0.032 (3) | −0.003 (2) | 0.009 (2) | 0.002 (2) |
C32 | 0.046 (3) | 0.032 (3) | 0.049 (4) | −0.002 (3) | −0.005 (3) | 0.002 (3) |
C33 | 0.052 (4) | 0.035 (3) | 0.061 (4) | −0.005 (3) | 0.003 (3) | −0.010 (3) |
C34 | 0.048 (4) | 0.061 (4) | 0.043 (4) | −0.009 (3) | −0.004 (3) | −0.006 (3) |
C35 | 0.034 (3) | 0.062 (4) | 0.048 (4) | 0.009 (3) | −0.003 (3) | −0.002 (3) |
C36 | 0.035 (3) | 0.038 (3) | 0.037 (3) | 0.004 (2) | 0.002 (2) | −0.004 (2) |
C37 | 0.023 (3) | 0.037 (3) | 0.033 (3) | 0.006 (2) | 0.011 (2) | 0.005 (2) |
C38 | 0.034 (3) | 0.064 (4) | 0.034 (3) | 0.003 (3) | 0.002 (2) | 0.009 (3) |
C39 | 0.043 (4) | 0.092 (6) | 0.035 (3) | 0.016 (4) | 0.006 (3) | 0.010 (3) |
C40 | 0.058 (4) | 0.077 (5) | 0.053 (4) | 0.034 (4) | 0.018 (3) | 0.030 (4) |
C41 | 0.063 (4) | 0.049 (4) | 0.062 (4) | 0.019 (3) | 0.028 (4) | 0.020 (3) |
C42 | 0.043 (3) | 0.042 (4) | 0.045 (3) | 0.013 (3) | 0.019 (3) | 0.004 (3) |
C43 | 0.028 (3) | 0.019 (3) | 0.033 (3) | 0.001 (2) | 0.005 (2) | −0.002 (2) |
C44 | 0.035 (3) | 0.040 (3) | 0.029 (3) | 0.004 (2) | 0.005 (2) | 0.001 (2) |
C45 | 0.030 (3) | 0.044 (3) | 0.047 (3) | 0.005 (2) | 0.016 (3) | 0.008 (3) |
C46 | 0.023 (3) | 0.038 (3) | 0.051 (4) | 0.000 (2) | 0.003 (2) | 0.004 (3) |
C47 | 0.035 (3) | 0.039 (3) | 0.034 (3) | −0.004 (2) | 0.002 (2) | −0.001 (2) |
C48 | 0.030 (3) | 0.030 (3) | 0.037 (3) | 0.000 (2) | 0.010 (2) | 0.000 (2) |
C49 | 0.025 (3) | 0.027 (3) | 0.029 (3) | 0.006 (2) | 0.008 (2) | −0.001 (2) |
C50 | 0.035 (3) | 0.027 (3) | 0.042 (3) | 0.003 (2) | 0.011 (2) | 0.002 (2) |
C51 | 0.056 (4) | 0.039 (3) | 0.036 (3) | 0.014 (3) | 0.012 (3) | 0.012 (3) |
C52 | 0.041 (3) | 0.052 (4) | 0.032 (3) | 0.021 (3) | 0.001 (3) | −0.002 (3) |
C53 | 0.039 (3) | 0.046 (4) | 0.036 (3) | 0.001 (3) | −0.003 (3) | −0.006 (3) |
C54 | 0.033 (3) | 0.031 (3) | 0.039 (3) | 0.002 (2) | 0.003 (2) | 0.003 (2) |
C55 | 0.034 (3) | 0.035 (3) | 0.028 (3) | 0.008 (2) | 0.005 (2) | −0.002 (2) |
C56 | 0.062 (4) | 0.037 (4) | 0.041 (3) | 0.009 (3) | 0.013 (3) | 0.000 (3) |
C57 | 0.087 (5) | 0.043 (4) | 0.048 (4) | 0.014 (4) | 0.017 (4) | −0.008 (3) |
C58 | 0.089 (6) | 0.067 (5) | 0.051 (4) | 0.036 (4) | 0.027 (4) | −0.002 (4) |
C59 | 0.066 (5) | 0.084 (6) | 0.065 (5) | 0.013 (4) | 0.037 (4) | 0.002 (4) |
C60 | 0.051 (4) | 0.051 (4) | 0.063 (4) | −0.003 (3) | 0.031 (3) | −0.005 (3) |
Ni1 | 0.0343 (4) | 0.0337 (4) | 0.0296 (4) | −0.0045 (3) | −0.0027 (3) | 0.0019 (3) |
Cl1 | 0.0703 (10) | 0.0470 (9) | 0.0309 (7) | −0.0074 (7) | 0.0042 (7) | −0.0045 (6) |
