Double cyclo­metallation of bis­[3-(3-methoxy­phenyl)­pyrazol-1-yl]­methane in a bis­[(acetyl­acetonato)­palladium(II)] complex

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].

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


 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

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)

Crystal data

[Pd2(C5H7O2)2(C21H18N4O2)]	F(000) = 1544
Mr = 769.41	Dx = 1.678 Mg m^−3
Monoclinic, P21/n	Cu Kα radiation, λ = 1.54178 Å
a = 14.3726 (7) Å	Cell parameters from 68 reflections
b = 14.6998 (11) Å	θ = 6.8–47.5°
c = 15.9304 (9) Å	µ = 9.94 mm^−1
β = 115.156 (4)°	T = 296 K
V = 3046.5 (3) Å^3	Irregular_cut, colorless
Z = 4	0.35 × 0.25 × 0.15 mm

Data collection

Bruker P4 diffractometer	3777 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.027
Graphite monochromator	θmax = 56.7°, θmin = 3.5°
ω scans	h = −1→15
Absorption correction: ψ scan (XPREP; Bruker, 2000)	k = −1→15
Tmin = 0.341, Tmax = 0.779	l = −17→16
4996 measured reflections	3 standard reflections every 97 reflections
4011 independent reflections	intensity decay: none

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.033	H-atom parameters constrained
wR(F^2) = 0.088	w = 1/[σ^2(Fo^2) + (0.0519P)^2 + 4.3327P] where P = (Fo^2 + 2Fc^2)/3
S = 1.07	(Δ/σ)max = 0.006
4011 reflections	Δρmax = 1.26 e Å^−3
395 parameters	Δρmin = −0.65 e Å^−3
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.00038 (4)

