metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoSTRUCTURAL
CHEMISTRY
ISSN: 2053-2296

Bis­(tetra-n-butyl­ammonium) (μ-N,N′-diselenium dinitride)­bis­­[tri­bromo­palladate(II)]

aChemistry Department, Loughborough University, Loughborough, Leicestershire LE11 3TU, England
*Correspondence e-mail: p.f.kelly@lboro.ac.uk

(Received 12 October 2004; accepted 25 October 2004; online 11 November 2004)

The reaction of Se4N4 with (Bu4N)2[Pd2Br6] gives the title compound, (C16H36N)2[Pd2Br6(N2Se2)], in good yield. The [Pd2(Se2N2)Br6]2− anion lies on an inversion centre, and therefore the asymmetric unit contains half a formula unit. The crystal structure confirms the coordination of the Se2N2 unit to Pd through the N atoms, as previously assigned by IR spectroscopic analysis [Kelly, Slawin & Soriano-Rama (1997[Kelly, P. F., Slawin, A. M. Z. & Soriano-Rama, A. (1997). J. Chem. Soc. Dalton Trans. pp. 559-562.]). J. Chem. Soc. Dalton Trans. pp. 559–562]. The title compound contains the longest Pd—N bond so far observed for such systems.

Comment

During the course of our work on the reactivity of Se4N4 towards metal centres, we have successfully demonstrated that, under the right circumstances, adducts of diselenium dinitride, Se2N2, can be generated. Examples so far fully characterized by X-ray crystallography are (AlBr3)2(Se2N2) (Kelly & Slawin, 1996[Kelly, P. F. & Slawin, A. M. Z. (1996). J. Chem. Soc. Dalton Trans. pp. 4029-4030.]), (PPh4)2[Pd2(Se2N2)Br6] (Kelly et al., 1997[Kelly, P. F., Slawin, A. M. Z. & Soriano-Rama, A. (1997). J. Chem. Soc. Dalton Trans. pp. 559-562.]) and (PPh4)2[Pd2(Se2N2)Cl6] (Kelly & Slawin, 1995[Kelly, P. F. & Slawin, A. M. Z. (1995). Angew. Chem. Int. Ed. Engl. 34, 1758-1759.]). All are of great interest due to the fact that, unlike its sulfur analogue (the four-membered ring S2N2), Se2N2 is unknown in the free state. Thus, these compounds have the potential to act as sources of the free material via appropriate substitution reactions.

In terms of performing such reactions, however, the aluminium compound is hampered by its extreme air-sensitivity, while the tetra­phenyl­phospho­nium salts of the air-stable palladium adducts form in rather poor yield. By far the best yield thus far obtained for one of these palladium adducts occurs when Se4N4 is reacted with (Bu4N)2[Pd2Br6] to give (Bu4N)2[Pd2(Se2N2)Br6], (I[link]) [typically ca 67% yield, compared with ca 20% for the tetraphenylphosphonium salts]. However, in our previous report on this compound, we used only IR spectroscopy and microanalysis as characterization techniques (Kelly et al., 1997[Kelly, P. F., Slawin, A. M. Z. & Soriano-Rama, A. (1997). J. Chem. Soc. Dalton Trans. pp. 559-562.]). Given that, thanks to its high yield, this compound is the obvious starting point for investigations into the ability of such adducts to act as sources of the free nitride, and in the light of the general lack of structural data on complexes of Se2N2, confirmation of the structure of (I[link]) by X-ray crystallography becomes desirable.

[Scheme 1]

The X-ray crystal structure of (I[link]) confirms the presence of the four-membered Se2N2 ring, N-bound to the Pd centres, with the [Pd2(Se2N2)Br6]2− anion situated on an inversion centre. The asymmetric unit therefore contains half a formula unit. The Se—N bond lengths are almost equivalent, in direct contrast with the other examples shown in Table 2[link]. Co-crystallization of the anion with tetra­phenyl­phospho­nium cations results in a greater asymmetry in the Se—N bond lengths than seen in (I[link]). In comparison with (PPh4)2[Pd2(Se2N2)Br6] (Kelly et al., 1997[Kelly, P. F., Slawin, A. M. Z. & Soriano-Rama, A. (1997). J. Chem. Soc. Dalton Trans. pp. 559-562.]), the presence of the tetra­butyl­ammonium cations in (I[link]) appears to result in a lengthening of the Pd—N bond, in addition to an increase in the symmetry of the Se2N2 unit.

