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The cyclo­metallation of aryl and pyrazolyl rings yields the bis­[acetyl­acetonatopalladium(II)] complex, [Pd2(C5H7O2)2C19­H12Br2N4)]·0.5C2H3N, with five- and six-membered chelate rings. The five-membered ring PdNCCC [Pd-C 1.969 (9) and Pd-N 2.013 (8) Å] is planar, whereas the six-membered ring PdNNCNC [Pd-C 1.971 (9) and Pd-N 2.023 (7) Å] has a boat conformation. The Pd-O(acac) distances clearly demonstrate a trans influence, the O atoms in trans positions to carbon forming longer Pd-O bonds than those in trans positions to nitro­gen [Pd-O 2.092 (6) Å versus 2.014 (6) Å for the Pd atom in the five-membered ring and 2.044 (7) Å versus 1.999 (6) Å for the Pd atom in the six-membered ring].

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801019419/ya6071sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536801019419/ya6071Isup2.hkl
Contains datablock I

CCDC reference: 177187

Key indicators

  • Single-crystal X-ray study
  • T = 297 K
  • Mean [sigma](C-C) = 0.016 Å
  • Disorder in solvent or counterion
  • R factor = 0.055
  • wR factor = 0.143
  • Data-to-parameter ratio = 10.5

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


Red Alert Alert Level A:
THETM_01 Alert A The value of sine(theta_max)/wavelength is less than 0.550 Calculated sin(theta_max)/wavelength = 0.5427
Yellow Alert Alert Level C:
PLAT_302 Alert C Anion/Solvent Disorder ....................... 40.00 Perc. General Notes
ABSTM_02 When printed, the submitted absorption T values will be replaced by the scaled T values. Since the ratio of scaled T's is identical to the ratio of reported T values, the scaling does not imply a change to the absorption corrections used in the study. Ratio of Tmax expected/reported 0.242 Tmax scaled 0.225 Tmin scaled 0.091
1 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
1 Alert Level C = Please check

Computing details top

Data collection: XSCANS (Bruker, 2000); cell refinement: XSCANS; data reduction: SHELXTL (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

(I) top
Crystal data top
[Pd2(C5H7O2)2(C19H12Br2N4)]·0.5C2H3NF(000) = 3464
Mr = 887.66Dx = 1.858 Mg m3
Monoclinic, C2/cCu Kα radiation, λ = 1.54178 Å
a = 35.262 (3) ÅCell parameters from 55 reflections
b = 8.3791 (5) Åθ = 5.5–45.0°
c = 24.9461 (17) ŵ = 12.44 mm1
β = 120.536 (6)°T = 297 K
V = 6348.4 (8) Å3Prismatic, colorless
Z = 80.18 × 0.15 × 0.12 mm
Data collection top
Bruker P4
diffractometer
3848 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.040
Graphite monochromatorθmax = 56.8°, θmin = 2.9°
ω scansh = 381
Absorption correction: ψ scan
(XPREP; Bruker, 2000)
k = 91
Tmin = 0.377, Tmax = 0.929l = 2327
5165 measured reflections3 standard reflections every 97 reflections
4209 independent reflections intensity decay: none
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.055H-atom parameters constrained
wR(F2) = 0.143 w = 1/[σ2(Fo2) + (0.0563P)2 + 138.5779P]
where P = (Fo2 + 2Fc2)/3
S = 1.12(Δ/σ)max < 0.001
4209 reflectionsΔρmax = 2.45 e Å3
399 parametersΔρmin = 1.10 e Å3
0 restraintsExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.000049 (9)
Special details top

Experimental. Azimuthal psi-scans of 12 reflections at 10° intervals.

