


Supporting information
![]() | Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536808016632/ng2417sup1.cif |
![]() | Structure factor file (CIF format) https://doi.org/10.1107/S1600536808016632/ng2417Isup2.hkl |
CCDC reference: 700549
Key indicators
- Single-crystal X-ray study
- T = 200 K
- Mean
(C-C) = 0.003 Å
- R factor = 0.035
- wR factor = 0.077
- Data-to-parameter ratio = 18.3
checkCIF/PLATON results
No syntax errors found Datablock: I
Alert level C STRVA01_ALERT_4_C Flack test results are ambiguous. From the CIF: _refine_ls_abs_structure_Flack 0.400 From the CIF: _refine_ls_abs_structure_Flack_su 0.050 PLAT333_ALERT_2_C Large Average Benzene C-C Dist. C4A -C12A 1.46 Ang. PLAT333_ALERT_2_C Large Average Benzene C-C Dist. C4B -C12B 1.46 Ang. PLAT335_ALERT_2_C Large Benzene C-C Range ....... C4A -C12A 0.16 Ang. PLAT335_ALERT_2_C Large Benzene C-C Range ....... C4B -C12B 0.17 Ang. PLAT369_ALERT_2_C Long C(sp2)-C(sp2) Bond C5A - C6A ... 1.55 Ang. PLAT369_ALERT_2_C Long C(sp2)-C(sp2) Bond C5B - C6B ... 1.55 Ang. PLAT432_ALERT_2_C Short Inter X...Y Contact O1A .. C4B .. 3.01 Ang. PLAT432_ALERT_2_C Short Inter X...Y Contact O1B .. C3A .. 2.94 Ang. PLAT432_ALERT_2_C Short Inter X...Y Contact O2A .. C8B .. 2.99 Ang. PLAT432_ALERT_2_C Short Inter X...Y Contact O12 .. C5B .. 2.96 Ang. PLAT432_ALERT_2_C Short Inter X...Y Contact O22 .. C5A .. 2.97 Ang. PLAT033_ALERT_4_C Flack Parameter Value Deviates from Zero ....... 0.40 PLAT062_ALERT_4_C Rescale T(min) & T(max) by ..................... 0.95 PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given ....... ? PLAT244_ALERT_4_C Low 'Solvent' Ueq as Compared to Neighbors for C1 PLAT244_ALERT_4_C Low 'Solvent' Ueq as Compared to Neighbors for C2 PLAT720_ALERT_4_C Number of Unusual/Non-Standard Labels .......... 12 PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd. # 2 C12 H7 N2 O2
Alert level G ABSTM02_ALERT_3_G When printed, the submitted absorption T values will be replaced by the scaled T values. Since the ratio of scaled T's is identical to the ratio of reported T values, the scaling does not imply a change to the absorption corrections used in the study. Ratio of Tmax expected/reported 0.948 Tmax scaled 0.948 Tmin scaled 0.850 REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is correct. If it is not, please give the correct count in the _publ_section_exptl_refinement section of the submitted CIF. From the CIF: _diffrn_reflns_theta_max 32.54 From the CIF: _reflns_number_total 7960 Count of symmetry unique reflns 5247 Completeness (_total/calc) 151.71% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 2713 Fraction of Friedel pairs measured 0.517 Are heavy atom types Z>Si present yes
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 19 ALERT level C = Check and explain 2 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 11 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 9 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
A flask containing 1,10-phenanthroline hydrate (1.00 g, 5.04 mmol) and potassium bromide (5.95 g, 50.0 mmol) was placed in an ice bath. Concentrated sulfuric acid (20 ml) was added in small portions, followed by drop wise addition of concentrated nitric acid (10 ml). The resulting solution was heated for 2 h at 80–85° C and cooled to room temperature. The solution was then poured into 400 ml water and neutralized with sodium bicarbonate, after which the phendione was extracted with dichloromethane, and recrystallized using a methanol–water mixture.
The title compound was synthesized in an atmosphere saturated with N2. To a solution of silver trifluoromethanesulfonate (0.079 g) in 10 ml CH3CN (acidified to pH 2 using concentrated triflic acid), was added a solution (10 ml) of CH3CN containing 0.065 g of phendione (acidified to pH 2 using triflic acid). The final yellowish solution was filtered and allowed to slowly evaporate yield reddish brown crystals of the title compound.
H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms with a C—H distance of 0.95 Å and Uiso(H) = 1.2Ueq(C). The H atoms attached to N in the phendione cation were idealized with an N—H distance of 0.88 Å.