Analysis of the salts (PPh4)2[Pd2(Se2N2)Br6] (Kelly et al., 1997[Kelly, P. F., Slawin, A. M. Z. & Soriano-Rama, A. (1997). J. Chem. Soc. Dalton Trans. pp. 559-562.]) and (PPh4)2[Pd2(Se2N2)Cl6] (Kelly & Slawin, 1995[Kelly, P. F. & Slawin, A. M. Z. (1995). Angew. Chem. Int. Ed. Engl. 34, 1758-1759.]) shows that there are interactions between the cations and anions which are absent from compound (I[link]). In the case of (PPh4)2[Pd2(Se2N2)Br6], there are C—H⋯Se interactions having C⋯Se distances of the order of 4.5 Å and C—H⋯Br interactions having C⋯Br distances in the range 3.8–3.95 Å. In addition, there is weak ππ stacking, with the Se2N2 unit held between two benzene rings, at a distance of 4.3 Å from each benzene ring. This weak ππ stacking is not observed in (PPh4)2[Pd2(Se2N2)Cl6]; instead, there are C—H⋯Se interactions having C⋯Se distances of the order of 4.3 Å and C—H⋯Cl interactions having C⋯Cl distances of the order of 3.6 Å. It is possible that the absence from (I[link]) of relatively acidic C—H donors, such as the aromatic C—H groups of the tetra­phenyl­phospho­nium cations, may thus lead to a greater symmetry in the Se2N2 unit in the former.

A potentially important feature of (I[link]) is the fact that the Pd—N bond is the longest so far observed for such systems (Tables 1[link] and 2[link]). This fact, along with the high yield of the compound, suggests that it is likely to be the most effective starting material for studies into the liberation of the Se2N2 unit.

[Figure 1]
Figure 1
A view of (I[link]), showing the atom-labelling scheme and with displacement ellipsoids drawn at the 50% probability level. H atoms have been omitted for clarity. [Symmetry code: (i) 1 − x, 1 − y, 2 − z.]

Experimental

The title compound was prepared according to the literature method of Kelly et al. (1997[Kelly, P. F., Slawin, A. M. Z. & Soriano-Rama, A. (1997). J. Chem. Soc. Dalton Trans. pp. 559-562.]) and single crystals were grown by slow diffusion of diethyl ether into a CH2Cl2 solution.

Crystal data
  • (C16H36N)2[Pd2Br6(N2Se2)]

  • Mr = 1363.12

  • Triclinic, [P\overline 1]

  • a = 9.081 (2) Å

  • b = 10.671 (3) Å

  • c = 12.415 (3) Å

  • α = 95.131 (4)°

  • β = 98.598 (4)°

  • γ = 98.689 (4)°

  • V = 1168.1 (5) Å3

  • Z = 1

  • Dx = 1.938 Mg m−3

  • Mo Kα radiation

  • Cell parameters from 2921 reflections

  • θ = 2.4–27.2°

  • μ = 7.49 mm−1

  • T = 150 (2) K

  • Lath, orange

  • 0.30 × 0.20 × 0.09 mm

Data collection
  • Bruker SMART 1000 CCD area-detector diffractometer

  • ω rotation scans with narrow frames

  • Absorption correction: multi-scan (SADABS; Sheldrick, 2003[Sheldrick, G. M. (2003). SADABS. Version 2.08. University of Göttingen, Germany.]) Tmin = 0.195, Tmax = 0.508

  • 8065 measured reflections

  • 4049 independent reflections

  • 3002 reflections with I > 2σ(I)

  • Rint = 0.037

  • θmax = 25.0°

  • h = −10 → 10

  • k = −12 → 12

  • l = −14 → 14

Refinement
  • Refinement on F2

  • R[F2 > 2σ(F2)] = 0.050

  • wR(F2) = 0.131

  • S = 1.04

  • 4049 reflections

  • 212 parameters

  • H-atom parameters constrained

  • w = 1/[σ2(Fo2) + (0.046P)2 + 10.845P] where P = (Fo2 + 2Fc2)/3

  • (Δ/σ)max = 0.001

  • Δρmax = 0.85 e Å−3

  • Δρmin = −1.50 e Å−3

Table 1
Selected geometric parameters (Å, °)

