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

In the title complex, [Pd(N(3))(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 (phen) ligand and two N atoms from two azide anions. The azido ligands are slightly bent with bond angles of 174.8 (4) and 174.5 (5)°. The complex mol-ecules are stacked in columns along the a axis and are connected by inter-molecular C-H⋯N hydrogen bonds, forming a three-dimensional network. In the columns, numerous inter-molecular π-π inter-actions between the six-membered rings are present, the shortest ring centroid-centroid distance being 3.607 (2) Å.

Related literature

For the syntheses of [PdX 2(phen)] (X = Cl, Br, I or SCN), see: Cheng et al. (1977 ▶). For the crystal structures of [PdX 2(phen)] (X = Cl, Br or I), see: Ha (2010 ▶).

Experimental

Crystal data

[Pd(N3)2(C12H8N2)]

M = 370.66

Orthorhombic,

a = 7.0724 (3) Å

b = 18.3069 (7) Å

c = 19.1309 (7) Å

V = 2476.95 (17) Å3

Z = 8

Mo Kα radiation

μ = 1.51 mm−1

T = 200 K

0.25 × 0.13 × 0.12 mm

Data collection

Bruker SMART 1000 CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2000 ▶) T min = 0.886, T max = 1.000

17018 measured reflections

3058 independent reflections

2244 reflections with I > 2σ(I)

R int = 0.040

Refinement

R[F 2 > 2σ(F 2)] = 0.033

wR(F 2) = 0.084

S = 1.09

3058 reflections

190 parameters

H-atom parameters constrained

Δρmax = 1.20 e Å−3

Δρmin = −0.62 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 datablock(s) global. DOI: 10.1107/S1600536812001201/wm2583sup1.cif

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

[Pd(N3)2(C12H8N2)]	F(000) = 1456
Mr = 370.66	Dx = 1.988 Mg m−3
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 6741 reflections
a = 7.0724 (3) Å	θ = 2.5–28.3°
b = 18.3069 (7) Å	µ = 1.51 mm−1
c = 19.1309 (7) Å	T = 200 K
V = 2476.95 (17) Å3	Block, yellow
Z = 8	0.25 × 0.13 × 0.12 mm

Bruker SMART 1000 CCD diffractometer	3058 independent reflections
Radiation source: fine-focus sealed tube	2244 reflections with I > 2σ(I)
graphite	Rint = 0.040
φ and ω scans	θmax = 28.3°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −8→9
Tmin = 0.886, Tmax = 1.000	k = −24→24
17018 measured reflections	l = −25→23

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)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.084	H-atom parameters constrained
S = 1.09	w = 1/[σ2(Fo2) + (0.0259P)2 + 3.9659P] where P = (Fo2 + 2Fc2)/3
3058 reflections	(Δ/σ)max = 0.001
190 parameters	Δρmax = 1.20 e Å−3
0 restraints	Δρmin = −0.62 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	0.42841 (4)	0.384720 (15)	0.171291 (14)	0.03115 (10)
N1	0.3530 (4)	0.48761 (16)	0.20092 (16)	0.0328 (7)
N2	0.4398 (4)	0.37116 (16)	0.27707 (15)	0.0322 (7)
N3	0.4003 (5)	0.41288 (19)	0.07018 (17)	0.0443 (8)
N4	0.4887 (5)	0.38609 (18)	0.02351 (18)	0.0408 (8)
N5	0.5675 (6)	0.3639 (2)	−0.02492 (19)	0.0547 (10)
N6	0.5003 (6)	0.27920 (19)	0.15822 (18)	0.0463 (9)
N7	0.5375 (5)	0.25334 (19)	0.10364 (19)	0.0479 (9)
N8	0.5816 (8)	0.2236 (2)	0.0529 (2)	0.0781 (15)
C1	0.3151 (5)	0.5454 (2)	0.1609 (2)	0.0391 (9)
H1	0.3208	0.5405	0.1115	0.047*
C2	0.2672 (6)	0.6127 (2)	0.1898 (2)	0.0450 (10)
H2	0.2401	0.6529	0.1600	0.054*
C3	0.2592 (6)	0.6212 (2)	0.2605 (2)	0.0461 (10)
H3	0.2269	0.6673	0.2800	0.055*
C4	0.2989 (5)	0.5615 (2)	0.3045 (2)	0.0397 (9)
C5	0.2938 (6)	0.5635 (2)	0.3793 (2)	0.0465 (10)
H5	0.2607	0.6076	0.4023	0.056*
C6	0.3351 (6)	0.5037 (2)	0.4177 (2)	0.0472 (10)
H6	0.3288	0.5068	0.4673	0.057*
C7	0.3880 (5)	0.4360 (2)	0.3861 (2)	0.0391 (9)
C8	0.4377 (6)	0.3725 (3)	0.4225 (2)	0.0452 (10)
H8	0.4366	0.3722	0.4721	0.054*
C9	0.4880 (6)	0.3106 (2)	0.3863 (2)	0.0461 (10)
H9	0.5228	0.2675	0.4107	0.055*
C10	0.4876 (6)	0.3116 (2)	0.3135 (2)	0.0398 (9)
H10	0.5223	0.2685	0.2889	0.048*
C11	0.3921 (5)	0.4327 (2)	0.31269 (19)	0.0330 (8)
C12	0.3466 (5)	0.49549 (19)	0.27182 (19)	0.0330 (8)

