Bis(2-acetylpyridine-κN,O)silver(I) tetra-fluoridoborate: a complex with silver in a seesaw coordination geometry.

The reaction of 2-acetylpyridine with silver(I) tetra-fluorido-borate leads to the discrete title complex, [Ag(C(7)H(7)NO)(2)]BF(4), in the cation of which the Ag atom is coordinated by two 2-acetylpyridine ligands, each of which is N,O-bidentate, albeit with stronger bonding to the N atoms [Ag-N = 2.2018 (15) and 2.2088 (14) Å; Ag-O = 2.5380 (13) and 2.5454 (13) Å]. The four-coordinate Ag atom has a seesaw coordination geometry with a τ(4) index of 0.51. The tetra-fluoridoborate anion is disordered over two orientations with 0.568 (10):0.432 (10) occupancies.

Related literature

For other silver complexes with the same ligand, see: Bowmaker et al. (2005 ▶); Drew et al. (2005 ▶); Di Nicola et al. (2010 ▶). For examples of our previous work on silver complexes, see: Steel (2005 ▶); Fitchett & Steel (2006 ▶); O’Keefe & Steel (2007) ▶; Steel & Fitchett (2008 ▶); Golder et al. (2010 ▶). For details of the coordination geometry of four-coordinate silver, see: Young & Hanton (2008 ▶). For a definition of the τ4 index, see: Yang et al. (2007 ▶). 2-acetylpyridine coordin­ates to a variety of transition metals, usually as an N,O-chelating ligand, although it has been reported to act as an O-monodentate donor to a zinc porphyrin, see: Byrn et al. (1993 ▶).

Experimental

Crystal data

[Ag(C7H7NO)2]BF4

M = 436.95

Triclinic,

a = 7.2635 (2) Å

b = 9.7091 (3) Å

c = 11.7390 (4) Å

α = 85.624 (2)°

β = 81.452 (2)°

γ = 75.054 (2)°

V = 790.34 (4) Å3

Z = 2

Mo Kα radiation

μ = 1.33 mm−1

T = 116 K

0.37 × 0.36 × 0.14 mm

Data collection

Bruker SMART CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.805, T max = 1.000

18086 measured reflections

3661 independent reflections

3255 reflections with I > 2σ(I)

R int = 0.042

Refinement

R[F 2 > 2σ(F 2)] = 0.024

wR(F 2) = 0.051

S = 1.01

3661 reflections

247 parameters

H-atom parameters constrained

Δρmax = 0.33 e Å−3

Δρmin = −0.47 e Å−3

Data collection: SMART (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810048014/zs2079sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810048014/zs2079Isup2.hkl

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

[Ag(C7H7NO)2]BF4	Z = 2
Mr = 436.95	F(000) = 432
Triclinic, P1	Dx = 1.836 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.2635 (2) Å	Cell parameters from 8378 reflections
b = 9.7091 (3) Å	θ = 2.7–27.6°
c = 11.7390 (4) Å	µ = 1.33 mm−1
α = 85.624 (2)°	T = 116 K
β = 81.452 (2)°	Block, colourless
γ = 75.054 (2)°	0.37 × 0.36 × 0.14 mm
V = 790.34 (4) Å3

Bruker SMART CCD area-detector diffractometer	3661 independent reflections
Radiation source: fine-focus sealed tube	3255 reflections with I > 2σ(I)
graphite	Rint = 0.042
φ and ω scans	θmax = 27.6°, θmin = 2.7°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −9→9
Tmin = 0.805, Tmax = 1.000	k = −12→12
18086 measured reflections	l = −15→15