Pd1—N1 1.978 (7)
Pd1—Br1 2.4299 (12)
Pd1—Br2 2.4066 (13)
Pd1—Br3 2.4316 (12)
Se1—N1i 1.806 (7)
Se1—N1 1.809 (7)
N1—Pd1—Br2 176.6 (2)
N1—Pd1—Br1 85.4 (2)
Br2—Pd1—Br1 94.39 (4)
N1—Pd1—Br3 85.7 (2)
Br2—Pd1—Br3 94.61 (4)
Br1—Pd1—Br3 170.88 (5)
Se1i—N1—Se1 97.9 (3)
Se1i—N1—Pd1 130.5 (4)
Se1—N1—Pd1 130.2 (4)
N1i—Se1—N1 82.1 (3)
Symmetry code: (i) 1-x,1-y,2-z.

Table 2
Selected bond lengths (Å) in (I[link]) and related compounds

Compound Metal—N Se—N Reference
(I[link]) 1.978 (7) 1.806 (7), 1.809 (7) a
(AlBr3)2(Se2N2) 1.92 (2) 1.77 (1), 1.81 (1) b
(PPh4)2[Pd2(Se2N2)Br6] 1.875 (9) 1.809 (10), 1.920 (9) c
(PPh4)2[Pd2(Se2N2)Cl6] 1.946 (4) 1.804 (5), 1.779 (4) d
(a) This work; (b) Kelly & Slawin (1996[Kelly, P. F. & Slawin, A. M. Z. (1996). J. Chem. Soc. Dalton Trans. pp. 4029-4030.]); (c) Kelly et al. (1997[Kelly, P. F., Slawin, A. M. Z. & Soriano-Rama, A. (1997). J. Chem. Soc. Dalton Trans. pp. 559-562.]); (d) Kelly & Slawin (1995[Kelly, P. F. & Slawin, A. M. Z. (1995). Angew. Chem. Int. Ed. Engl. 34, 1758-1759.]).

Methyl­ene (C—H = 0.99 Å) and methyl (C—H = 0.98 Å) H atoms were placed in geometric positions and refined using a riding model. Uiso(H) values were set at 1.2Ueq(C) for methyl­ene and 1.5Ueq(C) for methyl H atoms. The data set was truncated at 2θ = 50°, as only statistically insignificant data were present above this limit.

Data collection: SMART (Bruker, 2001[Bruker (2001). SMART (Version 5.611) and SAINT (Version 6.02a). Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2001[Bruker (2001). SMART (Version 5.611) and SAINT (Version 6.02a). Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2000[Sheldrick, G. M. (2000). SHELXTL. Version 6.10. Bruker AXS Inc., Madison, Wisconsin, USA.]); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and local programs.

Supporting information


Comment top

During the course of work on the reactivity of Se4N4 towards metal centres, we have successfully demonstrated that, in the right circumstances, adducts of diselenium dinitride, Se2N2, can be generated. Examples so far fully characterized by X-ray crystallography are (AlBr3)2(Se2N2) (Kelly & Slawin, 1996), [PPh4]2[Pd2(Se2N2)Br6] (Kelly et al., 1997) and [PPh4]2[Pd2(Se2N2)Cl6] (Kelly & Slawin, 1995). All are of great interest due to the fact that, unlike the sulfur analogue, the four-membered rings S2N2 or Se2N2 are unknown in the free state. Text altered by Coeditor - please confirm. Thus, these compounds have the potential to act as sources of the free material via appropriate substitution reactions.

In terms of performing such reactions, however, the aluminium compound is hampered by its extreme air-sensitivity, while the tetraphenylphosphonium salts of the air-stable palladium adducts form in rather poor yield. By far the best yield thus far obtained for one of these palladium adducts occurs when Se4N4 is reacted with (Bu4N)2[Pd2Br6] to give (Bu4N)2[Pd2(Se2N2)Br6], (I) [typically ca 67% yield, compared with ca 20% for the (PPh4)+ salts]. However, in our previous report on this compound, we only used IR spectroscopy and microanalysis as characterization techniques (Kelly et al., 1997). Given that, thanks to its high yield, this compound is the obvious starting point for investigations into the ability of such adducts to act as sources of the free nitride, and in the light of the general lack of structural data on complexes of Se2N2, confirmation of the structure of (I) by X-ray crystallography becomes desirable. \sch

The X-ray crystal structure of (I) confirms the presence of the four-membered Se2N2 ring, N-bound to the Pd centres, with the [Pd2(Se2N2)Br6]2− anion situated on an inversion centre. The asymmetric unit therefore contains half of a formula unit. The Se—N bond lengths are almost equivalent, in direct contrast with the examples shown in Table 2. Co-crystallization of the anion with tetraphenylphosphonium cations results in a greater asymmetry in the Se—N bond lengths than seen in (I). In comparison with (PPh4)2[Pd2(Se2N2)Br6] (Kelly et al., 1997), the presence of the tetrabutylammonium cations in (I) appears to result in a lengthening of the Pd—N bond, in addition to an increase in the symmetry of the Se2N2 unit.