	U11	U22	U33	U12	U13	U23
Pd1	0.03266 (17)	0.03068 (16)	0.03012 (16)	−0.00224 (12)	0.00067 (12)	0.00230 (11)
N1	0.0282 (16)	0.0314 (16)	0.0388 (16)	−0.0041 (13)	0.0002 (13)	0.0026 (13)
N2	0.0284 (16)	0.0370 (17)	0.0313 (15)	−0.0040 (13)	0.0022 (12)	0.0056 (13)
N3	0.053 (2)	0.047 (2)	0.0330 (18)	0.0048 (17)	−0.0011 (16)	0.0055 (15)
N4	0.049 (2)	0.0395 (18)	0.0344 (18)	−0.0017 (16)	−0.0096 (16)	0.0081 (15)
N5	0.070 (3)	0.059 (2)	0.035 (2)	0.011 (2)	0.0021 (18)	0.0054 (17)
N6	0.064 (2)	0.0362 (18)	0.038 (2)	0.0020 (17)	0.0047 (17)	0.0028 (15)
N7	0.065 (3)	0.0349 (18)	0.044 (2)	0.0002 (17)	−0.0084 (18)	0.0033 (16)
N8	0.137 (5)	0.052 (3)	0.046 (2)	0.019 (3)	−0.008 (3)	−0.010 (2)
C1	0.031 (2)	0.037 (2)	0.049 (2)	−0.0024 (16)	−0.0033 (17)	0.0074 (18)
C2	0.032 (2)	0.035 (2)	0.068 (3)	0.0002 (17)	−0.0020 (19)	0.0091 (19)
C3	0.036 (2)	0.033 (2)	0.070 (3)	−0.0016 (18)	0.004 (2)	−0.0076 (19)
C4	0.029 (2)	0.035 (2)	0.055 (2)	−0.0043 (16)	0.0066 (17)	−0.0083 (18)
C5	0.040 (2)	0.046 (2)	0.053 (3)	−0.0063 (19)	0.009 (2)	−0.017 (2)
C6	0.042 (2)	0.059 (3)	0.041 (2)	−0.010 (2)	0.0051 (18)	−0.009 (2)
C7	0.033 (2)	0.048 (2)	0.037 (2)	−0.0090 (17)	0.0038 (16)	0.0000 (17)
C8	0.041 (2)	0.065 (3)	0.030 (2)	−0.007 (2)	0.0000 (17)	0.0056 (19)
C9	0.044 (2)	0.052 (3)	0.041 (2)	−0.006 (2)	−0.0018 (19)	0.016 (2)
C10	0.040 (2)	0.038 (2)	0.041 (2)	−0.0007 (18)	0.0014 (17)	0.0057 (17)
C11	0.0246 (19)	0.039 (2)	0.0354 (19)	−0.0052 (15)	0.0025 (14)	−0.0003 (16)
C12	0.0259 (18)	0.0317 (18)	0.041 (2)	−0.0063 (15)	0.0002 (15)	0.0015 (16)

