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Complexes of the composition trans-[Pd(L)2(OAc)2] have been postulated as intermediates during cyclopalladation. The first structural characterization of such a precursor has now been achieved and its role in the reaction sequence has been established. Diacetato-κ2O-bis[(S)-1-(4-fluorophenyl)ethylamine-κN]palladium(II), [Pd(O2CMe)2(4-FC6H3CHMeNH2)2] or [Pd(C2H3O2)2(C8H10FN)2], (I), was obtained from palladium(II) acetate and (S)-NH2CHMeC6H3F-4 in a 1:2 molar ratio. The intermediate was then reacted with additional palladium(II) acetate to give the acetate-bridged dinuclear complex di-μ-acetato-κ4O:O′-bis{[(S)-2-(1-aminoethyl)-5-fluorophenyl-κ2C1,N]palladium(II)} benzene hemisolvate, [Pd(4-FC6H3CHMeNH2)2(μ-O2CMe)]2·0.5C6H6 or [Pd2(C8H9FN)2(C2H3O2)2]·0.5C6H6, (II).
Supporting information
CCDC references: 245854; 245855
Pd(OAc)2 and (S)—NH2CHMeC6H3F-4 were stirred in benzene in a molar ratio of 1:2 at room temperature for 2 h. The resulting mixture was filtered and the filtrate concentrated in vacuo. Addition of hexane afforded greenish-yellow crystals of the mononuclear intermediate complex, (I) (yield 89%). This product underwent further reaction with an additional equivalent of Pd(OAc)2 in benzene at 333 K for 1 d. The mixture was filtered and concentrated and the product, (II), was precipitated with hexane (yield 93%). Single crystals suitable for X-ray structure determination were obtained from solutions in a 1:1 benzene-hexane mixture. Alternatively, complex (II) may be obtained by reaction of equimolar amounts of Pd(OAc)2 and (S)—NH2CHMeC6H3F-4 in refluxing acetonitrile for 4 h.
Please give brief details of the constraints used in the H-atom treatment.
For both compounds, data collection: SMART (Bruker, 2001); cell refinement: SMART; data reduction: SMART; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 1990); software used to prepare material for publication: Please provide missing details.
(I) Diacetato-
κ2O-bis[(
S)-1-(1-aminoethyl)-4-fluorophenyl-
κN]palladium(II)
top
Crystal data top
[Pd(C2H3O2)2(C8H10FN)2] | F(000) = 1024 |
Mr = 502.83 | Dx = 1.568 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2yb | Cell parameters from 8096 reflections |
a = 10.589 (2) Å | θ = 1.8–28.4° |
b = 17.537 (3) Å | µ = 0.92 mm−1 |
c = 11.686 (2) Å | T = 110 K |
β = 100.954 (3)° | Irregular, yellow |
V = 2130.6 (7) Å3 | 0.80 × 0.70 × 0.60 mm |
Z = 4 | |
Data collection top
Make Model CCD area-detector diffractometer | 10628 independent reflections |
Radiation source: fine-focus sealed tube | 10531 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.017 |
ϕ and ω scans | θmax = 28.4°, θmin = 1.8° |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | h = −14→14 |
Tmin = 0.500, Tmax = 0.577 | k = −23→23 |
29128 measured reflections | l = −15→15 |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.022 | H-atom parameters constrained |
wR(F2) = 0.061 | w = 1/[σ2(Fo2) + (0.0388P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.06 | (Δ/σ)max = 0.001 |
10628 reflections | Δρmax = 0.65 e Å−3 |
531 parameters | Δρmin = −0.30 e Å−3 |
1 restraint | Absolute structure: Flack (1983), with 5132 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.017 (11) |
Crystal data top
[Pd(C2H3O2)2(C8H10FN)2] | V = 2130.6 (7) Å3 |
Mr = 502.83 | Z = 4 |
Monoclinic, P21 | Mo Kα radiation |
a = 10.589 (2) Å | µ = 0.92 mm−1 |
b = 17.537 (3) Å | T = 110 K |
c = 11.686 (2) Å | 0.80 × 0.70 × 0.60 mm |
β = 100.954 (3)° | |
Data collection top
Make Model CCD area-detector diffractometer | 10628 independent reflections |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | 10531 reflections with I > 2σ(I) |
Tmin = 0.500, Tmax = 0.577 | Rint = 0.017 |
29128 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.022 | H-atom parameters constrained |
wR(F2) = 0.061 | Δρmax = 0.65 e Å−3 |
S = 1.06 | Δρmin = −0.30 e Å−3 |
10628 reflections | Absolute structure: Flack (1983), with 5132 Friedel pairs |
531 parameters | Absolute structure parameter: −0.017 (11) |
1 restraint | |
Special details top
Experimental. The values of Tmin and Tmax are 0.774044 and 1.000000 from SADABS. |
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Pd1 | 0.096419 (12) | 0.385100 (7) | 0.230795 (11) | 0.01805 (4) | |
Pd2 | 0.446083 (12) | 0.454140 (6) | 0.300154 (11) | 0.01847 (4) | |
O13 | 0.04554 (14) | 0.47488 (8) | 0.32146 (12) | 0.0225 (3) | |
O23 | 0.39907 (15) | 0.54937 (8) | 0.37889 (12) | 0.0233 (3) | |
O21 | 0.49798 (14) | 0.36485 (8) | 0.21080 (12) | 0.0246 (3) | |
O11 | 0.13978 (15) | 0.28894 (8) | 0.15140 (12) | 0.0237 (3) | |
O12 | 0.20817 (15) | 0.35311 (8) | 0.00792 (13) | 0.0270 (3) | |
O24 | 0.32661 (15) | 0.48133 (8) | 0.51600 (13) | 0.0246 (3) | |
O22 | 0.45830 (16) | 0.27696 (9) | 0.33982 (14) | 0.0292 (3) | |
O14 | 0.09150 (17) | 0.56157 (9) | 0.19412 (16) | 0.0333 (3) | |
F12 | 0.52473 (15) | 0.22813 (8) | 0.86008 (12) | 0.0381 (3) | |
F22 | 0.93546 (14) | 0.26060 (9) | 0.87157 (13) | 0.0399 (3) | |
F21 | 0.02159 (17) | 0.59145 (9) | −0.33874 (13) | 0.0425 (3) | |
F11 | −0.41247 (15) | 0.55856 (10) | −0.35410 (13) | 0.0418 (3) | |
N11 | −0.01178 (16) | 0.42527 (10) | 0.07677 (14) | 0.0218 (3) | |
H11A | −0.0081 | 0.4794 | 0.0794 | 0.028* | |
H11B | 0.0297 | 0.4096 | 0.0154 | 0.028* | |
N12 | 0.21167 (16) | 0.34972 (9) | 0.38167 (14) | 0.0187 (3) | |
H12A | 0.2689 | 0.3122 | 0.3623 | 0.024* | |
H12B | 0.2624 | 0.3919 | 0.4142 | 0.024* | |
N21 | 0.32929 (15) | 0.48916 (9) | 0.14876 (14) | 0.0193 (3) | |
H21A | 0.3191 | 0.4475 | 0.0958 | 0.025* | |
H21B | 0.2469 | 0.5001 | 0.1657 | 0.025* | |
