In the crystal structure of the title compound, C
12H
28N
2O
42+·2PF
6−, the center of the diprotonated macrocycle 18N
2O
4-2H
2+ (18N
2O
4-2H
2+ is the 1,4,10,13-tetraoxa-7,16-diazoniacyclooctadecane dication) coincides with a crystallographic inversion center. The structure displays N—H
F interactions between H atoms of the cationic N atoms of the macrocycle and the F atoms of the PF
6− anions. The H
F distances are in the range 2.15 (3)–2.42 (4) Å. The structure is nearly isostructural with the previously determined iodide salt, with PF
6− acting as a pseudohalide anion.
Supporting information
CCDC reference: 605193
Key indicators
- Single-crystal X-ray study
- T = 183 K
- Mean (C-C) = 0.004 Å
- R factor = 0.051
- wR factor = 0.130
- Data-to-parameter ratio = 12.7
checkCIF/PLATON results
No syntax errors found
Alert level C
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ?
PLAT244_ALERT_4_C Low 'Solvent' Ueq as Compared to Neighbors for P1
0 ALERT level A = In general: serious problem
0 ALERT level B = Potentially serious problem
2 ALERT level C = Check and explain
0 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
1 ALERT type 4 Improvement, methodology, query or suggestion
Data collection: CrystalClear (Rigaku, 2000); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELX97 (Sheldrick, 1997); program(s) used to refine structure: SHELX97 (Sheldrick, 1997); molecular graphics: Mercury (Version 1.4; Bruno et al., 2002); software used to prepare material for publication: Mercury.
1,4,10,13-Tetraoxa-7,16-diazoniacyclooctadecane bis(hexafluorophosphate)
top
Crystal data top
C12H28N2O42+·2F6P− | F(000) = 568 |
Mr = 554.30 | Dx = 1.675 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 7032 reflections |
a = 9.269 (2) Å | θ = 2.4–26.0° |
b = 10.333 (2) Å | µ = 0.32 mm−1 |
c = 12.264 (3) Å | T = 183 K |
β = 110.647 (7)° | Block, colorless |
V = 1099.2 (4) Å3 | 0.43 × 0.43 × 0.22 mm |
Z = 2 | |
Data collection top
Rigaku CCD diffractometer | 1948 independent reflections |
Radiation source: sealed tube | 1785 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.024 |
Detector resolution: 14.6199 pixels mm-1 | θmax = 25.1°, θmin = 2.7° |
ω scans | h = −11→11 |
Absorption correction: multi-scan (CrystalClear; Rigaku, 2000) | k = −12→12 |
Tmin = 0.874, Tmax = 0.933 | l = −14→14 |
9148 measured reflections | |
Refinement top
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)] = 0.051 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.130 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0685P)2 + 1.4259P] where P = (Fo2 + 2Fc2)/3 |
1948 reflections | (Δ/σ)max < 0.001 |
153 parameters | Δρmax = 0.52 e Å−3 |
0 restraints | Δρmin = −0.40 e Å−3 |
Special details top
Experimental. FT–IR (KBr, cm-1): 3241 (N—H), 3172 (N—H), 2974, 2905, 2899, 1603, 1491,