Cl2 | 0.0373 (8) | 0.0790 (12) | 0.0660 (11) | 0.0071 (8) | −0.0121 (7) | 0.0174 (9) |
Cl3 | 0.0343 (7) | 0.0340 (7) | 0.0437 (8) | −0.0041 (6) | 0.0011 (6) | −0.0060 (6) |
Cl4 | 0.0627 (10) | 0.0424 (9) | 0.0474 (9) | −0.0060 (7) | 0.0077 (7) | 0.0110 (7) |
O1 | 0.106 (5) | 0.114 (5) | 0.080 (4) | −0.022 (4) | 0.031 (4) | −0.001 (4) |
C61 | 0.063 (6) | 0.172 (11) | 0.138 (10) | −0.017 (7) | 0.002 (6) | 0.068 (9) |
C62 | 0.128 (10) | 0.147 (11) | 0.220 (16) | −0.082 (9) | −0.050 (10) | 0.032 (11) |
C63 | 0.191 (12) | 0.114 (9) | 0.075 (7) | 0.044 (8) | 0.029 (7) | −0.010 (6) |
C64 | 0.281 (18) | 0.105 (9) | 0.134 (11) | −0.074 (11) | 0.023 (11) | −0.022 (8) |
Au1—P1 | 2.3109 (13) | C29—H31 | 0.9500 |
Au1—P3 | 2.3129 (13) | C30—H32 | 0.9500 |
Au2—P2 | 2.3013 (13) | C31—C32 | 1.389 (7) |
Au2—P4 | 2.3050 (13) | C31—C36 | 1.395 (7) |
P1—C13 | 1.78 (4) | C32—C33 | 1.378 (7) |
P1—C19 | 1.820 (5) | C32—H33 | 0.9500 |
P1—C1 | 1.822 (5) | C33—C34 | 1.364 (8) |
P1—C7 | 1.87 (5) | C33—H34 | 0.9500 |
P2—C25 | 1.815 (5) | C34—C35 | 1.378 (8) |
P2—C31 | 1.816 (5) | C34—H35 | 0.9500 |
P2—C3 | 1.833 (5) | C35—C36 | 1.377 (7) |
P3—C43 | 1.820 (5) | C35—H36 | 0.9500 |
P3—C37 | 1.824 (5) | C36—H37 | 0.9500 |
P3—C4 | 1.834 (5) | C37—C42 | 1.377 (7) |
P4—C49 | 1.816 (5) | C37—C38 | 1.379 (7) |
P4—C6 | 1.828 (5) | C38—C39 | 1.388 (8) |
P4—C55 | 1.829 (5) | C38—H38 | 0.9500 |
C1—C2 | 1.528 (7) | C39—C40 | 1.378 (9) |
C1—H1 | 0.9900 | C39—H39 | 0.9500 |
C1—H2 | 0.9900 | C40—C41 | 1.363 (9) |
C2—C3 | 1.535 (6) | C40—H40 | 0.9500 |
C2—H3 | 0.9900 | C41—C42 | 1.390 (8) |
C2—H4 | 0.9900 | C41—H41 | 0.9500 |
C3—H5 | 0.9900 | C42—H42 | 0.9500 |
C3—H6 | 0.9900 | C43—C48 | 1.391 (7) |
C4—C5 | 1.545 (6) | C43—C44 | 1.402 (7) |
C4—H7 | 0.9900 | C44—C45 | 1.393 (7) |
C4—H8 | 0.9900 | C44—H43 | 0.9500 |
C5—C6 | 1.526 (6) | C45—C46 | 1.375 (7) |
C5—H9 | 0.9900 | C45—H44 | 0.9500 |
C5—H10 | 0.9900 | C46—C47 | 1.379 (7) |
C6—H11 | 0.9900 | C46—H45 | 0.9500 |
C6—H12 | 0.9900 | C47—C48 | 1.405 (7) |
C7—C8 | 1.33 (5) | C47—H46 | 0.9500 |
C7—C12 | 1.34 (4) | C48—H47 | 0.9500 |
C8—C9 | 1.44 (3) | C49—C54 | 1.392 (7) |
C8—H13 | 0.9500 | C49—C50 | 1.403 (7) |
C9—C10 | 1.33 (3) | C50—C51 | 1.402 (7) |
C9—H14 | 0.9500 | C50—H48 | 0.9500 |
C10—C11 | 1.30 (3) | C51—C52 | 1.373 (8) |
C10—H15 | 0.9500 | C51—H49 | 0.9500 |
C11—C12 | 1.40 (2) | C52—C53 | 1.383 (8) |
C11—H16 | 0.9500 | C52—H50 | 0.9500 |
C12—H17 | 0.9500 | C53—C54 | 1.372 (7) |
