Synthesis, crystal structure and DFT calculations of (2′,6′-di­fluoro-2,3′-bi­pyridine-κN2)[2,6-di­fluoro-3-(pyridin-2-yl)phenyl-κ2C1,N3]methyl­platinum(II)

Moon, S.-H.; Choi, S.; Kang, Y.

doi:10.1107/S2056989022010519

Synthesis, crystal structure and DFT calculations of (2′,6′-difluoro-2,3′-bipyridine-κN²)[2,6-difluoro-3-(pyridin-2-yl)phenyl-κ²C¹,N³]methylplatinum(II)

The title complex adopts a square-planar structure, consisting of a C,N bidentate anion, an N-coordinating neutral ligand and a methyl ligand. The emission of the title complex originates from a ligand-centered π–π* transition mixed with a metal-to-ligand charge-transfer transition.

Keywords: crystal structure; biipyridine ligand; photophysical properties; DFT calculation.

Read article Similar articles

Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S2056989022010519/hb8042sup1.cif Contains datablock I
	Structure factor file (CIF format) https://doi.org/10.1107/S2056989022010519/hb8042Isup2.hkl Contains datablock I

CCDC reference: 2216704

checkCIF report

Key indicators

Structure: I

Single-crystal X-ray study
T = 173 K
Mean (C-C) = 0.005 Å
R factor = 0.026
wR factor = 0.066
Data-to-parameter ratio = 18.0

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT971_ALERT_2_C Check Calcd Resid. Dens.  0.74Ang From Pt1             1.89 eA-3
PLAT971_ALERT_2_C Check Calcd Resid. Dens.  0.88Ang From Pt1             1.65 eA-3
PLAT971_ALERT_2_C Check Calcd Resid. Dens.  0.79Ang From Pt1             1.63 eA-3
PLAT972_ALERT_2_C Check Calcd Resid. Dens.  0.78Ang From Pt1            -1.67 eA-3
PLAT972_ALERT_2_C Check Calcd Resid. Dens.  0.69Ang From Pt1            -1.61 eA-3
PLAT972_ALERT_2_C Check Calcd Resid. Dens.  0.77Ang From Pt1            -1.61 eA-3
PLAT972_ALERT_2_C Check Calcd Resid. Dens.  0.44Ang From Pt1            -1.57 eA-3
PLAT972_ALERT_2_C Check Calcd Resid. Dens.  0.81Ang From Pt1            -1.56 eA-3
PLAT972_ALERT_2_C Check Calcd Resid. Dens.  0.71Ang From Pt1            -1.56 eA-3
PLAT972_ALERT_2_C Check Calcd Resid. Dens.  0.71Ang From Pt1            -1.56 eA-3
PLAT972_ALERT_2_C Check Calcd Resid. Dens.  0.84Ang From Pt1            -1.52 eA-3

Alert level G
PLAT434_ALERT_2_G Short Inter HL..HL Contact F3       ..F3       .       2.83 Ang.
                                                1-x,2-y,1-z  =      3_676 Check
PLAT794_ALERT_5_G Tentative Bond Valency for Pt1       (II)      .       1.94 Info
PLAT802_ALERT_4_G CIF Input Record(s) with more than 80 Characters          1 Info
PLAT883_ALERT_1_G No Info/Value for _atom_sites_solution_primary .     Please Do !
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600         12 Note
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density.          1 Info

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

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

Computing details top

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).

(2',6'-Difluoro-2,3'-bipyridine-κN²)[2,6-difluoro-3-(pyridin-2-yl)phenyl-κ²C¹,N³]methylplatinum(II) top

Crystal data top

[Pt(CH₃)(C₁₀H₅F₂N₂)(C₁₀H₆F₂N₂)]	F(000) = 1128
M_r = 593.45	D_x = 2.012 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 11.1590 (4) Å	Cell parameters from 9651 reflections
b = 11.4767 (4) Å	θ = 2.6–28.3°
c = 16.1918 (5) Å	µ = 7.21 mm⁻¹
β = 109.1050 (12)°	T = 173 K
V = 1959.44 (12) Å³	Block, yellow
Z = 4	0.51 × 0.31 × 0.20 mm

Data collection top

Bruker APEXII CCD diffractometer	4088 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.050
Absorption correction: multi-scan (SADABS; Bruker, 2014)	θ_max = 28.3°, θ_min = 1.9°
T_min = 0.258, T_max = 0.746	h = −14→13
35428 measured reflections	k = −15→14
4873 independent reflections	l = −21→21

