








Supporting information
![]() | Crystallographic Information File (CIF) https://doi.org/10.1107/S010827011004672X/fg3206sup1.cif |
![]() | Structure factor file (CIF format) https://doi.org/10.1107/S010827011004672X/fg3206Isup2.hkl |
![]() | Structure factor file (CIF format) https://doi.org/10.1107/S010827011004672X/fg3206IIsup3.hkl |
![]() | Structure factor file (CIF format) https://doi.org/10.1107/S010827011004672X/fg3206IIIsup4.hkl |
CCDC references: 810025; 810026; 810027
The title compounds were synthesized by heating together for 10 min under reflux, 1 mmol quantities of piperidine-4-carboxamide (isonipecotamide) and 2,4,6-trinitrophenol (picric acid) [for (I)] or 3,5-dinitrosalicylic acid [for (II) and (III)] in 50 ml of 50% ethanol–water. After concentration to circa 30 ml, partial room-temperature evaporation [(I) and (III)] or evaporation to dryness [(II)] of the hot-filtered solutions gave yellow prisms of (I) (m.p. 452 K) or yellow plates of (II) and (III) (m.p. 475 K).
H atoms involved in hydrogen-bonding interactions were located by difference methods and with the exception of the carboxylic H in both (II) and (III) which were allowed to ride, their positional and isotropic displacement parameters were refined. The other H atoms were included in the refinements at calculated positions [C–H(aliphatic) = 0.99, 1.00 Å and C–H(aromatic) = 0.95 Å] while using a riding model approximation, with Uiso(H) = 1.2Ueq(C).
For all compounds, data collection: CrysAlis PRO (Oxford Diffraction, 2009); cell refinement: CrysAlis PRO (Oxford Diffraction, 2009). Data reduction: CrysAlis PRO? for (I); CrysAlis PRO (Oxford Diffraction, 2009) for (II), (III). Program(s) used to solve structure: SHELXS97 (Sheldrick, 2008) for (I); SIR92 (Altomare et al., 1994) for (II), (III). Program(s) used to refine structure: SHELXL97 (Sheldrick, 2008) for (I); SHELXL97 (Sheldrick, 2008) within WinGX (Farrugia, 1999) for (II), (III). For all compounds, molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: PLATON (Spek, 2009).
C6H13N2O+·C6H2N3O7− | F(000) = 744 |
Mr = 357.29 | Dx = 1.562 Mg m−3 |
Monoclinic, P21/c | Melting point: 452 K |
Hall symbol: -P 2ybc | Mo Kα radiation, λ = 0.71073 Å |
a = 13.4426 (11) Å | Cell parameters from 3090 reflections |
b = 13.7495 (13) Å | θ = 2.9–28.8° |
c = 8.3662 (15) Å | µ = 0.13 mm−1 |
β = 100.752 (13)° | T = 200 K |
V = 1519.2 (3) Å3 | Prism, yellow |
Z = 4 | 0.25 × 0.20 × 0.15 mm |
Oxford Diffraction Gemini-S Ultra CCD-detector diffractometer | 2994 independent reflections |
Radiation source: Enhance (Mo) X-ray source | 2279 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.034 |
Detector resolution: 16.0774 pixels mm-1 | θmax = 26.0°, θmin = 2.9° |
ω scans | h = −12→16 |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009) | k = −15→16 |
Tmin = 0.950, Tmax = 0.981 | l = −10→10 |
10181 measured reflections |
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)] = 0.036 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.107 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.93 | w = 1/[σ2(Fo2) + (0.0765P)2] where P = (Fo2 + 2Fc2)/3 |
3422 reflections | (Δ/σ)max = 0.001 |
238 parameters | Δρmax = 0.26 e Å−3 |
0 restraints | Δρmin = −0.28 e Å−3 |
C6H13N2O+·C6H2N3O7− | V = 1519.2 (3) Å3 |
Mr = 357.29 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 13.4426 (11) Å | µ = 0.13 mm−1 |
b = 13.7495 (13) Å | T = 200 K |
c = 8.3662 (15) Å | 0.25 × 0.20 × 0.15 mm |
β = 100.752 (13)° |
Oxford Diffraction Gemini-S Ultra CCD-detector diffractometer | 2994 independent reflections |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009) | 2279 reflections with I > 2σ(I) |
Tmin = 0.950, Tmax = 0.981 | Rint = 0.034 |
10181 measured reflections |
R[F2 > 2σ(F2)] = 0.036 | 0 restraints |
wR(F2) = 0.107 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.93 | Δρmax = 0.26 e Å−3 |
3422 reflections | Δρmin = −0.28 e Å−3 |
238 parameters |
Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles |
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 | ||
O41A | −0.06810 (9) | 0.34764 (8) | 0.56686 (13) | 0.0274 (3) | |
N1A | 0.18005 (10) | 0.49429 (10) | 0.32222 (18) | 0.0260 (4) | |
N41A | −0.10370 (12) | 0.23181 (10) | 0.37156 (19) | 0.0301 (4) | |
C2A | 0.21777 (12) | 0.41247 (12) | 0.4365 (2) | 0.0274 (5) | |
C3A | 0.13100 (11) | 0.36829 (12) | 0.50578 (19) | 0.0254 (5) | |
C4A | 0.04262 (11) | 0.33613 (11) | 0.37166 (18) | 0.0216 (5) | |
C5A | 0.00917 (11) | 0.42038 (12) | 0.2511 (2) | 0.0261 (5) | |
C6A | 0.09878 (12) | 0.46169 (12) | 0.1850 (2) | 0.0290 (5) | |
C41A | −0.04822 (11) | 0.30525 (11) | 0.44474 (18) | 0.0220 (4) | |
O1 | 0.28293 (8) | 0.59470 (8) | 0.11898 (15) | 0.0331 (4) | |
O21 | 0.25094 (10) | 0.55147 (11) | −0.21660 (18) | 0.0546 (5) | |
O22 | 0.31332 (10) | 0.68092 (12) | −0.30871 (19) | 0.0561 (5) | |
O41 | 0.68551 (10) | 0.66623 (11) | −0.13490 (17) | 0.0497 (5) | |
O42 | 0.74513 (9) | 0.66687 (9) | 0.12388 (16) | 0.0405 (4) | |
O61 | 0.52197 (10) | 0.64070 (10) | 0.49982 (15) | 0.0439 (5) | |
O62 | 0.38267 (11) | 0.56120 (12) | 0.43166 (17) | 0.0579 (5) | |
N2 | 0.31372 (11) | 0.61673 (11) | −0.20480 (18) | 0.0339 (5) | |
N4 | 0.67462 (11) | 0.65838 (10) | 0.00737 (18) | 0.0294 (4) | |
N6 | 0.45444 (11) | 0.60545 (10) | 0.39560 (17) | 0.0307 (5) | |
C1 | 0.37218 (11) | 0.60584 (10) | 0.0979 (2) | 0.0235 (5) | |
C2 | 0.39689 (12) | 0.61842 (11) | −0.0630 (2) | 0.0248 (5) | |
C3 | 0.49200 (12) | 0.63475 (11) | −0.0946 (2) | 0.0247 (5) | |
C4 | 0.57333 (12) | 0.63959 (10) | 0.0369 (2) | 0.0235 (5) | |
C5 | 0.55838 (12) | 0.63183 (11) | 0.19544 (19) | 0.0238 (5) | |
C6 | 0.46230 (12) | 0.61382 (11) | 0.22471 (19) | 0.0248 (5) | |
H4A | 0.06500 | 0.28000 | 0.31120 | 0.0260* | |
H11A | 0.2335 (13) | 0.5220 (13) | 0.281 (2) | 0.0310* | |
H12A | 0.1553 (14) | 0.5433 (13) | 0.377 (2) | 0.0310* | |
H21A | 0.27020 | 0.43720 | 0.52640 | 0.0330* | |
H22A | 0.24900 | 0.36180 | 0.37780 | 0.0330* | |
H31A | 0.10610 | 0.41670 | 0.57660 | 0.0300* | |
H32A | 0.15640 | 0.31140 | 0.57380 | 0.0300* | |
H43A | −0.0917 (14) | 0.2098 (14) | 0.280 (2) | 0.0360* | |
H44A | −0.1644 (14) | 0.2184 (13) | 0.400 (2) | 0.0360* | |
H51A | −0.04260 | 0.39640 | 0.15960 | 0.0310* | |
H52A | −0.02190 | 0.47260 | 0.30700 | 0.0310* | |
H61A | 0.12610 | 0.41130 | 0.12040 | 0.0350* | |
H62A | 0.07600 | 0.51750 | 0.11250 | 0.0350* | |
H3 | 0.50250 | 0.64260 | −0.20310 | 0.0300* | |
H5 | 0.61380 | 0.63880 | 0.28360 | 0.0290* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O41A | 0.0285 (6) | 0.0316 (6) | 0.0246 (6) | 0.0003 (5) | 0.0118 (5) | −0.0026 (5) |
