Bis­(tetra­methyl­ammonium) tetra­chloro­palladate(II)

The structure of a room-temperature phase of bis­(tetra­methyl­ammonium) tetra­chloro­palladate(II), (C₄H₁₂N)₂[PdCl₄], is reported. All the H atoms were observed in a Fourier map. The presence of C—H...Cl hydrogen bonds, with H...Cl distances as short as 2.92 Å, was confirmed by vibrational spectroscopy. The symmetry of the cation and anion are and mmm, respectively.

Key indicators

• Single-crystal X-ray study
• T = 292 K
• Mean [sigma](Pd-Cl) = 0.001 Å
• R factor = 0.022
• wR factor = 0.075
• Data-to-parameter ratio = 40.1

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT063_ALERT_3_C Crystal Probably too Large for Beam Size .......       0.61 mm
PLAT242_ALERT_2_C Check Low    U(eq) as Compared to Neighbors ....        Pd1
PLAT480_ALERT_4_C Long H...A H-Bond Reported H1     ..  CL2     ..       3.03 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H2     ..  CL2     ..       3.14 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H3     ..  CL1     ..       2.92 Ang.
PLAT481_ALERT_4_C Long D...A H-Bond Reported C1     ..  CL2     ..       4.02 Ang.
PLAT601_ALERT_2_C Structure Contains Solvent Accessible VOIDS of .      48.00 A   3  

Alert level G
ABSTM02_ALERT_3_G  The ratio of expected to reported Tmax/Tmin(RR) is > 1.10
            Tmin and Tmax reported:      0.553     0.814
            Tmin and Tmax expected:      0.460     0.827
            RR =      1.221
            Please check that your absorption correction is appropriate.
REFLT03_ALERT_1_G ALERT: Expected hkl max differ from CIF values
           From the CIF: _diffrn_reflns_theta_max           40.47
           From the CIF: _reflns_number_total                962
           From the CIF: _diffrn_reflns_limit_ max hkl   12.   16.   15.
           From the CIF: _diffrn_reflns_limit_ min hkl  -12.  -16.    0.
           TEST1: Expected hkl limits for theta max
           Calculated maximum hkl   16.   16.   20.
           Calculated minimum hkl  -16.  -16.  -20.

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

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

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Computing details

Data collection: KM4B8 (Gałdecki et al., 1997); cell refinement: KM4B8; data reduction: JANA2000 (Petříček & Dusěk, 2000); program(s) used to solve structure: SIR97 (Cascarano et al., 1996); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

bis(tetramethylammonium) tetrachloropalladate(II)

Crystal data

(C4H12N)2[PdCl4]	Dx = 1.479 Mg m^−3
Mr = 396.49	Mo Kα radiation, λ = 0.71069 Å
Tetragonal, P42/mnm	Cell parameters from 46 reflections
Hall symbol: -P 4n 2n	θ = 10.4–14.0°
a = 8.8281 (10) Å	µ = 1.62 mm^−1
c = 11.4206 (10) Å	T = 292 K
V = 890.07 (16) Å^3	Plate, red
Z = 2	0.61 × 0.41 × 0.12 mm
F(000) = 400

Data collection

XCalibur (KUMA) diffractometer	639 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.039
Graphite monochromator	θmax = 40.5°, θmin = 2.9°
ω/2q scans	h = −12→12
Absorption correction: gaussian JANA2000 (Petříček, V. & Dušek, M., 2000)	k = −16→16
Tmin = 0.553, Tmax = 0.814	l = 0→15
5577 measured reflections	3 standard reflections every 100 reflections
962 independent reflections	intensity decay: 4.2%

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)] = 0.022	Hydrogen site location: difference Fourier map
wR(F^2) = 0.075	H-atom parameters constrained
S = 1.12	w = 1/[σ^2(Fo^2) + (0.0375P)^2 + 0.0815P] where P = (Fo^2 + 2Fc^2)/3
962 reflections	(Δ/σ)max < 0.001
24 parameters	Δρmax = 0.58 e Å^−3
0 restraints	Δρmin = −0.70 e Å^−3
9 constraints

Special details

Experimental. The sample was prepared about 10 years ago.

