Synthesis, crystal structure and photophysical properties of bis­[2,6-di­fluoro-3-(pyridin-2-yl)pyridine-κN](tri­fluoro­methane­sulfonato-κO)silver(I)

The Ag^I atom in the title compound, which exhibits strong blue emission, adopts a highly distorted trigonal–planar geometry coordinated by two pyridine N atoms of two crystallographically independent 2′,6′-di­fluoro-2,3′-bi­pyridine ligands and one O atom of the tri­fluoro­metane­sulfonate anion.

Key indicators

• Single-crystal X-ray study
• T = 193 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.025
• wR factor = 0.067
• Data-to-parameter ratio = 16.8

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT241_ALERT_2_C High   'MainMol' Ueq as Compared to Neighbors of         O1 Check
PLAT911_ALERT_3_C Missing FCF Refl Between Thmin & STh/L=    0.600          5 Report

Alert level G
PLAT042_ALERT_1_G Calc. and Reported Moiety Formula Strings Differ     Please Check
PLAT045_ALERT_1_G Calculated and Reported Z Differ by a Factor ...       0.50 Check
PLAT154_ALERT_1_G The s.u.'s on the Cell Angles are Equal ..(Note)     0.0011 Degree
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X)  Ag1      --O1       .        8.1 s.u.
PLAT242_ALERT_2_G Low    'MainMol' Ueq as Compared to Neighbors of        C21 Check
PLAT432_ALERT_2_G Short Inter X...Y Contact  C5       ..C5               3.17 Ang.
                                                  1-x,-y,-z  =      2_655 Check
PLAT910_ALERT_3_G Missing # of FCF Reflection(s) Below Theta(Min).          3 Note
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600         28 Note
PLAT933_ALERT_2_G Number of OMIT Records in Embedded .res File ...          4 Note
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density.          2 Info

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   2 ALERT level C = Check. Ensure it is not caused by an omission or oversight
  10 ALERT level G = General information/check it is not something unexpected

   3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   6 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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Computing details

Data collection: APEX2 (Bruker, 2014); cell refinement: SAINT (Bruker, 2014); data reduction: SAINT (Bruker, 2014); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014/7 (Sheldrick, 2015); molecular graphics: DIAMOND (Brandenburg, 2010); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and publCIF (Westrip, 2010).

Bis[2,6-difluoro-3-(pyridin-2-yl)pyridine-κN](trifluoromethanesulfonato-κO)silver(I)

Crystal data

[Ag(CF3O3S)(C10H6F2N2)2]	Z = 2
Mr = 641.28	F(000) = 632
Triclinic, P1	Dx = 1.874 Mg m^−3
a = 9.0627 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.9637 (3) Å	Cell parameters from 9858 reflections
c = 12.5727 (3) Å	θ = 2.5–28.3°
α = 82.4508 (11)°	µ = 1.07 mm^−1
β = 73.7215 (11)°	T = 193 K
γ = 71.5490 (11)°	Block, colourless
V = 1136.26 (5) Å^3	0.38 × 0.33 × 0.32 mm

Data collection

Bruker APEXII CCD diffractometer	5262 reflections with I > 2σ(I)
φ and ω scans	Rint = 0.029
Absorption correction: multi-scan (SADABS; Bruker, 2014)	θmax = 28.3°, θmin = 2.5°
Tmin = 0.610, Tmax = 0.746	h = −12→11
19973 measured reflections	k = −14→14
5623 independent reflections	l = −16→14

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.025	H-atom parameters constrained
wR(F^2) = 0.067	w = 1/[σ^2(Fo^2) + (0.0356P)^2 + 0.2813P] where P = (Fo^2 + 2Fc^2)/3
S = 1.12	(Δ/σ)max = 0.001
5623 reflections	Δρmax = 0.33 e Å^−3
334 parameters	Δρmin = −0.76 e Å^−3
0 restraints