Special details

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/ų was found close to Pd2 and has no chemical sense.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Pd1	1.12145 (2)	0.81397 (2)	0.44828 (2)	0.03819 (14)
Pd2	0.83482 (3)	0.49867 (2)	0.38703 (2)	0.04017 (15)
N1	0.9064 (3)	0.6191 (2)	0.4219 (2)	0.0401 (8)
N2	0.9943 (3)	0.6565 (2)	0.4237 (2)	0.0394 (9)
N3	1.0781 (3)	0.6517 (2)	0.3259 (2)	0.0411 (9)
N4	1.1126 (3)	0.7389 (2)	0.3372 (2)	0.0392 (8)
O1	0.7491 (3)	0.3852 (2)	0.3621 (2)	0.0520 (8)
O2	0.9328 (3)	0.4363 (2)	0.3373 (2)	0.0548 (8)
O3	0.5428 (3)	0.7442 (3)	0.4769 (3)	0.0733 (11)
O4	1.1122 (2)	0.8919 (2)	0.5461 (2)	0.0491 (8)
O5	1.2513 (2)	0.8792 (2)	0.4561 (2)	0.0530 (8)
O6	1.1294 (4)	1.0966 (3)	0.2740 (3)	0.0824 (12)
C1	0.6805 (4)	0.2432 (3)	0.3044 (4)	0.0627 (14)
H1A	0.6794	0.2274	0.3625	0.094*
H1B	0.6963	0.1901	0.2778	0.094*
H1C	0.6144	0.2663	0.2629	0.094*
C2	0.7606 (4)	0.3143 (3)	0.3202 (3)	0.0497 (13)
C3	0.8356 (4)	0.3012 (3)	0.2878 (4)	0.0544 (13)
H3	0.8315	0.2474	0.2557	0.065*
C4	0.9155 (4)	0.3594 (3)	0.2981 (4)	0.0553 (13)
C5	0.9887 (5)	0.3326 (4)	0.2574 (5)	0.0810 (19)
H5A	0.9893	0.3790	0.2152	0.121*
H5B	0.9669	0.2760	0.2248	0.121*
H5C	1.0565	0.3258	0.3063	0.121*
C6	0.4413 (5)	0.7161 (6)	0.4601 (7)	0.116 (3)
H6A	0.4055	0.6964	0.3969	0.175*
H6B	0.4051	0.7662	0.4711	0.175*
H6C	0.4449	0.6668	0.5009	0.175*
C7	0.6041 (4)	0.6824 (4)	0.4597 (3)	0.0546 (13)
C8	0.5785 (4)	0.5914 (4)	0.4365 (4)	0.0590 (14)
H8	0.5167	0.5686	0.4333	0.071*
C9	0.6448 (4)	0.5348 (4)	0.4181 (3)	0.0536 (12)
H9	0.6262	0.4745	0.4023	0.064*
C10	0.7376 (3)	0.5654 (3)	0.4228 (3)	0.0431 (11)
C11	0.7631 (3)	0.6578 (3)	0.4473 (3)	0.0417 (10)
C12	0.6977 (4)	0.7148 (4)	0.4659 (3)	0.0519 (12)
H12	0.7163	0.7750	0.4826	0.062*
C13	0.8607 (4)	0.6862 (3)	0.4471 (3)	0.0410 (11)
C14	0.9183 (3)	0.7662 (3)	0.4633 (3)	0.0424 (11)
H14	0.9023	0.8222	0.4810	0.051*
C15	1.0034 (3)	0.7462 (3)	0.4480 (3)	0.0388 (10)
C16	1.0670 (3)	0.6061 (3)	0.4024 (3)	0.0424 (10)
H16A	1.0428	0.5443	0.3849	0.051*
H16B	1.1327	0.6037	0.4562	0.051*
C17	1.0598 (4)	0.6198 (3)	0.2421 (3)	0.0499 (12)
H17	1.0348	0.5624	0.2189	0.060*
C18	1.0848 (4)	0.6874 (3)	0.1968 (4)	0.0557 (13)
H18	1.0820	0.6845	0.1375	0.067*
C19	1.1153 (3)	0.7615 (3)	0.2563 (3)	0.0428 (11)
C20	1.1480 (3)	0.8509 (3)	0.2377 (3)	0.0459 (11)
C21	1.2104 (4)	0.8549 (4)	0.1917 (4)	0.0607 (14)
H21	1.2326	0.8015	0.1746	0.073*
C22	1.2400 (4)	0.9381 (5)	0.1710 (4)	0.0702 (16)
H22	1.2803	0.9406	0.1384	0.084*
C23	1.2107 (4)	1.0160 (4)	0.1980 (4)	0.0677 (16)
H23	1.2311	1.0717	0.1837	0.081*
C24	1.1508 (4)	1.0138 (3)	0.2464 (4)	0.0579 (14)
C25	1.1157 (4)	0.9314 (3)	0.2636 (4)	0.0515 (12)
H25	1.0711	0.9297	0.2921	0.062*
C26	1.0676 (7)	1.0974 (5)	0.3222 (5)	0.103 (3)
H26A	0.9980	1.0830	0.2804	0.155*
H26B	1.0698	1.1566	0.3483	0.155*
H26C	1.0925	1.0530	0.3711	0.155*
C27	1.1438 (5)	1.0126 (4)	0.6493 (4)	0.0695 (16)
H27A	1.0722	1.0282	0.6211	0.104*
H27B	1.1843	1.0672	0.6678	0.104*
H27C	1.1581	0.9751	0.7027	0.104*
C28	1.1702 (4)	0.9619 (3)	0.5811 (3)	0.0498 (12)
C29	1.2495 (4)	0.9910 (3)	0.5627 (4)	0.0590 (14)
H29	1.2830	1.0436	0.5930	0.071*
