(IUCr) Crystallography Journals Online

Abstract top

In the title compound, [NH₃(CH₂)₅NH₃][PdCl₄], the square-planar [PdCl₄]^2- anions are centrosymmetric while the diammonium cation lies in a general position. In addition to electrostatic interactions, the two species are linked through N-HCl hydrogen bonds to form a three-dimensional network.

Comment top

Extensive studies have been carried out on the crystal structures, phase transitions and physical properties of two-dimensional perovskite-like compounds of the families (C_nH_2n+1NH₃)₂MX₄ and [NH₃-(CH₂)_n-NH₃]MX₄, where X represents a halogen atom and M is a divalent metal. A few tetrachloropalladate compounds of these families have been structurally characterized: (C₃H₇NH₃)₂ [PdC1₄] (Willett & Willett, 1977), [NH₃-(CH₂)₂-NH₃][PdC1₄] (Berg & Søtofte, 1976) and [NH₃-(CH₂)₄-NH₃][PdC1₄] (Maris et al., 1996). We report here the crystal structure, determined at room temperature, of the title palladium-chloride compound [NH₃-(CH₂)₅-NH₃][PdCl₄] (I).

The asymmetric unit of (I) contains one cation in general position and two distinct half [PdCl₄]^2- units (Fig. 1). The Pd atoms lie on inversion centers and display a square-planar coordination environment with four Cl^- ligands. The Pd—Cl distances range from 2.3129 (4) to 2.3207 (6) Å (Table 1). The [PdCl₄] moieties pack via longer Pd—Cl contacts (3.0244 (9) and 3.1788 (9) Å) to form puckered two-dimensional layers in the (a,b) plane. The cations are located between these layers and the whole crystallographic organization can be described as a succession of organic and inorganic layers. The diammonium chain adopts a left-handed conformation at one end with a terminal C—C—C—N torsion angles of 67.86 (12)°. The whole chain makes an angle of 83.55 (3)° with the palladium layer.

The link between the two moieties and the crystal packing is achieved by several hydrogen bonds involving the H atoms of the ammonium groups and the Cl atoms. The three shortest hydrogen bonds (Fig. 2) show a pattern similar to the hydrogen bond scheme found in the tetrachloro and tetrabromocuprate(II) analogues. (Garland et al. 1990). Additional contacts (Table 2) with longer hydrogen chlorine distances and more acute N—H···Cl angles are also present.

Pentane-1,5-diammonium tetrachloridopalladate(II) top

Crystal data top

(C₅H₁₆N₂)[PdCl₄]	F₀₀₀ = 696
M_r = 352.40	D_x = 1.928 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 25 reflections
a = 8.091 (2) Å	θ = 7.5–16.8º
b = 7.276 (2) Å	µ = 2.37 mm⁻¹
c = 20.843 (5) Å	T = 298 K
β = 98.279 (2)º	Plate, dark red
V = 1214.2 (5) Å³	0.19 × 0.15 × 0.08 mm
Z = 4

Data collection top

Enraf–Nonius CAD-4 diffractometer	R_int = 0.025
Radiation source: fine-focus sealed tube	θ_max = 27.4º
Monochromator: graphite	θ_min = 2.0º
T = 298 K	h = −10→10
ω/2θ scans	k = 0→9
Absorption correction: integration (Blessing; 1989)	l = 0→26
T_min = 0.662, T_max = 0.833	5 standard reflections
2816 measured reflections	every 60 min
2783 independent reflections	intensity decay: none
2771 reflections with I > 2σ(I)

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.036	H-atom parameters constrained
wR(F²) = 0.089	w = 1/[σ²(F_o²) + (0.0883P)²] where P = (F_o² + 2F_c²)/3
S = 0.99	(Δ/σ)_max = 0.003
2783 reflections	Δρ_max = 0.74 e Å⁻³
112 parameters	Δρ_min = −0.68 e Å⁻³
Primary atom site location: structure-invariant direct methods	Extinction correction: none

