The silver(I) complex [HB{3-(CF₃),5-(CH₃)Pz}₃]AgNCCH₃ supported by a partially fluorinated scorpionate ligand

Tris(pyrazol­yl)borates are used extensively in metal coordination chemistry and belong to a class of ligands generally referred to as scorpionates. The steric and electronic properties of these ligands can be modified quite easily by varying the substituents on the 3-, 4-, and 5-positions of the pyrazolyl moieties on the B atom. Fluorinated tris­(pyrazol­yl)borates are useful in the stabilization of rare silver(I) complexes. The silver(I) adduct (aceto­nitrile-[kappa]N){tris[5-methyl-3-(tri­fluoro­meth­yl)pyrazol-1-yl-[kappa]N²]hydro­borato}silver(I), [Ag(C₁₅H₁₃BF₉N₆)(CH₃CN)] or [HB{3-(CF₃),5-(CH₃)Pz}₃]AgNCCH₃, was ob­tained by treating [HB{3-(CF₃),5-(CH₃)Pz}₃]Na with CF₃SO₃Ag in the presence of aceto­nitrile, and was isolated in 85% yield. Single-crystal X-ray diffraction analysis reveals that the Ag^I center has a pseudo-tetra­hedral all-nitro­gen coordination sphere, and is supported by a tris­(pyrazol­yl)borate ligand that binds to the Ag^I center in a [kappa]³-fashion.

Computing details

Data collection: APEX2 (Bruker, 2014); cell refinement: SAINT (Bruker, 2015); data reduction: SAINT (Bruker, 2015); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

(Acetonitrile-κN){tris[5-methyl-3-(trifluoromethyl)pyrazol-1-yl-κN²]hydroborato}silver(I)

Crystal data

[Ag(C15H13BF9N6)(C2H3N)]	Z = 2
Mr = 608.05	F(000) = 600
Triclinic, P1	Dx = 1.811 Mg m^−3
a = 8.9547 (7) Å	Mo Kα radiation, λ = 0.71073 Å
b = 11.3267 (8) Å	Cell parameters from 9042 reflections
c = 11.8011 (9) Å	θ = 4.0–37.9°
α = 102.919 (1)°	µ = 1.00 mm^−1
β = 103.564 (1)°	T = 100 K
γ = 96.901 (1)°	Cube, colourless
V = 1115.14 (15) Å^3	0.22 × 0.21 × 0.16 mm

Data collection

Bruker D8 Quest with a Photon 100 CMOS diffractometer	4696 reflections with I > 2σ(I)
φ and ω scans	Rint = 0.010
Absorption correction: multi-scan (SADABS; Bruker, 2015)	θmax = 27.0°, θmin = 3.8°
Tmin = 0.689, Tmax = 0.748	h = −11→11
11629 measured reflections	k = −14→14
4790 independent reflections	l = −15→15

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.021	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.055	w = 1/[σ^2(Fo^2) + (0.0177P)^2 + 1.6248P] where P = (Fo^2 + 2Fc^2)/3
S = 1.06	(Δ/σ)max = 0.001
4790 reflections	Δρmax = 0.57 e Å^−3
324 parameters	Δρmin = −0.49 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