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
Ag1	0.39687 (2)	0.11579 (2)	0.28356 (2)	0.02967 (5)
S1	0.58088 (5)	−0.20353 (4)	0.43046 (4)	0.02529 (9)
O1	0.47418 (19)	−0.09076 (14)	0.39174 (14)	0.0444 (4)
O2	0.54144 (16)	−0.22732 (14)	0.54886 (11)	0.0356 (3)
O3	0.74849 (17)	−0.22309 (15)	0.37857 (12)	0.0400 (3)
C21	0.5358 (3)	−0.3333 (2)	0.38115 (18)	0.0392 (4)
F5	0.5511 (2)	−0.31983 (18)	0.27233 (12)	0.0745 (5)
F6	0.6317 (2)	−0.44672 (13)	0.40282 (16)	0.0701 (5)
F7	0.38549 (17)	−0.33477 (14)	0.42807 (13)	0.0562 (4)
F1	0.7648 (2)	−0.33112 (13)	−0.01970 (14)	0.0698 (5)
F2	0.63399 (17)	0.08741 (13)	−0.11751 (10)	0.0460 (3)
N1	0.7033 (2)	−0.12143 (18)	−0.06736 (14)	0.0414 (4)
N2	0.57260 (17)	0.21084 (14)	0.17341 (12)	0.0249 (3)
C1	0.7501 (3)	−0.21237 (19)	0.00565 (19)	0.0430 (5)
C2	0.7813 (3)	−0.1947 (2)	0.10241 (18)	0.0414 (5)
H2	0.8198	−0.2652	0.1500	0.050*
C3	0.7538 (2)	−0.06916 (18)	0.12668 (16)	0.0334 (4)
H3	0.7695	−0.0515	0.1940	0.040*
C4	0.7031 (2)	0.03212 (17)	0.05317 (14)	0.0277 (3)
C5	0.6836 (2)	−0.00397 (19)	−0.04231 (15)	0.0324 (4)
C6	0.6718 (2)	0.16833 (17)	0.07537 (14)	0.0274 (3)
C7	0.7452 (3)	0.2481 (2)	−0.00157 (18)	0.0443 (5)
H7	0.8157	0.2158	−0.0700	0.053*
C8	0.7154 (3)	0.3738 (2)	0.0216 (2)	0.0518 (6)
H8	0.7646	0.4294	−0.0304	0.062*
C9	0.6128 (3)	0.4179 (2)	0.12161 (18)	0.0408 (5)
H9	0.5885	0.5049	0.1393	0.049*
C10	0.5462 (2)	0.33348 (18)	0.19542 (16)	0.0313 (4)
H10	0.4783	0.3635	0.2652	0.038*
F3	0.13496 (19)	0.67539 (12)	0.27171 (13)	0.0583 (4)
F4	−0.07604 (18)	0.40180 (14)	0.17706 (12)	0.0545 (4)
N3	0.0298 (2)	0.53662 (16)	0.22662 (15)	0.0401 (4)
N4	0.14448 (16)	0.10066 (14)	0.33810 (12)	0.0244 (3)
C11	0.1051 (2)	0.56069 (17)	0.29307 (18)	0.0381 (4)
C12	0.1546 (2)	0.48149 (18)	0.37758 (17)	0.0348 (4)
H12	0.2070	0.5058	0.4234	0.042*
C13	0.1239 (2)	0.36367 (17)	0.39263 (15)	0.0280 (3)
H13	0.1566	0.3044	0.4499	0.034*
C14	0.04554 (19)	0.33106 (16)	0.32476 (14)	0.0259 (3)
C15	0.0017 (2)	0.42467 (19)	0.24485 (16)	0.0337 (4)
C16	0.0162 (2)	0.20399 (16)	0.33730 (14)	0.0252 (3)
C17	−0.1363 (2)	0.19243 (19)	0.35044 (16)	0.0327 (4)
H17	−0.2251	0.2670	0.3494	0.039*
C18	−0.1577 (2)	0.0716 (2)	0.36507 (17)	0.0356 (4)
H18	−0.2613	0.0619	0.3747	0.043*
C19	−0.0260 (2)	−0.03498 (18)	0.36549 (16)	0.0333 (4)
H19	−0.0369	−0.1194	0.3747	0.040*
C20	0.1222 (2)	−0.01603 (17)	0.35223 (15)	0.0289 (3)
H20	0.2124	−0.0894	0.3532	0.035*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ag1	0.02256 (8)	0.02807 (8)	0.03687 (9)	−0.01100 (5)	−0.00184 (5)	0.00012 (5)
S1	0.0262 (2)	0.02496 (19)	0.0277 (2)	−0.00994 (16)	−0.01063 (16)	0.00272 (15)