N1A | 0.0228 (7) | 0.0261 (7) | 0.0316 (8) | −0.0025 (6) | 0.0117 (6) | 0.0006 (6) |
N41A | 0.0291 (7) | 0.0333 (8) | 0.0313 (8) | −0.0088 (6) | 0.0141 (7) | −0.0070 (6) |
C2A | 0.0209 (8) | 0.0319 (9) | 0.0293 (9) | 0.0012 (7) | 0.0045 (7) | 0.0022 (7) |
C3A | 0.0223 (8) | 0.0308 (9) | 0.0233 (8) | 0.0000 (6) | 0.0047 (7) | 0.0024 (7) |
C4A | 0.0222 (8) | 0.0234 (8) | 0.0207 (8) | −0.0003 (6) | 0.0082 (6) | −0.0014 (6) |
C5A | 0.0232 (8) | 0.0316 (9) | 0.0229 (8) | −0.0034 (7) | 0.0031 (7) | 0.0034 (7) |
C6A | 0.0284 (9) | 0.0348 (9) | 0.0238 (8) | −0.0043 (7) | 0.0048 (7) | 0.0053 (7) |
C41A | 0.0224 (8) | 0.0225 (7) | 0.0219 (8) | 0.0022 (6) | 0.0061 (6) | 0.0033 (6) |
O1 | 0.0234 (6) | 0.0373 (7) | 0.0415 (7) | −0.0023 (5) | 0.0133 (5) | 0.0051 (5) |
O21 | 0.0421 (8) | 0.0604 (10) | 0.0551 (10) | −0.0176 (7) | −0.0073 (7) | −0.0047 (7) |
O22 | 0.0400 (8) | 0.0741 (10) | 0.0504 (9) | 0.0066 (7) | −0.0010 (7) | 0.0275 (8) |
O41 | 0.0316 (7) | 0.0863 (11) | 0.0356 (8) | −0.0006 (7) | 0.0177 (6) | 0.0039 (7) |
O42 | 0.0243 (6) | 0.0549 (8) | 0.0410 (8) | −0.0084 (5) | 0.0028 (6) | 0.0005 (6) |
O61 | 0.0457 (8) | 0.0594 (9) | 0.0269 (7) | −0.0170 (6) | 0.0072 (6) | −0.0069 (6) |
O62 | 0.0535 (9) | 0.0866 (11) | 0.0366 (8) | −0.0385 (8) | 0.0163 (7) | 0.0014 (8) |
N2 | 0.0250 (8) | 0.0412 (9) | 0.0347 (9) | 0.0031 (7) | 0.0033 (6) | −0.0010 (7) |
N4 | 0.0244 (7) | 0.0333 (8) | 0.0324 (8) | 0.0003 (6) | 0.0106 (6) | 0.0009 (6) |
N6 | 0.0354 (8) | 0.0317 (8) | 0.0265 (8) | −0.0055 (6) | 0.0099 (7) | −0.0013 (6) |
C1 | 0.0249 (8) | 0.0173 (7) | 0.0303 (9) | −0.0009 (6) | 0.0105 (7) | 0.0002 (6) |
C2 | 0.0234 (8) | 0.0228 (8) | 0.0276 (9) | 0.0007 (6) | 0.0031 (7) | −0.0011 (6) |
C3 | 0.0278 (8) | 0.0232 (8) | 0.0246 (8) | 0.0016 (6) | 0.0087 (7) | −0.0006 (6) |
C4 | 0.0210 (8) | 0.0230 (7) | 0.0278 (9) | 0.0006 (6) | 0.0079 (7) | −0.0003 (6) |
C5 | 0.0238 (8) | 0.0217 (8) | 0.0255 (9) | −0.0010 (6) | 0.0038 (7) | −0.0005 (6) |
C6 | 0.0302 (8) | 0.0213 (8) | 0.0246 (8) | −0.0021 (6) | 0.0094 (7) | −0.0006 (6) |
O41A—C41A | 1.2477 (19) | C4A—C5A | 1.547 (2) |
O1—C1 | 1.2542 (19) | C4A—C41A | 1.524 (2) |
O21—N2 | 1.223 (2) | C5A—C6A | 1.526 (2) |
O22—N2 | 1.238 (2) | C2A—H21A | 0.9900 |
O41—N4 | 1.231 (2) | C2A—H22A | 0.9900 |
O42—N4 | 1.232 (2) | C3A—H32A | 0.9900 |
O61—N6 | 1.235 (2) | C3A—H31A | 0.9900 |
O62—N6 | 1.225 (2) | C4A—H4A | 1.0000 |
N1A—C2A | 1.502 (2) | C5A—H51A | 0.9900 |
N1A—C6A | 1.498 (2) | C5A—H52A | 0.9900 |
N41A—C41A | 1.334 (2) | C6A—H61A | 0.9900 |
N1A—H12A | 0.912 (18) | C6A—H62A | 0.9900 |
N1A—H11A | 0.934 (18) | C1—C2 | 1.456 (2) |
N41A—H43A | 0.866 (17) | C1—C6 | 1.458 (2) |
N41A—H44A | 0.910 (19) | C2—C3 | 1.372 (2) |
N2—C2 | 1.471 (2) | C3—C4 | 1.401 (2) |
N4—C4 | 1.452 (2) | C4—C5 | 1.382 (2) |
N6—C6 | 1.458 (2) | C5—C6 | 1.381 (2) |
C2A—C3A | 1.522 (2) | C3—H3 | 0.9500 |
C3A—C4A | 1.539 (2) | C5—H5 | 0.9500 |
C2A—N1A—C6A | 112.03 (13) | C2A—C3A—H32A | 109.00 |
H11A—N1A—H12A | 105.2 (16) | H31A—C3A—H32A | 108.00 |
C2A—N1A—H12A | 110.2 (11) | C4A—C3A—H32A | 109.00 |
C6A—N1A—H11A | 109.9 (10) | C3A—C4A—H4A | 109.00 |
C2A—N1A—H11A | 110.4 (11) | C5A—C4A—H4A | 109.00 |
C6A—N1A—H12A | 108.9 (11) | C41A—C4A—H4A | 109.00 |
C41A—N41A—H44A | 119.0 (11) | C4A—C5A—H51A | 109.00 |
H43A—N41A—H44A | 119.0 (16) | C4A—C5A—H52A | 109.00 |
C41A—N41A—H43A | 119.3 (13) | H51A—C5A—H52A | 108.00 |
O22—N2—C2 | 117.27 (14) | C6A—C5A—H52A | 109.00 |
O21—N2—O22 | 123.62 (16) | C6A—C5A—H51A | 109.00 |
O21—N2—C2 | 119.07 (14) | N1A—C6A—H62A | 110.00 |
O41—N4—C4 | 117.70 (14) | N1A—C6A—H61A | 110.00 |
O42—N4—C4 | 119.33 (14) | H61A—C6A—H62A | 108.00 |
O41—N4—O42 | 122.97 (15) | C5A—C6A—H61A | 110.00 |
O62—N6—C6 | 119.03 (14) | C5A—C6A—H62A | 110.00 |
O61—N6—C6 | 118.91 (14) | O1—C1—C2 | 122.27 (15) |
O61—N6—O62 | 122.02 (15) | O1—C1—C6 | 126.42 (15) |
N1A—C2A—C3A | 110.46 (13) | C2—C1—C6 | 111.22 (13) |
C2A—C3A—C4A | 112.28 (13) | N2—C2—C1 | 118.28 (14) |
C3A—C4A—C41A | 110.78 (12) | N2—C2—C3 | 116.28 (14) |
C5A—C4A—C41A | 108.24 (12) | C1—C2—C3 | 125.41 (15) |
C3A—C4A—C5A | 110.56 (13) | C2—C3—C4 | 118.40 (15) |
C4A—C5A—C6A | 111.23 (13) | N4—C4—C3 | 119.63 (15) |
N1A—C6A—C5A | 110.23 (13) | N4—C4—C5 | 119.08 (15) |
O41A—C41A—N41A | 122.85 (15) | C3—C4—C5 | 121.21 (15) |
O41A—C41A—C4A | 120.55 (14) | C4—C5—C6 | 119.48 (15) |
N41A—C41A—C4A | 116.60 (14) | N6—C6—C1 | 120.35 (14) |
C3A—C2A—H21A | 110.00 | N6—C6—C5 | 115.43 (14) |
C3A—C2A—H22A | 110.00 | C1—C6—C5 | 124.20 (14) |
H21A—C2A—H22A | 108.00 | C2—C3—H3 | 121.00 |
N1A—C2A—H22A | 110.00 | C4—C3—H3 | 121.00 |
N1A—C2A—H21A | 110.00 | C4—C5—H5 | 120.00 |
C4A—C3A—H31A | 109.00 | C6—C5—H5 | 120.00 |
C2A—C3A—H31A | 109.00 | ||
C6A—N1A—C2A—C3A | −58.04 (17) | C3A—C4A—C5A—C6A | 53.09 (17) |
C2A—N1A—C6A—C5A | 59.34 (17) | C3A—C4A—C41A—O41A | 35.27 (19) |
O21—N2—C2—C1 | −47.9 (2) | C3A—C4A—C41A—N41A | −144.72 (14) |
O21—N2—C2—C3 | 133.90 (16) | C4A—C5A—C6A—N1A | −56.52 (17) |
O22—N2—C2—C1 | 134.13 (16) | O1—C1—C2—N2 | −0.7 (2) |
O22—N2—C2—C3 | −44.1 (2) | O1—C1—C2—C3 | 177.28 (15) |
O42—N4—C4—C3 | 176.78 (14) | C6—C1—C2—N2 | −177.39 (13) |
O42—N4—C4—C5 | 0.1 (2) | C6—C1—C2—C3 | 0.6 (2) |
O41—N4—C4—C5 | −179.05 (15) | O1—C1—C6—N6 | 2.3 (2) |
O41—N4—C4—C3 | −2.4 (2) | O1—C1—C6—C5 | −175.98 (15) |
O61—N6—C6—C5 | 20.3 (2) | C2—C1—C6—N6 | 178.77 (13) |
O62—N6—C6—C1 | 24.0 (2) | C2—C1—C6—C5 | 0.5 (2) |
O61—N6—C6—C1 | −158.11 (14) | N2—C2—C3—C4 | 178.33 (13) |
O62—N6—C6—C5 | −157.57 (16) | C1—C2—C3—C4 | 0.3 (2) |
N1A—C2A—C3A—C4A | 54.42 (17) | C2—C3—C4—N4 | −178.99 (14) |
C2A—C3A—C4A—C5A | −52.28 (17) | C2—C3—C4—C5 | −2.4 (2) |
C2A—C3A—C4A—C41A | −172.27 (13) | N4—C4—C5—C6 | −179.91 (14) |
C5A—C4A—C41A—N41A | 93.90 (16) | C3—C4—C5—C6 | 3.5 (2) |
C41A—C4A—C5A—C6A | 174.60 (13) | C4—C5—C6—N6 | 179.13 (13) |
C5A—C4A—C41A—O41A | −86.10 (17) | C4—C5—C6—C1 | −2.5 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1A—H11A···O1 | 0.934 (18) | 1.901 (17) | 2.7545 (19) | 150.8 (15) |
N1A—H11A···O62 | 0.934 (18) | 2.227 (17) | 2.859 (2) | 124.3 (13) |
N1A—H12A···O41Ai | 0.912 (18) | 2.012 (18) | 2.8932 (19) | 162.0 (16) |
N41A—H43A···O41Aii | 0.866 (17) | 2.029 (17) | 2.894 (2) | 177 (2) |
N41A—H44A···O1iii | 0.910 (19) | 2.316 (19) | 3.072 (2) | 140.3 (15) |
N41A—H44A···O22iv | 0.910 (19) | 2.437 (19) | 3.017 (2) | 121.8 (14) |
C3—H3···O61v | 0.95 | 2.55 | 3.492 (2) | 172 |
C2A—H21A···O62 | 0.99 | 2.50 | 3.022 (2) | 112 |
C2A—H22A···O41vi | 0.99 | 2.39 | 3.233 (2) | 142 |
Symmetry codes: (i) −x, −y+1, −z+1; (ii) x, −y+1/2, z−1/2; (iii) −x, y−1/2, −z+1/2; (iv) −x, −y+1, −z; (v) x, y, z−1; (vi) −x+1, −y+1, −z. |
C6H13N2O+·C7H3N2O7− | F(000) = 744 |
Mr = 356.30 | Dx = 1.530 Mg m−3 |
Monoclinic, P21/n | Melting point: 475 K |