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

	x	y	z	Uiso*/Ueq
Ag	0.79253 (2)	0.73463 (2)	0.35462 (2)	0.01743 (5)
F1	0.84943 (15)	0.32176 (13)	0.11826 (12)	0.0332 (3)
F2	0.88850 (14)	0.39485 (12)	0.30885 (11)	0.0281 (3)
F3	0.94071 (13)	0.51447 (12)	0.20110 (13)	0.0304 (3)
F4	0.84728 (17)	0.97886 (16)	0.25707 (14)	0.0474 (4)
F5	0.75572 (18)	0.92612 (13)	0.06444 (13)	0.0393 (3)
F6	0.7019 (2)	1.08659 (12)	0.16787 (16)	0.0494 (4)
F7	0.89067 (14)	0.77285 (12)	0.67192 (13)	0.0360 (3)
F8	0.79463 (15)	0.93628 (10)	0.67402 (12)	0.0307 (3)
F9	0.74840 (16)	0.82567 (14)	0.79101 (11)	0.0367 (3)
N1	0.48770 (16)	0.53594 (12)	0.21063 (12)	0.0104 (3)
N2	0.64496 (16)	0.54225 (13)	0.24945 (13)	0.0118 (3)
N3	0.44240 (17)	0.75452 (13)	0.22281 (12)	0.0125 (3)
N4	0.59141 (17)	0.80266 (13)	0.22742 (13)	0.0146 (3)
N5	0.46608 (16)	0.66972 (12)	0.40832 (12)	0.0107 (3)
N6	0.60581 (16)	0.74482 (13)	0.47027 (13)	0.0122 (3)
N7	1.03406 (18)	0.81917 (15)	0.43558 (14)	0.0199 (3)
C1	0.67485 (19)	0.44259 (15)	0.17984 (15)	0.0123 (3)
C2	0.5399 (2)	0.37110 (16)	0.09580 (15)	0.0142 (3)
H2	0.5310	0.2963	0.0368	0.017*
C3	0.4216 (2)	0.43391 (15)	0.11785 (14)	0.0127 (3)
C4	0.8375 (2)	0.41858 (17)	0.20202 (16)	0.0161 (3)
C5	0.2508 (2)	0.40134 (17)	0.05559 (17)	0.0194 (4)
H5A	0.1936	0.3767	0.1104	0.029*
H5B	0.2319	0.3330	−0.0166	0.029*
H5C	0.2148	0.4730	0.0321	0.029*
C6	0.5790 (2)	0.89832 (16)	0.17965 (15)	0.0174 (3)
C7	0.4245 (2)	0.91337 (17)	0.14344 (16)	0.0195 (4)
H7	0.3862	0.9747	0.1073	0.023*
C8	0.3391 (2)	0.81930 (16)	0.17175 (15)	0.0158 (3)
C9	0.7215 (3)	0.97188 (18)	0.16823 (18)	0.0246 (4)
C10	0.1667 (2)	0.78850 (19)	0.15200 (17)	0.0215 (4)
H10A	0.1279	0.7037	0.1022	0.032*
H10B	0.1158	0.8451	0.1108	0.032*
H10C	0.1430	0.7965	0.2301	0.032*
C11	0.61991 (19)	0.74711 (15)	0.58592 (15)	0.0123 (3)
C12	0.4927 (2)	0.67492 (15)	0.60112 (15)	0.0138 (3)
H12	0.4760	0.6621	0.6744	0.017*
C13	0.39584 (19)	0.62585 (15)	0.48507 (15)	0.0121 (3)
C14	0.7632 (2)	0.81977 (16)	0.67992 (16)	0.0157 (3)
C15	0.2415 (2)	0.54119 (16)	0.44456 (16)	0.0166 (3)
H15A	0.1579	0.5881	0.4261	0.025*
H15B	0.2278	0.5027	0.5089	0.025*
H15C	0.2375	0.4772	0.3721	0.025*
C16	1.1605 (2)	0.86796 (16)	0.47450 (16)	0.0158 (3)
C17	1.3233 (2)	0.92851 (17)	0.52025 (18)	0.0196 (4)
H17A	1.3766	0.9085	0.4567	0.029*
H17B	1.3737	0.9000	0.5898	0.029*
H17C	1.3292	1.0179	0.5451	0.029*
B1	0.4069 (2)	0.63860 (17)	0.26830 (16)	0.0115 (3)
