(2,2′-Bi­pyridine)­di­chloro­gold(III) nitrate

Bjernemose, J.K.; Raithby, P.R.; Toftlund, H.

doi:10.1107/S1600536804026558

metal-organic compounds

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ISSN: 2056-9890

Volume 60| Part 11| November 2004| Pages m1719-m1721

https://doi.org/10.1107/S1600536804026558

(2,2′-Bipyridine)dichlorogold(III) nitrate

Jens K. Bjernemose,^a ^* Paul R. Raithby ^b and Hans Toftlund ^a

^aDepartment of Chemistry, University of Southern Denmark, Campusvej 55, DK-5230 Odense M, Denmark, and ^bDepartment of Chemistry, University of Bath, Claverton Down, Bath, BA2 7AY, United Kingdom
^*Correspondence e-mail: jkb@chem.sdu.dk

(Received 18 October 2004; accepted 20 October 2004; online 30 October 2004)

The title compound, [AuCl₂(C₁₀H₈N₂)]NO₃, is layered parallel to ( $[\overline 1]$ 01) by π–π stacking. The individual { $[\overline 1]$ 01} layers are held together by extensive C—H⋯O and C—H⋯Cl hydrogen bonding.

Comment

The title compound, [Au(bipy)Cl₂]NO₃, (I), was synthesized by reaction of the corresponding chloride with ammonium nitrate in an attempt to synthesize [Au(bipy)(NH₃)₂](NO₃)₃.

Compound (I) (Fig. 1) is closely related to the previously characterized [Au(bipy)Cl₂]BF₄ salt, (II) [Cambridge Structural Database Version 5.25 (Allen, 2002 ) refcode ZENFED (McInnes et al., 1995 )], which has the same cation. Indeed, no change is observed in the intramolecular geometry of the cation in the two structures. It should noted that, while the cation in (II) has approximate C_2v symmetry, this is exact in (I) by being imposed by the space group (cf. Fig. 1). There are significant differences in the packing between the two structures. Nitrate is a stronger donor than tetrafluoroborate and this is observed in the structure. (I) and (II) both show axial interactions to the peripheral atoms of their counter-ions, NO₃⁻ and BF₄⁻, respectively, but these are found to be much shorter in (I) than in (II): Au⋯O = 3.008 (5) Å versus Au⋯F = 3.165–3.781 Å.

More important are the short C—H⋯O and C—H⋯Cl interactions (Table 2) illustrated in Fig. 2. The nitrate ion is seen to be coplanar with the complex cation, except for a small twist induced by the Au⋯O interactions. These hydrogen bonds link cations and anions into sheets parallel to the ( $[\overline 1]$ 01) plane. The sheets are then held together by Au⋯O interactions and π–π stacking between the pyridine rings, with centroid-to-centroid and plane-to-plane distances of 3.662 (3) and 3.336 Å, respectively. This is vastly different from the situation in (II), where no π–π stacking is observed and the molecules pack in a herringbone manner through C—H⋯F interactions, comparable to the C—H⋯F seen in (I), together with weaker C—H⋯Cl, C—H⋯π and Cl⋯π interactions.

Figure 1
View of (I

), shown with 50% probability displacement ellipsoids for the asymmetric unit only. [Symmetry codes: (i) −x, y, $[{1 \over 2}]$ − z; (ii) 1 − x, y, $[{1 \over 2}]$ − z.]

Figure 2
The short C—H⋯O and C—H⋯Cl interactions (dashed lines) in the (40 $[\overline 4]$ ) plane.

Experimental

The title compound was produced according to an established procedure (McInnes et al., 1995). In an attempt to replace the coordinated chloride with ammonia, a solution of the crude product was mixed with a concentrated solution of ammonium nitrate (4 M). Crystals of (I) precipitated after one day at room temperature.

Crystal data

[AuCl₂(C₁₀H₈N₂)]NO₃
M_r = 486.06
Monoclinic, C2/c
a = 6.9236 (2) Å
b = 14.0458 (4) Å
c = 13.0559 (4) Å
β = 96.5623 (13)°
V = 1261.44 (6) Å³
Z = 4
D_x = 2.559 Mg m⁻³
Mo Kα radiation
Cell parameters from 6608 reflections
θ = 2.9–27.5°
μ = 12.09 mm⁻¹
T = 150 (2) K
Block, pale yellow
0.30 × 0.10 × 0.05 mm

Data collection

Nonius Kappa CCD diffractometer
φ and ω scans
Absorption correction: multi-scan (SORTAV; Blessing, 1995 ) T_min = 0.461, T_max = 0.544
10491 measured reflections
1247 independent reflections
1097 reflections with I > 2σ(I)
R_int = 0.071
θ_max = 26°
h = −8 → 8
k = −17 → 17
l = −16 → 16

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.026
wR(F²) = 0.053
S = 1.06
1247 reflections
88 parameters
H-atom parameters constrained
w = 1/[σ²(F_o²) + (0.0222P)²] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max = 0.001
Δρ_max = 0.54 e Å⁻³
Δρ_min = −0.96 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

Au1—N1	2.030 (4)
Au1—Cl1	2.2510 (15)

N1—Au1—N1ⁱⁱ	80.6 (2)
N1—Au1—Cl1	95.46 (12)
N1—Au1—Cl1ⁱⁱ	176.06 (11)
Cl1—Au1—Cl1ⁱⁱ	88.45 (9)
Symmetry code: (ii) $[1-x,y,{\script{1\over 2}}-z]$ .

