









Supporting information
![]() | Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270110045750/su3056sup1.cif |
![]() | Structure factor file (CIF format) https://doi.org/10.1107/S0108270110045750/su3056Isup2.hkl |
![]() | Structure factor file (CIF format) https://doi.org/10.1107/S0108270110045750/su3056IIsup3.hkl |
![]() | Structure factor file (CIF format) https://doi.org/10.1107/S0108270110045750/su3056IIIsup4.hkl |
![]() | Structure factor file (CIF format) https://doi.org/10.1107/S0108270110045750/su3056IVsup5.hkl |
CCDC references: 810028; 810029; 810030; 810031
The title compounds were synthesized by heating together for 10 min under reflux 4-carbamoylpiperidine (isonipecotamide) (1 mmol) with 2-nitrobenzoic acid (1 mmol) [for (I)], 3-nitrobenzoic acid (1 mmol) [for (II)], 4-nitrobenzic acid (1 mmol) [for (III)] or 3,5-dinitrobenzoic acid (1 mmol) [for (IV)] in 50% ethanol–water (50 ml). After concentration to ca 30 ml, partial room-temperature evaporation of the hot-filtered solutions gave colourless prisms of (I)–(III) [CIF states needle for (I) - please clarify] (m.p. 429, 452 and 537–539 K, respectively) and yellow plates of (IV) (m.p. 473–475 K).
H atoms involved in hydrogen-bonding interactions were located in difference electron-density maps and were freely refined. The other H atoms were included in calculated positions and refined using a riding model approximation, with C—H(aromatic) = 0.93 Å and C—H(aliphatic) = 0.97–0.98 Å, and 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); 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+·C7H4NO4− | F(000) = 1248 |
Mr = 295.30 | Dx = 1.354 Mg m−3 |
Monoclinic, C2/c | Melting point: 429 K |
Hall symbol: -C 2yc | Mo Kα radiation, λ = 0.71073 Å |
a = 29.035 (3) Å | Cell parameters from 3737 reflections |
b = 9.7660 (9) Å | θ = 3.9–27.1° |
c = 10.5779 (12) Å | µ = 0.11 mm−1 |
β = 105.020 (12)° | T = 200 K |
V = 2897.0 (5) Å3 | Needle, colourless |
Z = 8 | 0.50 × 0.26 × 0.12 mm |
Oxford Gemini-S Ultra CCD area-detector diffractometer | 2832 independent reflections |
Radiation source: Enhance (Mo) X-ray tube | 2076 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.029 |
Detector resolution: 16.077 pixels mm-1 | θmax = 26.0°, θmin = 3.9° |
ω scans | h = −35→34 |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009) | k = −12→12 |
Tmin = 0.940, Tmax = 0.980 | l = −12→13 |
9784 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)] = 0.035 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.087 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.93 | w = 1/[σ2(Fo2) + (0.0528P)2] where P = (Fo2 + 2Fc2)/3 |
2832 reflections | (Δ/σ)max = 0.001 |
206 parameters | Δρmax = 0.15 e Å−3 |
0 restraints | Δρmin = −0.17 e Å−3 |
C6H13N2O+·C7H4NO4− | V = 2897.0 (5) Å3 |
Mr = 295.30 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 29.035 (3) Å | µ = 0.11 mm−1 |
b = 9.7660 (9) Å | T = 200 K |
c = 10.5779 (12) Å | 0.50 × 0.26 × 0.12 mm |
β = 105.020 (12)° |
Oxford Gemini-S Ultra CCD area-detector diffractometer | 2832 independent reflections |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009) | 2076 reflections with I > 2σ(I) |
Tmin = 0.940, Tmax = 0.980 | Rint = 0.029 |
9784 measured reflections |
R[F2 > 2σ(F2)] = 0.035 | 0 restraints |
wR(F2) = 0.087 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.93 | Δρmax = 0.15 e Å−3 |
2832 reflections | Δρmin = −0.17 e Å−3 |
206 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 | 0.05495 (4) | 0.52146 (13) | −0.05296 (10) | 0.0523 (4) | |
N1A | 0.21327 (5) | 0.68599 (12) | 0.11530 (12) | 0.0316 (4) | |
