μ-2,2′,6,6′-Tetra­methyl-4,4′-bipyridine-κ²N¹:N^1′-bis­[(diethyl­ene­tri­amine-κ³N,N′,N′′)palladium(II)] tetra­nitrate

The title compound, [Pd₂(C₄H₁₃N₃)₂(C₁₄H₁₆N₂)](NO₃)₄, com­prises discrete tetra­cationic dumbbell-type dinuclear complex mol­ecules and noncoordinating nitrate anions. Two Pd(dien)²⁺ moieties (dien is diethyl­enetriamine) are joined by the rigid linear exo-bidentate bridging 2,2′,6,6′-tetra­methyl-4,4′-bipyri­dine ligand to form the dinuclear complex, which lies across a centre of inversion in the space group P2₁/n, so that the rings in the 2,2′,6,6′-tetra­methyl-4,4′-bipyridine bridging ligand are parallel. In the crystal, the primary and secondary amino groups of the dien ligand act as hydrogen-bond donors towards the nitrate anions to form a three-dimensional hydrogen-bond network.

Computing details

Data collection: CrysAlis PRO (Agilent, 2011); cell refinement: CrysAlis PRO (Agilent, 2011); data reduction: CrysAlis PRO (Agilent, 2011); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2011); software used to prepare material for publication: enCIFer (Allen et al., 2004).

µ-2,2',6,6'-Tetramethyl-4,4'-bipyridine-κ²N¹:N^1'- bis[(diethylenetriamine-κ³N,N',N'')palladium(II)] tetranitrate

Crystal data

[Pd2(C4H13N3)2(C14H16N2)](NO3)4	F(000) = 892
Mr = 879.48	Dx = 1.760 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 3950 reflections
a = 10.7697 (6) Å	θ = 3.2–28.2°
b = 8.0282 (4) Å	µ = 1.16 mm^−1
c = 19.6442 (12) Å	T = 110 K
β = 102.323 (6)°	Prism, pale yellow
V = 1659.33 (17) Å^3	0.30 × 0.16 × 0.08 mm
Z = 2

Data collection

Oxford Diffraction Xcalibur2 diffractometer	3799 independent reflections
Radiation source: Enhance (Mo) X-ray Source	2767 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.062
Detector resolution: 8.4171 pixels mm^-1	θmax = 28.2°, θmin = 3.2°
ω scans	h = −13→13
Absorption correction: multi-scan (ABSPACK in CrysAlis PRO; Agilent, 2011)	k = −10→10
Tmin = 0.722, Tmax = 0.913	l = −24→25
14710 measured reflections

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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.076	H-atom parameters constrained
S = 1.02	w = 1/[σ^2(Fo^2) + (0.0267P)^2 + 0.5726P] where P = (Fo^2 + 2Fc^2)/3
3799 reflections	(Δ/σ)max = 0.001
219 parameters	Δρmax = 0.68 e Å^−3
0 restraints	Δρmin = −0.66 e Å^−3

Special details

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.

