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The cyclo­metallation of aryl and pyrazolyl rings yields the title bis­[(acetyl­acetonato)­palladium(II)] complex, {μ-bis­[3-(3-methoxy­phenyl)­pyrazol-1-yl]­methane}bis­[(acetyl­acetonato)­palladium(II)], [Pd2(C5H7O2)2(C21H18N4O2)], with five- and six-membered chelate rings. The five-membered ring PdNCCC [Pd—C 1.980 (5) Å and Pd—N 2.004 (3) Å] is planar, whereas the six-membered ring PdNNCNC [Pd—C 1.966 (5) Å and Pd—N 2.043 (4) Å] has a boat conformation. The Pd—O(acac) distances clearly demonstrate a trans influence, the O atoms in trans positions with respect to carbon forming longer Pd—O bonds than those in trans positions to nitro­gen [Pd—O 2.097 (3) Å versus 2.010 (3) Å for the Pd atom in the five-membered ring and 2.054 (3) Å versus 1.984 (3) Å for the Pd atom in the six-membered ring].

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801018712/ya6067sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536801018712/ya6067Isup2.hkl
Contains datablock I

CCDC reference: 177181

Key indicators

  • Single-crystal X-ray study
  • T = 296 K
  • Mean [sigma](C-C) = 0.008 Å
  • R factor = 0.033
  • wR factor = 0.088
  • Data-to-parameter ratio = 10.2

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 = 0.5421
Author response: The calculated sin(theta_max)/wavelength is 0.5424. That value is because our four circle diffractometer, Bruker P4, has a problem and it is not posible to increase the 2theta angle more than 113.5 degrees. But the calculated sin(theta_max)/wavelength is very close to the limit 0.550
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 0.289 Tmax scaled 0.225 Tmin scaled 0.099
1 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
0 Alert Level C = Please check

Computing details top

Data collection: XSCANS (Siemens, 1996); cell refinement: XSCANS; data reduction: SHELXTL (Sheldrick, 1997b); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

(I) top
Crystal data top
[Pd2(C5H7O2)2(C21H18N4O2)]F(000) = 1544
Mr = 769.41Dx = 1.678 Mg m3
Monoclinic, P21/nCu Kα radiation, λ = 1.54178 Å
a = 14.3726 (7) ÅCell parameters from 68 reflections
b = 14.6998 (11) Åθ = 6.8–47.5°
c = 15.9304 (9) ŵ = 9.94 mm1
β = 115.156 (4)°T = 296 K
V = 3046.5 (3) Å3Irregular_cut, colorless
Z = 40.35 × 0.25 × 0.15 mm
Data collection top
Bruker P4
diffractometer
3777 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.027
Graphite monochromatorθmax = 56.7°, θmin = 3.5°
ω scansh = 115
Absorption correction: ψ scan
(XPREP; Bruker, 2000)
k = 115
Tmin = 0.341, Tmax = 0.779l = 1716
4996 measured reflections3 standard reflections every 97 reflections
4011 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)] = 0.033H-atom parameters constrained
wR(F2) = 0.088 w = 1/[σ2(Fo2) + (0.0519P)2 + 4.3327P]
where P = (Fo2 + 2Fc2)/3
S = 1.07(Δ/σ)max = 0.006
4011 reflectionsΔρmax = 1.26 e Å3
395 parametersΔρmin = 0.65 e Å3
0 restraintsExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.00038 (4)
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.