Hall symbol: -P 2yn | Mo Kα radiation, λ = 0.71073 Å |
a = 11.7131 (12) Å | Cell parameters from 5903 reflections |
b = 12.6450 (11) Å | θ = 3.1–28.9° |
c = 11.8521 (14) Å | µ = 0.13 mm−1 |
β = 118.196 (14)° | T = 200 K |
V = 1547.1 (3) Å3 | Plate, yellow |
Z = 4 | 0.40 × 0.40 × 0.20 mm |
Oxford Diffraction Gemini-S Ultra CCD-detector diffractometer | 3048 independent reflections |
Radiation source: Enhance (Mo) X-ray source | 2456 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.033 |
ω scans | θmax = 26.0°, θmin = 3.2° |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009) | h = −14→14 |
Tmin = 0.93, Tmax = 0.98 | k = −15→15 |
19733 measured reflections | l = −14→14 |
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) = 0.098 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0505P)2 + 0.3254P] where P = (Fo2 + 2Fc2)/3 |
3048 reflections | (Δ/σ)max < 0.001 |
242 parameters | Δρmax = 0.31 e Å−3 |
0 restraints | Δρmin = −0.24 e Å−3 |
C6H13N2O+·C7H3N2O7− | V = 1547.1 (3) Å3 |
Mr = 356.30 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 11.7131 (12) Å | µ = 0.13 mm−1 |
b = 12.6450 (11) Å | T = 200 K |
c = 11.8521 (14) Å | 0.40 × 0.40 × 0.20 mm |
β = 118.196 (14)° |
Oxford Diffraction Gemini-S Ultra CCD-detector diffractometer | 3048 independent reflections |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009) | 2456 reflections with I > 2σ(I) |
Tmin = 0.93, Tmax = 0.98 | Rint = 0.033 |
19733 measured reflections |
R[F2 > 2σ(F2)] = 0.039 | 0 restraints |
wR(F2) = 0.098 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | Δρmax = 0.31 e Å−3 |
3048 reflections | Δρmin = −0.24 e Å−3 |
242 parameters |
Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles |
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 | ||
O41A | 0.91435 (11) | 0.16355 (8) | 0.34281 (12) | 0.0376 (4) | |
N1A | 0.64157 (13) | 0.46323 (12) | 0.24420 (14) | 0.0302 (4) | |
N41A | 1.07432 (14) | 0.25715 (14) | 0.33428 (14) | 0.0326 (5) | |
C2A | 0.66526 (17) | 0.43037 (14) | 0.13574 (16) | 0.0389 (6) | |
C3A | 0.74700 (16) | 0.33094 (13) | 0.16879 (16) | 0.0356 (5) | |
C4A | 0.87494 (14) | 0.34730 (11) | 0.29070 (15) | 0.0251 (5) | |
C5A | 0.84626 (16) | 0.37753 (14) | 0.40008 (16) | 0.0344 (5) | |
C6A | 0.76398 (16) | 0.47717 (14) | 0.36640 (16) | 0.0350 (5) | |
C41A | 0.95693 (14) | 0.24793 (12) | 0.32469 (14) | 0.0257 (5) | |
O2 | 0.47303 (10) | 0.29794 (9) | 0.22748 (12) | 0.0371 (4) | |
O11 | 0.37954 (11) | −0.01363 (9) | 0.21453 (13) | 0.0417 (4) | |
O12 | 0.53269 (11) | 0.10794 (10) | 0.26508 (12) | 0.0405 (4) | |
O31 | 0.37968 (13) | 0.49662 (10) | 0.18436 (18) | 0.0641 (6) | |
O32 | 0.18116 (14) | 0.51899 (10) | 0.04687 (15) | 0.0565 (5) | |
O51 | −0.13172 (11) | 0.24904 (11) | −0.05034 (14) | 0.0496 (4) | |
O52 | −0.07272 (12) | 0.09399 (11) | 0.03421 (15) | 0.0569 (5) | |
N3 | 0.27091 (14) | 0.46176 (11) | 0.11677 (15) | 0.0344 (5) | |
N5 | −0.04816 (12) | 0.18363 (11) | 0.01234 (14) | 0.0342 (5) | |
C1 | 0.31189 (14) | 0.16553 (11) | 0.17075 (14) | 0.0240 (5) | |
C2 | 0.35196 (14) | 0.27440 (12) | 0.17692 (14) | 0.0252 (5) | |
C3 | 0.24707 (15) | 0.34884 (11) | 0.12059 (15) | 0.0256 (5) | |
C4 | 0.11787 (14) | 0.31943 (12) | 0.06519 (15) | 0.0265 (5) | |
C5 | 0.08755 (14) | 0.21438 (12) | 0.06551 (15) | 0.0259 (4) | |
C6 | 0.18314 (14) | 0.13709 (12) | 0.11806 (14) | 0.0251 (5) | |
C11 | 0.41058 (15) | 0.07888 (12) | 0.21983 (15) | 0.0283 (5) | |
H4A | 0.92350 | 0.40640 | 0.27660 | 0.0300* | |
H11A | 0.591 (2) | 0.4179 (17) | 0.2527 (19) | 0.049 (6)* | |
H12A | 0.5991 (18) | 0.5283 (15) | 0.2205 (17) | 0.040 (5)* | |
H21A | 0.71010 | 0.48810 | 0.11600 | 0.0470* | |
H22A | 0.58130 | 0.41750 | 0.05860 | 0.0470* | |
H31A | 0.76450 | 0.31250 | 0.09720 | 0.0430* | |
H32A | 0.69900 | 0.27150 | 0.18120 | 0.0430* | |
H41A | 1.1000 (17) | 0.3199 (16) | 0.3247 (17) | 0.035 (5)* | |
H42A | 1.120 (2) | 0.2035 (18) | 0.3522 (19) | 0.048 (6)* | |
H51A | 0.79990 | 0.31880 | 0.41610 | 0.0410* | |
H52A | 0.92870 | 0.38960 | 0.47930 | 0.0410* | |
H61A | 0.74310 | 0.49380 | 0.43620 | 0.0420* | |
H62A | 0.81360 | 0.53730 | 0.35790 | 0.0420* | |
H4 | 0.05130 | 0.37100 | 0.02760 | 0.0320* | |
H6 | 0.15980 | 0.06510 | 0.11760 | 0.0300* | |
H12 | 0.53160 | 0.18860 | 0.2602 | 0.0490* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O41A | 0.0362 (7) | 0.0224 (6) | 0.0581 (8) | 0.0004 (5) | 0.0254 (6) | 0.0015 (5) |
N1A | 0.0211 (7) | 0.0230 (7) | 0.0474 (9) | 0.0011 (6) | 0.0170 (6) | 0.0042 (6) |
N41A | 0.0254 (7) | 0.0316 (8) | 0.0422 (9) | 0.0052 (7) | 0.0172 (6) | 0.0031 (7) |
C2A | 0.0396 (10) | 0.0368 (10) | 0.0302 (9) | 0.0097 (8) | 0.0082 (8) | 0.0017 (8) |
C3A | 0.0368 (9) | 0.0349 (9) | 0.0274 (9) | 0.0075 (7) | 0.0089 (7) | −0.0053 (7) |
C4A | 0.0227 (7) | 0.0212 (8) | 0.0336 (9) | −0.0009 (6) | 0.0151 (7) | −0.0002 (6) |
C5A | 0.0333 (9) | 0.0375 (10) | 0.0278 (9) | 0.0101 (7) | 0.0106 (7) | −0.0024 (7) |
C6A | 0.0349 (9) | 0.0343 (9) | 0.0355 (9) | 0.0060 (7) | 0.0165 (8) | −0.0060 (7) |
C41A | 0.0241 (8) | 0.0254 (8) | 0.0271 (8) | −0.0008 (6) | 0.0117 (6) | −0.0036 (6) |
O2 | 0.0219 (6) | 0.0299 (6) | 0.0541 (8) | −0.0046 (5) | 0.0136 (5) | 0.0031 (5) |
O11 | 0.0366 (7) | 0.0244 (7) | 0.0637 (9) | 0.0042 (5) | 0.0234 (6) | 0.0040 (6) |
O12 | 0.0244 (6) | 0.0329 (7) | 0.0585 (8) | 0.0043 (5) | 0.0149 (6) | 0.0053 (6) |
O31 | 0.0362 (8) | 0.0295 (7) | 0.1270 (14) | −0.0099 (6) | 0.0388 (9) | −0.0149 (8) |
O32 | 0.0602 (9) | 0.0290 (7) | 0.0753 (10) | 0.0087 (6) | 0.0278 (8) | 0.0154 (7) |
O51 | 0.0225 (6) | 0.0539 (8) | 0.0652 (9) | 0.0069 (6) | 0.0148 (6) | 0.0013 (7) |
O52 | 0.0348 (7) | 0.0396 (8) | 0.0948 (12) | −0.0138 (6) | 0.0293 (8) | −0.0057 (7) |
N3 | 0.0359 (8) | 0.0252 (7) | 0.0537 (9) | −0.0016 (6) | 0.0306 (7) | −0.0009 (7) |
N5 | 0.0229 (7) | 0.0359 (8) | 0.0448 (9) | −0.0032 (6) | 0.0169 (6) | −0.0085 (7) |
C1 | 0.0244 (8) | 0.0236 (8) | 0.0271 (8) | −0.0003 (6) | 0.0147 (6) | −0.0006 (6) |
C2 | 0.0236 (8) | 0.0267 (8) | 0.0269 (8) | −0.0038 (6) | 0.0133 (6) | −0.0006 (6) |
C3 | 0.0298 (8) | 0.0208 (8) | 0.0308 (9) | −0.0016 (6) | 0.0180 (7) | −0.0002 (6) |
C4 | 0.0251 (8) | 0.0273 (8) | 0.0299 (8) | 0.0040 (6) | 0.0152 (7) | 0.0016 (6) |
C5 | 0.0218 (7) | 0.0299 (8) | 0.0286 (8) | −0.0029 (6) | 0.0140 (6) | −0.0039 (7) |
C6 | 0.0269 (8) | 0.0231 (8) | 0.0295 (8) | −0.0036 (6) | 0.0168 (7) | −0.0039 (6) |
C11 | 0.0277 (8) | 0.0264 (8) | 0.0318 (9) | 0.0022 (7) | 0.0149 (7) | 0.0005 (7) |
O41A—C41A | 1.239 (2) | C4A—C41A | 1.516 (2) |
O2—C2 | 1.287 (2) | C5A—C6A | 1.521 (3) |
O11—C11 | 1.218 (2) | C2A—H22A | 0.9900 |
O12—C11 | 1.320 (2) | C2A—H21A | 0.9900 |
O31—N3 | 1.223 (2) | C3A—H32A | 0.9900 |
