Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270111020518/su3064sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270111020518/su3064Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270111020518/su3064IIsup3.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270111020518/su3064IIIsup4.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270111020518/su3064IVsup5.hkl | |
Chemical Markup Language (CML) file https://doi.org/10.1107/S0108270111020518/su3064Isup6.cml | |
Chemical Markup Language (CML) file https://doi.org/10.1107/S0108270111020518/su3064IIsup7.cml | |
Chemical Markup Language (CML) file https://doi.org/10.1107/S0108270111020518/su3064IIIsup8.cml |
CCDC references: 838165; 838166; 838167; 838168
The title compounds were synthesized by heating together under reflux for 10 min 4-piperidinecarboxamide (isonipecotamide, 1 mmol) with either 4-nitrophthalic acid (1 mmol) for (I), 4,5-dichlorophthalic acid (1 mmol) for (II), 5-nitroisophthalic acid (1 mmol) for (III) or terephthalic acid (1 mmol) for (IV) in either methanol (50 ml) for (III), methanol–water (80%, 50 ml) for (I) and (IV) or ethanol–water (50%, 50 ml) for (II). After concentration to ca 30 ml, partial room-temperature evaporation of the hot-filtered solutions gave colourless plates of (I) and (III), blocks of (II) or prisms of (IV).
H atoms involved in hydrogen-bonding interactions were located by difference methods and, with the exception of the carboxylic acid H atoms, which were set invariant in the final cycles of refinement, their positional and isotropic displacement parameters were refined. Other H atoms were included in the refinements at calculated positions [C—H(aliphatic) = 0.97 or 0.98 Å, and C—H(aromatic) = 0.93 Å] 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 (Oxford Diffraction, 2009). Program(s) used to solve structure: SIR92 (Altomare et al., 1994) for (I), (II), (III); SHELXS97 (Sheldrick, 2008) for (IV). For all compounds, program(s) used to refine structure: SHELXL97 (Sheldrick, 2008) within WinGX (Farrugia, 1999); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: PLATON (Spek, 2009).
C6H13N2O+·C8H4NO6− | F(000) = 712 |
Mr = 339.31 | Dx = 1.483 Mg m−3 |
Monoclinic, P21/n | Melting point: 467 K |
Hall symbol: -P 2yn | Mo Kα radiation, λ = 0.71073 Å |
a = 5.8637 (5) Å | Cell parameters from 4796 reflections |
b = 11.2707 (8) Å | θ = 3.2–28.8° |
c = 23.0268 (19) Å | µ = 0.12 mm−1 |
β = 93.082 (8)° | T = 200 K |
V = 1519.6 (2) Å3 | Plate, colourless |
Z = 4 | 0.40 × 0.40 × 0.12 mm |
Oxford Gemini-S CCD area-detector diffractometer | 2989 independent reflections |
Radiation source: Enhance (Mo) X-ray source | 2375 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.023 |
ω scans | θmax = 26.0°, θmin = 3.2° |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009) | h = −7→6 |
Tmin = 0.915, Tmax = 0.980 | k = −13→13 |
10364 measured reflections | l = −28→26 |
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)] = 0.046 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.114 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0482P)2 + 0.9247P] where P = (Fo2 + 2Fc2)/3 |
2989 reflections | (Δ/σ)max < 0.001 |
233 parameters | Δρmax = 0.35 e Å−3 |
0 restraints | Δρmin = −0.26 e Å−3 |
C6H13N2O+·C8H4NO6− | V = 1519.6 (2) Å3 |
Mr = 339.31 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 5.8637 (5) Å | µ = 0.12 mm−1 |
b = 11.2707 (8) Å | T = 200 K |
c = 23.0268 (19) Å | 0.40 × 0.40 × 0.12 mm |
β = 93.082 (8)° |
Oxford Gemini-S CCD area-detector diffractometer | 2989 independent reflections |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009) | 2375 reflections with I > 2σ(I) |
Tmin = 0.915, Tmax = 0.980 | Rint = 0.023 |
10364 measured reflections |
R[F2 > 2σ(F2)] = 0.046 | 0 restraints |
wR(F2) = 0.114 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | Δρmax = 0.35 e Å−3 |
2989 reflections | Δρmin = −0.26 e Å−3 |
233 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 | 0.5071 (3) | 0.87661 (14) | 0.55291 (7) | 0.0470 (6) | |
N1A | 0.0153 (3) | 0.63006 (16) | 0.65455 (8) | 0.0299 (6) | |
N41A | 0.2315 (4) | 0.9218 (2) | 0.48579 (9) | 0.0430 (7) | |
C2A | 0.0994 (5) | 0.5737 (2) | 0.60175 (11) | 0.0455 (8) | |
C3A | 0.2620 (4) | 0.65623 (19) | 0.57243 (11) | 0.0436 (8) | |
C4A | 0.1494 (4) | 0.77453 (18) | 0.55762 (8) | 0.0304 (6) | |
C5A | 0.0609 (4) | 0.82942 (19) | 0.61283 (10) | 0.0348 (7) | |
C6A | −0.0971 (4) | 0.7461 (2) | 0.64247 (11) | 0.0424 (8) | |
C41A | 0.3124 (4) | 0.86121 (18) | 0.53162 (8) | 0.0298 (6) | |
O11 | 0.6413 (3) | 0.51227 (13) | 0.69033 (6) | 0.0360 (5) | |
O12 | 0.4026 (2) | 0.46519 (13) | 0.75858 (6) | 0.0348 (5) | |
O21 | 0.3549 (3) | 0.72451 (13) | 0.73146 (7) | 0.0406 (5) | |
O22 | 0.3569 (2) | 0.84857 (12) | 0.80634 (6) | 0.0307 (4) | |
O41 | 1.0325 (3) | 0.85304 (16) | 0.93918 (7) | 0.0484 (6) | |
O42 | 1.2952 (3) | 0.71969 (18) | 0.93283 (8) | 0.0547 (6) | |
N4 | 1.1086 (3) | 0.76236 (17) | 0.91794 (7) | 0.0358 (6) | |
C1 | 0.7105 (3) | 0.58879 (16) | 0.78603 (8) | 0.0219 (5) | |
C2 | 0.6377 (3) | 0.69872 (16) | 0.80700 (8) | 0.0205 (5) | |
C3 | 0.7680 (3) | 0.75455 (17) | 0.85112 (8) | 0.0244 (5) | |
C4 | 0.9697 (3) | 0.70127 (17) | 0.87223 (8) | 0.0259 (6) | |
C5 | 1.0447 (3) | 0.59532 (19) | 0.85117 (9) | 0.0309 (6) | |
C6 | 0.9130 (3) | 0.53851 (18) | 0.80846 (9) | 0.0295 (6) | |
C11 | 0.5745 (3) | 0.51917 (16) | 0.74006 (9) | 0.0243 (6) | |
C21 | 0.4318 (3) | 0.75916 (16) | 0.77889 (8) | 0.0219 (5) | |
H4A | 0.02000 | 0.76110 | 0.52970 | 0.0370* | |
H11A | −0.098 (5) | 0.578 (2) | 0.6715 (11) | 0.050 (7)* | |
H12A | 0.138 (5) | 0.641 (2) | 0.6813 (11) | 0.046 (7)* | |
H21A | −0.02880 | 0.55490 | 0.57500 | 0.0550* | |
H22A | 0.17740 | 0.50030 | 0.61220 | 0.0550* | |
H31A | 0.31080 | 0.61940 | 0.53710 | 0.0520* | |
H32A | 0.39630 | 0.66940 | 0.59810 | 0.0520* | |
H42A | 0.318 (5) | 0.983 (2) | 0.4725 (12) | 0.053 (8)* | |
H43A | 0.104 (5) | 0.902 (3) | 0.4714 (13) | 0.059 (9)* | |
H51A | 0.18920 | 0.84900 | 0.63940 | 0.0420* | |
H52A | −0.01990 | 0.90240 | 0.60290 | 0.0420* | |
H61A | −0.14110 | 0.78110 | 0.67870 | 0.0510* | |
H62A | −0.23450 | 0.73400 | 0.61780 | 0.0510* | |
H3 | 0.72110 | 0.82640 | 0.86630 | 0.0290* | |
H5 | 1.18200 | 0.56250 | 0.86550 | 0.0370* | |
H6 | 0.96000 | 0.46560 | 0.79440 | 0.0350* | |
H22 | 0.25130 | 0.89510 | 0.78030 | 0.0370* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O41A | 0.0394 (10) | 0.0472 (10) | 0.0533 (10) | −0.0162 (8) | −0.0076 (8) | 0.0227 (8) |