The highest residual peak of 1.26 e/Å3 was found close to Pd2 and has no chemical sense.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Pd11.12145 (2)0.81397 (2)0.44828 (2)0.03819 (14)
Pd20.83482 (3)0.49867 (2)0.38703 (2)0.04017 (15)
N10.9064 (3)0.6191 (2)0.4219 (2)0.0401 (8)
N20.9943 (3)0.6565 (2)0.4237 (2)0.0394 (9)
N31.0781 (3)0.6517 (2)0.3259 (2)0.0411 (9)
N41.1126 (3)0.7389 (2)0.3372 (2)0.0392 (8)
O10.7491 (3)0.3852 (2)0.3621 (2)0.0520 (8)
O20.9328 (3)0.4363 (2)0.3373 (2)0.0548 (8)
O30.5428 (3)0.7442 (3)0.4769 (3)0.0733 (11)
O41.1122 (2)0.8919 (2)0.5461 (2)0.0491 (8)
O51.2513 (2)0.8792 (2)0.4561 (2)0.0530 (8)
O61.1294 (4)1.0966 (3)0.2740 (3)0.0824 (12)
C10.6805 (4)0.2432 (3)0.3044 (4)0.0627 (14)
H1A0.67940.22740.36250.094*
H1B0.69630.19010.27780.094*
H1C0.61440.26630.26290.094*
C20.7606 (4)0.3143 (3)0.3202 (3)0.0497 (13)
C30.8356 (4)0.3012 (3)0.2878 (4)0.0544 (13)
H30.83150.24740.25570.065*
C40.9155 (4)0.3594 (3)0.2981 (4)0.0553 (13)
C50.9887 (5)0.3326 (4)0.2574 (5)0.0810 (19)
H5A0.98930.37900.21520.121*
H5B0.96690.27600.22480.121*
H5C1.05650.32580.30630.121*
C60.4413 (5)0.7161 (6)0.4601 (7)0.116 (3)
H6A0.40550.69640.39690.175*
H6B0.40510.76620.47110.175*
H6C0.44490.66680.50090.175*
C70.6041 (4)0.6824 (4)0.4597 (3)0.0546 (13)
C80.5785 (4)0.5914 (4)0.4365 (4)0.0590 (14)
H80.51670.56860.43330.071*
C90.6448 (4)0.5348 (4)0.4181 (3)0.0536 (12)
H90.62620.47450.40230.064*
C100.7376 (3)0.5654 (3)0.4228 (3)0.0431 (11)
C110.7631 (3)0.6578 (3)0.4473 (3)0.0417 (10)
C120.6977 (4)0.7148 (4)0.4659 (3)0.0519 (12)
H120.71630.77500.48260.062*
C130.8607 (4)0.6862 (3)0.4471 (3)0.0410 (11)
C140.9183 (3)0.7662 (3)0.4633 (3)0.0424 (11)
H140.90230.82220.48100.051*
C151.0034 (3)0.7462 (3)0.4480 (3)0.0388 (10)
C161.0670 (3)0.6061 (3)0.4024 (3)0.0424 (10)
H16A1.04280.54430.38490.051*
H16B1.13270.60370.45620.051*
C171.0598 (4)0.6198 (3)0.2421 (3)0.0499 (12)
H171.03480.56240.21890.060*
C181.0848 (4)0.6874 (3)0.1968 (4)0.0557 (13)
H181.08200.68450.13750.067*
C191.1153 (3)0.7615 (3)0.2563 (3)0.0428 (11)
C201.1480 (3)0.8509 (3)0.2377 (3)0.0459 (11)
C211.2104 (4)0.8549 (4)0.1917 (4)0.0607 (14)
H211.23260.80150.17460.073*
C221.2400 (4)0.9381 (5)0.1710 (4)0.0702 (16)
H221.28030.94060.13840.084*
C231.2107 (4)1.0160 (4)0.1980 (4)0.0677 (16)
H231.23111.07170.18370.081*
C241.1508 (4)1.0138 (3)0.2464 (4)0.0579 (14)
C251.1157 (4)0.9314 (3)0.2636 (4)0.0515 (12)
H251.07110.92970.29210.062*
C261.0676 (7)1.0974 (5)0.3222 (5)0.103 (3)
H26A0.99801.08300.28040.155*
H26B1.06981.15660.34830.155*
H26C1.09251.05300.37110.155*
C271.1438 (5)1.0126 (4)0.6493 (4)0.0695 (16)
H27A1.07221.02820.62110.104*
H27B1.18431.06720.66780.104*
H27C1.15810.97510.70270.104*
