Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270103018481/sq1026sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270103018481/sq1026Isup2.hkl |
CCDC reference: 224503
1,3-Bis(4-nitrophenyl)triazene (28.7 mg, 0.1 mmol) was dissolved in absolute tetrahydrofuran (20 ml) and treated with small portions of metallic sodium powder until H2 evolution stopped. The resulting intense-red mixture was filtered over a sintered-glass frit to eliminate the excess of metallic sodium. A solution of Ph3PAuCl (49.5 mg, 0.1 mmol) in absolute tetrahydrofuran was added slowly with continuous stirring. After stirring at room temperature for 1 h, the yellow precipitate of the complex was filtered off and dried in vacuo. Red prism-shaped crystals of (I) suitable for X-ray diffraction were obtained by slow evaporation at room temperature of a solution of the complex in pyridine (yield: 41 mg, 55%; m.p. 506–507 K).
The positional parameters of the H atoms were obtained geometrically, with the C—H distances fixed (0.93 Å for Csp2), and H atoms were refined as riding on their respective C atoms, with Uiso(H) = 1.2Ueq(Csp2). The nitro O atoms show a large thermal motion, indicated by their elongated displacement ellipsoids (Fig. 1). Split peaks for these atoms were not observed and consequently a disorder model was not used in the refinement.
Data collection: COLLECT (Nonius BV, 1997-2000); cell refinement: HKL SCALEPACK (Otwinowski & Minor 1997); data reduction: HKL DENZO (Otwinowski & Minor 1997) and SCALEPACK; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and DIAMOND (Brandenburg, 1996); software used to prepare material for publication: WinGX (Farrugia, 1999).
[Au(C12H8N5O4)(C18H15P)] | Z = 2 |
Mr = 745.47 | F(000) = 728 |
Triclinic, P1 | Dx = 1.701 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 10.2034 (4) Å | Cell parameters from 11145 reflections |
b = 10.7550 (2) Å | θ = 1.0–27.5° |
c = 14.0941 (5) Å | µ = 5.15 mm−1 |
α = 93.987 (2)° | T = 296 K |
β = 102.148 (2)° | Prism, red |
γ = 103.930 (2)° | 0.30 × 0.20 × 0.10 mm |
V = 1455.73 (8) Å3 |
Nonius KappaCCD area-detector diffractometer | 6639 independent reflections |
Radiation source: fine-focus sealed tube | 5647 reflections with I > 2σ(I) |
Horizonally mounted graphite crystal monochromator | Rint = 0.034 |
Detector resolution: 9 pixels mm-1 | θmax = 27.5°, θmin = 2.3° |
CCD scans | h = −13→13 |
Absorption correction: analytical (Alcock, 1970) | k = −13→11 |
Tmin = 0.438, Tmax = 0.648 | l = −18→17 |
15644 measured reflections |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.047 | w = 1/[σ2(Fo2) + (0.0698P)2 + 3.1565P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.133 | (Δ/σ)max < 0.001 |
S = 1.09 | Δρmax = 1.27 e Å−3 |
6639 reflections | Δρmin = −1.20 e Å−3 |
370 parameters |
[Au(C12H8N5O4)(C18H15P)] | γ = 103.930 (2)° |
Mr = 745.47 | V = 1455.73 (8) Å3 |
Triclinic, P1 | Z = 2 |
a = 10.2034 (4) Å | Mo Kα radiation |
b = 10.7550 (2) Å | µ = 5.15 mm−1 |
c = 14.0941 (5) Å | T = 296 K |
α = 93.987 (2)° | 0.30 × 0.20 × 0.10 mm |
β = 102.148 (2)° |
Nonius KappaCCD area-detector diffractometer | 6639 independent reflections |