Data collection: CrysAlis CCD (Oxford Diffraction, 2007); cell refinement: CrysAlis RED (Oxford Diffraction, 2007); data reduction: CrysAlis RED (Oxford Diffraction, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
C12H7N2O2+·CF3O3S− | F(000) = 728 |
Mr = 360.27 | Dx = 1.703 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
a = 6.4896 (2) Å | Cell parameters from 5857 reflections |
b = 16.3963 (5) Å | θ = 4.7–32.5° |
c = 13.2430 (3) Å | µ = 0.30 mm−1 |
β = 94.393 (2)° | T = 200 K |
V = 1404.99 (7) Å3 | Needle, yellow-orange |
Z = 4 | 0.51 × 0.22 × 0.18 mm |
Oxford Diffraction Gemini diffractometer | 7960 independent reflections |
Radiation source: fine-focus sealed tube | 5208 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.023 |
Detector resolution: 10.5081 pixels mm-1 | θmax = 32.5°, θmin = 4.7° |
ϕ and ω scans | h = −9→7 |
Absorption correction: multi-scan [Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm (Oxford Diffraction, 2007)] | k = −24→21 |
Tmin = 0.897, Tmax = 1.000 | l = −19→19 |
13319 measured reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.034 | H-atom parameters constrained |
wR(F2) = 0.077 | w = 1/[σ2(Fo2) + (0.0394P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.94 | (Δ/σ)max = 0.001 |
7960 reflections | Δρmax = 0.24 e Å−3 |
434 parameters | Δρmin = −0.38 e Å−3 |
1 restraint | Absolute structure: Flack (1983), with 2713 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.40 (5) |
C12H7N2O2+·CF3O3S− | V = 1404.99 (7) Å3 |
Mr = 360.27 | Z = 4 |
Monoclinic, P21 | Mo Kα radiation |
a = 6.4896 (2) Å | µ = 0.30 mm−1 |
b = 16.3963 (5) Å | T = 200 K |
c = 13.2430 (3) Å | 0.51 × 0.22 × 0.18 mm |
β = 94.393 (2)° |
Oxford Diffraction Gemini diffractometer | 7960 independent reflections |
Absorption correction: multi-scan [Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm (Oxford Diffraction, 2007)] | 5208 reflections with I > 2σ(I) |
Tmin = 0.897, Tmax = 1.000 | Rint = 0.023 |
13319 measured reflections |
R[F2 > 2σ(F2)] = 0.034 | H-atom parameters constrained |
wR(F2) = 0.077 | Δρmax = 0.24 e Å−3 |
S = 0.94 | Δρmin = −0.38 e Å−3 |
7960 reflections | Absolute structure: Flack (1983), with 2713 Friedel pairs |
434 parameters | Absolute structure parameter: 0.40 (5) |
1 restraint |
Experimental. The data were measured to a 2θ limit of 50 °, but the low completeness was caused by |
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 | ||
S1 | 0.64118 (7) | 0.25922 (3) | 0.84492 (4) | 0.02642 (11) | |
S2 | 0.86022 (7) | 0.38484 (3) | 0.23321 (3) | 0.02618 (11) | |
F11 | 0.7237 (3) | 0.10424 (9) | 0.86156 (13) | 0.0732 (5) | |
F12 | 0.9730 (2) | 0.17770 (11) | 0.81474 (14) | 0.0735 (5) | |
F13 | 0.7153 (2) | 0.14825 (10) | 0.70995 (11) | 0.0604 (4) | |
F21 | 0.7945 (2) | 0.49049 (10) | 0.37563 (11) | 0.0648 (4) | |
F22 | 0.7727 (3) | 0.54033 (10) | 0.22511 (15) | 0.0759 (5) | |
F23 | 0.5298 (2) | 0.46511 (10) | 0.27365 (13) | 0.0636 (4) | |
