[4'-(4-Amino-phen-yl)-2,2':6',2''-terpyridine]-chloridopalladium(II) chloride.

The Pd(II) atom in the complex cation of the title compound, [PdCl(C(21)H(16)N(4))]Cl, is coordinated by three N atoms derived from the terpyridine ligand and a chloride ion, which define a distorted PdClN(3) square-planar coordination geometry. In the crystal, the presence of N-H⋯Cl hydrogen bonds involving the amino H atom and chloride anions link two cations and two anions into a four-ion aggregate via centrosymmetric eight-membered [⋯H-N-H⋯Cl](2) synthons. Layers of cations are inter-spersed with the chloride anions with stabilization provided by C-H⋯Cl inter-actions involving both Cl atoms, as well as π-π inter-actions [the closest inter-action of 3.489 (6) Å occurs between a chelate ring and a pyridyl residue].

Related literature

For background to metal–n class="Chemical">terpyridine complexes, see: Storrier et al. (1997 ▶); Hofmeier & Schubert (2004 ▶); Eryazici et al. (2008 ▶). For the synthesis, see: Tu et al. (2007 ▶); Laine et al. (2002 ▶).

Experimental

Crystal data

[PdCl(n class="CellLine">C21H16N4)]Cl

M = 501.68

Monoclinic,

a = 10.853 (3) Å

b = 13.151 (3) Å

c = 13.654 (3) Å

β = 105.215 (6)°

V = 1880.5 (7) Å3

Z = 4

Mo Kα radiation

μ = 1.29 mm−1

T = 98 K

0.10 × 0.04 × 0.04 mm

Data collection

Rigaku AFC12/SATURN724 diffractometer

Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ▶) T min = 0.412, T max = 1

15599 measured reflections

3296 independent reflections

2809 reflections with I > 2σ(I)

R int = 0.079

Refinement

R[F 2 > 2σ(F 2)] = 0.098

wR(F 2) = 0.239

S = 1.16

3296 reflections

259 parameters

3 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 3.59 e Å−3

Δρmin = −2.15 e Å−3

Data collection: CrystalClear (Molecular Structure Corporation & Rigaku, 2005 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: PATTY in DIRDIF (Beurskens et al., 1992 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶) and DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811018125/hb5880sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811018125/hb5880Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[PdCl(C21H16N4)]Cl	F(000) = 1000
Mr = 501.68	Dx = 1.772 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71070 Å
Hall symbol: -P 2yn	Cell parameters from 7657 reflections
a = 10.853 (3) Å	θ = 2.1–30.3°
b = 13.151 (3) Å	µ = 1.29 mm−1
c = 13.654 (3) Å	T = 98 K
β = 105.215 (6)°	Prism, red
V = 1880.5 (7) Å3	0.10 × 0.04 × 0.04 mm
Z = 4

Rigaku AFC12/SATURN724 diffractometer	3296 independent reflections
Radiation source: fine-focus sealed tube	2809 reflections with I > 2σ(I)
graphite	Rint = 0.079
ω scans	θmax = 25.0°, θmin = 2.1°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −12→11
Tmin = 0.412, Tmax = 1	k = −15→15
15599 measured reflections	l = −16→16

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.098	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.239	H atoms treated by a mixture of independent and constrained refinement
S = 1.16	w = 1/[σ2(Fo2) + (0.094P)2 + 20.7984P] where P = (Fo2 + 2Fc2)/3
3296 reflections	(Δ/σ)max < 0.001
259 parameters	Δρmax = 3.59 e Å−3
3 restraints	Δρmin = −2.15 e Å−3

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.