Absorption correction: analytical (Alcock, 1970) | 5647 reflections with I > 2σ(I) |
Tmin = 0.438, Tmax = 0.648 | Rint = 0.034 |
15644 measured reflections |
R[F2 > 2σ(F2)] = 0.047 | 0 restraints |
wR(F2) = 0.133 | H-atom parameters constrained |
S = 1.09 | Δρmax = 1.27 e Å−3 |
6639 reflections | Δρmin = −1.20 e Å−3 |
370 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. Mean-plane data from final SHELXL refinement run:- Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane) - 6.1857 (0.0721) x − 2.9505 (0.1357) y + 11.6709 (0.0375) z = 0.2513 (0.1783) * 0.0000 (0.0001) O1A * 0.0000 (0.0001) N6 * 0.0000 (0.0000) O2A Rms deviation of fitted atoms = 0.0000 − 6.7618 (0.0233) x − 2.9225 (0.0294) y + 10.9800 (0.0289) z = 0.2845 (0.0295) Angle to previous plane (with approximate e.s.d.) = 4.94 (1.11) * 0.0076 (0.0048) C1A * −0.0048 (0.0051) C2A * −0.0019 (0.0051) C3A * 0.0058 (0.0050) C4A * −0.0028 (0.0055) C5A * −0.0039 (0.0054) C6A Rms deviation of fitted atoms = 0.0048 − 7.1155 (0.0520) x − 2.9413 (0.0393) y + 10.4335 (0.0632) z = 0.2553 (0.0253) Angle to previous plane (with approximate e.s.d.) = 3.48 (0.73) * 0.0000 (0.0000) N3 * 0.0000 (0.0000) N2 * 0.0000 (0.0000) N1 Rms deviation of fitted atoms = 0.0000 5.5093 (0.0236) x + 4.0238 (0.0253) y − 11.5604 (0.0205) z = 0.4091 (0.0117) Angle to previous plane (with approximate e.s.d.) = 11.58 (0.65) * −0.0069 (0.0042) C1B * 0.0050 (0.0047) C2B * 0.0027 (0.0048) C3B * −0.0086 (0.0046) C4B * 0.0066 (0.0045) C5B * 0.0012 (0.0044) C6B Rms deviation of fitted atoms = 0.0057 5.1427 (0.0462) x + 4.5787 (0.1156) y − 11.4231 (0.1220) z = 0.5547 (0.0386) Angle to previous plane (with approximate e.s.d.) = 3.30 (1.24) * 0.0000 (0.0000) O1B * 0.0000 (0.0000) N5 * 0.0000 (0.0000) O2B Rms deviation of fitted atoms = 0.0000 − 6.7618 (0.0233) x − 2.9225 (0.0294) y + 10.9800 (0.0289) z = 0.2845 (0.0295) Angle to previous plane (with approximate e.s.d.) = 11.77 (1.06) * 0.0076 (0.0048) C1A * −0.0048 (0.0051) C2A * −0.0019 (0.0051) C3A * 0.0058 (0.0050) C4A * −0.0028 (0.0055) C5A * −0.0039 (0.0054) C6A Rms deviation of fitted atoms = 0.0048 5.5093 (0.0236) x + 4.0238 (0.0253) y − 11.5604 (0.0205) z = 0.4091 (0.0117) Angle to previous plane (with approximate e.s.d.) = 8.93 (0.42) * −0.0069 (0.0042) C1B * 0.0050 (0.0047) C2B * 0.0027 (0.0048) C3B * −0.0086 (0.0046) C4B * 0.0066 (0.0045) C5B * 0.0012 (0.0044) C6B Rms deviation of fitted atoms = 0.0057 − 6.3657 (0.0087) x − 3.1303 (0.0047) y + 11.3320 (0.0084) z = 0.0744 (0.0046) Angle to previous plane (with approximate e.s.d.) = 6.27 (0.30) * 0.0095 (0.0049) O1A * −0.0280 (0.0054) N6 * −0.0782 (0.0066) O2A * 0.0450 (0.0056) C1A * −0.0392 (0.0072) C2A * −0.0745 (0.0068) C3A * −0.0311 (0.0061) C4A * 0.0317 (0.0074) C5A * 0.0677 (0.0072) C6A * 0.1032 (0.0047) N3 * 0.0039 (0.0044) N2 * 0.0655 (0.0046) N1 * 0.0197 (0.0051) C1B * 0.1239 (0.0066) C2B * 0.1032 (0.0068) C3B * −0.0298 (0.0059) C4B * −0.1614 (0.0059) C5B * −0.1312 (0.0056) C6B * 0.0684 (0.0057) O1B * −0.0686 (0.0061) N5 Rms deviation of fitted atoms = 0.0767 − 9.9485 (0.0063) x + 