O32—N3 | 1.222 (2) | C3A—H31A | 0.9900 |
O51—N5 | 1.228 (2) | C4A—H4A | 1.0000 |
O52—N5 | 1.227 (2) | C5A—H51A | 0.9900 |
O12—H12 | 1.01 | C5A—H52A | 0.9900 |
N1A—C6A | 1.491 (2) | C6A—H61A | 0.9900 |
N1A—C2A | 1.496 (2) | C6A—H62A | 0.9900 |
N41A—C41A | 1.330 (3) | C1—C6 | 1.380 (2) |
N1A—H12A | 0.93 (2) | C1—C11 | 1.497 (2) |
N1A—H11A | 0.86 (2) | C1—C2 | 1.445 (2) |
N41A—H42A | 0.83 (2) | C2—C3 | 1.437 (2) |
N41A—H41A | 0.88 (2) | C3—C4 | 1.386 (3) |
N3—C3 | 1.460 (2) | C4—C5 | 1.376 (2) |
N5—C5 | 1.459 (2) | C5—C6 | 1.392 (2) |
C2A—C3A | 1.515 (3) | C4—H4 | 0.9500 |
C3A—C4A | 1.527 (2) | C6—H6 | 0.9500 |
C4A—C5A | 1.533 (2) | ||
C11—O12—H12 | 106.00 | C4A—C3A—H32A | 110.00 |
C2A—N1A—C6A | 112.57 (15) | C41A—C4A—H4A | 109.00 |
H11A—N1A—H12A | 109 (2) | C3A—C4A—H4A | 109.00 |
C6A—N1A—H11A | 111.3 (14) | C5A—C4A—H4A | 109.00 |
C2A—N1A—H11A | 109.4 (14) | C4A—C5A—H52A | 110.00 |
C2A—N1A—H12A | 106.0 (12) | C4A—C5A—H51A | 110.00 |
C6A—N1A—H12A | 108.6 (12) | C6A—C5A—H51A | 110.00 |
H41A—N41A—H42A | 124 (2) | C6A—C5A—H52A | 110.00 |
C41A—N41A—H41A | 118.3 (14) | H51A—C5A—H52A | 108.00 |
C41A—N41A—H42A | 117.9 (17) | H61A—C6A—H62A | 108.00 |
O32—N3—C3 | 118.99 (16) | N1A—C6A—H62A | 109.00 |
O31—N3—C3 | 119.19 (15) | C5A—C6A—H61A | 109.00 |
O31—N3—O32 | 121.82 (15) | N1A—C6A—H61A | 109.00 |
O51—N5—C5 | 118.44 (14) | C5A—C6A—H62A | 109.00 |
O52—N5—C5 | 118.12 (15) | C2—C1—C6 | 122.05 (15) |
O51—N5—O52 | 123.43 (17) | C2—C1—C11 | 120.33 (15) |
N1A—C2A—C3A | 111.06 (14) | C6—C1—C11 | 117.61 (13) |
C2A—C3A—C4A | 110.49 (13) | O2—C2—C3 | 125.23 (14) |
C5A—C4A—C41A | 110.26 (13) | C1—C2—C3 | 114.49 (15) |
C3A—C4A—C5A | 108.95 (15) | O2—C2—C1 | 120.27 (15) |
C3A—C4A—C41A | 110.77 (12) | N3—C3—C2 | 121.40 (16) |
C4A—C5A—C6A | 110.46 (14) | C2—C3—C4 | 123.14 (14) |
N1A—C6A—C5A | 110.88 (14) | N3—C3—C4 | 115.46 (15) |
O41A—C41A—C4A | 120.24 (16) | C3—C4—C5 | 118.91 (15) |
N41A—C41A—C4A | 116.72 (15) | N5—C5—C6 | 119.21 (14) |
O41A—C41A—N41A | 123.04 (16) | C4—C5—C6 | 121.68 (16) |
C3A—C2A—H22A | 109.00 | N5—C5—C4 | 119.09 (15) |
N1A—C2A—H22A | 109.00 | C1—C6—C5 | 119.71 (14) |
C3A—C2A—H21A | 109.00 | O11—C11—C1 | 121.76 (17) |
H21A—C2A—H22A | 108.00 | O12—C11—C1 | 116.34 (14) |
N1A—C2A—H21A | 109.00 | O11—C11—O12 | 121.87 (16) |
C4A—C3A—H31A | 110.00 | C3—C4—H4 | 121.00 |
C2A—C3A—H32A | 110.00 | C5—C4—H4 | 121.00 |
H31A—C3A—H32A | 108.00 | C1—C6—H6 | 120.00 |
C2A—C3A—H31A | 110.00 | C5—C6—H6 | 120.00 |
C6A—N1A—C2A—C3A | 55.3 (2) | C6—C1—C2—O2 | 179.58 (15) |
C2A—N1A—C6A—C5A | −55.14 (19) | C6—C1—C2—C3 | −1.8 (2) |
O31—N3—C3—C2 | −15.0 (3) | C11—C1—C2—O2 | −1.7 (2) |
O31—N3—C3—C4 | 165.79 (17) | C11—C1—C2—C3 | 176.98 (14) |
O32—N3—C3—C2 | 165.64 (17) | C2—C1—C6—C5 | 1.9 (2) |
O32—N3—C3—C4 | −13.5 (2) | C11—C1—C6—C5 | −176.90 (14) |
O52—N5—C5—C4 | −166.78 (16) | C2—C1—C11—O11 | −179.15 (16) |
O52—N5—C5—C6 | 11.7 (2) | C2—C1—C11—O12 | −1.4 (2) |
O51—N5—C5—C6 | −169.32 (15) | C6—C1—C11—O11 | −0.4 (2) |
O51—N5—C5—C4 | 12.2 (2) | C6—C1—C11—O12 | 177.40 (14) |
N1A—C2A—C3A—C4A | −56.8 (2) | O2—C2—C3—N3 | −0.3 (3) |
C2A—C3A—C4A—C5A | 58.26 (18) | O2—C2—C3—C4 | 178.83 (16) |
C2A—C3A—C4A—C41A | 179.72 (15) | C1—C2—C3—N3 | −178.86 (15) |
C41A—C4A—C5A—C6A | −179.97 (15) | C1—C2—C3—C4 | 0.3 (2) |
C3A—C4A—C41A—O41A | −58.1 (2) | N3—C3—C4—C5 | −179.72 (15) |
C3A—C4A—C41A—N41A | 122.29 (16) | C2—C3—C4—C5 | 1.1 (3) |
C5A—C4A—C41A—O41A | 62.58 (19) | C3—C4—C5—N5 | 177.34 (15) |
C5A—C4A—C41A—N41A | −117.03 (16) | C3—C4—C5—C6 | −1.1 (2) |
C3A—C4A—C5A—C6A | −58.22 (18) | N5—C5—C6—C1 | −178.80 (14) |
C4A—C5A—C6A—N1A | 56.7 (2) | C4—C5—C6—C1 | −0.4 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1A—H11A···O2 | 0.86 (2) | 1.98 (2) | 2.817 (2) | 164 (2) |
N1A—H11A···O31 | 0.86 (2) | 2.43 (2) | 2.835 (3) | 109.7 (17) |
N1A—H12A···O31 | 0.93 (2) | 2.43 (2) | 2.835 (3) | 106.1 (15) |
N1A—H12A···O41Ai | 0.93 (2) | 1.844 (19) | 2.6964 (19) | 151 (2) |
N41A—H41A···O11i | 0.88 (2) | 2.19 (2) | 3.053 (2) | 168 (2) |
O12—H12···O2 | 1.01 | 1.52 | 2.4829 (17) | 157 |
C4A—H4A···O11i | 1.00 | 2.48 | 3.396 (2) | 153 |
C6—H6···O52ii | 0.95 | 2.57 | 3.356 (2) | 141 |
C6A—H61A···O52iii | 0.99 | 2.52 | 3.329 (3) | 138 |
Symmetry codes: (i) −x+3/2, y+1/2, −z+1/2; (ii) −x, −y, −z; (iii) −x+1/2, y+1/2, −z+1/2. |
C6H13N2O+·C7H3N2O7− | Z = 4 |
Mr = 356.30 | F(000) = 744 |
Triclinic, P1 | Dx = 1.559 Mg m−3 |
Hall symbol: -P 1 | Melting point: 475 K |
a = 6.4628 (4) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 10.2375 (5) Å | Cell parameters from 6525 reflections |
c = 23.8964 (12) Å | θ = 3.2–26.3° |
α = 98.644 (4)° | µ = 0.13 mm−1 |
β = 96.905 (5)° | T = 200 K |
γ = 100.753 (5)° | Plate, yellow |
V = 1517.65 (15) Å3 | 0.40 × 0.30 × 0.18 mm |
Oxford Diffraction Gemini S Ultra CCD-detector diffractometer | 5940 independent reflections |
Radiation source: Enhance (Mo) X-ray source | 4477 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.026 |
Detector resolution: 16.0774 pixels mm-1 | θmax = 26.0°, θmin = 3.2° |
ω scans | h = −7→7 |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009) | k = −12→12 |
Tmin = 0.96, Tmax = 0.98 | l = −29→29 |
19052 measured reflections |
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) = 0.095 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.82 | w = 1/[σ2(Fo2) + (0.0513P)2 + 0.942P] where P = (Fo2 + 2Fc2)/3 |
5940 reflections | (Δ/σ)max = 0.001 |
475 parameters | Δρmax = 0.23 e Å−3 |
0 restraints | Δρmin = −0.23 e Å−3 |
C6H13N2O+·C7H3N2O7− | γ = 100.753 (5)° |
Mr = 356.30 | V = 1517.65 (15) Å3 |
Triclinic, P1 | Z = 4 |
a = 6.4628 (4) Å | Mo Kα radiation |
b = 10.2375 (5) Å | µ = 0.13 mm−1 |
c = 23.8964 (12) Å | T = 200 K |
α = 98.644 (4)° | 0.40 × 0.30 × 0.18 mm |
β = 96.905 (5)° |
Oxford Diffraction Gemini S Ultra CCD-detector diffractometer | 5940 independent reflections |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009) | 4477 reflections with I > 2σ(I) |
Tmin = 0.96, Tmax = 0.98 | Rint = 0.026 |
19052 measured reflections |
R[F2 > 2σ(F2)] = 0.039 | 0 restraints |
wR(F2) = 0.095 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.82 | Δρmax = 0.23 e Å−3 |
5940 reflections | Δρmin = −0.23 e Å−3 |
475 parameters |
Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles |
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 | ||
O41A | 0.4007 (2) | 0.55488 (13) | 0.15540 (6) | 0.0393 (5) | |
N1A | 0.3377 (3) | 0.28117 (17) | 0.30206 (6) | 0.0303 (5) | |
N41A | 0.3364 (3) | 0.36629 (19) | 0.08796 (7) | 0.0326 (5) | |
C2A | 0.4617 (3) | 0.22154 (19) | 0.25964 (7) | 0.0313 (6) | |
C3A | 0.5066 (3) | 0.31061 (18) | 0.21499 (7) | 0.0271 (5) | |
C4A | 0.3010 (3) | 0.34102 (16) | 0.18570 (7) | 0.0224 (5) | |