N41A | 0.04668 (5) | 0.52323 (15) | 0.15267 (13) | 0.0445 (5) | |
C2A | 0.20653 (5) | 0.54186 (14) | 0.06848 (13) | 0.0339 (4) | |
C3A | 0.15361 (5) | 0.51160 (14) | 0.01937 (13) | 0.0302 (4) | |
C4A | 0.12662 (4) | 0.54143 (13) | 0.12264 (12) | 0.0282 (4) | |
C5A | 0.13775 (5) | 0.68601 (14) | 0.17882 (13) | 0.0313 (4) | |
C6A | 0.19110 (5) | 0.71037 (15) | 0.22545 (13) | 0.0328 (4) | |
C41A | 0.07312 (5) | 0.52602 (15) | 0.06678 (13) | 0.0351 (5) | |
O11 | 0.34239 (4) | 0.65328 (10) | 0.08264 (10) | 0.0506 (4) | |
O12 | 0.30583 (3) | 0.76968 (10) | 0.20967 (9) | 0.0359 (3) | |
O21 | 0.29603 (4) | 0.52504 (10) | 0.35102 (10) | 0.0423 (3) | |
O22 | 0.30846 (4) | 0.65247 (12) | 0.52331 (12) | 0.0608 (5) | |
N2 | 0.32150 (4) | 0.59869 (12) | 0.43449 (11) | 0.0362 (4) | |
C1 | 0.37897 (5) | 0.66222 (13) | 0.30968 (13) | 0.0320 (4) | |
C2 | 0.37084 (5) | 0.62362 (13) | 0.42810 (13) | 0.0316 (4) | |
C3 | 0.40692 (6) | 0.60594 (16) | 0.54097 (15) | 0.0473 (6) | |
C4 | 0.45340 (6) | 0.6284 (2) | 0.53539 (19) | 0.0635 (7) | |
C5 | 0.46291 (6) | 0.6659 (2) | 0.4197 (2) | 0.0656 (7) | |
C6 | 0.42626 (5) | 0.68194 (17) | 0.30750 (17) | 0.0487 (6) | |
C11 | 0.33875 (5) | 0.69610 (14) | 0.19034 (13) | 0.0321 (4) | |
H4A | 0.13700 | 0.47550 | 0.19420 | 0.0340* | |
H11A | 0.1983 (6) | 0.7453 (17) | 0.0468 (17) | 0.052 (5)* | |
H12A | 0.2461 (6) | 0.7102 (15) | 0.1426 (14) | 0.043 (4)* | |
H21A | 0.22090 | 0.48000 | 0.13940 | 0.0410* | |
H22A | 0.22200 | 0.52810 | −0.00160 | 0.0410* | |
H31A | 0.14930 | 0.41600 | −0.00600 | 0.0360* | |
H32A | 0.14030 | 0.56670 | −0.05770 | 0.0360* | |
H41A | 0.0150 (7) | 0.5153 (16) | 0.1217 (17) | 0.053 (5)* | |
H42A | 0.0607 (5) | 0.5226 (15) | 0.2368 (16) | 0.039 (4)* | |
H51A | 0.12370 | 0.75290 | 0.11210 | 0.0380* | |
H52A | 0.12350 | 0.69830 | 0.25150 | 0.0380* | |
H61A | 0.19720 | 0.80370 | 0.25660 | 0.0390* | |
H62A | 0.20500 | 0.64890 | 0.29730 | 0.0390* | |
H3 | 0.40020 | 0.57960 | 0.61870 | 0.0570* | |
H4 | 0.47830 | 0.61800 | 0.61040 | 0.0760* | |
H5 | 0.49430 | 0.68060 | 0.41680 | 0.0790* | |
H6 | 0.43330 | 0.70620 | 0.22950 | 0.0580* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O41A | 0.0292 (6) | 0.0985 (9) | 0.0272 (6) | −0.0100 (5) | 0.0039 (5) | 0.0010 (5) |
N1A | 0.0273 (7) | 0.0409 (7) | 0.0264 (6) | −0.0066 (5) | 0.0067 (5) | 0.0000 (5) |
N41A | 0.0252 (7) | 0.0793 (10) | 0.0288 (7) | −0.0068 (6) | 0.0067 (6) | 0.0010 (6) |
C2A | 0.0290 (7) | 0.0411 (8) | 0.0320 (7) | 0.0026 (6) | 0.0085 (6) | −0.0033 (6) |
C3A | 0.0301 (7) | 0.0305 (7) | 0.0296 (7) | −0.0014 (6) | 0.0069 (6) | −0.0034 (6) |
C4A | 0.0260 (7) | 0.0336 (7) | 0.0238 (7) | −0.0004 (6) | 0.0043 (6) | 0.0048 (6) |
C5A | 0.0326 (8) | 0.0370 (8) | 0.0259 (7) | 0.0013 (6) | 0.0106 (6) | −0.0002 (6) |
C6A | 0.0363 (8) | 0.0392 (8) | 0.0232 (7) | −0.0066 (6) | 0.0084 (6) | −0.0022 (6) |
C41A | 0.0296 (8) | 0.0455 (8) | 0.0294 (8) | −0.0045 (6) | 0.0064 (6) | 0.0018 (6) |
O11 | 0.0788 (8) | 0.0450 (6) | 0.0270 (6) | 0.0085 (6) | 0.0120 (5) | −0.0029 (5) |
O12 | 0.0304 (5) | 0.0385 (6) | 0.0367 (6) | −0.0021 (4) | 0.0048 (4) | 0.0009 (4) |
O21 | 0.0458 (6) | 0.0399 (6) | 0.0383 (6) | −0.0091 (5) | 0.0059 (5) | −0.0013 (5) |
O22 | 0.0752 (9) | 0.0667 (8) | 0.0533 (7) | −0.0077 (6) | 0.0396 (7) | −0.0178 (6) |
N2 | 0.0460 (8) | 0.0345 (7) | 0.0299 (6) | −0.0016 (6) | 0.0129 (6) | 0.0007 (5) |
C1 | 0.0338 (8) | 0.0286 (7) | 0.0340 (8) | 0.0011 (6) | 0.0095 (6) | −0.0028 (6) |
C2 | 0.0360 (8) | 0.0277 (7) | 0.0299 (7) | 0.0011 (6) | 0.0066 (6) | −0.0030 (6) |