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
xyzUiso*/UeqOcc. (<1)
Pd10.14213 (2)0.52398 (8)0.20933 (3)0.0347 (2)
Pd20.01548 (2)0.17770 (8)0.02577 (3)0.0355 (2)
Br10.07862 (5)0.5772 (2)0.36921 (7)0.0843 (5)
Br20.19930 (4)0.1049 (2)0.05757 (7)0.0873 (5)
O10.1910 (2)0.6033 (8)0.1979 (3)0.0471 (17)
O20.1601 (2)0.6661 (8)0.2851 (3)0.0473 (17)
O30.0313 (2)0.2698 (8)0.0062 (3)0.0458 (16)
O40.0323 (2)0.0781 (9)0.1050 (3)0.0482 (17)
N10.0926 (2)0.4313 (9)0.2181 (3)0.0321 (17)
N20.0533 (2)0.3943 (9)0.1674 (3)0.0358 (18)
N30.0784 (2)0.3646 (9)0.0973 (3)0.0342 (18)
N40.0697 (2)0.2664 (10)0.0487 (3)0.0384 (19)
C10.2511 (4)0.7534 (19)0.2135 (7)0.084 (4)
H1A0.27570.68140.23260.126*
H1B0.26130.86050.22660.126*
H1C0.23740.74640.16910.126*
C20.2183 (3)0.7092 (13)0.2328 (5)0.052 (3)
C30.2205 (3)0.7859 (13)0.2828 (5)0.052 (3)
H30.24270.86160.30280.062*
C40.1925 (3)0.7610 (12)0.3069 (5)0.048 (3)
C50.1995 (4)0.8559 (15)0.3630 (6)0.069 (3)
H5A0.17250.90800.35340.104*
H5B0.22200.93460.37330.104*
H5C0.20840.78520.39760.104*
C60.1690 (3)0.3188 (14)0.3440 (5)0.049 (3)
H60.17000.26400.31240.058*
C70.2061 (4)0.3266 (16)0.4023 (6)0.067 (3)
H70.23210.27850.40980.080*
C80.2044 (4)0.4064 (17)0.4497 (6)0.070 (4)
H80.22940.41120.48910.084*
C90.1664 (4)0.4782 (15)0.4390 (5)0.064 (3)
H90.16550.53200.47090.076*
C100.1293 (4)0.4701 (13)0.3803 (5)0.052 (3)
C110.1296 (3)0.3926 (12)0.3317 (4)0.040 (2)
C120.0910 (3)0.3819 (11)0.2680 (4)0.038 (2)
C130.0498 (3)0.3163 (13)0.2478 (5)0.049 (3)
H130.03960.27470.27270.059*
C140.0273 (3)0.3243 (13)0.1852 (5)0.045 (2)
H140.00120.28770.15900.054*
C150.0446 (3)0.4329 (12)0.1064 (4)0.038 (2)
H15A0.04420.54790.10160.046*
H15B0.01610.39130.07550.046*
C160.1223 (3)0.3871 (11)0.1355 (4)0.035 (2)
C170.1427 (3)0.3041 (12)0.1097 (4)0.040 (2)
H170.17290.29860.12500.048*
C180.1097 (3)0.2293 (11)0.0560 (4)0.037 (2)
C190.1054 (3)0.1317 (11)0.0046 (4)0.039 (2)
C200.1389 (3)0.0766 (13)0.0040 (5)0.045 (2)
C210.1303 (4)0.0048 (14)0.0569 (5)0.054 (3)
H210.15350.04120.06150.065*
C220.0880 (4)0.0319 (14)0.1025 (6)0.060 (3)
H220.08200.08420.13880.072*
C230.0534 (4)0.0190 (14)0.0947 (5)0.053 (3)
H230.02450.00280.12540.064*
C240.0613 (3)0.1003 (12)0.0424 (4)0.038 (2)
C250.1007 (3)0.3239 (14)0.0182 (5)0.056 (3)
H25A0.09960.26000.01450.083*
H25B0.13060.33130.05200.083*
H25C0.08970.42880.00270.083*
C260.0728 (3)0.2476 (13)0.0410 (5)0.043 (2)
C270.0930 (3)0.1666 (12)0.0967 (5)0.046 (3)
H270.12360.16530.11800.055*
C280.0732 (3)0.0862 (12)0.1250 (5)0.047 (3)
C290.1017 (3)0.0028 (13)0.1859 (5)0.055 (3)
H29A0.09170.10530.18310.083*
H29B0.09980.05740.21830.083*
H29C0.13170.00280.19530.083*