O11 | 0.7135 (2) | 0.26580 (11) | 0.94979 (10) | 0.0419 (4) | |
O12 | 0.7202 (2) | 0.32177 (10) | 0.78073 (11) | 0.0340 (3) | |
O13 | 0.4246 (2) | 0.24330 (10) | 0.82584 (11) | 0.0376 (4) | |
O21 | 1.0772 (2) | 0.40075 (10) | 0.25085 (11) | 0.0390 (4) | |
O22 | 0.7848 (2) | 0.32033 (9) | 0.29570 (11) | 0.0346 (4) | |
O23 | 0.7822 (2) | 0.38146 (11) | 0.12885 (10) | 0.0422 (4) | |
O1A | −0.2484 (2) | 0.12049 (10) | 0.20079 (13) | 0.0400 (4) | |
O2A | −0.2548 (2) | 0.12362 (10) | 0.40583 (13) | 0.0457 (4) | |
O1B | 1.7556 (2) | 0.51876 (9) | 0.87690 (12) | 0.0386 (4) | |
O2B | 1.7531 (2) | 0.52437 (10) | 0.67146 (12) | 0.0431 (4) | |
N1A | 0.4031 (2) | 0.24850 (11) | 0.22669 (12) | 0.0254 (4) | |
H1AB | 0.5045 | 0.2692 | 0.2666 | 0.030* | |
N2A | 0.4147 (3) | 0.24527 (12) | 0.42945 (13) | 0.0319 (4) | |
N1B | 1.1004 (2) | 0.39478 (11) | 0.85110 (12) | 0.0258 (4) | |
H1BB | 1.0012 | 0.3723 | 0.8115 | 0.031* | |
N2B | 1.0923 (3) | 0.39406 (12) | 0.64828 (13) | 0.0327 (4) | |
C1 | 0.7697 (4) | 0.16729 (15) | 0.80584 (17) | 0.0387 (6) | |
C2 | 0.7337 (4) | 0.47486 (15) | 0.27958 (18) | 0.0402 (6) | |
C1A | 0.4191 (3) | 0.25021 (14) | 0.12634 (15) | 0.0314 (5) | |
H1AA | 0.5384 | 0.2729 | 0.0999 | 0.038* | |
C2A | 0.2629 (3) | 0.21907 (14) | 0.06179 (17) | 0.0322 (5) | |
H2AA | 0.2737 | 0.2197 | −0.0093 | 0.039* | |
C3A | 0.0900 (3) | 0.18683 (13) | 0.10145 (17) | 0.0301 (5) | |
H3AA | −0.0202 | 0.1658 | 0.0577 | 0.036* | |
C4A | 0.0781 (3) | 0.18525 (12) | 0.20630 (15) | 0.0241 (4) | |
C5A | −0.1030 (3) | 0.14900 (13) | 0.25125 (17) | 0.0289 (5) | |
C6A | −0.1038 (3) | 0.14924 (13) | 0.36802 (17) | 0.0315 (5) | |
C7A | 0.0806 (3) | 0.18109 (13) | 0.42748 (16) | 0.0288 (5) | |
C8A | 0.0996 (4) | 0.17678 (15) | 0.53295 (16) | 0.0389 (5) | |
H8AA | −0.0078 | 0.1535 | 0.5684 | 0.047* | |
C9A | 0.2741 (4) | 0.20637 (15) | 0.58490 (18) | 0.0444 (6) | |
H9AA | 0.2901 | 0.2038 | 0.6567 | 0.053* | |
C10A | 0.4267 (4) | 0.23999 (16) | 0.53074 (17) | 0.0432 (6) | |
H10B | 0.5472 | 0.2606 | 0.5674 | 0.052* | |
C11A | 0.2440 (3) | 0.21495 (12) | 0.37991 (15) | 0.0246 (4) | |
C12A | 0.2397 (3) | 0.21671 (12) | 0.26908 (15) | 0.0216 (4) | |
C1B | 1.0812 (3) | 0.39649 (13) | 0.95094 (14) | 0.0286 (4) | |
H1BA | 0.9613 | 0.3742 | 0.9774 | 0.034* | |
C2B | 1.2347 (3) | 0.43041 (13) | 1.01586 (15) | 0.0318 (5) | |
H2BA | 1.2203 | 0.4329 | 1.0866 | 0.038* | |
C3B | 1.4085 (3) | 0.46050 (13) | 0.97591 (15) | 0.0305 (5) | |
H3BA | 1.5180 | 0.4824 | 1.0194 | 0.037* | |
C4B | 1.4242 (3) | 0.45896 (12) | 0.87118 (15) | 0.0245 (4) | |
C5B | 1.6077 (3) | 0.49192 (13) | 0.82586 (16) | 0.0284 (5) | |
C6B | 1.6070 (3) | 0.49306 (13) | 0.70872 (16) | 0.0303 (5) | |
C7B | 1.4283 (3) | 0.45768 (13) | 0.65019 (15) | 0.0289 (5) | |
C8B | 1.4144 (4) | 0.45842 (15) | 0.54424 (17) | 0.0393 (6) | |
H8BA | 1.5239 | 0.4797 | 0.5085 | 0.047* | |
C9B | 1.2398 (4) | 0.42780 (16) | 0.49305 (17) | 0.0463 (7) | |
H9BA | 1.2255 | 0.4283 | 0.4211 | 0.056* | |