C13—C18 | 1.36 (3) | C53—H51 | 0.9500 |
C13—C14 | 1.44 (4) | C54—H52 | 0.9500 |
C14—C15 | 1.35 (2) | C55—C60 | 1.383 (7) |
C14—H18 | 0.9500 | C55—C56 | 1.384 (7) |
C15—C16 | 1.44 (3) | C56—C57 | 1.379 (8) |
C15—H19 | 0.9500 | C56—H53 | 0.9500 |
C16—C17 | 1.32 (2) | C57—C58 | 1.359 (9) |
C16—H20 | 0.9500 | C57—H54 | 0.9500 |
C17—C18 | 1.380 (17) | C58—C59 | 1.368 (10) |
C17—H21 | 0.9500 | C58—H55 | 0.9500 |
C18—H22 | 0.9500 | C59—C60 | 1.401 (8) |
C19—C24 | 1.400 (7) | C59—H56 | 0.9500 |
C19—C20 | 1.401 (7) | C60—H57 | 0.9500 |
C20—C21 | 1.399 (7) | Ni1—Cl4 | 2.2359 (15) |
C20—H23 | 0.9500 | Ni1—Cl2 | 2.2548 (16) |
C21—C22 | 1.382 (8) | Ni1—Cl1 | 2.2558 (15) |
C21—H24 | 0.9500 | Ni1—Cl3 | 2.2780 (14) |
C22—C23 | 1.375 (8) | O1—C61 | 1.370 (10) |
C22—H25 | 0.9500 | O1—C63 | 1.418 (10) |
C23—C24 | 1.386 (7) | C61—C62 | 1.477 (15) |
C23—H26 | 0.9500 | C61—H58 | 0.9900 |
C24—H27 | 0.9500 | C61—H59 | 0.9900 |
C25—C30 | 1.384 (7) | C62—H60 | 0.9800 |
C25—C26 | 1.390 (7) | C62—H61 | 0.9800 |
C26—C27 | 1.399 (8) | C62—H62 | 0.9800 |
C26—H28 | 0.9500 | C63—C64 | 1.492 (14) |
C27—C28 | 1.380 (9) | C63—H63 | 0.9900 |
C27—H29 | 0.9500 | C63—H64 | 0.9900 |
C28—C29 | 1.375 (9) | C64—H65 | 0.9800 |
C28—H30 | 0.9500 | C64—H66 | 0.9800 |
C29—C30 | 1.379 (8) | C64—H67 | 0.9800 |
P1—Au1—P3 | 176.68 (5) | C29—C28—H30 | 120.0 |
P2—Au2—P4 | 177.98 (5) | C27—C28—H30 | 120.0 |
C13—P1—C19 | 105.0 (8) | C28—C29—C30 | 120.4 (6) |
C13—P1—C1 | 104.7 (10) | C28—C29—H31 | 119.8 |
C19—P1—C1 | 107.1 (2) | C30—C29—H31 | 119.8 |
C19—P1—C7 | 105.8 (11) | C29—C30—C25 | 120.4 (6) |
C1—P1—C7 | 106.9 (12) | C29—C30—H32 | 119.8 |
C13—P1—Au1 | 118.7 (11) | C25—C30—H32 | 119.8 |
C19—P1—Au1 | 113.35 (17) | C32—C31—C36 | 117.5 (5) |
C1—P1—Au1 | 107.16 (16) | C32—C31—P2 | 122.9 (4) |
C7—P1—Au1 | 116.0 (14) | C36—C31—P2 | 119.3 (4) |
C25—P2—C31 | 108.1 (2) | C33—C32—C31 | 120.5 (5) |
C25—P2—C3 | 106.5 (2) | C33—C32—H33 | 119.8 |
C31—P2—C3 | 105.6 (2) | C31—C32—H33 | 119.8 |
C25—P2—Au2 | 112.19 (17) | C34—C33—C32 | 121.2 (6) |
C31—P2—Au2 | 113.28 (16) | C34—C33—H34 | 119.4 |
C3—P2—Au2 | 110.65 (16) | C32—C33—H34 | 119.4 |
C43—P3—C37 | 106.5 (2) | C33—C34—C35 | 119.5 (6) |
C43—P3—C4 | 106.4 (2) | C33—C34—H35 | 120.2 |
C37—P3—C4 | 105.2 (2) | C35—C34—H35 | 120.2 |
C43—P3—Au1 | 110.24 (15) | C36—C35—C34 | 119.7 (5) |
C37—P3—Au1 | 112.76 (18) | C36—C35—H36 | 120.1 |
C4—P3—Au1 | 115.17 (16) | C34—C35—H36 | 120.1 |
C49—P4—C6 | 107.6 (2) | C35—C36—C31 | 121.5 (5) |
C49—P4—C55 | 103.2 (2) | C35—C36—H37 | 119.2 |