N22 | 0.55926 (16) | 0.41683 (10) | 0.45278 (14) | 0.0228 (3) | |
H22A | 0.5484 | 0.4512 | 0.5130 | 0.030* | |
H22B | 0.5275 | 0.3686 | 0.4714 | 0.030* | |
C203 | 0.28024 (19) | 0.56805 (10) | −0.02839 (17) | 0.0211 (3) | |
C116 | 0.2575 (2) | 0.32802 (11) | 0.68430 (18) | 0.0252 (4) | |
H116 | 0.1981 | 0.3697 | 0.6921 | 0.033* | |
C103 | −0.21799 (18) | 0.44650 (11) | −0.06276 (16) | 0.0234 (3) | |
C111 | 0.2473 (2) | 0.29111 (11) | 0.57724 (17) | 0.0225 (4) | |
C207 | 0.2037 (2) | 0.53067 (12) | −0.22982 (18) | 0.0311 (4) | |
H207 | 0.2109 | 0.4990 | −0.2974 | 0.040* | |
C114 | 0.4320 (2) | 0.24803 (12) | 0.76651 (18) | 0.0267 (4) | |
C218 | 0.49619 (19) | 0.29564 (12) | 0.24995 (17) | 0.0239 (4) | |
C113 | 0.4248 (2) | 0.20862 (12) | 0.6633 (2) | 0.0286 (4) | |
H113 | 0.4837 | 0.1664 | 0.6569 | 0.037* | |
C105 | −0.39921 (19) | 0.45376 (15) | −0.22561 (17) | 0.0297 (4) | |
H105 | −0.4789 | 0.4325 | −0.2708 | 0.039* | |
C115 | 0.3502 (2) | 0.30693 (11) | 0.78045 (17) | 0.0271 (4) | |
H115 | 0.3570 | 0.3331 | 0.8554 | 0.035* | |
C212 | 0.87573 (19) | 0.40098 (12) | 0.63917 (18) | 0.0260 (4) | |
H212 | 0.9116 | 0.4492 | 0.6174 | 0.034* | |
C206 | 0.1081 (2) | 0.58488 (13) | −0.23618 (19) | 0.0300 (4) | |
C119 | −0.0051 (2) | 0.60398 (12) | 0.3519 (2) | 0.0303 (4) | |
H11C | 0.0336 | 0.6535 | 0.3401 | 0.039* | |
H11D | 0.0142 | 0.5908 | 0.4348 | 0.039* | |
H11E | −0.0985 | 0.6069 | 0.3253 | 0.039* | |
C120 | 0.04962 (19) | 0.54350 (11) | 0.28273 (18) | 0.0236 (4) | |
C205 | 0.0958 (2) | 0.63255 (13) | −0.14480 (19) | 0.0281 (4) | |
H205 | 0.0281 | 0.6713 | −0.1531 | 0.037* | |
C215 | 0.7758 (2) | 0.26266 (12) | 0.7017 (2) | 0.0298 (4) | |
H215 | 0.7409 | 0.2144 | 0.7242 | 0.039* | |
C112 | 0.3308 (2) | 0.23068 (12) | 0.56785 (18) | 0.0267 (4) | |
H112 | 0.3234 | 0.2034 | 0.4937 | 0.035* | |
C213 | 0.9337 (2) | 0.36368 (13) | 0.74238 (18) | 0.0283 (4) | |
H213 | 1.0092 | 0.3855 | 0.7933 | 0.037* | |
C220 | 0.35084 (18) | 0.54252 (11) | 0.47249 (16) | 0.0207 (3) | |
C118 | 0.18528 (19) | 0.29346 (11) | 0.05590 (18) | 0.0234 (4) | |
C217 | 0.5492 (3) | 0.23635 (14) | 0.1771 (2) | 0.0369 (5) | |
H21C | 0.6434 | 0.2361 | 0.1975 | 0.048* | |
H21D | 0.5223 | 0.2487 | 0.0942 | 0.048* | |
H21E | 0.5162 | 0.1859 | 0.1924 | 0.048* | |
C208 | 0.2894 (2) | 0.52228 (12) | −0.12465 (18) | 0.0289 (4) | |
H208 | 0.3573 | 0.4837 | −0.1178 | 0.038* | |
C214 | 0.8819 (2) | 0.29580 (13) | 0.77002 (18) | 0.0292 (4) | |
C210 | 0.70061 (18) | 0.40882 (11) | 0.45497 (17) | 0.0230 (4) | |
H210 | 0.7108 | 0.3755 | 0.3900 | 0.030* | |
C106 | −0.3505 (2) | 0.52204 (14) | −0.25641 (18) | 0.0311 (4) | |
C211 | 0.76736 (18) | 0.36986 (11) | 0.56750 (17) | 0.0229 (4) | |
C102 | −0.14873 (19) | 0.40337 (11) | 0.04398 (18) | 0.0245 (4) | |
H102 | −0.1525 | 0.3489 | 0.0251 | 0.032* | |
C204 | 0.1833 (2) | 0.62347 (12) | −0.04032 (18) | 0.0252 (4) | |
H204 | 0.1769 | 0.6565 | 0.0260 | 0.033* | |
C216 | 0.7195 (2) | 0.30024 (11) | 0.59878 (19) | 0.0268 (4) | |
H216 | 0.6450 | 0.2773 | 0.5478 | 0.035* | |
C110 | 0.14693 (19) | 0.31729 (12) | 0.47414 (17) | 0.0249 (4) | |
H110 | 0.0968 | 0.3582 | 0.5012 | 0.032* | |
C108 | −0.1748 (2) | 0.51666 (12) | −0.09654 (19) | 0.0305 (4) | |
H108 | −0.0970 | 0.5394 | −0.0503 | 0.040* | |
C202 | 0.37134 (18) | 0.55688 (10) | 0.08777 (16) | 0.0211 (3) | |
H202 | 0.3644 | 0.6019 | 0.1359 | 0.027* | |
C107 | −0.2398 (2) | 0.55505 (13) | −0.1944 (2) | 0.0328 (5) | |
H107 | −0.2083 | 0.6039 | −0.2185 | 0.043* | |
C104 | −0.33140 (19) | 0.41574 (13) | −0.12787 (18) | 0.0262 (4) | |
H104 | −0.3636 | 0.3669 | −0.1045 | 0.034* | |
C209 | 0.7559 (2) | 0.48621 (13) | 0.4330 (2) | 0.0304 (4) | |
H20A | 0.7039 | 0.5091 | 0.3630 | 0.040* | |
H20B | 0.8446 | 0.4800 | 0.4215 | 0.040* | |
H20C | 0.7548 | 0.5195 | 0.5001 | 0.040* | |
C201 | 0.5118 (2) | 0.54898 (14) | 0.0762 (2) | 0.0321 (4) | |
H20D | 0.5669 | 0.5518 | 0.1536 | 0.042* | |
H20E | 0.5342 | 0.5903 | 0.0272 | 0.042* | |
H20F | 0.5245 | 0.4997 | 0.0404 | 0.042* | |
C109 | 0.0542 (3) | 0.25476 (17) | 0.4234 (2) | 0.0487 (7) | |
H10A | −0.0107 | 0.2757 | 0.3601 | 0.063* | |
H10B | 0.0117 | 0.2343 | 0.4843 | 0.063* | |
H10C | 0.1015 | 0.2139 | 0.3929 | 0.063* | |
C219 | 0.3263 (2) | 0.61772 (11) | 0.52821 (19) | 0.0288 (4) | |
H21F | 0.2542 | 0.6440 | 0.4787 | 0.037* | |
H21G | 0.4035 | 0.6496 | 0.5369 | 0.037* | |
H21H | 0.3052 | 0.6082 | 0.6051 | 0.037* | |
C117 | 0.2085 (3) | 0.21667 (12) | 0.0039 (2) | 0.0344 (5) | |
H11F | 0.2165 | 0.2234 | −0.0777 | 0.045* | |
H11G | 0.1360 | 0.1826 | 0.0080 | 0.045* | |
H11H | 0.2879 | 0.1943 | 0.0478 | 0.045* | |
C101 | −0.2151 (2) | 0.41534 (17) | 0.1475 (2) | 0.0378 (5) | |
H10D | −0.1674 | 0.3882 | 0.2156 | 0.049* | |
H10E | −0.3031 | 0.3955 | 0.1285 | 0.049* | |
H10F | −0.2173 | 0.4699 | 0.1650 | 0.049* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Pd1 | 0.01752 (6) | 0.01968 (6) | 0.01785 (6) | 0.00038 (5) | 0.00560 (5) | 0.00184 (5) |
Pd2 | 0.01913 (7) | 0.02034 (6) | 0.01676 (6) | −0.00213 (5) | 0.00550 (5) | 0.00189 (4) |
O13 | 0.0222 (6) | 0.0242 (6) | 0.0219 (6) | 0.0018 (5) | 0.0065 (5) | 0.0019 (5) |
O23 | 0.0307 (7) | 0.0195 (6) | 0.0200 (6) | −0.0028 (5) | 0.0051 (5) | 0.0015 (5) |
O21 | 0.0242 (7) | 0.0291 (7) | 0.0217 (7) | 0.0034 (5) | 0.0078 (5) | 0.0014 (5) |
O11 | 0.0275 (7) | 0.0218 (6) | 0.0229 (7) | 0.0017 (5) | 0.0079 (5) | 0.0014 (5) |
O12 | 0.0323 (8) | 0.0242 (6) | 0.0281 (7) | −0.0015 (6) | 0.0148 (6) | −0.0008 (5) |
O24 | 0.0300 (7) | 0.0194 (6) | 0.0261 (7) | −0.0030 (5) | 0.0097 (6) | −0.0003 (5) |
O22 | 0.0331 (8) | 0.0273 (7) | 0.0301 (8) | 0.0022 (6) | 0.0134 (6) | 0.0002 (6) |