N1A | 0.0290 (10) | 0.0349 (10) | 0.0257 (9) | −0.0114 (8) | 0.0004 (8) | 0.0048 (7) |
N41A | 0.0359 (12) | 0.0520 (13) | 0.0407 (12) | −0.0080 (10) | −0.0005 (9) | 0.0226 (10) |
C2A | 0.0645 (17) | 0.0317 (12) | 0.0421 (13) | −0.0095 (12) | 0.0186 (12) | 0.0007 (10) |
C3A | 0.0569 (16) | 0.0316 (12) | 0.0446 (14) | −0.0015 (11) | 0.0232 (12) | 0.0045 (10) |
C4A | 0.0325 (11) | 0.0348 (11) | 0.0234 (10) | −0.0111 (9) | −0.0043 (8) | 0.0043 (8) |
C5A | 0.0317 (12) | 0.0311 (11) | 0.0422 (13) | 0.0008 (9) | 0.0085 (10) | 0.0070 (9) |
C6A | 0.0335 (13) | 0.0444 (13) | 0.0505 (14) | −0.0008 (10) | 0.0134 (11) | 0.0102 (11) |
C41A | 0.0357 (12) | 0.0308 (11) | 0.0230 (10) | −0.0024 (9) | 0.0033 (9) | 0.0016 (8) |
O11 | 0.0379 (9) | 0.0366 (8) | 0.0348 (8) | −0.0131 (7) | 0.0137 (7) | −0.0089 (7) |
O12 | 0.0297 (8) | 0.0386 (8) | 0.0369 (8) | −0.0172 (7) | 0.0107 (6) | −0.0063 (7) |
O21 | 0.0411 (9) | 0.0388 (9) | 0.0396 (9) | 0.0146 (7) | −0.0194 (7) | −0.0125 (7) |
O22 | 0.0334 (8) | 0.0281 (7) | 0.0303 (8) | 0.0120 (6) | −0.0015 (6) | −0.0022 (6) |
O41 | 0.0539 (11) | 0.0506 (10) | 0.0396 (9) | −0.0067 (9) | −0.0078 (8) | −0.0139 (8) |
O42 | 0.0345 (10) | 0.0814 (13) | 0.0458 (10) | 0.0067 (9) | −0.0198 (8) | −0.0017 (9) |
N4 | 0.0351 (11) | 0.0448 (11) | 0.0268 (9) | −0.0070 (9) | −0.0033 (8) | 0.0032 (8) |
C1 | 0.0190 (9) | 0.0212 (9) | 0.0261 (10) | −0.0015 (7) | 0.0065 (7) | 0.0042 (7) |
C2 | 0.0185 (9) | 0.0203 (9) | 0.0228 (9) | −0.0028 (7) | 0.0024 (7) | 0.0026 (7) |
C3 | 0.0277 (10) | 0.0217 (9) | 0.0239 (9) | −0.0015 (8) | 0.0023 (8) | 0.0017 (8) |
C4 | 0.0234 (10) | 0.0332 (11) | 0.0208 (9) | −0.0075 (8) | −0.0023 (8) | 0.0045 (8) |
C5 | 0.0223 (10) | 0.0341 (11) | 0.0363 (11) | 0.0046 (9) | 0.0005 (9) | 0.0075 (9) |
C6 | 0.0240 (11) | 0.0244 (10) | 0.0404 (12) | 0.0044 (8) | 0.0052 (9) | 0.0005 (9) |
C11 | 0.0234 (10) | 0.0169 (9) | 0.0331 (11) | 0.0015 (8) | 0.0075 (8) | −0.0010 (8) |
C21 | 0.0224 (10) | 0.0183 (9) | 0.0250 (9) | −0.0010 (7) | 0.0010 (8) | 0.0008 (7) |
O41A—C41A | 1.230 (3) | C2A—H21A | 0.9700 |
O11—C11 | 1.233 (2) | C2A—H22A | 0.9700 |
O12—C11 | 1.271 (2) | C3A—H31A | 0.9700 |
O21—C21 | 1.223 (2) | C3A—H32A | 0.9700 |
O22—C21 | 1.280 (2) | C4A—H4A | 0.9800 |
O41—N4 | 1.227 (3) | C5A—H51A | 0.9700 |
O42—N4 | 1.227 (3) | C5A—H52A | 0.9700 |
O22—H22 | 0.9900 | C6A—H62A | 0.9700 |
N1A—C2A | 1.480 (3) | C6A—H61A | 0.9700 |
N1A—C6A | 1.484 (3) | C1—C2 | 1.405 (3) |
N41A—C41A | 1.323 (3) | C1—C11 | 1.510 (3) |
N1A—H12A | 0.93 (3) | C1—C6 | 1.390 (3) |
N1A—H11A | 0.98 (3) | C2—C3 | 1.389 (3) |
N41A—H42A | 0.92 (3) | C2—C21 | 1.502 (3) |
N41A—H43A | 0.83 (3) | C3—C4 | 1.391 (3) |
N4—C4 | 1.467 (3) | C4—C5 | 1.370 (3) |
C2A—C3A | 1.516 (3) | C5—C6 | 1.376 (3) |
C3A—C4A | 1.519 (3) | C3—H3 | 0.9300 |
C4A—C41A | 1.513 (3) | C5—H5 | 0.9300 |
C4A—C5A | 1.529 (3) | C6—H6 | 0.9300 |
C5A—C6A | 1.508 (3) | ||
C21—O22—H22 | 110.00 | C3A—C4A—H4A | 109.00 |
C2A—N1A—C6A | 112.87 (18) | C4A—C5A—H52A | 109.00 |
C2A—N1A—H12A | 108.7 (16) | C6A—C5A—H51A | 109.00 |
C6A—N1A—H11A | 107.3 (15) | C4A—C5A—H51A | 109.00 |
C2A—N1A—H11A | 109.4 (14) | C6A—C5A—H52A | 109.00 |
H11A—N1A—H12A | 109 (2) | H51A—C5A—H52A | 108.00 |
C6A—N1A—H12A | 109.1 (14) | N1A—C6A—H62A | 109.00 |
H42A—N41A—H43A | 125 (3) | C5A—C6A—H61A | 110.00 |
C41A—N41A—H43A | 117 (2) | C5A—C6A—H62A | 109.00 |
C41A—N41A—H42A | 118.2 (18) | N1A—C6A—H61A | 109.00 |
O41—N4—O42 | 123.56 (19) | H61A—C6A—H62A | 108.00 |
O41—N4—C4 | 118.48 (17) | C2—C1—C11 | 122.71 (16) |
O42—N4—C4 | 117.95 (18) | C6—C1—C11 | 117.19 (16) |
N1A—C2A—C3A | 110.35 (18) | C2—C1—C6 | 120.09 (17) |
C2A—C3A—C4A | 111.3 (2) | C1—C2—C21 | 120.26 (16) |
C5A—C4A—C41A | 108.52 (17) | C3—C2—C21 | 120.50 (16) |
C3A—C4A—C5A | 109.35 (17) | C1—C2—C3 | 119.07 (16) |
C3A—C4A—C41A | 112.31 (19) | C2—C3—C4 | 118.96 (17) |
C4A—C5A—C6A | 111.62 (18) | N4—C4—C3 | 118.49 (17) |
N1A—C6A—C5A | 110.86 (18) | C3—C4—C5 | 122.39 (17) |
O41A—C41A—C4A | 121.73 (18) | N4—C4—C5 | 119.11 (16) |
N41A—C41A—C4A | 116.2 (2) | C4—C5—C6 | 118.70 (17) |
O41A—C41A—N41A | 122.0 (2) | C1—C6—C5 | 120.76 (18) |
H21A—C2A—H22A | 108.00 | O11—C11—C1 | 120.12 (17) |
N1A—C2A—H22A | 110.00 | O12—C11—C1 | 114.33 (17) |
N1A—C2A—H21A | 110.00 | O11—C11—O12 | 125.39 (18) |
C3A—C2A—H22A | 110.00 | O21—C21—C2 | 119.29 (17) |
C3A—C2A—H21A | 110.00 | O22—C21—C2 | 115.69 (16) |
C2A—C3A—H31A | 109.00 | O21—C21—O22 | 124.94 (17) |
C4A—C3A—H31A | 109.00 | C2—C3—H3 | 121.00 |
H31A—C3A—H32A | 108.00 | C4—C3—H3 | 121.00 |
C2A—C3A—H32A | 109.00 | C4—C5—H5 | 121.00 |
C4A—C3A—H32A | 109.00 | C6—C5—H5 | 121.00 |
C41A—C4A—H4A | 109.00 | C1—C6—H6 | 120.00 |
C5A—C4A—H4A | 109.00 | C5—C6—H6 | 120.00 |
C6A—N1A—C2A—C3A | 56.6 (3) | C11—C1—C2—C21 | −7.4 (3) |
C2A—N1A—C6A—C5A | −55.9 (3) | C2—C1—C6—C5 | −0.1 (3) |
O41—N4—C4—C3 | 6.0 (3) | C11—C1—C6—C5 | −178.87 (18) |
O41—N4—C4—C5 | −175.20 (18) | C2—C1—C11—O11 | 107.7 (2) |
O42—N4—C4—C3 | −174.03 (18) | C2—C1—C11—O12 | −76.7 (2) |
O42—N4—C4—C5 | 4.8 (3) | C6—C1—C11—O11 | −73.6 (2) |
N1A—C2A—C3A—C4A | −56.8 (3) | C6—C1—C11—O12 | 102.0 (2) |
C2A—C3A—C4A—C5A | 56.0 (2) | C1—C2—C3—C4 | 1.6 (3) |
C2A—C3A—C4A—C41A | 176.54 (18) | C21—C2—C3—C4 | −173.75 (17) |
C5A—C4A—C41A—O41A | 75.2 (3) | C1—C2—C21—O21 | −14.0 (3) |
C5A—C4A—C41A—N41A | −103.0 (2) | C1—C2—C21—O22 | 169.25 (16) |
C3A—C4A—C41A—O41A | −45.8 (3) | C3—C2—C21—O21 | 161.27 (18) |
C3A—C4A—C5A—C6A | −55.2 (2) | C3—C2—C21—O22 | −15.5 (3) |
C41A—C4A—C5A—C6A | −178.04 (18) | C2—C3—C4—N4 | 178.65 (17) |
C3A—C4A—C41A—N41A | 136.0 (2) | C2—C3—C4—C5 | −0.2 (3) |
C4A—C5A—C6A—N1A | 54.9 (2) | N4—C4—C5—C6 | 179.79 (17) |
C6—C1—C2—C3 | −1.4 (3) | C3—C4—C5—C6 | −1.4 (3) |
C6—C1—C2—C21 | 173.89 (17) | C4—C5—C6—C1 | 1.5 (3) |
C11—C1—C2—C3 | 177.23 (17) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1A—H11A···O11i | 0.98 (3) | 1.77 (3) | 2.729 (2) | 163 (2) |
N1A—H12A···O21 | 0.93 (3) | 1.92 (3) | 2.803 (2) | 158 (2) |
N41A—H42A···O41Aii | 0.92 (3) | 1.99 (3) | 2.907 (3) | 176 (2) |
N41A—H43A···O42iii | 0.83 (3) | 2.40 (3) | 3.200 (3) | 161 (3) |
O22—H22···O12iv | 0.99 | 1.47 | 2.4562 (19) | 179 |
C4A—H4A···O42iii | 0.98 | 2.54 | 3.454 (3) | 156 |
C2A—H22A···O22v | 0.97 | 2.55 | 3.305 (3) | 134 |
Symmetry codes: (i) x−1, y, z; (ii) −x+1, −y+2, −z+1; (iii) x−3/2, −y+3/2, z−1/2; (iv) −x+1/2, y+1/2, −z+3/2; (v) −x+1/2, y−1/2, −z+3/2. |
C6H13N2O+·C8H3Cl2O4− | F(000) = 752 |