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.026	H-atom parameters constrained
wR(F²) = 0.066	w = 1/[σ²(F_o²) + (0.0339P)² + 1.3145P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max = 0.002
4873 reflections	Δρ_max = 1.91 e Å⁻³
271 parameters	Δρ_min = −1.66 e Å⁻³

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
Pt1	0.79889 (2)	0.62391 (2)	0.38446 (2)	0.02333 (6)
F1	0.8075 (3)	0.4105 (2)	0.68292 (16)	0.0611 (7)
F2	1.1104 (2)	0.6711 (2)	0.70353 (13)	0.0498 (6)
F3	0.4034 (2)	0.9425 (2)	0.43326 (16)	0.0567 (7)
F4	0.7227 (2)	0.9395 (2)	0.32471 (16)	0.0525 (6)
N1	0.9578 (3)	0.7325 (2)	0.42974 (17)	0.0273 (6)
N2	0.9587 (3)	0.5417 (3)	0.69091 (18)	0.0356 (7)
N3	0.7423 (3)	0.6787 (2)	0.25218 (17)	0.0259 (6)
N4	0.5636 (3)	0.9383 (3)	0.37943 (19)	0.0374 (7)
C1	0.8571 (3)	0.5774 (3)	0.5081 (2)	0.0254 (7)
C2	0.8049 (4)	0.4979 (3)	0.5511 (2)	0.0333 (8)
H2	0.7332	0.4526	0.5197	0.040*
C3	0.8589 (4)	0.4860 (3)	0.6398 (2)	0.0363 (8)
C4	1.0080 (4)	0.6150 (3)	0.6493 (2)	0.0319 (8)
C5	0.9668 (3)	0.6381 (3)	0.5607 (2)	0.0259 (7)
C6	1.0230 (3)	0.7225 (3)	0.5166 (2)	0.0274 (7)
C7	1.1322 (4)	0.7899 (4)	0.5540 (2)	0.0404 (9)
H7	1.1767	0.7851	0.6149	0.048*
C8	1.1747 (4)	0.8630 (4)	0.5023 (3)	0.0493 (11)
H8	1.2493	0.9079	0.5273	0.059*
C9	1.1092 (4)	0.8711 (3)	0.4146 (3)	0.0437 (10)
H9	1.1380	0.9207	0.3781	0.052*
C10	0.9997 (4)	0.8051 (3)	0.3804 (2)	0.0359 (8)
H10	0.9530	0.8117	0.3200	0.043*
C11	0.4600 (4)	0.7447 (3)	0.2797 (3)	0.0381 (9)
H11	0.4238	0.6785	0.2454	0.046*
C12	0.4010 (4)	0.7948 (4)	0.3344 (3)	0.0406 (9)
H12	0.3245	0.7640	0.3392	0.049*
C13	0.4575 (4)	0.8898 (4)	0.3807 (3)	0.0390 (9)
C14	0.6162 (4)	0.8884 (3)	0.3281 (3)	0.0356 (9)
C15	0.5722 (3)	0.7921 (3)	0.2758 (2)	0.0292 (7)
C16	0.6394 (3)	0.7474 (3)	0.2168 (2)	0.0284 (7)
C17	0.5998 (4)	0.7774 (3)	0.1295 (2)	0.0380 (9)
H17	0.5262	0.8241	0.1059	0.046*
C18	0.6668 (4)	0.7397 (3)	0.0763 (2)	0.0382 (9)
H18	0.6413	0.7617	0.0164	0.046*
C19	0.7699 (4)	0.6705 (3)	0.1114 (2)	0.0364 (8)
H19	0.8172	0.6424	0.0763	0.044*
C20	0.8051 (4)	0.6414 (3)	0.1992 (2)	0.0342 (8)
H20	0.8771	0.5928	0.2231	0.041*
C21	0.6504 (4)	0.5106 (3)	0.3531 (2)	0.0383 (9)
H21A	0.6027	0.5169	0.2906	0.057*
H21B	0.6824	0.4309	0.3665	0.057*