C10B | 1.0845 (4) | 0.39614 (16) | 0.54748 (17) | 0.0400 (6) | |
H10A | 0.9652 | 0.3746 | 0.5108 | 0.048* | |
C11B | 1.2622 (3) | 0.42491 (13) | 0.69772 (16) | 0.0271 (5) | |
C12B | 1.2647 (3) | 0.42594 (12) | 0.80881 (15) | 0.0240 (4) |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0252 (2) | 0.0305 (3) | 0.0237 (2) | −0.0019 (2) | 0.00264 (19) | −0.0019 (2) |
S2 | 0.0248 (2) | 0.0314 (3) | 0.0226 (2) | −0.0042 (2) | 0.00331 (18) | −0.0024 (2) |
F11 | 0.1143 (14) | 0.0318 (9) | 0.0735 (11) | 0.0060 (8) | 0.0075 (10) | 0.0159 (8) |
F12 | 0.0368 (8) | 0.0750 (12) | 0.1081 (14) | 0.0217 (7) | 0.0024 (9) | −0.0140 (11) |
F13 | 0.0798 (11) | 0.0579 (11) | 0.0435 (8) | 0.0118 (8) | 0.0049 (8) | −0.0213 (8) |
F21 | 0.0776 (10) | 0.0674 (11) | 0.0500 (9) | 0.0049 (8) | 0.0100 (8) | −0.0305 (8) |
F22 | 0.0961 (13) | 0.0334 (9) | 0.1013 (14) | 0.0024 (8) | 0.0285 (10) | 0.0186 (9) |
F23 | 0.0363 (8) | 0.0633 (11) | 0.0922 (12) | 0.0136 (7) | 0.0116 (8) | 0.0001 (9) |
O11 | 0.0484 (9) | 0.0540 (10) | 0.0229 (7) | −0.0107 (8) | −0.0002 (6) | −0.0049 (8) |
O12 | 0.0317 (8) | 0.0321 (8) | 0.0381 (9) | −0.0046 (6) | 0.0024 (6) | 0.0069 (7) |
O13 | 0.0217 (7) | 0.0516 (11) | 0.0399 (8) | −0.0076 (6) | 0.0049 (6) | −0.0031 (7) |
O21 | 0.0282 (8) | 0.0530 (11) | 0.0364 (8) | −0.0054 (7) | 0.0052 (6) | −0.0039 (8) |
O22 | 0.0327 (8) | 0.0309 (8) | 0.0404 (9) | −0.0049 (6) | 0.0029 (7) | 0.0057 (7) |
O23 | 0.0457 (9) | 0.0574 (11) | 0.0230 (7) | −0.0121 (8) | 0.0003 (6) | −0.0062 (8) |
O1A | 0.0307 (9) | 0.0350 (9) | 0.0533 (10) | −0.0088 (7) | −0.0043 (8) | −0.0005 (8) |
O2A | 0.0434 (9) | 0.0411 (10) | 0.0555 (10) | −0.0126 (7) | 0.0222 (8) | −0.0002 (8) |
O1B | 0.0320 (8) | 0.0346 (9) | 0.0485 (9) | −0.0093 (7) | −0.0009 (7) | 0.0006 (8) |
O2B | 0.0392 (9) | 0.0411 (10) | 0.0517 (10) | −0.0075 (7) | 0.0203 (8) | 0.0029 (8) |
N1A | 0.0210 (8) | 0.0285 (10) | 0.0262 (9) | −0.0027 (7) | −0.0010 (7) | −0.0005 (8) |
N2A | 0.0312 (9) | 0.0345 (11) | 0.0293 (9) | 0.0017 (8) | −0.0032 (7) | −0.0019 (8) |
N1B | 0.0229 (8) | 0.0292 (10) | 0.0253 (8) | −0.0002 (7) | 0.0029 (7) | 0.0010 (8) |
N2B | 0.0330 (9) | 0.0372 (11) | 0.0271 (9) | 0.0027 (8) | −0.0025 (7) | −0.0025 (9) |
C1 | 0.0394 (13) | 0.0381 (15) | 0.0387 (13) | 0.0038 (10) | 0.0031 (10) | −0.0039 (11) |
C2 | 0.0443 (14) | 0.0356 (14) | 0.0419 (14) | 0.0010 (10) | 0.0107 (11) | 0.0003 (11) |
C1A | 0.0306 (11) | 0.0344 (13) | 0.0300 (11) | −0.0026 (9) | 0.0079 (9) | 0.0066 (11) |
C2A | 0.0375 (13) | 0.0355 (13) | 0.0238 (11) | 0.0049 (9) | 0.0041 (9) | 0.0040 (10) |
C3A | 0.0310 (11) | 0.0265 (12) | 0.0319 (12) | 0.0017 (8) | −0.0045 (10) | 0.0019 (9) |
C4A | 0.0271 (11) | 0.0184 (10) | 0.0266 (10) | 0.0017 (8) | 0.0019 (9) | 0.0005 (8) |
C5A | 0.0258 (11) | 0.0200 (11) | 0.0417 (13) | 0.0024 (8) | 0.0073 (9) | 0.0004 (10) |
C6A | 0.0356 (12) | 0.0199 (11) | 0.0403 (12) | 0.0027 (9) | 0.0101 (9) | −0.0012 (9) |
C7A | 0.0334 (11) | 0.0234 (11) | 0.0302 (11) | 0.0021 (8) | 0.0058 (9) | −0.0007 (9) |