O14 | 0.0393 (9) | 0.0282 (8) | 0.0384 (9) | 0.0009 (7) | 0.0226 (7) | 0.0034 (7) |
F12 | 0.0471 (8) | 0.0368 (7) | 0.0279 (6) | 0.0108 (6) | 0.0003 (6) | 0.0066 (5) |
F22 | 0.0382 (7) | 0.0483 (8) | 0.0300 (7) | 0.0053 (6) | −0.0017 (5) | 0.0095 (6) |
F21 | 0.0584 (10) | 0.0387 (8) | 0.0252 (7) | 0.0049 (7) | −0.0053 (6) | 0.0047 (5) |
F11 | 0.0398 (8) | 0.0528 (9) | 0.0271 (7) | 0.0066 (7) | −0.0080 (6) | 0.0009 (6) |
N11 | 0.0198 (7) | 0.0283 (8) | 0.0180 (7) | 0.0025 (6) | 0.0051 (6) | 0.0020 (6) |
N12 | 0.0204 (7) | 0.0174 (7) | 0.0194 (7) | −0.0012 (6) | 0.0069 (6) | 0.0036 (5) |
N21 | 0.0201 (7) | 0.0212 (7) | 0.0174 (7) | −0.0029 (6) | 0.0054 (6) | 0.0018 (6) |
N22 | 0.0193 (7) | 0.0274 (8) | 0.0222 (8) | 0.0015 (6) | 0.0057 (6) | 0.0033 (6) |
C203 | 0.0249 (9) | 0.0188 (8) | 0.0215 (8) | −0.0002 (7) | 0.0090 (7) | 0.0037 (6) |
C116 | 0.0325 (10) | 0.0191 (8) | 0.0272 (9) | 0.0046 (7) | 0.0135 (8) | 0.0030 (7) |
C103 | 0.0211 (8) | 0.0258 (9) | 0.0229 (8) | 0.0045 (7) | 0.0032 (6) | −0.0043 (7) |
C111 | 0.0267 (9) | 0.0212 (8) | 0.0218 (8) | −0.0001 (7) | 0.0102 (7) | 0.0050 (7) |
C207 | 0.0509 (13) | 0.0214 (9) | 0.0216 (9) | 0.0038 (9) | 0.0085 (9) | −0.0009 (7) |
C114 | 0.0334 (10) | 0.0243 (9) | 0.0230 (10) | 0.0040 (8) | 0.0068 (8) | 0.0075 (7) |
C218 | 0.0191 (8) | 0.0271 (9) | 0.0244 (9) | 0.0031 (7) | 0.0018 (7) | −0.0004 (7) |
C113 | 0.0350 (11) | 0.0226 (9) | 0.0294 (10) | 0.0092 (8) | 0.0095 (8) | 0.0025 (7) |
C105 | 0.0211 (8) | 0.0441 (11) | 0.0234 (9) | 0.0009 (9) | 0.0028 (7) | −0.0086 (9) |
C115 | 0.0391 (11) | 0.0233 (9) | 0.0203 (8) | 0.0012 (8) | 0.0095 (8) | −0.0002 (7) |
C212 | 0.0230 (9) | 0.0307 (10) | 0.0261 (9) | −0.0022 (7) | 0.0090 (7) | −0.0039 (7) |
C206 | 0.0417 (12) | 0.0263 (10) | 0.0207 (9) | 0.0011 (9) | 0.0025 (8) | 0.0056 (8) |
C119 | 0.0338 (11) | 0.0230 (9) | 0.0377 (11) | −0.0026 (8) | 0.0158 (9) | −0.0033 (8) |
C120 | 0.0197 (8) | 0.0244 (9) | 0.0273 (9) | 0.0005 (7) | 0.0058 (7) | −0.0008 (7) |
C205 | 0.0297 (10) | 0.0292 (10) | 0.0265 (10) | 0.0058 (8) | 0.0081 (8) | 0.0045 (8) |
C215 | 0.0300 (10) | 0.0251 (9) | 0.0335 (11) | 0.0033 (8) | 0.0042 (8) | −0.0002 (8) |
C112 | 0.0372 (11) | 0.0250 (9) | 0.0198 (9) | 0.0019 (8) | 0.0101 (8) | −0.0001 (7) |
C213 | 0.0197 (8) | 0.0422 (11) | 0.0231 (9) | −0.0022 (8) | 0.0047 (7) | −0.0041 (8) |
C220 | 0.0207 (8) | 0.0206 (8) | 0.0198 (8) | −0.0007 (6) | 0.0017 (6) | 0.0007 (6) |
C118 | 0.0230 (9) | 0.0231 (8) | 0.0244 (9) | 0.0008 (7) | 0.0058 (7) | −0.0030 (7) |
C217 | 0.0446 (13) | 0.0336 (12) | 0.0349 (11) | 0.0088 (9) | 0.0140 (10) | −0.0039 (9) |
C208 | 0.0396 (11) | 0.0210 (8) | 0.0275 (10) | 0.0075 (8) | 0.0102 (8) | 0.0023 (7) |
C214 | 0.0286 (10) | 0.0331 (11) | 0.0253 (10) | 0.0089 (8) | 0.0039 (8) | 0.0015 (8) |
C210 | 0.0201 (8) | 0.0275 (9) | 0.0221 (8) | −0.0023 (7) | 0.0058 (7) | −0.0018 (7) |
C106 | 0.0286 (10) | 0.0398 (11) | 0.0222 (9) | 0.0082 (9) | −0.0018 (7) | −0.0057 (8) |
C211 | 0.0203 (8) | 0.0256 (9) | 0.0233 (8) | 0.0025 (7) | 0.0056 (7) | −0.0039 (7) |
C102 | 0.0219 (8) | 0.0226 (8) | 0.0286 (10) | −0.0016 (7) | 0.0039 (7) | 0.0008 (7) |
C204 | 0.0291 (10) | 0.0253 (8) | 0.0232 (9) | 0.0034 (7) | 0.0099 (7) | −0.0005 (7) |
C216 | 0.0274 (9) | 0.0230 (9) | 0.0290 (10) | 0.0015 (7) | 0.0026 (7) | −0.0042 (7) |
C110 | 0.0261 (9) | 0.0275 (9) | 0.0228 (8) | −0.0016 (7) | 0.0092 (7) | 0.0080 (7) |
C108 | 0.0304 (10) | 0.0248 (9) | 0.0315 (10) | −0.0002 (8) | −0.0064 (8) | −0.0037 (8) |
C202 | 0.0214 (8) | 0.0204 (8) | 0.0225 (8) | 0.0001 (6) | 0.0070 (6) | 0.0032 (7) |
C107 | 0.0376 (12) | 0.0254 (9) | 0.0315 (11) | 0.0012 (9) | −0.0035 (9) | −0.0007 (8) |
C104 | 0.0207 (9) | 0.0346 (10) | 0.0237 (9) | −0.0023 (7) | 0.0053 (7) | −0.0077 (8) |
C209 | 0.0270 (10) | 0.0327 (10) | 0.0321 (10) | −0.0064 (8) | 0.0068 (8) | 0.0056 (8) |
C201 | 0.0225 (9) | 0.0409 (11) | 0.0351 (11) | 0.0003 (8) | 0.0107 (8) | 0.0122 (9) |
C109 | 0.0442 (14) | 0.0514 (15) | 0.0450 (14) | −0.0276 (12) | −0.0054 (11) | 0.0224 (12) |
C219 | 0.0365 (11) | 0.0211 (9) | 0.0285 (10) | 0.0019 (8) | 0.0055 (8) | −0.0017 (7) |
C117 | 0.0489 (14) | 0.0213 (9) | 0.0370 (12) | 0.0042 (9) | 0.0182 (10) | −0.0019 (8) |
C101 | 0.0201 (9) | 0.0622 (15) | 0.0320 (11) | 0.0046 (9) | 0.0074 (8) | 0.0125 (10) |
Geometric parameters (Å, º) top
Pd1—O11 | 2.0192 (15) | C212—C213 | 1.406 (3) |
Pd1—O13 | 2.0271 (14) | C212—H212 | 0.9800 |
Pd1—N12 | 2.0409 (16) | C206—C205 | 1.382 (3) |
Pd1—N11 | 2.0652 (16) | C119—C120 | 1.514 (3) |
Pd2—O23 | 2.0144 (14) | C119—H11C | 0.9801 |
Pd2—O21 | 2.0155 (14) | C119—H11D | 0.9801 |
Pd2—N21 | 2.0507 (16) | C119—H11E | 0.9801 |
Pd2—N22 | 2.0575 (17) | C205—C204 | 1.395 (3) |
O13—C120 | 1.289 (2) | C205—H205 | 0.9800 |
O23—C220 | 1.298 (2) | C215—C214 | 1.377 (3) |
O21—C218 | 1.299 (2) | C215—C216 | 1.401 (3) |
O11—C118 | 1.299 (2) | C215—H215 | 0.9800 |
O12—C118 | 1.233 (2) | C112—H112 | 0.9800 |
O24—C220 | 1.235 (2) | C213—C214 | 1.375 (3) |
O22—C218 | 1.237 (3) | C213—H213 | 0.9800 |
O14—C120 | 1.243 (3) | C220—C219 | 1.515 (3) |
F12—C114 | 1.369 (2) | C118—C117 | 1.516 (3) |
F22—C214 | 1.362 (2) | C217—H21C | 0.9801 |
F21—C206 | 1.368 (3) | C217—H21D | 0.9801 |
F11—C106 | 1.364 (2) | C217—H21E | 0.9801 |
N11—C102 | 1.479 (2) | C208—H208 | 0.9800 |
N11—H11A | 0.9500 | C210—C209 | 1.519 (3) |
N11—H11B | 0.9500 | C210—C211 | 1.530 (3) |
N12—C110 | 1.498 (2) | C210—H210 | 0.9800 |
N12—H12A | 0.9500 | C106—C107 | 1.382 (3) |
N12—H12B | 0.9500 | C211—C216 | 1.397 (3) |
N21—C202 | 1.496 (2) | C102—C101 | 1.524 (3) |
N21—H21A | 0.9500 | C102—H102 | 0.9800 |
N21—H21B | 0.9500 | C204—H204 | 0.9800 |
N22—C210 | 1.499 (2) | C216—H216 | 0.9800 |