C3 | 0.0569 (11) | 0.0434 (9) | 0.0349 (9) | 0.0038 (8) | −0.0003 (8) | 0.0018 (7) |
C4 | 0.0425 (11) | 0.0709 (13) | 0.0616 (12) | 0.0057 (9) | −0.0146 (9) | 0.0071 (10) |
C5 | 0.0310 (9) | 0.0795 (14) | 0.0822 (15) | 0.0030 (8) | 0.0071 (10) | 0.0072 (11) |
C6 | 0.0389 (9) | 0.0574 (11) | 0.0524 (10) | 0.0023 (7) | 0.0167 (8) | 0.0028 (8) |
C11 | 0.0411 (9) | 0.0270 (7) | 0.0278 (7) | −0.0079 (6) | 0.0080 (6) | 0.0001 (6) |
O41A—C41A | 1.2403 (17) | C2A—H21A | 0.9700 |
O11—C11 | 1.2435 (17) | C3A—H32A | 0.9700 |
O12—C11 | 1.2542 (17) | C3A—H31A | 0.9700 |
O21—N2 | 1.2269 (16) | C4A—H4A | 0.9800 |
O22—N2 | 1.2191 (17) | C5A—H52A | 0.9700 |
N1A—C2A | 1.4882 (18) | C5A—H51A | 0.9700 |
N1A—C6A | 1.4891 (19) | C6A—H62A | 0.9700 |
N41A—C41A | 1.333 (2) | C6A—H61A | 0.9700 |
N1A—H11A | 0.941 (17) | C1—C2 | 1.3857 (19) |
N1A—H12A | 0.951 (18) | C1—C6 | 1.393 (2) |
N41A—H42A | 0.878 (16) | C1—C11 | 1.518 (2) |
N41A—H41A | 0.90 (2) | C2—C3 | 1.380 (2) |
N2—C2 | 1.4719 (19) | C3—C4 | 1.384 (3) |
C2A—C3A | 1.518 (2) | C4—C5 | 1.372 (3) |
C3A—C4A | 1.5284 (19) | C5—C6 | 1.382 (3) |
C4A—C5A | 1.5335 (19) | C3—H3 | 0.9300 |
C4A—C41A | 1.5196 (19) | C4—H4 | 0.9300 |
C5A—C6A | 1.518 (2) | C5—H5 | 0.9300 |
C2A—H22A | 0.9700 | C6—H6 | 0.9300 |
C2A—N1A—C6A | 111.43 (11) | C5A—C4A—H4A | 108.00 |
H11A—N1A—H12A | 107.9 (14) | C3A—C4A—H4A | 108.00 |
C2A—N1A—H12A | 111.8 (9) | C4A—C5A—H51A | 109.00 |
C6A—N1A—H11A | 107.3 (11) | C4A—C5A—H52A | 109.00 |
C2A—N1A—H11A | 109.3 (10) | C6A—C5A—H51A | 109.00 |
C6A—N1A—H12A | 109.0 (9) | C6A—C5A—H52A | 109.00 |
C41A—N41A—H42A | 119.6 (10) | H51A—C5A—H52A | 108.00 |
H41A—N41A—H42A | 122.2 (15) | N1A—C6A—H62A | 110.00 |
C41A—N41A—H41A | 118.1 (12) | H61A—C6A—H62A | 108.00 |
O22—N2—C2 | 117.68 (12) | C5A—C6A—H61A | 110.00 |
O21—N2—O22 | 123.88 (13) | C5A—C6A—H62A | 110.00 |
O21—N2—C2 | 118.44 (11) | N1A—C6A—H61A | 110.00 |
N1A—C2A—C3A | 109.40 (12) | C2—C1—C6 | 116.89 (14) |
C2A—C3A—C4A | 112.29 (11) | C2—C1—C11 | 122.46 (13) |
C3A—C4A—C41A | 111.41 (11) | C6—C1—C11 | 120.37 (13) |
C5A—C4A—C41A | 109.48 (11) | N2—C2—C1 | 118.84 (12) |
C3A—C4A—C5A | 110.91 (11) | N2—C2—C3 | 117.99 (13) |
C4A—C5A—C6A | 111.41 (11) | C1—C2—C3 | 123.17 (14) |
N1A—C6A—C5A | 109.42 (11) | C2—C3—C4 | 118.26 (15) |
O41A—C41A—C4A | 121.47 (13) | C3—C4—C5 | 120.28 (17) |
O41A—C41A—N41A | 121.84 (14) | C4—C5—C6 | 120.52 (17) |
N41A—C41A—C4A | 116.63 (12) | C1—C6—C5 | 120.87 (16) |
N1A—C2A—H21A | 110.00 | O11—C11—O12 | 126.25 (13) |
H21A—C2A—H22A | 108.00 | O11—C11—C1 | 117.32 (13) |
N1A—C2A—H22A | 110.00 | O12—C11—C1 | 116.36 (12) |
C3A—C2A—H21A | 110.00 | C2—C3—H3 | 121.00 |
C3A—C2A—H22A | 110.00 | C4—C3—H3 | 121.00 |
C2A—C3A—H31A | 109.00 | C3—C4—H4 | 120.00 |
C2A—C3A—H32A | 109.00 | C5—C4—H4 | 120.00 |
C4A—C3A—H31A | 109.00 | C4—C5—H5 | 120.00 |
H31A—C3A—H32A | 108.00 | C6—C5—H5 | 120.00 |
C4A—C3A—H32A | 109.00 | C1—C6—H6 | 120.00 |
C41A—C4A—H4A | 108.00 | C5—C6—H6 | 120.00 |
C6A—N1A—C2A—C3A | 60.90 (14) | C6—C1—C2—N2 | −178.69 (12) |
C2A—N1A—C6A—C5A | −61.94 (15) | C6—C1—C2—C3 | 0.7 (2) |
O21—N2—C2—C1 | 48.67 (17) | C11—C1—C2—N2 | 7.42 (19) |
O21—N2—C2—C3 | −130.73 (14) | C11—C1—C2—C3 | −173.22 (13) |
O22—N2—C2—C1 | −131.60 (13) | C2—C1—C6—C5 | −1.2 (2) |
O22—N2—C2—C3 | 49.00 (18) | C11—C1—C6—C5 | 172.83 (15) |
N1A—C2A—C3A—C4A | −55.32 (14) | C2—C1—C11—O11 | −138.93 (14) |
C2A—C3A—C4A—C5A | 51.32 (14) | C2—C1—C11—O12 | 43.84 (18) |
C2A—C3A—C4A—C41A | 173.54 (11) | C6—C1—C11—O11 | 47.39 (19) |
C5A—C4A—C41A—O41A | 107.81 (15) | C6—C1—C11—O12 | −129.85 (15) |
C5A—C4A—C41A—N41A | −69.58 (16) | N2—C2—C3—C4 | 179.61 (14) |