C8A | 0.0489 (14) | 0.0395 (13) | 0.0301 (12) | 0.0058 (11) | 0.0155 (10) | 0.0058 (10) |
C9A | 0.0619 (17) | 0.0460 (16) | 0.0253 (11) | 0.0075 (12) | 0.0035 (11) | 0.0035 (11) |
C10A | 0.0506 (14) | 0.0438 (16) | 0.0331 (12) | 0.0044 (11) | −0.0100 (11) | −0.0022 (11) |
C11A | 0.0258 (10) | 0.0240 (11) | 0.0240 (10) | 0.0009 (8) | 0.0027 (8) | −0.0020 (9) |
C12A | 0.0198 (10) | 0.0210 (11) | 0.0247 (10) | 0.0019 (7) | 0.0063 (8) | 0.0006 (9) |
C1B | 0.0270 (10) | 0.0299 (12) | 0.0297 (10) | 0.0019 (8) | 0.0070 (8) | 0.0036 (10) |
C2B | 0.0400 (12) | 0.0339 (12) | 0.0215 (10) | −0.0014 (9) | 0.0024 (9) | 0.0033 (9) |
C3B | 0.0341 (11) | 0.0292 (12) | 0.0271 (11) | −0.0014 (8) | −0.0056 (9) | −0.0014 (9) |
C4B | 0.0253 (10) | 0.0209 (10) | 0.0272 (11) | 0.0042 (8) | 0.0009 (9) | 0.0025 (9) |
C5B | 0.0277 (11) | 0.0211 (11) | 0.0361 (11) | 0.0032 (8) | 0.0011 (9) | 0.0037 (9) |
C6B | 0.0322 (12) | 0.0242 (12) | 0.0357 (12) | 0.0060 (9) | 0.0106 (9) | 0.0037 (10) |
C7B | 0.0350 (12) | 0.0272 (11) | 0.0253 (10) | 0.0061 (8) | 0.0078 (9) | 0.0045 (9) |
C8B | 0.0535 (15) | 0.0378 (13) | 0.0282 (12) | 0.0080 (11) | 0.0137 (11) | 0.0028 (11) |
C9B | 0.0656 (18) | 0.0520 (16) | 0.0208 (11) | 0.0117 (13) | 0.0006 (12) | −0.0013 (11) |
C10B | 0.0466 (13) | 0.0407 (15) | 0.0312 (12) | 0.0047 (11) | −0.0072 (10) | −0.0047 (11) |
C11B | 0.0315 (11) | 0.0258 (11) | 0.0243 (10) | 0.0066 (9) | 0.0033 (9) | 0.0019 (9) |
C12B | 0.0241 (10) | 0.0209 (11) | 0.0270 (10) | 0.0053 (8) | 0.0008 (8) | 0.0033 (9) |
S1—O13 | 1.4330 (14) | C3A—C4A | 1.397 (3) |
S1—O11 | 1.4355 (15) | C3A—H3AA | 0.9500 |
S1—O12 | 1.4507 (16) | C4A—C12A | 1.387 (3) |
S1—C1 | 1.817 (2) | C4A—C5A | 1.482 (3) |
S2—O21 | 1.4337 (14) | C5A—C6A | 1.547 (3) |
S2—O23 | 1.4362 (14) | C6A—C7A | 1.477 (3) |
S2—O22 | 1.4509 (16) | C7A—C11A | 1.390 (3) |
S2—C2 | 1.819 (2) | C7A—C8A | 1.394 (3) |
F11—C1 | 1.318 (3) | C8A—C9A | 1.369 (3) |
F12—C1 | 1.327 (3) | C8A—H8AA | 0.9500 |
F13—C1 | 1.329 (3) | C9A—C10A | 1.381 (4) |
F21—C2 | 1.328 (3) | C9A—H9AA | 0.9500 |
F22—C2 | 1.328 (3) | C10A—H10B | 0.9500 |
F23—C2 | 1.329 (3) | C11A—C12A | 1.466 (3) |
O1A—C5A | 1.208 (2) | C1B—C2B | 1.382 (3) |
O2A—C6A | 1.209 (2) | C1B—H1BA | 0.9500 |
O1B—C5B | 1.214 (2) | C2B—C3B | 1.374 (3) |
O2B—C6B | 1.216 (2) | C2B—H2BA | 0.9500 |
N1A—C1A | 1.341 (3) | C3B—C4B | 1.399 (3) |
N1A—C12A | 1.343 (2) | C3B—H3BA | 0.9500 |
N1A—H1AB | 0.8800 | C4B—C12B | 1.384 (3) |
N2A—C11A | 1.339 (2) | C4B—C5B | 1.476 (3) |
N2A—C10A | 1.340 (3) | C5B—C6B | 1.551 (3) |
N1B—C1B | 1.338 (2) | C6B—C7B | 1.464 (3) |
N1B—C12B | 1.343 (3) | C7B—C11B | 1.396 (3) |
N1B—H1BB | 0.8800 | C7B—C8B | 1.399 (3) |
N2B—C10B | 1.332 (3) | C8B—C9B | 1.371 (3) |
N2B—C11B | 1.338 (3) | C8B—H8BA | 0.9500 |
C1A—C2A | 1.373 (3) | C9B—C10B | 1.384 (3) |
C1A—H1AA | 0.9500 | C9B—H9BA | 0.9500 |
C2A—C3A | 1.380 (3) | C10B—H10A | 0.9500 |
C2A—H2AA | 0.9500 | C11B—C12B | 1.470 (3) |
