Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807046776/is2210sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807046776/is2210Isup2.hkl |
CCDC reference: 663847
Key indicators
- Single-crystal X-ray study
- T = 291 K
- Mean (C-C) = 0.002 Å
- R factor = 0.039
- wR factor = 0.109
- Data-to-parameter ratio = 13.4
checkCIF/PLATON results
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Alert level G PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature . 293 K
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 0 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 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 0 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
The title compound N,N'-bis(2,3,4,5-tetrafluorobenzoyl) piperazine was synthesized by the reaction of tetrafluorobenzoyl chloride (1.4 g, 10 mmol) with piperazine (0.42 g, 5 mmol) in the presence of triethylamine (1.01 g, 10 mmol) in ethanol (50 ml). Colorless block crystals were obtained by recrystallization from an ethanol solution (yield 80%). Elemental analysis, calculated for C18H10F8N2O2: C 49.33, H 2.30, N 6.39%; found: C 49.26, H 2.28, N 6.30%.
H atoms were located in a difference map and were refined as riding, with C—H = 0.93–0.97 Å and Uiso(H) = 1.2Ueq(C).
Recently, the supramolecular structures of systems containing piperazine unit, which includes both of hydrogen-bonded systems and of metal coordination complexes, have been extensively studied. (Kartha et al., 1981; Luo & Palmore, 2002; Varughese & Kartha, 1982). To date, many piperazine derivatives with various substitutes have been synthesized (Zheng et al., 2005; Sarangarajan et al., 2005). Herein, we report the structure of a new compound N,N'-bis(2,3,4,5-tetrafluorobenzoyl)piperazine (I).
The geometry and labeling scheme of the title compound are depicted in Figure 1. The compound is a centrosymmetric compound N,N'-bis(2,3,4,5-tetrafluorobenzoyl)piperazine. The piperazine ring adopts a chair conformation and the two tetrafluorophenyl rings are strict parallel to each other due to the centrosymmetry. All atoms from tetrafluorophenyl ring is nearly strict planar with the largest deviation of 0.0105 (18) Å from the mean plane. The carbonyl group bond distance is 1.2275 (18) Å for C7—O1 and the amide bond distance is 1.3409 (19) Å for C7—N1, which are very similar to those of its derivative N,N'-dibenzoylpiperazine (Zheng et al., 2005). The C—F bond lengths range from 1.334 (2) to 1.334 (2) Å.
In the title compound, the N,N'-bis(2,3,4,5-tetrafluorobenzoyl)piperazine units were connected together by the intermolecular C—H···O hydrogen bonds, leading to a one-dimensional chain-like supramolecular structure as shown in Figure 2.
For related literature, see: Kartha et al. (1981); Luo & Palmore (2002); Sarangarajan et al. (2005); Varughese & Kartha (1982); Zheng et al. (2005).
Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP (Sheldrick, 1998); software used to prepare material for publication: XP (Sheldrick, 1998).
