Dibromido(1,10-phenanthroline-κN,N')palladium(II).

In the title complex, [PdBr(2)(C(12)H(8)N(2))], the Pd(II) ion is four-coordinated in a slightly distorted square-planar environment by two N atoms of the chelating 1,10-phenanthroline ligand and two bromide ions. The complex displays numerous inter-molecular π-π inter-actions between adjacent six-membered rings, the shortest centroid-centroid distance being 3.680 (4) Å. The nearly planar [maximum deviation 0.143 (2) Å] mol-ecules stack in columns parallel to (101) with a Pd⋯Pd distance of 4.8466 (9) Å.

Related literature

For the syntheses of [PdX 2(phen)] complexes (phen = 1,10-phenanthroline; X = Cl, Br, I or SCN), see: Cheng et al. (1977 ▶). For the crystal structure of yellow [PtCl2(phen)] which is isotypic to the title complex, see: Grzesiak & Matzger (2007 ▶). For the crystal structures of related Pd-bipy complexes, [PdX 2(bipy)] (bipy = 2,2′-bipyridine; X = Cl, Br or I), see: Maekawa et al. (1991 ▶); Smeets et al. (1997 ▶); Ha (2009 ▶).

Experimental

Crystal data

[PdBr2(C12H8N2)]

M = 446.42

Monoclinic,

a = 9.9099 (6) Å

b = 17.4897 (10) Å

c = 7.2598 (4) Å

β = 109.106 (1)°

V = 1188.96 (12) Å3

Z = 4

Mo Kα radiation

μ = 8.26 mm−1

T = 200 K

0.22 × 0.06 × 0.04 mm

Data collection

Bruker SMART 1000 CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2000 ▶) T min = 0.420, T max = 0.719

8695 measured reflections

2933 independent reflections

1729 reflections with I > 2σ(I)

R int = 0.082

Refinement

R[F 2 > 2σ(F 2)] = 0.045

wR(F 2) = 0.091

S = 1.00

2933 reflections

154 parameters

H-atom parameters constrained

Δρmax = 1.37 e Å−3

Δρmin = −1.54 e Å−3

Data collection: SMART (Bruker, 2000 ▶); cell refinement: SAINT (Bruker, 2000 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶) and PLATON (Spek, 2009 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053680905168X/xu2703sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053680905168X/xu2703Isup2.hkl

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

[PdBr2(C12H8N2)]	F(000) = 840
Mr = 446.42	Dx = 2.494 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1837 reflections
a = 9.9099 (6) Å	θ = 2.3–28.2°
b = 17.4897 (10) Å	µ = 8.26 mm−1
c = 7.2598 (4) Å	T = 200 K
β = 109.106 (1)°	Needle, yellow
V = 1188.96 (12) Å3	0.22 × 0.06 × 0.04 mm
Z = 4

Bruker SMART 1000 CCD diffractometer	2933 independent reflections
Radiation source: fine-focus sealed tube	1729 reflections with I > 2σ(I)
graphite	Rint = 0.082
φ and ω scans	θmax = 28.3°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −13→12
Tmin = 0.420, Tmax = 0.719	k = −23→23
8695 measured reflections	l = −9→9

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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.091	H-atom parameters constrained
S = 1.00	w = 1/[σ2(Fo2) + (0.0152P)2] where P = (Fo2 + 2Fc2)/3
2933 reflections	(Δ/σ)max < 0.001
154 parameters	Δρmax = 1.37 e Å−3
0 restraints	Δρmin = −1.54 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
Pd1	0.70926 (6)	0.34181 (3)	−0.10593 (9)	0.02059 (16)
Br1	0.74510 (9)	0.47817 (4)	−0.08022 (13)	0.0299 (2)
Br2	0.46176 (9)	0.36087 (5)	−0.29008 (13)	0.0352 (2)
N1	0.6966 (7)	0.2243 (3)	−0.1180 (9)	0.0251 (15)
N2	0.9155 (6)	0.3173 (3)	0.0591 (8)	0.0172 (13)
C1	0.5885 (8)	0.1797 (4)	−0.2101 (11)	0.0285 (19)
H1	0.5012	0.2027	−0.2859	0.034*
C2	0.5963 (10)	0.1002 (4)	−0.2012 (12)	0.036 (2)
H2	0.5169	0.0698	−0.2723	0.043*
C3	0.7203 (9)	0.0668 (4)	−0.0885 (12)	0.033 (2)
H3	0.7257	0.0127	−0.0787	0.040*
C4	0.8411 (9)	0.1110 (4)	0.0142 (12)	0.0251 (19)
C5	0.9779 (9)	0.0822 (4)	0.1358 (12)	0.032 (2)
H5	0.9912	0.0286	0.1554	0.039*
C6	1.0848 (9)	0.1291 (4)	0.2199 (11)	0.0277 (19)
H6	1.1740	0.1079	0.2954	0.033*
C7	1.0718 (8)	0.2103 (4)	0.2022 (11)	0.0217 (17)
C8	1.1806 (8)	0.2624 (4)	0.2872 (11)	0.0249 (18)
H8	1.2718	0.2449	0.3664	0.030*
C9	1.1558 (8)	0.3383 (4)	0.2568 (12)	0.0297 (19)
H9	1.2298	0.3739	0.3152	0.036*
C10	1.0228 (8)	0.3643 (4)	0.1406 (11)	0.0226 (18)
H10	1.0085	0.4177	0.1190	0.027*
C11	0.9395 (7)	0.2402 (4)	0.0878 (10)	0.0167 (16)
C12	0.8238 (8)	0.1901 (4)	−0.0051 (10)	0.0188 (17)