Table 2
Hydrogen-bonding geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3⋯O2ⁱⁱⁱ	0.95	2.42	3.307 (7)	156
C4—H4⋯O2^iv	0.95	2.55	3.205 (7)	126
C5—H5⋯O1^v	0.95	2.65	3.582 (5)	167
C5—H5⋯O2^iv	0.95	2.71	3.287 (7)	120
C6—H6⋯Cl1	0.95	2.64	3.231 (6)	121
C6—H6⋯Cl1^vi	0.95	2.69	3.476 (5)	141
Symmetry codes: (iii) $[{\script{1\over 2}}-x,{\script{1\over 2}}+y,{\script{1\over 2}}-z]$ ; (iv) $[x,1-y,z-{\script{1\over 2}}]$ ; (v) -x,1-y,-z; (vi) $[{\script{1\over 2}}-x,{\script{1\over 2}}-y,-z]$ .

All H atoms were constrained to have optimum geometry in the riding model, with C—H distances of 0.95 Å and U_iso(H) = 1.2U_eq(C).

Data collection: COLLECT (Nonius, 1997–2000 ); cell refinement: HKL SCALEPACK (Otwinowski & Minor, 1997 ); data reduction: HKL DENZO (Otwinowski & Minor, 1997) and SCALEPACK; program(s) used to solve structure: DIRDIF99 (Beurskens et al., 1999 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997 ); molecular graphics: X-SEED (Barbour, 2001 ); software used to prepare material for publication: WinGX publication routines (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536804026558/ng6054sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536804026558/ng6054Isup2.hkl

Computing details top

Data collection: COLLECT (Nonius, 1997-2000); cell refinement: HKL SCALEPACK (Otwinowski & Minor, 1997); data reduction: HKL DENZO (Otwinowski & Minor, 1997) and SCALEPACK; program(s) used to solve structure: DIRDIF99 (Beurskens et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: WinGX publication routines (Farrugia, 1999).

(2,2'-Bipyridine)dichlorogold(III) nitrate top

Crystal data top

[AuCl₂(C₁₀H₈N₂)]NO₃	F(000) = 904
M_r = 486.06	D_x = 2.559 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 6608 reflections
a = 6.9240 (2) Å	θ = 2.9–27.5°
b = 14.0460 (4) Å	µ = 12.09 mm⁻¹
c = 13.0560 (4) Å	T = 150 K
β = 96.562 (1)°	Block, pale yellow
V = 1261.44 (6) Å³	0.3 × 0.1 × 0.05 mm
Z = 4

Data collection top

Nonius Kappa CCD diffractometer	1097 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.071
φ and ω scans	θ_max = 26°, θ_min = 3.8°
Absorption correction: multi-scan (SORTAV; Blessing, 1995)	h = −8→8
T_min = 0.461, T_max = 0.544	k = −17→17
10491 measured reflections	l = −16→16
1247 independent reflections

Refinement top

Refinement on F²	Primary atom site location: heavy-atom method
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.026	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.053	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0222P)²] where P = (F_o² + 2F_c²)/3
1247 reflections	(Δ/σ)_max = 0.001
88 parameters	Δρ_max = 0.54 e Å⁻³
0 restraints	Δρ_min = −0.96 e Å⁻³