Mr = 363.19 | Dx = 1.536 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 8871 reflections |
a = 6.6897 (4) Å | θ = 3.1–28.9° |
b = 9.7392 (5) Å | µ = 0.44 mm−1 |
c = 24.1222 (13) Å | T = 200 K |
β = 92.479 (4)° | Block, colourless |
V = 1570.15 (15) Å3 | 0.30 × 0.25 × 0.20 mm |
Z = 4 |
Oxford Gemini S CCD area-detector diffractometer | 3084 independent reflections |
Radiation source: Enhance (Mo) X-ray source | 2777 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.028 |
ω scans | θmax = 26.0°, θmin = 3.1° |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009) | h = −8→8 |
Tmin = 0.908, Tmax = 0.980 | k = −12→12 |
19231 measured reflections | l = −29→29 |
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)] = 0.046 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.113 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.30 | w = 1/[σ2(Fo2) + (0.0177P)2 + 2.734P] where P = (Fo2 + 2Fc2)/3 |
3084 reflections | (Δ/σ)max = 0.001 |
224 parameters | Δρmax = 0.37 e Å−3 |
0 restraints | Δρmin = −0.29 e Å−3 |
C6H13N2O+·C8H3Cl2O4− | V = 1570.15 (15) Å3 |
Mr = 363.19 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 6.6897 (4) Å | µ = 0.44 mm−1 |
b = 9.7392 (5) Å | T = 200 K |
c = 24.1222 (13) Å | 0.30 × 0.25 × 0.20 mm |
β = 92.479 (4)° |
Oxford Gemini S CCD area-detector diffractometer | 3084 independent reflections |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009) | 2777 reflections with I > 2σ(I) |
Tmin = 0.908, Tmax = 0.980 | Rint = 0.028 |
19231 measured reflections |
R[F2 > 2σ(F2)] = 0.046 | 0 restraints |
wR(F2) = 0.113 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.30 | Δρmax = 0.37 e Å−3 |
3084 reflections | Δρmin = −0.29 e Å−3 |
224 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 | 0.7063 (4) | 0.2890 (2) | 0.24101 (10) | 0.0453 (9) | |
N1A | 0.8063 (4) | 0.4798 (3) | 0.42405 (10) | 0.0251 (8) | |
N41A | 0.7344 (5) | 0.5032 (4) | 0.20550 (11) | 0.0379 (10) | |
C2A | 0.9600 (4) | 0.5342 (3) | 0.38672 (11) | 0.0278 (9) | |
C3A | 0.9429 (4) | 0.4642 (3) | 0.33052 (12) | 0.0284 (9) | |
C4A | 0.7313 (4) | 0.4792 (3) | 0.30467 (11) | 0.0234 (8) | |
C5A | 0.5823 (5) | 0.4163 (3) | 0.34351 (12) | 0.0283 (9) | |
C6A | 0.5975 (4) | 0.4870 (3) | 0.39972 (12) | 0.0278 (9) | |
C41A | 0.7207 (5) | 0.4135 (3) | 0.24744 (12) | 0.0292 (9) | |
Cl4 | 0.70276 (15) | 1.20000 (9) | 0.67633 (3) | 0.0436 (3) | |
Cl5 | 0.73906 (13) | 0.88021 (9) | 0.70518 (3) | 0.0346 (2) | |
O11 | 0.7966 (3) | 0.6468 (2) | 0.51891 (8) | 0.0312 (7) | |
O12 | 0.7517 (4) | 0.7842 (2) | 0.44724 (8) | 0.0365 (7) | |
O21 | 0.7440 (3) | 1.0235 (2) | 0.42476 (8) | 0.0309 (7) | |
O22 | 0.7514 (4) | 1.2225 (2) | 0.46816 (9) | 0.0393 (8) | |
C1 | 0.7580 (4) | 0.8846 (3) | 0.53926 (11) | 0.0194 (7) | |
C2 | 0.7464 (4) | 1.0267 (3) | 0.52629 (11) | 0.0201 (8) | |
C3 | 0.7329 (4) | 1.1194 (3) | 0.57002 (12) | 0.0250 (8) | |
C4 | 0.7292 (4) | 1.0782 (3) | 0.62488 (11) | 0.0245 (8) | |
C5 | 0.7429 (4) | 0.9395 (3) | 0.63756 (11) | 0.0231 (8) | |
C6 | 0.7570 (4) | 0.8455 (3) | 0.59506 (11) | 0.0219 (8) | |
C11 | 0.7709 (4) | 0.7639 (3) | 0.49947 (11) | 0.0237 (8) | |
C21 | 0.7479 (4) | 1.0964 (3) | 0.46933 (12) | 0.0246 (8) | |
H4A | 0.70120 | 0.57720 | 0.30060 | 0.0280* | |
H11A | 0.818 (5) | 0.531 (4) | 0.4561 (15) | 0.041 (10)* | |
H12A | 0.827 (5) | 0.394 (4) | 0.4321 (15) | 0.041 (10)* | |
H21A | 1.09250 | 0.51870 | 0.40350 | 0.0330* | |
H22A | 0.94170 | 0.63240 | 0.38200 | 0.0330* | |
H31A | 0.97510 | 0.36750 | 0.33480 | 0.0340* | |
H32A | 1.03810 | 0.50460 | 0.30610 | 0.0340* | |
H41A | 0.737 (5) | 0.467 (4) | 0.1749 (16) | 0.038 (10)* | |
H42A | 0.759 (6) | 0.595 (4) | 0.2140 (15) | 0.043 (11)* | |
H51A | 0.44760 | 0.42620 | 0.32750 | 0.0340* | |
H52A | 0.60990 | 0.31900 | 0.34810 | 0.0340* | |
H61A | 0.55780 | 0.58240 | 0.39550 | 0.0330* | |
H62A | 0.50710 | 0.44320 | 0.42460 | 0.0330* | |
H3 | 0.72610 | 1.21270 | 0.56200 | 0.0300* | |
H6 | 0.76610 | 0.75270 | 0.60390 | 0.0260* | |
H12 | 0.74890 | 0.88380 | 0.43800 | 0.0440* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O41A | 0.0668 (18) | 0.0325 (14) | 0.0373 (13) | −0.0036 (12) | 0.0091 (12) | −0.0144 (10) |
N1A | 0.0399 (15) | 0.0181 (13) | 0.0176 (12) | 0.0011 (11) | 0.0035 (10) | 0.0015 (10) |
N41A | 0.0473 (18) | 0.0476 (19) | 0.0188 (13) | 0.0047 (15) | 0.0016 (12) | 0.0000 (13) |
C2A | 0.0276 (16) | 0.0319 (16) | 0.0238 (14) | −0.0008 (13) | 0.0002 (12) | 0.0005 (12) |
C3A | 0.0281 (16) | 0.0329 (17) | 0.0246 (14) | 0.0010 (13) | 0.0052 (12) | −0.0023 (12) |
C4A | 0.0325 (16) | 0.0161 (13) | 0.0218 (13) | 0.0015 (12) | 0.0034 (12) | 0.0005 (11) |
C5A | 0.0291 (16) | 0.0296 (16) | 0.0263 (14) | −0.0068 (13) | 0.0036 (12) | −0.0041 (12) |
C6A | 0.0308 (16) | 0.0283 (16) | 0.0250 (14) | −0.0024 (13) | 0.0085 (12) | −0.0018 (12) |
C41A | 0.0291 (17) | 0.0332 (18) | 0.0256 (14) | 0.0019 (13) | 0.0032 (12) | −0.0046 (13) |
Cl4 | 0.0669 (6) | 0.0320 (4) | 0.0322 (4) | −0.0029 (4) | 0.0072 (4) | −0.0148 (3) |
Cl5 | 0.0467 (5) | 0.0405 (4) | 0.0167 (3) | −0.0004 (4) | 0.0042 (3) | 0.0023 (3) |
O11 | 0.0497 (14) | 0.0189 (10) | 0.0250 (10) | 0.0022 (10) | 0.0033 (9) | −0.0003 (8) |
O12 | 0.0677 (16) | 0.0235 (11) | 0.0182 (10) | 0.0047 (11) | 0.0001 (10) | −0.0018 (8) |
O21 | 0.0436 (13) | 0.0308 (12) | 0.0184 (10) | −0.0001 (10) | 0.0018 (9) | 0.0055 (8) |
O22 | 0.0601 (16) | 0.0216 (12) | 0.0364 (12) | −0.0040 (11) | 0.0031 (11) | 0.0110 (9) |
C1 | 0.0193 (13) | 0.0200 (13) | 0.0190 (12) | −0.0016 (11) | 0.0012 (10) | −0.0004 (10) |
C2 | 0.0173 (13) | 0.0215 (14) | 0.0214 (13) | −0.0008 (11) | 0.0004 (10) | 0.0012 (11) |
C3 | 0.0281 (15) | 0.0174 (13) | 0.0296 (15) | −0.0021 (12) | 0.0016 (12) | 0.0002 (12) |
C4 | 0.0270 (15) | 0.0236 (15) | 0.0230 (14) | −0.0032 (12) | 0.0018 (11) | −0.0071 (11) |
C5 | 0.0230 (14) | 0.0292 (15) | 0.0171 (13) | −0.0027 (12) | 0.0012 (11) | 0.0008 (11) |
C6 | 0.0248 (14) | 0.0193 (14) | 0.0216 (13) | −0.0006 (11) | 0.0026 (11) | 0.0023 (11) |
C11 | 0.0269 (15) | 0.0229 (14) | 0.0214 (13) | −0.0014 (12) | 0.0036 (11) | −0.0009 (11) |
C21 | 0.0221 (14) | 0.0245 (15) | 0.0272 (15) | −0.0018 (12) | 0.0026 (11) | 0.0066 (12) |
Cl4—C4 | 1.731 (3) | C2A—H22A | 0.9700 |
Cl5—C5 | 1.732 (3) | C2A—H21A | 0.9700 |
O41A—C41A | 1.226 (4) | C3A—H31A | 0.9700 |
O11—C11 | 1.242 (3) | C3A—H32A | 0.9700 |
O12—C11 | 1.276 (3) | C4A—H4A | 0.9800 |
O21—C21 | 1.288 (3) | C5A—H51A | 0.9700 |
O22—C21 | 1.229 (4) | C5A—H52A | 0.9700 |