N22—H22A | 0.9500 | C110—C109 | 1.516 (3) |
N22—H22B | 0.9500 | C110—H110 | 0.9800 |
C203—C208 | 1.400 (3) | C108—C107 | 1.391 (3) |
C203—C204 | 1.401 (3) | C108—H108 | 0.9800 |
C203—C202 | 1.521 (3) | C202—C201 | 1.525 (3) |
C116—C115 | 1.395 (3) | C202—H202 | 0.9800 |
C116—C111 | 1.395 (3) | C107—H107 | 0.9800 |
C116—H116 | 0.9800 | C104—H104 | 0.9800 |
C103—C108 | 1.396 (3) | C209—H20A | 0.9801 |
C103—C104 | 1.402 (3) | C209—H20B | 0.9801 |
C103—C102 | 1.522 (3) | C209—H20C | 0.9801 |
C111—C112 | 1.397 (3) | C201—H20D | 0.9801 |
C111—C110 | 1.518 (3) | C201—H20E | 0.9801 |
C207—C206 | 1.380 (3) | C201—H20F | 0.9801 |
C207—C208 | 1.390 (3) | C109—H10A | 0.9801 |
C207—H207 | 0.9800 | C109—H10B | 0.9801 |
C114—C115 | 1.378 (3) | C109—H10C | 0.9801 |
C114—C113 | 1.380 (3) | C219—H21F | 0.9801 |
C218—C217 | 1.518 (3) | C219—H21G | 0.9801 |
C113—C112 | 1.401 (3) | C219—H21H | 0.9801 |
C113—H113 | 0.9800 | C117—H11F | 0.9801 |
C105—C106 | 1.378 (4) | C117—H11G | 0.9801 |
C105—C104 | 1.398 (3) | C117—H11H | 0.9801 |
C105—H105 | 0.9800 | C101—H10D | 0.9801 |
C115—H115 | 0.9800 | C101—H10E | 0.9801 |
C212—C211 | 1.397 (3) | C101—H10F | 0.9801 |
| | | |
O11—Pd1—O13 | 174.33 (6) | O24—C220—C219 | 120.88 (17) |
O11—Pd1—N12 | 89.55 (6) | O23—C220—C219 | 114.15 (16) |
O13—Pd1—N12 | 87.67 (6) | O12—C118—O11 | 125.41 (18) |
O11—Pd1—N11 | 91.22 (6) | O12—C118—C117 | 120.71 (18) |
O13—Pd1—N11 | 91.83 (6) | O11—C118—C117 | 113.87 (18) |
N12—Pd1—N11 | 176.65 (7) | C218—C217—H21C | 109.5 |
O23—Pd2—O21 | 174.96 (6) | C218—C217—H21D | 109.5 |
O23—Pd2—N21 | 89.13 (6) | H21C—C217—H21D | 109.5 |
O21—Pd2—N21 | 87.98 (6) | C218—C217—H21E | 109.5 |
O23—Pd2—N22 | 91.23 (6) | H21C—C217—H21E | 109.5 |
O21—Pd2—N22 | 91.77 (7) | H21D—C217—H21E | 109.5 |
N21—Pd2—N22 | 178.36 (7) | C207—C208—C203 | 121.11 (19) |
C120—O13—Pd1 | 120.77 (12) | C207—C208—H208 | 119.4 |
C220—O23—Pd2 | 118.64 (12) | C203—C208—H208 | 119.4 |
C218—O21—Pd2 | 121.33 (12) | F22—C214—C213 | 118.6 (2) |
C118—O11—Pd1 | 119.84 (13) | F22—C214—C215 | 118.2 (2) |
C102—N11—Pd1 | 119.45 (12) | C213—C214—C215 | 123.2 (2) |
C102—N11—H11A | 107.5 | N22—C210—C209 | 109.22 (17) |
Pd1—N11—H11A | 107.5 | N22—C210—C211 | 110.68 (15) |
C102—N11—H11B | 107.5 | C209—C210—C211 | 114.48 (17) |
Pd1—N11—H11B | 107.5 | N22—C210—H210 | 107.4 |
H11A—N11—H11B | 107.0 | C209—C210—H210 | 107.4 |
C110—N12—Pd1 | 117.27 (12) | C211—C210—H210 | 107.4 |
C110—N12—H12A | 108.0 | F11—C106—C105 | 118.84 (19) |
Pd1—N12—H12A | 108.0 | F11—C106—C107 | 117.9 (2) |
C110—N12—H12B | 108.0 | C105—C106—C107 | 123.3 (2) |
Pd1—N12—H12B | 108.0 | C212—C211—C216 | 118.83 (19) |
H12A—N12—H12B | 107.2 | C212—C211—C210 | 122.24 (18) |
C202—N21—Pd2 | 117.62 (12) | C216—C211—C210 | 118.92 (17) |
C202—N21—H21A | 107.9 | N11—C102—C103 | 112.30 (16) |
Pd2—N21—H21A | 107.9 | N11—C102—C101 | 109.61 (17) |
C202—N21—H21B | 107.9 | C103—C102—C101 | 111.03 (17) |
Pd2—N21—H21B | 107.9 | N11—C102—H102 | 107.9 |
H21A—N21—H21B | 107.2 | C103—C102—H102 | 107.9 |
C210—N22—Pd2 | 117.38 (12) | C101—C102—H102 | 107.9 |
C210—N22—H22A | 108.0 | C205—C204—C203 | 121.24 (19) |
Pd2—N22—H22A | 108.0 | C205—C204—H204 | 119.4 |
C210—N22—H22B | 108.0 | C203—C204—H204 | 119.4 |
Pd2—N22—H22B | 108.0 | C211—C216—C215 | 121.26 (19) |
H22A—N22—H22B | 107.2 | C211—C216—H216 | 119.4 |
C208—C203—C204 | 118.61 (19) | C215—C216—H216 | 119.4 |
C208—C203—C202 | 120.95 (17) | N12—C110—C109 | 110.10 (18) |
C204—C203—C202 | 120.42 (17) | N12—C110—C111 | 109.87 (15) |
C115—C116—C111 | 121.47 (19) | C109—C110—C111 | 113.31 (17) |
C115—C116—H116 | 119.3 | N12—C110—H110 | 107.8 |
C111—C116—H116 | 119.3 | C109—C110—H110 | 107.8 |
C108—C103—C104 | 118.60 (19) | C111—C110—H110 | 107.8 |
C108—C103—C102 | 122.48 (17) | C107—C108—C103 | 121.44 (19) |
C104—C103—C102 | 118.90 (18) | C107—C108—H108 | 119.3 |
C116—C111—C112 | 118.72 (19) | C103—C108—H108 | 119.3 |
C116—C111—C110 | 119.63 (18) | N21—C202—C203 | 109.37 (15) |
C112—C111—C110 | 121.65 (18) | N21—C202—C201 | 110.71 (16) |
C206—C207—C208 | 118.00 (19) | C203—C202—C201 | 113.36 (16) |
C206—C207—H207 | 121.0 | N21—C202—H202 | 107.7 |
C208—C207—H207 | 121.0 | C203—C202—H202 | 107.7 |
F12—C114—C115 | 117.93 (19) | C201—C202—H202 | 107.7 |
F12—C114—C113 | 118.90 (19) | C106—C107—C108 | 117.8 (2) |
C115—C114—C113 | 123.2 (2) | C106—C107—H107 | 121.1 |
O22—C218—O21 | 125.12 (18) | C108—C107—H107 | 121.1 |
O22—C218—C217 | 120.60 (19) | C105—C104—C103 | 120.9 (2) |
O21—C218—C217 | 114.27 (18) | C105—C104—H104 | 119.5 |
C114—C113—C112 | 118.08 (19) | C103—C104—H104 | 119.5 |
C114—C113—H113 | 121.0 | C210—C209—H20A | 109.5 |
C112—C113—H113 | 121.0 | C210—C209—H20B | 109.5 |
C106—C105—C104 | 117.92 (18) | H20A—C209—H20B | 109.5 |
C106—C105—H105 | 121.0 | C210—C209—H20C | 109.5 |
C104—C105—H105 | 121.0 | H20A—C209—H20C | 109.5 |
C114—C115—C116 | 117.78 (19) | H20B—C209—H20C | 109.5 |
C114—C115—H115 | 121.1 | C202—C201—H20D | 109.5 |
C116—C115—H115 | 121.1 | C202—C201—H20E | 109.5 |
C211—C212—C213 | 120.51 (19) | H20D—C201—H20E | 109.5 |
C211—C212—H212 | 119.7 | C202—C201—H20F | 109.5 |
C213—C212—H212 | 119.7 | H20D—C201—H20F | 109.5 |
F21—C206—C207 | 117.9 (2) | H20E—C201—H20F | 109.5 |
F21—C206—C205 | 118.7 (2) | C110—C109—H10A | 109.5 |
C207—C206—C205 | 123.4 (2) | C110—C109—H10B | 109.5 |
C120—C119—H11C | 109.5 | H10A—C109—H10B | 109.5 |
C120—C119—H11D | 109.5 | C110—C109—H10C | 109.5 |
H11C—C119—H11D | 109.5 | H10A—C109—H10C | 109.5 |
C120—C119—H11E | 109.5 | H10B—C109—H10C | 109.5 |
H11C—C119—H11E | 109.5 | C220—C219—H21F | 109.5 |
H11D—C119—H11E | 109.5 | C220—C219—H21G | 109.5 |
O14—C120—O13 | 124.87 (18) | H21F—C219—H21G | 109.5 |