N1S1.00000.028 (4)0.75000.132 (9)
C1S0.9838 (12)0.126 (4)0.7640 (15)0.091 (10)0.50
C2S0.9679 (13)0.256 (5)0.7794 (17)0.116 (12)0.50
H2S10.97910.25650.82350.173*0.50
H2S20.93630.25230.75750.173*0.50
H2S30.97720.35190.76810.173*0.50
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Pd10.0280 (4)0.0364 (4)0.0401 (4)0.0058 (3)0.0177 (3)0.0012 (3)
Pd20.0279 (4)0.0376 (4)0.0383 (4)0.0006 (3)0.0149 (3)0.0019 (3)
Br10.0788 (10)0.0961 (11)0.0864 (10)0.0206 (8)0.0481 (8)0.0166 (8)
Br20.0368 (7)0.1275 (14)0.0919 (10)0.0110 (8)0.0286 (7)0.0287 (10)
O10.040 (4)0.050 (4)0.057 (4)0.012 (3)0.029 (3)0.006 (4)
O20.043 (4)0.042 (4)0.054 (4)0.004 (3)0.022 (3)0.004 (3)
O30.032 (4)0.049 (4)0.053 (4)0.002 (3)0.019 (3)0.004 (3)
O40.033 (4)0.056 (4)0.045 (4)0.000 (3)0.012 (3)0.004 (3)
N10.026 (4)0.032 (4)0.038 (4)0.001 (3)0.016 (4)0.001 (3)
N20.026 (4)0.043 (5)0.039 (4)0.004 (3)0.018 (4)0.002 (4)
N30.026 (4)0.036 (4)0.036 (4)0.002 (3)0.012 (3)0.003 (3)
N40.030 (4)0.047 (5)0.041 (4)0.001 (4)0.021 (4)0.007 (4)
C10.065 (8)0.088 (10)0.112 (11)0.036 (8)0.055 (8)0.015 (9)
C20.027 (5)0.045 (6)0.069 (7)0.012 (5)0.015 (5)0.009 (6)
C30.036 (6)0.042 (6)0.066 (7)0.016 (5)0.018 (5)0.014 (5)
C40.045 (6)0.033 (5)0.057 (6)0.002 (5)0.019 (5)0.001 (5)
C50.069 (8)0.059 (8)0.069 (8)0.010 (6)0.027 (7)0.017 (6)
C60.038 (6)0.061 (7)0.052 (6)0.007 (5)0.026 (5)0.005 (5)
C70.040 (6)0.079 (9)0.074 (8)0.009 (6)0.023 (6)0.014 (7)
C80.053 (7)0.090 (10)0.050 (7)0.009 (7)0.014 (6)0.002 (7)
C90.070 (8)0.066 (8)0.054 (7)0.013 (7)0.032 (6)0.010 (6)
C100.059 (7)0.053 (7)0.054 (7)0.002 (5)0.035 (6)0.002 (5)
C110.043 (5)0.042 (6)0.043 (5)0.003 (5)0.027 (5)0.005 (5)
C120.034 (5)0.037 (5)0.042 (5)0.002 (4)0.020 (4)0.001 (4)
C130.042 (6)0.060 (7)0.056 (7)0.007 (5)0.032 (5)0.011 (5)
C140.028 (5)0.055 (6)0.057 (7)0.002 (5)0.025 (5)0.004 (5)
C150.025 (5)0.048 (6)0.044 (5)0.008 (4)0.018 (4)0.001 (4)
C160.029 (5)0.037 (5)0.041 (5)0.005 (4)0.020 (4)0.003 (4)
C170.021 (5)0.047 (6)0.051 (6)0.000 (4)0.017 (4)0.003 (5)
C180.033 (5)0.036 (5)0.045 (5)0.002 (4)0.022 (5)0.002 (4)
C190.038 (5)0.036 (5)0.042 (5)0.003 (4)0.019 (5)0.009 (4)
C200.036 (5)0.049 (6)0.055 (6)0.002 (5)0.027 (5)0.004 (5)
C210.053 (7)0.060 (7)0.073 (8)0.001 (6)0.050 (6)0.002 (6)
C220.077 (9)0.055 (7)0.058 (7)0.001 (6)0.041 (7)0.012 (6)
C230.047 (6)0.063 (7)0.045 (6)0.009 (6)0.020 (5)0.005 (5)
C240.035 (5)0.039 (5)0.037 (5)0.000 (4)0.017 (4)0.008 (4)
C250.043 (6)0.055 (7)0.068 (7)0.002 (5)0.028 (6)0.011 (6)
C260.037 (6)0.045 (6)0.048 (6)0.005 (5)0.022 (5)0.011 (5)
C270.029 (5)0.045 (6)0.059 (7)0.004 (5)0.018 (5)0.009 (5)
C280.038 (6)0.035 (6)0.051 (6)0.001 (5)0.010 (5)0.009 (5)