0.9374 (0.0282) y + 5.3709 (0.0353) z = 0.1036 (0.0236) Angle to previous plane (with approximate e.s.d.) = 38.71 (0.19) * −0.0049 (0.0041) C1C * 0.0095 (0.0044) C2C * −0.0058 (0.0048) C3C * −0.0025 (0.0048) C4C * 0.0071 (0.0049) C5C * −0.0034 (0.0046) C6C Rms deviation of fitted atoms = 0.0060 2.1252 (0.0271) x − 6.7522 (0.0225) y + 11.0287 (0.0226) z = 0.7383 (0.0181) Angle to previous plane (with approximate e.s.d.) = 89.25 (0.21) * 0.0051 (0.0042) C1D * 0.0075 (0.0045) C2D * −0.0142 (0.0050) C3D * 0.0079 (0.0051) C4D * 0.0049 (0.0050) C5D * −0.0114 (0.0046) C6D Rms deviation of fitted atoms = 0.0091 0.9741 (0.0414) x + 5.8984 (0.0319) y + 9.6600 (0.0357) z = 6.1329 (0.0078) Angle to previous plane (with approximate e.s.d.) = 72.99 (1/5) * 0.0051 (0.0051) C1E * 0.0020 (0.0053) C2E * −0.0072 (0.0060) C3E * 0.0055 (0.0073) C4E * 0.0015 (0.0082) C5E * −0.0069 (0.0067) C6E Rms deviation of fitted atoms = 0.0052 |
x | y | z | Uiso*/Ueq | ||
Au | 0.04392 (3) | 0.48136 (2) | 0.193131 (19) | 0.04855 (11) | |
N1 | −0.1232 (5) | 0.4729 (5) | 0.0738 (4) | 0.0362 (10) | |
N2 | −0.1732 (5) | 0.5756 (4) | 0.0686 (3) | 0.0341 (10) | |
N3 | −0.1045 (5) | 0.6639 (4) | 0.1404 (4) | 0.0357 (10) | |
C1A | −0.1527 (6) | 0.7755 (6) | 0.1390 (4) | 0.0364 (12) | |
C2A | −0.2665 (7) | 0.7906 (6) | 0.0718 (5) | 0.0486 (15) | |
H2A | −0.3161 | 0.7236 | 0.0225 | 0.058* | |
C3A | −0.3077 (7) | 0.9047 (6) | 0.0771 (5) | 0.0496 (15) | |
H3A | −0.3844 | 0.9145 | 0.0321 | 0.06* | |
C4A | −0.2315 (8) | 1.0034 (6) | 0.1509 (5) | 0.0460 (14) | |
C5A | −0.1167 (8) | 0.9917 (7) | 0.2177 (5) | 0.0552 (17) | |
H5A | −0.0665 | 1.0595 | 0.2662 | 0.066* | |
C6A | −0.0773 (8) | 0.8787 (7) | 0.2118 (5) | 0.0539 (17) | |
H6A | 0.0003 | 0.8702 | 0.2566 | 0.065* | |
N6 | −0.2785 (7) | 1.1216 (6) | 0.1574 (5) | 0.0543 (15) | |
O1A | −0.3852 (6) | 1.1250 (5) | 0.1018 (4) | 0.0644 (14) | |
O2A | −0.2052 (8) | 1.2113 (6) | 0.2190 (5) | 0.0844 (19) | |
C1B | −0.1939 (6) | 0.3699 (5) | 0.0015 (4) | 0.0364 (12) | |
C2B | −0.3204 (8) | 0.3624 (6) | −0.0624 (5) | 0.0493 (15) | |
H2B | −0.3613 | 0.4306 | −0.059 | 0.059* | |
C3B | −0.3861 (9) | 0.2562 (8) | −0.1304 (5) | 0.063 (2) | |
H3B | −0.4708 | 0.2519 | −0.1728 | 0.076* | |
C4B | −0.3232 (9) | 0.1539 (6) | −0.1351 (5) | 0.0555 (19) | |
C5B | −0.1975 (8) | 0.1594 (6) | −0.0746 (5) | 0.0538 (17) | |
H5B | −0.1561 | 0.0918 | −0.0796 | 0.065* | |
C6B | −0.1321 (7) | 0.2676 (6) | −0.0053 (5) | 0.0464 (14) | |
H6B | −0.047 | 0.2718 | 0.0366 | 0.056* | |
N5 | −0.3935 (11) | 0.0416 (8) | −0.2090 (5) | 0.078 (2) | |
O1B | −0.5043 (9) | 0.0394 (7) | −0.2598 (5) | 0.099 (3) | |
O2B | −0.3348 (10) | −0.0426 (7) | −0.2164 (6) | 0.106 (3) | |
P | 0.22000 (14) | 0.48593 (12) | 0.32131 (10) | 0.0300 (3) | |
C1C | 0.2678 (5) | 0.6348 (5) | 0.4035 (4) | 0.0305 (10) | |
C2C | 0.2551 (6) | 0.7473 (5) | 0.3632 (4) | 0.0369 (12) | |
H2C | 0.2169 | 0.7432 | 0.2967 | 0.044* | |
C3C | 0.2998 (8) | 0.8659 (6) | 0.4223 (5) | 0.0473 (15) | |
H3C | 0.2933 | 0.9411 | 0.395 | 0.057* | |
C4C | 0.3537 (7) | 0.8720 (6) | 0.5218 (5) | 0.0451 (14) | |
H4C | 0.383 | 0.951 | 0.5614 | 0.054* | |