O14—C120—C119 | 119.96 (18) | C220—C219—H21H | 109.5 |
O13—C120—C119 | 115.15 (17) | H21F—C219—H21H | 109.5 |
C206—C205—C204 | 117.6 (2) | H21G—C219—H21H | 109.5 |
C206—C205—H205 | 121.2 | C118—C117—H11F | 109.5 |
C204—C205—H205 | 121.2 | C118—C117—H11G | 109.5 |
C214—C215—C216 | 117.8 (2) | H11F—C117—H11G | 109.5 |
C214—C215—H215 | 121.1 | C118—C117—H11H | 109.5 |
C216—C215—H215 | 121.1 | H11F—C117—H11H | 109.5 |
C111—C112—C113 | 120.75 (19) | H11G—C117—H11H | 109.5 |
C111—C112—H112 | 119.6 | C102—C101—H10D | 109.5 |
C113—C112—H112 | 119.6 | C102—C101—H10E | 109.5 |
C214—C213—C212 | 118.39 (19) | H10D—C101—H10E | 109.5 |
C214—C213—H213 | 120.8 | C102—C101—H10F | 109.5 |
C212—C213—H213 | 120.8 | H10D—C101—H10F | 109.5 |
O24—C220—O23 | 124.97 (17) | H10E—C101—H10F | 109.5 |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N11—H11A···O14 | 0.95 | 2.11 | 2.867 (2) | 136 |
N11—H11B···O12 | 0.95 | 2.15 | 2.896 (2) | 134 |
N12—H12A···O22 | 0.95 | 2.16 | 3.029 (2) | 151 |
N12—H12B···O24 | 0.95 | 2.01 | 2.923 (2) | 161 |
N21—H21A···O12 | 0.95 | 2.17 | 3.040 (2) | 151 |
N21—H21B···O14 | 0.95 | 2.05 | 2.956 (2) | 160 |
N22—H22A···O24 | 0.95 | 2.41 | 2.930 (2) | 114 |
N22—H22B···O22 | 0.95 | 2.25 | 2.892 (2) | 124 |
(II) di-µ-acetato-
κ4O:
O'-bis{[(
S)-1-(1-aminoethyl)-4-fluorophenyl- k
2C
2,
N]palladium(II)} benzene hemisolvate
top
Crystal data top
[Pd2(C2H3O2)2(C8H9FN)2]·0.5C6H6 | F(000) = 1284 |
Mr = 646.27 | Dx = 1.794 Mg m−3 |
Monoclinic, C2 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: C 2y | Cell parameters from 8096 reflections |
a = 22.504 (5) Å | θ = 1.9–28.4° |
b = 9.1632 (19) Å | µ = 1.55 mm−1 |
c = 12.279 (3) Å | T = 110 K |
β = 109.131 (4)° | Rod, yellow |
V = 2392.2 (9) Å3 | 0.64 × 0.10 × 0.03 mm |
Z = 4 | |
Data collection top
Make Model CCD area-detector diffractometer | 5876 independent reflections |
Radiation source: fine-focus sealed tube | 5354 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.038 |
ϕ and ω scans | θmax = 28.3°, θmin = 1.8° |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | h = −30→30 |
Tmin = 0.437, Tmax = 0.955 | k = −11→12 |
12301 measured reflections | l = −16→14 |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.036 | H-atom parameters constrained |
wR(F2) = 0.070 | w = 1/[σ2(Fo2) + (0.0282P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.01 | (Δ/σ)max = 0.002 |
5876 reflections | Δρmax = 0.88 e Å−3 |
303 parameters | Δρmin = −0.80 e Å−3 |
1 restraint | Absolute structure: Flack (1983), with 2732 Fridel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.09 (3) |
Crystal data top
[Pd2(C2H3O2)2(C8H9FN)2]·0.5C6H6 | V = 2392.2 (9) Å3 |
Mr = 646.27 | Z = 4 |
Monoclinic, C2 | Mo Kα radiation |
a = 22.504 (5) Å | µ = 1.55 mm−1 |
b = 9.1632 (19) Å | T = 110 K |
c = 12.279 (3) Å | 0.64 × 0.10 × 0.03 mm |
β = 109.131 (4)° | |
Data collection top
Make Model CCD area-detector diffractometer | 5876 independent reflections |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | 5354 reflections with I > 2σ(I) |
Tmin = 0.437, Tmax = 0.955 | Rint = 0.038 |
12301 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.036 | H-atom parameters constrained |
wR(F2) = 0.070 | Δρmax = 0.88 e Å−3 |
S = 1.01 | Δρmin = −0.80 e Å−3 |
5876 reflections | Absolute structure: Flack (1983), with 2732 Fridel pairs |
303 parameters | Absolute structure parameter: −0.09 (3) |
1 restraint | |
Special details top
Experimental. The values of Tmin and Tmax are 0.702264 and 1.000000 from SADABS. |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Pd1 | 0.802745 (14) | 0.49553 (4) | 0.96888 (3) | 0.01569 (8) | |
Pd2 | 0.926332 (14) | 0.57378 (3) | 0.96899 (3) | 0.01476 (8) | |
O11 | 0.84187 (13) | 0.5838 (4) | 1.1387 (2) | 0.0199 (6) | |
O21 | 0.92259 (14) | 0.6997 (4) | 1.1068 (3) | 0.0194 (7) | |
O22 | 0.94070 (13) | 0.3776 (4) | 1.0736 (3) | 0.0181 (7) | |
O12 | 0.84135 (14) | 0.2947 (3) | 1.0289 (3) | 0.0190 (7) | |
F1 | 0.75675 (14) | 0.1274 (3) | 0.6132 (2) | 0.0345 (7) | |
F2 | 0.91083 (14) | 1.1354 (3) | 0.8504 (3) | 0.0333 (8) | |
N2 | 0.92915 (17) | 0.4592 (4) | 0.8281 (3) | 0.0177 (8) | |
H2A | 0.9655 | 0.3989 | 0.8504 | 0.023* | |
H2B | 0.8935 | 0.3970 | 0.8037 | 0.023* | |
N1 | 0.76473 (17) | 0.6888 (4) | 0.9021 (3) | 0.0200 (8) | |
H1A | 0.7399 | 0.7240 | 0.9460 | 0.026* | |
H1B | 0.7978 | 0.7567 | 0.9106 | 0.026* | |
C108 | 0.7653 (2) | 0.4295 (6) | 0.8086 (4) | 0.0205 (10) | |
C208 | 0.92068 (19) | 0.7396 (5) | 0.8673 (4) | 0.0159 (9) | |
C206 | 0.91397 (19) | 0.9933 (6) | 0.8188 (4) | 0.0231 (10) | |
C104 | 0.71066 (19) | 0.5051 (7) | 0.6127 (4) | 0.0262 (10) | |
H104 | 0.6891 | 0.5808 | 0.5575 | 0.034* | |
C202 | 0.93027 (19) | 0.5505 (5) | 0.7278 (4) | 0.0169 (9) | |
H202 | 0.9714 | 0.5385 | 0.7175 | 0.022* | |
C201 | 0.8796 (2) | 0.4982 (6) | 0.6186 (4) | 0.0280 (10) | |
H20A | 0.8385 | 0.5026 | 0.6296 | 0.036* | |
H20B | 0.8885 | 0.3973 | 0.6022 | 0.036* | |
H20C | 0.8794 | 0.5609 | 0.5538 | 0.036* | |
C207 | 0.9157 (2) | 0.8863 (5) | 0.8967 (4) | 0.0208 (10) | |
H207 | 0.9134 | 0.9114 | 0.9728 | 0.027* | |
C110 | 0.9006 (2) | 0.2808 (5) | 1.0737 (4) | 0.0179 (9) | |
C109 | 0.9257 (2) | 0.1395 (6) | 1.1328 (4) | 0.0235 (10) | |
H10A | 0.9464 | 0.1572 | 1.2153 | 0.031* | |
H10B | 0.9561 | 0.0983 | 1.0996 | 0.031* | |
H10C | 0.8909 | 0.0707 | 1.1221 | 0.031* | |
C209 | 0.9022 (2) | 0.7483 (6) | 1.2806 (4) | 0.0269 (12) | |
H20D | 0.8674 | 0.8138 | 1.2781 | 0.035* | |
H20E | 0.9410 | 0.8051 | 1.2959 | 0.035* | |
H20F | 0.9076 | 0.6761 | 1.3420 | 0.035* | |
C210 | 0.8877 (2) | 0.6706 (5) | 1.1659 (4) | 0.0188 (9) | |
C107 | 0.7726 (2) | 0.2917 (5) | 0.7699 (4) | 0.0193 (10) | |