Pd1—N1	2.038 (3)	C3—C4	1.407 (6)
Pd1—N2	2.040 (3)	C3—H3	0.9500
Pd1—N3	2.012 (3)	C4—C12	1.402 (5)
Pd1—N6	2.013 (3)	C4—C5	1.432 (6)
N1—C1	1.333 (5)	C5—C6	1.350 (6)
N1—C12	1.365 (5)	C5—H5	0.9500
N2—C10	1.338 (5)	C6—C7	1.430 (6)
N2—C11	1.360 (5)	C6—H6	0.9500
N3—N4	1.195 (5)	C7—C8	1.399 (6)
N4—N5	1.155 (5)	C7—C11	1.407 (5)
N6—N7	1.176 (5)	C8—C9	1.374 (6)
N7—N8	1.156 (5)	C8—H8	0.9500
C1—C2	1.392 (5)	C9—C10	1.392 (5)
C1—H1	0.9500	C9—H9	0.9500
C2—C3	1.363 (6)	C10—H10	0.9500
C2—H2	0.9500	C11—C12	1.427 (5)
N1—Pd1—N2	81.20 (12)	C12—C4—C5	118.2 (4)
N3—Pd1—N6	98.71 (14)	C3—C4—C5	125.0 (4)
N3—Pd1—N1	90.27 (13)	C6—C5—C4	121.3 (4)
N6—Pd1—N1	170.93 (13)	C6—C5—H5	119.4
N3—Pd1—N2	171.39 (13)	C4—C5—H5	119.4
N6—Pd1—N2	89.80 (13)	C5—C6—C7	121.9 (4)
C1—N1—C12	118.7 (3)	C5—C6—H6	119.0
C1—N1—Pd1	128.8 (3)	C7—C6—H6	119.0
C12—N1—Pd1	112.5 (2)	C8—C7—C11	117.1 (4)
C10—N2—C11	118.5 (3)	C8—C7—C6	125.2 (4)
C10—N2—Pd1	128.8 (3)	C11—C7—C6	117.7 (4)
C11—N2—Pd1	112.7 (2)	C9—C8—C7	120.0 (4)
N4—N3—Pd1	124.1 (3)	C9—C8—H8	120.0
N5—N4—N3	174.8 (4)	C7—C8—H8	120.0
N7—N6—Pd1	123.6 (3)	C8—C9—C10	119.5 (4)
N8—N7—N6	174.5 (5)	C8—C9—H9	120.2
N1—C1—C2	121.6 (4)	C10—C9—H9	120.2
N1—C1—H1	119.2	N2—C10—C9	122.1 (4)
C2—C1—H1	119.2	N2—C10—H10	118.9
C3—C2—C1	120.3 (4)	C9—C10—H10	118.9
C3—C2—H2	119.9	N2—C11—C7	122.7 (3)
C1—C2—H2	119.9	N2—C11—C12	116.7 (3)
C2—C3—C4	119.8 (4)	C7—C11—C12	120.6 (4)
C2—C3—H3	120.1	N1—C12—C4	122.8 (3)
C4—C3—H3	120.1	N1—C12—C11	116.9 (3)
C12—C4—C3	116.8 (4)	C4—C12—C11	120.3 (3)
N3—Pd1—N1—C1	−3.1 (3)	C7—C8—C9—C10	−0.5 (6)
N2—Pd1—N1—C1	178.1 (3)	C11—N2—C10—C9	0.6 (6)
N3—Pd1—N1—C12	178.3 (3)	Pd1—N2—C10—C9	−179.8 (3)
N2—Pd1—N1—C12	−0.5 (2)	C8—C9—C10—N2	0.1 (6)
N6—Pd1—N2—C10	2.4 (3)	C10—N2—C11—C7	−1.0 (5)
N1—Pd1—N2—C10	−178.7 (3)	Pd1—N2—C11—C7	179.3 (3)
N6—Pd1—N2—C11	−178.0 (3)	C10—N2—C11—C12	178.5 (3)
N1—Pd1—N2—C11	0.9 (2)	Pd1—N2—C11—C12	−1.2 (4)
N6—Pd1—N3—N4	−30.7 (4)	C8—C7—C11—N2	0.6 (5)
N3—Pd1—N6—N7	9.6 (4)	C6—C7—C11—N2	−179.9 (3)
N2—Pd1—N6—N7	−171.7 (4)	C8—C7—C11—C12	−178.9 (3)
C12—N1—C1—C2	−0.8 (5)	C6—C7—C11—C12	0.6 (5)
Pd1—N1—C1—C2	−179.3 (3)	C1—N1—C12—C4	1.0 (5)
N1—C1—C2—C3	0.4 (6)	Pd1—N1—C12—C4	179.7 (3)
C1—C2—C3—C4	−0.2 (6)	C1—N1—C12—C11	−178.7 (3)
C2—C3—C4—C12	0.4 (6)	Pd1—N1—C12—C11	0.0 (4)
C2—C3—C4—C5	−179.5 (4)	C3—C4—C12—N1	−0.8 (6)
C12—C4—C5—C6	0.5 (6)	C5—C4—C12—N1	179.1 (3)
C3—C4—C5—C6	−179.6 (4)	C3—C4—C12—C11	178.9 (3)
C4—C5—C6—C7	0.8 (6)	C5—C4—C12—C11	−1.2 (5)
C5—C6—C7—C8	178.1 (4)	N2—C11—C12—N1	0.8 (5)
C5—C6—C7—C11	−1.3 (6)	C7—C11—C12—N1	−179.7 (3)
C11—C7—C8—C9	0.1 (6)	N2—C11—C12—C4	−178.9 (3)
C6—C7—C8—C9	−179.3 (4)	C7—C11—C12—C4	0.6 (5)

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···N3	0.95	2.53	3.044 (5)	114
C1—H1···N5i	0.95	2.54	3.196 (5)	127
C5—H5···N8ii	0.95	2.55	3.324 (6)	139
C8—H8···N8iii	0.95	2.55	3.218 (6)	127
C10—H10···N6	0.95	2.51	3.031 (5)	114

Pd1—N1	2.038 (3)
Pd1—N2	2.040 (3)
Pd1—N3	2.012 (3)
Pd1—N6	2.013 (3)

N1—Pd1—N2	81.20 (12)
N3—Pd1—N6	98.71 (14)

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1⋯N3	0.95	2.53	3.044 (5)	114
C1—H1⋯N5i	0.95	2.54	3.196 (5)	127
C5—H5⋯N8ii	0.95	2.55	3.324 (6)	139
C8—H8⋯N8iii	0.95	2.55	3.218 (6)	127
C10—H10⋯N6	0.95	2.51	3.031 (5)	114

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