H1	0.284 (3)	0.609 (2)	0.2417 (19)	0.013 (5)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ag	0.01223 (7)	0.01820 (8)	0.01916 (8)	−0.00170 (5)	0.00309 (5)	0.00302 (5)
F1	0.0245 (6)	0.0380 (7)	0.0300 (7)	0.0139 (5)	0.0082 (5)	−0.0107 (5)
F2	0.0249 (6)	0.0449 (7)	0.0233 (6)	0.0201 (5)	0.0082 (5)	0.0174 (5)
F3	0.0127 (5)	0.0336 (7)	0.0474 (8)	0.0009 (5)	0.0068 (5)	0.0188 (6)
F4	0.0320 (7)	0.0631 (10)	0.0404 (8)	−0.0210 (7)	−0.0052 (6)	0.0316 (7)
F5	0.0460 (8)	0.0406 (8)	0.0347 (7)	−0.0025 (6)	0.0231 (6)	0.0095 (6)
F6	0.0675 (11)	0.0182 (6)	0.0721 (11)	0.0013 (7)	0.0317 (9)	0.0206 (7)
F7	0.0159 (6)	0.0302 (7)	0.0459 (8)	0.0092 (5)	−0.0059 (5)	−0.0101 (6)
F8	0.0346 (7)	0.0136 (5)	0.0320 (6)	−0.0044 (5)	−0.0089 (5)	0.0054 (5)
F9	0.0381 (7)	0.0503 (8)	0.0120 (5)	−0.0100 (6)	−0.0004 (5)	0.0056 (5)
N1	0.0097 (6)	0.0104 (6)	0.0101 (6)	0.0006 (5)	0.0014 (5)	0.0026 (5)
N2	0.0100 (6)	0.0122 (6)	0.0127 (6)	0.0012 (5)	0.0026 (5)	0.0032 (5)
N3	0.0143 (7)	0.0125 (6)	0.0107 (6)	0.0035 (5)	0.0025 (5)	0.0032 (5)
N4	0.0167 (7)	0.0125 (7)	0.0133 (7)	−0.0003 (5)	0.0022 (5)	0.0045 (5)
N5	0.0102 (6)	0.0099 (6)	0.0117 (6)	0.0015 (5)	0.0029 (5)	0.0023 (5)
N6	0.0105 (6)	0.0118 (6)	0.0128 (7)	0.0014 (5)	0.0020 (5)	0.0022 (5)
N7	0.0164 (8)	0.0203 (8)	0.0204 (8)	−0.0013 (6)	0.0050 (6)	0.0023 (6)
C1	0.0136 (8)	0.0135 (7)	0.0110 (7)	0.0022 (6)	0.0053 (6)	0.0038 (6)
C2	0.0172 (8)	0.0133 (8)	0.0107 (7)	0.0019 (6)	0.0040 (6)	0.0009 (6)
C3	0.0149 (8)	0.0123 (7)	0.0096 (7)	0.0003 (6)	0.0017 (6)	0.0031 (6)
C4	0.0159 (8)	0.0179 (8)	0.0151 (8)	0.0046 (7)	0.0056 (6)	0.0028 (7)
C5	0.0145 (8)	0.0188 (8)	0.0185 (8)	0.0001 (7)	−0.0019 (7)	−0.0002 (7)
C6	0.0272 (9)	0.0121 (8)	0.0117 (8)	0.0017 (7)	0.0039 (7)	0.0033 (6)
C7	0.0318 (10)	0.0144 (8)	0.0133 (8)	0.0094 (7)	0.0044 (7)	0.0052 (6)
C8	0.0227 (9)	0.0165 (8)	0.0085 (7)	0.0096 (7)	0.0032 (6)	0.0016 (6)
C9	0.0351 (11)	0.0182 (9)	0.0209 (9)	−0.0013 (8)	0.0069 (8)	0.0095 (7)
C10	0.0208 (9)	0.0290 (10)	0.0164 (8)	0.0135 (8)	0.0037 (7)	0.0060 (7)
C11	0.0135 (8)	0.0108 (7)	0.0125 (7)	0.0043 (6)	0.0023 (6)	0.0029 (6)
C12	0.0174 (8)	0.0126 (7)	0.0131 (8)	0.0041 (6)	0.0050 (6)	0.0048 (6)
C13	0.0135 (8)	0.0103 (7)	0.0146 (8)	0.0040 (6)	0.0054 (6)	0.0046 (6)
C14	0.0177 (8)	0.0135 (8)	0.0141 (8)	0.0032 (6)	0.0013 (6)	0.0028 (6)
C15	0.0153 (8)	0.0151 (8)	0.0197 (8)	0.0000 (6)	0.0059 (7)	0.0052 (7)
C16	0.0191 (9)	0.0130 (8)	0.0162 (8)	0.0042 (7)	0.0065 (7)	0.0029 (6)
C17	0.0139 (8)	0.0144 (8)	0.0261 (9)	0.0012 (6)	0.0018 (7)	0.0009 (7)
B1	0.0113 (8)	0.0118 (8)	0.0109 (8)	0.0024 (6)	0.0021 (6)	0.0025 (7)