H107 | 0.7942 | 0.2150 | 0.8240 | 0.025* | |
C102 | 0.7245 (2) | 0.6845 (5) | 0.7774 (4) | 0.0226 (10) | |
H102 | 0.6806 | 0.6904 | 0.7748 | 0.029* | |
C103 | 0.73326 (19) | 0.5379 (5) | 0.7297 (4) | 0.0184 (10) | |
C203 | 0.92310 (19) | 0.7083 (5) | 0.7565 (4) | 0.0188 (10) | |
C101 | 0.7371 (3) | 0.8170 (6) | 0.7133 (5) | 0.0325 (13) | |
H10D | 0.7809 | 0.8153 | 0.7149 | 0.042* | |
H10E | 0.7295 | 0.9063 | 0.7507 | 0.042* | |
H10F | 0.7090 | 0.8147 | 0.6332 | 0.042* | |
C105 | 0.7182 (2) | 0.3665 (6) | 0.5724 (5) | 0.0284 (12) | |
H105 | 0.7023 | 0.3434 | 0.4900 | 0.037* | |
C205 | 0.9163 (2) | 0.9668 (5) | 0.7092 (4) | 0.0262 (11) | |
H205 | 0.9153 | 1.0467 | 0.6556 | 0.034* | |
C106 | 0.7484 (2) | 0.2639 (6) | 0.6520 (5) | 0.0266 (11) | |
C204 | 0.9202 (2) | 0.8215 (5) | 0.6784 (4) | 0.0229 (11) | |
H204 | 0.9208 | 0.7983 | 0.6009 | 0.030* | |
C1 | 0.5000 | 0.8842 (11) | 0.5000 | 0.042 (2) | |
H1 | 0.5000 | 0.9912 | 0.5000 | 0.055* | |
C3 | 0.5522 (2) | 0.6557 (8) | 0.5667 (5) | 0.0424 (16) | |
H3 | 0.5896 | 0.6020 | 0.6131 | 0.055* | |
C2 | 0.5518 (3) | 0.8086 (8) | 0.5681 (5) | 0.0466 (17) | |
H2 | 0.5885 | 0.8620 | 0.6176 | 0.061* | |
C4 | 0.5000 | 0.5816 (11) | 0.5000 | 0.0386 (18) | |
H4 | 0.5000 | 0.4746 | 0.5000 | 0.050* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Pd1 | 0.01406 (14) | 0.01669 (17) | 0.01679 (17) | −0.00081 (14) | 0.00571 (12) | −0.00112 (15) |
Pd2 | 0.01459 (14) | 0.01257 (16) | 0.01806 (17) | 0.00014 (14) | 0.00661 (12) | 0.00017 (15) |
O11 | 0.0215 (14) | 0.0223 (17) | 0.0166 (15) | 0.0001 (15) | 0.0073 (12) | −0.0043 (15) |
O21 | 0.0217 (16) | 0.0198 (18) | 0.0187 (17) | −0.0029 (14) | 0.0096 (14) | −0.0048 (14) |
O22 | 0.0164 (15) | 0.0184 (18) | 0.0179 (17) | 0.0008 (13) | 0.0035 (13) | 0.0039 (14) |
O12 | 0.0189 (15) | 0.0188 (17) | 0.0190 (17) | −0.0029 (13) | 0.0057 (13) | 0.0016 (14) |
F1 | 0.0471 (18) | 0.0259 (16) | 0.0298 (16) | −0.0044 (14) | 0.0116 (14) | −0.0110 (14) |
F2 | 0.0414 (17) | 0.0141 (15) | 0.0440 (19) | 0.0034 (13) | 0.0137 (15) | 0.0028 (15) |
N2 | 0.0183 (18) | 0.015 (2) | 0.019 (2) | 0.0000 (14) | 0.0049 (16) | −0.0001 (15) |
N1 | 0.0206 (18) | 0.019 (2) | 0.023 (2) | 0.0034 (16) | 0.0107 (17) | −0.0015 (17) |
C108 | 0.015 (2) | 0.021 (2) | 0.025 (3) | −0.0045 (19) | 0.0061 (19) | 0.000 (2) |
C208 | 0.0123 (19) | 0.014 (2) | 0.020 (2) | −0.0009 (17) | 0.0028 (17) | 0.0046 (19) |
C206 | 0.0178 (19) | 0.012 (2) | 0.037 (3) | 0.001 (2) | 0.0056 (19) | 0.001 (3) |
C104 | 0.019 (2) | 0.038 (3) | 0.022 (2) | 0.003 (2) | 0.0059 (18) | 0.006 (3) |
C202 | 0.0149 (18) | 0.018 (2) | 0.020 (2) | 0.0011 (16) | 0.0080 (16) | −0.0013 (18) |
C201 | 0.034 (2) | 0.026 (3) | 0.022 (2) | −0.004 (3) | 0.0070 (19) | −0.003 (3) |
C207 | 0.018 (2) | 0.021 (3) | 0.022 (3) | 0.0004 (19) | 0.006 (2) | −0.003 (2) |
C110 | 0.022 (2) | 0.017 (2) | 0.014 (2) | −0.0029 (19) | 0.0066 (18) | −0.003 (2) |
C109 | 0.026 (2) | 0.020 (2) | 0.023 (2) | 0.002 (2) | 0.006 (2) | 0.003 (2) |
C209 | 0.027 (3) | 0.032 (3) | 0.020 (3) | −0.005 (2) | 0.006 (2) | −0.010 (2) |
C210 | 0.017 (2) | 0.021 (2) | 0.016 (2) | 0.0029 (18) | 0.0030 (18) | 0.0014 (19) |
C107 | 0.016 (2) | 0.021 (3) | 0.021 (2) | −0.0017 (18) | 0.0056 (19) | 0.003 (2) |
C102 | 0.020 (2) | 0.024 (3) | 0.025 (3) | 0.002 (2) | 0.008 (2) | 0.004 (2) |
C103 | 0.0148 (19) | 0.021 (3) | 0.022 (2) | −0.0033 (16) | 0.0087 (18) | 0.0012 (18) |
C203 | 0.0105 (18) | 0.022 (2) | 0.022 (3) | −0.0019 (17) | 0.0024 (18) | 0.001 (2) |
C101 | 0.034 (3) | 0.031 (3) | 0.031 (3) | 0.001 (2) | 0.009 (3) | 0.005 (3) |
C105 | 0.023 (2) | 0.040 (3) | 0.023 (3) | 0.000 (2) | 0.008 (2) | −0.004 (2) |
C205 | 0.024 (2) | 0.023 (3) | 0.028 (3) | 0.0009 (19) | 0.003 (2) | 0.007 (2) |
C106 | 0.024 (2) | 0.026 (3) | 0.030 (3) | −0.006 (2) | 0.010 (2) | −0.010 (2) |
C204 | 0.020 (2) | 0.022 (3) | 0.023 (3) | −0.0003 (19) | 0.002 (2) | 0.005 (2) |
C1 | 0.032 (4) | 0.063 (6) | 0.032 (5) | 0.000 | 0.011 (4) | 0.000 |
C3 | 0.027 (3) | 0.075 (5) | 0.026 (3) | 0.011 (3) | 0.009 (2) | 0.010 (3) |
C2 | 0.031 (3) | 0.070 (5) | 0.036 (3) | −0.008 (3) | 0.007 (3) | 0.001 (3) |
C4 | 0.043 (4) | 0.049 (5) | 0.029 (4) | 0.000 | 0.019 (3) | 0.000 |
Geometric parameters (Å, º) top
Pd1—C108 | 1.965 (5) | C201—H20B | 0.9801 |
Pd1—N1 | 2.020 (4) | C201—H20C | 0.9801 |
Pd1—O12 | 2.065 (3) | C207—H207 | 0.9800 |
Pd1—O11 | 2.139 (3) | C110—C109 | 1.501 (7) |
Pd1—Pd2 | 2.8717 (7) | C109—H10A | 0.9801 |
Pd2—C208 | 1.944 (4) | C109—H10B | 0.9801 |
Pd2—N2 | 2.042 (4) | C109—H10C | 0.9801 |
Pd2—O21 | 2.072 (3) | C209—C210 | 1.516 (6) |
Pd2—O22 | 2.172 (3) | C209—H20D | 0.9801 |
Pd2—Pd2i | 3.1494 (9) | C209—H20E | 0.9801 |
O11—C210 | 1.259 (5) | C209—H20F | 0.9801 |
O21—C210 | 1.259 (5) | C107—C106 | 1.392 (7) |
O22—C110 | 1.265 (5) | C107—H107 | 0.9800 |
O12—C110 | 1.272 (5) | C102—C103 | 1.504 (6) |
F1—C106 | 1.373 (6) | C102—C101 | 1.523 (7) |
F2—C206 | 1.366 (6) | C102—H102 | 0.9800 |
N2—C202 | 1.495 (6) | C203—C204 | 1.399 (7) |
N2—H2A | 0.9500 | C101—H10D | 0.9801 |
N2—H2B | 0.9500 | C101—H10E | 0.9801 |
N1—C102 | 1.503 (6) | C101—H10F | 0.9801 |
N1—H1A | 0.9500 | C105—C106 | 1.366 (8) |
N1—H1B | 0.9500 | C105—H105 | 0.9800 |
C108—C107 | 1.378 (7) | C205—C204 | 1.394 (7) |
C108—C103 | 1.410 (6) | C205—H205 | 0.9800 |
C208—C207 | 1.405 (7) | C204—H204 | 0.9800 |
C208—C203 | 1.409 (7) | C1—C2ii | 1.379 (8) |
C206—C207 | 1.362 (7) | C1—C2 | 1.379 (8) |
C206—C205 | 1.385 (7) | C1—H1 | 0.9800 |
C104—C103 | 1.391 (6) | C3—C4 | 1.372 (8) |
C104—C105 | 1.393 (8) | C3—C2 | 1.401 (10) |
C104—H104 | 0.9800 | C3—H3 | 0.9800 |
C202—C203 | 1.509 (6) | C2—H2 | 0.9800 |