O12—H12 | 1.0000 | C6A—H62A | 0.9700 |
N1A—C2A | 1.493 (4) | C6A—H61A | 0.9700 |
N1A—C6A | 1.493 (4) | C1—C2 | 1.420 (4) |
N41A—C41A | 1.343 (4) | C1—C11 | 1.522 (4) |
N1A—H12A | 0.87 (4) | C1—C6 | 1.399 (4) |
N1A—H11A | 0.92 (4) | C2—C21 | 1.533 (4) |
N41A—H42A | 0.93 (4) | C2—C3 | 1.394 (4) |
N41A—H41A | 0.82 (4) | C3—C4 | 1.384 (4) |
C2A—C3A | 1.517 (4) | C4—C5 | 1.387 (4) |
C3A—C4A | 1.529 (4) | C5—C6 | 1.381 (4) |
C4A—C41A | 1.521 (4) | C3—H3 | 0.9300 |
C4A—C5A | 1.526 (4) | C6—H6 | 0.9300 |
C5A—C6A | 1.520 (4) | ||
C11—O12—H12 | 112.00 | C6A—C5A—H52A | 110.00 |
C2A—N1A—C6A | 113.8 (2) | H51A—C5A—H52A | 108.00 |
C6A—N1A—H11A | 110 (2) | C4A—C5A—H52A | 110.00 |
C2A—N1A—H11A | 106 (2) | C4A—C5A—H51A | 110.00 |
C2A—N1A—H12A | 112 (2) | C5A—C6A—H61A | 109.00 |
C6A—N1A—H12A | 106 (2) | N1A—C6A—H61A | 109.00 |
H11A—N1A—H12A | 109 (3) | N1A—C6A—H62A | 110.00 |
H41A—N41A—H42A | 127 (4) | H61A—C6A—H62A | 108.00 |
C41A—N41A—H42A | 118 (2) | C5A—C6A—H62A | 109.00 |
C41A—N41A—H41A | 114 (3) | C2—C1—C11 | 128.1 (2) |
N1A—C2A—C3A | 110.6 (2) | C2—C1—C6 | 118.3 (3) |
C2A—C3A—C4A | 110.7 (2) | C6—C1—C11 | 113.5 (2) |
C5A—C4A—C41A | 112.5 (2) | C1—C2—C21 | 128.8 (2) |
C3A—C4A—C5A | 109.2 (2) | C1—C2—C3 | 118.0 (2) |
C3A—C4A—C41A | 109.6 (2) | C3—C2—C21 | 113.2 (3) |
C4A—C5A—C6A | 110.2 (2) | C2—C3—C4 | 122.7 (3) |
N1A—C6A—C5A | 110.8 (2) | Cl4—C4—C5 | 121.1 (2) |
O41A—C41A—N41A | 123.8 (3) | C3—C4—C5 | 119.3 (3) |
O41A—C41A—C4A | 122.1 (3) | Cl4—C4—C3 | 119.6 (2) |
N41A—C41A—C4A | 114.1 (3) | C4—C5—C6 | 119.2 (2) |
N1A—C2A—H22A | 110.00 | Cl5—C5—C4 | 121.9 (2) |
N1A—C2A—H21A | 109.00 | Cl5—C5—C6 | 118.9 (2) |
H21A—C2A—H22A | 108.00 | C1—C6—C5 | 122.5 (3) |
C3A—C2A—H21A | 110.00 | O11—C11—C1 | 118.8 (2) |
C3A—C2A—H22A | 109.00 | O12—C11—C1 | 119.8 (2) |
C4A—C3A—H31A | 109.00 | O11—C11—O12 | 121.4 (3) |
C4A—C3A—H32A | 110.00 | O22—C21—C2 | 117.7 (3) |
H31A—C3A—H32A | 108.00 | O21—C21—O22 | 122.1 (3) |
C2A—C3A—H32A | 110.00 | O21—C21—C2 | 120.2 (2) |
C2A—C3A—H31A | 109.00 | C2—C3—H3 | 119.00 |
C5A—C4A—H4A | 108.00 | C4—C3—H3 | 119.00 |
C3A—C4A—H4A | 108.00 | C1—C6—H6 | 119.00 |
C41A—C4A—H4A | 109.00 | C5—C6—H6 | 119.00 |
C6A—C5A—H51A | 110.00 | ||
C6A—N1A—C2A—C3A | −53.9 (3) | C2—C1—C11—O11 | 174.1 (3) |
C2A—N1A—C6A—C5A | 54.3 (3) | C2—C1—C11—O12 | −7.1 (4) |
N1A—C2A—C3A—C4A | 55.6 (3) | C6—C1—C11—O11 | −6.2 (4) |
C2A—C3A—C4A—C5A | −58.7 (3) | C6—C1—C11—O12 | 172.6 (3) |
C2A—C3A—C4A—C41A | 177.6 (2) | C1—C2—C3—C4 | −0.4 (4) |
C3A—C4A—C5A—C6A | 58.8 (3) | C21—C2—C3—C4 | 180.0 (2) |
C41A—C4A—C5A—C6A | −179.2 (2) | C1—C2—C21—O21 | 5.9 (4) |
C3A—C4A—C41A—O41A | 78.8 (4) | C1—C2—C21—O22 | −174.7 (3) |
C3A—C4A—C41A—N41A | −99.4 (3) | C3—C2—C21—O21 | −174.6 (2) |
C5A—C4A—C41A—O41A | −43.0 (4) | C3—C2—C21—O22 | 4.9 (4) |
C5A—C4A—C41A—N41A | 138.9 (3) | C2—C3—C4—Cl4 | −177.6 (2) |
C4A—C5A—C6A—N1A | −56.3 (3) | C2—C3—C4—C5 | 1.2 (4) |
C6—C1—C2—C3 | −0.5 (4) | Cl4—C4—C5—Cl5 | −1.2 (3) |
C6—C1—C2—C21 | 179.0 (3) | Cl4—C4—C5—C6 | 177.8 (2) |
C11—C1—C2—C3 | 179.1 (3) | C3—C4—C5—Cl5 | −180.0 (2) |
C11—C1—C2—C21 | −1.3 (5) | C3—C4—C5—C6 | −0.9 (4) |
C2—C1—C6—C5 | 0.8 (4) | Cl5—C5—C6—C1 | 179.0 (2) |
C11—C1—C6—C5 | −179.0 (2) | C4—C5—C6—C1 | 0.0 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1A—H11A···O11 | 0.92 (4) | 1.90 (4) | 2.810 (3) | 170 (3) |
N1A—H11A···O12 | 0.92 (4) | 2.51 (4) | 3.042 (4) | 117 (3) |
N1A—H12A···O22i | 0.87 (4) | 1.96 (4) | 2.753 (3) | 152 (3) |
N41A—H41A···O21ii | 0.82 (4) | 2.48 (4) | 3.158 (3) | 142 (4) |
N41A—H42A···O41Aiii | 0.93 (4) | 2.19 (4) | 3.086 (4) | 163 (3) |
O12—H12···O21 | 1.00 | 1.40 | 2.393 (3) | 180 |
C3—H3···O22 | 0.93 | 2.28 | 2.662 (4) | 104 |
C4A—H4A···O41Aiii | 0.98 | 2.39 | 3.245 (4) | 146 |
C6—H6···O11 | 0.93 | 2.31 | 2.689 (3) | 104 |
C2A—H21A···O11iv | 0.97 | 2.56 | 3.259 (3) | 129 |
C2A—H22A···O12 | 0.97 | 2.54 | 3.190 (4) | 124 |
Symmetry codes: (i) x, y−1, z; (ii) −x+3/2, y−1/2, −z+1/2; (iii) −x+3/2, y+1/2, −z+1/2; (iv) −x+2, −y+1, −z+1. |
C6H13N2O+·C8H4NO6− | F(000) = 712 |
Mr = 339.31 | Dx = 1.500 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 4846 reflections |
a = 9.4117 (4) Å | θ = 3.2–28.7° |
b = 14.3552 (5) Å | µ = 0.12 mm−1 |
c = 11.4490 (5) Å | T = 200 K |
β = 103.787 (4)° | Plate, colourless |
V = 1502.27 (11) Å3 | 0.45 × 0.40 × 0.18 mm |
Z = 4 |
Oxford Gemini-S CCD area-detector diffractometer | 2940 independent reflections |
Radiation source: fine-focus sealed tube | 2284 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.025 |
ω scans | θmax = 26.0°, θmin = 3.4° |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009) | h = −11→11 |
Tmin = 0.98, Tmax = 0.99 | k = −17→17 |
9866 measured reflections | l = −14→12 |
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)] = 0.037 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.106 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.01 | w = 1/[σ2(Fo2) + (0.0694P)2] where P = (Fo2 + 2Fc2)/3 |
2940 reflections | (Δ/σ)max = 0.001 |
237 parameters | Δρmax = 0.35 e Å−3 |
0 restraints | Δρmin = −0.24 e Å−3 |
C6H13N2O+·C8H4NO6− | V = 1502.27 (11) Å3 |
Mr = 339.31 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 9.4117 (4) Å | µ = 0.12 mm−1 |
b = 14.3552 (5) Å | T = 200 K |
c = 11.4490 (5) Å | 0.45 × 0.40 × 0.18 mm |
β = 103.787 (4)° |
Oxford Gemini-S CCD area-detector diffractometer | 2940 independent reflections |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009) | 2284 reflections with I > 2σ(I) |
Tmin = 0.98, Tmax = 0.99 | Rint = 0.025 |
9866 measured reflections |
R[F2 > 2σ(F2)] = 0.037 | 0 restraints |
wR(F2) = 0.106 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.01 | Δρmax = 0.35 e Å−3 |
2940 reflections | Δρmin = −0.24 e Å−3 |
237 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 | 0.59457 (16) | 0.89483 (8) | 0.55593 (10) | 0.0441 (4) | |
N1A | 0.75063 (17) | 0.59544 (9) | 0.44483 (12) | 0.0274 (4) | |
N41A | 0.45092 (16) | 0.91398 (9) | 0.37052 (13) | 0.0276 (4) | |
C2A | 0.6261 (2) | 0.60070 (10) | 0.50398 (16) | 0.0329 (5) | |
C3A | 0.5943 (2) | 0.70018 (11) | 0.53417 (15) | 0.0308 (5) | |
C4A | 0.56894 (18) | 0.76325 (10) | 0.42330 (14) | 0.0259 (5) | |
C5A | 0.7036 (2) | 0.75760 (10) | 0.37175 (14) | 0.0297 (5) | |
C6A | 0.7315 (2) | 0.65785 (10) | 0.33822 (14) | 0.0335 (6) | |
C41A | 0.53807 (19) | 0.86299 (10) | 0.45496 (14) | 0.0263 (5) | |
O11 | 0.72771 (14) | 0.40335 (7) | 0.39084 (10) | 0.0310 (4) | |
O12 | 0.90850 (18) | 0.42023 (8) | 0.55448 (11) | 0.0504 (5) | |