Crystal data top

(C₅H₁₆N₂)[PdCl₄]	V = 1214.2 (5) Å³
M_r = 352.40	Z = 4
Monoclinic, P2₁/c	Mo Kα
a = 8.091 (2) Å	µ = 2.37 mm⁻¹
b = 7.276 (2) Å	T = 298 K
c = 20.843 (5) Å	0.19 × 0.15 × 0.08 mm
β = 98.279 (2)º

Data collection top

Enraf–Nonius CAD-4 diffractometer	2771 reflections with I > 2σ(I)
Absorption correction: integration (Blessing; 1989)	R_int = 0.025
T_min = 0.662, T_max = 0.833	5 standard reflections
2816 measured reflections	every 60 min
2783 independent reflections	intensity decay: none

Refinement top

R[F² > 2σ(F²)] = 0.036	112 parameters
wR(F²) = 0.089	H-atom parameters constrained
S = 0.99	Δρ_max = 0.74 e Å⁻³
2783 reflections	Δρ_min = −0.68 e Å⁻³

Special details top

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 > 2σ(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.

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 > 2σ(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 (Å²) top

	x	y	z	U_iso*/U_eq
Pd1	0.0000	0.0000	0.0000	0.01948 (10)
Cl1	0.09323 (3)	0.01856 (2)	0.110313 (8)	0.03247 (10)
Cl2	−0.195673 (16)	−0.21942 (2)	0.017283 (7)	0.02727 (10)
Pd2	0.5000	0.5000	0.0000	0.01998 (10)
Cl3	0.711649 (16)	0.285055 (19)	0.022152 (8)	0.02908 (10)
Cl4	0.51179 (2)	0.46485 (3)	−0.109913 (8)	0.03058 (10)
N1	0.07248 (18)	0.49394 (9)	0.10015 (5)	0.0386 (2)
H1A	0.0198	0.5472	0.0645	0.058*
H1B	0.0736	0.3727	0.0945	0.058*
H1C	0.1769	0.5355	0.1080	0.058*
C2	−0.01184 (11)	0.53613 (14)	0.15356 (5)	0.03569 (19)
H2A	−0.1260	0.4924	0.1441	0.043*
H2B	−0.0157	0.6686	0.1583	0.043*
C3	0.06862 (13)	0.45279 (14)	0.21793 (4)	0.0467 (2)
H3A	−0.0062	0.4706	0.2498	0.056*
H3B	0.0809	0.3215	0.2121	0.056*
C4	0.23397 (14)	0.5307 (2)	0.24383 (5)	0.0461 (3)
H4A	0.2259	0.6637	0.2437	0.055*
H4B	0.3137	0.4964	0.2154	0.055*
C5	0.29934 (12)	0.46619 (13)	0.31257 (4)	0.04003 (19)
H5A	0.2217	0.5039	0.3415	0.048*
H5B	0.3047	0.3330	0.3132	0.048*
C6	0.46483 (13)	0.54043 (14)	0.33643 (4)	0.0408 (2)
H6A	0.4639	0.6727	0.3306	0.049*
H6B	0.5461	0.4890	0.3115	0.049*
N7	0.51365 (16)	0.49611 (10)	0.40599 (6)	0.0420 (2)
H7A	0.6148	0.5415	0.4195	0.063*
H7B	0.5151	0.3747	0.4112	0.063*
H7C	0.4403	0.5456	0.4289	0.063*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Pd1	0.01015 (15)	0.01755 (17)	0.03049 (14)	−0.00113 (1)	0.00208 (12)	−0.00208 (2)
Cl1	0.02387 (16)	0.04333 (16)	0.02952 (15)	−0.00249 (6)	0.00153 (11)	0.00146 (5)
Cl2	0.01297 (15)	0.02395 (15)	0.04395 (15)	−0.00589 (4)	0.00088 (10)	0.00250 (5)
Pd2	0.01077 (15)	0.01766 (17)	0.03179 (14)	0.00019 (1)	0.00401 (12)	−0.00195 (2)
Cl3	0.01415 (15)	0.02303 (15)	0.04964 (15)	0.00526 (5)	0.00317 (10)	−0.00050 (5)
Cl4	0.02803 (16)	0.03239 (15)	0.03202 (15)	−0.00018 (7)	0.00674 (10)	0.00025 (5)
N1	0.0377 (5)	0.0413 (5)	0.0359 (4)	−0.0059 (2)	0.0023 (4)	−0.0095 (2)
C2	0.0383 (5)	0.0295 (3)	0.0379 (4)	0.0061 (3)	0.0008 (3)	−0.0068 (3)
C3	0.0466 (5)	0.0525 (5)	0.0396 (4)	−0.0105 (4)	0.0016 (3)	0.0077 (4)
C4	0.0370 (5)	0.0562 (5)	0.0433 (5)	−0.0005 (4)	−0.0005 (4)	0.0053 (4)
C5	0.0324 (5)	0.0496 (4)	0.0390 (4)	−0.0051 (3)	0.0082 (3)	0.0042 (3)
C6	0.0456 (5)	0.0268 (3)	0.0465 (4)	−0.0104 (4)	−0.0055 (4)	0.0088 (3)
N7	0.0300 (5)	0.0518 (5)	0.0443 (5)	−0.0080 (2)	0.0057 (5)	0.0125 (3)