C5A | 0.1867 (3) | 0.40601 (19) | 0.23145 (7) | 0.0309 (6) | |
C6A | 0.1381 (3) | 0.3132 (2) | 0.27419 (8) | 0.0336 (6) | |
C41A | 0.3492 (3) | 0.43050 (17) | 0.14166 (7) | 0.0249 (5) | |
O41B | 0.2595 (2) | 0.04969 (13) | 0.34894 (6) | 0.0386 (4) | |
N1B | −0.2843 (3) | −0.21807 (18) | 0.19773 (7) | 0.0383 (5) | |
N41B | 0.0602 (3) | −0.02188 (17) | 0.41370 (7) | 0.0318 (5) | |
C2B | −0.3944 (3) | −0.1694 (2) | 0.24597 (8) | 0.0343 (6) | |
C3B | −0.2408 (3) | −0.06578 (17) | 0.29159 (7) | 0.0281 (5) | |
C4B | −0.0528 (3) | −0.12542 (16) | 0.31373 (7) | 0.0224 (5) | |
C5B | 0.0566 (3) | −0.17283 (19) | 0.26336 (8) | 0.0313 (6) | |
C6B | −0.0969 (3) | −0.2745 (2) | 0.21742 (8) | 0.0387 (6) | |
C41B | 0.1025 (3) | −0.02486 (17) | 0.36037 (7) | 0.0258 (5) | |
O2C | 0.7910 (2) | 0.36537 (14) | 0.64334 (5) | 0.0357 (4) | |
O11C | 0.3216 (2) | 0.12946 (16) | 0.52181 (6) | 0.0499 (5) | |
O12C | 0.4301 (2) | 0.22647 (16) | 0.61149 (6) | 0.0452 (5) | |
O31C | 1.1939 (2) | 0.47632 (15) | 0.67064 (6) | 0.0505 (5) | |
O32C | 1.3761 (2) | 0.52172 (14) | 0.60282 (7) | 0.0487 (5) | |
O51C | 1.1336 (3) | 0.31938 (16) | 0.40967 (6) | 0.0515 (5) | |
O52C | 0.8068 (3) | 0.21578 (15) | 0.38024 (5) | 0.0466 (5) | |
N3C | 1.2125 (3) | 0.46726 (15) | 0.61903 (7) | 0.0334 (5) | |
N5C | 0.9529 (3) | 0.27440 (15) | 0.41862 (6) | 0.0343 (5) | |
C1C | 0.6723 (3) | 0.26236 (17) | 0.54569 (7) | 0.0242 (5) | |
C2C | 0.8319 (3) | 0.34157 (16) | 0.59197 (7) | 0.0232 (5) | |
C3C | 1.0354 (3) | 0.38988 (16) | 0.57617 (7) | 0.0236 (5) | |
C4C | 1.0726 (3) | 0.36687 (16) | 0.52000 (7) | 0.0248 (5) | |
C5C | 0.9110 (3) | 0.29343 (17) | 0.47753 (7) | 0.0255 (5) | |
C6C | 0.7112 (3) | 0.23996 (16) | 0.48980 (7) | 0.0259 (5) | |
C11C | 0.4610 (3) | 0.19998 (18) | 0.55862 (8) | 0.0272 (5) | |
O2D | −0.25480 (19) | −0.09966 (12) | −0.01267 (5) | 0.0320 (4) | |
O11D | −0.1786 (2) | 0.05121 (15) | 0.15760 (5) | 0.0407 (5) | |
O12D | −0.2154 (2) | −0.12496 (14) | 0.08783 (6) | 0.0392 (5) | |
O31D | −0.3012 (3) | −0.04976 (14) | −0.11857 (6) | 0.0465 (5) | |
O32D | −0.2836 (3) | 0.15379 (15) | −0.13274 (5) | 0.0476 (5) | |
O51D | −0.2266 (3) | 0.52462 (14) | 0.01892 (6) | 0.0520 (5) | |
O52D | −0.1368 (3) | 0.50050 (15) | 0.10611 (6) | 0.0520 (5) | |
N3D | −0.2812 (2) | 0.07086 (15) | −0.10056 (6) | 0.0271 (5) | |
N5D | −0.1895 (2) | 0.45422 (16) | 0.05479 (6) | 0.0330 (5) | |
C1D | −0.2129 (2) | 0.09091 (17) | 0.06083 (7) | 0.0236 (5) | |
C2D | −0.2419 (2) | 0.02863 (17) | 0.00131 (7) | 0.0229 (5) | |
C3D | −0.2541 (2) | 0.11969 (17) | −0.03879 (7) | 0.0225 (5) | |
C4D | −0.2388 (3) | 0.25717 (17) | −0.02187 (7) | 0.0244 (5) | |
C5D | −0.2093 (3) | 0.31009 (17) | 0.03614 (7) | 0.0246 (5) | |
C6D | −0.1967 (2) | 0.22769 (18) | 0.07723 (7) | 0.0255 (5) | |
C11D | −0.2005 (3) | 0.0049 (2) | 0.10630 (8) | 0.0300 (6) | |
H4A | 0.20640 | 0.25370 | 0.16560 | 0.0270* | |
H11A | 0.423 (3) | 0.355 (2) | 0.3248 (8) | 0.034 (5)* | |
H12A | 0.308 (3) | 0.217 (2) | 0.3255 (9) | 0.040 (6)* | |
H21A | 0.38030 | 0.13100 | 0.24020 | 0.0380* | |
H22A | 0.59830 | 0.21040 | 0.28000 | 0.0380* | |
H31A | 0.57780 | 0.26460 | 0.18580 | 0.0320* | |
H32A | 0.60460 | 0.39650 | 0.23370 | 0.0320* | |
H41A | 0.295 (3) | 0.280 (2) | 0.0779 (9) | 0.043 (6)* | |
H42A | 0.356 (3) | 0.416 (2) | 0.0597 (10) | 0.050 (6)* | |
H51A | 0.27760 | 0.49310 | 0.25170 | 0.0370* | |
H52A | 0.05220 | 0.42450 | 0.21300 | 0.0370* | |
H61A | 0.06650 | 0.35730 | 0.30380 | 0.0400* | |
H62A | 0.03990 | 0.22850 | 0.25430 | 0.0400* | |
H4B | −0.11020 | −0.20610 | 0.33050 | 0.0270* | |
H11B | −0.383 (4) | −0.284 (2) | 0.1729 (10) | 0.056 (7)* | |
H12B | −0.244 (4) | −0.140 (3) | 0.1801 (10) | 0.063 (7)* | |
H21B | −0.45650 | −0.24700 | 0.26320 | 0.0410* | |
H22B | −0.51220 | −0.12860 | 0.23100 | 0.0410* | |
H31B | −0.31580 | −0.03800 | 0.32370 | 0.0340* | |
H32B | −0.18760 | 0.01530 | 0.27530 | 0.0340* | |
H41B | −0.057 (4) | −0.073 (2) | 0.4221 (9) | 0.048 (6)* | |
H42B | 0.148 (3) | 0.035 (2) | 0.4421 (9) | 0.036 (5)* | |
H51B | 0.11740 | −0.09390 | 0.24680 | 0.0380* | |
H52B | 0.17520 | −0.21410 | 0.27740 | 0.0380* | |
H61B | −0.02320 | −0.29860 | 0.18460 | 0.0460* | |
H62B | −0.14600 | −0.35770 | 0.23270 | 0.0460* | |
H4C | 1.20870 | 0.40150 | 0.51070 | 0.0300* | |
H6C | 0.60260 | 0.18860 | 0.46010 | 0.0310* | |
H12C | 0.584 | 0.292 | 0.635 | 0.061* | |
H4D | −0.24830 | 0.31420 | −0.04960 | 0.0290* | |
H6D | −0.17690 | 0.26600 | 0.11670 | 0.0310* | |
H12D | −0.229 | −0.131 | 0.0410 | 0.048* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O41A | 0.0525 (9) | 0.0241 (7) | 0.0370 (8) | −0.0035 (6) | 0.0072 (6) | 0.0057 (6) |
N1A | 0.0369 (9) | 0.0298 (9) | 0.0194 (8) | −0.0044 (7) | 0.0028 (6) | 0.0048 (7) |
N41A | 0.0425 (10) | 0.0328 (10) | 0.0202 (8) | 0.0018 (8) | 0.0045 (7) | 0.0056 (7) |
C2A | 0.0342 (10) | 0.0344 (10) | 0.0258 (9) | 0.0074 (8) | 0.0031 (8) | 0.0074 (8) |
C3A | 0.0247 (9) | 0.0328 (10) | 0.0221 (9) | 0.0023 (7) | 0.0034 (7) | 0.0046 (7) |
C4A | 0.0257 (9) | 0.0206 (8) | 0.0177 (8) | −0.0002 (7) | 0.0022 (6) | 0.0006 (7) |
C5A | 0.0363 (10) | 0.0311 (10) | 0.0263 (9) | 0.0091 (8) | 0.0081 (8) | 0.0034 (8) |
C6A | 0.0337 (10) | 0.0413 (11) | 0.0257 (9) | 0.0052 (8) | 0.0103 (8) | 0.0046 (8) |
C41A | 0.0243 (9) | 0.0247 (9) | 0.0237 (9) | 0.0022 (7) | 0.0010 (7) | 0.0036 (7) |
O41B | 0.0317 (7) | 0.0352 (7) | 0.0434 (8) | −0.0082 (6) | 0.0022 (6) | 0.0111 (6) |
N1B | 0.0475 (10) | 0.0366 (10) | 0.0215 (8) | −0.0117 (8) | −0.0017 (7) | 0.0075 (7) |
N41B | 0.0339 (9) | 0.0302 (9) | 0.0253 (8) | −0.0020 (7) | −0.0024 (7) | 0.0029 (7) |
C2B | 0.0301 (10) | 0.0386 (11) | 0.0306 (10) | 0.0001 (8) | −0.0015 (8) | 0.0085 (8) |
C3B | 0.0293 (9) | 0.0266 (9) | 0.0272 (9) | 0.0038 (7) | 0.0014 (7) | 0.0059 (7) |
C4B | 0.0251 (9) | 0.0198 (8) | 0.0218 (8) | 0.0013 (7) | 0.0039 (7) | 0.0058 (7) |
C5B | 0.0324 (10) | 0.0329 (10) | 0.0299 (10) | 0.0053 (8) | 0.0110 (8) | 0.0068 (8) |
C6B | 0.0526 (13) | 0.0319 (10) | 0.0303 (10) | 0.0032 (9) | 0.0170 (9) | 0.0004 (8) |
C41B | 0.0259 (9) | 0.0214 (8) | 0.0302 (10) | 0.0043 (7) | 0.0007 (7) | 0.0085 (7) |
O2C | 0.0387 (7) | 0.0458 (8) | 0.0198 (6) | 0.0046 (6) | 0.0062 (5) | 0.0005 (6) |
O11C | 0.0328 (8) | 0.0577 (10) | 0.0478 (9) | −0.0064 (7) | −0.0050 (7) | 0.0024 (7) |
O12C | 0.0376 (8) | 0.0566 (10) | 0.0425 (9) | 0.0027 (7) | 0.0149 (7) | 0.0143 (7) |
O31C | 0.0596 (10) | 0.0517 (9) | 0.0265 (8) | −0.0039 (7) | −0.0128 (7) | −0.0009 (7) |
O32C | 0.0325 (8) | 0.0397 (8) | 0.0647 (10) | −0.0095 (6) | 0.0050 (7) | 0.0033 (7) |
O51C | 0.0669 (11) | 0.0529 (9) | 0.0361 (8) | 0.0041 (8) | 0.0292 (8) | 0.0061 (7) |
O52C | 0.0700 (10) | 0.0488 (9) | 0.0191 (7) | 0.0191 (8) | −0.0010 (7) | −0.0022 (6) |