C202—C201 | 1.525 (6) | C4—C3ii | 1.372 (8) |
C202—H202 | 0.9800 | C4—H4 | 0.9800 |
C201—H20A | 0.9801 | | |
| | | |
C108—Pd1—N1 | 83.00 (18) | C206—C207—H207 | 120.2 |
C108—Pd1—O12 | 94.32 (17) | C208—C207—H207 | 120.2 |
N1—Pd1—O12 | 177.14 (14) | O22—C110—O12 | 125.2 (4) |
C108—Pd1—O11 | 175.70 (19) | O22—C110—C109 | 116.8 (4) |
N1—Pd1—O11 | 92.76 (15) | O12—C110—C109 | 118.0 (4) |
O12—Pd1—O11 | 89.90 (13) | C110—C109—H10A | 109.5 |
C108—Pd1—Pd2 | 100.06 (12) | C110—C109—H10B | 109.5 |
N1—Pd1—Pd2 | 93.59 (11) | H10A—C109—H10B | 109.5 |
O12—Pd1—Pd2 | 85.89 (8) | C110—C109—H10C | 109.5 |
O11—Pd1—Pd2 | 79.39 (8) | H10A—C109—H10C | 109.5 |
C208—Pd2—N2 | 82.62 (18) | H10B—C109—H10C | 109.5 |
C208—Pd2—O21 | 94.42 (17) | C210—C209—H20D | 109.5 |
N2—Pd2—O21 | 177.03 (14) | C210—C209—H20E | 109.5 |
C208—Pd2—O22 | 173.12 (16) | H20D—C209—H20E | 109.5 |
N2—Pd2—O22 | 92.04 (13) | C210—C209—H20F | 109.5 |
O21—Pd2—O22 | 90.93 (13) | H20D—C209—H20F | 109.5 |
C208—Pd2—Pd1 | 109.59 (12) | H20E—C209—H20F | 109.5 |
N2—Pd2—Pd1 | 99.79 (10) | O11—C210—O21 | 126.4 (4) |
O21—Pd2—Pd1 | 80.85 (8) | O11—C210—C209 | 116.8 (4) |
O22—Pd2—Pd1 | 75.52 (8) | O21—C210—C209 | 116.9 (4) |
C208—Pd2—Pd2i | 89.85 (12) | C108—C107—C106 | 118.5 (5) |
N2—Pd2—Pd2i | 83.24 (10) | C108—C107—H107 | 120.8 |
O21—Pd2—Pd2i | 97.12 (8) | C106—C107—H107 | 120.8 |
O22—Pd2—Pd2i | 85.19 (8) | N1—C102—C103 | 107.9 (4) |
Pd1—Pd2—Pd2i | 160.532 (15) | N1—C102—C101 | 110.7 (4) |
C210—O11—Pd1 | 122.5 (3) | C103—C102—C101 | 116.1 (4) |
C210—O21—Pd2 | 123.5 (3) | N1—C102—H102 | 107.2 |
C110—O22—Pd2 | 127.8 (3) | C103—C102—H102 | 107.2 |
C110—O12—Pd1 | 120.2 (3) | C101—C102—H102 | 107.2 |
C202—N2—Pd2 | 115.0 (3) | C104—C103—C108 | 119.3 (4) |
C202—N2—H2A | 108.5 | C104—C103—C102 | 123.0 (4) |
Pd2—N2—H2A | 108.5 | C108—C103—C102 | 117.7 (4) |
C202—N2—H2B | 108.5 | C204—C203—C208 | 120.2 (5) |
Pd2—N2—H2B | 108.5 | C204—C203—C202 | 122.4 (4) |
H2A—N2—H2B | 107.5 | C208—C203—C202 | 117.5 (4) |
C102—N1—Pd1 | 115.1 (3) | C102—C101—H10D | 109.5 |
C102—N1—H1A | 108.5 | C102—C101—H10E | 109.5 |
Pd1—N1—H1A | 108.5 | H10D—C101—H10E | 109.5 |
C102—N1—H1B | 108.5 | C102—C101—H10F | 109.5 |
Pd1—N1—H1B | 108.5 | H10D—C101—H10F | 109.5 |
H1A—N1—H1B | 107.5 | H10E—C101—H10F | 109.5 |
C107—C108—C103 | 120.0 (4) | C106—C105—C104 | 117.6 (5) |
C107—C108—Pd1 | 124.6 (4) | C106—C105—H105 | 121.2 |
C103—C108—Pd1 | 115.2 (3) | C104—C105—H105 | 121.2 |
C207—C208—C203 | 118.3 (4) | C206—C205—C204 | 117.2 (5) |
C207—C208—Pd2 | 125.2 (4) | C206—C205—H205 | 121.4 |
C203—C208—Pd2 | 116.5 (3) | C204—C205—H205 | 121.4 |
C207—C206—F2 | 118.6 (4) | C105—C106—F1 | 118.1 (4) |
C207—C206—C205 | 123.7 (5) | C105—C106—C107 | 123.4 (5) |
F2—C206—C205 | 117.7 (5) | F1—C106—C107 | 118.4 (5) |
C103—C104—C105 | 121.2 (5) | C205—C204—C203 | 121.0 (5) |
C103—C104—H104 | 119.4 | C205—C204—H204 | 119.5 |
C105—C104—H104 | 119.4 | C203—C204—H204 | 119.5 |
N2—C202—C203 | 108.2 (3) | C2ii—C1—C2 | 119.7 (9) |
N2—C202—C201 | 109.8 (4) | C2ii—C1—H1 | 120.2 |
C203—C202—C201 | 113.6 (4) | C2—C1—H1 | 120.2 |
N2—C202—H202 | 108.4 | C4—C3—C2 | 119.6 (6) |
C203—C202—H202 | 108.4 | C4—C3—H3 | 120.2 |
C201—C202—H202 | 108.4 | C2—C3—H3 | 120.2 |
C202—C201—H20A | 109.5 | C1—C2—C3 | 120.2 (6) |
C202—C201—H20B | 109.5 | C1—C2—H2 | 119.9 |
H20A—C201—H20B | 109.5 | C3—C2—H2 | 119.9 |
C202—C201—H20C | 109.5 | C3ii—C4—C3 | 120.7 (9) |
H20A—C201—H20C | 109.5 | C3ii—C4—H4 | 119.7 |
H20B—C201—H20C | 109.5 | C3—C4—H4 | 119.7 |
C206—C207—C208 | 119.7 (5) | | |
Symmetry codes: (i) −x+2, y, −z+2; (ii) −x+1, y, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O12iii | 0.95 | 2.06 | 2.947 (5) | 155 |
N2—H2A···O22i | 0.95 | 2.02 | 2.877 (5) | 149 |
Symmetry codes: (i) −x+2, y, −z+2; (iii) −x+3/2, y+1/2, −z+2. |
Experimental details
| (I) | (II) |
Crystal data |
Chemical formula | [Pd(C2H3O2)2(C8H10FN)2] | [Pd2(C2H3O2)2(C8H9FN)2]·0.5C6H6 |
Mr | 502.83 | 646.27 |
Crystal system, space group | Monoclinic, P21 | Monoclinic, C2 |
Temperature (K) | 110 | 110 |
a, b, c (Å) | 10.589 (2), 17.537 (3), 11.686 (2) | 22.504 (5), 9.1632 (19), 12.279 (3) |
β (°) | 100.954 (3) | 109.131 (4) |
V (Å3) | 2130.6 (7) | 2392.2 (9) |
Z | 4 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.92 | 1.55 |
Crystal size (mm) | 0.80 × 0.70 × 0.60 | 0.64 × 0.10 × 0.03 |
|
Data collection |
Diffractometer | Make Model CCD area-detector diffractometer | Make Model CCD area-detector diffractometer |
Absorption correction | Empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | Empirical (using intensity measurements) (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.500, 0.577 | 0.437, 0.955 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 29128, 10628, 10531 | 12301, 5876, 5354 |
Rint | 0.017 | 0.038 |
(sin θ/λ)max (Å−1) | 0.668 | 0.668 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.022, 0.061, 1.06 | 0.036, 0.070, 1.01 |
No. of reflections | 10628 | 5876 |
No. of parameters | 531 | 303 |
No. of restraints | 1 | 1 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.65, −0.30 | 0.88, −0.80 |
Absolute structure | Flack (1983), with 5132 Friedel pairs | Flack (1983), with 2732 Fridel pairs |
Absolute structure parameter | −0.017 (11) | −0.09 (3) |
Selected geometric parameters (Å, º) for (I) topPd1—O11 | 2.0192 (15) | O13—C120 | 1.289 (2) |
Pd1—O13 | 2.0271 (14) | O23—C220 | 1.298 (2) |
Pd1—N12 | 2.0409 (16) | O21—C218 | 1.299 (2) |
Pd1—N11 | 2.0652 (16) | O11—C118 | 1.299 (2) |
Pd2—O23 | 2.0144 (14) | O12—C118 | 1.233 (2) |
Pd2—O21 | 2.0155 (14) | O24—C220 | 1.235 (2) |
Pd2—N21 | 2.0507 (16) | O22—C218 | 1.237 (3) |
Pd2—N22 | 2.0575 (17) | O14—C120 | 1.243 (3) |
| | | |
