Double cyclo­metallation of bis­[3-(3-bromo­phenyl)­pyrazol-1-yl]­methane in the bis­[acetyl­acetonatopalladium(II)] complex

The cyclo­metallation of aryl and pyrazolyl rings yields the bis­[acetyl­acetonatopalladium(II)] complex, [Pd₂(C₅H₇O₂)₂C_19­H₁₂Br₂N₄)]·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].

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


 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


 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

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)

Crystal data

[Pd2(C5H7O2)2(C19H12Br2N4)]·0.5C2H3N	F(000) = 3464
Mr = 887.66	Dx = 1.858 Mg m^−3
Monoclinic, C2/c	Cu Kα radiation, λ = 1.54178 Å
a = 35.262 (3) Å	Cell parameters from 55 reflections
b = 8.3791 (5) Å	θ = 5.5–45.0°
c = 24.9461 (17) Å	µ = 12.44 mm^−1
β = 120.536 (6)°	T = 297 K
V = 6348.4 (8) Å^3	Prismatic, colorless
Z = 8	0.18 × 0.15 × 0.12 mm

Data collection

Bruker P4 diffractometer	3848 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.040
Graphite monochromator	θmax = 56.8°, θmin = 2.9°
ω scans	h = −38→1
Absorption correction: ψ scan (XPREP; Bruker, 2000)	k = −9→1
Tmin = 0.377, Tmax = 0.929	l = −23→27
5165 measured reflections	3 standard reflections every 97 reflections
4209 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)] = 0.055	H-atom parameters constrained
wR(F^2) = 0.143	w = 1/[σ^2(Fo^2) + (0.0563P)^2 + 138.5779P] where P = (Fo^2 + 2Fc^2)/3
S = 1.12	(Δ/σ)max < 0.001
4209 reflections	Δρmax = 2.45 e Å^−3
399 parameters	Δρmin = −1.10 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: 0.000049 (9)