	U11	U22	U33	U12	U13	U23
Pd1	0.0183 (3)	0.0196 (3)	0.0226 (3)	−0.0008 (3)	0.0051 (2)	0.0000 (3)
Br1	0.0289 (5)	0.0197 (4)	0.0388 (5)	0.0016 (4)	0.0078 (4)	0.0009 (4)
Br2	0.0193 (4)	0.0391 (5)	0.0408 (6)	0.0006 (4)	0.0013 (4)	0.0039 (4)
N1	0.026 (4)	0.026 (3)	0.026 (4)	−0.005 (3)	0.012 (3)	0.001 (3)
N2	0.014 (3)	0.016 (3)	0.018 (3)	−0.003 (3)	−0.001 (3)	0.001 (3)
C1	0.015 (4)	0.039 (5)	0.027 (5)	−0.007 (4)	0.001 (3)	−0.005 (4)
C2	0.046 (6)	0.032 (5)	0.029 (5)	−0.014 (5)	0.011 (4)	−0.008 (4)
C3	0.053 (6)	0.021 (4)	0.034 (5)	−0.010 (4)	0.024 (5)	−0.008 (4)
C4	0.038 (5)	0.014 (4)	0.030 (5)	−0.009 (4)	0.020 (4)	−0.003 (3)
C5	0.047 (6)	0.015 (4)	0.042 (6)	0.013 (4)	0.025 (5)	0.011 (4)
C6	0.032 (5)	0.028 (4)	0.026 (5)	0.007 (4)	0.012 (4)	0.011 (4)
C7	0.023 (4)	0.025 (4)	0.022 (4)	0.008 (4)	0.014 (4)	0.004 (4)
C8	0.014 (4)	0.033 (5)	0.024 (5)	0.005 (4)	0.001 (3)	0.004 (4)
C9	0.025 (5)	0.025 (4)	0.036 (5)	0.000 (4)	0.006 (4)	0.002 (4)
C10	0.024 (5)	0.019 (4)	0.026 (5)	−0.005 (3)	0.009 (4)	0.004 (3)
C11	0.012 (4)	0.025 (4)	0.016 (4)	−0.004 (3)	0.009 (3)	0.000 (3)
C12	0.020 (4)	0.018 (4)	0.018 (4)	0.000 (3)	0.007 (3)	0.001 (3)