O11—Pd1—O13 | 174.33 (6) | O23—Pd2—O21 | 174.96 (6) |
O11—Pd1—N12 | 89.55 (6) | O23—Pd2—N21 | 89.13 (6) |
O13—Pd1—N12 | 87.67 (6) | O21—Pd2—N21 | 87.98 (6) |
O11—Pd1—N11 | 91.22 (6) | O23—Pd2—N22 | 91.23 (6) |
O13—Pd1—N11 | 91.83 (6) | O21—Pd2—N22 | 91.77 (7) |
N12—Pd1—N11 | 176.65 (7) | N21—Pd2—N22 | 178.36 (7) |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
N11—H11A···O14 | 0.95 | 2.11 | 2.867 (2) | 136 |
N11—H11B···O12 | 0.95 | 2.15 | 2.896 (2) | 134 |
N12—H12A···O22 | 0.95 | 2.16 | 3.029 (2) | 151 |
N12—H12B···O24 | 0.95 | 2.01 | 2.923 (2) | 161 |
N21—H21A···O12 | 0.95 | 2.17 | 3.040 (2) | 151 |
N21—H21B···O14 | 0.95 | 2.05 | 2.956 (2) | 160 |
N22—H22A···O24 | 0.95 | 2.41 | 2.930 (2) | 114 |
N22—H22B···O22 | 0.95 | 2.25 | 2.892 (2) | 124 |
Selected geometric parameters (Å, º) for (II) topPd1—C108 | 1.965 (5) | Pd2—O21 | 2.072 (3) |
Pd1—N1 | 2.020 (4) | Pd2—O22 | 2.172 (3) |
Pd1—O12 | 2.065 (3) | Pd2—Pd2i | 3.1494 (9) |
Pd1—O11 | 2.139 (3) | O11—C210 | 1.259 (5) |
Pd1—Pd2 | 2.8717 (7) | O21—C210 | 1.259 (5) |
Pd2—C208 | 1.944 (4) | O22—C110 | 1.265 (5) |
Pd2—N2 | 2.042 (4) | O12—C110 | 1.272 (5) |
| | | |
C108—Pd1—N1 | 83.00 (18) | C208—Pd2—N2 | 82.62 (18) |
C108—Pd1—O12 | 94.32 (17) | C208—Pd2—O21 | 94.42 (17) |
N1—Pd1—O12 | 177.14 (14) | N2—Pd2—O21 | 177.03 (14) |
C108—Pd1—O11 | 175.70 (19) | C208—Pd2—O22 | 173.12 (16) |
N1—Pd1—O11 | 92.76 (15) | N2—Pd2—O22 | 92.04 (13) |
O12—Pd1—O11 | 89.90 (13) | O21—Pd2—O22 | 90.93 (13) |
Symmetry code: (i) −x+2, y, −z+2. |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O12ii | 0.95 | 2.06 | 2.947 (5) | 155 |
N2—H2A···O22i | 0.95 | 2.02 | 2.877 (5) | 149 |
Symmetry codes: (i) −x+2, y, −z+2; (ii) −x+3/2, y+1/2, −z+2. |
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The reaction of palladium(II) acetate and benzylamines under certain conditions results in the formation of a five-membered metallocycle, with the metal coordinated both to the amino N atom and the ortho C atom of the aromatic ring. Ryabov (1990) first postulated that this special case of orthometallation, often called cyclopalladation (Cope & Friedrich, 1968), proceeds via formation of an intermediate trans-bisacetato-bis(amino-ligand) complex. Our interest in building blocks for quasi-racemic crystals (Englert et al., 2000, 2002; Kalf et al., 2002; Reemers & Englert, 2002) induced us to study this reaction. In this context, we have recently performed a structural study of this pathway for primary amines (Calmuschi & Englert, 2002), a relatively new class of substrates for cyclopalladation (Calmuschi et al., 2003).
Vicente et al. (1997) infringed the historical second rule of Cope & Friedrich (Cope & Friedrich, 1968) by cyclopalladating primary amines which even contained electron-withdrawing substituents on the aryl ring. They confirmed Ryabov's theory about the intermediate bis(ligand) complex and reported NMR data for this class of compounds. We have now achieved the isolation and structural characterization of the first trans-[Pd(L)2(OAc)2] precursor complex: palladium(II)acetate and (S)-1-(4-fluorophenyl)ethylamine in a 1:2 molar ratio give [Pd(O2CMe)2(4-FC6H3CHMeNH2)2], (I). The reaction pathway is shown in the scheme. \sch
To the best of our knowledge, only one other PdII compound containing terminal acetate ligands and primary amines has been reported to date. That dinuclear complex represents a second intermediate in the cyclopalladation pathway and was separated and fully characterized by Vicente et al. (1997).
Complex (I) crystallizes in the monoclinic space group P21. The asymmetric unit contains two molecules of quite similar conformation, with the acetate groups and the H atoms of the amine N directed to the same face of the coordination plane (Fig. 1). The symmetrically independent molecules approach each other in a face-to-face fashion, hence interacting via two pairs of hydrogen bridges, each pair between an amine NH2 donor and uncoordinated acetate O atoms as acceptors. This conformation is probably stabilized by the intermolecular interactions and is therefore limited to the solid state. Table 2 gives geometric information about the hydrogen bonds in (I).
In terms of intramolecular geometry, complex (I) may best be compared with bis(acetato-O)bis(diethylamine-N)palladium(II). This mononuclear square-planar PdII complex, with two monodentate acetate and two secondary amine ligands coordinated to the metal in a trans geometry (Kravtsova et al., 1996), exhibits metal-ligand distances similar to those observed in (I). Due to the different hydrogen-bond donor-acceptor balance, this kind of interaction is limited to just one intramolecular hydrogen bond in the asymmetric unit of the centrosymmetric complex.
Further reaction of (I) with palladium(II) acetate results in the formation of [{Pd(µ-O2CMe)(4-FC6H3CHMeNH2)2], (II), thus proving the role of (I) as the primary intermediate in cyclopalladation. The orthometallated complex (II) crystallizes from benzene with 0.5 equivalents of solvent; the benzene molecules occupy the twofold axes in space group C2. The geometry of this acetate dimer corresponds to the inner isomer, with both methyl groups attached at the chiral atom pointing towards each other (Fig. 2). The Pd···Pd distance is 2.8733 (10) Å, slightly shorter than in the dinuclear complex of the unsubstituted amine ligand (Calmuschi & Englert, 2002). A two-dimensional network of hydrogen bonds in the ab plane is formed in (II) (Fig. 3). Table 4 gives details of the intermolecular hydrogen bonds. Both complexes (I) and (II) exhibit rather weak non-classical intermolecular hydrogen bonds.