Geometric parameters (Å, °) top

Pd1—Cl2	2.3129 (4)	C3—C4	1.4814 (13)
Pd1—Cl2ⁱ	2.3129 (4)	C3—H3A	0.9700
Pd1—Cl1	2.3183 (6)	C3—H3B	0.9700
Pd1—Cl1ⁱ	2.3183 (6)	C4—C5	1.5279 (16)
Pd2—Cl3ⁱⁱ	2.3160 (4)	C4—H4A	0.9700
Pd2—Cl3	2.3160 (4)	C4—H4B	0.9700
Pd2—Cl4	2.3207 (6)	C5—C6	1.4629 (13)
Pd2—Cl4ⁱⁱ	2.3207 (6)	C5—H5A	0.9700
N1—C2	1.4205 (14)	C5—H5B	0.9700
N1—H1A	0.8900	C6—N7	1.4822 (14)
N1—H1B	0.8900	C6—H6A	0.9700
N1—H1C	0.8900	C6—H6B	0.9700
C2—C3	1.5298 (13)	N7—H7A	0.8900
C2—H2A	0.9700	N7—H7B	0.8900
C2—H2B	0.9700	N7—H7C	0.8900

Pd1···Cl3ⁱⁱⁱ	3.2044 (9)	Pd2···Cl2^v	3.1788 (9)
Pd1···Cl3^iv	3.2044 (9)	Pd2···Cl2^vi	3.1789 (9)

Cl2—Pd1—Cl2ⁱ	180.0	C4—C3—H3B	108.6
Cl2—Pd1—Cl1	91.031 (9)	C2—C3—H3B	108.6
Cl2ⁱ—Pd1—Cl1	88.970 (10)	H3A—C3—H3B	107.6
Cl2—Pd1—Cl1ⁱ	88.969 (10)	C3—C4—C5	113.37 (10)
Cl2ⁱ—Pd1—Cl1ⁱ	91.030 (10)	C3—C4—H4A	108.9
Cl1—Pd1—Cl1ⁱ	180.000 (3)	C5—C4—H4A	108.9
Cl3ⁱⁱ—Pd2—Cl3	180.0	C3—C4—H4B	108.9
Cl3ⁱⁱ—Pd2—Cl4	90.681 (8)	C5—C4—H4B	108.9
Cl3—Pd2—Cl4	89.317 (8)	H4A—C4—H4B	107.7
Cl3ⁱⁱ—Pd2—Cl4ⁱⁱ	89.320 (9)	C6—C5—C4	112.44 (8)
Cl3—Pd2—Cl4ⁱⁱ	90.682 (8)	C6—C5—H5A	109.1
Cl4—Pd2—Cl4ⁱⁱ	180.0	C4—C5—H5A	109.1
C2—N1—H1A	109.5	C6—C5—H5B	109.1
C2—N1—H1B	109.5	C4—C5—H5B	109.1
H1A—N1—H1B	109.5	H5A—C5—H5B	107.8
C2—N1—H1C	109.5	C5—C6—N7	110.74 (8)
H1A—N1—H1C	109.5	C5—C6—H6A	109.5
H1B—N1—H1C	109.5	N7—C6—H6A	109.5
N1—C2—C3	114.20 (9)	C5—C6—H6B	109.5
N1—C2—H2A	108.7	N7—C6—H6B	109.5
C3—C2—H2A	108.7	H6A—C6—H6B	108.1
N1—C2—H2B	108.7	C6—N7—H7A	109.5
C3—C2—H2B	108.7	C6—N7—H7B	109.5
H2A—C2—H2B	107.6	H7A—N7—H7B	109.5
C4—C3—C2	114.57 (9)	C6—N7—H7C	109.5
C4—C3—H3A	108.6	H7A—N7—H7C	109.5
C2—C3—H3A	108.6	H7B—N7—H7C	109.5