Geometric parameters (Å, º)

Ag—N2	2.3161 (14)	C2—H2	0.9500
Ag—N4	2.3818 (15)	C2—C3	1.387 (2)
Ag—N6	2.3913 (14)	C3—C5	1.494 (2)
Ag—N7	2.1521 (16)	C5—H5A	0.9800
F1—C4	1.336 (2)	C5—H5B	0.9800
F2—C4	1.335 (2)	C5—H5C	0.9800
F3—C4	1.343 (2)	C6—C7	1.392 (3)
F4—C9	1.327 (3)	C6—C9	1.488 (3)
F5—C9	1.339 (2)	C7—H7	0.9500
F6—C9	1.333 (2)	C7—C8	1.384 (3)
F7—C14	1.329 (2)	C8—C10	1.492 (3)
F8—C14	1.337 (2)	C10—H10A	0.9800
F9—C14	1.336 (2)	C10—H10B	0.9800
N1—N2	1.3626 (19)	C10—H10C	0.9800
N1—C3	1.360 (2)	C11—C12	1.391 (2)
N1—B1	1.555 (2)	C11—C14	1.492 (2)
N2—C1	1.335 (2)	C12—H12	0.9500
N3—N4	1.363 (2)	C12—C13	1.387 (2)
N3—C8	1.362 (2)	C13—C15	1.491 (2)
N3—B1	1.552 (2)	C15—H15A	0.9800
N4—C6	1.333 (2)	C15—H15B	0.9800
N5—N6	1.3641 (19)	C15—H15C	0.9800
N5—C13	1.363 (2)	C16—C17	1.453 (2)
N5—B1	1.555 (2)	C17—H17A	0.9800
N6—C11	1.335 (2)	C17—H17B	0.9800
N7—C16	1.136 (2)	C17—H17C	0.9800
C1—C2	1.394 (2)	B1—H1	1.06 (2)
C1—C4	1.487 (2)
N2—Ag—N4	82.63 (5)	C8—C7—H7	127.6
N2—Ag—N6	85.05 (5)	N3—C8—C7	107.30 (16)
N4—Ag—N6	79.66 (5)	N3—C8—C10	123.86 (16)
N7—Ag—N2	138.88 (6)	C7—C8—C10	128.85 (17)
N7—Ag—N4	129.54 (6)	F4—C9—F5	107.06 (19)
N7—Ag—N6	121.30 (5)	F4—C9—F6	107.57 (18)
N2—N1—B1	121.00 (13)	F4—C9—C6	112.80 (16)
C3—N1—N2	110.71 (13)	F5—C9—C6	112.46 (16)
C3—N1—B1	128.26 (14)	F6—C9—F5	105.47 (16)
N1—N2—Ag	116.54 (10)	F6—C9—C6	111.05 (18)
C1—N2—Ag	133.46 (11)	C8—C10—H10A	109.5
C1—N2—N1	105.30 (13)	C8—C10—H10B	109.5
N4—N3—B1	121.09 (13)	C8—C10—H10C	109.5
C8—N3—N4	110.78 (14)	H10A—C10—H10B	109.5
C8—N3—B1	128.10 (15)	H10A—C10—H10C	109.5
N3—N4—Ag	115.62 (10)	H10B—C10—H10C	109.5
C6—N4—Ag	136.66 (12)	N6—C11—C12	112.26 (15)
C6—N4—N3	105.29 (14)	N6—C11—C14	119.47 (15)
N6—N5—B1	121.73 (13)	C12—C11—C14	128.25 (16)
C13—N5—N6	110.72 (13)	C11—C12—H12	127.8
C13—N5—B1	127.50 (14)	C13—C12—C11	104.36 (15)
N5—N6—Ag	112.24 (10)	C13—C12—H12	127.8
C11—N6—Ag	131.37 (11)	N5—C13—C12	107.54 (14)
C11—N6—N5	105.13 (13)	N5—C13—C15	123.51 (15)
C16—N7—Ag	176.36 (16)	C12—C13—C15	128.95 (15)
N2—C1—C2	112.04 (15)	F7—C14—F8	106.10 (15)
N2—C1—C4	119.19 (15)	F7—C14—F9	107.20 (15)
C2—C1—C4	128.72 (15)	F7—C14—C11	112.92 (14)
C1—C2—H2	127.8	F8—C14—C11	112.77 (14)
C3—C2—C1	104.31 (14)	F9—C14—F8	106.12 (15)
C3—C2—H2	127.8	F9—C14—C11	111.29 (15)
N1—C3—C2	107.63 (14)	C13—C15—H15A	109.5
N1—C3—C5	123.52 (15)	C13—C15—H15B	109.5
C2—C3—C5	128.86 (15)	C13—C15—H15C	109.5
F1—C4—F3	106.90 (15)	H15A—C15—H15B	109.5
F1—C4—C1	111.43 (15)	H15A—C15—H15C	109.5