C6—P4—C55 | 108.8 (2) | C31—C36—H37 | 119.2 |
C49—P4—Au2 | 112.99 (16) | C42—C37—C38 | 119.4 (5) |
C6—P4—Au2 | 111.52 (16) | C42—C37—P3 | 120.6 (4) |
C55—P4—Au2 | 112.28 (17) | C38—C37—P3 | 119.9 (4) |
C2—C1—P1 | 111.4 (3) | C37—C38—C39 | 121.0 (6) |
C2—C1—H1 | 109.4 | C37—C38—H38 | 119.5 |
P1—C1—H1 | 109.4 | C39—C38—H38 | 119.5 |
C2—C1—H2 | 109.4 | C40—C39—C38 | 118.7 (6) |
P1—C1—H2 | 109.4 | C40—C39—H39 | 120.6 |
H1—C1—H2 | 108.0 | C38—C39—H39 | 120.6 |
C1—C2—C3 | 113.7 (4) | C41—C40—C39 | 120.9 (6) |
C1—C2—H3 | 108.8 | C41—C40—H40 | 119.5 |
C3—C2—H3 | 108.8 | C39—C40—H40 | 119.5 |
C1—C2—H4 | 108.8 | C40—C41—C42 | 120.1 (6) |
C3—C2—H4 | 108.8 | C40—C41—H41 | 120.0 |
H3—C2—H4 | 107.7 | C42—C41—H41 | 120.0 |
C2—C3—P2 | 109.0 (3) | C37—C42—C41 | 119.9 (6) |
C2—C3—H5 | 109.9 | C37—C42—H42 | 120.1 |
P2—C3—H5 | 109.9 | C41—C42—H42 | 120.1 |
C2—C3—H6 | 109.9 | C48—C43—C44 | 118.4 (4) |
P2—C3—H6 | 109.9 | C48—C43—P3 | 122.4 (4) |
H5—C3—H6 | 108.3 | C44—C43—P3 | 118.7 (4) |
C5—C4—P3 | 112.7 (3) | C45—C44—C43 | 120.5 (5) |
C5—C4—H7 | 109.1 | C45—C44—H43 | 119.7 |
P3—C4—H7 | 109.1 | C43—C44—H43 | 119.7 |
C5—C4—H8 | 109.1 | C46—C45—C44 | 120.7 (5) |
P3—C4—H8 | 109.1 | C46—C45—H44 | 119.7 |
H7—C4—H8 | 107.8 | C44—C45—H44 | 119.7 |
C6—C5—C4 | 112.2 (4) | C45—C46—C47 | 119.7 (5) |
C6—C5—H9 | 109.2 | C45—C46—H45 | 120.2 |
C4—C5—H9 | 109.2 | C47—C46—H45 | 120.2 |
C6—C5—H10 | 109.2 | C46—C47—C48 | 120.4 (5) |
C4—C5—H10 | 109.2 | C46—C47—H46 | 119.8 |
H9—C5—H10 | 107.9 | C48—C47—H46 | 119.8 |
C5—C6—P4 | 111.6 (3) | C43—C48—C47 | 120.4 (5) |
C5—C6—H11 | 109.3 | C43—C48—H47 | 119.8 |
P4—C6—H11 | 109.3 | C47—C48—H47 | 119.8 |
C5—C6—H12 | 109.3 | C54—C49—C50 | 119.4 (5) |
P4—C6—H12 | 109.3 | C54—C49—P4 | 118.5 (4) |
H11—C6—H12 | 108.0 | C50—C49—P4 | 122.1 (4) |
C8—C7—C12 | 120 (4) | C51—C50—C49 | 118.5 (5) |
C8—C7—P1 | 119 (3) | C51—C50—H48 | 120.8 |
C12—C7—P1 | 121 (3) | C49—C50—H48 | 120.8 |
C7—C8—C9 | 119 (2) | C52—C51—C50 | 121.0 (5) |
C7—C8—H13 | 120.4 | C52—C51—H49 | 119.5 |
C9—C8—H13 | 120.4 | C50—C51—H49 | 119.5 |
C10—C9—C8 | 119 (2) | C51—C52—C53 | 120.1 (5) |
C10—C9—H14 | 120.4 | C51—C52—H50 | 120.0 |
C8—C9—H14 | 120.4 | C53—C52—H50 | 120.0 |
C11—C10—C9 | 121 (2) | C54—C53—C52 | 119.9 (5) |
C11—C10—H15 | 119.5 | C54—C53—H51 | 120.0 |
C9—C10—H15 | 119.5 | C52—C53—H51 | 120.0 |
C10—C11—C12 | 120.6 (17) | C53—C54—C49 | 121.0 (5) |
C10—C11—H16 | 119.7 | C53—C54—H52 | 119.5 |
C12—C11—H16 | 119.7 | C49—C54—H52 | 119.5 |