C30	1.2863 (4)	0.9502 (4)	0.5032 (4)	0.0567 (13)
C31	1.3764 (5)	0.9923 (5)	0.4920 (6)	0.086 (2)
H31A	1.4317	0.9492	0.5103	0.130*
H31B	1.3990	1.0456	0.5303	0.130*
H31C	1.3558	1.0089	0.4283	0.130*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Pd1	0.0387 (2)	0.0339 (2)	0.0365 (2)	−0.00951 (13)	0.01071 (15)	−0.00254 (13)
Pd2	0.0500 (2)	0.0294 (2)	0.0350 (2)	−0.00941 (14)	0.01227 (17)	0.00046 (13)
N1	0.046 (2)	0.034 (2)	0.0384 (19)	−0.0085 (17)	0.0163 (17)	0.0027 (16)
N2	0.044 (2)	0.032 (2)	0.039 (2)	−0.0076 (17)	0.0142 (17)	0.0008 (16)
N3	0.045 (2)	0.033 (2)	0.044 (2)	0.0016 (17)	0.0184 (17)	0.0031 (17)
N4	0.042 (2)	0.029 (2)	0.043 (2)	0.0001 (16)	0.0144 (17)	0.0037 (16)
O1	0.064 (2)	0.0358 (19)	0.0528 (19)	−0.0147 (16)	0.0213 (17)	−0.0020 (16)
O2	0.057 (2)	0.0342 (19)	0.066 (2)	−0.0061 (15)	0.0190 (17)	−0.0098 (16)
O3	0.062 (2)	0.081 (3)	0.089 (3)	−0.016 (2)	0.044 (2)	−0.032 (2)
O4	0.0557 (19)	0.0406 (18)	0.0461 (18)	−0.0170 (16)	0.0171 (15)	−0.0118 (15)
O5	0.0442 (17)	0.051 (2)	0.059 (2)	−0.0141 (16)	0.0177 (16)	−0.0029 (17)
O6	0.107 (3)	0.048 (2)	0.092 (3)	0.000 (2)	0.042 (3)	0.010 (2)
C1	0.065 (3)	0.038 (3)	0.064 (3)	−0.011 (3)	0.008 (3)	0.000 (3)
C2	0.057 (3)	0.030 (3)	0.036 (2)	−0.006 (2)	−0.004 (2)	0.007 (2)
C3	0.055 (3)	0.029 (3)	0.062 (3)	−0.001 (2)	0.009 (3)	−0.002 (2)
C4	0.056 (3)	0.031 (3)	0.064 (3)	0.005 (2)	0.011 (2)	0.005 (2)
C5	0.078 (4)	0.051 (3)	0.119 (6)	0.004 (3)	0.047 (4)	−0.015 (4)
C6	0.069 (4)	0.133 (7)	0.165 (8)	−0.028 (5)	0.066 (5)	−0.073 (6)
C7	0.054 (3)	0.064 (4)	0.049 (3)	−0.008 (3)	0.025 (3)	−0.011 (2)
C8	0.052 (3)	0.068 (4)	0.056 (3)	−0.025 (3)	0.022 (3)	−0.012 (3)
C9	0.059 (3)	0.047 (3)	0.053 (3)	−0.019 (3)	0.022 (2)	−0.009 (2)
C10	0.051 (3)	0.041 (3)	0.034 (2)	−0.013 (2)	0.015 (2)	−0.004 (2)
C11	0.050 (3)	0.041 (3)	0.033 (2)	−0.012 (2)	0.018 (2)	−0.006 (2)
C12	0.061 (3)	0.047 (3)	0.052 (3)	−0.013 (2)	0.028 (3)	−0.011 (2)
C13	0.054 (3)	0.037 (3)	0.032 (2)	−0.008 (2)	0.019 (2)	0.0008 (19)
C14	0.054 (3)	0.033 (3)	0.040 (2)	−0.009 (2)	0.020 (2)	−0.004 (2)
C15	0.050 (3)	0.031 (2)	0.031 (2)	−0.013 (2)	0.013 (2)	−0.0035 (19)
C16	0.044 (2)	0.034 (2)	0.045 (2)	0.001 (2)	0.015 (2)	0.006 (2)
C17	0.056 (3)	0.041 (3)	0.053 (3)	0.003 (2)	0.024 (2)	−0.006 (2)
C18	0.067 (3)	0.053 (3)	0.049 (3)	0.005 (3)	0.027 (3)	−0.001 (2)
C19	0.045 (2)	0.042 (3)	0.045 (3)	0.002 (2)	0.022 (2)	0.002 (2)
C20	0.044 (2)	0.048 (3)	0.044 (3)	−0.002 (2)	0.016 (2)	0.007 (2)
C21	0.060 (3)	0.066 (4)	0.065 (3)	0.002 (3)	0.035 (3)	0.006 (3)
C22	0.061 (3)	0.084 (5)	0.072 (4)	−0.004 (3)	0.035 (3)	0.021 (3)
C23	0.055 (3)	0.067 (4)	0.074 (4)	−0.014 (3)	0.021 (3)	0.017 (3)
C24	0.062 (3)	0.044 (3)	0.055 (3)	−0.001 (2)	0.012 (3)	0.005 (2)
C25	0.054 (3)	0.046 (3)	0.055 (3)	0.002 (2)	0.024 (2)	0.009 (2)
C26	0.168 (8)	0.054 (4)	0.090 (5)	0.032 (5)	0.058 (6)	0.014 (4)
C27	0.096 (4)	0.051 (3)	0.056 (3)	−0.018 (3)	0.026 (3)	−0.015 (3)
C28	0.059 (3)	0.039 (3)	0.038 (2)	−0.004 (2)	0.007 (2)	0.003 (2)
C29	0.058 (3)	0.043 (3)	0.061 (3)	−0.021 (2)	0.011 (3)	−0.006 (2)
C30	0.042 (3)	0.050 (3)	0.065 (3)	−0.012 (2)	0.010 (2)	0.006 (3)
C31	0.064 (4)	0.082 (5)	0.112 (6)	−0.033 (3)	0.036 (4)	−0.007 (4)