O31 | 1.04577 (13) | 0.14479 (7) | 0.82832 (9) | 0.0309 (4) | |
O32 | 0.96788 (14) | 0.00396 (7) | 0.75335 (10) | 0.0318 (4) | |
O51 | 0.75616 (14) | −0.03200 (7) | 0.32869 (10) | 0.0342 (4) | |
O52 | 0.6672 (2) | 0.08685 (8) | 0.22188 (12) | 0.0623 (5) | |
N51 | 0.73297 (16) | 0.05155 (9) | 0.31637 (11) | 0.0280 (4) | |
C1 | 0.82957 (18) | 0.26747 (10) | 0.49770 (13) | 0.0224 (4) | |
C2 | 0.89685 (18) | 0.22902 (10) | 0.60935 (13) | 0.0232 (4) | |
C3 | 0.90771 (17) | 0.13329 (10) | 0.62527 (13) | 0.0217 (4) | |
C4 | 0.85331 (17) | 0.07377 (10) | 0.52947 (13) | 0.0221 (4) | |
C5 | 0.78839 (17) | 0.11326 (10) | 0.41904 (13) | 0.0216 (4) | |
C6 | 0.77429 (18) | 0.20842 (10) | 0.40177 (13) | 0.0223 (4) | |
C11 | 0.8197 (2) | 0.37206 (10) | 0.47962 (13) | 0.0276 (5) | |
C31 | 0.98111 (18) | 0.09530 (10) | 0.74656 (14) | 0.0239 (5) | |
H4A | 0.48430 | 0.73990 | 0.36310 | 0.0310* | |
H11A | 0.836 (2) | 0.6109 (14) | 0.5012 (19) | 0.051 (6)* | |
H12A | 0.756 (3) | 0.5313 (15) | 0.417 (2) | 0.061 (6)* | |
H21A | 0.64880 | 0.56400 | 0.57720 | 0.0390* | |
H22A | 0.53950 | 0.57420 | 0.45090 | 0.0390* | |
H31A | 0.67590 | 0.72390 | 0.59530 | 0.0370* | |
H32A | 0.50810 | 0.70120 | 0.56670 | 0.0370* | |
H41A | 0.414 (2) | 0.8948 (12) | 0.3024 (17) | 0.036 (5)* | |
H42A | 0.433 (2) | 0.9761 (13) | 0.3885 (16) | 0.036 (5)* | |
H51A | 0.68950 | 0.79680 | 0.30090 | 0.0360* | |
H52A | 0.78810 | 0.78060 | 0.43070 | 0.0360* | |
H61A | 0.64980 | 0.63620 | 0.27550 | 0.0400* | |
H62A | 0.81880 | 0.65580 | 0.30720 | 0.0400* | |
H2 | 0.93490 | 0.26820 | 0.67390 | 0.0280* | |
H4 | 0.86020 | 0.00950 | 0.53900 | 0.0260* | |
H6 | 0.72840 | 0.23250 | 0.32690 | 0.0270* | |
H32 | 1.026 (3) | −0.0185 (15) | 0.825 (2) | 0.067 (7)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O41A | 0.0673 (10) | 0.0278 (6) | 0.0267 (6) | 0.0133 (6) | −0.0098 (6) | −0.0068 (5) |
N1A | 0.0347 (9) | 0.0150 (6) | 0.0268 (7) | 0.0030 (6) | −0.0038 (7) | 0.0000 (5) |
N41A | 0.0314 (8) | 0.0216 (7) | 0.0259 (7) | 0.0066 (6) | −0.0006 (6) | −0.0016 (6) |
C2A | 0.0344 (10) | 0.0223 (8) | 0.0382 (9) | −0.0032 (7) | 0.0013 (8) | 0.0105 (7) |
C3A | 0.0349 (11) | 0.0273 (8) | 0.0324 (9) | 0.0030 (7) | 0.0122 (8) | 0.0065 (7) |
C4A | 0.0296 (10) | 0.0183 (8) | 0.0247 (8) | 0.0009 (7) | −0.0034 (7) | −0.0012 (6) |
C5A | 0.0500 (12) | 0.0167 (7) | 0.0233 (8) | 0.0047 (7) | 0.0105 (8) | 0.0025 (6) |
C6A | 0.0558 (13) | 0.0198 (8) | 0.0245 (8) | 0.0087 (8) | 0.0088 (8) | 0.0020 (6) |
C41A | 0.0298 (9) | 0.0213 (8) | 0.0266 (8) | 0.0019 (7) | 0.0044 (7) | −0.0006 (6) |
O11 | 0.0418 (8) | 0.0170 (5) | 0.0285 (6) | 0.0040 (5) | −0.0028 (5) | 0.0024 (4) |
O12 | 0.0814 (11) | 0.0200 (6) | 0.0343 (7) | −0.0081 (6) | −0.0166 (7) | −0.0063 (5) |
O31 | 0.0363 (7) | 0.0286 (6) | 0.0227 (6) | −0.0010 (5) | −0.0033 (5) | 0.0027 (4) |
O32 | 0.0415 (8) | 0.0226 (6) | 0.0255 (6) | −0.0028 (5) | −0.0033 (6) | 0.0085 (4) |
O51 | 0.0482 (8) | 0.0149 (5) | 0.0383 (7) | −0.0017 (5) | 0.0078 (6) | −0.0053 (4) |
O52 | 0.1003 (13) | 0.0318 (7) | 0.0324 (7) | 0.0136 (7) | −0.0285 (8) | −0.0090 (5) |
N51 | 0.0335 (9) | 0.0211 (7) | 0.0258 (7) | 0.0015 (6) | 0.0001 (6) | −0.0038 (5) |
C1 | 0.0267 (9) | 0.0177 (7) | 0.0210 (7) | −0.0002 (6) | 0.0020 (7) | −0.0007 (6) |
C2 | 0.0274 (9) | 0.0202 (7) | 0.0201 (7) | −0.0027 (7) | 0.0019 (6) | −0.0021 (5) |
C3 | 0.0213 (8) | 0.0213 (7) | 0.0219 (8) | −0.0010 (6) | 0.0040 (6) | 0.0030 (6) |
C4 | 0.0238 (8) | 0.0151 (7) | 0.0261 (8) | 0.0013 (6) | 0.0037 (7) | 0.0026 (6) |
C5 | 0.0230 (8) | 0.0177 (7) | 0.0227 (7) | 0.0007 (6) | 0.0027 (6) | −0.0026 (6) |
C6 | 0.0266 (9) | 0.0182 (7) | 0.0196 (7) | 0.0025 (6) | 0.0005 (6) | 0.0019 (6) |
C11 | 0.0393 (10) | 0.0184 (7) | 0.0223 (8) | 0.0007 (7) | 0.0019 (7) | −0.0013 (6) |
C31 | 0.0234 (9) | 0.0237 (8) | 0.0231 (8) | −0.0005 (7) | 0.0027 (7) | 0.0042 (6) |
O41A—C41A | 1.2390 (19) | C2A—H21A | 0.9700 |
O11—C11 | 1.251 (2) | C2A—H22A | 0.9700 |
O12—C11 | 1.253 (2) | C3A—H31A | 0.9700 |
O31—C31 | 1.2165 (18) | C3A—H32A | 0.9700 |
O32—C31 | 1.3211 (18) | C4A—H4A | 0.9800 |
O51—N51 | 1.2212 (16) | C5A—H51A | 0.9700 |
O52—N51 | 1.2211 (19) | C5A—H52A | 0.9700 |
O32—H32 | 0.93 (2) | C6A—H62A | 0.9700 |
N1A—C2A | 1.489 (2) | C6A—H61A | 0.9700 |
N1A—C6A | 1.490 (2) | C1—C2 | 1.398 (2) |
N41A—C41A | 1.329 (2) | C1—C11 | 1.515 (2) |
N1A—H12A | 0.98 (2) | C1—C6 | 1.387 (2) |
N1A—H11A | 0.93 (2) | C2—C3 | 1.387 (2) |
N41A—H41A | 0.822 (19) | C3—C4 | 1.388 (2) |
N41A—H42A | 0.940 (19) | C3—C31 | 1.499 (2) |
N51—C5 | 1.4650 (19) | C4—C5 | 1.387 (2) |
C2A—C3A | 1.516 (2) | C5—C6 | 1.382 (2) |
C3A—C4A | 1.531 (2) | C2—H2 | 0.9300 |
C4A—C41A | 1.522 (2) | C4—H4 | 0.9300 |
C4A—C5A | 1.522 (3) | C6—H6 | 0.9300 |
C5A—C6A | 1.521 (2) | ||
C31—O32—H32 | 110.7 (14) | C3A—C4A—H4A | 109.00 |
C2A—N1A—C6A | 112.81 (14) | C4A—C5A—H52A | 109.00 |
C2A—N1A—H12A | 107.6 (16) | C6A—C5A—H51A | 109.00 |
C6A—N1A—H11A | 109.9 (13) | C4A—C5A—H51A | 109.00 |
C2A—N1A—H11A | 108.4 (12) | C6A—C5A—H52A | 109.00 |
H11A—N1A—H12A | 110 (2) | H51A—C5A—H52A | 108.00 |
C6A—N1A—H12A | 107.7 (13) | N1A—C6A—H62A | 110.00 |
H41A—N41A—H42A | 117.9 (17) | C5A—C6A—H61A | 110.00 |
C41A—N41A—H42A | 118.4 (11) | C5A—C6A—H62A | 109.00 |
C41A—N41A—H41A | 123.6 (13) | N1A—C6A—H61A | 109.00 |
O51—N51—O52 | 123.29 (13) | H61A—C6A—H62A | 108.00 |
O51—N51—C5 | 118.79 (12) | C2—C1—C11 | 121.05 (13) |
O52—N51—C5 | 117.92 (12) | C6—C1—C11 | 119.88 (13) |
N1A—C2A—C3A | 111.79 (13) | C2—C1—C6 | 119.05 (13) |
C2A—C3A—C4A | 111.61 (14) | C1—C2—C3 | 120.97 (13) |
C5A—C4A—C41A | 111.49 (13) | C2—C3—C31 | 119.06 (13) |
C3A—C4A—C5A | 108.07 (13) | C4—C3—C31 | 120.66 (13) |
C3A—C4A—C41A | 111.09 (13) | C2—C3—C4 | 120.28 (13) |
C4A—C5A—C6A | 110.96 (13) | C3—C4—C5 | 117.90 (13) |
N1A—C6A—C5A | 110.71 (13) | N51—C5—C6 | 118.63 (13) |
O41A—C41A—C4A | 120.36 (14) | C4—C5—C6 | 122.73 (14) |
N41A—C41A—C4A | 117.70 (14) | N51—C5—C4 | 118.64 (13) |
O41A—C41A—N41A | 121.93 (14) | C1—C6—C5 | 119.06 (13) |
H21A—C2A—H22A | 108.00 | O11—C11—C1 | 118.34 (13) |
N1A—C2A—H22A | 109.00 | O12—C11—C1 | 116.37 (14) |
N1A—C2A—H21A | 109.00 | O11—C11—O12 | 125.26 (14) |
C3A—C2A—H22A | 109.00 | O31—C31—C3 | 122.42 (13) |
C3A—C2A—H21A | 109.00 | O32—C31—C3 | 112.74 (13) |
C2A—C3A—H31A | 109.00 | O31—C31—O32 | 124.84 (14) |
C4A—C3A—H31A | 109.00 | C1—C2—H2 | 120.00 |
H31A—C3A—H32A | 108.00 | C3—C2—H2 | 120.00 |
C2A—C3A—H32A | 109.00 | C3—C4—H4 | 121.00 |
C4A—C3A—H32A | 109.00 | C5—C4—H4 | 121.00 |