Analysis of the salts (PPh4)2[Pd2(Se2N2)Br6] (Kelly et al., 1997) and (PPh4)2[Pd2(Se2N2)Cl6] (Kelly & Slawin, 1995) shows that there are interactions between the cations and anions which are absent from compound (I). In the case of (PPh4)2[Pd2(Se2N2)Br6], there are C—H···Se interactions having C···Se distances of the order of 4.5 Å and C—H···Br interactions having C···Br distances in the range 3.8–3.95 Å. In addition, there is weak ππ stacking, with the Se2N2 unit held between two Ph rings, at a distance of 4.3 Å from each Se2N2 unit. This weak ππ stacking is not observed in (PPh4)2[Pd2(Se2N2)Cl6]. Instead, there are C—H···Se interactions having C···Se distances of the order of 4.3 Å and C—H···Cl interactions having C···Cl distances of the order of 3.6 Å. It is possible that the absence from (I) of relatively acidic C—H donors, such as the aromatic C—H groups of the tetraphenylphosphonium cations, may thus lead to a greater symmetry in the Se2N2 unit in the former. From the Coeditor: Minor changes in last sentence OK?

A potentially important feature of (I) is the fact that the Pd—N bond length is the longest so far measured for such systems (Tables 1 and 2). This fact, alongside the high yield of the material, suggests that this is likely to be the most effective starting material for studies into the liberation of the Se2N2 unit.

Experimental top

The title compound was prepared using the literature method of Kelly et al. (1997) and single crystals were grown by slow diffusion of diethyl ether into a CH2Cl2 solution.

Refinement top

Methylene (C—H = 0.99 Å) and methyl (C—H = 0.98 Å) H atoms were placed in geometric positions and refined using a riding model. Uiso(H) values were set at 1.2Ueq(C) for methylene H and 1.5Ueq(C) for methyl H. The data set was truncated at θ = 50°, as only statistically insignificant data were present above this limit. From the Coeditor: Please note and check re-ordering of references.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2000); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and local programs.