C7—C12—C11 | 120 (3) | C60—C55—C56 | 119.7 (5) |
C7—C12—H17 | 120.0 | C60—C55—P4 | 119.3 (4) |
C11—C12—H17 | 120.0 | C56—C55—P4 | 120.9 (4) |
C18—C13—C14 | 117 (3) | C57—C56—C55 | 119.7 (6) |
C18—C13—P1 | 121 (2) | C57—C56—H53 | 120.2 |
C14—C13—P1 | 121 (2) | C55—C56—H53 | 120.2 |
C15—C14—C13 | 121.8 (18) | C58—C57—C56 | 120.8 (6) |
C15—C14—H18 | 119.1 | C58—C57—H54 | 119.6 |
C13—C14—H18 | 119.1 | C56—C57—H54 | 119.6 |
C14—C15—C16 | 116.9 (19) | C57—C58—C59 | 120.7 (6) |
C14—C15—H19 | 121.5 | C57—C58—H55 | 119.7 |
C16—C15—H19 | 121.5 | C59—C58—H55 | 119.7 |
C17—C16—C15 | 122 (2) | C58—C59—C60 | 119.4 (6) |
C17—C16—H20 | 119.0 | C58—C59—H56 | 120.3 |
C15—C16—H20 | 119.0 | C60—C59—H56 | 120.3 |
C16—C17—C18 | 119.7 (15) | C55—C60—C59 | 119.7 (6) |
C16—C17—H21 | 120.1 | C55—C60—H57 | 120.1 |
C18—C17—H21 | 120.1 | C59—C60—H57 | 120.1 |
C13—C18—C17 | 122 (2) | Cl4—Ni1—Cl2 | 104.33 (6) |
C13—C18—H22 | 118.9 | Cl4—Ni1—Cl1 | 106.27 (6) |
C17—C18—H22 | 118.9 | Cl2—Ni1—Cl1 | 104.24 (7) |
C24—C19—C20 | 119.1 (5) | Cl4—Ni1—Cl3 | 124.65 (6) |
C24—C19—P1 | 122.6 (4) | Cl2—Ni1—Cl3 | 109.20 (6) |
C20—C19—P1 | 118.3 (4) | Cl1—Ni1—Cl3 | 106.45 (6) |
C21—C20—C19 | 119.8 (5) | C61—O1—C63 | 116.0 (8) |
C21—C20—H23 | 120.1 | O1—C61—C62 | 113.0 (9) |
C19—C20—H23 | 120.1 | O1—C61—H58 | 109.0 |
C22—C21—C20 | 120.4 (6) | C62—C61—H58 | 109.0 |
C22—C21—H24 | 119.8 | O1—C61—H59 | 109.0 |
C20—C21—H24 | 119.8 | C62—C61—H59 | 109.0 |
C23—C22—C21 | 119.7 (5) | H58—C61—H59 | 107.8 |
C23—C22—H25 | 120.2 | C61—C62—H60 | 109.5 |
C21—C22—H25 | 120.2 | C61—C62—H61 | 109.5 |
C22—C23—C24 | 121.2 (6) | H60—C62—H61 | 109.5 |
C22—C23—H26 | 119.4 | C61—C62—H62 | 109.5 |
C24—C23—H26 | 119.4 | H60—C62—H62 | 109.5 |
C23—C24—C19 | 119.8 (5) | H61—C62—H62 | 109.5 |
C23—C24—H27 | 120.1 | O1—C63—C64 | 109.2 (9) |
C19—C24—H27 | 120.1 | O1—C63—H63 | 109.8 |
C30—C25—C26 | 119.5 (5) | C64—C63—H63 | 109.8 |
C30—C25—P2 | 118.2 (4) | O1—C63—H64 | 109.8 |
C26—C25—P2 | 122.4 (4) | C64—C63—H64 | 109.8 |
C25—C26—C27 | 119.7 (6) | H63—C63—H64 | 108.3 |
C25—C26—H28 | 120.1 | C63—C64—H65 | 109.5 |
C27—C26—H28 | 120.1 | C63—C64—H66 | 109.5 |
C28—C27—C26 | 119.9 (6) | H65—C64—H66 | 109.5 |
C28—C27—H29 | 120.1 | C63—C64—H67 | 109.5 |
C26—C27—H29 | 120.1 | H65—C64—H67 | 109.5 |
C29—C28—C27 | 120.1 (6) | H66—C64—H67 | 109.5 |
C13—P1—C1—C2 | −175.8 (10) | C26—C25—C30—C29 | −1.1 (9) |
C19—P1—C1—C2 | −64.6 (4) | P2—C25—C30—C29 | 178.4 (5) |
C7—P1—C1—C2 | −177.7 (13) | C25—P2—C31—C32 | −91.2 (5) |