C3A—C4A—C41A—O41A | −15.24 (19) | C1—C2—C3—C4 | 0.2 (2) |
C3A—C4A—C5A—C6A | −51.84 (14) | C2—C3—C4—C5 | −0.6 (3) |
C41A—C4A—C5A—C6A | −175.18 (11) | C3—C4—C5—C6 | 0.1 (3) |
C3A—C4A—C41A—N41A | 167.38 (13) | C4—C5—C6—C1 | 0.8 (3) |
C4A—C5A—C6A—N1A | 56.75 (14) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1A—H11A···O11i | 0.941 (17) | 1.848 (17) | 2.7759 (17) | 168.3 (17) |
N1A—H12A···O12 | 0.951 (18) | 1.792 (17) | 2.7380 (17) | 172.5 (13) |
N41A—H41A···O41Aii | 0.90 (2) | 2.00 (2) | 2.8978 (19) | 174.6 (15) |
N41A—H42A···O41Aiii | 0.878 (16) | 2.313 (16) | 3.0914 (17) | 147.8 (13) |
C6A—H61A···O21iv | 0.97 | 2.47 | 3.2240 (18) | 134 |
Symmetry codes: (i) −x+1/2, −y+3/2, −z; (ii) −x, −y+1, −z; (iii) x, −y+1, z+1/2; (iv) −x+1/2, y+1/2, −z+1/2. |
C6H13N2O+·C7H4NO4− | F(000) = 624 |
Mr = 295.30 | Dx = 1.444 Mg m−3 |
Monoclinic, P21/c | Melting point: 452 K |
Hall symbol: -P 2ybc | Mo Kα radiation, λ = 0.71073 Å |
a = 14.2504 (15) Å | Cell parameters from 3622 reflections |
b = 6.8276 (5) Å | θ = 3.2–28.8° |
c = 15.4580 (17) Å | µ = 0.11 mm−1 |
β = 115.410 (13)° | T = 200 K |
V = 1358.5 (2) Å3 | Prism, colourless |
Z = 4 | 0.30 × 0.20 × 0.15 mm |
Oxford Gemini S Ultra CCD area-detector diffractometer | 2669 independent reflections |
Radiation source: Enhance (Mo) X-ray source | 1982 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.026 |
ω scans | θmax = 26.0°, θmin = 3.2° |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009) | h = −17→17 |
Tmin = 0.948, Tmax = 0.980 | k = −8→8 |
9250 measured reflections | l = −19→13 |
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)] = 0.038 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.093 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | w = 1/[σ2(Fo2) + (0.055P)2 + 0.0538P] where P = (Fo2 + 2Fc2)/3 |
2669 reflections | (Δ/σ)max < 0.001 |
206 parameters | Δρmax = 0.21 e Å−3 |
0 restraints | Δρmin = −0.20 e Å−3 |
C6H13N2O+·C7H4NO4− | V = 1358.5 (2) Å3 |
Mr = 295.30 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 14.2504 (15) Å | µ = 0.11 mm−1 |
b = 6.8276 (5) Å | T = 200 K |
c = 15.4580 (17) Å | 0.30 × 0.20 × 0.15 mm |
β = 115.410 (13)° |
Oxford Gemini S Ultra CCD area-detector diffractometer | 2669 independent reflections |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009) | 1982 reflections with I > 2σ(I) |
Tmin = 0.948, Tmax = 0.980 | Rint = 0.026 |
9250 measured reflections |
R[F2 > 2σ(F2)] = 0.038 | 0 restraints |
wR(F2) = 0.093 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | Δρmax = 0.21 e Å−3 |
2669 reflections | Δρmin = −0.20 e Å−3 |
206 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 | 0.45623 (8) | −0.33122 (16) | 0.54658 (7) | 0.0343 (3) | |
N1A | 0.38389 (10) | 0.13659 (19) | 0.30335 (11) | 0.0326 (4) | |
N41A | 0.31271 (11) | −0.5030 (2) | 0.45585 (11) | 0.0324 (5) | |
C2A | 0.28255 (12) | 0.0745 (2) | 0.29981 (11) | 0.0295 (5) | |
C3A | 0.29881 (11) | −0.0660 (2) | 0.38042 (10) | 0.0265 (5) | |
C4A | 0.36431 (11) | −0.2434 (2) | 0.37976 (10) | 0.0230 (4) | |
C5A | 0.46462 (11) | −0.1781 (2) | 0.37580 (11) | 0.0282 (5) | |
C6A | 0.44431 (12) | −0.0342 (3) | 0.29464 (11) | 0.0341 (5) | |
C41A | 0.38334 (11) | −0.3643 (2) | 0.46824 (10) | 0.0250 (5) | |
O11 | 0.31363 (8) | 0.45491 (18) | 0.18250 (8) | 0.0401 (4) | |
O12 | 0.25353 (10) | 0.19447 (18) | 0.08824 (8) | 0.0443 (4) | |
O31 | −0.06945 (10) | 0.2634 (2) | −0.20416 (9) | 0.0513 (5) | |
O32 | −0.11616 (10) | 0.5492 (2) | −0.26766 (9) | 0.0588 (5) | |
N3 | −0.06099 (10) | 0.4411 (2) | −0.20179 (9) | 0.0368 (5) | |