H21C	0.5947	0.5294	0.3871	0.057*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Pt1	0.02173 (9)	0.02615 (9)	0.01832 (7)	−0.00107 (5)	0.00136 (5)	−0.00167 (4)
F1	0.086 (2)	0.0583 (15)	0.0389 (13)	−0.0253 (15)	0.0204 (13)	0.0103 (12)
F2	0.0438 (14)	0.0766 (16)	0.0194 (10)	−0.0193 (13)	−0.0028 (9)	−0.0036 (10)
F3	0.0405 (14)	0.0813 (19)	0.0549 (15)	0.0043 (13)	0.0243 (12)	−0.0113 (14)
F4	0.0407 (13)	0.0626 (16)	0.0616 (15)	−0.0250 (12)	0.0267 (12)	−0.0259 (13)
N1	0.0235 (14)	0.0344 (16)	0.0218 (13)	−0.0019 (12)	0.0044 (11)	−0.0006 (11)
N2	0.0425 (18)	0.0406 (18)	0.0239 (14)	0.0026 (15)	0.0110 (13)	0.0027 (12)
N3	0.0252 (14)	0.0243 (14)	0.0231 (13)	−0.0043 (12)	0.0008 (11)	−0.0029 (11)
N4	0.0296 (17)	0.048 (2)	0.0330 (16)	−0.0036 (15)	0.0080 (13)	−0.0094 (14)
C1	0.0286 (18)	0.0247 (17)	0.0218 (15)	0.0005 (14)	0.0066 (13)	−0.0037 (13)
C2	0.039 (2)	0.0299 (18)	0.0281 (17)	−0.0070 (16)	0.0071 (15)	−0.0012 (14)
C3	0.048 (2)	0.033 (2)	0.0296 (17)	−0.0009 (17)	0.0154 (16)	0.0039 (15)
C4	0.0282 (19)	0.042 (2)	0.0219 (16)	0.0013 (16)	0.0025 (14)	−0.0040 (14)
C5	0.0211 (16)	0.0328 (19)	0.0223 (15)	0.0010 (14)	0.0051 (13)	−0.0029 (13)
C6	0.0244 (17)	0.0363 (19)	0.0205 (15)	−0.0004 (15)	0.0062 (13)	−0.0027 (13)
C7	0.037 (2)	0.058 (3)	0.0226 (16)	−0.0141 (19)	0.0048 (15)	−0.0071 (16)
C8	0.042 (2)	0.065 (3)	0.038 (2)	−0.029 (2)	0.0086 (18)	−0.0128 (19)
C9	0.044 (3)	0.054 (3)	0.034 (2)	−0.016 (2)	0.0139 (18)	−0.0024 (17)
C10	0.035 (2)	0.045 (2)	0.0272 (17)	−0.0077 (17)	0.0085 (15)	0.0037 (15)
C11	0.029 (2)	0.033 (2)	0.046 (2)	−0.0004 (16)	0.0039 (16)	0.0021 (16)
C12	0.0227 (19)	0.044 (2)	0.053 (2)	−0.0001 (17)	0.0097 (17)	0.0070 (19)
C13	0.028 (2)	0.055 (3)	0.034 (2)	0.0036 (18)	0.0094 (16)	0.0003 (17)
C14	0.032 (2)	0.040 (2)	0.0322 (19)	−0.0058 (16)	0.0069 (16)	−0.0042 (15)
C15	0.0227 (17)	0.0321 (19)	0.0266 (16)	0.0024 (15)	−0.0004 (13)	0.0061 (14)
C16	0.0265 (17)	0.0286 (18)	0.0241 (15)	−0.0045 (14)	0.0002 (13)	−0.0017 (13)
C17	0.037 (2)	0.041 (2)	0.0276 (17)	0.0062 (17)	−0.0014 (15)	0.0065 (15)
C18	0.049 (2)	0.037 (2)	0.0223 (16)	−0.0066 (18)	0.0031 (16)	0.0015 (14)
C19	0.046 (2)	0.036 (2)	0.0278 (17)	−0.0094 (18)	0.0136 (16)	−0.0063 (15)
C20	0.037 (2)	0.034 (2)	0.0293 (18)	0.0016 (16)	0.0073 (16)	−0.0023 (14)
C21	0.033 (2)	0.040 (2)	0.0319 (18)	−0.0073 (17)	−0.0022 (15)	−0.0036 (16)