Figures top
[Figure 1] Fig. 1. A view of (I), showing the atom-labelling scheme and with displacement ellipsoids drawn at the 50% probability level. H atoms have been omitted for clarity. [Symmetry code: (i) 1 − x, 1 − y, 2 − z.] From the Coeditor: Original caption was contradictory - please check this.
Bis(tetra-n-butylammonium) (µ-N,N'-diselenium dinitride)bis[tribromopalladate(II)] top
Crystal data top
(C16H36N)2[Pd2Br6(N2Se2)]Z = 1
Mr = 1363.12F(000) = 662
Triclinic, P1Dx = 1.938 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 9.081 (2) ÅCell parameters from 2921 reflections
b = 10.671 (3) Åθ = 2.4–27.2°
c = 12.415 (3) ŵ = 7.49 mm1
α = 95.131 (4)°T = 150 K
β = 98.598 (4)°Lath, orange
γ = 98.689 (4)°0.30 × 0.20 × 0.09 mm
V = 1168.1 (5) Å3
Data collection top
Bruker SMART 1000 CCD area-detector
diffractometer
4049 independent reflections
Radiation source: sealed tube3002 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.037
ω rotation with narrow frames scansθmax = 25.0°, θmin = 1.7°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
h = 1010
Tmin = 0.195, Tmax = 0.508k = 1212
8065 measured reflectionsl = 1414
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.050Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.131H-atom parameters constrained
S = 1.04 w = 1/[σ2(Fo2) + (0.046P)2 + 10.845P]
where P = (Fo2 + 2Fc2)/3
4049 reflections(Δ/σ)max = 0.001
212 parametersΔρmax = 0.85 e Å3
0 restraintsΔρmin = 1.50 e Å3
Crystal data top
(C16H36N)2[Pd2Br6(N2Se2)]γ = 98.689 (4)°
Mr = 1363.12V = 1168.1 (5) Å3
Triclinic, P1Z = 1
a = 9.081 (2) ÅMo Kα radiation
b = 10.671 (3) ŵ = 7.49 mm1
c = 12.415 (3) ÅT = 150 K
α = 95.131 (4)°0.30 × 0.20 × 0.09 mm
β = 98.598 (4)°
Data collection top
Bruker SMART 1000 CCD area-detector
diffractometer
4049 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
3002 reflections with I > 2σ(I)
Tmin = 0.195, Tmax = 0.508Rint = 0.037
8065 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0500 restraints
wR(F2) = 0.131H-atom parameters constrained
S = 1.04 w = 1/[σ2(Fo2) + (0.046P)2 + 10.845P]
where P = (Fo2 + 2Fc2)/3
4049 reflectionsΔρmax = 0.85 e Å3
212 parametersΔρmin = 1.50 e Å3
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Pd10.38454 (7)0.27271 (7)0.81142 (5)0.0250 (2)
Br10.60510 (11)0.35536 (10)0.73407 (8)0.0389 (3)
Br20.31511 (11)0.08397 (11)0.68135 (9)0.0453 (3)
Br30.17092 (11)0.22292 (10)0.90619 (8)0.0355 (3)
N10.4496 (8)0.4223 (7)0.9237 (6)0.0273 (17)
Se10.37705 (10)0.46360 (9)1.04779 (7)0.0267 (2)
N20.7449 (7)0.8942 (7)0.7313 (6)0.0203 (15)
C10.5911 (9)0.8135 (8)0.7296 (7)0.0214 (18)
H1A0.59670.76890.79630.026*
H1B0.51700.87200.73490.026*
C20.5298 (9)0.7150 (9)0.6320 (7)0.027 (2)
H2A0.59900.65220.62650.032*
H2B0.52120.75680.56380.032*
C30.3748 (10)0.6478 (9)0.6468 (7)0.029 (2)
H3A0.30400.71000.64510.035*
H3B0.38260.61560.71950.035*
C40.3115 (10)0.5358 (10)0.5569 (8)0.036 (2)
H4A0.29690.56820.48530.053*
H4B0.21450.49250.57120.053*
H4C0.38280.47550.55690.053*
C50.7997 (9)0.9643 (9)0.8442 (7)0.0229 (19)