Geometric parameters (Å, º)

Pd1—C15	1.966 (4)	C2—C3	1.392 (8)
Pd1—O4	1.984 (3)	C3—C4	1.385 (7)
Pd1—N4	2.043 (4)	C4—C5	1.503 (8)
Pd1—O5	2.054 (3)	C7—C12	1.390 (7)
Pd2—C10	1.980 (5)	C7—C8	1.395 (8)
Pd2—N1	2.004 (3)	C8—C9	1.387 (8)
Pd2—O1	2.010 (3)	C9—C10	1.379 (7)
Pd2—O2	2.097 (3)	C10—C11	1.417 (6)
N1—C13	1.338 (6)	C11—C12	1.383 (7)
N1—N2	1.367 (5)	C11—C13	1.465 (6)
N2—C15	1.365 (6)	C13—C14	1.398 (6)
N2—C16	1.433 (6)	C14—C15	1.377 (6)
N3—C17	1.332 (6)	C17—C18	1.363 (7)
N3—N4	1.360 (5)	C18—C19	1.387 (7)
N3—C16	1.458 (6)	C19—C20	1.468 (7)
N4—C19	1.346 (6)	C20—C21	1.380 (7)
O1—C2	1.285 (6)	C20—C25	1.396 (7)
O2—C4	1.265 (6)	C21—C22	1.380 (8)
O3—C7	1.372 (6)	C22—C23	1.352 (9)
O3—C6	1.428 (7)	C23—C24	1.378 (8)
O4—C28	1.292 (6)	C24—C25	1.383 (7)
O5—C30	1.259 (6)	C27—C28	1.493 (8)
O6—C24	1.373 (7)	C28—C29	1.360 (7)
O6—C26	1.400 (8)	C29—C30	1.401 (8)
C1—C2	1.494 (7)	C30—C31	1.513 (7)
C15—Pd1—O4	87.05 (15)	C9—C8—C7	120.2 (5)
C15—Pd1—N4	89.36 (15)	C10—C9—C8	121.9 (5)
O4—Pd1—N4	172.81 (13)	C9—C10—C11	117.3 (5)
C15—Pd1—O5	176.01 (15)	C9—C10—Pd2	127.4 (4)
O4—Pd1—O5	92.61 (13)	C11—C10—Pd2	115.0 (3)
N4—Pd1—O5	91.40 (14)	C12—C11—C10	121.3 (4)
C10—Pd2—N1	79.89 (16)	C12—C11—C13	124.6 (4)
C10—Pd2—O1	91.16 (16)	C10—C11—C13	114.1 (4)
N1—Pd2—O1	170.81 (14)	C11—C12—C7	120.2 (5)
C10—Pd2—O2	174.25 (15)	N1—C13—C14	110.4 (4)
N1—Pd2—O2	98.19 (14)	N1—C13—C11	112.6 (4)
O1—Pd2—O2	90.92 (13)	C14—C13—C11	137.0 (4)
C13—N1—N2	105.3 (3)	C15—C14—C13	106.7 (4)
C13—N1—Pd2	118.3 (3)	N2—C15—C14	105.8 (4)
N2—N1—Pd2	136.2 (3)	N2—C15—Pd1	117.9 (3)
C15—N2—N1	111.7 (4)	C14—C15—Pd1	136.2 (3)
C15—N2—C16	125.1 (4)	N2—C16—N3	108.1 (3)
N1—N2—C16	123.2 (4)	N3—C17—C18	106.9 (4)
C17—N3—N4	111.7 (4)	C17—C18—C19	106.8 (4)
C17—N3—C16	129.2 (4)	N4—C19—C18	109.4 (4)
N4—N3—C16	119.1 (3)	N4—C19—C20	123.8 (4)
C19—N4—N3	105.3 (4)	C18—C19—C20	126.8 (4)
C19—N4—Pd1	132.8 (3)	C21—C20—C25	119.6 (5)
N3—N4—Pd1	120.6 (3)	C21—C20—C19	118.8 (5)
C2—O1—Pd2	125.0 (3)	C25—C20—C19	121.6 (4)
C4—O2—Pd2	123.7 (3)	C20—C21—C22	120.0 (6)
C7—O3—C6	117.6 (5)	C23—C22—C21	120.4 (5)
C28—O4—Pd1	123.5 (3)	C22—C23—C24	120.7 (5)
C30—O5—Pd1	123.0 (3)	O6—C24—C23	115.9 (5)
C24—O6—C26	117.6 (5)	O6—C24—C25	124.2 (5)
O1—C2—C3	126.5 (4)	C23—C24—C25	119.9 (5)
O1—C2—C1	113.3 (5)	C24—C25—C20	119.3 (5)
C3—C2—C1	120.2 (5)	O4—C28—C29	127.1 (5)
C4—C3—C2	127.2 (5)	O4—C28—C27	113.2 (5)
O2—C4—C3	126.1 (5)	C29—C28—C27	119.6 (5)
O2—C4—C5	114.8 (5)	C28—C29—C30	127.1 (5)
C3—C4—C5	119.0 (5)	O5—C30—C29	126.0 (5)
O3—C7—C12	116.3 (5)	O5—C30—C31	114.5 (5)
O3—C7—C8	124.6 (5)	C29—C30—C31	119.5 (5)
C12—C7—C8	119.1 (5)