C18H10F8N2O2 | F(000) = 880 |
Mr = 438.28 | Dx = 1.659 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 1816 reflections |
a = 30.158 (4) Å | θ = 1.4–26.5° |
b = 8.9113 (12) Å | µ = 0.17 mm−1 |
c = 6.5744 (9) Å | T = 291 K |
β = 96.594 (2)° | Block, colourless |
V = 1755.2 (4) Å3 | 0.21 × 0.17 × 0.10 mm |
Z = 4 |
Bruker APEXII CCD area-detector diffractometer | 1816 independent reflections |
Radiation source: fine-focus sealed tube | 1505 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.018 |
φ and ω scans | θmax = 26.5°, θmin = 1.4° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | h = −37→37 |
Tmin = 0.964, Tmax = 0.982 | k = −11→11 |
6914 measured reflections | l = −8→8 |
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)] = 0.039 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.109 | H-atom parameters constrained |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0513P)2 + 0.9211P] where P = (Fo2 + 2Fc2)/3 |
1816 reflections | (Δ/σ)max < 0.001 |
136 parameters | Δρmax = 0.17 e Å−3 |
0 restraints | Δρmin = −0.21 e Å−3 |
C18H10F8N2O2 | V = 1755.2 (4) Å3 |
Mr = 438.28 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 30.158 (4) Å | µ = 0.17 mm−1 |
b = 8.9113 (12) Å | T = 291 K |
c = 6.5744 (9) Å | 0.21 × 0.17 × 0.10 mm |
β = 96.594 (2)° |
Bruker APEXII CCD area-detector diffractometer | 1816 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 1505 reflections with I > 2σ(I) |
Tmin = 0.964, Tmax = 0.982 | Rint = 0.018 |
6914 measured reflections |
R[F2 > 2σ(F2)] = 0.039 | 0 restraints |
wR(F2) = 0.109 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.17 e Å−3 |
1816 reflections | Δρmin = −0.21 e Å−3 |
136 parameters |
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 | ||
F1 | 0.35977 (4) | 0.55322 (14) | 0.1733 (2) | 0.0882 (5) | |
F2 | 0.44756 (5) | 0.51144 (15) | 0.2847 (3) | 0.1033 (5) | |
F3 | 0.49652 (4) | 0.72402 (17) | 0.4995 (2) | 0.0858 (4) | |
F4 | 0.45729 (4) | 0.97811 (16) | 0.6065 (2) | 0.0817 (4) | |
O1 | 0.30498 (4) | 0.85478 (16) | 0.07758 (16) | 0.0567 (4) | |
N1 | 0.28391 (4) | 0.80494 (15) | 0.38982 (18) | 0.0394 (3) | |
C1 | 0.38334 (6) | 0.6604 (2) | 0.2813 (3) | 0.0540 (4) | |
C2 | 0.42821 (6) | 0.6382 (2) | 0.3369 (3) | 0.0624 (5) | |
C3 | 0.45290 (5) | 0.7449 (2) | 0.4468 (3) | 0.0566 (5) | |
C4 | 0.43232 (6) | 0.8737 (2) | 0.5014 (3) | 0.0511 (4) | |
C5 | 0.38765 (5) | 0.89670 (19) | 0.4480 (2) | 0.0454 (4) | |
H5 | 0.3743 | 0.9846 | 0.4870 | 0.054* | |
C6 | 0.36230 (5) | 0.78895 (17) | 0.3356 (2) | 0.0401 (4) | |
C7 | 0.31433 (5) | 0.81783 (17) | 0.2572 (2) | 0.0394 (3) | |
C8 | 0.23774 (5) | 0.84858 (19) | 0.3295 (2) | 0.0410 (4) | |
H8A | 0.2329 | 0.8623 | 0.1822 | 0.049* | |
H8B | 0.2318 | 0.9433 | 0.3936 | 0.049* | |
C9 | 0.29394 (5) | 0.76986 (19) | 0.6077 (2) | 0.0412 (4) | |
H9A | 0.2912 | 0.8601 | 0.6880 | 0.049* | |
H9B | 0.3244 | 0.7340 | 0.6347 | 0.049* |
U11 | U22 | U33 | U12 | U13 | U23 | |
F1 | 0.0746 (8) | 0.0620 (7) | 0.1262 (12) | −0.0065 (6) | 0.0041 (8) | −0.0388 (7) |