H5A0.90271.01170.84580.027*
H5B0.80790.90040.89690.027*
C60.7015 (9)1.0590 (9)0.8844 (7)0.0242 (19)
H6A0.70151.12910.83730.029*
H6B0.59611.01460.87790.029*
C70.7581 (12)1.1130 (12)0.9996 (8)0.047 (3)
H7A0.85881.16551.00340.056*
H7B0.77161.04171.04400.056*
C80.6588 (11)1.1934 (11)1.0505 (9)0.045 (3)
H8A0.68141.28101.03230.067*
H8B0.67771.19341.13030.067*
H8C0.55261.15831.02200.067*
C90.8593 (10)0.8099 (9)0.7057 (7)0.027 (2)
H9A0.82950.77100.62860.032*
H9B0.95890.86500.71160.032*
C100.8776 (10)0.7057 (9)0.7764 (8)0.029 (2)
H10A0.77940.64830.76980.035*
H10B0.90770.74320.85390.035*
C110.9946 (10)0.6288 (10)0.7454 (8)0.034 (2)
H11A1.08830.68800.74180.041*
H11B0.95750.58260.67120.041*
C121.0323 (11)0.5326 (10)0.8245 (9)0.042 (3)
H12A1.07410.57770.89750.063*
H12B1.10670.48490.79840.063*
H12C0.94030.47320.82860.063*
C130.7294 (9)0.9863 (9)0.6456 (7)0.025 (2)
H13A0.64261.02970.65540.030*
H13B0.70530.93630.57220.030*
C140.8670 (10)1.0875 (9)0.6474 (8)0.031 (2)
H14A0.95581.04550.64110.037*
H14B0.88791.14230.71850.037*
C150.8441 (11)1.1703 (9)0.5546 (8)0.033 (2)
H15A0.83221.11690.48340.040*
H15B0.75041.20660.55710.040*
C160.9753 (10)1.2765 (9)0.5632 (8)0.032 (2)
H16A0.98371.33200.63190.047*
H16B0.95961.32620.50110.047*
H16C1.06841.24060.56240.047*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Pd10.0231 (4)0.0280 (4)0.0221 (4)0.0029 (3)0.0017 (3)0.0002 (3)
Br10.0377 (6)0.0458 (6)0.0350 (5)0.0040 (5)0.0167 (4)0.0014 (5)
Br20.0327 (6)0.0482 (7)0.0475 (6)0.0093 (5)0.0050 (5)0.0194 (5)
Br30.0291 (5)0.0411 (6)0.0322 (5)0.0064 (4)0.0053 (4)0.0025 (4)
N10.028 (4)0.031 (4)0.021 (4)0.003 (3)0.007 (3)0.002 (3)
Se10.0243 (5)0.0294 (5)0.0255 (5)0.0028 (4)0.0093 (4)0.0007 (4)
N20.013 (3)0.025 (4)0.025 (4)0.004 (3)0.007 (3)0.005 (3)
C10.014 (4)0.029 (5)0.022 (4)0.001 (4)0.008 (3)0.001 (4)
C20.015 (4)0.036 (5)0.028 (5)0.003 (4)0.008 (4)0.002 (4)
C30.021 (5)0.038 (6)0.027 (5)0.001 (4)0.007 (4)0.003 (4)
C40.021 (5)0.040 (6)0.040 (6)0.002 (4)0.001 (4)0.006 (5)
C50.019 (4)0.032 (5)0.018 (4)0.004 (4)0.005 (3)0.004 (4)
C60.017 (4)0.032 (5)0.022 (4)0.012 (4)0.005 (3)0.002 (4)
C70.044 (6)0.061 (8)0.035 (6)0.028 (6)0.001 (5)0.012 (5)
C80.035 (6)0.056 (7)0.041 (6)0.010 (5)0.010 (5)0.015 (5)
C90.022 (4)0.035 (5)0.027 (5)0.011 (4)0.009 (4)0.001 (4)
C100.027 (5)0.029 (5)0.032 (5)0.000 (4)0.015 (4)0.004 (4)
C110.025 (5)0.046 (6)0.035 (5)0.012 (4)0.007 (4)0.006 (5)
C120.030 (5)0.048 (7)0.049 (6)0.018 (5)0.001 (5)0.009 (5)
C130.016 (4)0.035 (5)0.024 (5)0.003 (4)0.007 (4)0.000 (4)
C140.017 (4)0.033 (5)0.040 (5)0.005 (4)0.002 (4)0.016 (4)
C150.040 (6)0.023 (5)0.033 (5)0.005 (4)0.005 (4)0.007 (4)
C160.029 (5)0.031 (5)0.032 (5)0.002 (4)0.002 (4)0.005 (4)
Geometric parameters (Å, º) top
Pd1—N11.978 (7)C7—H7A0.9900
Pd1—Br12.4299 (12)C7—H7B0.9900
Pd1—Br22.4066 (13)C8—H8A0.9800
Pd1—Br32.4316 (12)C8—H8B0.9800
Se1—N1i1.806 (7)C8—H8C0.9800
Se1—N11.809 (7)C9—C101.491 (13)
N2—C51.504 (10)C9—H9A0.9900
N2—C131.517 (11)C9—H9B0.9900
N2—C11.522 (10)C10—C111.510 (12)
N2—C91.522 (10)C10—H10A0.9900
C1—C21.508 (12)C10—H10B0.9900