N3C | 0.0358 (9) | 0.0238 (8) | 0.0366 (9) | 0.0044 (7) | −0.0036 (7) | 0.0019 (7) |
N5C | 0.0581 (11) | 0.0267 (8) | 0.0219 (8) | 0.0150 (8) | 0.0114 (8) | 0.0044 (7) |
C1C | 0.0270 (9) | 0.0236 (9) | 0.0228 (9) | 0.0079 (7) | 0.0012 (7) | 0.0053 (7) |
C2C | 0.0307 (9) | 0.0213 (8) | 0.0182 (8) | 0.0080 (7) | 0.0017 (7) | 0.0038 (7) |
C3C | 0.0268 (9) | 0.0193 (8) | 0.0229 (9) | 0.0041 (7) | −0.0006 (7) | 0.0024 (7) |
C4C | 0.0289 (9) | 0.0200 (8) | 0.0272 (9) | 0.0061 (7) | 0.0074 (7) | 0.0055 (7) |
C5C | 0.0387 (10) | 0.0219 (9) | 0.0180 (8) | 0.0099 (7) | 0.0062 (7) | 0.0044 (7) |
C6C | 0.0338 (10) | 0.0207 (8) | 0.0211 (9) | 0.0070 (7) | −0.0030 (7) | 0.0015 (7) |
C11C | 0.0243 (9) | 0.0268 (9) | 0.0300 (10) | 0.0054 (7) | 0.0007 (7) | 0.0064 (8) |
O2D | 0.0330 (7) | 0.0273 (7) | 0.0343 (7) | 0.0052 (5) | 0.0024 (5) | 0.0050 (6) |
O11D | 0.0439 (8) | 0.0552 (9) | 0.0261 (7) | 0.0087 (7) | 0.0068 (6) | 0.0175 (6) |
O12D | 0.0438 (8) | 0.0368 (8) | 0.0389 (8) | 0.0057 (6) | 0.0036 (6) | 0.0185 (6) |
O31D | 0.0706 (10) | 0.0332 (8) | 0.0304 (7) | 0.0092 (7) | 0.0054 (7) | −0.0068 (6) |
O32D | 0.0774 (11) | 0.0471 (9) | 0.0194 (7) | 0.0168 (8) | 0.0021 (7) | 0.0088 (6) |
O51D | 0.0891 (12) | 0.0310 (8) | 0.0356 (8) | 0.0160 (8) | 0.0002 (8) | 0.0078 (7) |
O52D | 0.0804 (11) | 0.0389 (8) | 0.0272 (8) | 0.0085 (8) | −0.0055 (7) | −0.0084 (6) |
N3D | 0.0248 (8) | 0.0335 (9) | 0.0204 (7) | 0.0052 (6) | 0.0011 (6) | 0.0000 (7) |
N5D | 0.0385 (9) | 0.0301 (8) | 0.0271 (8) | 0.0041 (7) | 0.0024 (7) | 0.0004 (7) |
C1D | 0.0154 (8) | 0.0323 (10) | 0.0229 (9) | 0.0024 (7) | 0.0030 (6) | 0.0075 (7) |
C2D | 0.0141 (8) | 0.0277 (9) | 0.0263 (9) | 0.0026 (7) | 0.0030 (6) | 0.0048 (7) |
C3D | 0.0187 (8) | 0.0293 (9) | 0.0181 (8) | 0.0037 (7) | 0.0019 (6) | 0.0020 (7) |
C4D | 0.0230 (9) | 0.0301 (9) | 0.0202 (8) | 0.0038 (7) | 0.0031 (7) | 0.0074 (7) |
C5D | 0.0234 (8) | 0.0256 (9) | 0.0221 (9) | 0.0020 (7) | 0.0021 (7) | 0.0007 (7) |
C6D | 0.0196 (8) | 0.0386 (10) | 0.0168 (8) | 0.0036 (7) | 0.0025 (6) | 0.0039 (7) |
C11D | 0.0198 (9) | 0.0431 (11) | 0.0299 (10) | 0.0048 (8) | 0.0055 (7) | 0.0161 (9) |
O41A—C41A | 1.237 (2) | C2A—H22A | 0.9900 |
O41B—C41B | 1.236 (2) | C2A—H21A | 0.9900 |
O2C—C2C | 1.284 (2) | C3A—H31A | 0.9900 |
O11C—C11C | 1.218 (2) | C3A—H32A | 0.9900 |
O12C—C11C | 1.299 (2) | C4A—H4A | 1.0000 |
O31C—N3C | 1.245 (2) | C5A—H52A | 0.9900 |
O32C—N3C | 1.234 (2) | C5A—H51A | 0.9900 |
O51C—N5C | 1.229 (3) | C6A—H61A | 0.9900 |
O52C—N5C | 1.228 (2) | C6A—H62A | 0.9900 |
O12C—H12C | 1.12 | C2B—C3B | 1.516 (3) |
O2D—C2D | 1.290 (2) | C3B—C4B | 1.532 (3) |
O11D—C11D | 1.227 (2) | C4B—C5B | 1.530 (3) |
O12D—C11D | 1.318 (2) | C4B—C41B | 1.520 (2) |
O31D—N3D | 1.222 (2) | C5B—C6B | 1.511 (3) |
O32D—N3D | 1.229 (2) | C2B—H21B | 0.9900 |
O51D—N5D | 1.230 (2) | C2B—H22B | 0.9900 |
O52D—N5D | 1.229 (2) | C3B—H32B | 0.9900 |
O12D—H12D | 1.10 | C3B—H31B | 0.9900 |
N1A—C6A | 1.494 (3) | C4B—H4B | 1.0000 |
N1A—C2A | 1.495 (3) | C5B—H51B | 0.9900 |
N41A—C41A | 1.337 (2) | C5B—H52B | 0.9900 |
N1A—H12A | 0.93 (2) | C6B—H62B | 0.9900 |
N1A—H11A | 0.91 (2) | C6B—H61B | 0.9900 |
N41A—H41A | 0.86 (2) | C1C—C6C | 1.382 (2) |
N41A—H42A | 0.91 (2) | C1C—C11C | 1.484 (3) |
N1B—C6B | 1.493 (3) | C1C—C2C | 1.445 (2) |
N1B—C2B | 1.497 (3) | C2C—C3C | 1.432 (3) |
N41B—C41B | 1.332 (2) | C3C—C4C | 1.385 (2) |
N1B—H11B | 0.92 (2) | C4C—C5C | 1.382 (2) |
N1B—H12B | 0.97 (3) | C5C—C6C | 1.389 (3) |
N41B—H41B | 0.90 (2) | C4C—H4C | 0.9500 |
N41B—H42B | 0.89 (2) | C6C—H6C | 0.9500 |
N3C—C3C | 1.457 (2) | C1D—C11D | 1.502 (3) |
N5C—C5C | 1.457 (2) | C1D—C2D | 1.443 (2) |
N3D—C3D | 1.464 (2) | C1D—C6D | 1.377 (2) |
N5D—C5D | 1.453 (2) | C2D—C3D | 1.439 (2) |
C2A—C3A | 1.524 (3) | C3D—C4D | 1.386 (2) |
C3A—C4A | 1.533 (3) | C4D—C5D | 1.387 (2) |
C4A—C41A | 1.519 (2) | C5D—C6D | 1.392 (2) |
C4A—C5A | 1.531 (3) | C4D—H4D | 0.9500 |
C5A—C6A | 1.517 (3) | C6D—H6D | 0.9500 |
C11C—O12C—H12C | 105 | C4B—C5B—C6B | 111.68 (16) |
C11D—O12D—H12D | 103 | N1B—C6B—C5B | 110.62 (16) |
C2A—N1A—C6A | 112.62 (13) | O41B—C41B—C4B | 121.21 (15) |
H11A—N1A—H12A | 106.4 (18) | N41B—C41B—C4B | 116.54 (16) |
C2A—N1A—H12A | 105.4 (13) | O41B—C41B—N41B | 122.25 (17) |
C2A—N1A—H11A | 109.0 (12) | C3B—C2B—H21B | 109.00 |
C6A—N1A—H11A | 111.7 (13) | N1B—C2B—H22B | 109.00 |
C6A—N1A—H12A | 111.4 (12) | N1B—C2B—H21B | 109.00 |
H41A—N41A—H42A | 118 (2) | C3B—C2B—H22B | 109.00 |
C41A—N41A—H41A | 123.0 (14) | H21B—C2B—H22B | 108.00 |
C41A—N41A—H42A | 118.9 (14) | C2B—C3B—H31B | 110.00 |
C2B—N1B—C6B | 112.62 (15) | C4B—C3B—H31B | 110.00 |
C6B—N1B—H12B | 112.1 (16) | C4B—C3B—H32B | 110.00 |
C2B—N1B—H11B | 106.8 (16) | H31B—C3B—H32B | 108.00 |
H11B—N1B—H12B | 111 (2) | C2B—C3B—H32B | 110.00 |
C6B—N1B—H11B | 109.6 (15) | C5B—C4B—H4B | 108.00 |
C2B—N1B—H12B | 104.8 (15) | C3B—C4B—H4B | 108.00 |
C41B—N41B—H42B | 119.1 (13) | C41B—C4B—H4B | 108.00 |
H41B—N41B—H42B | 118.2 (19) | H51B—C5B—H52B | 108.00 |
C41B—N41B—H41B | 122.7 (13) | C4B—C5B—H51B | 109.00 |
O32C—N3C—C3C | 118.70 (16) | C6B—C5B—H51B | 109.00 |
O31C—N3C—O32C | 122.24 (17) | C4B—C5B—H52B | 109.00 |
O31C—N3C—C3C | 119.06 (17) | C6B—C5B—H52B | 109.00 |
O51C—N5C—O52C | 123.02 (16) | N1B—C6B—H62B | 110.00 |
O52C—N5C—C5C | 118.91 (18) | C5B—C6B—H61B | 109.00 |
O51C—N5C—C5C | 118.07 (15) | N1B—C6B—H61B | 110.00 |
O31D—N3D—O32D | 122.13 (15) | C5B—C6B—H62B | 110.00 |
O31D—N3D—C3D | 119.63 (14) | H61B—C6B—H62B | 108.00 |
O32D—N3D—C3D | 118.24 (14) | C2C—C1C—C11C | 119.10 (15) |
O51D—N5D—O52D | 122.75 (16) | C6C—C1C—C11C | 118.67 (16) |
O51D—N5D—C5D | 119.05 (14) | C2C—C1C—C6C | 122.21 (17) |
O52D—N5D—C5D | 118.20 (15) | O2C—C2C—C3C | 123.32 (16) |
N1A—C2A—C3A | 111.46 (15) | C1C—C2C—C3C | 115.22 (15) |
C2A—C3A—C4A | 111.45 (16) | O2C—C2C—C1C | 121.46 (17) |
C3A—C4A—C41A | 110.65 (16) | N3C—C3C—C4C | 117.13 (17) |
C3A—C4A—C5A | 108.97 (14) | N3C—C3C—C2C | 120.84 (15) |
C5A—C4A—C41A | 111.81 (14) | C2C—C3C—C4C | 122.03 (16) |
C4A—C5A—C6A | 110.43 (15) | C3C—C4C—C5C | 119.74 (17) |
N1A—C6A—C5A | 110.89 (16) | N5C—C5C—C6C | 119.97 (16) |
O41A—C41A—N41A | 122.69 (17) | C4C—C5C—C6C | 121.54 (16) |
N41A—C41A—C4A | 115.86 (16) | N5C—C5C—C4C | 118.49 (17) |
O41A—C41A—C4A | 121.44 (15) | C1C—C6C—C5C | 119.20 (16) |
H21A—C2A—H22A | 108.00 | O11C—C11C—O12C | 121.22 (18) |
C3A—C2A—H22A | 109.00 | O11C—C11C—C1C | 122.32 (17) |
C3A—C2A—H21A | 109.00 | O12C—C11C—C1C | 116.44 (16) |
N1A—C2A—H22A | 109.00 | C5C—C4C—H4C | 120.00 |
N1A—C2A—H21A | 109.00 | C3C—C4C—H4C | 120.00 |
C4A—C3A—H31A | 109.00 | C5C—C6C—H6C | 120.00 |
C2A—C3A—H31A | 109.00 | C1C—C6C—H6C | 120.00 |
H31A—C3A—H32A | 108.00 | C2D—C1D—C11D | 119.46 (15) |