Au1—P1—C1—C2 | 57.3 (4) | C3—P2—C31—C32 | 22.5 (5) |
P1—C1—C2—C3 | −175.6 (3) | Au2—P2—C31—C32 | 143.8 (4) |
C1—C2—C3—P2 | −163.2 (3) | C25—P2—C31—C36 | 95.1 (4) |
C25—P2—C3—C2 | −177.4 (3) | C3—P2—C31—C36 | −151.1 (4) |
C31—P2—C3—C2 | 67.7 (4) | Au2—P2—C31—C36 | −29.9 (4) |
Au2—P2—C3—C2 | −55.2 (4) | C36—C31—C32—C33 | −0.4 (8) |
C43—P3—C4—C5 | −173.8 (3) | P2—C31—C32—C33 | −174.2 (4) |
C37—P3—C4—C5 | 73.4 (4) | C31—C32—C33—C34 | 0.9 (9) |
Au1—P3—C4—C5 | −51.4 (4) | C32—C33—C34—C35 | −1.9 (10) |
P3—C4—C5—C6 | −177.7 (3) | C33—C34—C35—C36 | 2.4 (9) |
C4—C5—C6—P4 | −162.3 (4) | C34—C35—C36—C31 | −2.0 (9) |
C49—P4—C6—C5 | −67.3 (4) | C32—C31—C36—C35 | 1.0 (8) |
C55—P4—C6—C5 | −178.5 (4) | P2—C31—C36—C35 | 175.0 (4) |
Au2—P4—C6—C5 | 57.1 (4) | C43—P3—C37—C42 | −58.1 (4) |
C19—P1—C7—C8 | −67 (2) | C4—P3—C37—C42 | 54.6 (4) |
C1—P1—C7—C8 | 47 (2) | Au1—P3—C37—C42 | −179.1 (3) |
Au1—P1—C7—C8 | 166.4 (17) | C43—P3—C37—C38 | 123.6 (4) |
C19—P1—C7—C12 | 108 (2) | C4—P3—C37—C38 | −123.8 (4) |
C1—P1—C7—C12 | −138 (2) | Au1—P3—C37—C38 | 2.5 (4) |
Au1—P1—C7—C12 | −18 (3) | C42—C37—C38—C39 | −0.9 (8) |
C12—C7—C8—C9 | 1 (3) | P3—C37—C38—C39 | 177.4 (4) |
P1—C7—C8—C9 | 176.4 (18) | C37—C38—C39—C40 | 0.7 (8) |
C7—C8—C9—C10 | −3 (2) | C38—C39—C40—C41 | −1.0 (9) |
C8—C9—C10—C11 | 5 (4) | C39—C40—C41—C42 | 1.4 (9) |
C9—C10—C11—C12 | −6 (4) | C38—C37—C42—C41 | 1.4 (8) |
C8—C7—C12—C11 | −1 (4) | P3—C37—C42—C41 | −177.0 (4) |
P1—C7—C12—C11 | −176.9 (16) | C40—C41—C42—C37 | −1.6 (9) |
C10—C11—C12—C7 | 4 (3) | C37—P3—C43—C48 | 141.5 (4) |
C19—P1—C13—C18 | 146.0 (17) | C4—P3—C43—C48 | 29.6 (5) |
C1—P1—C13—C18 | −101 (2) | Au1—P3—C43—C48 | −95.9 (4) |
C7—P1—C13—C18 | 40 (31) | C37—P3—C43—C44 | −46.8 (4) |
Au1—P1—C13—C18 | 18 (2) | C4—P3—C43—C44 | −158.7 (4) |
C19—P1—C13—C14 | −43.2 (19) | Au1—P3—C43—C44 | 75.8 (4) |
C1—P1—C13—C14 | 69.5 (16) | C48—C43—C44—C45 | 0.2 (7) |
Au1—P1—C13—C14 | −171.1 (13) | P3—C43—C44—C45 | −171.8 (4) |
C18—C13—C14—C15 | −5 (2) | C43—C44—C45—C46 | −0.6 (8) |
P1—C13—C14—C15 | −176.5 (17) | C44—C45—C46—C47 | 0.0 (8) |
C13—C14—C15—C16 | 2 (2) | C45—C46—C47—C48 | 1.0 (8) |
C14—C15—C16—C17 | 2 (3) | C44—C43—C48—C47 | 0.8 (7) |
C15—C16—C17—C18 | −2 (3) | P3—C43—C48—C47 | 172.5 (4) |
C14—C13—C18—C17 | 5 (3) | C46—C47—C48—C43 | −1.4 (7) |
P1—C13—C18—C17 | 176.5 (14) | C6—P4—C49—C54 | 155.1 (4) |
C16—C17—C18—C13 | −2 (2) | C55—P4—C49—C54 | −89.9 (4) |
C13—P1—C19—C24 | 85.3 (12) | Au2—P4—C49—C54 | 31.6 (4) |
C1—P1—C19—C24 | −25.6 (5) | C6—P4—C49—C50 | −26.1 (5) |
