Bis(tropolonato)palladium(II)

A new type of highly symmetrical α-diketone palladium(II) complex, bis­(tropolonato)palladium(II) (tropolone = 2-hy­droxy-2,4,6-cyclo­hepta­trienone), [Pd(C₇O₂H₅)], crystallizes in a square-planar geometry with one mol­ecule in the asymmetric unit. The Pd—O bond distances and O—Pd—O inter­nal angles lie in the ranges 1.969 (2)–2.002 (2) Å and 81.83 (9)–99.28 (9)°, respectively. Weak inter­molecular C—H...O hydrogen bonds link the essentially planar mol­ecules into ribbons extending along the a axis.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.029
• wR factor = 0.075
• Data-to-parameter ratio = 17.5

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT199_ALERT_1_C Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_C Check the Reported _diffrn_ambient_temperature .        293 K

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   2 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion

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Computing details

Data collection: SMART (Bruker, 1998); cell refinement: SAINT-Plus (Bruker, 1999); data reduction: SHELXTL (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg, 2000); software used to prepare material for publication: SHELXL97.

Bis(tropolonato)palladium(II)

Crystal data

[Pd(C7H5O2)2]	F(000) = 688
Mr = 348.62	Dx = 1.891 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -p 2ybc	Cell parameters from 1024 reflections
a = 7.3474 (15) Å	θ = 3.3–27.7°
b = 10.972 (2) Å	µ = 1.52 mm^−1
c = 15.186 (3) Å	T = 293 K
β = 90.27 (3)°	Needle, red
V = 1224.3 (4) Å^3	0.54 × 0.09 × 0.08 mm
Z = 4

Data collection

Bruker SMART CCD area-detector diffractometer	3015 independent reflections
Radiation source: fine-focus sealed tube	2412 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.022
Detector resolution: 512 x 512 pixels mm^-1	θmax = 28.3°, θmin = 2.3°
ω scans	h = −9→9
Absorption correction: multi-scan (SADABS; Sheldrick, 1998)	k = −14→13
Tmin = 0.844, Tmax = 0.888	l = −20→17
8234 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.029	Hydrogen site location: riding model
wR(F^2) = 0.075	H-atom parameters constrained
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0346P)^2 + 0.851P] where P = (Fo^2 + 2Fc^2)/3
3015 reflections	(Δ/σ)max = 0.001
172 parameters	Δρmax = 0.39 e Å^−3
0 restraints	Δρmin = −0.37 e Å^−3