C2A—C3A—H32A | 109.00 | C2D—C1D—C6D | 121.72 (15) |
C4A—C3A—H32A | 109.00 | C6D—C1D—C11D | 118.82 (15) |
C3A—C4A—H4A | 108.00 | C1D—C2D—C3D | 115.03 (15) |
C5A—C4A—H4A | 108.00 | O2D—C2D—C3D | 124.73 (15) |
C41A—C4A—H4A | 109.00 | O2D—C2D—C1D | 120.24 (15) |
C6A—C5A—H51A | 110.00 | N3D—C3D—C2D | 121.03 (15) |
C6A—C5A—H52A | 110.00 | N3D—C3D—C4D | 116.14 (15) |
H51A—C5A—H52A | 108.00 | C2D—C3D—C4D | 122.83 (15) |
C4A—C5A—H52A | 110.00 | C3D—C4D—C5D | 118.93 (16) |
C4A—C5A—H51A | 110.00 | C4D—C5D—C6D | 121.24 (16) |
C5A—C6A—H61A | 109.00 | N5D—C5D—C4D | 119.79 (15) |
C5A—C6A—H62A | 109.00 | N5D—C5D—C6D | 118.98 (15) |
N1A—C6A—H62A | 109.00 | C1D—C6D—C5D | 120.26 (15) |
H61A—C6A—H62A | 108.00 | O12D—C11D—C1D | 115.85 (16) |
N1A—C6A—H61A | 110.00 | O11D—C11D—O12D | 121.42 (18) |
N1B—C2B—C3B | 111.12 (16) | O11D—C11D—C1D | 122.73 (18) |
C2B—C3B—C4B | 110.17 (15) | C3D—C4D—H4D | 120.00 |
C3B—C4B—C5B | 109.12 (14) | C5D—C4D—H4D | 121.00 |
C3B—C4B—C41B | 111.55 (14) | C1D—C6D—H6D | 120.00 |
C5B—C4B—C41B | 111.66 (16) | C5D—C6D—H6D | 120.00 |
C6A—N1A—C2A—C3A | 53.7 (2) | C6C—C1C—C2C—O2C | 177.56 (17) |
C2A—N1A—C6A—C5A | −55.8 (2) | C6C—C1C—C2C—C3C | −2.7 (3) |
C6B—N1B—C2B—C3B | 56.1 (2) | C11C—C1C—C2C—C3C | 175.82 (16) |
C2B—N1B—C6B—C5B | −54.9 (2) | C2C—C1C—C6C—C5C | 1.0 (3) |
O32C—N3C—C3C—C2C | −170.75 (16) | C11C—C1C—C2C—O2C | −4.0 (3) |
O31C—N3C—C3C—C2C | 9.2 (3) | C11C—C1C—C6C—C5C | −177.53 (16) |
O31C—N3C—C3C—C4C | −171.43 (16) | C2C—C1C—C11C—O11C | −178.18 (18) |
O32C—N3C—C3C—C4C | 8.6 (2) | C2C—C1C—C11C—O12C | 3.0 (3) |
O52C—N5C—C5C—C4C | −175.98 (17) | C6C—C1C—C11C—O11C | 0.4 (3) |
O52C—N5C—C5C—C6C | 3.1 (3) | C6C—C1C—C11C—O12C | −178.44 (17) |
O51C—N5C—C5C—C6C | −177.67 (17) | O2C—C2C—C3C—N3C | 1.8 (3) |
O51C—N5C—C5C—C4C | 3.3 (3) | O2C—C2C—C3C—C4C | −177.54 (17) |
O32D—N3D—C3D—C2D | −177.65 (15) | C1C—C2C—C3C—C4C | 2.7 (2) |
O32D—N3D—C3D—C4D | 1.6 (2) | C1C—C2C—C3C—N3C | −177.99 (15) |
O31D—N3D—C3D—C4D | −178.16 (17) | C2C—C3C—C4C—C5C | −1.0 (3) |
O31D—N3D—C3D—C2D | 2.6 (2) | N3C—C3C—C4C—C5C | 179.62 (16) |
O52D—N5D—C5D—C6D | 8.6 (3) | C3C—C4C—C5C—N5C | 178.15 (16) |
O51D—N5D—C5D—C6D | −171.10 (17) | C3C—C4C—C5C—C6C | −0.9 (3) |
O51D—N5D—C5D—C4D | 9.3 (3) | N5C—C5C—C6C—C1C | −178.11 (16) |
O52D—N5D—C5D—C4D | −170.94 (18) | C4C—C5C—C6C—C1C | 0.9 (3) |
N1A—C2A—C3A—C4A | −54.19 (19) | C6D—C1D—C2D—O2D | 179.44 (13) |
C2A—C3A—C4A—C41A | 179.66 (14) | C6D—C1D—C2D—C3D | −0.50 (19) |
C2A—C3A—C4A—C5A | 56.34 (18) | C11D—C1D—C2D—O2D | −0.7 (2) |
C5A—C4A—C41A—O41A | 36.6 (2) | C11D—C1D—C2D—C3D | 179.33 (14) |
C3A—C4A—C41A—O41A | −85.1 (2) | C2D—C1D—C6D—C5D | 0.4 (2) |
C3A—C4A—C5A—C6A | −58.21 (19) | C11D—C1D—C6D—C5D | −179.48 (16) |
C3A—C4A—C41A—N41A | 93.6 (2) | C2D—C1D—C11D—O11D | −179.09 (16) |
C5A—C4A—C41A—N41A | −144.70 (18) | C2D—C1D—C11D—O12D | 0.7 (2) |
C41A—C4A—C5A—C6A | 179.16 (15) | C6D—C1D—C11D—O11D | 0.8 (3) |
C4A—C5A—C6A—N1A | 58.2 (2) | C6D—C1D—C11D—O12D | −179.49 (15) |
N1B—C2B—C3B—C4B | −57.0 (2) | O2D—C2D—C3D—N3D | −0.6 (2) |
C2B—C3B—C4B—C5B | 57.19 (19) | O2D—C2D—C3D—C4D | −179.80 (15) |
C2B—C3B—C4B—C41B | −178.97 (15) | C1D—C2D—C3D—N3D | 179.38 (12) |
C41B—C4B—C5B—C6B | 179.07 (15) | C1D—C2D—C3D—C4D | 0.1 (2) |
C3B—C4B—C5B—C6B | −57.15 (19) | N3D—C3D—C4D—C5D | −178.91 (16) |
C5B—C4B—C41B—N41B | −151.11 (17) | C2D—C3D—C4D—C5D | 0.4 (3) |
C3B—C4B—C41B—O41B | −93.6 (2) | C3D—C4D—C5D—N5D | 179.03 (16) |
C3B—C4B—C41B—N41B | 86.5 (2) | C3D—C4D—C5D—C6D | −0.5 (3) |
C5B—C4B—C41B—O41B | 28.8 (2) | N5D—C5D—C6D—C1D | −179.39 (14) |
C4B—C5B—C6B—N1B | 55.7 (2) | C4D—C5D—C6D—C1D | 0.2 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1A—H11A···O32Ci | 0.91 (2) | 2.113 (19) | 2.980 (2) | 160.1 (17) |
N1A—H12A···O41B | 0.93 (2) | 1.86 (2) | 2.759 (2) | 159.7 (19) |
N1B—H11B···O41Aii | 0.92 (2) | 1.91 (2) | 2.757 (2) | 153 (2) |
N1B—H12B···O11D | 0.97 (3) | 2.09 (3) | 3.039 (2) | 167 (2) |
N1B—H12B···O12D | 0.97 (3) | 2.26 (2) | 2.980 (2) | 131 (2) |
N41A—H41A···O2Diii | 0.86 (2) | 2.18 (2) | 2.954 (2) | 148.8 (19) |
N41A—H42A···O51Div | 0.91 (2) | 2.18 (2) | 2.999 (2) | 149.0 (18) |
N41B—H41B···O11Cv | 0.90 (2) | 2.34 (2) | 3.176 (2) | 154.9 (18) |
N41B—H41B···O12Cv | 0.90 (2) | 2.58 (2) | 3.388 (2) | 149.5 (18) |
N41B—H42B···O11C | 0.89 (2) | 2.09 (2) | 2.950 (2) | 164.3 (19) |
O12C—H12C···O2C | 1.12 | 1.38 | 2.460 (2) | 157 |
O12D—H12D···O2D | 1.10 | 1.37 | 2.4422 (18) | 163 |
C4A—H4A···O31Diii | 1.00 | 2.44 | 3.167 (2) | 129 |
C2B—H22B···O32Dvi | 0.99 | 2.50 | 3.252 (2) | 132 |
C3A—H32A···O31Ci | 0.99 | 2.52 | 3.367 (2) | 143 |
C6B—H61B···O52Dvii | 0.99 | 2.50 | 3.197 (2) | 128 |
Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) x−1, y−1, z; (iii) −x, −y, −z; (iv) −x, −y+1, −z; (v) −x, −y, −z+1; (vi) −x−1, −y, −z; (vii) x, y−1, z. |
Experimental details
(I) | (II) | (III) | |
Crystal data | |||
Chemical formula | C6H13N2O+·C6H2N3O7− | C6H13N2O+·C7H3N2O7− | C6H13N2O+·C7H3N2O7− |
Mr | 357.29 | 356.30 | 356.30 |
Crystal system, space group | Monoclinic, P21/c | Monoclinic, P21/n | Triclinic, P1 |
Temperature (K) | 200 | 200 | 200 |
a, b, c (Å) | 13.4426 (11), 13.7495 (13), 8.3662 (15) | 11.7131 (12), 12.6450 (11), 11.8521 (14) | 6.4628 (4), 10.2375 (5), 23.8964 (12) |
α, β, γ (°) | 90, 100.752 (13), 90 | 90, 118.196 (14), 90 | 98.644 (4), 96.905 (5), 100.753 (5) |
V (Å3) | 1519.2 (3) | 1547.1 (3) | 1517.65 (15) |
Z | 4 | 4 | 4 |
Radiation type | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.13 | 0.13 | 0.13 |
Crystal size (mm) | 0.25 × 0.20 × 0.15 | 0.40 × 0.40 × 0.20 | 0.40 × 0.30 × 0.18 |
Data collection | |||
Diffractometer | Oxford Diffraction Gemini-S Ultra CCD-detector diffractometer | Oxford Diffraction Gemini-S Ultra CCD-detector diffractometer | Oxford Diffraction Gemini S Ultra CCD-detector diffractometer |
Absorption correction | Multi-scan (CrysAlis PRO; Oxford Diffraction, 2009) | Multi-scan (CrysAlis PRO; Oxford Diffraction, 2009) | Multi-scan (CrysAlis PRO; Oxford Diffraction, 2009) |
Tmin, Tmax | 0.950, 0.981 | 0.93, 0.98 | 0.96, 0.98 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 10181, 2994, 2279 | 19733, 3048, 2456 | 19052, 5940, 4477 |
Rint | 0.034 | 0.033 | 0.026 |
(sin θ/λ)max (Å−1) | 0.617 | 0.617 | 0.617 |
Refinement | |||
R[F2 > 2σ(F2)], wR(F2), S | 0.036, 0.107, 0.93 | 0.039, 0.098, 1.06 | 0.039, 0.095, 0.82 |
No. of reflections | 3422 | 3048 | 5940 |
No. of parameters | 238 | 242 | 475 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.26, −0.28 | 0.31, −0.24 | 0.23, −0.23 |
Computer programs: CrysAlis PRO (Oxford Diffraction, 2009), CrysAlis PRO?, SHELXS97 (Sheldrick, 2008), SIR92 (Altomare et al., 1994), SHELXL97 (Sheldrick, 2008) within WinGX (Farrugia, 1999), PLATON (Spek, 2009).