C5C | 0.3637 (7) | 0.7605 (7) | 0.5617 (5) | 0.0477 (15) | |
H5C | 0.3989 | 0.7645 | 0.6286 | 0.057* | |
C6C | 0.3224 (6) | 0.6430 (6) | 0.5036 (4) | 0.0412 (13) | |
H6C | 0.331 | 0.5686 | 0.5315 | 0.049* | |
C1D | 0.3771 (6) | 0.4734 (5) | 0.2846 (4) | 0.0320 (11) | |
C2D | 0.5019 (6) | 0.5664 (6) | 0.3177 (5) | 0.0411 (13) | |
H2D | 0.5085 | 0.6376 | 0.3615 | 0.049* | |
C3D | 0.6172 (7) | 0.5522 (8) | 0.2848 (6) | 0.0576 (19) | |
H3D | 0.7006 | 0.6159 | 0.305 | 0.069* | |
C4D | 0.6096 (8) | 0.4451 (8) | 0.2227 (6) | 0.0567 (18) | |
H4D | 0.6883 | 0.4351 | 0.203 | 0.068* | |
C5D | 0.4849 (9) | 0.3522 (7) | 0.1896 (5) | 0.0552 (18) | |
H5D | 0.4796 | 0.28 | 0.1472 | 0.066* | |
C6D | 0.3683 (7) | 0.3665 (6) | 0.2193 (5) | 0.0456 (14) | |
H6D | 0.2839 | 0.3049 | 0.1959 | 0.055* | |
C1E | 0.1837 (6) | 0.3591 (5) | 0.3976 (4) | 0.0360 (11) | |
C2E | 0.2779 (7) | 0.2876 (6) | 0.4314 (5) | 0.0483 (15) | |
H2E | 0.3626 | 0.3033 | 0.4137 | 0.058* | |
C3E | 0.2459 (11) | 0.1952 (7) | 0.4902 (6) | 0.069 (2) | |
H3E | 0.3079 | 0.1467 | 0.512 | 0.083* | |
C4E | 0.1159 (13) | 0.1734 (8) | 0.5179 (7) | 0.084 (3) | |
H4E | 0.0938 | 0.1116 | 0.559 | 0.101* | |
C5E | 0.0294 (11) | 0.2392 (12) | 0.4860 (9) | 0.093 (3) | |
H5E | −0.0548 | 0.2234 | 0.5045 | 0.112* | |
C6E | 0.0580 (8) | 0.3334 (9) | 0.4247 (7) | 0.066 (2) | |
H6E | −0.0068 | 0.3788 | 0.4022 | 0.079* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Au | 0.04395 (16) | 0.05158 (16) | 0.04696 (17) | 0.01641 (11) | 0.00138 (11) | −0.00027 (10) |
N1 | 0.036 (2) | 0.038 (2) | 0.037 (2) | 0.0136 (19) | 0.007 (2) | 0.0094 (19) |
N2 | 0.034 (2) | 0.033 (2) | 0.040 (3) | 0.0132 (18) | 0.013 (2) | 0.0095 (19) |
N3 | 0.032 (2) | 0.037 (2) | 0.039 (3) | 0.0152 (19) | 0.005 (2) | 0.0060 (19) |
C1A | 0.037 (3) | 0.041 (3) | 0.035 (3) | 0.017 (2) | 0.008 (2) | 0.007 (2) |
C2A | 0.044 (3) | 0.042 (3) | 0.054 (4) | 0.021 (3) | −0.008 (3) | 0.000 (3) |
C3A | 0.053 (4) | 0.050 (3) | 0.051 (4) | 0.029 (3) | 0.003 (3) | 0.009 (3) |
C4A | 0.062 (4) | 0.044 (3) | 0.044 (3) | 0.027 (3) | 0.022 (3) | 0.009 (3) |
C5A | 0.059 (4) | 0.050 (4) | 0.051 (4) | 0.021 (3) | −0.002 (3) | −0.011 (3) |
C6A | 0.056 (4) | 0.054 (4) | 0.049 (4) | 0.028 (3) | −0.007 (3) | −0.002 (3) |
N6 | 0.078 (4) | 0.046 (3) | 0.058 (4) | 0.033 (3) | 0.033 (3) | 0.016 (3) |
O1A | 0.075 (4) | 0.065 (3) | 0.077 (4) | 0.047 (3) | 0.030 (3) | 0.023 (3) |
O2A | 0.122 (6) | 0.056 (3) | 0.086 (4) | 0.047 (4) | 0.022 (4) | −0.002 (3) |
C1B | 0.039 (3) | 0.039 (3) | 0.033 (3) | 0.009 (2) | 0.012 (2) | 0.010 (2) |
C2B | 0.058 (4) | 0.044 (3) | 0.041 (3) | 0.010 (3) | 0.000 (3) | 0.013 (3) |
C3B | 0.062 (5) | 0.069 (5) | 0.037 (4) | −0.012 (4) | −0.005 (3) | 0.018 (3) |
C4B | 0.080 (5) | 0.043 (3) | 0.030 (3) | −0.012 (3) | 0.019 (3) | 0.000 (2) |
C5B | 0.069 (5) | 0.041 (3) | 0.054 (4) | 0.005 (3) | 0.032 (4) | 0.001 (3) |
C6B | 0.047 (4) | 0.041 (3) | 0.055 (4) | 0.011 (3) | 0.021 (3) | 0.006 (3) |
N5 | 0.107 (7) | 0.063 (4) | 0.047 (4) | −0.020 (4) | 0.031 (4) | 0.002 (3) |
O1B | 0.111 (6) | 0.098 (5) | 0.048 (4) | −0.032 (4) | 0.012 (4) | −0.013 (3) |