	x	y	z	Uiso*/Ueq
Pd	0.52238 (8)	0.61084 (7)	−0.12448 (6)	0.0406 (4)
Cl1	0.3256 (3)	0.6393 (3)	−0.2332 (2)	0.0602 (9)
Cl2	1.5657 (3)	0.6930 (2)	0.4574 (2)	0.0521 (8)
N1	0.5776 (9)	0.7570 (7)	−0.0888 (7)	0.042 (2)
N2	0.6866 (8)	0.5872 (7)	−0.0316 (6)	0.037 (2)
N3	0.5215 (8)	0.4571 (7)	−0.1273 (6)	0.038 (2)
N4	1.4174 (9)	0.4831 (8)	0.3621 (7)	0.044 (2)
H1N	1.469 (9)	0.534 (5)	0.387 (7)	0.053*
H2N	1.428 (11)	0.435 (5)	0.408 (6)	0.053*
C1	0.5076 (12)	0.8421 (10)	−0.1202 (9)	0.051 (3)
H1	0.4249	0.8365	−0.1656	0.061*
C2	0.5559 (14)	0.9367 (9)	−0.0865 (10)	0.053 (3)
H2	0.5049	0.9954	−0.1074	0.063*
C3	0.6765 (15)	0.9472 (10)	−0.0233 (10)	0.057 (4)
H3	0.7108	1.0125	−0.0021	0.068*
C4	0.7472 (13)	0.8592 (8)	0.0090 (9)	0.047 (3)
H4	0.8303	0.8637	0.0539	0.056*
C5	0.6961 (11)	0.7660 (8)	−0.0245 (8)	0.040 (3)
C6	0.7595 (11)	0.6664 (8)	0.0078 (8)	0.037 (2)
C7	0.8789 (11)	0.6510 (8)	0.0711 (8)	0.038 (3)
H7	0.9300	0.7078	0.0993	0.045*
C8	0.9263 (10)	0.5522 (7)	0.0949 (8)	0.033 (2)
C9	0.8437 (10)	0.4710 (8)	0.0530 (7)	0.032 (2)
H9	0.8708	0.4029	0.0690	0.038*
C10	0.7247 (10)	0.4895 (8)	−0.0106 (8)	0.035 (2)
C11	0.6283 (9)	0.4156 (8)	−0.0622 (8)	0.033 (2)
C12	0.4354 (10)	0.3957 (10)	−0.1824 (8)	0.043 (3)
H12	0.3622	0.4250	−0.2275	0.052*
C13	0.4449 (11)	0.2911 (11)	−0.1785 (9)	0.051 (3)
H13	0.3806	0.2501	−0.2211	0.061*
C14	0.5489 (11)	0.2470 (9)	−0.1120 (8)	0.043 (3)
H14	0.5565	0.1751	−0.1065	0.052*
C15	0.6434 (10)	0.3105 (9)	−0.0527 (8)	0.038 (3)
H15	0.7166	0.2822	−0.0067	0.046*
C16	1.0522 (11)	0.5334 (8)	0.1615 (8)	0.036 (2)
C17	1.0953 (11)	0.4342 (8)	0.1970 (8)	0.037 (2)
H17	1.0409	0.3775	0.1750	0.045*
C18	1.2149 (10)	0.4190 (8)	0.2630 (8)	0.036 (2)
H18	1.2403	0.3521	0.2860	0.044*
C19	1.2991 (10)	0.5001 (9)	0.2966 (8)	0.038 (3)
C20	1.2611 (10)	0.5949 (8)	0.2590 (8)	0.033 (2)
H20	1.3183	0.6504	0.2784	0.040*
C21	1.1426 (10)	0.6120 (8)	0.1938 (8)	0.035 (2)
H21	1.1208	0.6791	0.1697	0.042*