D—H···A | D—H | H···A | D···A | D—H···A |
N1A—H11A···O1 | 0.934 (18) | 1.901 (17) | 2.7545 (19) | 150.8 (15) |
N1A—H11A···O62 | 0.934 (18) | 2.227 (17) | 2.859 (2) | 124.3 (13) |
N1A—H12A···O41Ai | 0.912 (18) | 2.012 (18) | 2.8932 (19) | 162.0 (16) |
N41A—H43A···O41Aii | 0.866 (17) | 2.029 (17) | 2.894 (2) | 177 (2) |
N41A—H44A···O1iii | 0.910 (19) | 2.316 (19) | 3.072 (2) | 140.3 (15) |
N41A—H44A···O22iv | 0.910 (19) | 2.437 (19) | 3.017 (2) | 121.8 (14) |
Symmetry codes: (i) −x, −y+1, −z+1; (ii) x, −y+1/2, z−1/2; (iii) −x, y−1/2, −z+1/2; (iv) −x, −y+1, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1A—H11A···O2 | 0.86 (2) | 1.98 (2) | 2.817 (2) | 164 (2) |
N1A—H11A···O31 | 0.86 (2) | 2.43 (2) | 2.835 (3) | 109.7 (17) |
N1A—H12A···O31 | 0.93 (2) | 2.43 (2) | 2.835 (3) | 106.1 (15) |
N1A—H12A···O41Ai | 0.93 (2) | 1.844 (19) | 2.6964 (19) | 151 (2) |
N41A—H41A···O11i | 0.88 (2) | 2.19 (2) | 3.053 (2) | 168 (2) |
O12—H12···O2 | 1.01 | 1.52 | 2.4829 (17) | 157 |
Symmetry code: (i) −x+3/2, y+1/2, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1A—H11A···O32Ci | 0.91 (2) | 2.113 (19) | 2.980 (2) | 160.1 (17) |
N1A—H12A···O41B | 0.93 (2) | 1.86 (2) | 2.759 (2) | 159.7 (19) |
N1B—H11B···O41Aii | 0.92 (2) | 1.91 (2) | 2.757 (2) | 153 (2) |
N1B—H12B···O11D | 0.97 (3) | 2.09 (3) | 3.039 (2) | 167 (2) |
N1B—H12B···O12D | 0.97 (3) | 2.26 (2) | 2.980 (2) | 131 (2) |
N41A—H41A···O2Diii | 0.86 (2) | 2.18 (2) | 2.954 (2) | 148.8 (19) |
N41A—H42A···O51Div | 0.91 (2) | 2.18 (2) | 2.999 (2) | 149.0 (18) |
N41B—H41B···O11Cv | 0.90 (2) | 2.34 (2) | 3.176 (2) | 154.9 (18) |
N41B—H41B···O12Cv | 0.90 (2) | 2.58 (2) | 3.388 (2) | 149.5 (18) |
N41B—H42B···O11C | 0.89 (2) | 2.09 (2) | 2.950 (2) | 164.3 (19) |
O12C—H12C···O2C | 1.12 | 1.38 | 2.460 (2) | 157 |
O12D—H12D···O2D | 1.10 | 1.37 | 2.4422 (18) | 163 |
Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) x−1, y−1, z; (iii) −x, −y, −z; (iv) −x, −y+1, −z; (v) −x, −y, −z+1. |
The structures of 4-piperidinecarboxylic acid (isonipecotic acid) (O'Neil, 2001) and its derivatives are uncommon in the crystallographic literature. Both anhydrous isonipecotic acid (Mora et al., 2005) and its monohydrate (Delgado et al., 2001) show the presence of piperidinium–carboxylate zwitterions while the structure of the hydrochloride is also known (Ma & Li, 2006; Adams et al., 2006; Szafran et al., 2007). However, neither the structures of its amide (isonipecotamide, INIPA) nor any of its derivatives have been reported, although the structures of the acetate (Smith & Wermuth, 2010) and the bipyridine-4,4'-disulfonate (Smith et al., 2010) are now known. Picric acid has been used to produce stable crystalline Lewis base salts suitable for X-ray analysis and the number of picrate structures in the literature reflects this. Similarly, 3,5-dinitrosalicylic acid (DNSA) has proved to be a versatile synthon for crystal engineering usage (Kumar et al., 1999) and a large number of structures of proton-transfer compounds with this acid have also been reported (Smith et al., 2002, 2003, 2007). With these, the majority (circa 70%) are phenolates rather than carboxylates, the H atom being anti-located on the carboxyl O within an intramolecular hydrogen bond.
We therefore carried out 1:1 stoichiometric reactions of isonipecotamide with a number of aromatic acids including picric acid and 3,5-dinitrosalicylic acid in 50% aqueous ethanol, with a view to obtaining crystals suitable for X-ray analysis, hence allowing description of the hydrogen-bonding present in these compounds. We obtained good crystals of the anhydrous picrate salt 4-carbamoylpiperidinium picrate, C6H13N2O+ C6H2N3O7-, (I), as well as two anhydrous polymorphic salts with DNSA, 4-carbamoylpiperidinium 2-carboxy-4,6-dinitrophenolate, C6H13N2O+ C7H3N2O7-: the monoclinic (α) polymorph, (II), and the triclinic (β) polymorph, (III). The crystals of (II) were obtained after partial room-temperature evaporation of solvent whereas with the identical parallel reaction in which the solution was taken to dryness, the second anhydrous triclinic polymorph, (III), was obtained. The structures of (I)–(III) are described here, representing the first reported aromatic organic acid salts of the Lewis base isonipecotamide [excluding the biphenyl-4,4'-disulfonate salt (Smith & Wermuth, 2010)]. It was of particular interest to determine what differences, if any, might be found in the hydrogen bonding in the two polymorphic salts, (II) and (III).
With salts (I)–(III) (Figs. 1–3), proton transfer occurs to the hetero-N of the piperidine ring and in each the resulting group, along with the amine substituent group, are subsequently involved in hydrogen-bonding interactions (Tables 1–3). All three salts are phenolates and form hydrogen-bonded structures, one-dimensional in (II), two-dimensional in (I) and three-dimensional in (III). A feature of hydrogen-bonding motifs in (II) and (III) is the presence of homomolecular head-to-tail piperidinium N—H···Oamide interactions giving infinite zigzag chain structures.
In (I), the two piperidinium H donors give three hydrogen-bonding interactions. One of the H atoms gives a symmetric cyclic R12(6) association (Etter et al., 1990) with phenolate O and nitro O-acceptors of the anion (Fig. 1). The second proton forms a hydrogen bond with an amide O-acceptor giving a centrosymmetric cyclic head-to-tail homodimer [graph set R22(14)] (Table 1 and Fig. 4). This ring is conjoint with a piperidine–amide N—H···O cyclic R42(8) association and the previously mentioned R12(6) association. These rings are linked by other amide–nitro N—H···O interactions into a two-dimensional network structure which lies in the (O11) plane with the picrate ring systems layering down the b axis of the unit cell. The ortho-related nitro-substituent groups of the picrate anion are significantly rotated out of the benzene plane [torsion angles: C1—C2—N2—O22 = 134.13 (16)° and C5—C6—N6—O62 = -157.57 (16)°], compared with 176.78 (14)° for C3—C4—N4—O42 for the para-nitro group.
In the monoclinic α-polymorph of the 3,5-dinitrosalicylic acid salt, (II), a cyclic R12(6) proximal piperidinium–phenol/nitro N—H···O,O cation–anion association similar to that in (I) is present (Fig. 2). This is also similar to the association found in a number of DNSA proton-transfer compounds (Smith et al., 2007) but in (II), with an additional conjoint symmetrical R12(4) piperidinium N—H···O,O' interaction (Fig. 2). Head-to-tail piperidinium–amide N—H···O hydrogen bonds (Table 2) give ribbon structures which extend along the b cell direction and enclose R43(20) ring systems (Fig. 5). The short intramolecular hydrogen bond which is characteristic of the DNSA anion is found in (II) as well as in the triclinic polymorph, (III). In both structures the anti-related proton is located on the carboxyl group rather than on the phenolic O, but this is the majority case with the DNSA anions in the known structures of the proton-transfer salts of this acid (Smith et al., 2002, 2003, 2007).
The triclinic modification (the β-polymorph) of the isonipecotamide-DNSA compound, (III), has two INPA cations (A and B) as well as two anions (C and D) in the asymmetric unit (Fig. 3). Although there is not any major difference in the amide side-chain conformations of the two independent cations in (III) [as indicated by the torsion angle C3—C4—C41—N41 of 93.6 (2)° for cation A cf. 86.5 (2)° for cation B], these differ significantly from that found in (II) [122.29 (16)°]. With the DNSA anions the differences are less obvious. As expected, because of the presence of the intramolecular hydrogen bond, the carboxylic acid group is essentially coplanar with the benzene ring in all three anions [torsion angle C2—C1—C11—O11 = -179.15 (16)° for (II), -178.18 (18)° for (IIIC) and -179.09 (16)° for (IIID)]. Both nitro groups in the two polymorphs are slightly rotated out of the plane [torsion angles: C2—C3—N3—O32 = 165.64 (17)° for (II) -170.75 (16)° for (IIIC), -177.65 (15)° for (IIID); C4—C5—N5—O52 = -166.78 (16)° for (II), -175.98 (17)° for (IIIC) and -170.94 (18)° for (IIID)]. However, the hydrogen-bonding differences between (II) and (III) are very significant (Table 3). There is an absence of the proximal piperidinium–phenolate/nitro N—H···O,O interaction with either of the DNSA anions. Instead, one of the cations (B) gives an N—H···O,O''carboxylate interaction with a D anion [graph set R12(4)], the other (A) acting as a bridge between cation B amide O and anion nitro O-atom acceptors. The anions also form the zigzag head-to-tail piperidinium–amide N—H···O bridged chain hydrogen-bonded chain substructures also found in (II) (Fig. 6). In addition, the hydrogen bonding in the overall three-dimensional framework structure features a centrosymmetric duplex amide H—N—H-bridged bis(cation–anion) R42(8) ring system (Fig. 6).
The structures reported here demonstrate the utility of the isonipecotamide cation as a synthon with previously unrecognized potential for structure assembly applications. Furthermore, the structures of the two polymorphic 3,5-dinitrosalicylic acid salts (II) and (III) show unusually diverse hydrogen-bonding characteristics with only slight molecular conformational differences. In the absence of any additive induced effects during crystallization, the observed polymorphism can be seen as an artefact of solvent gradient effects, considering that the parallel crystallizations occurred from identical ethanol–water solvent mixtures.