O2B | 0.148 (8) | 0.058 (4) | 0.087 (5) | −0.006 (4) | 0.024 (5) | −0.020 (3) |
P | 0.0272 (6) | 0.0302 (6) | 0.0321 (7) | 0.0122 (5) | 0.0014 (5) | 0.0008 (5) |
C1C | 0.027 (2) | 0.031 (2) | 0.037 (3) | 0.0130 (19) | 0.008 (2) | 0.003 (2) |
C2C | 0.048 (3) | 0.034 (3) | 0.030 (3) | 0.015 (2) | 0.010 (2) | 0.005 (2) |
C3C | 0.065 (4) | 0.031 (3) | 0.050 (4) | 0.012 (3) | 0.021 (3) | 0.009 (2) |
C4C | 0.046 (3) | 0.037 (3) | 0.047 (4) | 0.008 (2) | 0.007 (3) | −0.009 (2) |
C5C | 0.052 (4) | 0.056 (4) | 0.032 (3) | 0.021 (3) | −0.002 (3) | 0.001 (3) |
C6C | 0.046 (3) | 0.038 (3) | 0.037 (3) | 0.019 (2) | −0.004 (3) | 0.004 (2) |
C1D | 0.036 (3) | 0.033 (2) | 0.032 (3) | 0.018 (2) | 0.007 (2) | 0.008 (2) |
C2D | 0.039 (3) | 0.042 (3) | 0.045 (3) | 0.015 (2) | 0.013 (3) | 0.007 (2) |
C3D | 0.032 (3) | 0.068 (4) | 0.081 (5) | 0.016 (3) | 0.022 (3) | 0.028 (4) |
C4D | 0.062 (5) | 0.069 (4) | 0.063 (4) | 0.042 (4) | 0.034 (4) | 0.021 (4) |
C5D | 0.075 (5) | 0.059 (4) | 0.049 (4) | 0.040 (4) | 0.026 (4) | 0.010 (3) |
C6D | 0.048 (4) | 0.044 (3) | 0.045 (3) | 0.017 (3) | 0.009 (3) | −0.004 (3) |
C1E | 0.033 (3) | 0.030 (2) | 0.042 (3) | 0.005 (2) | 0.006 (2) | 0.002 (2) |
C2E | 0.055 (4) | 0.038 (3) | 0.057 (4) | 0.018 (3) | 0.014 (3) | 0.014 (3) |
C3E | 0.108 (7) | 0.036 (3) | 0.067 (5) | 0.028 (4) | 0.013 (5) | 0.014 (3) |
C4E | 0.109 (8) | 0.052 (5) | 0.070 (6) | −0.018 (5) | 0.019 (6) | 0.020 (4) |
C5E | 0.067 (6) | 0.109 (8) | 0.103 (8) | −0.006 (6) | 0.042 (6) | 0.043 (7) |
C6E | 0.036 (4) | 0.091 (6) | 0.077 (5) | 0.015 (4) | 0.021 (4) | 0.029 (4) |
Au—N1 | 2.108 (5) | P—C1E | 1.812 (6) |
Au—P | 2.2524 (13) | P—C1D | 1.816 (5) |
N1—N2 | 1.324 (6) | C1C—C6C | 1.391 (8) |
N1—C1B | 1.390 (8) | C1C—C2C | 1.394 (7) |
N2—N3 | 1.290 (7) | C2C—C3C | 1.394 (8) |
N3—C1A | 1.402 (7) | C2C—H2C | 0.93 |
N3—C6Bi | 3.357 (8) | C3C—C4C | 1.384 (10) |
C1A—C2A | 1.386 (8) | C3C—H3C | 0.93 |
C1A—C6A | 1.406 (9) | C4C—C5C | 1.376 (9) |
C2A—C3A | 1.392 (9) | C4C—O1Biv | 3.304 (9) |
C2A—H2A | 0.93 | C4C—H4C | 0.93 |
C3A—C4A | 1.387 (10) | C5C—C6C | 1.378 (9) |
C3A—H3A | 0.93 | C5C—H5C | 0.93 |
C4A—C5A | 1.378 (10) | C6C—H6C | 0.93 |
C4A—N6 | 1.466 (8) | C1D—C2D | 1.382 (9) |
C5A—C6A | 1.371 (9) | C1D—C6D | 1.394 (8) |
C5A—H5A | 0.93 | C2D—C3D | 1.389 (9) |
C6A—H6A | 0.93 | C2D—H2D | 0.93 |
N6—O1A | 1.211 (9) | C3D—C4D | 1.374 (11) |
N6—O2A | 1.227 (9) | C3D—H3D | 0.93 |
N6—C6Bii | 3.282 (8) | C4D—C5D | 1.380 (12) |
C1B—C2B | 1.391 (9) | C4D—H4D | 0.93 |
C1B—C6B | 1.401 (9) | C5D—C6D | 1.380 (9) |
C2B—C3B | 1.372 (10) | C5D—O1Av | 3.330 (8) |
C2B—H2B | 0.93 | C5D—H5D | 0.93 |
C3B—C4B | 1.405 (12) | C6D—H6D | 0.93 |
C3B—H3B | 0.93 | C1E—C6E | 1.384 (9) |
C4B—C5B | 1.368 (12) | C1E—C2E | 1.398 (8) |
C4B—N5 | 1.467 (9) | C2E—C3E | 1.361 (10) |
C5B—C6B | 1.395 (9) | C2E—H2E | 0.93 |
C5B—H5B | 0.93 | C3E—C4E | 1.432 (15) |
C6B—H6B | 0.93 | C3E—H3E | 0.93 |
N5—O1B | 1.198 (12) | C4E—C5E | 1.289 (15) |
N5—O2B | 1.209 (12) | C4E—H4E | 0.93 |
N5—O1Aiii | 3.234 (9) | C5E—C6E | 1.395 (13) |
O1B—N6iii | 3.136 (9) | C5E—H5E | 0.93 |
P—C1C | 1.809 (5) | C6E—H6E | 0.93 |
N1—Au—P | 178.70 (13) | C1D—P—Au | 112.76 (18) |