IR and Raman spectra were recorded on a FT–IR spectrometer Nicolet Magna 760 equipped with a Nicolet Nexus FT Raman module. The spectra were collected under following conditions: IR spectrum - fluorolube mull, 2 cm$^{{-1}$ resolution, 32 scans, Happ-Genzel apodization; Raman spectrum - polycrystalline sample in glass vial, 2 cm$}{-1}$ resolution, 512 scans, Happ-Genzel apodization, 260 mW N d:YVO4 laser excitation at 1064 nm.

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.

Extinction parameter if refined converged to 0.0000 (11).

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

	x	y	z	Uiso*/Ueq
Pd1	0.0000	0.0000	0.5000	0.04453 (13)
Cl1	0.0000	0.0000	0.70113 (11)	0.0688 (3)
Cl2	0.18511 (7)	0.18511 (7)	0.5000	0.0630 (2)
N1	0.0000	0.5000	0.2500	0.0505 (6)
C1	0.1211 (3)	0.5647 (3)	0.3257 (2)	0.0773 (6)
H1	0.1595	0.4873	0.3767	0.116*
H2	0.0801	0.6460	0.3716	0.116*
H3	0.2018	0.6025	0.2775	0.116*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Pd1	0.03364 (11)	0.03364 (11)	0.0663 (3)	0.00231 (12)	0.000	0.000
Cl1	0.0688 (4)	0.0688 (4)	0.0688 (6)	−0.0168 (4)	0.000	0.000
Cl2	0.0514 (3)	0.0514 (3)	0.0862 (6)	−0.0134 (4)	0.000	0.000
N1	0.0438 (8)	0.0438 (8)	0.0639 (18)	0.000	0.000	0.000
C1	0.0558 (11)	0.0837 (15)	0.0925 (16)	−0.0078 (11)	−0.0123 (11)	−0.0142 (14)

Geometric parameters (Å, º)

Pd1—Cl1	2.2971 (13)	N1—C1^iii	1.489 (2)
Pd1—Cl1^i	2.2971 (13)	N1—C1^iv	1.489 (2)
Pd1—Cl2^i	2.3110 (9)	C1—H1	0.9600
Pd1—Cl2	2.3110 (9)	C1—H2	0.9600
N1—C1	1.489 (2)	C1—H3	0.9600
N1—C1^ii	1.489 (2)
Cl1—Pd1—Cl1^i	180.0	C1—N1—C1^iv	109.0 (2)
Cl1—Pd1—Cl2^i	90.0	C1^ii—N1—C1^iv	109.70 (10)
Cl1^i—Pd1—Cl2^i	90.0	C1^iii—N1—C1^iv	109.70 (10)
Cl1—Pd1—Cl2	90.0	N1—C1—H1	109.5
Cl1^i—Pd1—Cl2	90.0	N1—C1—H2	109.5
Cl2^i—Pd1—Cl2	180.00 (4)	H1—C1—H2	109.5
C1—N1—C1^ii	109.70 (10)	N1—C1—H3	109.5
C1—N1—C1^iii	109.70 (10)	H1—C1—H3	109.5
C1^ii—N1—C1^iii	109.0 (2)	H2—C1—H3	109.5

Symmetry codes: (i) −x, −y, −z+1; (ii) y−1/2, −x+1/2, −z+1/2; (iii) −y+1/2, x+1/2, −z+1/2; (iv) −x, −y+1, z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···Cl2	0.96	3.03	3.939 (3)	160
C1—H2···Cl2^v	0.96	3.14	4.019 (3)	153
C1—H3···Cl1^vi	0.96	2.92	3.679 (3)	137

Symmetry codes: (v) −x, −y+1, −z+1; (vi) −y+1/2, x+1/2, z−1/2.