1465, 1426, 1383, 1323, 1245, 1146, 1111, 943, 922, 861, 831 (s, PF6-),
560 (s, PF6-), 525. |
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
P1 | 0.65663 (7) | 0.26270 (6) | −0.06318 (5) | 0.0271 (2) | |
F2 | 0.7663 (2) | 0.25962 (17) | 0.07096 (15) | 0.0465 (5) | |
F3 | 0.7801 (2) | 0.18019 (17) | −0.09689 (16) | 0.0450 (5) | |
F4 | 0.5334 (2) | 0.34191 (19) | −0.02799 (16) | 0.0490 (5) | |
F5 | 0.58359 (19) | 0.12772 (16) | −0.03861 (15) | 0.0419 (4) | |
F6 | 0.5416 (3) | 0.2559 (2) | −0.19484 (15) | 0.0653 (7) | |
O2 | 0.4565 (2) | 0.19368 (19) | 0.17057 (15) | 0.0308 (4) | |
O1 | 0.7832 (2) | −0.15238 (18) | 0.06001 (15) | 0.0298 (4) | |
N1 | 0.6808 (2) | 0.0113 (2) | 0.19904 (18) | 0.0256 (5) | |
C2 | 0.8891 (3) | −0.0622 (3) | 0.1333 (2) | 0.0302 (6) | |
H2A | 0.8866 | 0.0197 | 0.0908 | 0.036* | |
H2B | 0.9951 | −0.0975 | 0.1587 | 0.036* | |
F1 | 0.7295 (3) | 0.39283 (19) | −0.0849 (2) | 0.0701 (7) | |
C3 | 0.8422 (3) | −0.0386 (3) | 0.2365 (2) | 0.0305 (6) | |
H3A | 0.9130 | 0.0251 | 0.2890 | 0.037* | |
H3B | 0.8498 | −0.1203 | 0.2804 | 0.037* | |
C4 | 0.6335 (3) | 0.0518 (3) | 0.2984 (2) | 0.0344 (6) | |
H4A | 0.6455 | −0.0219 | 0.3524 | 0.041* | |
H4B | 0.7010 | 0.1229 | 0.3418 | 0.041* | |
C5 | 0.4688 (3) | 0.0963 (3) | 0.2547 (2) | 0.0360 (6) | |
H5A | 0.3990 | 0.0233 | 0.2192 | 0.043* | |
H5B | 0.4408 | 0.1316 | 0.3197 | 0.043* | |
C6 | 0.3103 (3) | 0.2574 (3) | 0.1245 (2) | 0.0371 (7) | |
H6A | 0.3222 | 0.3361 | 0.0824 | 0.045* | |
H6B | 0.2791 | 0.2853 | 0.1902 | 0.045* | |
C1 | 0.8153 (3) | −0.1761 (3) | −0.0437 (2) | 0.0381 (7) | |
H1A | 0.9154 | −0.2213 | −0.0244 | 0.046* | |
H1B | 0.8220 | −0.0930 | −0.0818 | 0.046* | |
H1D | 0.624 (3) | −0.047 (3) | 0.162 (3) | 0.028 (8)* | |
H1C | 0.671 (3) | 0.079 (3) | 0.151 (3) | 0.037 (8)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
P1 | 0.0302 (4) | 0.0269 (4) | 0.0249 (4) | 0.0038 (3) | 0.0107 (3) | 0.0014 (2) |
F2 | 0.0474 (10) | 0.0432 (10) | 0.0347 (9) | 0.0033 (8) | −0.0034 (8) | −0.0092 (7) |
F3 | 0.0473 (10) | 0.0420 (10) | 0.0586 (11) | 0.0108 (8) | 0.0347 (9) | 0.0036 (8) |
F4 | 0.0545 (11) | 0.0513 (11) | 0.0479 (10) | 0.0241 (9) | 0.0264 (9) | 0.0058 (8) |
F5 | 0.0423 (9) | 0.0373 (9) | 0.0471 (10) | −0.0088 (7) | 0.0170 (8) | −0.0026 (8) |
F6 | 0.0846 (15) | 0.0691 (14) | 0.0258 (9) | 0.0310 (12) | −0.0008 (9) | 0.0018 (9) |
O2 | 0.0269 (9) | 0.0371 (10) | 0.0266 (9) | 0.0047 (8) | 0.0071 (7) | −0.0003 (8) |
O1 | 0.0283 (9) | 0.0368 (10) | 0.0247 (9) | −0.0004 (8) | 0.0100 (7) | −0.0031 (8) |
N1 | 0.0269 (11) | 0.0242 (11) | 0.0230 (10) | −0.0013 (9) | 0.0056 (9) | −0.0015 (9) |
C2 | 0.0230 (12) | 0.0284 (13) | 0.0380 (14) | −0.0012 (10) | 0.0091 (10) | 0.0021 (11) |
F1 | 0.1007 (17) | 0.0325 (10) | 0.1048 (18) | −0.0068 (11) | 0.0705 (15) | 0.0095 (11) |
C3 | 0.0260 (13) | 0.0276 (13) | 0.0301 (13) | 0.0008 (10) | 0.0003 (10) | −0.0044 (10) |