N2—N1—C1B | 114.8 (5) | C6C—C1C—C2C | 118.9 (5) |
N2—N1—Au | 116.8 (4) | C6C—C1C—P | 123.2 (4) |
C1B—N1—Au | 128.3 (4) | C2C—C1C—P | 117.9 (4) |
N3—N2—N1 | 110.4 (5) | C3C—C2C—C1C | 120.2 (5) |
N2—N3—C1A | 113.1 (5) | C3C—C2C—H2C | 119.9 |
N2—N3—C6Bi | 85.1 (3) | C1C—C2C—H2C | 119.9 |
C1A—N3—C6Bi | 101.1 (3) | C4C—C3C—C2C | 120.1 (5) |
C2A—C1A—N3 | 125.0 (5) | C4C—C3C—H3C | 120 |
C2A—C1A—C6A | 118.9 (5) | C2C—C3C—H3C | 120 |
N3—C1A—C6A | 116.1 (5) | C5C—C4C—C3C | 119.6 (5) |
C1A—C2A—C3A | 120.9 (6) | C5C—C4C—O1Biv | 89.5 (4) |
C1A—C2A—H2A | 119.6 | C3C—C4C—O1Biv | 150.9 (4) |
C3A—C2A—H2A | 119.6 | C5C—C4C—H4C | 120.2 |
C4A—C3A—C2A | 118.4 (6) | C3C—C4C—H4C | 120.2 |
C4A—C3A—H3A | 120.8 | O1Biv—C4C—H4C | 30.7 |
C2A—C3A—H3A | 120.8 | C4C—C5C—C6C | 120.8 (6) |
C5A—C4A—C3A | 121.9 (6) | C4C—C5C—H5C | 119.6 |
C5A—C4A—N6 | 120.3 (6) | C6C—C5C—H5C | 119.6 |
C3A—C4A—N6 | 117.8 (6) | C5C—C6C—C1C | 120.5 (5) |
C6A—C5A—C4A | 119.2 (6) | C5C—C6C—H6C | 119.8 |
C6A—C5A—H5A | 120.4 | C1C—C6C—H6C | 119.8 |
C4A—C5A—H5A | 120.4 | C2D—C1D—C6D | 120.0 (5) |
C5A—C6A—C1A | 120.8 (6) | C2D—C1D—P | 122.3 (4) |
C5A—C6A—H6A | 119.6 | C6D—C1D—P | 117.7 (5) |
C1A—C6A—H6A | 119.6 | C1D—C2D—C3D | 119.3 (6) |
O1A—N6—O2A | 124.4 (6) | C1D—C2D—H2D | 120.4 |
O1A—N6—C4A | 118.4 (6) | C3D—C2D—H2D | 120.4 |
O2A—N6—C4A | 117.1 (7) | C4D—C3D—C2D | 120.8 (7) |
O1A—N6—C6Bii | 83.6 (4) | C4D—C3D—H3D | 119.6 |
O2A—N6—C6Bii | 87.7 (5) | C2D—C3D—H3D | 119.6 |
C4A—N6—C6Bii | 98.7 (4) | C3D—C4D—C5D | 119.9 (6) |
N1—C1B—C2B | 124.4 (6) | C3D—C4D—H4D | 120 |
N1—C1B—C6B | 116.6 (6) | C5D—C4D—H4D | 120 |
C2B—C1B—C6B | 119.0 (6) | C6D—C5D—C4D | 120.1 (6) |
C3B—C2B—C1B | 121.2 (7) | C6D—C5D—O1Av | 140.8 (5) |
C3B—C2B—H2B | 119.4 | C4D—C5D—O1Av | 96.7 (4) |
C1B—C2B—H2B | 119.4 | C6D—C5D—H5D | 120 |
C2B—C3B—C4B | 118.8 (7) | C4D—C5D—H5D | 120 |
C2B—C3B—H3B | 120.6 | O1Av—C5D—H5D | 26.7 |
C4B—C3B—H3B | 120.6 | C5D—C6D—C1D | 119.9 (6) |
C5B—C4B—C3B | 121.4 (6) | C5D—C6D—H6D | 120 |
C5B—C4B—N5 | 120.3 (8) | C1D—C6D—H6D | 120 |
C3B—C4B—N5 | 118.3 (8) | C6E—C1E—C2E | 118.8 (6) |
C4B—C5B—C6B | 119.2 (7) | C6E—C1E—P | 118.4 (5) |
C4B—C5B—H5B | 120.4 | C2E—C1E—P | 122.8 (5) |
C6B—C5B—H5B | 120.4 | C3E—C2E—C1E | 120.2 (7) |
C5B—C6B—C1B | 120.3 (7) | C3E—C2E—H2E | 119.9 |
C5B—C6B—H6B | 119.8 | C1E—C2E—H2E | 119.9 |
C1B—C6B—H6B | 119.8 | C2E—C3E—C4E | 119.2 (8) |
O1B—N5—O2B | 123.7 (8) | C2E—C3E—H3E | 120.4 |
O1B—N5—C4B | 118.3 (10) | C4E—C3E—H3E | 120.4 |
O2B—N5—C4B | 117.9 (10) | C5E—C4E—C3E | 120.1 (8) |
O1B—N5—O1Aiii | 75.9 (5) | C5E—C4E—H4E | 119.9 |
O2B—N5—O1Aiii | 94.1 (5) | C3E—C4E—H4E | 119.9 |
C4B—N5—O1Aiii | 101.8 (4) | C4E—C5E—C6E | 122.1 (9) |
N5—O1B—N6iii | 104.7 (5) | C4E—C5E—H5E | 119 |
C1C—P—C1E | 104.9 (3) | C6E—C5E—H5E | 119 |
C1C—P—C1D | 106.0 (2) | C1E—C6E—C5E | 119.5 (8) |
C1E—P—C1D | 105.8 (2) | C1E—C6E—H6E | 120.2 |
C1C—P—Au | 111.92 (17) | C5E—C6E—H6E | 120.2 |
C1E—P—Au | 114.72 (19) |
Symmetry codes: (i) −x, −y+1, −z; (ii) x, y+1, z; (iii) −x−1, −y+1, −z; (iv) x+1, y+1, z+1; (v) x+1, y−1, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
C4C—H4C···O1Biv | 0.93 | 2.55 | 3.304 (9) | 139 |