O13—S1—O11 | 115.34 (9) | C8A—C7A—C6A | 121.5 (2) |
O13—S1—O12 | 114.30 (9) | C9A—C8A—C7A | 119.5 (2) |
O11—S1—O12 | 114.19 (9) | C9A—C8A—H8AA | 120.3 |
O13—S1—C1 | 105.30 (10) | C7A—C8A—H8AA | 120.3 |
O11—S1—C1 | 102.40 (10) | C8A—C9A—C10A | 118.6 (2) |
O12—S1—C1 | 103.23 (10) | C8A—C9A—H9AA | 120.7 |
O21—S2—O23 | 115.69 (9) | C10A—C9A—H9AA | 120.7 |
O21—S2—O22 | 114.19 (9) | N2A—C10A—C9A | 123.8 (2) |
O23—S2—O22 | 114.28 (9) | N2A—C10A—H10B | 118.1 |
O21—S2—C2 | 105.11 (11) | C9A—C10A—H10B | 118.1 |
O23—S2—C2 | 102.77 (11) | N2A—C11A—C7A | 123.88 (19) |
O22—S2—C2 | 102.61 (10) | N2A—C11A—C12A | 115.77 (18) |
C1A—N1A—C12A | 123.07 (17) | C7A—C11A—C12A | 120.33 (17) |
C1A—N1A—H1AB | 118.5 | N1A—C12A—C4A | 118.63 (17) |
C12A—N1A—H1AB | 118.5 | N1A—C12A—C11A | 118.10 (16) |
C11A—N2A—C10A | 116.7 (2) | C4A—C12A—C11A | 123.25 (17) |
C1B—N1B—C12B | 122.78 (17) | N1B—C1B—C2B | 120.40 (18) |
C1B—N1B—H1BB | 118.6 | N1B—C1B—H1BA | 119.8 |
C12B—N1B—H1BB | 118.6 | C2B—C1B—H1BA | 119.8 |
C10B—N2B—C11B | 116.6 (2) | C3B—C2B—C1B | 118.62 (19) |
F11—C1—F12 | 108.5 (2) | C3B—C2B—H2BA | 120.7 |
F11—C1—F13 | 107.22 (19) | C1B—C2B—H2BA | 120.7 |
F12—C1—F13 | 107.7 (2) | C2B—C3B—C4B | 119.98 (19) |
F11—C1—S1 | 111.27 (16) | C2B—C3B—H3BA | 120.0 |
F12—C1—S1 | 110.05 (16) | C4B—C3B—H3BA | 120.0 |
F13—C1—S1 | 111.92 (16) | C12B—C4B—C3B | 119.40 (19) |
F21—C2—F22 | 108.0 (2) | C12B—C4B—C5B | 119.35 (18) |
F21—C2—F23 | 107.5 (2) | C3B—C4B—C5B | 121.25 (18) |
F22—C2—F23 | 107.18 (19) | O1B—C5B—C4B | 122.31 (19) |
F21—C2—S2 | 111.81 (17) | O1B—C5B—C6B | 119.62 (18) |
F22—C2—S2 | 111.26 (16) | C4B—C5B—C6B | 118.06 (17) |
F23—C2—S2 | 110.84 (16) | O2B—C6B—C7B | 124.3 (2) |
N1A—C1A—C2A | 119.98 (19) | O2B—C6B—C5B | 117.92 (19) |
N1A—C1A—H1AA | 120.0 | C7B—C6B—C5B | 117.79 (18) |
C2A—C1A—H1AA | 120.0 | C11B—C7B—C8B | 117.6 (2) |
C1A—C2A—C3A | 119.2 (2) | C11B—C7B—C6B | 121.40 (19) |
C1A—C2A—H2AA | 120.4 | C8B—C7B—C6B | 121.0 (2) |
C3A—C2A—H2AA | 120.4 | C9B—C8B—C7B | 118.7 (2) |
C2A—C3A—C4A | 119.6 (2) | C9B—C8B—H8BA | 120.7 |
C2A—C3A—H3AA | 120.2 | C7B—C8B—H8BA | 120.7 |
C4A—C3A—H3AA | 120.2 | C8B—C9B—C10B | 119.2 (2) |
C12A—C4A—C3A | 119.47 (18) | C8B—C9B—H9BA | 120.4 |
C12A—C4A—C5A | 119.66 (18) | C10B—C9B—H9BA | 120.4 |
C3A—C4A—C5A | 120.85 (19) | N2B—C10B—C9B | 123.9 (2) |
O1A—C5A—C4A | 122.9 (2) | N2B—C10B—H10A | 118.0 |
O1A—C5A—C6A | 119.47 (19) | C9B—C10B—H10A | 118.0 |
C4A—C5A—C6A | 117.65 (18) | N2B—C11B—C7B | 124.1 (2) |
O2A—C6A—C7A | 123.4 (2) | N2B—C11B—C12B | 116.08 (19) |
O2A—C6A—C5A | 118.55 (19) | C7B—C11B—C12B | 119.79 (18) |
C7A—C6A—C5A | 118.00 (18) | N1B—C12B—C4B | 118.77 (18) |
C11A—C7A—C8A | 117.5 (2) | N1B—C12B—C11B | 117.69 (17) |
C11A—C7A—C6A | 120.98 (19) | C4B—C12B—C11B | 123.52 (18) |
O13—S1—C1—F11 | −63.50 (18) | C1A—N1A—C12A—C11A | 177.25 (18) |
O11—S1—C1—F11 | 57.46 (18) | C3A—C4A—C12A—N1A | 0.5 (3) |
O12—S1—C1—F11 | 176.32 (16) | C5A—C4A—C12A—N1A | 179.33 (19) |
O13—S1—C1—F12 | 176.18 (16) | C3A—C4A—C12A—C11A | −177.69 (18) |