C1 | 0.17035 (11) | 0.5008 (2) | 0.03219 (10) | 0.0230 (4) | |
C2 | 0.09472 (11) | 0.4156 (2) | −0.04977 (10) | 0.0229 (4) | |
C3 | 0.01941 (11) | 0.5338 (2) | −0.11617 (10) | 0.0259 (4) | |
C4 | 0.01652 (13) | 0.7342 (2) | −0.10502 (11) | 0.0324 (5) | |
C5 | 0.09258 (13) | 0.8171 (2) | −0.02317 (12) | 0.0346 (5) | |
C6 | 0.16832 (12) | 0.7015 (2) | 0.04443 (11) | 0.0284 (5) | |
C11 | 0.25286 (12) | 0.3729 (2) | 0.10671 (11) | 0.0285 (5) | |
H4A | 0.32430 | −0.32240 | 0.32280 | 0.0280* | |
H11A | 0.4258 (15) | 0.203 (3) | 0.3627 (14) | 0.056 (6)* | |
H12A | 0.3673 (17) | 0.223 (4) | 0.2523 (16) | 0.074 (7)* | |
H21A | 0.24150 | 0.01150 | 0.23890 | 0.0350* | |
H22A | 0.24470 | 0.18850 | 0.30500 | 0.0350* | |
H31A | 0.23180 | −0.11080 | 0.37470 | 0.0320* | |
H32A | 0.33310 | 0.00200 | 0.44110 | 0.0320* | |
H41A | 0.2578 (14) | −0.502 (2) | 0.4021 (13) | 0.040 (5)* | |
H42A | 0.3112 (14) | −0.564 (3) | 0.5072 (14) | 0.051 (6)* | |
H51A | 0.50950 | −0.11700 | 0.43610 | 0.0340* | |
H52A | 0.50050 | −0.29190 | 0.36720 | 0.0340* | |
H61A | 0.50990 | 0.01050 | 0.29680 | 0.0410* | |
H62A | 0.40580 | −0.09890 | 0.23370 | 0.0410* | |
H2 | 0.09480 | 0.28130 | −0.05980 | 0.0280* | |
H4 | −0.03470 | 0.81080 | −0.15090 | 0.0390* | |
H5 | 0.09270 | 0.95160 | −0.01360 | 0.0410* | |
H6 | 0.21870 | 0.75950 | 0.09900 | 0.0340* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O41A | 0.0332 (6) | 0.0366 (6) | 0.0222 (6) | −0.0043 (5) | 0.0015 (5) | 0.0007 (5) |
N1A | 0.0268 (7) | 0.0304 (8) | 0.0298 (8) | −0.0023 (6) | 0.0018 (6) | 0.0088 (6) |
N41A | 0.0272 (8) | 0.0356 (8) | 0.0266 (8) | −0.0060 (6) | 0.0041 (6) | 0.0058 (6) |
C2A | 0.0228 (8) | 0.0278 (8) | 0.0321 (9) | 0.0047 (7) | 0.0062 (6) | 0.0009 (7) |
C3A | 0.0223 (8) | 0.0314 (8) | 0.0235 (8) | 0.0028 (7) | 0.0077 (6) | −0.0004 (7) |
C4A | 0.0224 (8) | 0.0230 (7) | 0.0199 (7) | 0.0000 (6) | 0.0055 (6) | −0.0032 (6) |
C5A | 0.0235 (8) | 0.0318 (8) | 0.0285 (8) | 0.0056 (7) | 0.0105 (6) | 0.0026 (7) |
C6A | 0.0244 (8) | 0.0466 (10) | 0.0304 (9) | −0.0002 (8) | 0.0110 (7) | 0.0066 (8) |
C41A | 0.0232 (8) | 0.0255 (8) | 0.0241 (8) | 0.0032 (6) | 0.0080 (6) | −0.0013 (6) |
O11 | 0.0340 (7) | 0.0478 (7) | 0.0261 (6) | −0.0036 (6) | 0.0012 (5) | 0.0020 (5) |
O12 | 0.0611 (8) | 0.0365 (7) | 0.0306 (6) | 0.0218 (6) | 0.0153 (6) | 0.0027 (5) |
O31 | 0.0489 (8) | 0.0543 (9) | 0.0421 (8) | −0.0168 (7) | 0.0114 (6) | −0.0188 (7) |
O32 | 0.0358 (7) | 0.0842 (10) | 0.0344 (7) | 0.0154 (7) | −0.0058 (6) | 0.0003 (7) |
N3 | 0.0242 (7) | 0.0551 (10) | 0.0286 (8) | −0.0021 (7) | 0.0090 (6) | −0.0075 (7) |
C1 | 0.0234 (8) | 0.0269 (8) | 0.0217 (7) | −0.0010 (6) | 0.0125 (6) | 0.0013 (6) |
C2 | 0.0258 (8) | 0.0212 (7) | 0.0246 (8) | −0.0021 (6) | 0.0135 (6) | −0.0006 (6) |
C3 | 0.0204 (8) | 0.0352 (8) | 0.0210 (7) | −0.0026 (7) | 0.0079 (6) | −0.0011 (7) |
C4 | 0.0291 (9) | 0.0348 (9) | 0.0327 (9) | 0.0086 (7) | 0.0128 (7) | 0.0102 (7) |
C5 | 0.0419 (10) | 0.0198 (8) | 0.0441 (10) | −0.0003 (7) | 0.0205 (8) | 0.0020 (7) |
C6 | 0.0283 (8) | 0.0290 (8) | 0.0270 (8) | −0.0071 (7) | 0.0111 (6) | −0.0036 (7) |
C11 | 0.0274 (8) | 0.0381 (9) | 0.0212 (8) | 0.0032 (7) | 0.0117 (6) | 0.0041 (7) |
O41A—C41A | 1.2316 (18) | C2A—H21A | 0.9700 |
O11—C11 | 1.2511 (19) | C3A—H32A | 0.9700 |
O12—C11 | 1.2522 (19) | C3A—H31A | 0.9700 |
O31—N3 | 1.2182 (19) | C4A—H4A | 0.9800 |
O32—N3 | 1.2299 (19) | C5A—H52A | 0.9700 |
N1A—C2A | 1.483 (2) | C5A—H51A | 0.9700 |
N1A—C6A | 1.490 (2) | C6A—H62A | 0.9700 |
N41A—C41A | 1.335 (2) | C6A—H61A | 0.9700 |
N1A—H11A | 0.97 (2) | C1—C2 | 1.390 (2) |
N1A—H12A | 0.93 (2) | C1—C6 | 1.3853 (19) |