F2 | 0.0810 (9) | 0.0719 (9) | 0.1567 (15) | 0.0310 (7) | 0.0121 (9) | −0.0272 (9) |
F3 | 0.0411 (6) | 0.1097 (11) | 0.1053 (10) | 0.0177 (6) | 0.0028 (6) | −0.0016 (8) |
F4 | 0.0482 (6) | 0.1015 (10) | 0.0933 (9) | −0.0141 (6) | −0.0017 (6) | −0.0367 (7) |
O1 | 0.0500 (7) | 0.0867 (9) | 0.0341 (6) | −0.0045 (6) | 0.0081 (5) | 0.0078 (6) |
N1 | 0.0338 (7) | 0.0526 (8) | 0.0319 (6) | −0.0005 (5) | 0.0046 (5) | 0.0055 (5) |
C1 | 0.0522 (10) | 0.0468 (9) | 0.0638 (11) | −0.0052 (8) | 0.0103 (8) | −0.0084 (8) |
C2 | 0.0555 (11) | 0.0535 (11) | 0.0804 (13) | 0.0136 (9) | 0.0170 (10) | −0.0038 (9) |
C3 | 0.0374 (9) | 0.0736 (12) | 0.0596 (11) | 0.0064 (8) | 0.0095 (8) | 0.0056 (9) |
C4 | 0.0412 (9) | 0.0640 (11) | 0.0484 (9) | −0.0066 (8) | 0.0068 (7) | −0.0071 (8) |
C5 | 0.0417 (9) | 0.0508 (9) | 0.0448 (9) | 0.0009 (7) | 0.0099 (7) | −0.0076 (7) |
C6 | 0.0393 (8) | 0.0467 (8) | 0.0360 (7) | −0.0025 (6) | 0.0121 (6) | 0.0016 (6) |
C7 | 0.0409 (8) | 0.0431 (8) | 0.0348 (8) | −0.0057 (6) | 0.0068 (6) | −0.0014 (6) |
C8 | 0.0377 (8) | 0.0507 (9) | 0.0345 (7) | 0.0029 (7) | 0.0038 (6) | 0.0072 (6) |
C9 | 0.0356 (7) | 0.0561 (9) | 0.0317 (7) | −0.0019 (7) | 0.0025 (6) | 0.0043 (6) |
F1—C1 | 1.344 (2) | C3—C4 | 1.372 (3) |
F2—C2 | 1.334 (2) | C4—C5 | 1.368 (2) |
F3—C3 | 1.3343 (19) | C5—C6 | 1.386 (2) |
F4—C4 | 1.338 (2) | C5—H5 | 0.9300 |
O1—C7 | 1.2275 (18) | C6—C7 | 1.501 (2) |
N1—C7 | 1.3409 (19) | C8—C9i | 1.513 (2) |
N1—C8 | 1.4563 (19) | C8—H8A | 0.9700 |
N1—C9 | 1.4635 (18) | C8—H8B | 0.9700 |
C1—C2 | 1.375 (3) | C9—C8i | 1.513 (2) |
C1—C6 | 1.376 (2) | C9—H9A | 0.9700 |
C2—C3 | 1.363 (3) | C9—H9B | 0.9700 |
C7—N1—C8 | 120.27 (12) | C1—C6—C5 | 118.18 (15) |
C7—N1—C9 | 125.08 (13) | C1—C6—C7 | 120.56 (15) |
C8—N1—C9 | 114.04 (11) | C5—C6—C7 | 120.98 (14) |
F1—C1—C2 | 118.85 (16) | O1—C7—N1 | 123.36 (15) |
F1—C1—C6 | 119.81 (16) | O1—C7—C6 | 118.82 (13) |
C2—C1—C6 | 121.34 (17) | N1—C7—C6 | 117.81 (13) |
F2—C2—C3 | 119.90 (18) | N1—C8—C9i | 110.70 (13) |
F2—C2—C1 | 120.01 (18) | N1—C8—H8A | 109.5 |
C3—C2—C1 | 120.09 (17) | C9i—C8—H8A | 109.5 |
F3—C3—C2 | 120.17 (18) | N1—C8—H8B | 109.5 |
F3—C3—C4 | 120.72 (18) | C9i—C8—H8B | 109.5 |
C2—C3—C4 | 119.11 (16) | H8A—C8—H8B | 108.1 |
F4—C4—C5 | 120.50 (16) | N1—C9—C8i | 110.51 (12) |
F4—C4—C3 | 118.17 (16) | N1—C9—H9A | 109.5 |
C5—C4—C3 | 121.32 (16) | C8i—C9—H9A | 109.5 |
C4—C5—C6 | 119.97 (16) | N1—C9—H9B | 109.5 |
C4—C5—H5 | 120.0 | C8i—C9—H9B | 109.5 |
C6—C5—H5 | 120.0 | H9A—C9—H9B | 108.1 |
F1—C1—C2—F2 | −0.4 (3) | F1—C1—C6—C7 | −6.4 (2) |
C6—C1—C2—F2 | 178.96 (18) | C2—C1—C6—C7 | 174.31 (16) |
F1—C1—C2—C3 | −179.86 (18) | C4—C5—C6—C1 | 0.1 (2) |
C6—C1—C2—C3 | −0.5 (3) | C4—C5—C6—C7 | −173.87 (14) |
F2—C2—C3—F3 | 1.1 (3) | C8—N1—C7—O1 | −5.7 (2) |
C1—C2—C3—F3 | −179.42 (18) | C9—N1—C7—O1 | −176.22 (15) |
F2—C2—C3—C4 | −179.17 (18) | C8—N1—C7—C6 | 172.75 (13) |
C1—C2—C3—C4 | 0.3 (3) | C9—N1—C7—C6 | 2.3 (2) |
F3—C3—C4—F4 | 0.7 (3) | C1—C6—C7—O1 | −73.8 (2) |
C2—C3—C4—F4 | −178.98 (17) | C5—C6—C7—O1 | 100.00 (18) |