F2—C4—F1	106.78 (15)	H15B—C15—H15C	109.5
F2—C4—F3	105.93 (15)	N7—C16—C17	178.0 (2)
F2—C4—C1	112.65 (14)	C16—C17—H17A	109.5
F3—C4—C1	112.71 (15)	C16—C17—H17B	109.5
C3—C5—H5A	109.5	C16—C17—H17C	109.5
C3—C5—H5B	109.5	H17A—C17—H17B	109.5
C3—C5—H5C	109.5	H17A—C17—H17C	109.5
H5A—C5—H5B	109.5	H17B—C17—H17C	109.5
H5A—C5—H5C	109.5	N1—B1—N5	109.83 (13)
H5B—C5—H5C	109.5	N1—B1—H1	110.3 (12)
N4—C6—C7	111.91 (16)	N3—B1—N1	109.35 (13)
N4—C6—C9	119.77 (17)	N3—B1—N5	110.68 (13)
C7—C6—C9	128.31 (17)	N3—B1—H1	107.6 (12)
C6—C7—H7	127.6	N5—B1—H1	109.1 (11)
C8—C7—C6	104.73 (16)
Ag—N2—C1—C2	−153.68 (12)	C2—C1—C4—F2	−111.9 (2)
Ag—N2—C1—C4	28.6 (2)	C2—C1—C4—F3	128.32 (19)
Ag—N4—C6—C7	−160.73 (13)	C3—N1—N2—Ag	158.75 (10)
Ag—N4—C6—C9	20.6 (3)	C3—N1—N2—C1	−0.27 (17)
Ag—N6—C11—C12	−139.35 (13)	C3—N1—B1—N3	−103.21 (18)
Ag—N6—C11—C14	39.2 (2)	C3—N1—B1—N5	135.16 (16)
N1—N2—C1—C2	0.13 (18)	C4—C1—C2—C3	177.53 (16)
N1—N2—C1—C4	−177.62 (14)	C6—C7—C8—N3	0.43 (19)
N2—N1—C3—C2	0.31 (18)	C6—C7—C8—C10	−179.16 (17)
N2—N1—C3—C5	−179.86 (15)	C7—C6—C9—F4	148.4 (2)
N2—N1—B1—N3	74.80 (18)	C7—C6—C9—F5	−90.4 (2)
N2—N1—B1—N5	−46.84 (19)	C7—C6—C9—F6	27.5 (3)
N2—C1—C2—C3	0.05 (19)	C8—N3—N4—Ag	165.79 (10)
N2—C1—C4—F1	−174.55 (15)	C8—N3—N4—C6	0.51 (18)
N2—C1—C4—F2	65.5 (2)	C8—N3—B1—N1	127.72 (16)
N2—C1—C4—F3	−54.4 (2)	C8—N3—B1—N5	−111.15 (18)
N3—N4—C6—C7	−0.22 (19)	C9—C6—C7—C8	178.36 (18)
N3—N4—C6—C9	−178.85 (15)	C11—C12—C13—N5	−0.35 (18)
N4—N3—C8—C7	−0.60 (19)	C11—C12—C13—C15	−179.90 (16)
N4—N3—C8—C10	179.02 (15)	C12—C11—C14—F7	110.4 (2)
N4—N3—B1—N1	−50.19 (19)	C12—C11—C14—F8	−129.37 (19)
N4—N3—B1—N5	70.94 (18)	C12—C11—C14—F9	−10.2 (3)
N4—C6—C7—C8	−0.1 (2)	C13—N5—N6—Ag	147.85 (11)
N4—C6—C9—F4	−33.2 (3)	C13—N5—N6—C11	−0.39 (17)
N4—C6—C9—F5	88.0 (2)	C13—N5—B1—N1	−97.08 (18)
N4—C6—C9—F6	−154.09 (17)	C13—N5—B1—N3	142.08 (16)
N5—N6—C11—C12	0.16 (18)	C14—C11—C12—C13	−178.32 (16)
N5—N6—C11—C14	178.75 (14)	B1—N1—N2—Ag	−19.58 (18)
N6—N5—C13—C12	0.47 (18)	B1—N1—N2—C1	−178.60 (14)
N6—N5—C13—C15	−179.95 (15)	B1—N1—C3—C2	178.49 (15)
N6—N5—B1—N1	80.07 (18)	B1—N1—C3—C5	−1.7 (3)
N6—N5—B1—N3	−40.8 (2)	B1—N3—N4—Ag	−15.96 (18)
N6—C11—C12—C13	0.11 (19)	B1—N3—N4—C6	178.75 (14)
N6—C11—C14—F7	−68.0 (2)	B1—N3—C8—C7	−178.68 (15)
N6—C11—C14—F8	52.3 (2)	B1—N3—C8—C10	0.9 (3)
N6—C11—C14—F9	171.42 (15)	B1—N5—N6—Ag	−29.73 (17)
C1—C2—C3—N1	−0.22 (18)	B1—N5—N6—C11	−177.97 (14)
C1—C2—C3—C5	179.97 (17)	B1—N5—C13—C12	177.88 (15)
C2—C1—C4—F1	8.1 (3)	B1—N5—C13—C15	−2.5 (3)