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)] = 0.024	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.051	H-atom parameters constrained
S = 1.01	w = 1/[σ2(Fo2) + (0.0251P)2] where P = (Fo2 + 2Fc2)/3
3661 reflections	(Δ/σ)max = 0.001
247 parameters	Δρmax = 0.33 e Å−3
0 restraints	Δρmin = −0.47 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	Occ. (<1)
Ag1	0.62372 (2)	0.358455 (15)	0.216889 (12)	0.02670 (6)
N1	0.7431 (2)	0.40200 (16)	0.03743 (13)	0.0200 (3)
C2	0.8515 (3)	0.2955 (2)	−0.02733 (17)	0.0266 (4)
H2	0.8596	0.2001	0.0010	0.032*
C3	0.9529 (3)	0.3180 (3)	−0.13419 (18)	0.0338 (5)
H3	1.0279	0.2398	−0.1781	0.041*
C4	0.9425 (3)	0.4558 (3)	−0.17500 (17)	0.0350 (5)
H4	1.0125	0.4742	−0.2471	0.042*
C5	0.8291 (3)	0.5676 (2)	−0.10994 (16)	0.0279 (5)
H5	0.8186	0.6635	−0.1375	0.033*
C6	0.7311 (3)	0.53789 (19)	−0.00415 (15)	0.0200 (4)
O7	0.5413 (2)	0.62559 (14)	0.16893 (11)	0.0279 (3)
C7	0.6095 (3)	0.65429 (19)	0.07221 (16)	0.0227 (4)
C8	0.5744 (3)	0.8064 (2)	0.0268 (2)	0.0353 (5)
H8A	0.4863	0.8686	0.0840	0.053*
H8B	0.5175	0.8157	−0.0449	0.053*
H8C	0.6966	0.8340	0.0117	0.053*
N9	0.4948 (2)	0.26845 (16)	0.37767 (14)	0.0238 (4)
C10	0.3564 (3)	0.1997 (2)	0.37892 (17)	0.0281 (4)
H10	0.3117	0.1917	0.3082	0.034*
C11	0.2753 (3)	0.1397 (2)	0.47867 (18)	0.0299 (5)
H11	0.1757	0.0933	0.4765	0.036*
C12	0.3420 (3)	0.1486 (2)	0.58052 (17)	0.0299 (5)
H12	0.2899	0.1077	0.6500	0.036*
C13	0.4870 (3)	0.2183 (2)	0.58072 (16)	0.0262 (4)
H13	0.5360	0.2250	0.6502	0.031*
C14	0.5589 (3)	0.27780 (19)	0.47815 (15)	0.0211 (4)
O15	0.7480 (2)	0.43100 (16)	0.38824 (12)	0.0414 (4)
C15	0.7082 (3)	0.3619 (2)	0.47483 (16)	0.0235 (4)
C16	0.7981 (3)	0.3629 (2)	0.58006 (17)	0.0327 (5)
H16A	0.6993	0.4069	0.6420	0.049*
H16B	0.8956	0.4177	0.5638	0.049*
H16C	0.8587	0.2647	0.6040	0.049*
B25	0.9904 (3)	0.9500 (2)	0.7668 (2)	0.0297 (5)
F26	1.1442 (2)	0.96995 (15)	0.81393 (12)	0.0499 (4)
F27	1.0213 (7)	0.8050 (5)	0.7373 (6)	0.0530 (14)	0.568 (10)
F28	0.8389 (6)	0.9732 (7)	0.8535 (4)	0.0778 (17)	0.568 (10)
F29	0.9559 (8)	1.0366 (5)	0.6754 (4)	0.0486 (13)	0.568 (10)
F27'	0.8174 (6)	1.0520 (7)	0.7916 (8)	0.080 (3)	0.432 (10)
F28'	1.0393 (11)	0.9638 (11)	0.6459 (4)	0.059 (2)	0.432 (10)
F29'	0.9705 (11)	0.8213 (7)	0.7954 (6)	0.0507 (17)	0.432 (10)