	U11	U22	U33	U12	U13	U23
Pd	0.0386 (6)	0.0509 (6)	0.0318 (5)	0.0157 (4)	0.0086 (4)	0.0086 (4)
Cl1	0.0460 (18)	0.086 (2)	0.0437 (17)	0.0276 (17)	0.0025 (14)	0.0096 (16)
Cl2	0.0496 (17)	0.0452 (16)	0.0528 (18)	−0.0137 (13)	−0.0019 (14)	−0.0005 (13)
N1	0.056 (6)	0.044 (5)	0.031 (5)	0.020 (5)	0.023 (5)	0.012 (4)
N2	0.034 (5)	0.045 (5)	0.033 (5)	0.012 (4)	0.011 (4)	0.014 (4)
N3	0.032 (5)	0.053 (6)	0.030 (5)	−0.005 (4)	0.009 (4)	0.000 (4)
N4	0.036 (5)	0.057 (6)	0.035 (5)	−0.011 (5)	0.000 (4)	−0.008 (5)
C1	0.053 (7)	0.062 (8)	0.041 (7)	0.012 (6)	0.021 (6)	0.011 (6)
C2	0.079 (10)	0.037 (7)	0.051 (7)	0.012 (6)	0.033 (7)	0.006 (6)
C3	0.083 (10)	0.040 (7)	0.057 (8)	0.018 (6)	0.035 (8)	0.015 (6)
C4	0.073 (9)	0.035 (6)	0.036 (6)	0.014 (6)	0.021 (6)	0.000 (5)
C5	0.047 (7)	0.045 (6)	0.029 (6)	0.019 (5)	0.013 (5)	0.006 (5)
C6	0.051 (7)	0.033 (6)	0.033 (6)	0.005 (5)	0.023 (5)	0.006 (5)
C7	0.049 (7)	0.036 (6)	0.033 (6)	0.011 (5)	0.021 (5)	0.008 (5)
C8	0.038 (6)	0.024 (5)	0.038 (6)	−0.003 (4)	0.011 (5)	−0.002 (4)
C9	0.038 (6)	0.031 (5)	0.027 (5)	0.007 (4)	0.010 (5)	0.006 (4)
C10	0.039 (6)	0.031 (5)	0.032 (5)	0.006 (4)	0.006 (5)	0.007 (4)
C11	0.018 (5)	0.045 (6)	0.034 (6)	0.007 (4)	0.005 (4)	0.006 (5)
C12	0.029 (6)	0.065 (8)	0.035 (6)	0.001 (5)	0.009 (5)	0.001 (6)
C13	0.029 (6)	0.074 (9)	0.043 (7)	−0.009 (6)	0.000 (5)	−0.011 (6)
C14	0.041 (7)	0.052 (7)	0.038 (6)	−0.014 (5)	0.013 (6)	−0.010 (5)
C15	0.026 (5)	0.058 (7)	0.034 (6)	0.002 (5)	0.012 (5)	−0.001 (5)
C16	0.051 (7)	0.031 (5)	0.031 (5)	−0.003 (5)	0.021 (5)	−0.006 (4)
C17	0.046 (7)	0.034 (5)	0.031 (5)	−0.006 (5)	0.008 (5)	−0.007 (5)
C18	0.032 (6)	0.036 (6)	0.036 (6)	0.000 (5)	−0.001 (5)	−0.002 (5)
C19	0.042 (6)	0.049 (7)	0.026 (5)	0.002 (5)	0.010 (5)	−0.017 (5)
C20	0.036 (6)	0.031 (5)	0.030 (5)	−0.016 (4)	0.005 (5)	−0.006 (4)
C21	0.040 (6)	0.034 (6)	0.034 (6)	−0.008 (4)	0.014 (5)	0.000 (4)