Special details

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
Pd	0.62134 (3)	0.11506 (2)	0.427529 (15)	0.03689 (9)
O11	0.6511 (3)	0.2541 (2)	0.51047 (14)	0.0439 (5)
O12	0.3627 (3)	0.1619 (2)	0.43689 (15)	0.0458 (5)
C11	0.4970 (4)	0.3026 (3)	0.53307 (19)	0.0377 (6)
C12	0.3348 (4)	0.2510 (3)	0.49170 (18)	0.0350 (6)
C13	0.1550 (4)	0.2872 (3)	0.5063 (2)	0.0406 (7)
H13	0.0680	0.2422	0.4759	0.049*
C14	0.0854 (5)	0.3788 (3)	0.5585 (2)	0.0456 (7)
H14	−0.0406	0.3869	0.5569	0.055*
C15	0.1748 (5)	0.4599 (3)	0.6125 (2)	0.0522 (9)
H15	0.1027	0.5167	0.6414	0.063*
C16	0.3609 (5)	0.4666 (3)	0.6286 (3)	0.0579 (10)
H16	0.3966	0.5263	0.6686	0.069*
C17	0.4998 (5)	0.3981 (3)	0.5942 (2)	0.0502 (8)
H17	0.6151	0.4185	0.6150	0.060*
O21	0.5973 (3)	−0.0228 (2)	0.34190 (15)	0.0465 (5)
O22	0.8804 (3)	0.0704 (2)	0.42029 (14)	0.0412 (5)
C21	0.7544 (4)	−0.0721 (3)	0.32274 (19)	0.0349 (6)
C22	0.9124 (4)	−0.0211 (2)	0.36843 (17)	0.0328 (6)
C23	1.0928 (4)	−0.0598 (3)	0.36072 (19)	0.0370 (6)
H23	1.1759	−0.0163	0.3948	0.044*
C24	1.1680 (4)	−0.1522 (3)	0.3107 (2)	0.0410 (7)
H24	1.2932	−0.1619	0.3165	0.049*
C25	1.0834 (5)	−0.2321 (3)	0.2534 (2)	0.0455 (8)
H25	1.1583	−0.2888	0.2261	0.055*
C26	0.9006 (5)	−0.2379 (3)	0.2319 (2)	0.0453 (8)
H26	0.8692	−0.2976	0.1911	0.054*
C27	0.7571 (4)	−0.1672 (3)	0.2623 (2)	0.0408 (7)
H27	0.6441	−0.1869	0.2383	0.049*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Pd	0.03474 (13)	0.03666 (13)	0.03923 (14)	0.00059 (10)	−0.00333 (9)	−0.00333 (10)
O11	0.0346 (11)	0.0464 (12)	0.0506 (13)	0.0016 (10)	−0.0059 (9)	−0.0134 (10)
O12	0.0402 (12)	0.0458 (12)	0.0515 (13)	0.0019 (10)	−0.0085 (10)	−0.0140 (11)
C11	0.0365 (16)	0.0372 (15)	0.0393 (16)	−0.0010 (13)	−0.0017 (12)	0.0007 (13)
C12	0.0385 (15)	0.0333 (14)	0.0331 (15)	−0.0017 (12)	−0.0049 (12)	0.0010 (12)
C13	0.0375 (16)	0.0438 (17)	0.0403 (16)	−0.0018 (14)	−0.0055 (13)	−0.0021 (14)
C14	0.0378 (17)	0.0522 (19)	0.0468 (18)	0.0076 (15)	0.0013 (13)	0.0020 (15)
C15	0.0464 (19)	0.054 (2)	0.057 (2)	0.0095 (16)	0.0080 (16)	−0.0132 (17)
C16	0.058 (2)	0.053 (2)	0.063 (2)	0.0007 (18)	0.0028 (18)	−0.0251 (18)
C17	0.0427 (18)	0.050 (2)	0.058 (2)	−0.0085 (15)	−0.0043 (15)	−0.0164 (16)
O21	0.0374 (12)	0.0486 (13)	0.0533 (13)	0.0034 (10)	−0.0063 (10)	−0.0153 (11)
O22	0.0369 (11)	0.0412 (11)	0.0454 (12)	−0.0001 (9)	−0.0024 (9)	−0.0090 (10)
C21	0.0356 (15)	0.0327 (14)	0.0364 (15)	−0.0007 (12)	−0.0036 (12)	0.0022 (12)
C22	0.0421 (16)	0.0293 (14)	0.0271 (13)	−0.0046 (12)	−0.0013 (11)	0.0014 (11)
C23	0.0364 (16)	0.0369 (16)	0.0375 (16)	−0.0028 (13)	−0.0033 (12)	0.0000 (12)
C24	0.0352 (16)	0.0459 (17)	0.0421 (17)	0.0023 (13)	0.0032 (13)	0.0030 (14)
C25	0.0507 (19)	0.0417 (18)	0.0443 (18)	0.0077 (15)	0.0070 (15)	−0.0059 (14)
C26	0.058 (2)	0.0389 (17)	0.0394 (17)	−0.0010 (15)	−0.0035 (14)	−0.0073 (14)
C27	0.0409 (17)	0.0408 (16)	0.0407 (16)	−0.0033 (14)	−0.0103 (13)	−0.0043 (14)

Geometric parameters (Å, º)