N1—C2—C3—C4	67.86 (12)	C3—C4—C5—C6	178.30 (9)
C2—C3—C4—C5	171.37 (9)	C4—C5—C6—N7	172.18 (9)

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

Hydrogen-bond geometry (Å, °) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1B···Cl2ⁱ	0.89	2.88	3.4171 (11)	120
N1—H1C···Cl4ⁱⁱ	0.89	2.51	3.3539 (17)	158
N1—H1A···Cl2^vii	0.89	2.53	3.3107 (13)	147
N1—H1B···Cl1	0.89	2.60	3.4680 (12)	165
N7—H7A···Cl1^viii	0.89	2.53	3.2512 (15)	138
N7—H7B···Cl4^ix	0.89	2.51	3.3702 (12)	163
N7—H7C···Cl3^viii	0.89	2.44	3.2821 (13)	158
N7—H7A···Cl2^x	0.89	2.70	3.4614 (13)	145
N7—H7B···Cl3^ix	0.89	2.86	3.3907 (11)	120

Symmetry codes: (i) −x, −y, −z; (ii) −x+1, −y+1, −z; (vii) x, y+1, z; (viii) −x+1, y+1/2, −z+1/2; (ix) x, −y+1/2, z+1/2; (x) x+1, −y+1/2, z+1/2.

Table 1
Selected geometric parameters (Å) top

Pd1—Cl2	2.3129 (4)	C2—C3	1.5298 (13)
Pd1—Cl1	2.3183 (6)	C3—C4	1.4814 (13)
Pd2—Cl3	2.3160 (4)	C4—C5	1.5279 (16)
Pd2—Cl4	2.3207 (6)	C5—C6	1.4629 (13)
N1—C2	1.4205 (14)	C6—N7	1.4822 (14)

Table 2
Hydrogen-bond geometry (Å, °) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1B···Cl2ⁱ	0.89	2.88	3.4171 (11)	120
N1—H1C···Cl4ⁱⁱ	0.89	2.51	3.3539 (17)	158
N1—H1A···Cl2ⁱⁱⁱ	0.89	2.53	3.3107 (13)	147
N1—H1B···Cl1	0.89	2.60	3.4680 (12)	165
N7—H7A···Cl1^iv	0.89	2.53	3.2512 (15)	138
N7—H7B···Cl4^v	0.89	2.51	3.3702 (12)	163
N7—H7C···Cl3^iv	0.89	2.44	3.2821 (13)	158
N7—H7A···Cl2^vi	0.89	2.70	3.4614 (13)	145
N7—H7B···Cl3^v	0.89	2.86	3.3907 (11)	120

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

supplementary materials

Pentane-1,5-diammonium tetrachloridopalladate(II)

T. Maris

	Fig. 1. The structure of (I) with thermal ellipsoids shown at the 50% probability level. Symmetry codes: (i) -x, -y, -z; (ii) 1 - x, 1 - y, -z.
	Fig. 2. Packing diagram showing the shortest N—H···Cl hydrogen bond interactions as dashed lines. Symmetry codes: (ii) 1 - x, 1 - y, -z; (iii) x, y + 1, z; (iv) 1 - x, y + 1/2, 1/2 - z; (v) x, 1/2 - y, 1/2 + z.