	U11	U22	U33	U12	U13	U23
Ag1	0.03524 (10)	0.02888 (9)	0.01804 (8)	−0.01335 (7)	−0.00432 (6)	0.00624 (6)
N1	0.0188 (8)	0.0235 (8)	0.0192 (8)	−0.0063 (7)	−0.0057 (6)	−0.0002 (6)
C2	0.0221 (11)	0.0319 (11)	0.0285 (10)	−0.0069 (9)	−0.0088 (8)	−0.0063 (8)
C3	0.0235 (11)	0.0533 (15)	0.0262 (11)	−0.0086 (10)	−0.0028 (8)	−0.0161 (10)
C4	0.0231 (11)	0.0685 (16)	0.0166 (10)	−0.0177 (11)	−0.0005 (8)	−0.0047 (10)
C5	0.0226 (11)	0.0441 (13)	0.0214 (10)	−0.0163 (9)	−0.0076 (8)	0.0088 (9)
C6	0.0176 (10)	0.0269 (10)	0.0183 (9)	−0.0094 (8)	−0.0073 (7)	0.0039 (7)
O7	0.0334 (8)	0.0262 (7)	0.0217 (7)	−0.0048 (6)	−0.0011 (6)	−0.0005 (6)
C7	0.0180 (10)	0.0233 (10)	0.0286 (10)	−0.0070 (8)	−0.0081 (8)	0.0038 (8)
C8	0.0332 (13)	0.0251 (11)	0.0470 (14)	−0.0087 (9)	−0.0058 (10)	0.0083 (9)
N9	0.0267 (9)	0.0215 (8)	0.0229 (8)	−0.0064 (7)	−0.0042 (7)	0.0035 (6)
C10	0.0287 (12)	0.0309 (11)	0.0270 (10)	−0.0101 (9)	−0.0074 (8)	0.0015 (8)
C11	0.0241 (11)	0.0300 (11)	0.0353 (12)	−0.0102 (9)	0.0027 (9)	−0.0001 (9)
C12	0.0320 (12)	0.0300 (11)	0.0261 (11)	−0.0109 (9)	0.0063 (8)	−0.0005 (8)
C13	0.0306 (12)	0.0272 (10)	0.0198 (10)	−0.0072 (9)	0.0008 (8)	−0.0031 (8)
C14	0.0235 (10)	0.0177 (9)	0.0198 (9)	−0.0026 (7)	−0.0008 (7)	0.0001 (7)
O15	0.0635 (11)	0.0464 (10)	0.0277 (8)	−0.0383 (9)	−0.0109 (7)	0.0100 (7)
C15	0.0271 (11)	0.0206 (9)	0.0219 (10)	−0.0050 (8)	−0.0008 (8)	−0.0030 (7)
C16	0.0323 (12)	0.0444 (13)	0.0245 (11)	−0.0153 (10)	−0.0037 (9)	−0.0002 (9)
B25	0.0255 (13)	0.0262 (12)	0.0366 (13)	−0.0086 (10)	−0.0009 (10)	0.0049 (10)
F26	0.0574 (10)	0.0577 (9)	0.0475 (9)	−0.0335 (8)	−0.0209 (7)	0.0115 (7)
F27	0.040 (2)	0.0249 (14)	0.099 (4)	−0.0053 (14)	−0.028 (2)	−0.003 (2)
F28	0.047 (2)	0.097 (4)	0.071 (3)	−0.009 (2)	0.0300 (17)	0.005 (2)
F29	0.060 (3)	0.043 (2)	0.051 (2)	−0.026 (2)	−0.022 (2)	0.0213 (17)
F27'	0.043 (3)	0.065 (4)	0.118 (7)	0.018 (2)	−0.011 (3)	−0.027 (4)
F28'	0.065 (4)	0.098 (6)	0.031 (2)	−0.053 (4)	−0.006 (2)	0.015 (3)
F29'	0.063 (4)	0.034 (3)	0.067 (4)	−0.030 (3)	−0.022 (3)	0.022 (3)