Pd—N1	2.034 (10)	C7—H7	0.9500
Pd—N2	1.922 (9)	C8—C9	1.414 (14)
Pd—N3	2.022 (10)	C8—C16	1.451 (16)
Pd—Cl1	2.290 (3)	C9—C10	1.376 (15)
N1—C1	1.357 (15)	C9—H9	0.9500
N1—C5	1.359 (15)	C10—C11	1.466 (15)
N2—C6	1.333 (14)	C11—C15	1.395 (15)
N2—C10	1.357 (13)	C12—C13	1.379 (17)
N3—C12	1.312 (14)	C12—H12	0.9500
N3—C11	1.375 (13)	C13—C14	1.378 (17)
N4—C19	1.377 (14)	C13—H13	0.9500
N4—H1N	0.8800 (11)	C14—C15	1.403 (15)
N4—H2N	0.8800 (10)	C14—H14	0.9500
C1—C2	1.382 (19)	C15—H15	0.9500
C1—H1	0.9500	C16—C21	1.414 (14)
C2—C3	1.37 (2)	C16—C17	1.426 (15)
C2—H2	0.9500	C17—C18	1.387 (15)
C3—C4	1.394 (17)	C17—H17	0.9500
C3—H3	0.9500	C18—C19	1.401 (15)
C4—C5	1.374 (17)	C18—H18	0.9500
C4—H4	0.9500	C19—C20	1.370 (15)
C5—C6	1.492 (15)	C20—C21	1.377 (15)
C6—C7	1.371 (16)	C20—H20	0.9500
C7—C8	1.404 (15)	C21—H21	0.9500
N2—Pd—N3	81.3 (4)	C9—C8—C16	121.2 (9)
N2—Pd—N1	80.3 (4)	C10—C9—C8	120.8 (9)
N3—Pd—N1	161.6 (4)	C10—C9—H9	119.6
N2—Pd—Cl1	179.2 (3)	C8—C9—H9	119.6
N3—Pd—Cl1	98.8 (3)	N2—C10—C9	119.0 (10)
N1—Pd—Cl1	99.6 (3)	N2—C10—C11	112.7 (9)
C1—N1—C5	119.3 (11)	C9—C10—C11	128.3 (9)
C1—N1—Pd	126.7 (9)	N3—C11—C15	120.8 (10)
C5—N1—Pd	114.0 (7)	N3—C11—C10	115.0 (9)
C6—N2—C10	122.6 (9)	C15—C11—C10	124.1 (9)
C6—N2—Pd	119.3 (7)	N3—C12—C13	123.8 (11)
C10—N2—Pd	118.1 (8)	N3—C12—H12	118.1
C12—N3—C11	118.6 (10)	C13—C12—H12	118.1
C12—N3—Pd	128.7 (8)	C14—C13—C12	119.0 (11)
C11—N3—Pd	112.7 (7)	C14—C13—H13	120.5
C19—N4—H1N	121 (7)	C12—C13—H13	120.5
C19—N4—H2N	121 (7)	C13—C14—C15	118.6 (12)
H1N—N4—H2N	109 (8)	C13—C14—H14	120.7
N1—C1—C2	120.3 (13)	C15—C14—H14	120.7
N1—C1—H1	119.8	C11—C15—C14	119.1 (10)
C2—C1—H1	119.8	C11—C15—H15	120.5
C3—C2—C1	121.1 (12)	C14—C15—H15	120.5
C3—C2—H2	119.5	C21—C16—C17	115.1 (10)
C1—C2—H2	119.5	C21—C16—C8	122.2 (9)
C2—C3—C4	118.0 (13)	C17—C16—C8	122.6 (9)
C2—C3—H3	121.0	C18—C17—C16	121.3 (10)
C4—C3—H3	121.0	C18—C17—H17	119.3
C5—C4—C3	119.7 (13)	C16—C17—H17	119.3
C5—C4—H4	120.2	C17—C18—C19	121.5 (10)
C3—C4—H4	120.2	C17—C18—H18	119.3
N1—C5—C4	121.6 (10)	C19—C18—H18	119.3
N1—C5—C6	113.5 (10)	C20—C19—N4	121.9 (10)
C4—C5—C6	124.8 (11)	C20—C19—C18	117.6 (10)
N2—C6—C7	120.1 (10)	N4—C19—C18	120.4 (10)
N2—C6—C5	112.8 (10)	C19—C20—C21	122.0 (9)
C7—C6—C5	127.1 (11)	C19—C20—H20	119.0
C6—C7—C8	120.7 (11)	C21—C20—H20	119.0
C6—C7—H7	119.6	C20—C21—C16	122.4 (10)
C8—C7—H7	119.6	C20—C21—H21	118.8
C7—C8—C9	116.8 (10)	C16—C21—H21	118.8
C7—C8—C16	122.0 (9)