Geometric parameters (Å, º) top

Pt1—C1	1.966 (3)	C7—H7	0.9500
Pt1—C21	2.036 (4)	C8—C9	1.371 (6)
Pt1—N1	2.094 (3)	C8—H8	0.9500
Pt1—N3	2.120 (3)	C9—C10	1.389 (6)
F1—C3	1.352 (4)	C9—H9	0.9500
F2—C4	1.354 (4)	C10—H10	0.9500
F3—C13	1.339 (4)	C11—C15	1.386 (5)
F4—C14	1.342 (4)	C11—C12	1.390 (5)
N1—C10	1.340 (4)	C11—H11	0.9500
N1—C6	1.360 (4)	C12—C13	1.356 (6)
N2—C4	1.306 (5)	C12—H12	0.9500
N2—C3	1.316 (5)	C14—C15	1.382 (5)
N3—C20	1.343 (5)	C15—C16	1.484 (5)
N3—C16	1.356 (4)	C16—C17	1.379 (5)
N4—C14	1.297 (5)	C17—C18	1.383 (5)
N4—C13	1.314 (5)	C17—H17	0.9500
C1—C2	1.386 (5)	C18—C19	1.361 (6)
C1—C5	1.423 (5)	C18—H18	0.9500
C2—C3	1.371 (5)	C19—C20	1.386 (5)
C2—H2	0.9500	C19—H19	0.9500
C4—C5	1.382 (5)	C20—H20	0.9500
C5—C6	1.461 (5)	C21—H21A	0.9800
C6—C7	1.402 (5)	C21—H21B	0.9800
C7—C8	1.374 (6)	C21—H21C	0.9800

C1—Pt1—C21	92.94 (14)	C10—C9—H9	120.8
C1—Pt1—N1	81.10 (12)	N1—C10—C9	122.3 (3)
C21—Pt1—N1	174.00 (12)	N1—C10—H10	118.8
C1—Pt1—N3	177.73 (12)	C9—C10—H10	118.8
C21—Pt1—N3	89.33 (13)	C15—C11—C12	119.4 (4)
N1—Pt1—N3	96.63 (10)	C15—C11—H11	120.3
C10—N1—C6	119.7 (3)	C12—C11—H11	120.3
C10—N1—Pt1	125.6 (2)	C13—C12—C11	116.9 (4)
C6—N1—Pt1	114.7 (2)	C13—C12—H12	121.5
C4—N2—C3	113.7 (3)	C11—C12—H12	121.5
C20—N3—C16	117.6 (3)	N4—C13—F3	114.5 (3)
C20—N3—Pt1	120.3 (2)	N4—C13—C12	126.2 (4)
C16—N3—Pt1	122.0 (2)	F3—C13—C12	119.3 (4)
C14—N4—C13	114.9 (3)	N4—C14—F4	115.2 (3)
C2—C1—C5	116.3 (3)	N4—C14—C15	127.0 (4)
C2—C1—Pt1	129.6 (3)	F4—C14—C15	117.7 (3)
C5—C1—Pt1	114.1 (2)	C14—C15—C11	115.5 (3)
C3—C2—C1	118.6 (3)	C14—C15—C16	121.2 (3)
C3—C2—H2	120.7	C11—C15—C16	123.2 (3)
C1—C2—H2	120.7	N3—C16—C17	121.4 (3)
N2—C3—F1	113.7 (3)	N3—C16—C15	117.7 (3)
N2—C3—C2	127.0 (3)	C17—C16—C15	120.9 (3)
F1—C3—C2	119.3 (3)	C16—C17—C18	120.3 (4)
N2—C4—F2	112.4 (3)	C16—C17—H17	119.9
N2—C4—C5	127.3 (3)	C18—C17—H17	119.9
F2—C4—C5	120.4 (3)	C19—C18—C17	118.5 (3)
C4—C5—C1	117.1 (3)	C19—C18—H18	120.7
C4—C5—C6	125.7 (3)	C17—C18—H18	120.7
C1—C5—C6	117.1 (3)	C18—C19—C20	119.1 (4)
N1—C6—C7	119.7 (3)	C18—C19—H19	120.4
N1—C6—C5	113.0 (3)	C20—C19—H19	120.4
C7—C6—C5	127.4 (3)	N3—C20—C19	123.1 (4)
C8—C7—C6	119.9 (3)	N3—C20—H20	118.5
C8—C7—H7	120.0	C19—C20—H20	118.5
C6—C7—H7	120.0	Pt1—C21—H21A	109.5
C9—C8—C7	119.9 (4)	Pt1—C21—H21B	109.5
C9—C8—H8	120.1	H21A—C21—H21B	109.5
C7—C8—H8	120.1	Pt1—C21—H21C	109.5
C8—C9—C10	118.5 (4)	H21A—C21—H21C	109.5
C8—C9—H9	120.8	H21B—C21—H21C	109.5