C4 | 0.0504 (17) | 0.0307 (14) | 0.0230 (12) | 0.0087 (12) | 0.0141 (12) | 0.0024 (10) |
C5 | 0.0441 (16) | 0.0342 (15) | 0.0365 (15) | 0.0004 (12) | 0.0225 (13) | −0.0026 (12) |
C6 | 0.0337 (15) | 0.0436 (16) | 0.0333 (14) | 0.0094 (12) | 0.0110 (12) | −0.0056 (12) |
C1 | 0.0293 (14) | 0.0576 (19) | 0.0289 (14) | 0.0068 (13) | 0.0122 (11) | −0.0025 (13) |
Geometric parameters (Å, º) top
P1—F1 | 1.5690 (19) | C2—H2A | 0.9900 |
P1—F4 | 1.5838 (17) | C2—H2B | 0.9900 |
P1—F6 | 1.5921 (19) | C3—H3A | 0.9900 |
P1—F3 | 1.5938 (16) | C3—H3B | 0.9900 |
P1—F2 | 1.6003 (17) | C4—C5 | 1.501 (4) |
P1—F5 | 1.6243 (17) | C4—H4A | 0.9900 |
O2—C5 | 1.416 (3) | C4—H4B | 0.9900 |
O2—C6 | 1.431 (3) | C5—H5A | 0.9900 |
O1—C2 | 1.420 (3) | C5—H5B | 0.9900 |
O1—C1 | 1.426 (3) | C6—C1i | 1.493 (4) |
N1—C4 | 1.493 (3) | C6—H6A | 0.9900 |
N1—C3 | 1.493 (3) | C6—H6B | 0.9900 |
N1—H1D | 0.82 (3) | C1—C6i | 1.493 (4) |
N1—H1C | 0.90 (4) | C1—H1A | 0.9900 |
C2—C3 | 1.497 (4) | C1—H1B | 0.9900 |
| | | |
F1—P1—F4 | 89.91 (11) | C2—C3—H3A | 109.5 |
F1—P1—F6 | 92.31 (14) | N1—C3—H3A | 109.5 |
F4—P1—F6 | 90.54 (11) | C2—C3—H3B | 109.5 |
F1—P1—F3 | 91.32 (11) | N1—C3—H3B | 109.5 |
F4—P1—F3 | 178.66 (10) | H3A—C3—H3B | 108.1 |
F6—P1—F3 | 89.94 (11) | C5—C4—N1 | 110.5 (2) |
F1—P1—F2 | 92.06 (12) | C5—C4—H4A | 109.6 |
F4—P1—F2 | 89.29 (10) | N1—C4—H4A | 109.6 |
F6—P1—F2 | 175.62 (12) | C5—C4—H4B | 109.6 |
F3—P1—F2 | 90.13 (10) | N1—C4—H4B | 109.6 |
F1—P1—F5 | 179.02 (13) | H4A—C4—H4B | 108.1 |
F4—P1—F5 | 90.30 (10) | O2—C5—C4 | 106.8 (2) |
F6—P1—F5 | 88.65 (11) | O2—C5—H5A | 110.4 |
F3—P1—F5 | 88.46 (9) | C4—C5—H5A | 110.4 |
F2—P1—F5 | 86.98 (9) | O2—C5—H5B | 110.4 |
C5—O2—C6 | 115.9 (2) | C4—C5—H5B | 110.4 |
C2—O1—C1 | 111.3 (2) | H5A—C5—H5B | 108.6 |
C4—N1—C3 | 113.3 (2) | O2—C6—C1i | 114.3 (2) |
C4—N1—H1D | 110 (2) | O2—C6—H6A | 108.7 |
C3—N1—H1D | 107 (2) | C1i—C6—H6A | 108.7 |
C4—N1—H1C | 109 (2) | O2—C6—H6B | 108.7 |
C3—N1—H1C | 109 (2) | C1i—C6—H6B | 108.7 |
H1D—N1—H1C | 108 (3) | H6A—C6—H6B | 107.6 |
O1—C2—C3 | 107.5 (2) | O1—C1—C6i | 109.2 (2) |
O1—C2—H2A | 110.2 | O1—C1—H1A | 109.8 |
C3—C2—H2A | 110.2 | C6i—C1—H1A | 109.8 |
O1—C2—H2B | 110.2 | O1—C1—H1B | 109.8 |
C3—C2—H2B | 110.2 | C6i—C1—H1B | 109.8 |
H2A—C2—H2B | 108.5 | H1A—C1—H1B | 108.3 |
C2—C3—N1 | 110.7 (2) | | |
| | | |
C1—O1—C2—C3 | 177.3 (2) | C6—O2—C5—C4 | −175.0 (2) |
O1—C2—C3—N1 | −58.3 (3) | N1—C4—C5—O2 | −54.2 (3) |
C4—N1—C3—C2 | −173.1 (2) | C5—O2—C6—C1i | −72.1 (3) |
C3—N1—C4—C5 | −178.0 (2) | C2—O1—C1—C6i | −172.7 (2) |
Symmetry code: (i) −x+1, −y, −z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1C···F5 | 0.90 (4) | 2.23 (3) | 2.983 (3) | 141 (3) |
N1—H1D···F5i | 0.82 (3) | 2.15 (3) | 2.922 (3) | 156 (3) |
N1—H1C···F2 | 0.90 (4) | 2.42 (4) | 3.249 (3) | 154 (3) |
Symmetry code: (i) −x+1, −y, −z. |