O1	0.0493 (9)	0.0297 (7)	0.0602 (10)	−0.0111 (6)	−0.0309 (8)	0.0128 (7)
O2	0.0324 (7)	0.0467 (8)	0.0274 (7)	−0.0118 (6)	−0.0074 (5)	−0.0002 (6)
O3	0.0313 (7)	0.0560 (9)	0.0356 (7)	−0.0211 (6)	−0.0045 (6)	−0.0003 (6)
C21	0.0471 (11)	0.0352 (10)	0.0392 (11)	−0.0220 (9)	−0.0053 (9)	−0.0027 (8)
F5	0.1206 (15)	0.0919 (12)	0.0389 (8)	−0.0719 (12)	−0.0136 (9)	−0.0112 (8)
F6	0.0722 (10)	0.0270 (6)	0.1019 (14)	−0.0094 (7)	−0.0113 (9)	−0.0083 (7)
F7	0.0522 (8)	0.0609 (9)	0.0689 (10)	−0.0393 (7)	−0.0093 (7)	−0.0056 (7)
F1	0.0974 (13)	0.0359 (7)	0.0692 (10)	−0.0239 (8)	0.0022 (9)	−0.0199 (7)
F2	0.0640 (8)	0.0479 (7)	0.0289 (6)	−0.0161 (6)	−0.0189 (6)	0.0037 (5)
N1	0.0518 (11)	0.0434 (10)	0.0307 (9)	−0.0190 (8)	−0.0027 (7)	−0.0116 (7)
N2	0.0255 (7)	0.0279 (7)	0.0233 (7)	−0.0113 (6)	−0.0053 (5)	−0.0013 (5)
C1	0.0499 (12)	0.0298 (10)	0.0431 (12)	−0.0127 (9)	0.0041 (9)	−0.0126 (8)
C2	0.0435 (11)	0.0324 (10)	0.0394 (11)	−0.0061 (8)	−0.0046 (9)	0.0026 (8)
C3	0.0355 (10)	0.0351 (9)	0.0281 (9)	−0.0097 (8)	−0.0075 (7)	0.0003 (7)
C4	0.0286 (8)	0.0309 (8)	0.0229 (8)	−0.0108 (7)	−0.0028 (6)	−0.0022 (7)
C5	0.0373 (10)	0.0373 (10)	0.0228 (8)	−0.0135 (8)	−0.0047 (7)	−0.0017 (7)
C6	0.0299 (8)	0.0311 (8)	0.0232 (8)	−0.0128 (7)	−0.0061 (7)	−0.0003 (6)
C7	0.0578 (13)	0.0455 (11)	0.0290 (10)	−0.0285 (10)	0.0060 (9)	−0.0039 (8)
C8	0.0740 (16)	0.0464 (12)	0.0401 (12)	−0.0392 (12)	0.0005 (11)	0.0017 (10)
C9	0.0546 (13)	0.0319 (9)	0.0409 (11)	−0.0217 (9)	−0.0095 (9)	−0.0024 (8)
C10	0.0337 (9)	0.0309 (9)	0.0317 (9)	−0.0126 (7)	−0.0072 (7)	−0.0046 (7)
F3	0.0732 (10)	0.0287 (6)	0.0657 (9)	−0.0207 (6)	−0.0007 (7)	0.0006 (6)
F4	0.0618 (9)	0.0655 (9)	0.0485 (8)	−0.0220 (7)	−0.0370 (7)	0.0138 (7)
N3	0.0418 (9)	0.0312 (8)	0.0376 (9)	−0.0032 (7)	−0.0069 (7)	0.0060 (7)
N4	0.0206 (6)	0.0277 (7)	0.0248 (7)	−0.0079 (5)	−0.0052 (5)	−0.0006 (5)
C11	0.0393 (10)	0.0217 (8)	0.0430 (11)	−0.0070 (7)	0.0041 (8)	−0.0032 (8)
C12	0.0344 (10)	0.0314 (9)	0.0384 (10)	−0.0093 (7)	−0.0060 (8)	−0.0089 (8)
C13	0.0257 (8)	0.0286 (8)	0.0284 (9)	−0.0055 (6)	−0.0071 (7)	−0.0019 (7)
C14	0.0205 (7)	0.0268 (8)	0.0275 (8)	−0.0030 (6)	−0.0057 (6)	−0.0016 (6)
C15	0.0308 (9)	0.0368 (10)	0.0306 (9)	−0.0044 (7)	−0.0108 (7)	0.0010 (8)
C16	0.0226 (8)	0.0303 (8)	0.0228 (8)	−0.0074 (6)	−0.0063 (6)	−0.0015 (6)
C17	0.0219 (8)	0.0396 (10)	0.0364 (10)	−0.0064 (7)	−0.0077 (7)	−0.0069 (8)
C18	0.0241 (8)	0.0488 (11)	0.0380 (10)	−0.0162 (8)	−0.0032 (7)	−0.0121 (8)
C19	0.0326 (9)	0.0345 (9)	0.0365 (10)	−0.0173 (8)	−0.0034 (8)	−0.0074 (8)
C20	0.0271 (8)	0.0274 (8)	0.0307 (9)	−0.0085 (7)	−0.0048 (7)	−0.0006 (7)