C7—P1—C19—C24 | 88.2 (15) | C55—P4—C49—C50 | 88.8 (4) |
Au1—P1—C19—C24 | −143.6 (4) | Au2—P4—C49—C50 | −149.6 (4) |
C13—P1—C19—C20 | −94.0 (12) | C54—C49—C50—C51 | 1.1 (7) |
C1—P1—C19—C20 | 155.1 (4) | P4—C49—C50—C51 | −177.7 (4) |
C7—P1—C19—C20 | −91.0 (15) | C49—C50—C51—C52 | −0.6 (8) |
Au1—P1—C19—C20 | 37.1 (4) | C50—C51—C52—C53 | 0.6 (8) |
C24—C19—C20—C21 | −0.6 (8) | C51—C52—C53—C54 | −1.2 (8) |
P1—C19—C20—C21 | 178.7 (4) | C52—C53—C54—C49 | 1.7 (8) |
C19—C20—C21—C22 | 1.1 (8) | C50—C49—C54—C53 | −1.7 (7) |
C20—C21—C22—C23 | −1.5 (9) | P4—C49—C54—C53 | 177.1 (4) |
C21—C22—C23—C24 | 1.4 (9) | C49—P4—C55—C60 | 92.3 (5) |
C22—C23—C24—C19 | −0.9 (9) | C6—P4—C55—C60 | −153.6 (5) |
C20—C19—C24—C23 | 0.5 (8) | Au2—P4—C55—C60 | −29.7 (5) |
P1—C19—C24—C23 | −178.7 (4) | C49—P4—C55—C56 | −83.7 (5) |
C31—P2—C25—C30 | −167.5 (5) | C6—P4—C55—C56 | 30.4 (5) |
C3—P2—C25—C30 | 79.4 (5) | Au2—P4—C55—C56 | 154.3 (4) |
Au2—P2—C25—C30 | −41.8 (5) | C60—C55—C56—C57 | −0.7 (9) |
C31—P2—C25—C26 | 12.0 (5) | P4—C55—C56—C57 | 175.3 (5) |
C3—P2—C25—C26 | −101.1 (5) | C55—C56—C57—C58 | −0.4 (9) |
Au2—P2—C25—C26 | 137.7 (4) | C56—C57—C58—C59 | 0.7 (11) |
C30—C25—C26—C27 | 2.1 (8) | C57—C58—C59—C60 | 0.0 (11) |
P2—C25—C26—C27 | −177.4 (4) | C56—C55—C60—C59 | 1.4 (9) |
C25—C26—C27—C28 | −2.2 (9) | P4—C55—C60—C59 | −174.6 (5) |
C26—C27—C28—C29 | 1.3 (11) | C58—C59—C60—C55 | −1.1 (10) |
C27—C28—C29—C30 | −0.2 (12) | C63—O1—C61—C62 | −178.7 (9) |
C28—C29—C30—C25 | 0.1 (11) | C61—O1—C63—C64 | −171.8 (9) |
Experimental details
Crystal data | |
Chemical formula | [Au2(C27H26P2)2][NiCl4]·C4H10O |
Mr | 1493.40 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 200 |
a, b, c (Å) | 18.9290 (5), 16.1945 (7), 19.0895 (17) |
β (°) | 97.368 (7) |
V (Å3) | 5803.5 (6) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 5.70 |
Crystal size (mm) | 0.28 × 0.05 × 0.03 |
Data collection | |
Diffractometer | Rigaku R-AXIS VII diffractometer |
Absorption correction | Multi-scan (ABSCOR; Higashi, 1995) |
Tmin, Tmax | 0.580, 0.773 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 45449, 13273, 10666 |
Rint | 0.042 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.048, 0.083, 1.14 |
No. of reflections | 13273 |
No. of parameters | 685 |
No. of restraints | 78 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.16, −0.88 |
Computer programs: PROCESS-AUTO (Rigaku, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), Yadokari-XG 2009 (Kabuto et al., 2009).