C5D—H5D···O1Av | 0.93 | 2.53 | 3.330 (8) | 144 |
Symmetry codes: (iv) x+1, y+1, z+1; (v) x+1, y−1, z. |
Experimental details
Crystal data | |
Chemical formula | [Au(C12H8N5O4)(C18H15P)] |
Mr | 745.47 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 296 |
a, b, c (Å) | 10.2034 (4), 10.7550 (2), 14.0941 (5) |
α, β, γ (°) | 93.987 (2), 102.148 (2), 103.930 (2) |
V (Å3) | 1455.73 (8) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 5.15 |
Crystal size (mm) | 0.30 × 0.20 × 0.10 |
Data collection | |
Diffractometer | Nonius KappaCCD area-detector diffractometer |
Absorption correction | Analytical (Alcock, 1970) |
Tmin, Tmax | 0.438, 0.648 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 15644, 6639, 5647 |
Rint | 0.034 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.047, 0.133, 1.09 |
No. of reflections | 6639 |
No. of parameters | 370 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.27, −1.20 |
Computer programs: COLLECT (Nonius BV, 1997-2000), HKL SCALEPACK (Otwinowski & Minor 1997), HKL DENZO (Otwinowski & Minor 1997) and SCALEPACK, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997) and DIAMOND (Brandenburg, 1996), WinGX (Farrugia, 1999).
Au—N1 | 2.108 (5) | N6—O2A | 1.227 (9) |
Au—P | 2.2524 (13) | C4B—N5 | 1.467 (9) |
N1—N2 | 1.324 (6) | N5—O1B | 1.198 (12) |
N1—C1B | 1.390 (8) | N5—O2B | 1.209 (12) |
N2—N3 | 1.290 (7) | P—C1C | 1.809 (5) |
N3—C1A | 1.402 (7) | P—C1E | 1.812 (6) |
C4A—N6 | 1.466 (8) | P—C1D | 1.816 (5) |
N6—O1A | 1.211 (9) | ||
N1—Au—P | 178.70 (13) | N3—N2—N1 | 110.4 (5) |
D—H···A | D—H | H···A | D···A | D—H···A |
C4C—H4C···O1Bi | 0.93 | 2.55 | 3.304 (9) | 139 |
C5D—H5D···O1Aii | 0.93 | 2.53 | 3.330 (8) | 144 |
Symmetry codes: (i) x+1, y+1, z+1; (ii) x+1, y−1, z. |
Although metal complexes with 1,3-diaryl-substituted triazenide ligands, [ArNNNAr]−, have been extensively investigated in the past, only a few citations concerning mononuclear gold(I) complexes with monodentate triazenide ligands are found in the literature. More recently, monodentate diaryltriazenide complexes have received attention in connection with the fluxional behavior of such compounds, in which transition metal fragments MLn, such as AuPPh3, show N1—N3 σ–σ migration on the nitrogen chain (Peregudov et al., 1998, 2000). Beside the AuPPh3 group, to date only six monodentate diaryltriazenide complexes incorporating MLn fragments (where L is phosphine) have been characterized by single-crystal X-ray diffraction: cis-chlorobis(triphenylphosphine)(1,3-di-p-tolyltriazenido)palladium(II) and cis-chlorobis(triphenylphosphine)(1,3-di-p-tolyltriazenido)platinum(II) chloroform solvate (Bombieri et al., 1976), trans-hydridobis(triphenylphosphine)(1,3-di-p-tolyltriazenido)platinum(II) (Immirzi et al., 1976), cis-bis(triphenylphosphine)bis(1,3-diphenyltriazenido)platinum(II) benzene solvate (Brown et al., 1976), trans-carbonyl(1,3-di-p-tolyltriazenido)bis(triphenylphosphine)iridium(I) (Immirzi et al., 1980) and trans-[1,3-bis(4-fluorophenyl)-1-triazenato-N](2-methylphenyl)bis(triethyl- phosphine)nickel(II) (Peregudov et al., 2000).