Geometric parameters (Å, º)

Ag1—N2	2.2305 (14)	C8—C9	1.378 (3)
Ag1—N4	2.2496 (14)	C8—H8	0.9500
Ag1—O1	2.4879 (13)	C9—C10	1.377 (3)
S1—O1	1.4317 (14)	C9—H9	0.9500
S1—O3	1.4331 (14)	C10—H10	0.9500
S1—O2	1.4389 (14)	F3—C11	1.346 (2)
S1—C21	1.821 (2)	F4—C15	1.338 (2)
C21—F6	1.317 (3)	N3—C15	1.310 (3)
C21—F7	1.329 (2)	N3—C11	1.314 (3)
C21—F5	1.329 (3)	N4—C20	1.339 (2)
F1—C1	1.338 (2)	N4—C16	1.344 (2)
F2—C5	1.343 (2)	C11—C12	1.364 (3)
N1—C5	1.311 (3)	C12—C13	1.384 (3)
N1—C1	1.314 (3)	C12—H12	0.9500
N2—C10	1.341 (2)	C13—C14	1.393 (2)
N2—C6	1.345 (2)	C13—H13	0.9500
C1—C2	1.374 (3)	C14—C15	1.384 (2)
C2—C3	1.379 (3)	C14—C16	1.480 (2)
C2—H2	0.9500	C16—C17	1.390 (2)
C3—C4	1.394 (3)	C17—C18	1.380 (3)
C3—H3	0.9500	C17—H17	0.9500
C4—C5	1.385 (2)	C18—C19	1.382 (3)
C4—C6	1.478 (2)	C18—H18	0.9500
C6—C7	1.389 (3)	C19—C20	1.384 (2)
C7—C8	1.372 (3)	C19—H19	0.9500
C7—H7	0.9500	C20—H20	0.9500
N2—Ag1—N4	148.65 (5)	C7—C8—H8	120.6
N2—Ag1—O1	124.02 (5)	C9—C8—H8	120.6
N4—Ag1—O1	86.55 (5)	C10—C9—C8	118.71 (19)
O1—S1—O3	115.37 (9)	C10—C9—H9	120.6
O1—S1—O2	114.61 (9)	C8—C9—H9	120.6
O3—S1—O2	115.25 (8)	N2—C10—C9	123.12 (18)
O1—S1—C21	102.70 (10)	N2—C10—H10	118.4
O3—S1—C21	103.67 (10)	C9—C10—H10	118.4
O2—S1—C21	102.70 (9)	C15—N3—C11	115.31 (16)
S1—O1—Ag1	156.68 (10)	C20—N4—C16	118.07 (14)
F6—C21—F7	107.60 (17)	C20—N4—Ag1	119.02 (11)
F6—C21—F5	108.1 (2)	C16—N4—Ag1	121.76 (11)
F7—C21—F5	106.53 (18)	N3—C11—F3	114.28 (18)
F6—C21—S1	111.59 (15)	N3—C11—C12	126.40 (18)
F7—C21—S1	111.55 (15)	F3—C11—C12	119.3 (2)
F5—C21—S1	111.22 (14)	C11—C12—C13	116.10 (18)
C5—N1—C1	115.27 (18)	C11—C12—H12	121.9
C10—N2—C6	118.01 (15)	C13—C12—H12	121.9
C10—N2—Ag1	114.60 (12)	C12—C13—C14	120.70 (17)
C6—N2—Ag1	125.25 (11)	C12—C13—H13	119.7
N1—C1—F1	114.4 (2)	C14—C13—H13	119.7
N1—C1—C2	126.05 (19)	C15—C14—C13	114.98 (16)
F1—C1—C2	119.5 (2)	C15—C14—C16	123.52 (16)
C1—C2—C3	116.39 (19)	C13—C14—C16	121.49 (15)
C1—C2—H2	121.8	N3—C15—F4	114.67 (16)
C3—C2—H2	121.8	N3—C15—C14	126.49 (18)
C2—C3—C4	120.53 (18)	F4—C15—C14	118.84 (17)
C2—C3—H3	119.7	N4—C16—C17	121.95 (16)
C4—C3—H3	119.7	N4—C16—C14	116.22 (14)
C5—C4—C3	115.13 (17)	C17—C16—C14	121.82 (15)
C5—C4—C6	122.25 (16)	C18—C17—C16	119.40 (17)
C3—C4—C6	122.62 (16)	C18—C17—H17	120.3
N1—C5—F2	114.19 (16)	C16—C17—H17	120.3
N1—C5—C4	126.55 (18)	C17—C18—C19	118.87 (16)