Pd1—N1	2.059 (6)	C4—C12	1.395 (9)
Pd1—N2	2.048 (6)	C4—C5	1.445 (11)
Pd1—Br1	2.4095 (9)	C5—C6	1.321 (10)
Pd1—Br2	2.4016 (10)	C5—H5	0.9500
N1—C1	1.317 (9)	C6—C7	1.428 (9)
N1—C12	1.394 (9)	C6—H6	0.9500
N2—C10	1.321 (8)	C7—C8	1.392 (10)
N2—C11	1.373 (8)	C7—C11	1.404 (10)
C1—C2	1.392 (10)	C8—C9	1.355 (9)
C1—H1	0.9500	C8—H8	0.9500
C2—C3	1.365 (11)	C9—C10	1.388 (10)
C2—H2	0.9500	C9—H9	0.9500
C3—C4	1.414 (11)	C10—H10	0.9500
C3—H3	0.9500	C11—C12	1.426 (9)
N2—Pd1—N1	81.5 (2)	C6—C5—C4	121.0 (7)
N2—Pd1—Br2	175.30 (15)	C6—C5—H5	119.5
N1—Pd1—Br2	94.47 (19)	C4—C5—H5	119.5
N2—Pd1—Br1	93.91 (15)	C5—C6—C7	122.8 (8)
N1—Pd1—Br1	175.29 (19)	C5—C6—H6	118.6
Br2—Pd1—Br1	90.20 (3)	C7—C6—H6	118.6
C1—N1—C12	118.2 (6)	C8—C7—C11	117.1 (6)
C1—N1—Pd1	129.9 (6)	C8—C7—C6	125.3 (7)
C12—N1—Pd1	111.9 (5)	C11—C7—C6	117.6 (8)
C10—N2—C11	118.0 (6)	C9—C8—C7	119.8 (7)
C10—N2—Pd1	129.4 (5)	C9—C8—H8	120.1
C11—N2—Pd1	112.6 (4)	C7—C8—H8	120.1
N1—C1—C2	123.0 (8)	C8—C9—C10	120.4 (8)
N1—C1—H1	118.5	C8—C9—H9	119.8
C2—C1—H1	118.5	C10—C9—H9	119.8
C3—C2—C1	118.7 (8)	N2—C10—C9	122.2 (7)
C3—C2—H2	120.6	N2—C10—H10	118.9
C1—C2—H2	120.6	C9—C10—H10	118.9
C2—C3—C4	121.5 (7)	N2—C11—C7	122.5 (7)
C2—C3—H3	119.3	N2—C11—C12	117.3 (6)
C4—C3—H3	119.3	C7—C11—C12	120.1 (7)
C12—C4—C3	115.7 (8)	N1—C12—C4	122.8 (7)
C12—C4—C5	117.9 (7)	N1—C12—C11	116.6 (6)
C3—C4—C5	126.4 (7)	C4—C12—C11	120.6 (7)
N2—Pd1—N1—C1	−178.2 (7)	Pd1—N2—C10—C9	176.9 (5)
Br2—Pd1—N1—C1	4.2 (6)	C8—C9—C10—N2	1.3 (11)
N2—Pd1—N1—C12	3.5 (5)	C10—N2—C11—C7	1.2 (9)
Br2—Pd1—N1—C12	−174.1 (4)	Pd1—N2—C11—C7	−177.7 (5)
N1—Pd1—N2—C10	177.9 (6)	C10—N2—C11—C12	−178.5 (6)
Br1—Pd1—N2—C10	−1.2 (6)	Pd1—N2—C11—C12	2.6 (7)
N1—Pd1—N2—C11	−3.4 (5)	C8—C7—C11—N2	−0.2 (10)
Br1—Pd1—N2—C11	177.5 (4)	C6—C7—C11—N2	−179.3 (6)
C12—N1—C1—C2	−0.7 (11)	C8—C7—C11—C12	179.5 (6)
Pd1—N1—C1—C2	−178.9 (5)	C6—C7—C11—C12	0.3 (10)
N1—C1—C2—C3	1.6 (12)	C1—N1—C12—C4	0.0 (10)
C1—C2—C3—C4	−1.7 (12)	Pd1—N1—C12—C4	178.5 (5)
C2—C3—C4—C12	1.0 (11)	C1—N1—C12—C11	178.3 (6)
C2—C3—C4—C5	−179.3 (7)	Pd1—N1—C12—C11	−3.2 (7)
C12—C4—C5—C6	−2.5 (11)	C3—C4—C12—N1	−0.1 (10)
C3—C4—C5—C6	177.8 (7)	C5—C4—C12—N1	−179.8 (6)
C4—C5—C6—C7	2.0 (11)	C3—C4—C12—C11	−178.3 (6)
C5—C6—C7—C8	−179.9 (7)	C5—C4—C12—C11	2.0 (10)
C5—C6—C7—C11	−0.9 (11)	N2—C11—C12—N1	0.4 (9)
C11—C7—C8—C9	−0.3 (10)	C7—C11—C12—N1	−179.2 (6)
C6—C7—C8—C9	178.8 (7)	N2—C11—C12—C4	178.7 (6)
C7—C8—C9—C10	−0.3 (11)	C7—C11—C12—C4	−0.9 (10)
C11—N2—C10—C9	−1.8 (10)

Table 1

Selected bond lengths (Å)

Pd1—N1	2.059 (6)
Pd1—N2	2.048 (6)
Pd1—Br1	2.4095 (9)
Pd1—Br2	2.4016 (10)