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.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Pd1	0.14213 (2)	0.52398 (8)	0.20933 (3)	0.0347 (2)
Pd2	0.01548 (2)	0.17770 (8)	−0.02577 (3)	0.0355 (2)
Br1	0.07862 (5)	0.5772 (2)	0.36921 (7)	0.0843 (5)
Br2	0.19930 (4)	0.1049 (2)	0.05757 (7)	0.0873 (5)
O1	0.1910 (2)	0.6033 (8)	0.1979 (3)	0.0471 (17)
O2	0.1601 (2)	0.6661 (8)	0.2851 (3)	0.0473 (17)
O3	−0.0313 (2)	0.2698 (8)	−0.0062 (3)	0.0458 (16)
O4	−0.0323 (2)	0.0781 (9)	−0.1050 (3)	0.0482 (17)
N1	0.0926 (2)	0.4313 (9)	0.2181 (3)	0.0321 (17)
N2	0.0533 (2)	0.3943 (9)	0.1674 (3)	0.0358 (18)
N3	0.0784 (2)	0.3646 (9)	0.0973 (3)	0.0342 (18)
N4	0.0697 (2)	0.2664 (10)	0.0487 (3)	0.0384 (19)
C1	0.2511 (4)	0.7534 (19)	0.2135 (7)	0.084 (4)
H1A	0.2757	0.6814	0.2326	0.126*
H1B	0.2613	0.8605	0.2266	0.126*
H1C	0.2374	0.7464	0.1691	0.126*
C2	0.2183 (3)	0.7092 (13)	0.2328 (5)	0.052 (3)
C3	0.2205 (3)	0.7859 (13)	0.2828 (5)	0.052 (3)
H3	0.2427	0.8616	0.3028	0.062*
C4	0.1925 (3)	0.7610 (12)	0.3069 (5)	0.048 (3)
C5	0.1995 (4)	0.8559 (15)	0.3630 (6)	0.069 (3)
H5A	0.1725	0.9080	0.3534	0.104*
H5B	0.2220	0.9346	0.3733	0.104*
H5C	0.2084	0.7852	0.3976	0.104*
C6	0.1690 (3)	0.3188 (14)	0.3440 (5)	0.049 (3)
H6	0.1700	0.2640	0.3124	0.058*
C7	0.2061 (4)	0.3266 (16)	0.4023 (6)	0.067 (3)
H7	0.2321	0.2785	0.4098	0.080*
C8	0.2044 (4)	0.4064 (17)	0.4497 (6)	0.070 (4)
H8	0.2294	0.4112	0.4891	0.084*
C9	0.1664 (4)	0.4782 (15)	0.4390 (5)	0.064 (3)
H9	0.1655	0.5320	0.4709	0.076*
C10	0.1293 (4)	0.4701 (13)	0.3803 (5)	0.052 (3)
C11	0.1296 (3)	0.3926 (12)	0.3317 (4)	0.040 (2)
C12	0.0910 (3)	0.3819 (11)	0.2680 (4)	0.038 (2)
C13	0.0498 (3)	0.3163 (13)	0.2478 (5)	0.049 (3)
H13	0.0396	0.2747	0.2727	0.059*
C14	0.0273 (3)	0.3243 (13)	0.1852 (5)	0.045 (2)
H14	−0.0012	0.2877	0.1590	0.054*
C15	0.0446 (3)	0.4329 (12)	0.1064 (4)	0.038 (2)
H15A	0.0442	0.5479	0.1016	0.046*
H15B	0.0161	0.3913	0.0755	0.046*
C16	0.1223 (3)	0.3871 (11)	0.1355 (4)	0.035 (2)
C17	0.1427 (3)	0.3041 (12)	0.1097 (4)	0.040 (2)
H17	0.1729	0.2986	0.1250	0.048*
C18	0.1097 (3)	0.2293 (11)	0.0560 (4)	0.037 (2)
C19	0.1054 (3)	0.1317 (11)	0.0046 (4)	0.039 (2)
C20	0.1389 (3)	0.0766 (13)	−0.0040 (5)	0.045 (2)
C21	0.1303 (4)	−0.0048 (14)	−0.0569 (5)	0.054 (3)
H21	0.1535	−0.0412	−0.0615	0.065*
C22	0.0880 (4)	−0.0319 (14)	−0.1025 (6)	0.060 (3)
H22	0.0820	−0.0842	−0.1388	0.072*
C23	0.0534 (4)	0.0190 (14)	−0.0947 (5)	0.053 (3)
H23	0.0245	−0.0028	−0.1254	0.064*
C24	0.0613 (3)	0.1003 (12)	−0.0424 (4)	0.038 (2)
C25	−0.1007 (3)	0.3239 (14)	−0.0182 (5)	0.056 (3)
H25A	−0.0996	0.2600	0.0145	0.083*
H25B	−0.1306	0.3313	−0.0520	0.083*
H25C	−0.0897	0.4288	−0.0027	0.083*
C26	−0.0728 (3)	0.2476 (13)	−0.0410 (5)	0.043 (2)
C27	−0.0930 (3)	0.1666 (12)	−0.0967 (5)	0.046 (3)
H27	−0.1236	0.1653	−0.1180	0.055*
C28	−0.0732 (3)	0.0862 (12)	−0.1250 (5)	0.047 (3)
C29	−0.1017 (3)	0.0028 (13)	−0.1859 (5)	0.055 (3)
H29A	−0.0917	−0.1053	−0.1831	0.083*
H29B	−0.0998	0.0574	−0.2183	0.083*
H29C	−0.1317	0.0028	−0.1953	0.083*
N1S	1.0000	0.028 (4)	0.7500	0.132 (9)
C1S	0.9838 (12)	0.126 (4)	0.7640 (15)	0.091 (10)	0.50
C2S	0.9679 (13)	0.256 (5)	0.7794 (17)	0.116 (12)	0.50
H2S1	0.9791	0.2565	0.8235	0.173*	0.50
H2S2	0.9363	0.2523	0.7575	0.173*	0.50
H2S3	0.9772	0.3519	0.7681	0.173*	0.50