Pd—O11	1.990 (2)	C17—H17	0.9300
Pd—O12	1.974 (2)	C12—C13	1.398 (4)
Pd—O21	2.002 (2)	C27—C21	1.390 (4)
Pd—O22	1.969 (2)	C27—C26	1.390 (5)
O11—C11	1.299 (4)	C27—H27	0.9300
O12—C12	1.301 (4)	C23—C24	1.383 (4)
O21—C21	1.309 (4)	C23—H23	0.9300
O22—C22	1.298 (3)	C24—H24	0.9300
C22—C23	1.397 (4)	C26—H26	0.9300
C22—C21	1.461 (4)	C14—C15	1.375 (5)
C11—C17	1.400 (4)	C14—C13	1.379 (4)
C11—C12	1.459 (4)	C14—H14	0.9300
C25—C24	1.381 (5)	C15—C16	1.390 (5)
C25—C26	1.382 (4)	C15—H15	0.9300
C25—H25	0.9300	C16—H16	0.9300
C17—C16	1.373 (5)	C13—H13	0.9300
O11—Pd—O12	81.83 (9)	C21—C27—H27	114.7
O21—Pd—O22	81.86 (9)	C26—C27—H27	114.7
O11—Pd—O21	178.31 (9)	O21—C21—C27	118.2 (3)
O12—Pd—O21	99.28 (9)	O21—C21—C22	115.8 (3)
O11—Pd—O22	97.04 (9)	C27—C21—C22	126.0 (3)
O12—Pd—O22	178.83 (8)	C24—C23—C22	130.6 (3)
C12—O12—Pd	113.36 (18)	C24—C23—H23	114.7
C22—O22—Pd	113.81 (18)	C22—C23—H23	114.7
C21—O21—Pd	112.42 (18)	C25—C24—C23	129.2 (3)
C11—O11—Pd	112.84 (19)	C25—C24—H24	115.4
O22—C22—C23	117.4 (3)	C23—C24—H24	115.4
O22—C22—C21	116.0 (3)	C25—C26—C27	129.3 (3)
C23—C22—C21	126.6 (3)	C25—C26—H26	115.3
O11—C11—C17	118.2 (3)	C27—C26—H26	115.3
O11—C11—C12	116.0 (3)	C15—C14—C13	129.5 (3)
C17—C11—C12	125.8 (3)	C15—C14—H14	115.2
C24—C25—C26	127.7 (3)	C13—C14—H14	115.2
C24—C25—H25	116.1	C14—C15—C16	127.3 (3)
C26—C25—H25	116.1	C14—C15—H15	116.4
C16—C17—C11	130.8 (3)	C16—C15—H15	116.4
C16—C17—H17	114.6	C17—C16—C15	129.6 (3)
C11—C17—H17	114.6	C17—C16—H16	115.2
O12—C12—C13	117.9 (3)	C15—C16—H16	115.2
O12—C12—C11	115.9 (3)	C14—C13—C12	130.7 (3)
C13—C12—C11	126.3 (3)	C14—C13—H13	114.7
C21—C27—C26	130.7 (3)	C12—C13—H13	114.7
O11—Pd—O12—C12	−2.8 (2)	Pd—O21—C21—C27	−178.6 (2)
O21—Pd—O12—C12	178.5 (2)	Pd—O21—C21—C22	1.8 (3)
O11—Pd—O22—C22	−179.44 (19)	C26—C27—C21—O21	−177.9 (3)
O21—Pd—O22—C22	−0.7 (2)	C26—C27—C21—C22	1.6 (6)
O22—Pd—O21—C21	−0.7 (2)	O21—C21—C22—O22	−2.6 (4)
O12—Pd—O21—C21	179.6 (2)	C23—C22—C21—O21	178.4 (3)
O22—Pd—O11—C11	−176.9 (2)	O22—C22—C21—C27	177.9 (3)
O12—Pd—O11—C11	2.8 (2)	C23—C22—C21—C27	−1.1 (5)
Pd—O22—C22—C23	−179.0 (2)	O22—C22—C23—C24	−179.2 (3)
Pd—O22—C22—C21	1.9 (3)	C21—C22—C23—C24	−0.2 (5)
Pd—O11—C11—C17	177.3 (2)	C13—C14—C15—C16	−1.5 (7)
Pd—O11—C11—C12	−2.4 (3)	C23—C24—C25—C26	0.5 (6)
O11—C11—C17—C16	178.9 (4)	C22—C23—C24—C25	0.5 (6)
C12—C11—C17—C16	−1.4 (6)	C24—C25—C26—C27	−0.8 (6)
Pd—O12—C12—C13	−177.0 (2)	C21—C27—C26—C25	−0.4 (6)
Pd—O12—C12—C11	2.3 (3)	C11—C17—C16—C15	0.4 (7)
O11—C11—C12—O12	0.1 (4)	C14—C15—C16—C17	1.8 (7)
C17—C11—C12—O12	−179.6 (3)	C15—C14—C13—C12	−1.1 (6)
O11—C11—C12—C13	179.3 (3)	O12—C12—C13—C14	−178.5 (3)
C17—C11—C12—C13	−0.4 (5)	C11—C12—C13—C14	2.3 (5)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C23—H23···O12^i	0.93	2.47	3.342 (4)	156
C13—H13···O22^ii	0.93	2.48	3.378 (4)	162

Symmetry codes: (i) x+1, y, z; (ii) x−1, y, z.