N41A—H42A | 0.91 (2) | C1—C11 | 1.520 (2) |
N41A—H41A | 0.863 (19) | C2—C3 | 1.383 (2) |
N3—C3 | 1.471 (2) | C3—C4 | 1.3819 (19) |
C2A—C3A | 1.510 (2) | C4—C5 | 1.385 (2) |
C3A—C4A | 1.532 (2) | C5—C6 | 1.383 (2) |
C4A—C5A | 1.524 (2) | C2—H2 | 0.9300 |
C4A—C41A | 1.519 (2) | C4—H4 | 0.9300 |
C5A—C6A | 1.520 (2) | C5—H5 | 0.9300 |
C2A—H22A | 0.9700 | C6—H6 | 0.9300 |
C2A—N1A—C6A | 111.36 (13) | C5A—C4A—H4A | 109.00 |
H11A—N1A—H12A | 110 (2) | C3A—C4A—H4A | 109.00 |
C2A—N1A—H12A | 105.1 (16) | C4A—C5A—H51A | 109.00 |
C6A—N1A—H11A | 107.9 (13) | C4A—C5A—H52A | 109.00 |
C2A—N1A—H11A | 111.4 (14) | C6A—C5A—H51A | 109.00 |
C6A—N1A—H12A | 111.5 (16) | C6A—C5A—H52A | 109.00 |
C41A—N41A—H42A | 120.1 (13) | H51A—C5A—H52A | 108.00 |
H41A—N41A—H42A | 119.7 (19) | N1A—C6A—H62A | 110.00 |
C41A—N41A—H41A | 116.7 (11) | H61A—C6A—H62A | 108.00 |
O32—N3—C3 | 117.46 (13) | C5A—C6A—H61A | 110.00 |
O31—N3—O32 | 123.57 (14) | C5A—C6A—H62A | 110.00 |
O31—N3—C3 | 118.97 (13) | N1A—C6A—H61A | 110.00 |
N1A—C2A—C3A | 110.42 (14) | C2—C1—C6 | 119.00 (14) |
C2A—C3A—C4A | 112.03 (13) | C2—C1—C11 | 119.69 (12) |
C3A—C4A—C41A | 107.31 (12) | C6—C1—C11 | 121.30 (13) |
C5A—C4A—C41A | 112.78 (13) | C1—C2—C3 | 118.92 (13) |
C3A—C4A—C5A | 110.72 (12) | N3—C3—C2 | 118.27 (12) |
C4A—C5A—C6A | 111.88 (13) | N3—C3—C4 | 119.00 (13) |
N1A—C6A—C5A | 110.13 (14) | C2—C3—C4 | 122.72 (14) |
O41A—C41A—C4A | 122.35 (14) | C3—C4—C5 | 117.71 (14) |
O41A—C41A—N41A | 122.49 (14) | C4—C5—C6 | 120.54 (13) |
N41A—C41A—C4A | 115.10 (13) | C1—C6—C5 | 121.11 (14) |
N1A—C2A—H21A | 110.00 | O11—C11—O12 | 125.38 (15) |
H21A—C2A—H22A | 108.00 | O11—C11—C1 | 116.88 (13) |
N1A—C2A—H22A | 110.00 | O12—C11—C1 | 117.73 (14) |
C3A—C2A—H21A | 110.00 | C1—C2—H2 | 121.00 |
C3A—C2A—H22A | 110.00 | C3—C2—H2 | 121.00 |
C2A—C3A—H31A | 109.00 | C3—C4—H4 | 121.00 |
C2A—C3A—H32A | 109.00 | C5—C4—H4 | 121.00 |
C4A—C3A—H31A | 109.00 | C4—C5—H5 | 120.00 |
H31A—C3A—H32A | 108.00 | C6—C5—H5 | 120.00 |
C4A—C3A—H32A | 109.00 | C1—C6—H6 | 119.00 |
C41A—C4A—H4A | 109.00 | C5—C6—H6 | 119.00 |
C6A—N1A—C2A—C3A | 59.73 (16) | C4A—C5A—C6A—N1A | 55.67 (17) |
C2A—N1A—C6A—C5A | −59.64 (17) | C6—C1—C2—C3 | −0.5 (2) |
O31—N3—C3—C2 | 12.2 (2) | C11—C1—C2—C3 | 179.11 (15) |
O31—N3—C3—C4 | −167.54 (17) | C2—C1—C6—C5 | 0.1 (3) |
O32—N3—C3—C2 | −167.65 (16) | C11—C1—C6—C5 | −179.44 (17) |
O32—N3—C3—C4 | 12.7 (2) | C2—C1—C11—O11 | −174.27 (16) |
N1A—C2A—C3A—C4A | −55.58 (16) | C2—C1—C11—O12 | 4.6 (2) |
C2A—C3A—C4A—C5A | 51.69 (16) | C6—C1—C11—O11 | 5.3 (2) |
C2A—C3A—C4A—C41A | 175.15 (13) | C6—C1—C11—O12 | −175.90 (17) |
C5A—C4A—C41A—O41A | 35.9 (2) | C1—C2—C3—N3 | −179.09 (15) |
C5A—C4A—C41A—N41A | −147.04 (14) | C1—C2—C3—C4 | 0.6 (3) |
C3A—C4A—C41A—O41A | −86.34 (18) | N3—C3—C4—C5 | 179.31 (16) |
C3A—C4A—C5A—C6A | −51.69 (16) | C2—C3—C4—C5 | −0.4 (3) |
C41A—C4A—C5A—C6A | −171.94 (13) | C3—C4—C5—C6 | 0.0 (3) |
C3A—C4A—C41A—N41A | 90.77 (16) | C4—C5—C6—C1 | 0.1 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1A—H11A···O41Ai | 0.97 (2) | 1.88 (2) | 2.7933 (19) | 157 (2) |
N1A—H12A···O11 | 0.93 (2) | 1.88 (3) | 2.7587 (19) | 156 (2) |
N1A—H12A···O12 | 0.93 (2) | 2.36 (2) | 3.0599 (19) | 132 (2) |
N41A—H41A···O32ii | 0.863 (19) | 2.213 (19) | 3.068 (2) | 171.1 (13) |
N41A—H42A···O12iii | 0.91 (2) | 1.98 (2) | 2.844 (2) | 159 (2) |
C2A—H22A···O32iv | 0.97 | 2.45 | 3.385 (2) | 163 |
C6A—H61A···O11v | 0.97 | 2.42 | 3.314 (2) | 152 |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x, −y, −z; (iii) x, −y−1/2, z+1/2; (iv) −x, −y+1, −z; (v) −x+1, y−1/2, −z+1/2. |
C6H13N2O+·C7H4NO4− | F(000) = 624 |