Au1—P1 | 2.3109 (13) | Ni1—Cl4 | 2.2359 (15) |
Au1—P3 | 2.3129 (13) | Ni1—Cl2 | 2.2548 (16) |
Au2—P2 | 2.3013 (13) | Ni1—Cl1 | 2.2558 (15) |
Au2—P4 | 2.3050 (13) | Ni1—Cl3 | 2.2780 (14) |
In recent years, diphosphine-bridged cyclic digold(I) complexes have attracted considerable attention because of their intriguing photophysical properties that originate from the presence of an aurophilic interaction between gold(I) ions. A typical example is [Au2(dppm)2]2+ (dppm = bis(diphenylphosphanyl)methane), which is easily prepared from dppm having a methylene linker between two P atoms, in combination with an AuI ion. Analogous digold(I) complexes having a longer linker between two P atoms, such as 1,2-bis(diphenylphosphanyl)ethane (dppe) and 1,3-bis(diphenylphosphanyl)propane (dppp), have also been prepared, but only a few of them have been structurally characterized to date (Allen, 2002).
Recently, we started to investigate the creation of diphosphine-bridged digold(I) metalloligands and their coordination behavior toward various metal ions, with the aim of the rational construction of heterometallic multinuclear and metallosupramolecular structures (Lee et al., 2012; Igashira-Kamiyama et al., 2012; Hashimoto et al., 2010). In the course of this study, we found the formation of a diphosphine-bridged digold(I) complex, [Au2(dppp)2]2+ (dppp = 1,3-bis(diphenylphosphanyl)propane), which is cocrystallized with [NiCl4]2– to give single-crystals of [Au2(dppp)2][NiCl4].Et2O (I). Here, we report the synthesis and crystal structure of (I).
Treatment of [Au2Cl2(dppp)] (Mirabelli et al., 1987) with 1 equiv of N,N'-ethylene-bis-D-penicillamine (Howard-Lock et al., 1986; Blondeau et al., 1967) in ethanol/water in the presence of KOH gave a white powder. When this powder was reacted with NiCl2.6H2O in ethanol, blue needle crystals of [Au2(dppp)2][NiCl4].Et2O (I) were obtained by the vapor diffusion of diethylether into the reaction solution.
Compound (I) crystallized in a centrosymmetric space group P21/n, which contains one digold(I) complex cation, one nickel(II) complex anion and one solvate diethylether molecule in the asymmetric unit. The complex cation has a cyclic digold(I) structure in [Au2(dppp)2]2+, in which two dppp ligands bridge two AuI atoms. Each AuI atom adopts a slightly distorted linear geometry (176.68 (5)°, 177.98 (5)°) coordinated by two P atoms from two different dppp ligands (Fig. 1). The Au–P bond distances (2.3013 (13)–2.3129 (13) Å) are within the range observed for [Au2(dppp)2]2[Mo8O26], [Au2(dppp)2]2[PMo8O26] and [Au2(dppp)2](CF3CO2)2 (Au–P = 2.271–2.324 Å) (Gruber et al., 2010; Brandys et al., 2001). In the complex-cation of (I), two AuI atoms and four P atoms are deviated from co-planarity, with the dihedral angle between two Au2P2 planes being 21.94 (2)°. This structural feature is different from those found in [Au2(dppp)2]2[Mo8O26], [Au2(dppp)2]2[PMo8O26] and [Au2(dppp)2](CF3CO2)2, in which all the AuI and P atoms in each complex-cation are located nearly on the same plane (Gruber et al., 2010; Brandys et al., 2001). The distance between two AuI atoms in [Au2(dppp)2]2+ is 5.5424 (4) Å, indicative of the absence of an aurophilic interaction. In (I), a nickel(II) complex-anion, [NiCl4]2–, which has a distorted tetrahedral geometry, coexists with [Au2(dppp)2]2+ to balance the total charge. Note that [Au2(dppp)2]2+ and [NiCl4]2– are connected to each other through two Au···Cl bonding interactions (3.040 (1) Å and 3.021 (2) Å), while any other significant intermolecular interactions do not exist in (I) (Fig. 2).