F2—C5—C4	119.21 (17)	C17—C18—H18	120.6
N2—C6—C7	121.54 (17)	C19—C18—H18	120.6
N2—C6—C4	117.53 (15)	C18—C19—C20	118.52 (17)
C7—C6—C4	120.92 (17)	C18—C19—H19	120.7
C8—C7—C6	119.7 (2)	C20—C19—H19	120.7
C8—C7—H7	120.1	N4—C20—C19	123.19 (16)
C6—C7—H7	120.1	N4—C20—H20	118.4
C7—C8—C9	118.86 (19)	C19—C20—H20	118.4
O3—S1—O1—Ag1	−5.5 (3)	C4—C6—C7—C8	−179.3 (2)
O2—S1—O1—Ag1	131.9 (2)	C6—C7—C8—C9	0.1 (4)
C21—S1—O1—Ag1	−117.5 (3)	C7—C8—C9—C10	1.1 (4)
O1—S1—C21—F6	175.69 (16)	C6—N2—C10—C9	1.5 (3)
O3—S1—C21—F6	55.24 (17)	Ag1—N2—C10—C9	−162.77 (16)
O2—S1—C21—F6	−65.08 (17)	C8—C9—C10—N2	−2.0 (3)
O1—S1—C21—F7	−63.92 (17)	C15—N3—C11—F3	179.02 (17)
O3—S1—C21—F7	175.64 (15)	C15—N3—C11—C12	−0.4 (3)
O2—S1—C21—F7	55.32 (17)	N3—C11—C12—C13	1.2 (3)
O1—S1—C21—F5	54.86 (19)	F3—C11—C12—C13	−178.21 (17)
O3—S1—C21—F5	−65.58 (18)	C11—C12—C13—C14	−0.6 (3)
O2—S1—C21—F5	174.10 (16)	C12—C13—C14—C15	−0.6 (3)
C5—N1—C1—F1	178.08 (19)	C12—C13—C14—C16	178.07 (17)
C5—N1—C1—C2	−1.0 (3)	C11—N3—C15—F4	179.57 (17)
N1—C1—C2—C3	3.0 (4)	C11—N3—C15—C14	−1.1 (3)
F1—C1—C2—C3	−175.97 (19)	C13—C14—C15—N3	1.5 (3)
C1—C2—C3—C4	−2.4 (3)	C16—C14—C15—N3	−177.11 (18)
C2—C3—C4—C5	0.1 (3)	C13—C14—C15—F4	−179.13 (17)
C2—C3—C4—C6	179.92 (18)	C16—C14—C15—F4	2.2 (3)
C1—N1—C5—F2	−179.29 (18)	C20—N4—C16—C17	−0.1 (3)
C1—N1—C5—C4	−1.8 (3)	Ag1—N4—C16—C17	167.60 (13)
C3—C4—C5—N1	2.2 (3)	C20—N4—C16—C14	178.26 (15)
C6—C4—C5—N1	−177.59 (19)	Ag1—N4—C16—C14	−14.0 (2)
C3—C4—C5—F2	179.54 (17)	C15—C14—C16—N4	127.08 (18)
C6—C4—C5—F2	−0.2 (3)	C13—C14—C16—N4	−51.5 (2)
C10—N2—C6—C7	−0.1 (3)	C15—C14—C16—C17	−54.6 (3)
Ag1—N2—C6—C7	162.31 (15)	C13—C14—C16—C17	126.87 (19)
C10—N2—C6—C4	178.53 (15)	N4—C16—C17—C18	0.2 (3)
Ag1—N2—C6—C4	−19.0 (2)	C14—C16—C17—C18	−178.09 (17)
C5—C4—C6—N2	127.75 (19)	C16—C17—C18—C19	−0.4 (3)
C3—C4—C6—N2	−52.0 (2)	C17—C18—C19—C20	0.6 (3)
C5—C4—C6—C7	−53.6 (3)	C16—N4—C20—C19	0.3 (3)
C3—C4—C6—C7	126.7 (2)	Ag1—N4—C20—C19	−167.75 (14)
N2—C6—C7—C8	−0.7 (3)	C18—C19—C20—N4	−0.6 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C10—H10···O2^i	0.95	2.60	3.239 (2)	125
C13—H13···O2^i	0.95	2.60	3.173 (2)	119
C13—H13···O3^i	0.95	2.50	3.400 (2)	159
C19—H19···O3^ii	0.95	2.53	3.294 (2)	137
C20—H20···O1	0.95	2.55	3.197 (2)	126

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