Mr = 295.30 | Dx = 1.409 Mg m−3 |
Monoclinic, P21/c | Melting point = 537–539 K |
Hall symbol: -P 2ybc | Mo Kα radiation, λ = 0.71073 Å |
a = 7.5371 (6) Å | Cell parameters from 4862 reflections |
b = 12.4216 (12) Å | θ = 3.2–28.9° |
c = 15.0911 (13) Å | µ = 0.11 mm−1 |
β = 99.848 (7)° | T = 200 K |
V = 1392.1 (2) Å3 | Prism, colourless |
Z = 4 | 0.30 × 0.18 × 0.15 mm |
Oxford Gemini-S Ultra CCD area-detector diffractometer | 2727 independent reflections |
Radiation source: Enhance (Mo) X-ray source | 2279 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.042 |
ω scans | θmax = 26.0°, θmin = 3.2° |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009) | h = −9→9 |
Tmin = 0.952, Tmax = 0.980 | k = −15→15 |
14612 measured reflections | l = −18→18 |
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)] = 0.035 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.095 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.14 | w = 1/[σ2(Fo2) + (0.0539P)2 + 0.0719P] where P = (Fo2 + 2Fc2)/3 |
2727 reflections | (Δ/σ)max < 0.001 |
206 parameters | Δρmax = 0.21 e Å−3 |
0 restraints | Δρmin = −0.19 e Å−3 |
C6H13N2O+·C7H4NO4− | V = 1392.1 (2) Å3 |
Mr = 295.30 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 7.5371 (6) Å | µ = 0.11 mm−1 |
b = 12.4216 (12) Å | T = 200 K |
c = 15.0911 (13) Å | 0.30 × 0.18 × 0.15 mm |
β = 99.848 (7)° |
Oxford Gemini-S Ultra CCD area-detector diffractometer | 2727 independent reflections |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009) | 2279 reflections with I > 2σ(I) |
Tmin = 0.952, Tmax = 0.980 | Rint = 0.042 |
14612 measured reflections |
R[F2 > 2σ(F2)] = 0.035 | 0 restraints |
wR(F2) = 0.095 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.14 | Δρmax = 0.21 e Å−3 |
2727 reflections | Δρmin = −0.19 e Å−3 |
206 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 | 0.02263 (15) | 1.05263 (8) | 0.11414 (7) | 0.0380 (3) | |
N1A | 0.09525 (15) | 0.89654 (8) | 0.41329 (8) | 0.0234 (3) | |
N41A | 0.14124 (17) | 0.89959 (9) | 0.06854 (8) | 0.0308 (4) | |
C2A | 0.21319 (19) | 0.98633 (10) | 0.39172 (9) | 0.0282 (4) | |
C3A | 0.15409 (18) | 1.02313 (10) | 0.29510 (9) | 0.0249 (4) | |
C4A | 0.16009 (17) | 0.93024 (9) | 0.22941 (8) | 0.0217 (4) | |
C5A | 0.04143 (18) | 0.83686 (9) | 0.25324 (8) | 0.0233 (4) | |
C6A | 0.09620 (18) | 0.80295 (10) | 0.35103 (9) | 0.0243 (4) | |
C41A | 0.10137 (17) | 0.96574 (10) | 0.13201 (9) | 0.0239 (4) | |
O11 | 0.24349 (13) | 0.99568 (7) | 0.61984 (6) | 0.0310 (3) | |
O12 | 0.26652 (14) | 0.82492 (7) | 0.57656 (6) | 0.0353 (3) | |
O41 | 0.79560 (14) | 0.72149 (8) | 0.99299 (7) | 0.0395 (3) | |
O42 | 0.66121 (16) | 0.85260 (9) | 1.04955 (7) | 0.0476 (4) | |
N4 | 0.68785 (15) | 0.79664 (9) | 0.98578 (8) | 0.0289 (3) | |
C1 | 0.39884 (16) | 0.87176 (10) | 0.72586 (8) | 0.0210 (4) | |
C2 | 0.39457 (18) | 0.94083 (10) | 0.79822 (9) | 0.0281 (4) | |
C3 | 0.48704 (18) | 0.91611 (11) | 0.88355 (9) | 0.0304 (4) | |
C4 | 0.58553 (17) | 0.82173 (10) | 0.89532 (9) | 0.0236 (4) | |
C5 | 0.59296 (16) | 0.75004 (10) | 0.82531 (9) | 0.0222 (4) | |
C6 | 0.49811 (16) | 0.77620 (9) | 0.74027 (9) | 0.0214 (4) | |
C11 | 0.29466 (16) | 0.90024 (10) | 0.63323 (9) | 0.0225 (4) | |
H4A | 0.28460 | 0.90450 | 0.23630 | 0.0260* | |
H11A | −0.022 (2) | 0.9235 (12) | 0.4094 (11) | 0.038 (4)* | |
H12A | 0.137 (2) | 0.8721 (13) | 0.4718 (12) | 0.039 (4)* | |
H21A | 0.33730 | 0.96210 | 0.40010 | 0.0340* | |
H22A | 0.20620 | 1.04620 | 0.43230 | 0.0340* | |
H31A | 0.23260 | 1.08050 | 0.28160 | 0.0300* | |
H32A | 0.03250 | 1.05140 | 0.28790 | 0.0300* | |