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

	x	y	z	Uiso*/Ueq
Pd1	0.45046 (3)	0.78685 (4)	0.145689 (14)	0.01702 (9)
N1	0.5683 (3)	0.7249 (4)	0.08077 (15)	0.0216 (7)
H1A	0.5690	0.6112	0.0750	0.026*
H1B	0.5397	0.7730	0.0378	0.026*
C2	0.6989 (3)	0.7850 (5)	0.11167 (19)	0.0255 (8)
H2A	0.7622	0.7057	0.1006	0.031*
H2B	0.7130	0.8946	0.0915	0.031*
C3	0.7156 (4)	0.8001 (6)	0.1885 (2)	0.0303 (10)
H3A	0.7200	0.6883	0.2100	0.036*
H3B	0.7954	0.8603	0.2082	0.036*
N4	0.6062 (3)	0.8925 (4)	0.20256 (16)	0.0233 (7)
H4	0.6107	1.0004	0.1860	0.028*
C5	0.5889 (4)	0.9046 (6)	0.2744 (2)	0.0323 (10)
H5A	0.6528	0.9810	0.3016	0.039*
H5B	0.5991	0.7937	0.2969	0.039*
C6	0.4589 (4)	0.9692 (5)	0.2716 (2)	0.0299 (10)
H6A	0.4515	1.0845	0.2532	0.036*
H6B	0.4409	0.9706	0.3189	0.036*
N7	0.3666 (3)	0.8585 (4)	0.22508 (16)	0.0215 (7)
H7A	0.2922	0.9148	0.2077	0.026*
H7B	0.3483	0.7669	0.2493	0.026*
N11	0.2898 (3)	0.6775 (3)	0.08909 (14)	0.0159 (7)
C12	0.2639 (3)	0.5154 (4)	0.09975 (18)	0.0176 (8)
C13	0.1506 (3)	0.4443 (4)	0.06449 (19)	0.0197 (8)
H13	0.1335	0.3306	0.0724	0.024*
C14	0.0620 (3)	0.5371 (5)	0.01791 (18)	0.0174 (8)
C15	0.0932 (3)	0.7009 (5)	0.00698 (18)	0.0194 (8)
H15	0.0362	0.7671	−0.0257	0.023*
C16	0.2059 (3)	0.7693 (5)	0.04276 (18)	0.0181 (8)
C17	0.3562 (4)	0.4177 (5)	0.1515 (2)	0.0243 (9)
H17A	0.4429	0.4457	0.1474	0.036*
H17B	0.3412	0.2985	0.1427	0.036*
H17C	0.3454	0.4445	0.1986	0.036*
C18	0.2390 (3)	0.9474 (5)	0.0325 (2)	0.0237 (9)
H18A	0.2378	1.0107	0.0750	0.036*
H18B	0.1769	0.9948	−0.0065	0.036*
H18C	0.3241	0.9533	0.0223	0.036*
O1	0.6186 (3)	0.3750 (3)	0.06070 (16)	0.0393 (8)
O2	0.6424 (3)	0.2370 (4)	0.15749 (15)	0.0371 (7)
O3	0.5312 (3)	0.1326 (4)	0.06263 (14)	0.0332 (7)
N2	0.5969 (3)	0.2487 (4)	0.09303 (18)	0.0270 (8)
O4	0.3525 (2)	0.5824 (3)	0.32031 (14)	0.0289 (7)
O5	0.5519 (3)	0.5544 (4)	0.36587 (17)	0.0471 (9)
O6	0.4398 (3)	0.3380 (3)	0.33025 (16)	0.0384 (8)
N3	0.4499 (3)	0.4905 (4)	0.33889 (16)	0.0244 (7)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Pd1	0.01462 (14)	0.01550 (14)	0.02010 (14)	−0.00197 (13)	0.00185 (10)	−0.00170 (14)
N1	0.0206 (16)	0.0210 (16)	0.0232 (16)	0.0025 (14)	0.0048 (13)	0.0026 (14)
C2	0.0186 (19)	0.029 (2)	0.029 (2)	0.0020 (18)	0.0047 (16)	0.0028 (19)
C3	0.018 (2)	0.041 (3)	0.031 (2)	−0.0005 (19)	0.0016 (17)	0.002 (2)
N4	0.0220 (17)	0.0205 (18)	0.0277 (18)	−0.0037 (14)	0.0057 (14)	−0.0030 (14)
C5	0.030 (2)	0.041 (3)	0.024 (2)	−0.014 (2)	0.0013 (19)	−0.0066 (19)
C6	0.033 (2)	0.030 (2)	0.026 (2)	−0.0052 (19)	0.0060 (19)	−0.0096 (19)
N7	0.0174 (16)	0.0190 (16)	0.0288 (17)	−0.0009 (13)	0.0067 (14)	−0.0021 (15)
N11	0.0170 (16)	0.0143 (17)	0.0165 (15)	−0.0022 (12)	0.0037 (12)	−0.0018 (12)
C12	0.0182 (19)	0.0173 (19)	0.0179 (18)	−0.0008 (15)	0.0050 (15)	−0.0014 (15)
C13	0.022 (2)	0.0122 (18)	0.0232 (19)	−0.0048 (16)	0.0015 (16)	−0.0011 (16)
C14	0.0171 (19)	0.019 (2)	0.0173 (18)	−0.0031 (15)	0.0060 (15)	−0.0017 (16)
C15	0.0176 (18)	0.0184 (19)	0.0220 (18)	0.0031 (16)	0.0038 (15)	0.0040 (17)
C16	0.0148 (18)	0.021 (2)	0.0184 (17)	−0.0016 (15)	0.0025 (14)	0.0018 (16)
C17	0.023 (2)	0.019 (2)	0.028 (2)	−0.0047 (16)	−0.0016 (17)	0.0007 (17)
C18	0.024 (2)	0.018 (2)	0.028 (2)	−0.0061 (16)	0.0021 (17)	0.0032 (17)
O1	0.056 (2)	0.0190 (16)	0.0484 (19)	0.0001 (14)	0.0241 (17)	0.0042 (15)
O2	0.0357 (17)	0.042 (2)	0.0313 (16)	−0.0013 (14)	0.0023 (13)	−0.0052 (14)
O3	0.0402 (18)	0.0270 (16)	0.0294 (16)	−0.0085 (14)	0.0005 (14)	0.0000 (13)
N2	0.0277 (19)	0.027 (2)	0.0276 (18)	0.0039 (15)	0.0094 (15)	−0.0020 (15)
O4	0.0286 (16)	0.0215 (15)	0.0383 (17)	0.0041 (12)	0.0109 (13)	0.0026 (13)
O5	0.0333 (18)	0.0392 (19)	0.060 (2)	−0.0069 (15)	−0.0097 (17)	−0.0053 (17)
O6	0.0438 (19)	0.0186 (15)	0.0517 (19)	0.0005 (13)	0.0079 (15)	−0.0034 (14)
N3	0.0272 (19)	0.0257 (19)	0.0203 (17)	−0.0016 (16)	0.0053 (15)	0.0002 (15)

Geometric parameters (Å, º)