C1—H1A0.9900C11—C121.524 (13)
C1—H1B0.9900C11—H11A0.9900
C2—C31.525 (11)C11—H11B0.9900
C2—H2A0.9900C12—H12A0.9800
C2—H2B0.9900C12—H12B0.9800
C3—C41.539 (12)C12—H12C0.9800
C3—H3A0.9900C13—C141.519 (11)
C3—H3B0.9900C13—H13A0.9900
C4—H4A0.9800C13—H13B0.9900
C4—H4B0.9800C14—C151.522 (12)
C4—H4C0.9800C14—H14A0.9900
C5—C61.544 (11)C14—H14B0.9900
C5—H5A0.9900C15—C161.500 (12)
C5—H5B0.9900C15—H15A0.9900
C6—C71.478 (12)C15—H15B0.9900
C6—H6A0.9900C16—H16A0.9800
C6—H6B0.9900C16—H16B0.9800
C7—C81.502 (14)C16—H16C0.9800
N1—Pd1—Br2176.6 (2)C8—C7—H7B108.5
N1—Pd1—Br185.4 (2)H7A—C7—H7B107.5
Br2—Pd1—Br194.39 (4)C7—C8—H8A109.5
N1—Pd1—Br385.7 (2)C7—C8—H8B109.5
Br2—Pd1—Br394.61 (4)H8A—C8—H8B109.5
Br1—Pd1—Br3170.88 (5)C7—C8—H8C109.5
Se1i—N1—Se197.9 (3)H8A—C8—H8C109.5
Se1i—N1—Pd1130.5 (4)H8B—C8—H8C109.5
Se1—N1—Pd1130.2 (4)C10—C9—N2116.2 (7)
N1i—Se1—N182.1 (3)C10—C9—H9A108.2
C5—N2—C13111.3 (7)N2—C9—H9A108.2
C5—N2—C1108.9 (6)C10—C9—H9B108.2
C13—N2—C1108.7 (6)N2—C9—H9B108.2
C5—N2—C9108.1 (6)H9A—C9—H9B107.4
C13—N2—C9109.3 (6)C9—C10—C11112.1 (7)
C1—N2—C9110.6 (6)C9—C10—H10A109.2
C2—C1—N2117.6 (6)C11—C10—H10A109.2
C2—C1—H1A107.9C9—C10—H10B109.2
N2—C1—H1A107.9C11—C10—H10B109.2
C2—C1—H1B107.9H10A—C10—H10B107.9
N2—C1—H1B107.9C10—C11—C12114.0 (8)
H1A—C1—H1B107.2C10—C11—H11A108.8
C1—C2—C3108.5 (7)C12—C11—H11A108.8
C1—C2—H2A110.0C10—C11—H11B108.8
C3—C2—H2A110.0C12—C11—H11B108.8
C1—C2—H2B110.0H11A—C11—H11B107.7
C3—C2—H2B110.0C11—C12—H12A109.5
H2A—C2—H2B108.4C11—C12—H12B109.5
C2—C3—C4111.8 (7)H12A—C12—H12B109.5
C2—C3—H3A109.2C11—C12—H12C109.5
C4—C3—H3A109.2H12A—C12—H12C109.5
C2—C3—H3B109.2H12B—C12—H12C109.5
C4—C3—H3B109.2N2—C13—C14115.7 (7)
H3A—C3—H3B107.9N2—C13—H13A108.4
C3—C4—H4A109.5C14—C13—H13A108.4
C3—C4—H4B109.5N2—C13—H13B108.4
H4A—C4—H4B109.5C14—C13—H13B108.4
C3—C4—H4C109.5H13A—C13—H13B107.4
H4A—C4—H4C109.5C13—C14—C15111.8 (7)
H4B—C4—H4C109.5C13—C14—H14A109.3
N2—C5—C6116.2 (7)C15—C14—H14A109.3
N2—C5—H5A108.2C13—C14—H14B109.3
C6—C5—H5A108.2C15—C14—H14B109.3
N2—C5—H5B108.2H14A—C14—H14B107.9
C6—C5—H5B108.2C16—C15—C14111.1 (8)
H5A—C5—H5B107.4C16—C15—H15A109.4
C7—C6—C5111.4 (7)C14—C15—H15A109.4
C7—C6—H6A109.3C16—C15—H15B109.4
C5—C6—H6A109.3C14—C15—H15B109.4
C7—C6—H6B109.3H15A—C15—H15B108.0
C5—C6—H6B109.3C15—C16—H16A109.5
H6A—C6—H6B108.0C15—C16—H16B109.5
C6—C7—C8115.3 (8)H16A—C16—H16B109.5
C6—C7—H7A108.5C15—C16—H16C109.5
C8—C7—H7A108.5H16A—C16—H16C109.5
C6—C7—H7B108.5H16B—C16—H16C109.5
Br1—Pd1—N1—Se1i10.2 (5)C9—N2—C5—C6178.0 (7)
Br3—Pd1—N1—Se1i171.8 (5)N2—C5—C6—C7174.7 (8)
Br1—Pd1—N1—Se1173.1 (5)C5—C6—C7—C8172.6 (10)
Br3—Pd1—N1—Se19.0 (5)C5—N2—C9—C1064.2 (9)
Se1i—N1—Se1—N1i0.0C13—N2—C9—C10174.6 (7)
Pd1—N1—Se1—N1i166.9 (8)C1—N2—C9—C1054.9 (10)
Pd1—N1—Se1—Se1i166.9 (8)N2—C9—C10—C11179.3 (8)
C5—N2—C1—C2167.7 (8)C9—C10—C11—C12172.4 (8)
C13—N2—C1—C271.0 (9)C5—N2—C13—C1451.4 (9)
C9—N2—C1—C249.1 (10)C1—N2—C13—C14171.3 (7)
N2—C1—C2—C3179.0 (7)C9—N2—C13—C1467.9 (9)
C1—C2—C3—C4173.8 (8)N2—C13—C14—C15176.7 (7)
C13—N2—C5—C658.0 (9)C13—C14—C15—C16175.2 (8)
C1—N2—C5—C661.8 (9)
Symmetry code: (i) x+1, y+1, z+2.