C281.1702 (4)0.9619 (3)0.5811 (3)0.0498 (12)
C291.2495 (4)0.9910 (3)0.5627 (4)0.0590 (14)
H291.28301.04360.59300.071*
C301.2863 (4)0.9502 (4)0.5032 (4)0.0567 (13)
C311.3764 (5)0.9923 (5)0.4920 (6)0.086 (2)
H31A1.43170.94920.51030.130*
H31B1.39901.04560.53030.130*
H31C1.35581.00890.42830.130*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Pd10.0387 (2)0.0339 (2)0.0365 (2)0.00951 (13)0.01071 (15)0.00254 (13)
Pd20.0500 (2)0.0294 (2)0.0350 (2)0.00941 (14)0.01227 (17)0.00046 (13)
N10.046 (2)0.034 (2)0.0384 (19)0.0085 (17)0.0163 (17)0.0027 (16)
N20.044 (2)0.032 (2)0.039 (2)0.0076 (17)0.0142 (17)0.0008 (16)
N30.045 (2)0.033 (2)0.044 (2)0.0016 (17)0.0184 (17)0.0031 (17)
N40.042 (2)0.029 (2)0.043 (2)0.0001 (16)0.0144 (17)0.0037 (16)
O10.064 (2)0.0358 (19)0.0528 (19)0.0147 (16)0.0213 (17)0.0020 (16)
O20.057 (2)0.0342 (19)0.066 (2)0.0061 (15)0.0190 (17)0.0098 (16)
O30.062 (2)0.081 (3)0.089 (3)0.016 (2)0.044 (2)0.032 (2)
O40.0557 (19)0.0406 (18)0.0461 (18)0.0170 (16)0.0171 (15)0.0118 (15)
O50.0442 (17)0.051 (2)0.059 (2)0.0141 (16)0.0177 (16)0.0029 (17)
O60.107 (3)0.048 (2)0.092 (3)0.000 (2)0.042 (3)0.010 (2)
C10.065 (3)0.038 (3)0.064 (3)0.011 (3)0.008 (3)0.000 (3)
C20.057 (3)0.030 (3)0.036 (2)0.006 (2)0.004 (2)0.007 (2)
C30.055 (3)0.029 (3)0.062 (3)0.001 (2)0.009 (3)0.002 (2)
C40.056 (3)0.031 (3)0.064 (3)0.005 (2)0.011 (2)0.005 (2)
C50.078 (4)0.051 (3)0.119 (6)0.004 (3)0.047 (4)0.015 (4)
C60.069 (4)0.133 (7)0.165 (8)0.028 (5)0.066 (5)0.073 (6)
C70.054 (3)0.064 (4)0.049 (3)0.008 (3)0.025 (3)0.011 (2)
C80.052 (3)0.068 (4)0.056 (3)0.025 (3)0.022 (3)0.012 (3)
C90.059 (3)0.047 (3)0.053 (3)0.019 (3)0.022 (2)0.009 (2)
C100.051 (3)0.041 (3)0.034 (2)0.013 (2)0.015 (2)0.004 (2)
C110.050 (3)0.041 (3)0.033 (2)0.012 (2)0.018 (2)0.006 (2)
C120.061 (3)0.047 (3)0.052 (3)0.013 (2)0.028 (3)0.011 (2)
C130.054 (3)0.037 (3)0.032 (2)0.008 (2)0.019 (2)0.0008 (19)
C140.054 (3)0.033 (3)0.040 (2)0.009 (2)0.020 (2)0.004 (2)
C150.050 (3)0.031 (2)0.031 (2)0.013 (2)0.013 (2)0.0035 (19)
C160.044 (2)0.034 (2)0.045 (2)0.001 (2)0.015 (2)0.006 (2)
C170.056 (3)0.041 (3)0.053 (3)0.003 (2)0.024 (2)0.006 (2)
C180.067 (3)0.053 (3)0.049 (3)0.005 (3)0.027 (3)0.001 (2)
C190.045 (2)0.042 (3)0.045 (3)0.002 (2)0.022 (2)0.002 (2)
C200.044 (2)0.048 (3)0.044 (3)0.002 (2)0.016 (2)0.007 (2)
C210.060 (3)0.066 (4)0.065 (3)0.002 (3)0.035 (3)0.006 (3)
C220.061 (3)0.084 (5)0.072 (4)0.004 (3)0.035 (3)0.021 (3)
C230.055 (3)0.067 (4)0.074 (4)0.014 (3)0.021 (3)0.017 (3)
C240.062 (3)0.044 (3)0.055 (3)0.001 (2)0.012 (3)0.005 (2)
C250.054 (3)0.046 (3)0.055 (3)0.002 (2)0.024 (2)0.009 (2)
C260.168 (8)0.054 (4)0.090 (5)0.032 (5)0.058 (6)0.014 (4)
C270.096 (4)0.051 (3)0.056 (3)0.018 (3)0.026 (3)0.015 (3)