Pd1—N4	1.995 (3)	N11—C16	1.355 (4)
Pd1—N1	2.043 (3)	N11—C12	1.356 (4)
Pd1—N7	2.044 (3)	C12—C13	1.391 (5)
Pd1—N11	2.045 (3)	C12—C17	1.486 (5)
N1—C2	1.489 (4)	C13—C14	1.389 (5)
N1—H1A	0.9200	C13—H13	0.9500
N1—H1B	0.9200	C14—C15	1.385 (5)
C2—C3	1.486 (5)	C14—C14^i	1.493 (7)
C2—H2A	0.9900	C15—C16	1.380 (5)
C2—H2B	0.9900	C15—H15	0.9500
C3—N4	1.468 (5)	C16—C18	1.498 (5)
C3—H3A	0.9900	C17—H17A	0.9800
C3—H3B	0.9900	C17—H17B	0.9800
N4—C5	1.465 (5)	C17—H17C	0.9800
N4—H4	0.9300	C18—H18A	0.9800
C5—C6	1.483 (5)	C18—H18B	0.9800
C5—H5A	0.9900	C18—H18C	0.9800
C5—H5B	0.9900	O1—N2	1.245 (4)
C6—N7	1.492 (5)	O2—N2	1.260 (4)
C6—H6A	0.9900	O3—N2	1.244 (4)
C6—H6B	0.9900	O4—N3	1.270 (4)
N7—H7A	0.9200	O5—N3	1.226 (4)
N7—H7B	0.9200	O6—N3	1.238 (4)
N1—Pd1—N4	83.85 (12)	C6—N7—Pd1	106.8 (2)
N4—Pd1—N7	84.76 (12)	C6—N7—H7A	110.4
N1—Pd1—N7	168.20 (12)	Pd1—N7—H7A	110.4
N1—Pd1—N11	97.03 (11)	C6—N7—H7B	110.4
N7—Pd1—N11	94.32 (11)	Pd1—N7—H7B	110.4
N4—Pd1—N11	178.92 (12)	H7A—N7—H7B	108.6
C2—N1—Pd1	109.0 (2)	C16—N11—C12	119.7 (3)
C2—N1—H1A	109.9	C16—N11—Pd1	119.8 (2)
Pd1—N1—H1A	109.9	C12—N11—Pd1	120.4 (2)
C2—N1—H1B	109.9	N11—C12—C13	120.3 (3)
Pd1—N1—H1B	109.9	N11—C12—C17	118.8 (3)
H1A—N1—H1B	108.3	C13—C12—C17	120.8 (3)
C3—C2—N1	109.9 (3)	C14—C13—C12	120.9 (3)
C3—C2—H2A	109.7	C14—C13—H13	119.5
N1—C2—H2A	109.7	C12—C13—H13	119.5
C3—C2—H2B	109.7	C15—C14—C13	117.1 (3)
N1—C2—H2B	109.7	C15—C14—C14^i	121.9 (4)
H2A—C2—H2B	108.2	C13—C14—C14^i	121.0 (4)
N4—C3—C2	107.8 (3)	C16—C15—C14	121.0 (3)
N4—C3—H3A	110.2	C16—C15—H15	119.5
C2—C3—H3A	110.2	C14—C15—H15	119.5
N4—C3—H3B	110.2	N11—C16—C15	120.9 (3)
C2—C3—H3B	110.2	N11—C16—C18	117.7 (3)
H3A—C3—H3B	108.5	C15—C16—C18	121.4 (3)
C5—N4—C3	119.2 (3)	C12—C17—H17A	109.5
C5—N4—Pd1	107.6 (2)	C12—C17—H17B	109.5
C3—N4—Pd1	107.0 (2)	H17A—C17—H17B	109.5
C5—N4—H4	107.5	C12—C17—H17C	109.5
C3—N4—H4	107.5	H17A—C17—H17C	109.5
Pd1—N4—H4	107.5	H17B—C17—H17C	109.5
N4—C5—C6	107.5 (3)	C16—C18—H18A	109.5
N4—C5—H5A	110.2	C16—C18—H18B	109.5
C6—C5—H5A	110.2	H18A—C18—H18B	109.5
N4—C5—H5B	110.2	C16—C18—H18C	109.5
C6—C5—H5B	110.2	H18A—C18—H18C	109.5
H5A—C5—H5B	108.5	H18B—C18—H18C	109.5
C5—C6—N7	108.3 (3)	O3—N2—O1	121.0 (3)
C5—C6—H6A	110.0	O3—N2—O2	119.1 (3)
N7—C6—H6A	110.0	O1—N2—O2	119.9 (3)
C5—C6—H6B	110.0	O5—N3—O6	121.1 (3)
N7—C6—H6B	110.0	O5—N3—O4	119.4 (3)
H6A—C6—H6B	108.4	O6—N3—O4	119.5 (3)

Symmetry code: (i) −x, −y+1, −z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1	0.92	2.01	2.904 (4)	165
N1—H1B···O3^ii	0.92	2.10	3.017 (4)	176
N4—H4···O2^iii	0.93	2.03	2.955 (4)	173
N7—H7B···O4	0.92	2.03	2.925 (4)	165
N7—H7A···O4^iv	0.92	2.04	2.949 (4)	168

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