Recently, the analogy between the isolobal species [(Ph3P)Au]+ and H+ was connected with the formal zwitterionic bond structure of the complex N-(triphenylphosphinegold)-N-(5-methoxyquinolyl-8)–2,4,6-trinitroaniline, compared with the structure of the free N-(5-methoxyquinolyl-8)–2,4,6-trinitroaniline obtained by ab initio quantum chemical calculation (Kuz'mina et al., 2001).
Based on the fact that [(Ph3P)Au]+ and H+ are isolobal particles, and on the potential of triazenes for sigmatropic migration of the H atom on the nitrogen triad, our goal was to investigate the title complex, (I), resulting from the substitution of H+ on the diazoamino group of 1,3-bis-(4-nitrophenyl)triazene by the [(Ph3P)Au]+ cation, and the results are presented here. \sch
The crystal structure of (I) reveals discrete asymmetric two-coordinate mononuclear AuI complexes. The deprotonated 1,3-bis(4-nitrophenyl)triazenide ion acts as an N1–η1 monodentate (two-electron donor) ligand, while one neutral triphenylphosphine molecule completes the coordination environment of the metal ion to an almost linear arrangement (Fig. 1).
Deviations from normal N—N and N—Caryl bond lengths in (I) (Table 1) give evidence for the delocalization of the π electrons on the N—N═N group towards the terminal aryl substituents. The N2═N3 bond [1.290 (7) Å] is longer than the typical value for a double bond (1.24 Å), while N1—N2 [1.324 (6) Å] is shorter than the characteristic value for a single bond (1.44 Å; International Tables for X-Ray Crystallography, 1985, Vol III, p. 270). Both N1—C1B [1.390 (8) Å] and N3—C1A [1.402 (7) Å] are shorter than expected for an N—Caryl single bond [1.452 Å for secondary amines, NHR2, with R = Csp2; Orpen et al., 1989]. These values are in good agreement with the distances found in the related compound trans-[1,3-bis(4-fluorophenyl)-1-triazenato-N](2-methylphenyl)bis(triethyl phosphine)nickel(II) [N1═N2 1.298 (7) and N2—N3 1.326 (7) Å; Peregudov et al., 2000).
The Au—N1 bond distance of 2.108 (5) Å in (I) is close to the sum of the covalent radii (2.144 Å; Allen et al., 1987; Teatum et al., 1960) and corresponds to a covalent single bond. This value is longer than that observed in the related compound [Au(RN1═N2—N3—N4═N5R)(PPh3)], hereinafter (II) [where R is p-tolyl; Au—N3 2.082 (5) Å; Beck, 1988], suggesting that the 1,3-bis(4-nitrophenyl)triazenide ion possesses minor basicity compared with the 1,5-ditolyl-1,4-pentazadienide ion, [(tolN5tol)]−, as consequence of the π acidity of both terminal 4-nitrophenyl substituents. On the other hand, the Au—P bond distance of 2.2524 (13) Å in (I) is significantly shorter than the sum of the covalent radii (2.530 Å; Allen et al., 1987; Teatum et al., 1960) and is in good agreement with that found in (II) [Au1—P1 2.234 (3) Å].
The coordination angle of the AuI ion in (I) [N1—Au—P 178.70 (13)°] deviates only slightly from the ideal value of 180° and is very close to that found in (II) [N3—Au1—P1 178.35°]. Due to the delocalization of the π electrons over the nitro groups and the phenyl rings C1A—C6A and C1B—C6B towards the N1—N2═N3 chain, the triazenide ligand is nearly planar, with interplanar angles as follows: between the plane of atoms O1A, N6 and O2A and the C1A—C6A ring 5(1)°, between the C1A—C6A ring and N1—N2═N3 3.5 (7)°, between the C1B—C6B ring and N1—N2═N3 11.6 (7)°, between the plane of atoms O1B, N5 and O2B and the C1B—C6B ring 3(1)°, and between the C1A—C6A and C1B—C6B rings 8.9 (4)°.
The crystal structure of (I) reveals pairs of molecules generated by centrosymmetry, which are associated into a supramolecular array via C—H···O intermolecular interactions (Table 2), and via N···C and N···O π–π interactions (Fig. 2), with N6···C6Bi 3.282 (8), N3···C6Bii 3.357 (8), O1B···N6iii 3.136 (9) and N5···O1Aiii 3.234 (9) Å [symmetry codes: (i) x, 1 + y, z; (ii) −x, 1 − y, −z; (iii) x − 1, 1 − y, −z]. These values are similar to those for π–π contacts found in free 1,3-bis(3-nitrophenyl)triazene (Zhang et al., 1999) [N···C 3.387 (3), and N···O 2.992 (2), 3.304 (3) and 3.023 (2) Å]. On the other hand, simultaneous weak intermolecular N6···C6Bi and N3···C6Bii contacts hinder the coplanarity of the C1B—C6B phenyl ring with the plane defined by the N1—N2═N3 group [interplanar angle 11.6 (7)°]. All phenyl rings in (I) are planar to within experimental error (average r.m.s. deviation 0.0062 Å).