Crystal packing analysis of in situ cryocrystallized 2,2,2-tri­fluoro­aceto­phenone

In this present study, the crystal structure of 2,2,2-tri­fluoro­aceto­phenone (TFAP) is determined using in situ cryocrystallization techniques. The main objective of this work is to study its crystal packing associated with the various inter­molecular inter­actions, along with a detailed comparison with the features of substituted analogs. It is inter­esting to note how the chemical substitution of different functional groups influences the crystal packing, the electronic environment of the mol­ecule and the nature of the various inter­molecular inter­actions.

Key indicators

• Single-crystal X-ray study
• T = 110 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.024
• wR factor = 0.064
• Data-to-parameter ratio = 9.6

checkCIF/PLATON results

No syntax errors found



Alert level A
PLAT029_ALERT_3_A _diffrn_measured_fraction_theta_full value Low .      0.708 Why?

Author Response: Discussed in the text

Alert level B
PLAT480_ALERT_4_B Long H...A H-Bond Reported H6       ..F3               2.94 Ang.
PLAT480_ALERT_4_B Long H...A H-Bond Reported H5       ..F3               2.98 Ang.

Alert level C
PLAT088_ALERT_3_C Poor Data / Parameter Ratio ....................       9.59 Note
PLAT480_ALERT_4_C Long H...A H-Bond Reported H5       ..F2               2.63 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H4       ..O1               2.74 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H6       ..F2               2.69 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H3       ..O1               2.95 Ang.
PLAT481_ALERT_4_C Long D...A H-Bond Reported C3       ..O1               3.88 Ang.
PLAT911_ALERT_3_C Missing FCF Refl Between Thmin & STh/L=    0.600         48 Report

Alert level G
PLAT952_ALERT_5_G Calculated (ThMax) and CIF-Reported Lmax Differ           5 Units
PLAT958_ALERT_1_G Calculated (ThMax) and Actual (FCF) Lmax Differ           5 Units
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density.          1 Info

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

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

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Computing details

Data collection: APEX2 (Bruker, 2012); cell refinement: SAINT (Bruker, 2012); data reduction: SAINT (Bruker, 2012); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL2016/6 (Sheldrick, 2015); molecular graphics: Mercury (Macrae et al., 2008); software used to prepare material for publication: CIFTAB (Sheldrick, 2008) and PLATON (Spek, 2009).

2,2,2-Trifluoroacetophenone

Crystal data

C8H5F3O	F(000) = 704
Mr = 174.12	Dx = 1.589 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 13.8129 (3) Å	Cell parameters from 5549 reflections
b = 12.6034 (2) Å	θ = 2.2–30.2°
c = 8.3595 (2) Å	µ = 0.16 mm^−1
β = 90.396 (1)°	T = 110 K
V = 1455.27 (5) Å^3	Block, colorless
Z = 8	0.30 × 0.30 × 0.30 mm

Data collection

Bruker APEXII CCD diffractometer	944 reflections with I > 2σ(I)
Radiation source: fine focus sealed tube	Rint = 0.014
ω scans	θmax = 26.7°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −17→17
Tmin = 0.697, Tmax = 0.746	k = −15→15
9958 measured reflections	l = −5→5
1045 independent reflections