C290.041 (6)0.050 (7)0.061 (7)0.001 (5)0.015 (5)0.004 (5)
N1S0.15 (2)0.16 (3)0.056 (11)0.0000.035 (13)0.000
C1S0.12 (3)0.07 (2)0.08 (2)0.031 (18)0.051 (19)0.005 (16)
C2S0.13 (3)0.10 (3)0.12 (3)0.01 (2)0.06 (2)0.01 (2)
Geometric parameters (Å, º) top
Pd1—C161.971 (9)C4—C51.516 (16)
Pd1—O11.999 (6)C6—C71.377 (16)
Pd1—N12.023 (7)C6—C111.406 (14)
Pd1—O22.044 (7)C7—C81.385 (18)
Pd2—C241.969 (9)C8—C91.367 (18)
Pd2—N42.013 (8)C9—C101.384 (16)
Pd2—O42.014 (6)C10—C111.378 (14)
Pd2—O32.092 (6)C11—C121.479 (13)
Br1—C101.891 (11)C12—C131.387 (14)
Br2—C201.904 (10)C13—C141.346 (14)
O1—C21.272 (12)C16—C171.374 (14)
O2—C41.266 (12)C17—C181.400 (13)
O3—C261.279 (11)C18—C191.463 (14)
O4—C281.266 (12)C19—C201.381 (14)
N1—C121.340 (12)C19—C241.419 (13)
N1—N21.355 (10)C20—C211.378 (15)
N2—C141.339 (12)C21—C221.361 (16)
N2—C151.428 (12)C22—C231.397 (16)
N3—C161.358 (11)C23—C241.368 (14)
N3—N41.364 (11)C25—C261.507 (15)
N3—C151.438 (11)C26—C271.375 (15)
N4—C181.363 (11)C27—C281.392 (15)
C1—C21.508 (16)C28—C291.501 (15)
C2—C31.371 (16)N1S—C1S1.15 (3)
C3—C41.408 (16)C1S—C2S1.37 (4)
C16—Pd1—O189.0 (3)C11—C10—C9122.0 (11)
C16—Pd1—N187.8 (3)C11—C10—Br1121.5 (8)
O1—Pd1—N1176.5 (3)C9—C10—Br1116.5 (9)
C16—Pd1—O2177.6 (3)C10—C11—C6117.6 (9)
O1—Pd1—O293.1 (3)C10—C11—C12124.1 (9)
N1—Pd1—O290.1 (3)C6—C11—C12118.4 (9)
C24—Pd2—N479.7 (3)N1—C12—C13108.4 (8)
C24—Pd2—O491.4 (3)N1—C12—C11122.0 (8)
N4—Pd2—O4171.0 (3)C13—C12—C11129.5 (9)
C24—Pd2—O3177.2 (3)C14—C13—C12107.0 (9)
N4—Pd2—O398.1 (3)N2—C14—C13107.9 (8)
O4—Pd2—O390.9 (3)N2—C15—N3109.4 (7)
C2—O1—Pd1122.7 (7)N3—C16—C17106.4 (8)
C4—O2—Pd1123.4 (7)N3—C16—Pd1118.3 (6)
C26—O3—Pd2123.6 (6)C17—C16—Pd1135.3 (7)
C28—O4—Pd2125.7 (7)C16—C17—C18107.2 (8)
C12—N1—N2106.9 (7)N4—C18—C17109.0 (8)
C12—N1—Pd1131.7 (6)N4—C18—C19111.9 (8)
N2—N1—Pd1121.1 (5)C17—C18—C19139.0 (8)
C14—N2—N1109.7 (7)C20—C19—C24118.5 (9)
C14—N2—C15129.9 (8)C20—C19—C18127.3 (9)
N1—N2—C15120.4 (7)C24—C19—C18114.1 (8)
C16—N3—N4111.6 (7)C21—C20—C19121.7 (9)
C16—N3—C15125.0 (8)C21—C20—Br2116.5 (7)
N4—N3—C15123.4 (7)C19—C20—Br2121.9 (8)
C18—N4—N3105.7 (7)C22—C21—C20119.8 (10)
C18—N4—Pd2118.1 (6)C21—C22—C23120.0 (10)
N3—N4—Pd2136.2 (6)C24—C23—C22121.1 (10)
O1—C2—C3128.6 (10)C23—C24—C19119.1 (9)
O1—C2—C1112.9 (11)C23—C24—Pd2125.0 (7)
C3—C2—C1118.5 (10)C19—C24—Pd2116.0 (7)
C2—C3—C4126.2 (9)O3—C26—C27125.7 (9)
O2—C4—C3125.9 (10)O3—C26—C25115.0 (9)
O2—C4—C5114.4 (10)C27—C26—C25119.2 (9)
C3—C4—C5119.7 (10)C26—C27—C28128.0 (9)
C7—C6—C11120.9 (11)O4—C28—C27126.0 (10)
C6—C7—C8119.6 (11)O4—C28—C29114.6 (10)
C9—C8—C7120.6 (11)C27—C28—C29119.4 (9)
C8—C9—C10119.4 (12)N1S—C1S—C2S172 (4)
 

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