C280.059 (3)0.039 (3)0.038 (2)0.004 (2)0.007 (2)0.003 (2)
C290.058 (3)0.043 (3)0.061 (3)0.021 (2)0.011 (3)0.006 (2)
C300.042 (3)0.050 (3)0.065 (3)0.012 (2)0.010 (2)0.006 (3)
C310.064 (4)0.082 (5)0.112 (6)0.033 (3)0.036 (4)0.007 (4)
Geometric parameters (Å, º) top
Pd1—C151.966 (4)C2—C31.392 (8)
Pd1—O41.984 (3)C3—C41.385 (7)
Pd1—N42.043 (4)C4—C51.503 (8)
Pd1—O52.054 (3)C7—C121.390 (7)
Pd2—C101.980 (5)C7—C81.395 (8)
Pd2—N12.004 (3)C8—C91.387 (8)
Pd2—O12.010 (3)C9—C101.379 (7)
Pd2—O22.097 (3)C10—C111.417 (6)
N1—C131.338 (6)C11—C121.383 (7)
N1—N21.367 (5)C11—C131.465 (6)
N2—C151.365 (6)C13—C141.398 (6)
N2—C161.433 (6)C14—C151.377 (6)
N3—C171.332 (6)C17—C181.363 (7)
N3—N41.360 (5)C18—C191.387 (7)
N3—C161.458 (6)C19—C201.468 (7)
N4—C191.346 (6)C20—C211.380 (7)
O1—C21.285 (6)C20—C251.396 (7)
O2—C41.265 (6)C21—C221.380 (8)
O3—C71.372 (6)C22—C231.352 (9)
O3—C61.428 (7)C23—C241.378 (8)
O4—C281.292 (6)C24—C251.383 (7)
O5—C301.259 (6)C27—C281.493 (8)
O6—C241.373 (7)C28—C291.360 (7)
O6—C261.400 (8)C29—C301.401 (8)
C1—C21.494 (7)C30—C311.513 (7)
C15—Pd1—O487.05 (15)C9—C8—C7120.2 (5)
C15—Pd1—N489.36 (15)C10—C9—C8121.9 (5)
O4—Pd1—N4172.81 (13)C9—C10—C11117.3 (5)
C15—Pd1—O5176.01 (15)C9—C10—Pd2127.4 (4)
O4—Pd1—O592.61 (13)C11—C10—Pd2115.0 (3)
N4—Pd1—O591.40 (14)C12—C11—C10121.3 (4)
C10—Pd2—N179.89 (16)C12—C11—C13124.6 (4)
C10—Pd2—O191.16 (16)C10—C11—C13114.1 (4)
N1—Pd2—O1170.81 (14)C11—C12—C7120.2 (5)
C10—Pd2—O2174.25 (15)N1—C13—C14110.4 (4)
N1—Pd2—O298.19 (14)N1—C13—C11112.6 (4)
O1—Pd2—O290.92 (13)C14—C13—C11137.0 (4)
C13—N1—N2105.3 (3)C15—C14—C13106.7 (4)
C13—N1—Pd2118.3 (3)N2—C15—C14105.8 (4)
N2—N1—Pd2136.2 (3)N2—C15—Pd1117.9 (3)
C15—N2—N1111.7 (4)C14—C15—Pd1136.2 (3)
C15—N2—C16125.1 (4)N2—C16—N3108.1 (3)
N1—N2—C16123.2 (4)N3—C17—C18106.9 (4)
C17—N3—N4111.7 (4)C17—C18—C19106.8 (4)
C17—N3—C16129.2 (4)N4—C19—C18109.4 (4)
N4—N3—C16119.1 (3)N4—C19—C20123.8 (4)
C19—N4—N3105.3 (4)C18—C19—C20126.8 (4)
C19—N4—Pd1132.8 (3)C21—C20—C25119.6 (5)
N3—N4—Pd1120.6 (3)C21—C20—C19118.8 (5)
C2—O1—Pd2125.0 (3)C25—C20—C19121.6 (4)
C4—O2—Pd2123.7 (3)C20—C21—C22120.0 (6)
C7—O3—C6117.6 (5)C23—C22—C21120.4 (5)
C28—O4—Pd1123.5 (3)C22—C23—C24120.7 (5)
C30—O5—Pd1123.0 (3)O6—C24—C23115.9 (5)
C24—O6—C26117.6 (5)O6—C24—C25124.2 (5)
O1—C2—C3126.5 (4)C23—C24—C25119.9 (5)
O1—C2—C1113.3 (5)C24—C25—C20119.3 (5)
C3—C2—C1120.2 (5)O4—C28—C29127.1 (5)
C4—C3—C2127.2 (5)O4—C28—C27113.2 (5)
O2—C4—C3126.1 (5)C29—C28—C27119.6 (5)
O2—C4—C5114.8 (5)C28—C29—C30127.1 (5)
C3—C4—C5119.0 (5)O5—C30—C29126.0 (5)
O3—C7—C12116.3 (5)O5—C30—C31114.5 (5)
O3—C7—C8124.6 (5)C29—C30—C31119.5 (5)
C12—C7—C8119.1 (5)
 

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