C5—C1—C2—C3	2.0 (5)	C8—C9—C10—N1	−1.4 (6)
Pt1—C1—C2—C3	−175.8 (3)	C15—C11—C12—C13	0.7 (6)
C4—N2—C3—F1	−179.7 (3)	C14—N4—C13—F3	−179.5 (3)
C4—N2—C3—C2	−0.2 (6)	C14—N4—C13—C12	0.2 (6)
C1—C2—C3—N2	−0.9 (6)	C11—C12—C13—N4	−0.7 (6)
C1—C2—C3—F1	178.6 (3)	C11—C12—C13—F3	178.9 (4)
C3—N2—C4—F2	180.0 (3)	C13—N4—C14—F4	178.2 (3)
C3—N2—C4—C5	0.0 (6)	C13—N4—C14—C15	0.4 (6)
N2—C4—C5—C1	1.2 (6)	N4—C14—C15—C11	−0.4 (6)
F2—C4—C5—C1	−178.8 (3)	F4—C14—C15—C11	−178.1 (3)
N2—C4—C5—C6	178.7 (3)	N4—C14—C15—C16	177.0 (4)
F2—C4—C5—C6	−1.2 (5)	F4—C14—C15—C16	−0.8 (5)
C2—C1—C5—C4	−2.1 (5)	C12—C11—C15—C14	−0.2 (5)
Pt1—C1—C5—C4	176.0 (2)	C12—C11—C15—C16	−177.5 (3)
C2—C1—C5—C6	−179.9 (3)	C20—N3—C16—C17	0.5 (5)
Pt1—C1—C5—C6	−1.8 (4)	Pt1—N3—C16—C17	−176.6 (3)
C10—N1—C6—C7	1.2 (5)	C20—N3—C16—C15	−178.0 (3)
Pt1—N1—C6—C7	179.1 (3)	Pt1—N3—C16—C15	5.0 (4)
C10—N1—C6—C5	−178.7 (3)	C14—C15—C16—N3	81.1 (4)
Pt1—N1—C6—C5	−0.7 (4)	C11—C15—C16—N3	−101.7 (4)
C4—C5—C6—N1	−175.9 (3)	C14—C15—C16—C17	−97.3 (4)
C1—C5—C6—N1	1.6 (4)	C11—C15—C16—C17	79.8 (5)
C4—C5—C6—C7	4.2 (6)	N3—C16—C17—C18	−1.5 (5)
C1—C5—C6—C7	−178.2 (4)	C15—C16—C17—C18	176.9 (3)
N1—C6—C7—C8	−1.9 (6)	C16—C17—C18—C19	1.6 (6)
C5—C6—C7—C8	178.0 (4)	C17—C18—C19—C20	−0.8 (6)
C6—C7—C8—C9	0.9 (7)	C16—N3—C20—C19	0.4 (5)
C7—C8—C9—C10	0.7 (7)	Pt1—N3—C20—C19	177.5 (3)
C6—N1—C10—C9	0.5 (6)	C18—C19—C20—N3	−0.2 (6)
Pt1—N1—C10—C9	−177.3 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7···F2	0.95	2.24	2.858 (4)	122
C12—H12···F1ⁱ	0.95	2.44	3.259 (5)	144
C20—H20···N2ⁱⁱ	0.95	2.45	3.385 (5)	167

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

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Text
		Plain Text

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Text
		Plain Text

Search IUCr Journals		doi		Advanced search
Author		volume	page

Synthesis, crystal structure and DFT calculations of (2′,6′-di­fluoro-2,3′-bi­pyridine-κN2)[2,6-di­fluoro-3-(pyridin-2-yl)phenyl-κ2C1,N3]methyl­platinum(II)

Supporting information

Key indicators

checkCIF/PLATON results

Synthesis, crystal structure and DFT calculations of (2′,6′-difluoro-2,3′-bipyridine-κN²)[2,6-difluoro-3-(pyridin-2-yl)phenyl-κ²C¹,N³]methylplatinum(II)