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Au1	0.5	0.330309 (19)	0.25	0.03725 (13)
N1	0.4035 (6)	0.4405 (3)	0.1574 (3)	0.0347 (10)
N2	0	0.3842 (5)	0.25	0.0448 (15)
O1	0	0.4719 (4)	0.25	0.0720 (17)
O2	0.1008 (7)	0.3406 (3)	0.3192 (4)	0.0684 (13)
Cl1	0.3870 (3)	0.21547 (11)	0.13868 (13)	0.0662 (4)
C2	0.4463 (7)	0.5274 (3)	0.1986 (4)	0.0352 (11)
C3	0.3881 (8)	0.6077 (4)	0.1435 (4)	0.0467 (14)
H3	0.4177	0.6688	0.1722	0.056*
C4	0.2864 (8)	0.5996 (4)	0.0462 (5)	0.0519 (15)
H4	0.2466	0.6548	0.0074	0.062*
C5	0.2437 (7)	0.5101 (4)	0.0065 (4)	0.0481 (13)
H5	0.1751	0.5034	−0.0604	0.058*
C6	0.2995 (8)	0.4317 (4)	0.0628 (4)	0.0425 (12)
H6	0.2659	0.3703	0.0361	0.051*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Au1	0.03767 (19)	0.03693 (19)	0.03505 (18)	0	−0.00486 (12)	0
N1	0.035 (2)	0.034 (2)	0.034 (2)	0.0018 (19)	0.0003 (19)	0.0035 (19)
N2	0.045 (4)	0.043 (4)	0.046 (4)	0	0.004 (3)	0
O1	0.079 (4)	0.049 (4)	0.090 (5)	0	0.020 (4)	0
O2	0.073 (3)	0.072 (3)	0.056 (3)	0.011 (2)	−0.008 (2)	0.017 (2)
Cl1	0.0814 (11)	0.0485 (9)	0.0632 (10)	−0.0002 (8)	−0.0159 (9)	−0.0147 (8)
C2	0.036 (3)	0.036 (3)	0.034 (3)	0.001 (2)	0.006 (2)	0.003 (2)
C3	0.048 (3)	0.044 (3)	0.048 (3)	0.005 (3)	0.002 (3)	0.002 (3)
C4	0.048 (3)	0.052 (4)	0.054 (4)	0.016 (3)	0.001 (3)	0.016 (3)
C5	0.040 (3)	0.067 (4)	0.035 (3)	0.005 (3)	−0.007 (2)	0.002 (3)
C6	0.038 (3)	0.052 (3)	0.036 (3)	−0.001 (3)	−0.003 (2)	−0.003 (3)

Geometric parameters (Å, º) top

Au1—N1ⁱ	2.030 (4)	C2—C3	1.373 (7)
Au1—N1	2.030 (4)	C2—C2ⁱ	1.457 (9)
Au1—Cl1	2.2510 (15)	C3—C4	1.386 (8)
Au1—Cl1ⁱ	2.2510 (15)	C3—H3	0.95
N1—C2	1.353 (6)	C4—C5	1.379 (8)
N1—C6	1.362 (6)	C4—H4	0.95
N2—O1	1.232 (8)	C5—C6	1.356 (7)
N2—O2ⁱⁱ	1.239 (5)	C5—H5	0.95
N2—O2	1.239 (5)	C6—H6	0.95

N1—Au1—N1ⁱ	80.6 (2)	C3—C2—C2ⁱ	124.8 (3)
N1—Au1—Cl1	95.46 (12)	C2—C3—C4	120.1 (5)
N1—Au1—Cl1ⁱ	176.06 (11)	C2—C3—H3	120
N1ⁱ—Au1—Cl1	176.06 (11)	C4—C3—H3	120
N1ⁱ—Au1—Cl1ⁱ	95.46 (12)	C5—C4—C3	119.0 (5)
Cl1—Au1—Cl1ⁱ	88.45 (9)	C5—C4—H4	120.5
C2—N1—C6	120.8 (4)	C3—C4—H4	120.5
C2—N1—Au1	114.1 (3)	C6—C5—C4	120.0 (5)
C6—N1—Au1	125.1 (3)	C6—C5—H5	120
O1—N2—O2ⁱⁱ	119.7 (3)	C4—C5—H5	120
O1—N2—O2	119.7 (3)	C5—C6—N1	120.4 (5)
O2ⁱⁱ—N2—O2	120.7 (7)	C5—C6—H6	119.8
N1—C2—C3	119.6 (4)	N1—C6—H6	119.8
N1—C2—C2ⁱ	115.6 (3)

N1ⁱ—Au1—N1—C2	−0.1 (2)	N1—C2—C3—C4	−0.1 (8)
Cl1—Au1—N1—C2	−179.6 (3)	C2ⁱ—C2—C3—C4	180.0 (6)
N1ⁱ—Au1—N1—C6	−178.2 (5)	C2—C3—C4—C5	0.5 (9)
Cl1—Au1—N1—C6	2.3 (4)	C3—C4—C5—C6	0.6 (8)
C6—N1—C2—C3	−1.5 (7)	C4—C5—C6—N1	−2.2 (8)
Au1—N1—C2—C3	−179.8 (4)	C2—N1—C6—C5	2.7 (8)
C6—N1—C2—C2ⁱ	178.4 (5)	Au1—N1—C6—C5	−179.3 (4)
Au1—N1—C2—C2ⁱ	0.2 (7)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···O2ⁱⁱⁱ	0.95	2.42	3.307 (7)	156
C4—H4···O2^iv	0.95	2.55	3.205 (7)	126
C5—H5···O1^v	0.95	2.65	3.582 (5)	167
C5—H5···O2^iv	0.95	2.71	3.287 (7)	120
C6—H6···Cl1	0.95	2.64	3.231 (6)	121
C6—H6···Cl1^vi	0.95	2.69	3.476 (5)	141

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

Acknowledgements

We thank the EPSRC for funding for the purchase of the diffractometer.

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