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Pd1	0.0280 (4)	0.0364 (4)	0.0401 (4)	−0.0058 (3)	0.0177 (3)	−0.0012 (3)
Pd2	0.0279 (4)	0.0376 (4)	0.0383 (4)	0.0006 (3)	0.0149 (3)	0.0019 (3)
Br1	0.0788 (10)	0.0961 (11)	0.0864 (10)	0.0206 (8)	0.0481 (8)	−0.0166 (8)
Br2	0.0368 (7)	0.1275 (14)	0.0919 (10)	0.0110 (8)	0.0286 (7)	−0.0287 (10)
O1	0.040 (4)	0.050 (4)	0.057 (4)	−0.012 (3)	0.029 (3)	−0.006 (4)
O2	0.043 (4)	0.042 (4)	0.054 (4)	−0.004 (3)	0.022 (3)	−0.004 (3)
O3	0.032 (4)	0.049 (4)	0.053 (4)	0.002 (3)	0.019 (3)	−0.004 (3)
O4	0.033 (4)	0.056 (4)	0.045 (4)	0.000 (3)	0.012 (3)	−0.004 (3)
N1	0.026 (4)	0.032 (4)	0.038 (4)	−0.001 (3)	0.016 (4)	0.001 (3)
N2	0.026 (4)	0.043 (5)	0.039 (4)	0.004 (3)	0.018 (4)	0.002 (4)
N3	0.026 (4)	0.036 (4)	0.036 (4)	−0.002 (3)	0.012 (3)	−0.003 (3)
N4	0.030 (4)	0.047 (5)	0.041 (4)	0.001 (4)	0.021 (4)	0.007 (4)
C1	0.065 (8)	0.088 (10)	0.112 (11)	−0.036 (8)	0.055 (8)	−0.015 (9)
C2	0.027 (5)	0.045 (6)	0.069 (7)	−0.012 (5)	0.015 (5)	0.009 (6)
C3	0.036 (6)	0.042 (6)	0.066 (7)	−0.016 (5)	0.018 (5)	−0.014 (5)
C4	0.045 (6)	0.033 (5)	0.057 (6)	−0.002 (5)	0.019 (5)	0.001 (5)
C5	0.069 (8)	0.059 (8)	0.069 (8)	−0.010 (6)	0.027 (7)	−0.017 (6)
C6	0.038 (6)	0.061 (7)	0.052 (6)	0.007 (5)	0.026 (5)	0.005 (5)
C7	0.040 (6)	0.079 (9)	0.074 (8)	0.009 (6)	0.023 (6)	0.014 (7)
C8	0.053 (7)	0.090 (10)	0.050 (7)	−0.009 (7)	0.014 (6)	0.002 (7)
C9	0.070 (8)	0.066 (8)	0.054 (7)	−0.013 (7)	0.032 (6)	−0.010 (6)
C10	0.059 (7)	0.053 (7)	0.054 (7)	−0.002 (5)	0.035 (6)	−0.002 (5)
C11	0.043 (5)	0.042 (6)	0.043 (5)	−0.003 (5)	0.027 (5)	0.005 (5)
C12	0.034 (5)	0.037 (5)	0.042 (5)	0.002 (4)	0.020 (4)	0.001 (4)
C13	0.042 (6)	0.060 (7)	0.056 (7)	−0.007 (5)	0.032 (5)	0.011 (5)
C14	0.028 (5)	0.055 (6)	0.057 (7)	−0.002 (5)	0.025 (5)	−0.004 (5)
C15	0.025 (5)	0.048 (6)	0.044 (5)	0.008 (4)	0.018 (4)	0.001 (4)
C16	0.029 (5)	0.037 (5)	0.041 (5)	−0.005 (4)	0.020 (4)	0.003 (4)
C17	0.021 (5)	0.047 (6)	0.051 (6)	0.000 (4)	0.017 (4)	0.003 (5)
C18	0.033 (5)	0.036 (5)	0.045 (5)	0.002 (4)	0.022 (5)	0.002 (4)
C19	0.038 (5)	0.036 (5)	0.042 (5)	0.003 (4)	0.019 (5)	0.009 (4)
C20	0.036 (5)	0.049 (6)	0.055 (6)	−0.002 (5)	0.027 (5)	−0.004 (5)
C21	0.053 (7)	0.060 (7)	0.073 (8)	0.001 (6)	0.050 (6)	−0.002 (6)
C22	0.077 (9)	0.055 (7)	0.058 (7)	0.001 (6)	0.041 (7)	−0.012 (6)
C23	0.047 (6)	0.063 (7)	0.045 (6)	−0.009 (6)	0.020 (5)	−0.005 (5)
C24	0.035 (5)	0.039 (5)	0.037 (5)	0.000 (4)	0.017 (4)	0.008 (4)
C25	0.043 (6)	0.055 (7)	0.068 (7)	0.002 (5)	0.028 (6)	0.011 (6)
C26	0.037 (6)	0.045 (6)	0.048 (6)	0.005 (5)	0.022 (5)	0.011 (5)
C27	0.029 (5)	0.045 (6)	0.059 (7)	−0.004 (5)	0.018 (5)	0.009 (5)
C28	0.038 (6)	0.035 (6)	0.051 (6)	0.001 (5)	0.010 (5)	0.009 (5)
C29	0.041 (6)	0.050 (7)	0.061 (7)	0.001 (5)	0.015 (5)	−0.004 (5)
N1S	0.15 (2)	0.16 (3)	0.056 (11)	0.000	0.035 (13)	0.000
C1S	0.12 (3)	0.07 (2)	0.08 (2)	0.031 (18)	0.051 (19)	−0.005 (16)
C2S	0.13 (3)	0.10 (3)	0.12 (3)	0.01 (2)	0.06 (2)	−0.01 (2)

Geometric parameters (Å, º)