Experimental details

Crystal data
Chemical formula(C16H36N)2[Pd2Br6(N2Se2)]
Mr1363.12
Crystal system, space groupTriclinic, P1
Temperature (K)150
a, b, c (Å)9.081 (2), 10.671 (3), 12.415 (3)
α, β, γ (°)95.131 (4), 98.598 (4), 98.689 (4)
V3)1168.1 (5)
Z1
Radiation typeMo Kα
µ (mm1)7.49
Crystal size (mm)0.30 × 0.20 × 0.09
Data collection
DiffractometerBruker SMART 1000 CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2003)
Tmin, Tmax0.195, 0.508
No. of measured, independent and
observed [I > 2σ(I)] reflections
8065, 4049, 3002
Rint0.037
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.050, 0.131, 1.04
No. of reflections4049
No. of parameters212
H-atom treatmentH-atom parameters constrained
w = 1/[σ2(Fo2) + (0.046P)2 + 10.845P]
where P = (Fo2 + 2Fc2)/3
Δρmax, Δρmin (e Å3)0.85, 1.50

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SAINT, SHELXTL (Sheldrick, 2000), SHELXTL and local programs.

Selected geometric parameters (Å, º) top
Pd1—N11.978 (7)Pd1—Br32.4316 (12)
Pd1—Br12.4299 (12)Se1—N1i1.806 (7)
Pd1—Br22.4066 (13)Se1—N11.809 (7)
N1—Pd1—Br2176.6 (2)Br1—Pd1—Br3170.88 (5)
N1—Pd1—Br185.4 (2)Se1i—N1—Se197.9 (3)
Br2—Pd1—Br194.39 (4)Se1i—N1—Pd1130.5 (4)
N1—Pd1—Br385.7 (2)Se1—N1—Pd1130.2 (4)
Br2—Pd1—Br394.61 (4)N1i—Se1—N182.1 (3)
Symmetry code: (i) x+1, y+1, z+2.
Selected bond lengths from structures related to (I) (Å) top
CompoundMetal-NSe-NReference
(I)1.978 (7)1.806 (7), 1.809 (7)a
(AlBr3)2(Se2N2)1.92 (2)1.77 (1), 1.81 (1)b
(PPh4)2[Pd2(Se2N2)Br6]1.875 (9)1.809 (10), 1.920 (9)c
(PPh4)2[Pd2(Se2N2)Cl6]1.946 (4)1.804 (5), 1.779 (4)d
(a) this work; (b) Kelly & Slawin (1996); (c) Kelly et al. (1997); (d) Kelly & Slawin (1995).
 

Acknowledgements

The authors would like to acknowledge the EPSRC (UK) for the provision of a studentship (to KEH) and a Postdoctoral Research Assistantship (to SMA).

References

First citationBruker (2001). SMART (Version 5.611) and SAINT (Version 6.02a). Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationKelly, P. F. & Slawin, A. M. Z. (1995). Angew. Chem. Int. Ed. Engl. 34, 1758–1759.  CSD CrossRef CAS Web of Science Google Scholar
First citationKelly, P. F. & Slawin, A. M. Z. (1996). J. Chem. Soc. Dalton Trans. pp. 4029–4030.  CSD CrossRef Web of Science Google Scholar
First citationKelly, P. F., Slawin, A. M. Z. & Soriano-Rama, A. (1997). J. Chem. Soc. Dalton Trans. pp. 559–562.  CSD CrossRef Web of Science Google Scholar
First citationSheldrick, G. M. (2000). SHELXTL. Version 6.10. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationSheldrick, G. M. (2003). SADABS. Version 2.08. University of Göttingen, Germany.  Google Scholar

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