F3—C3—C4—C5 | 179.83 (16) | C1—C6—C7—N1 | 107.63 (17) |
C2—C3—C4—C5 | 0.1 (3) | C5—C6—C7—N1 | −78.54 (19) |
F4—C4—C5—C6 | 178.75 (15) | C7—N1—C8—C9i | 133.86 (15) |
C3—C4—C5—C6 | −0.3 (3) | C9—N1—C8—C9i | −54.65 (19) |
F1—C1—C6—C5 | 179.64 (15) | C7—N1—C9—C8i | −134.44 (15) |
C2—C1—C6—C5 | 0.3 (3) | C8—N1—C9—C8i | 54.55 (19) |
Symmetry code: (i) −x+1/2, −y+3/2, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
C9—H9A···O1ii | 0.97 | 2.55 | 3.161 (2) | 121 |
Symmetry code: (ii) x, y, z+1. |
Experimental details
Crystal data | |
Chemical formula | C18H10F8N2O2 |
Mr | 438.28 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 291 |
a, b, c (Å) | 30.158 (4), 8.9113 (12), 6.5744 (9) |
β (°) | 96.594 (2) |
V (Å3) | 1755.2 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.17 |
Crystal size (mm) | 0.21 × 0.17 × 0.10 |
Data collection | |
Diffractometer | Bruker APEXII CCD area-detector |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2003) |
Tmin, Tmax | 0.964, 0.982 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6914, 1816, 1505 |
Rint | 0.018 |
(sin θ/λ)max (Å−1) | 0.628 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.039, 0.109, 1.05 |
No. of reflections | 1816 |
No. of parameters | 136 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.17, −0.21 |
Computer programs: APEX2 (Bruker, 2004), SAINT-Plus (Bruker, 2001), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), XP (Sheldrick, 1998).
D—H···A | D—H | H···A | D···A | D—H···A |
C9—H9A···O1i | 0.971 | 2.548 | 3.161 (2) | 121.14 |
Symmetry code: (i) x, y, z+1. |
Recently, the supramolecular structures of systems containing piperazine unit, which includes both of hydrogen-bonded systems and of metal coordination complexes, have been extensively studied. (Kartha et al., 1981; Luo & Palmore, 2002; Varughese & Kartha, 1982). To date, many piperazine derivatives with various substitutes have been synthesized (Zheng et al., 2005; Sarangarajan et al., 2005). Herein, we report the structure of a new compound N,N'-bis(2,3,4,5-tetrafluorobenzoyl)piperazine (I).
The geometry and labeling scheme of the title compound are depicted in Figure 1. The compound is a centrosymmetric compound N,N'-bis(2,3,4,5-tetrafluorobenzoyl)piperazine. The piperazine ring adopts a chair conformation and the two tetrafluorophenyl rings are strict parallel to each other due to the centrosymmetry. All atoms from tetrafluorophenyl ring is nearly strict planar with the largest deviation of 0.0105 (18) Å from the mean plane. The carbonyl group bond distance is 1.2275 (18) Å for C7—O1 and the amide bond distance is 1.3409 (19) Å for C7—N1, which are very similar to those of its derivative N,N'-dibenzoylpiperazine (Zheng et al., 2005). The C—F bond lengths range from 1.334 (2) to 1.334 (2) Å.
In the title compound, the N,N'-bis(2,3,4,5-tetrafluorobenzoyl)piperazine units were connected together by the intermolecular C—H···O hydrogen bonds, leading to a one-dimensional chain-like supramolecular structure as shown in Figure 2.