O11—S1—C1—F12 | −62.86 (19) | C5A—C4A—C12A—C11A | 1.1 (3) |
O12—S1—C1—F12 | 56.00 (19) | N2A—C11A—C12A—N1A | −0.5 (3) |
O13—S1—C1—F13 | 56.44 (19) | C7A—C11A—C12A—N1A | −178.6 (2) |
O11—S1—C1—F13 | 177.40 (16) | N2A—C11A—C12A—C4A | 177.71 (19) |
O12—S1—C1—F13 | −63.74 (19) | C7A—C11A—C12A—C4A | −0.4 (3) |
O21—S2—C2—F21 | −55.78 (19) | C12B—N1B—C1B—C2B | −0.7 (3) |
O23—S2—C2—F21 | −177.22 (16) | N1B—C1B—C2B—C3B | −1.4 (3) |
O22—S2—C2—F21 | 63.91 (19) | C1B—C2B—C3B—C4B | 2.2 (3) |
O21—S2—C2—F22 | 65.10 (18) | C2B—C3B—C4B—C12B | −0.9 (3) |
O23—S2—C2—F22 | −56.34 (18) | C2B—C3B—C4B—C5B | 179.1 (2) |
O22—S2—C2—F22 | −175.21 (16) | C12B—C4B—C5B—O1B | −177.13 (19) |
O21—S2—C2—F23 | −175.74 (16) | C3B—C4B—C5B—O1B | 2.9 (3) |
O23—S2—C2—F23 | 62.82 (18) | C12B—C4B—C5B—C6B | 3.9 (3) |
O22—S2—C2—F23 | −56.05 (18) | C3B—C4B—C5B—C6B | −176.08 (17) |
C12A—N1A—C1A—C2A | 0.5 (3) | O1B—C5B—C6B—O2B | −3.0 (3) |
N1A—C1A—C2A—C3A | 0.5 (3) | C4B—C5B—C6B—O2B | 176.0 (2) |
C1A—C2A—C3A—C4A | −1.0 (3) | O1B—C5B—C6B—C7B | 178.08 (19) |
C2A—C3A—C4A—C12A | 0.5 (3) | C4B—C5B—C6B—C7B | −2.9 (3) |
C2A—C3A—C4A—C5A | −178.3 (2) | O2B—C6B—C7B—C11B | −177.9 (2) |
C12A—C4A—C5A—O1A | −179.9 (2) | C5B—C6B—C7B—C11B | 0.9 (3) |
C3A—C4A—C5A—O1A | −1.0 (3) | O2B—C6B—C7B—C8B | −0.5 (3) |
C12A—C4A—C5A—C6A | 0.9 (3) | C5B—C6B—C7B—C8B | 178.34 (19) |
C3A—C4A—C5A—C6A | 179.67 (18) | C11B—C7B—C8B—C9B | 0.5 (3) |
O1A—C5A—C6A—O2A | −2.9 (3) | C6B—C7B—C8B—C9B | −177.1 (2) |
C4A—C5A—C6A—O2A | 176.4 (2) | C7B—C8B—C9B—C10B | −0.9 (4) |
O1A—C5A—C6A—C7A | 177.2 (2) | C11B—N2B—C10B—C9B | 0.0 (4) |
C4A—C5A—C6A—C7A | −3.5 (3) | C8B—C9B—C10B—N2B | 0.7 (4) |
O2A—C6A—C7A—C11A | −175.5 (2) | C10B—N2B—C11B—C7B | −0.6 (3) |
C5A—C6A—C7A—C11A | 4.3 (3) | C10B—N2B—C11B—C12B | 177.13 (18) |
O2A—C6A—C7A—C8A | 5.9 (3) | C8B—C7B—C11B—N2B | 0.3 (3) |
C5A—C6A—C7A—C8A | −174.27 (19) | C6B—C7B—C11B—N2B | 177.9 (2) |
C11A—C7A—C8A—C9A | 0.7 (3) | C8B—C7B—C11B—C12B | −177.29 (18) |
C6A—C7A—C8A—C9A | 179.4 (2) | C6B—C7B—C11B—C12B | 0.3 (3) |
C7A—C8A—C9A—C10A | 0.2 (4) | C1B—N1B—C12B—C4B | 2.1 (3) |
C11A—N2A—C10A—C9A | −0.7 (4) | C1B—N1B—C12B—C11B | −176.33 (18) |
C8A—C9A—C10A—N2A | −0.2 (4) | C3B—C4B—C12B—N1B | −1.3 (3) |
C10A—N2A—C11A—C7A | 1.7 (3) | C5B—C4B—C12B—N1B | 178.77 (18) |
C10A—N2A—C11A—C12A | −176.33 (18) | C3B—C4B—C12B—C11B | 177.07 (17) |
C8A—C7A—C11A—N2A | −1.8 (3) | C5B—C4B—C12B—C11B | −2.9 (3) |
C6A—C7A—C11A—N2A | 179.60 (19) | N2B—C11B—C12B—N1B | 1.3 (3) |
C8A—C7A—C11A—C12A | 176.19 (18) | C7B—C11B—C12B—N1B | 179.1 (2) |
C6A—C7A—C11A—C12A | −2.4 (3) | N2B—C11B—C12B—C4B | −177.06 (19) |
C1A—N1A—C12A—C4A | −1.0 (3) | C7B—C11B—C12B—C4B | 0.7 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1A—H1AB···O22 | 0.88 | 2.01 | 2.830 (2) | 154 |
N1B—H1BB···O12 | 0.88 | 2.02 | 2.835 (2) | 154 |
C1A—H1AA···O11i | 0.95 | 2.37 | 3.141 (3) | 138 |
C1A—H1AA···O23 | 0.95 | 2.39 | 3.190 (3) | 141 |
C1B—H1BA···O11 | 0.95 | 2.41 | 3.206 (3) | 142 |