C41A—C4A—H4A | 109.00 | C1—C6—H6 | 120.00 |
C5A—C4A—H4A | 109.00 | C5—C6—H6 | 120.00 |
C6A—N1A—C2A—C3A | −52.98 (18) | C2—C1—C6—C5 | −0.5 (3) |
C2A—N1A—C6A—C5A | 54.44 (18) | C11—C1—C6—C5 | 177.98 (16) |
O51—N51—C5—C4 | −5.9 (2) | C2—C1—C11—O11 | −161.47 (16) |
O51—N51—C5—C6 | 173.90 (16) | C2—C1—C11—O12 | 20.3 (3) |
O52—N51—C5—C4 | 175.06 (17) | C6—C1—C11—O11 | 20.1 (3) |
O52—N51—C5—C6 | −5.2 (2) | C6—C1—C11—O12 | −158.15 (17) |
N1A—C2A—C3A—C4A | 54.6 (2) | C1—C2—C3—C4 | 0.9 (3) |
C2A—C3A—C4A—C5A | −57.05 (18) | C1—C2—C3—C31 | 179.86 (16) |
C2A—C3A—C4A—C41A | −179.65 (15) | C2—C3—C4—C5 | −0.2 (2) |
C5A—C4A—C41A—O41A | −88.89 (19) | C31—C3—C4—C5 | −179.10 (15) |
C5A—C4A—C41A—N41A | 90.25 (19) | C2—C3—C31—O31 | −8.3 (3) |
C3A—C4A—C41A—O41A | 31.7 (2) | C2—C3—C31—O32 | 172.04 (15) |
C3A—C4A—C5A—C6A | 58.75 (16) | C4—C3—C31—O31 | 170.71 (16) |
C41A—C4A—C5A—C6A | −178.89 (13) | C4—C3—C31—O32 | −9.0 (2) |
C3A—C4A—C41A—N41A | −149.14 (16) | C3—C4—C5—N51 | 178.81 (15) |
C4A—C5A—C6A—N1A | −58.01 (18) | C3—C4—C5—C6 | −1.0 (2) |
C6—C1—C2—C3 | −0.5 (3) | N51—C5—C6—C1 | −178.46 (15) |
C11—C1—C2—C3 | −179.03 (16) | C4—C5—C6—C1 | 1.3 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1A—H11A···O31i | 0.93 (2) | 2.06 (2) | 2.9236 (18) | 153.6 (17) |
N1A—H12A···O11 | 0.98 (2) | 1.87 (2) | 2.8229 (16) | 164 (2) |
N1A—H12A···O12 | 0.98 (2) | 2.45 (2) | 3.0366 (19) | 118.1 (17) |
N41A—H41A···O11ii | 0.822 (19) | 2.298 (19) | 3.0669 (19) | 155.9 (17) |
N41A—H42A···O41Aiii | 0.940 (19) | 1.996 (19) | 2.9321 (18) | 174.1 (16) |
O32—H32···O12iv | 0.93 (2) | 1.63 (2) | 2.5336 (17) | 164 (3) |
C2A—H22A···O52ii | 0.97 | 2.43 | 3.308 (2) | 151 |
C5A—H51A···O51v | 0.97 | 2.54 | 3.1187 (18) | 118 |
C6A—H61A···O41Avi | 0.97 | 2.48 | 3.2700 (19) | 138 |
Symmetry codes: (i) −x+2, y+1/2, −z+3/2; (ii) −x+1, y+1/2, −z+1/2; (iii) −x+1, −y+2, −z+1; (iv) −x+2, y−1/2, −z+3/2; (v) x, y+1, z; (vi) x, −y+3/2, z−1/2. |
2C6H13N2O8+·C8H4O42−·2H2O | Z = 1 |
Mr = 458.51 | F(000) = 246 |
Triclinic, P1 | Dx = 1.367 Mg m−3 |
Hall symbol: -P 1 | Melting point: 531 K |
a = 6.5099 (5) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 7.7777 (6) Å | Cell parameters from 3616 reflections |
c = 11.6865 (12) Å | θ = 3.4–28.7° |
α = 76.429 (8)° | µ = 0.11 mm−1 |
β = 76.968 (7)° | T = 200 K |
γ = 80.885 (7)° | Needle, colourless |
V = 556.89 (9) Å3 | 0.50 × 0.15 × 0.08 mm |
Oxford Gemini-S CCD are-detector diffractometer | 2177 independent reflections |
Radiation source: Enhance (Mo) X-ray source | 1746 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.024 |
ω scans | θmax = 26.0°, θmin = 3.4° |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009) | h = −8→8 |
Tmin = 0.965, Tmax = 0.990 | k = −9→9 |
6562 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)] = 0.034 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.093 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0583P)2] where P = (Fo2 + 2Fc2)/3 |
2177 reflections | (Δ/σ)max < 0.001 |
169 parameters | Δρmax = 0.23 e Å−3 |
0 restraints | Δρmin = −0.16 e Å−3 |
2C6H13N2O8+·C8H4O42−·2H2O | γ = 80.885 (7)° |
Mr = 458.51 | V = 556.89 (9) Å3 |
Triclinic, P1 | Z = 1 |
a = 6.5099 (5) Å | Mo Kα radiation |
b = 7.7777 (6) Å | µ = 0.11 mm−1 |
c = 11.6865 (12) Å | T = 200 K |
α = 76.429 (8)° | 0.50 × 0.15 × 0.08 mm |
β = 76.968 (7)° |
Oxford Gemini-S CCD are-detector diffractometer | 2177 independent reflections |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009) | 1746 reflections with I > 2σ(I) |
Tmin = 0.965, Tmax = 0.990 | Rint = 0.024 |
6562 measured reflections |
R[F2 > 2σ(F2)] = 0.034 | 0 restraints |
wR(F2) = 0.093 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | Δρmax = 0.23 e Å−3 |
2177 reflections | Δρmin = −0.16 e Å−3 |
169 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 | 0.02732 (15) | 0.38666 (12) | 0.39711 (9) | 0.0283 (3) | |
N1A | 0.49004 (18) | 0.84055 (14) | 0.16744 (10) | 0.0228 (3) | |
N41A | 0.3297 (2) | 0.23446 (15) | 0.44750 (11) | 0.0301 (4) | |
C2A | 0.6401 (2) | 0.69868 (17) | 0.22515 (12) | 0.0230 (4) | |
C3A | 0.5391 (2) | 0.52630 (16) | 0.27457 (12) | 0.0208 (4) | |
C4A | 0.32588 (19) | 0.55264 (16) | 0.36062 (11) | 0.0184 (4) | |
C5A | 0.1803 (2) | 0.70710 (16) | 0.30251 (12) | 0.0220 (4) | |
C6A | 0.2890 (2) | 0.87498 (17) | 0.25378 (13) | 0.0270 (4) | |
C41A | 0.2150 (2) | 0.38311 (16) | 0.40264 (11) | 0.0200 (4) | |
O11 | 0.37675 (16) | 0.82742 (12) | −0.04688 (9) | 0.0311 (3) | |
O12 | 0.17970 (16) | 0.92206 (12) | −0.18601 (9) | 0.0326 (3) | |
C1 | 0.1102 (2) | 0.65006 (16) | −0.04709 (11) | 0.0183 (4) | |
C2 | −0.0742 (2) | 0.63855 (16) | −0.08456 (12) | 0.0219 (4) | |
C6 | 0.1841 (2) | 0.50915 (16) | 0.03731 (11) | 0.0206 (4) | |
C11 | 0.2303 (2) | 0.81224 (16) | −0.09757 (11) | 0.0208 (4) | |
O1W | 0.79377 (16) | 0.11269 (13) | 0.41900 (10) | 0.0298 (3) | |
H4A | 0.35440 | 0.58400 | 0.43160 | 0.0220* | |
H11A | 0.457 (3) | 0.811 (2) | 0.0983 (15) | 0.042 (5)* | |
H12A | 0.554 (3) | 0.952 (2) | 0.1349 (16) | 0.052 (5)* | |
H21A | 0.67890 | 0.73720 | 0.28980 | 0.0280* | |
H22A | 0.76840 | 0.67870 | 0.16660 | 0.0280* | |
H31A | 0.63500 | 0.43890 | 0.31670 | 0.0250* | |
H32A | 0.51720 | 0.48040 | 0.20840 | 0.0250* | |
H41A | 0.266 (3) | 0.130 (2) | 0.4741 (17) | 0.054 (5)* | |
H42A | 0.477 (3) | 0.233 (2) | 0.4429 (15) | 0.046 (5)* | |
H51A | 0.13640 | 0.67330 | 0.23760 | 0.0260* | |
H52A | 0.05400 | 0.73060 | 0.36160 | 0.0260* | |
H61A | 0.19520 | 0.96740 | 0.21370 | 0.0320* | |
H62A | 0.31990 | 0.91630 | 0.31950 | 0.0320* | |
H2 | −0.12420 | 0.73060 | −0.14170 | 0.0260* | |
H6 | 0.30850 | 0.51440 | 0.06220 | 0.0250* | |
H11W | 0.876 (3) | 0.189 (2) | 0.4192 (15) | 0.044 (5)* | |
H12W | 0.810 (3) | 0.102 (2) | 0.3396 (17) | 0.044 (5)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O41A | 0.0233 (6) | 0.0260 (5) | 0.0360 (6) | −0.0110 (4) | −0.0049 (4) | −0.0025 (4) |
N1A | 0.0258 (6) | 0.0174 (5) | 0.0238 (6) | −0.0098 (5) | −0.0039 (5) | 0.0023 (5) |
N41A | 0.0265 (7) | 0.0181 (6) | 0.0404 (7) | −0.0075 (5) | −0.0037 (6) | 0.0048 (5) |
C2A | 0.0183 (7) | 0.0237 (7) | 0.0260 (7) | −0.0069 (5) | −0.0031 (5) | −0.0011 (5) |
C3A | 0.0180 (7) | 0.0175 (6) | 0.0245 (7) | −0.0032 (5) | −0.0041 (5) | 0.0010 (5) |
C4A | 0.0195 (7) | 0.0175 (6) | 0.0180 (6) | −0.0055 (5) | −0.0034 (5) | −0.0012 (5) |
C5A | 0.0181 (7) | 0.0184 (6) | 0.0266 (7) | −0.0032 (5) | −0.0012 (5) | −0.0012 (5) |
C6A | 0.0262 (8) | 0.0166 (6) | 0.0346 (8) | −0.0017 (5) | −0.0035 (6) | −0.0013 (6) |