Pd1—C16	1.971 (9)	C4—C5	1.516 (16)
Pd1—O1	1.999 (6)	C6—C7	1.377 (16)
Pd1—N1	2.023 (7)	C6—C11	1.406 (14)
Pd1—O2	2.044 (7)	C7—C8	1.385 (18)
Pd2—C24	1.969 (9)	C8—C9	1.367 (18)
Pd2—N4	2.013 (8)	C9—C10	1.384 (16)
Pd2—O4	2.014 (6)	C10—C11	1.378 (14)
Pd2—O3	2.092 (6)	C11—C12	1.479 (13)
Br1—C10	1.891 (11)	C12—C13	1.387 (14)
Br2—C20	1.904 (10)	C13—C14	1.346 (14)
O1—C2	1.272 (12)	C16—C17	1.374 (14)
O2—C4	1.266 (12)	C17—C18	1.400 (13)
O3—C26	1.279 (11)	C18—C19	1.463 (14)
O4—C28	1.266 (12)	C19—C20	1.381 (14)
N1—C12	1.340 (12)	C19—C24	1.419 (13)
N1—N2	1.355 (10)	C20—C21	1.378 (15)
N2—C14	1.339 (12)	C21—C22	1.361 (16)
N2—C15	1.428 (12)	C22—C23	1.397 (16)
N3—C16	1.358 (11)	C23—C24	1.368 (14)
N3—N4	1.364 (11)	C25—C26	1.507 (15)
N3—C15	1.438 (11)	C26—C27	1.375 (15)
N4—C18	1.363 (11)	C27—C28	1.392 (15)
C1—C2	1.508 (16)	C28—C29	1.501 (15)
C2—C3	1.371 (16)	N1S—C1S	1.15 (3)
C3—C4	1.408 (16)	C1S—C2S	1.37 (4)
C16—Pd1—O1	89.0 (3)	C11—C10—C9	122.0 (11)
C16—Pd1—N1	87.8 (3)	C11—C10—Br1	121.5 (8)
O1—Pd1—N1	176.5 (3)	C9—C10—Br1	116.5 (9)
C16—Pd1—O2	177.6 (3)	C10—C11—C6	117.6 (9)
O1—Pd1—O2	93.1 (3)	C10—C11—C12	124.1 (9)
N1—Pd1—O2	90.1 (3)	C6—C11—C12	118.4 (9)
C24—Pd2—N4	79.7 (3)	N1—C12—C13	108.4 (8)
C24—Pd2—O4	91.4 (3)	N1—C12—C11	122.0 (8)
N4—Pd2—O4	171.0 (3)	C13—C12—C11	129.5 (9)
C24—Pd2—O3	177.2 (3)	C14—C13—C12	107.0 (9)
N4—Pd2—O3	98.1 (3)	N2—C14—C13	107.9 (8)
O4—Pd2—O3	90.9 (3)	N2—C15—N3	109.4 (7)
C2—O1—Pd1	122.7 (7)	N3—C16—C17	106.4 (8)
C4—O2—Pd1	123.4 (7)	N3—C16—Pd1	118.3 (6)
C26—O3—Pd2	123.6 (6)	C17—C16—Pd1	135.3 (7)
C28—O4—Pd2	125.7 (7)	C16—C17—C18	107.2 (8)
C12—N1—N2	106.9 (7)	N4—C18—C17	109.0 (8)
C12—N1—Pd1	131.7 (6)	N4—C18—C19	111.9 (8)
N2—N1—Pd1	121.1 (5)	C17—C18—C19	139.0 (8)
C14—N2—N1	109.7 (7)	C20—C19—C24	118.5 (9)
C14—N2—C15	129.9 (8)	C20—C19—C18	127.3 (9)
N1—N2—C15	120.4 (7)	C24—C19—C18	114.1 (8)
C16—N3—N4	111.6 (7)	C21—C20—C19	121.7 (9)
C16—N3—C15	125.0 (8)	C21—C20—Br2	116.5 (7)
N4—N3—C15	123.4 (7)	C19—C20—Br2	121.9 (8)
C18—N4—N3	105.7 (7)	C22—C21—C20	119.8 (10)
C18—N4—Pd2	118.1 (6)	C21—C22—C23	120.0 (10)
N3—N4—Pd2	136.2 (6)	C24—C23—C22	121.1 (10)
O1—C2—C3	128.6 (10)	C23—C24—C19	119.1 (9)
O1—C2—C1	112.9 (11)	C23—C24—Pd2	125.0 (7)
C3—C2—C1	118.5 (10)	C19—C24—Pd2	116.0 (7)
C2—C3—C4	126.2 (9)	O3—C26—C27	125.7 (9)
O2—C4—C3	125.9 (10)	O3—C26—C25	115.0 (9)
O2—C4—C5	114.4 (10)	C27—C26—C25	119.2 (9)
C3—C4—C5	119.7 (10)	C26—C27—C28	128.0 (9)
C7—C6—C11	120.9 (11)	O4—C28—C27	126.0 (10)
C6—C7—C8	119.6 (11)	O4—C28—C29	114.6 (10)
C9—C8—C7	120.6 (11)	C27—C28—C29	119.4 (9)
C8—C9—C10	119.4 (12)	N1S—C1S—C2S	172 (4)