C1B—H1BA···O23ii | 0.95 | 2.40 | 3.175 (2) | 139 |
C2A—H2AA···O13i | 0.95 | 2.49 | 3.395 (3) | 159 |
C9A—H9AA···O13 | 0.95 | 2.43 | 3.320 (3) | 156 |
C2B—H2BA···O21ii | 0.95 | 2.49 | 3.384 (3) | 158 |
C9B—H9BA···O21 | 0.95 | 2.43 | 3.328 (3) | 159 |
Symmetry codes: (i) x, y, z−1; (ii) x, y, z+1. |
Experimental details
Crystal data | |
Chemical formula | C12H7N2O2+·CF3O3S− |
Mr | 360.27 |
Crystal system, space group | Monoclinic, P21 |
Temperature (K) | 200 |
a, b, c (Å) | 6.4896 (2), 16.3963 (5), 13.2430 (3) |
β (°) | 94.393 (2) |
V (Å3) | 1404.99 (7) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.30 |
Crystal size (mm) | 0.51 × 0.22 × 0.18 |
Data collection | |
Diffractometer | Oxford Diffraction Gemini diffractometer |
Absorption correction | Multi-scan [Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm (Oxford Diffraction, 2007)] |
Tmin, Tmax | 0.897, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 13319, 7960, 5208 |
Rint | 0.023 |
(sin θ/λ)max (Å−1) | 0.757 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.034, 0.077, 0.94 |
No. of reflections | 7960 |
No. of parameters | 434 |
No. of restraints | 1 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.24, −0.38 |
Absolute structure | Flack (1983), with 2713 Friedel pairs |
Absolute structure parameter | 0.40 (5) |
Computer programs: CrysAlis CCD (Oxford Diffraction, 2007), CrysAlis RED (Oxford Diffraction, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
D—H···A | D—H | H···A | D···A | D—H···A |
N1A—H1AB···O22 | 0.88 | 2.01 | 2.830 (2) | 154 |
N1B—H1BB···O12 | 0.88 | 2.02 | 2.835 (2) | 154 |
Phendione (1,10-phenanthroline-5,6-dione) is an excellent ligand that incorporates two functional groups with different coordination properties (Ma et al., 2002; Calderazzo et al., 1999, 2002; Calucci et al., 2006; Galet et al., 2005; Lei et al., 1996; Okamura et al., 2006). This well known ligand posssesses both the α-diimine and orthoquinone moieties. While phendione usually binds to metals through its imine N atoms, in some cases both the N and O donors are used simultaneously (Calderazzo et al., 1999; Fox et al., 1991; Shavaleev et al., 2003a,b; Ruiz et al., 1999; Paw & Eisenberg, 1997). In this paper as part of our study of phendione chemistry (Udeochu et al., 2007; Onuegbu et al., 2007) we report the synthesis and characterization of the trifluoromethanesulfonate salt of mono-protonated 1,10-phenanthroline-5,6-dione.
The structure consists of a mono-protonated phendione cation and a trifluoromethanesulfonate (CF3SO3-) anion. The C═O bond lengths in the phendione cation (1.208 (2), 1.209 (2) and the metrical parameters involving the phendione N atoms are comparable in value to those found in neutral 1,10-phenanthroline-5,6-dione.
The N—H protons participate in hydrogen bonds with adjoining phendione cations. In addition there is an extensive network of weak C—H···O interactions to both phendione O and trifluoromethanesulfonate O atoms.