C41A | 0.0228 (7) | 0.0185 (6) | 0.0171 (6) | −0.0063 (5) | 0.0006 (5) | −0.0023 (5) |
O11 | 0.0333 (6) | 0.0305 (5) | 0.0332 (6) | −0.0195 (4) | −0.0111 (5) | 0.0010 (4) |
O12 | 0.0415 (6) | 0.0215 (5) | 0.0345 (6) | −0.0135 (4) | −0.0131 (5) | 0.0067 (4) |
C1 | 0.0183 (7) | 0.0163 (6) | 0.0200 (6) | −0.0047 (5) | −0.0003 (5) | −0.0049 (5) |
C2 | 0.0238 (7) | 0.0163 (6) | 0.0245 (7) | −0.0040 (5) | −0.0073 (6) | 0.0013 (5) |
C6 | 0.0182 (7) | 0.0211 (6) | 0.0242 (7) | −0.0053 (5) | −0.0065 (5) | −0.0038 (5) |
C11 | 0.0226 (7) | 0.0176 (6) | 0.0224 (7) | −0.0072 (5) | −0.0006 (5) | −0.0051 (5) |
O1W | 0.0315 (6) | 0.0240 (5) | 0.0336 (6) | −0.0134 (4) | −0.0084 (5) | 0.0036 (4) |
O41A—C41A | 1.2336 (17) | C5A—C6A | 1.5139 (19) |
O11—C11 | 1.2637 (17) | C2A—H22A | 0.9700 |
O12—C11 | 1.2476 (16) | C2A—H21A | 0.9700 |
O1W—H12W | 0.932 (19) | C3A—H31A | 0.9700 |
O1W—H11W | 0.861 (18) | C3A—H32A | 0.9700 |
N1A—C6A | 1.4909 (18) | C4A—H4A | 0.9800 |
N1A—C2A | 1.4943 (18) | C5A—H52A | 0.9700 |
N41A—C41A | 1.3370 (18) | C5A—H51A | 0.9700 |
N1A—H12A | 0.979 (17) | C6A—H61A | 0.9700 |
N1A—H11A | 0.966 (17) | C6A—H62A | 0.9700 |
N41A—H42A | 0.95 (2) | C1—C6 | 1.3947 (18) |
N41A—H41A | 0.927 (17) | C1—C11 | 1.5184 (18) |
C2A—C3A | 1.5192 (19) | C1—C2 | 1.3894 (19) |
C3A—C4A | 1.5353 (18) | C2—C6i | 1.3860 (18) |
C4A—C5A | 1.5327 (18) | C2—H2 | 0.9300 |
C4A—C41A | 1.5292 (18) | C6—H6 | 0.9300 |
H11W—O1W—H12W | 106.9 (16) | H31A—C3A—H32A | 108.00 |
C2A—N1A—C6A | 111.57 (10) | C2A—C3A—H31A | 109.00 |
C2A—N1A—H12A | 111.2 (11) | C5A—C4A—H4A | 108.00 |
C6A—N1A—H11A | 109.2 (12) | C41A—C4A—H4A | 108.00 |
C2A—N1A—H11A | 111.9 (10) | C3A—C4A—H4A | 108.00 |
H11A—N1A—H12A | 103.9 (15) | C4A—C5A—H52A | 109.00 |
C6A—N1A—H12A | 108.8 (10) | C6A—C5A—H51A | 109.00 |
H41A—N41A—H42A | 120.6 (15) | C6A—C5A—H52A | 109.00 |
C41A—N41A—H42A | 120.5 (10) | H51A—C5A—H52A | 108.00 |
C41A—N41A—H41A | 118.5 (12) | C4A—C5A—H51A | 109.00 |
N1A—C2A—C3A | 110.62 (11) | N1A—C6A—H61A | 110.00 |
C2A—C3A—C4A | 112.00 (11) | N1A—C6A—H62A | 110.00 |
C3A—C4A—C41A | 112.20 (10) | C5A—C6A—H62A | 110.00 |
C5A—C4A—C41A | 110.45 (11) | H61A—C6A—H62A | 108.00 |
C3A—C4A—C5A | 110.71 (10) | C5A—C6A—H61A | 110.00 |
C4A—C5A—C6A | 111.97 (11) | C2—C1—C6 | 118.76 (12) |
N1A—C6A—C5A | 110.47 (11) | C2—C1—C11 | 120.76 (11) |
O41A—C41A—C4A | 120.74 (11) | C6—C1—C11 | 120.48 (12) |
N41A—C41A—C4A | 116.78 (12) | C1—C2—C6i | 120.46 (12) |
O41A—C41A—N41A | 122.47 (12) | C1—C6—C2i | 120.77 (12) |
N1A—C2A—H21A | 110.00 | O11—C11—C1 | 117.52 (11) |
C3A—C2A—H21A | 110.00 | O12—C11—C1 | 118.61 (12) |
C3A—C2A—H22A | 110.00 | O11—C11—O12 | 123.87 (12) |
N1A—C2A—H22A | 110.00 | C1—C2—H2 | 120.00 |
H21A—C2A—H22A | 108.00 | C6i—C2—H2 | 120.00 |
C2A—C3A—H32A | 109.00 | C1—C6—H6 | 120.00 |
C4A—C3A—H31A | 109.00 | C2i—C6—H6 | 120.00 |
C4A—C3A—H32A | 109.00 | ||
C6A—N1A—C2A—C3A | 58.63 (14) | C4A—C5A—C6A—N1A | 55.90 (14) |
C2A—N1A—C6A—C5A | −59.19 (14) | C6—C1—C2—C6i | 1.03 (19) |
N1A—C2A—C3A—C4A | −54.73 (14) | C11—C1—C2—C6i | −179.41 (12) |
C2A—C3A—C4A—C5A | 51.45 (14) | C2—C1—C6—C2i | −1.03 (19) |
C2A—C3A—C4A—C41A | 175.35 (11) | C11—C1—C6—C2i | 179.41 (12) |
C3A—C4A—C5A—C6A | −52.06 (14) | C2—C1—C11—O11 | 169.25 (12) |
C41A—C4A—C5A—C6A | −176.96 (11) | C2—C1—C11—O12 | −10.82 (18) |
C3A—C4A—C41A—O41A | −130.14 (13) | C6—C1—C11—O11 | −11.19 (18) |
C3A—C4A—C41A—N41A | 51.36 (15) | C6—C1—C11—O12 | 168.74 (12) |
C5A—C4A—C41A—O41A | −6.10 (16) | C1—C2—C6i—C1i | −1.05 (19) |
C5A—C4A—C41A—N41A | 175.41 (11) |
Symmetry code: (i) −x, −y+1, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1A—H11A···O11 | 0.966 (17) | 1.856 (18) | 2.7937 (16) | 162.9 (14) |
N1A—H12A···O11ii | 0.979 (17) | 1.847 (17) | 2.8030 (15) | 164.7 (17) |
N1A—H12A···O12ii | 0.979 (17) | 2.367 (19) | 3.1200 (16) | 133.3 (14) |
N41A—H41A···O1Wiii | 0.927 (17) | 2.045 (17) | 2.9181 (16) | 156.5 (17) |
N41A—H42A···O1W | 0.95 (2) | 2.111 (19) | 2.9870 (17) | 153.2 (14) |
O1W—H11W···O41Aiv | 0.861 (18) | 1.892 (18) | 2.7410 (15) | 168.7 (17) |
O1W—H12W···O12v | 0.932 (19) | 1.833 (19) | 2.7632 (15) | 175.6 (19) |
C6A—H61A···O12vi | 0.97 | 2.52 | 3.3773 (18) | 147 |
Symmetry codes: (ii) −x+1, −y+2, −z; (iii) −x+1, −y, −z+1; (iv) x+1, y, z; (v) −x+1, −y+1, −z; (vi) −x, −y+2, −z. |
Experimental details
(I) | (II) | (III) | (IV) | |
Crystal data | ||||
Chemical formula | C6H13N2O+·C8H4NO6− | C6H13N2O+·C8H3Cl2O4− | C6H13N2O+·C8H4NO6− | 2C6H13N2O8+·C8H4O42−·2H2O |
Mr | 339.31 | 363.19 | 339.31 | 458.51 |
Crystal system, space group | Monoclinic, P21/n | Monoclinic, P21/n | Monoclinic, P21/c | Triclinic, P1 |
Temperature (K) | 200 | 200 | 200 | 200 |
a, b, c (Å) | 5.8637 (5), 11.2707 (8), 23.0268 (19) | 6.6897 (4), 9.7392 (5), 24.1222 (13) | 9.4117 (4), 14.3552 (5), 11.4490 (5) | 6.5099 (5), 7.7777 (6), 11.6865 (12) |
α, β, γ (°) | 90, 93.082 (8), 90 | 90, 92.479 (4), 90 | 90, 103.787 (4), 90 | 76.429 (8), 76.968 (7), 80.885 (7) |
V (Å3) | 1519.6 (2) | 1570.15 (15) | 1502.27 (11) | 556.89 (9) |
Z | 4 | 4 | 4 | 1 |
Radiation type | Mo Kα | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.12 | 0.44 | 0.12 | 0.11 |
Crystal size (mm) | 0.40 × 0.40 × 0.12 | 0.30 × 0.25 × 0.20 | 0.45 × 0.40 × 0.18 | 0.50 × 0.15 × 0.08 |
Data collection | ||||
Diffractometer | Oxford Gemini-S CCD area-detector diffractometer | Oxford Gemini S CCD area-detector diffractometer | Oxford Gemini-S CCD area-detector diffractometer | Oxford Gemini-S CCD are-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) | Multi-scan (CrysAlis PRO; Oxford Diffraction, 2009) |
Tmin, Tmax | 0.915, 0.980 | 0.908, 0.980 | 0.98, 0.99 | 0.965, 0.990 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 10364, 2989, 2375 | 19231, 3084, 2777 | 9866, 2940, 2284 | 6562, 2177, 1746 |
Rint | 0.023 | 0.028 | 0.025 | 0.024 |
(sin θ/λ)max (Å−1) | 0.617 | 0.617 | 0.617 | 0.617 |
Refinement | ||||
R[F2 > 2σ(F2)], wR(F2), S | 0.046, 0.114, 1.05 | 0.046, 0.113, 1.30 | 0.037, 0.106, 1.01 | 0.034, 0.093, 1.05 |
No. of reflections | 2989 | 3084 | 2940 | 2177 |
No. of parameters | 233 | 224 | 237 | 169 |
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 | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.35, −0.26 | 0.37, −0.29 | 0.35, −0.24 | 0.23, −0.16 |
Computer programs: CrysAlis PRO (Oxford Diffraction, 2009), SIR92 (Altomare et al., 1994), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008) within WinGX (Farrugia, 1999), PLATON (Spek, 2009).