Ag1—N1	2.2088 (14)	C10—C11	1.388 (3)
Ag1—N9	2.2018 (15)	C10—H10	0.9500
Ag1—O7	2.5454 (13)	C11—C12	1.372 (3)
Ag1—O15	2.5380 (15)	C11—H11	0.9500
N1—C2	1.338 (2)	C12—C13	1.391 (3)
N1—C6	1.357 (2)	C12—H12	0.9500
C2—C3	1.389 (3)	C13—C14	1.385 (2)
C2—H2	0.9500	C13—H13	0.9500
C3—C4	1.373 (3)	C14—C15	1.510 (3)
C3—H3	0.9500	O15—C15	1.215 (2)
C4—C5	1.385 (3)	C15—C16	1.482 (3)
C4—H4	0.9500	C16—H16A	0.9800
C5—C6	1.386 (2)	C16—H16B	0.9800
C5—H5	0.9500	C16—H16C	0.9800
C6—C7	1.505 (3)	B25—F29'	1.307 (6)
O7—C7	1.212 (2)	B25—F29	1.324 (4)
C7—C8	1.502 (2)	B25—F28	1.368 (4)
C8—H8A	0.9800	B25—F26	1.380 (3)
C8—H8B	0.9800	B25—F27'	1.393 (5)
C8—H8C	0.9800	B25—F28'	1.415 (5)
N9—C10	1.340 (2)	B25—F27	1.428 (5)
N9—C14	1.348 (2)
N9—Ag1—N1	165.92 (6)	N9—C10—C11	123.05 (19)
N9—Ag1—O15	70.09 (5)	N9—C10—H10	118.5
N1—Ag1—O15	122.03 (5)	C11—C10—H10	118.5
N9—Ag1—O7	121.62 (5)	C12—C11—C10	118.66 (19)
N1—Ag1—O7	69.62 (5)	C12—C11—H11	120.7
O15—Ag1—O7	83.23 (5)	C10—C11—H11	120.7
C2—N1—C6	118.14 (16)	C11—C12—C13	119.11 (17)
C2—N1—Ag1	120.49 (12)	C11—C12—H12	120.4
C6—N1—Ag1	120.74 (13)	C13—C12—H12	120.4
N1—C2—C3	122.97 (19)	C14—C13—C12	119.07 (19)
N1—C2—H2	118.5	C14—C13—H13	120.5
C3—C2—H2	118.5	C12—C13—H13	120.5
C4—C3—C2	118.6 (2)	N9—C14—C13	122.03 (17)
C4—C3—H3	120.7	N9—C14—C15	116.76 (15)
C2—C3—H3	120.7	C13—C14—C15	121.16 (18)
C3—C4—C5	119.31 (18)	C15—O15—Ag1	110.96 (13)
C3—C4—H4	120.3	O15—C15—C16	121.06 (18)
C5—C4—H4	120.3	O15—C15—C14	120.05 (18)
C4—C5—C6	119.22 (19)	C16—C15—C14	118.84 (15)
C4—C5—H5	120.4	C15—C16—H16A	109.5
C6—C5—H5	120.4	C15—C16—H16B	109.5
N1—C6—C5	121.73 (18)	H16A—C16—H16B	109.5
N1—C6—C7	116.32 (15)	C15—C16—H16C	109.5
C5—C6—C7	121.93 (17)	H16A—C16—H16C	109.5
C7—O7—Ag1	112.42 (12)	H16B—C16—H16C	109.5
O7—C7—C8	120.55 (19)	F29—B25—F28	112.6 (3)
O7—C7—C6	120.42 (16)	F29'—B25—F26	109.0 (3)
C8—C7—C6	119.04 (17)	F29—B25—F26	111.2 (2)
C7—C8—H8A	109.5	F28—B25—F26	105.6 (3)
C7—C8—H8B	109.5	F29'—B25—F27'	111.3 (4)
H8A—C8—H8B	109.5	F26—B25—F27'	115.8 (3)
C7—C8—H8C	109.5	F29'—B25—F28'	109.9 (4)
H8A—C8—H8C	109.5	F26—B25—F28'	105.7 (3)
H8B—C8—H8C	109.5	F27'—B25—F28'	104.8 (3)
C10—N9—C14	118.07 (16)	F29—B25—F27	110.4 (3)
C10—N9—Ag1	121.89 (13)	F28—B25—F27	105.7 (3)
C14—N9—Ag1	120.00 (12)	F26—B25—F27	111.2 (3)

Table 1

Selected bond angles (°)

N9—Ag1—N1	165.92 (6)
N9—Ag1—O15	70.09 (5)
N1—Ag1—O15	122.03 (5)
N9—Ag1—O7	121.62 (5)
N1—Ag1—O7	69.62 (5)
O15—Ag1—O7	83.23 (5)