N2—Pd—N1—C1	−176.1 (9)	C6—C7—C8—C16	179.9 (9)
N3—Pd—N1—C1	−173.8 (9)	C7—C8—C9—C10	2.2 (14)
Cl1—Pd—N1—C1	3.2 (9)	C16—C8—C9—C10	−179.6 (9)
N2—Pd—N1—C5	1.9 (7)	C6—N2—C10—C9	−0.7 (15)
N3—Pd—N1—C5	4.2 (15)	Pd—N2—C10—C9	177.8 (7)
Cl1—Pd—N1—C5	−178.8 (6)	C6—N2—C10—C11	179.7 (9)
N3—Pd—N2—C6	178.0 (8)	Pd—N2—C10—C11	−1.8 (11)
N1—Pd—N2—C6	−2.7 (7)	C8—C9—C10—N2	−0.9 (15)
N3—Pd—N2—C10	−0.5 (7)	C8—C9—C10—C11	178.6 (10)
N1—Pd—N2—C10	178.7 (8)	C12—N3—C11—C15	−1.7 (14)
N2—Pd—N3—C12	−176.4 (9)	Pd—N3—C11—C15	179.0 (7)
N1—Pd—N3—C12	−178.7 (9)	C12—N3—C11—C10	174.7 (9)
Cl1—Pd—N3—C12	4.4 (9)	Pd—N3—C11—C10	−4.6 (11)
N2—Pd—N3—C11	2.9 (7)	N2—C10—C11—N3	4.2 (13)
N1—Pd—N3—C11	0.6 (14)	C9—C10—C11—N3	−175.3 (9)
Cl1—Pd—N3—C11	−176.3 (6)	N2—C10—C11—C15	−179.5 (9)
C5—N1—C1—C2	−0.5 (15)	C9—C10—C11—C15	0.9 (17)
Pd—N1—C1—C2	177.4 (8)	C11—N3—C12—C13	0.4 (16)
N1—C1—C2—C3	1.9 (17)	Pd—N3—C12—C13	179.7 (8)
C1—C2—C3—C4	−2.3 (17)	N3—C12—C13—C14	1.4 (18)
C2—C3—C4—C5	1.3 (17)	C12—C13—C14—C15	−1.9 (17)
C1—N1—C5—C4	−0.5 (15)	N3—C11—C15—C14	1.1 (15)
Pd—N1—C5—C4	−178.7 (8)	C10—C11—C15—C14	−174.9 (9)
C1—N1—C5—C6	177.1 (9)	C13—C14—C15—C11	0.7 (15)
Pd—N1—C5—C6	−1.0 (11)	C7—C8—C16—C21	−10.2 (15)
C3—C4—C5—N1	0.1 (16)	C9—C8—C16—C21	171.7 (9)
C3—C4—C5—C6	−177.3 (10)	C7—C8—C16—C17	171.5 (9)
C10—N2—C6—C7	0.9 (15)	C9—C8—C16—C17	−6.6 (15)
Pd—N2—C6—C7	−177.6 (7)	C21—C16—C17—C18	3.5 (14)
C10—N2—C6—C5	−178.7 (9)	C8—C16—C17—C18	−178.1 (9)
Pd—N2—C6—C5	2.9 (11)	C16—C17—C18—C19	−0.8 (16)
N1—C5—C6—N2	−1.0 (12)	C17—C18—C19—C20	−2.4 (15)
C4—C5—C6—N2	176.5 (10)	C17—C18—C19—N4	−179.9 (9)
N1—C5—C6—C7	179.4 (9)	N4—C19—C20—C21	−179.8 (9)
C4—C5—C6—C7	−3.0 (17)	C18—C19—C20—C21	2.8 (15)
N2—C6—C7—C8	0.5 (15)	C19—C20—C21—C16	0.1 (16)
C5—C6—C7—C8	180.0 (9)	C17—C16—C21—C20	−3.2 (14)
C6—C7—C8—C9	−1.9 (14)	C8—C16—C21—C20	178.4 (9)

D—H···A	D—H	H···A	D···A	D—H···A
N4—H1n···Cl2	0.88 (9)	2.42 (7)	3.287 (11)	167 (8)
N4—H2n···Cl2i	0.88 (7)	2.48 (8)	3.352 (10)	173 (10)
C13—H13···Cl1ii	0.95	2.61	3.493 (14)	156
C15—H15···Cl2iii	0.95	2.56	3.449 (12)	155

Table 1

Selected bond lengths (Å)

Pd—N1	2.034 (10)
Pd—N2	1.922 (9)
Pd—N3	2.022 (10)
Pd—Cl1	2.290 (3)

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H1n⋯Cl2	0.88 (9)	2.42 (7)	3.287 (11)	167 (8)
N4—H2n⋯Cl2i	0.88 (7)	2.48 (8)	3.352 (10)	173 (10)
C13—H13⋯Cl1ii	0.95	2.61	3.493 (14)	156
C15—H15⋯Cl2iii	0.95	2.56	3.449 (12)	155

Symmetry codes: (i) ; (ii) ; (iii) .