D—H···A | D—H | H···A | D···A | D—H···A |
N1A—H11A···O11i | 0.98 (3) | 1.77 (3) | 2.729 (2) | 163 (2) |
N1A—H12A···O21 | 0.93 (3) | 1.92 (3) | 2.803 (2) | 158 (2) |
N41A—H42A···O41Aii | 0.92 (3) | 1.99 (3) | 2.907 (3) | 176 (2) |
N41A—H43A···O42iii | 0.83 (3) | 2.40 (3) | 3.200 (3) | 161 (3) |
O22—H22···O12iv | 0.99 | 1.47 | 2.4562 (19) | 179 |
Symmetry codes: (i) x−1, y, z; (ii) −x+1, −y+2, −z+1; (iii) x−3/2, −y+3/2, z−1/2; (iv) −x+1/2, y+1/2, −z+3/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1A—H11A···O11 | 0.92 (4) | 1.90 (4) | 2.810 (3) | 170 (3) |
N1A—H12A···O22i | 0.87 (4) | 1.96 (4) | 2.753 (3) | 152 (3) |
N41A—H41A···O21ii | 0.82 (4) | 2.48 (4) | 3.158 (3) | 142 (4) |
N41A—H42A···O41Aiii | 0.93 (4) | 2.19 (4) | 3.086 (4) | 163 (3) |
O12—H12···O21 | 1.00 | 1.40 | 2.393 (3) | 180 |
Symmetry codes: (i) x, y−1, z; (ii) −x+3/2, y−1/2, −z+1/2; (iii) −x+3/2, y+1/2, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1A—H11A···O31i | 0.93 (2) | 2.06 (2) | 2.9236 (18) | 153.6 (17) |
N1A—H12A···O11 | 0.98 (2) | 1.87 (2) | 2.8229 (16) | 164 (2) |
N1A—H12A···O12 | 0.98 (2) | 2.45 (2) | 3.0366 (19) | 118.1 (17) |
N41A—H41A···O11ii | 0.822 (19) | 2.298 (19) | 3.0669 (19) | 155.9 (17) |
N41A—H42A···O41Aiii | 0.940 (19) | 1.996 (19) | 2.9321 (18) | 174.1 (16) |
O32—H32···O12iv | 0.93 (2) | 1.63 (2) | 2.5336 (17) | 164 (3) |
Symmetry codes: (i) −x+2, y+1/2, −z+3/2; (ii) −x+1, y+1/2, −z+1/2; (iii) −x+1, −y+2, −z+1; (iv) −x+2, y−1/2, −z+3/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1A—H11A···O11 | 0.966 (17) | 1.856 (18) | 2.7937 (16) | 162.9 (14) |
N1A—H12A···O11i | 0.979 (17) | 1.847 (17) | 2.8030 (15) | 164.7 (17) |
N1A—H12A···O12i | 0.979 (17) | 2.367 (19) | 3.1200 (16) | 133.3 (14) |
N41A—H41A···O1Wii | 0.927 (17) | 2.045 (17) | 2.9181 (16) | 156.5 (17) |
N41A—H42A···O1W | 0.95 (2) | 2.111 (19) | 2.9870 (17) | 153.2 (14) |
O1W—H11W···O41Aiii | 0.861 (18) | 1.892 (18) | 2.7410 (15) | 168.7 (17) |
O1W—H12W···O12iv | 0.932 (19) | 1.833 (19) | 2.7632 (15) | 175.6 (19) |
Symmetry codes: (i) −x+1, −y+2, −z; (ii) −x+1, −y, −z+1; (iii) x+1, y, z; (iv) −x+1, −y+1, −z. |
Our project of investigating the hydrogen-bonding modes in salts of the Lewis base 4-piperidinecarboxamide (isonipecotamide; INIPA) with carboxylic acids has provided a considerable number of structures, the majority being anhydrous 1:1 salts with aromatic acids (Smith & Wermuth, 2010d,f, 2011a). Solvated examples are the nicotinate (a partial hydrate; Smith & Wermuth, 2011c), the acetate (a monohydrate; Smith & Wermuth, 2010e) and the 6-carboxypyridine-2-carboxylate (a methanol monosolvate; Smith & Wermuth, 2011c), while with o-phthalic acid a 1:1 hydrogen phthalate–phthalic acid salt adduct is found (Smith & Wermuth, 2011b). Anhydrous picrates are also known (Smith & Wermuth, 2010c), together with a 2:1 salt with bipyridine-4,4'-disulfonate (Smith et al., 2010). In the light of the unusual formation of a 1:1:1 cation–anion–phthalic acid adduct from a 1:1 stoichiometric reaction (Smith & Wermuth, 2011b), our further aim was to investigate the nature of the products formed from similar reactions of INIPA with a series of aromatic dicarboxylic acids in various alcoholic and aqueous alcoholic solutions. Examples included 4-nitrophthalic acid (NPHA), 4,5-dichlorophthalic acid (DCPA), 5-nitroisophthalic acid (NIPA) and terephthalic acid (TPA), which provided good crystalline products. The 1:1 anhydrous salts of 4-carbamoylpiperidinium 2-carboxy-4-nitrobenzoate, (I), 4-carbamoylpiperidinium 2-carboxy-4,5-dichlorobenzoate, (II), and 4-carbamoylpiperidinium 3-carboxy-5-nitrobenzoate, (III), were obtained, and the 2:1 hydrated salt of the terephthalate, bis(4-carbamoylpiperidinium) benzene-1,2-dicarboxylate dihydrate, (IV), was also identified. The structures of (I)–(IV) are described here.
With the 1:1 salts, (I)–(III) (Figs. 1–4), proton transfer has occurred to the hetero N atom of the piperidine ring, while with the terephthalate salt, (IV), it involves a two-proton transfer with the formation of a dianion. The resulting piperidinium group of the anion in each salt, together with the hydrogen donor and acceptor p-related substituent amide group, are subsequently involved in hydrogen-bonding interactions. These result in supramolecular structures, which are three-dimensional in (I), (III) and (IV) and one-dimensional in (II) (Figs. 5–8). A feature of the hydrogen-bonding in (I) and (III) is the presence of the centrosymmetric cyclic homomolecular N—H···O hydrogen-bonded amide–amide motif (Allen et al., 1998), with graph set R22(8) (Etter et al., 1990; Bernstein et al., 1995). This motif has now been found in 11 of the 24 known structures of INIPA proton-transfer salts, including the present examples.
In the structure of the 1:1 INIPA salt with 4-nitrophthalic acid, (I), the 1-carboxy rather than the 2-carboxy group is deprotonated (Fig. 1), giving a primary piperidinium N—H···Ocarboxyl ion-pair interaction. The hydrogen phthalate anions form head-to-tail hydrogen-bonded chain substructures featuring short carboxylic acid O—H···Ocarboxyl hydrogen bonds [graph set C(7); Fig. 5]. These substructures are common among hydrogen phthalate salt structures (Glidewell et al., 2005; Smith & Wermuth, 2010b). The peripherally bound INIPA anions give structure extension across (011) through classic centrosymmetric R22(8) amide–amide N—H···O hydrogen-bonded dimer associations. In addition, amide N—H···Onitro and piperidinium N—H···Ocarboxyl associations (Table 1) result in a three-dimensional structure. In the nitrophthalate anion, the carboxylate group is rotated significantly out of the benzene plane [torsion angle C2—C1—C11—O12 = -76.7 (2)°], while the carboxylic acid and nitro groups are essentially coplanar with the benzene plane [torsion angles C1—C2—C21—O22 = 169.25 (16)° and C3—C4—N4—O42 = -174.03 (18)°, respectively].
In the structure of the 1:1 INIPA salt with 4,5-dichlorophthalic acid, (II) (Fig. 2), one of the two primary piperidinium cation–anion associations also involves a secondary longer three-centre interaction [N1A···O12 = 3.044 (4) Å and N1A—H11A···O12 = 118 (3)° Please check - 3.042 (4) and 117 (3) in CIF data tables], which is probably an artefact of the overall cyclic hydrogen-bonding motif. This association [graph set R43(17)] involves piperidinium N—H···Ocarboxy, amide N—H···Ocarboxy and amide N—H···Oamide hydrogen bonds from two INIPA cations and one DCPA anion, and is closed by the intramolecular carboxylic acid O—H···Ocarboxyl hydrogen bond (Fig. 6). A second cyclic association [graph set R33(13)] involves one piperidinium and two amide–carboxyl hydrogen bonds (Table 2), and the two motifs link the DCPA anions peripherally into head-to-head N—H···O amide-linked cation chain substructures. This results in one-dimensional ribbon structures which extend along the b cell direction. In the crystal structures of DCPA salts with Lewis bases, this low dimensionality in the hydrogen-bonded structures is commonly associated with the `planar' DCPA monoanion, which features the cyclic intramolecular carboxylic acid O—H···Ocarboxyl hydrogen-bonding association [graph set S(7); Smith et al., 2010]. The short hydrogen bond [2.393 (3) Å] in the `planar' DCPA anion in (II) results in a C2—C1—C11—O11 torsion angle of 174.1 (3)°, while another feature of this conformation is elongation of the C1—C11 and C2—C21 bonds [1.522 (4) and 1.534 (4) Å, respectively] and distortion of the external bond angles at C1 and C2 [128.8 (2) and 128.1 (2)°, respectively; Smith et al., 2010].
In the structure of the hydrogen 5-nitroisphthalate salt, (III) (Fig. 3), the primary cation–anion interaction has a second longer N—H···Ocarboxyl contact [N1A···O12 = 3.0366 (17) Å and N1A—H12A···O12 = 118.1 (7)° Please check - 3.0366 (19) and 118.1 (17) in CIF data tables], similar to that in (II). The cation–anion associations are also similar in some respects to those of (I). The hydrogen isophthalate anions give zig-zag head-to-tail hydrogen-bonded chain substructures through carboxylic acid O—H···Ocarboxyl hydrogen bonds (Table 3) but these are classified as graph set C(8), rather than C(7) as in (I). In addition, the centrosymmetric R22(8) hydrogen-bonded INPA amide–amide dimers give peripheral structure extension through piperidinium N—H···Ocarboxyl hydrogen bonds which involve two anions, enclosing cyclic R33(10) rings (Fig. 7). The three-dimensional framework structure is generated through amide N—H···Ocarboxyl hydrogen-bonding associations. The nitro O atoms are unassociated, except for weak intermolecular cation C—H···O associations [C2A···O52ii = 3.308 (2) Å and C2A—H22A···O52ii = 151°] (see Table 3 for symmetry code). The anion in (III) is essentially planar, but with the carboxylate group rotated slightly out of the plane of the benzene ring [torsion angle C2—C1—C11—O11 = -161.47 (16)°, cf. C2—C3—C31—O32 = 172.04 (15)° (the carboxylic acid group) and C4—C5—N51—O52 = 175.06 (17)° (the nitro group)].
With the terephthalate salt, (IV), one of the piperidinium N—H···Ocarboxyl hydrogen bonds seen in Fig. 4 is accompanied by an asymmetric three-centre N–H···O,O'carboxyl interaction [graph set R21(4)] with the centrosymmetric terephthalate dianion (Fig. 8). This second association links two INIPA cations to the terephthalate dianion, which is extended longitudinally in the approximate b cell direction through centrosymmetric cyclic water-bridged amide–amide associations [graph set R44(12)]. The water molecules also act as acceptors in bridging these chains laterally through amide N—H···O hydrogen bonds (Table 4), forming centrosymmetric cyclic R42(8) associations. The lateral piperidinium N—H···Ocarboxyl hydrogen bonds shown in Fig. 4, together with the water O—H···Ocarboxyl associations [graph sets R43(10), R33(18) and R64(22)], complete a three-dimensional framework structure. The centrosymmetric terephthalate dianion deviates slightly from planarity [torsion angle C2—C1—C11—O11 = 169.25 (12)°].
The structures reported here further demonstrate the utility of the isonipecotamide cation as a synthon for the generation of stable hydrogen-bonded structures. An additional example of INIPA cation–anion association is also shown in the asymmetric three-centre piperidinium N—H···O,O'carboxyl interaction in the first-reported structure of a 2:1 isonipecotamide carboxylate salt.