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.024	H-atom parameters constrained
wR(F^2) = 0.064	w = 1/[σ^2(Fo^2) + (0.0305P)^2 + 0.8314P] where P = (Fo^2 + 2Fc^2)/3
S = 1.08	(Δ/σ)max < 0.001
1045 reflections	Δρmax = 0.19 e Å^−3
109 parameters	Δρmin = −0.20 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
F1	0.27357 (5)	0.43371 (5)	0.83259 (12)	0.0310 (3)
F2	0.33321 (6)	0.40770 (6)	1.06711 (16)	0.0376 (4)
F3	0.42716 (5)	0.44771 (5)	0.87193 (13)	0.0331 (3)
O1	0.36355 (6)	0.21263 (7)	0.98806 (15)	0.0268 (3)
C4	0.39488 (8)	0.16370 (10)	0.3960 (2)	0.0278 (5)
H4	0.402903	0.138083	0.290060	0.033*
C5	0.38764 (9)	0.27193 (10)	0.4248 (2)	0.0273 (5)
H5	0.390579	0.320406	0.337898	0.033*
C6	0.37625 (8)	0.30955 (9)	0.5781 (2)	0.0223 (5)
H6	0.371252	0.383735	0.596420	0.027*
C1	0.37202 (7)	0.23921 (9)	0.7068 (2)	0.0176 (5)
C7	0.36188 (7)	0.27209 (9)	0.8742 (2)	0.0200 (5)
C8	0.34856 (9)	0.39204 (9)	0.9128 (3)	0.0241 (5)
C3	0.39028 (9)	0.09306 (9)	0.5237 (2)	0.0259 (5)
H3	0.395028	0.018927	0.504787	0.031*
C2	0.37893 (8)	0.12990 (9)	0.6766 (2)	0.0235 (5)
H2	0.375707	0.081052	0.762999	0.028*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
F1	0.0323 (4)	0.0267 (4)	0.0339 (10)	0.0079 (3)	0.0017 (4)	0.0015 (3)
F2	0.0604 (5)	0.0314 (4)	0.0210 (13)	0.0015 (3)	0.0051 (5)	−0.0069 (4)
F3	0.0336 (4)	0.0239 (3)	0.0420 (9)	−0.0065 (3)	0.0030 (4)	−0.0046 (3)
O1	0.0382 (5)	0.0281 (4)	0.0142 (12)	−0.0003 (3)	0.0004 (4)	0.0047 (5)
C4	0.0263 (6)	0.0403 (7)	0.0169 (16)	−0.0026 (5)	0.0001 (6)	−0.0063 (7)
C5	0.0330 (6)	0.0347 (7)	0.0141 (19)	−0.0028 (5)	0.0007 (6)	0.0079 (7)
C6	0.0281 (6)	0.0234 (6)	0.0156 (18)	−0.0001 (4)	0.0004 (6)	0.0031 (6)
C1	0.0193 (5)	0.0217 (5)	0.0118 (17)	−0.0007 (4)	−0.0007 (5)	0.0013 (6)
C7	0.0207 (5)	0.0220 (6)	0.0171 (17)	−0.0011 (4)	−0.0002 (5)	0.0032 (7)
C8	0.0296 (6)	0.0248 (6)	0.018 (2)	−0.0003 (4)	0.0021 (6)	−0.0021 (6)
C3	0.0338 (6)	0.0253 (6)	0.0187 (17)	−0.0013 (4)	0.0001 (6)	−0.0048 (7)
C2	0.0293 (6)	0.0215 (6)	0.0197 (18)	−0.0011 (4)	−0.0012 (6)	0.0026 (6)

Geometric parameters (Å, º)

F1—C8	1.3373 (17)	C6—C1	1.396 (2)
F2—C8	1.324 (2)	C6—H6	0.9500
F3—C8	1.3389 (15)	C1—C2	1.4040 (15)
O1—C7	1.2112 (18)	C1—C7	1.467 (2)
C4—C5	1.3888 (19)	C7—C8	1.5569 (16)
C4—C3	1.392 (2)	C3—C2	1.370 (2)
C4—H4	0.9500	C3—H3	0.9500
C5—C6	1.377 (2)	C2—H2	0.9500
C5—H5	0.9500
C5—C4—C3	119.46 (17)	C1—C7—C8	118.93 (13)
C5—C4—H4	120.3	F2—C8—F1	107.54 (12)
C3—C4—H4	120.3	F2—C8—F3	107.82 (12)
C6—C5—C4	120.53 (15)	F1—C8—F3	107.05 (12)
C6—C5—H5	119.7	F2—C8—C7	111.48 (12)
C4—C5—H5	119.7	F1—C8—C7	111.71 (12)
C5—C6—C1	120.32 (13)	F3—C8—C7	111.03 (11)
C5—C6—H6	119.8	C2—C3—C4	120.33 (13)
C1—C6—H6	119.8	C2—C3—H3	119.8
C6—C1—C2	118.78 (16)	C4—C3—H3	119.8
C6—C1—C7	124.10 (12)	C3—C2—C1	120.58 (14)
C2—C1—C7	117.11 (13)	C3—C2—H2	119.7
O1—C7—C1	124.96 (12)	C1—C2—H2	119.7
O1—C7—C8	116.10 (16)
C3—C4—C5—C6	0.17 (18)	C1—C7—C8—F2	175.26 (9)
C4—C5—C6—C1	0.12 (17)	O1—C7—C8—F1	−125.49 (14)
C5—C6—C1—C2	−0.42 (16)	C1—C7—C8—F1	54.91 (16)
C5—C6—C1—C7	178.79 (10)	O1—C7—C8—F3	115.10 (15)
C6—C1—C7—O1	−175.62 (11)	C1—C7—C8—F3	−64.50 (17)
C2—C1—C7—O1	3.60 (16)	C5—C4—C3—C2	−0.15 (18)
C6—C1—C7—C8	3.94 (15)	C4—C3—C2—C1	−0.15 (17)
C2—C1—C7—C8	−176.84 (10)	C6—C1—C2—C3	0.43 (16)
O1—C7—C8—F2	−5.15 (14)	C7—C1—C2—C3	−178.83 (10)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6···F1	0.95	2.48	3.004 (2)	115
C6—H6···F3	0.95	2.55	3.088 (2)	116
C5—H5···F2^i	0.95	2.63	3.522 (2)	156
C4—H4···O1^i	0.95	2.74	3.490 (2)	136
C6—H6···F2^ii	0.95	2.69	3.614 (2)	163
C6—H6···F3^ii	0.95	2.94	3.584 (2)	126
C5—H5···F3^ii	0.95	2.98	3.603 (2)	124
C3—H3···O1^iii	0.95	2.95	3.882 (2)	166

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