H41A | 0.098 (2) | 0.9159 (13) | 0.0072 (13) | 0.047 (5)* | |
H42A | 0.190 (2) | 0.8355 (13) | 0.0803 (10) | 0.033 (4)* | |
H51A | −0.08370 | 0.85930 | 0.24280 | 0.0280* | |
H52A | 0.05270 | 0.77590 | 0.21440 | 0.0280* | |
H61A | 0.01360 | 0.74830 | 0.36530 | 0.0290* | |
H62A | 0.21590 | 0.77170 | 0.35960 | 0.0290* | |
H2 | 0.32890 | 1.00440 | 0.78930 | 0.0340* | |
H3 | 0.48280 | 0.96210 | 0.93180 | 0.0370* | |
H5 | 0.65900 | 0.68660 | 0.83480 | 0.0270* | |
H6 | 0.50090 | 0.72940 | 0.69240 | 0.0260* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O41A | 0.0629 (7) | 0.0281 (5) | 0.0214 (5) | 0.0176 (5) | 0.0024 (5) | 0.0030 (4) |
N1A | 0.0288 (6) | 0.0244 (6) | 0.0161 (6) | 0.0014 (5) | 0.0011 (4) | 0.0030 (4) |
N41A | 0.0482 (7) | 0.0247 (6) | 0.0189 (7) | 0.0109 (5) | 0.0037 (5) | 0.0024 (5) |
C2A | 0.0356 (7) | 0.0258 (7) | 0.0215 (7) | −0.0073 (5) | 0.0002 (5) | −0.0018 (5) |
C3A | 0.0332 (7) | 0.0203 (6) | 0.0213 (7) | −0.0047 (5) | 0.0046 (5) | 0.0007 (5) |
C4A | 0.0254 (6) | 0.0209 (6) | 0.0185 (7) | 0.0026 (5) | 0.0030 (5) | 0.0030 (5) |
C5A | 0.0311 (7) | 0.0186 (6) | 0.0195 (7) | −0.0010 (5) | 0.0027 (5) | −0.0002 (5) |
C6A | 0.0305 (7) | 0.0191 (6) | 0.0228 (7) | 0.0013 (5) | 0.0032 (5) | 0.0023 (5) |
C41A | 0.0310 (7) | 0.0213 (6) | 0.0192 (7) | 0.0013 (5) | 0.0036 (5) | 0.0020 (5) |
O11 | 0.0365 (5) | 0.0274 (5) | 0.0269 (5) | 0.0071 (4) | −0.0004 (4) | 0.0061 (4) |
O12 | 0.0538 (7) | 0.0247 (5) | 0.0218 (5) | −0.0050 (4) | −0.0097 (4) | 0.0019 (4) |
O41 | 0.0494 (6) | 0.0317 (5) | 0.0321 (6) | 0.0128 (5) | −0.0081 (5) | 0.0029 (4) |
O42 | 0.0634 (8) | 0.0534 (7) | 0.0219 (6) | 0.0176 (6) | −0.0040 (5) | −0.0085 (5) |
N4 | 0.0346 (6) | 0.0271 (6) | 0.0225 (6) | 0.0016 (5) | −0.0025 (5) | 0.0000 (5) |
C1 | 0.0202 (6) | 0.0214 (6) | 0.0208 (7) | −0.0026 (5) | 0.0019 (5) | 0.0022 (5) |
C2 | 0.0318 (7) | 0.0232 (6) | 0.0270 (7) | 0.0080 (5) | −0.0013 (6) | −0.0018 (5) |
C3 | 0.0382 (8) | 0.0279 (7) | 0.0230 (8) | 0.0073 (6) | −0.0009 (6) | −0.0066 (6) |
C4 | 0.0246 (7) | 0.0253 (6) | 0.0188 (7) | −0.0005 (5) | −0.0019 (5) | 0.0009 (5) |
C5 | 0.0220 (6) | 0.0191 (6) | 0.0247 (7) | 0.0012 (5) | 0.0021 (5) | 0.0006 (5) |
C6 | 0.0248 (6) | 0.0195 (6) | 0.0199 (7) | −0.0026 (5) | 0.0035 (5) | −0.0024 (5) |
C11 | 0.0231 (6) | 0.0229 (6) | 0.0210 (7) | −0.0040 (5) | 0.0022 (5) | 0.0031 (5) |
O41A—C41A | 1.2390 (16) | C2A—H21A | 0.9700 |
O11—C11 | 1.2524 (15) | C3A—H32A | 0.9700 |
O12—C11 | 1.2608 (16) | C3A—H31A | 0.9700 |
O41—N4 | 1.2299 (15) | C4A—H4A | 0.9800 |
O42—N4 | 1.2312 (16) | C5A—H52A | 0.9700 |
N1A—C2A | 1.4964 (17) | C5A—H51A | 0.9700 |
N1A—C6A | 1.4955 (17) | C6A—H62A | 0.9700 |
N41A—C41A | 1.3347 (18) | C6A—H61A | 0.9700 |
N1A—H11A | 0.938 (15) | C1—C2 | 1.3934 (18) |
N1A—H12A | 0.936 (18) | C1—C6 | 1.4002 (17) |
N41A—H42A | 0.882 (16) | C1—C11 | 1.5233 (18) |
N41A—H41A | 0.949 (19) | C2—C3 | 1.3897 (19) |
N4—C4 | 1.4817 (18) | C3—C4 | 1.3827 (19) |
C2A—C3A | 1.5203 (19) | C4—C5 | 1.3902 (18) |
C3A—C4A | 1.5269 (17) | C5—C6 | 1.3964 (19) |
C4A—C5A | 1.5442 (17) | C2—H2 | 0.9300 |
C4A—C41A | 1.5259 (18) | C3—H3 | 0.9300 |
C5A—C6A | 1.5223 (18) | C5—H5 | 0.9300 |
C2A—H22A | 0.9700 | C6—H6 | 0.9300 |
C2A—N1A—C6A | 112.08 (10) | C5A—C4A—H4A | 108.00 |
H11A—N1A—H12A | 109.7 (14) | C3A—C4A—H4A | 108.00 |
C2A—N1A—H12A | 109.3 (10) | C4A—C5A—H51A | 109.00 |
C6A—N1A—H11A | 110.1 (10) | C4A—C5A—H52A | 109.00 |
C2A—N1A—H11A | 108.0 (9) | C6A—C5A—H51A | 109.00 |
C6A—N1A—H12A | 107.7 (10) | C6A—C5A—H52A | 109.00 |
C41A—N41A—H42A | 123.3 (10) | H51A—C5A—H52A | 108.00 |
H41A—N41A—H42A | 116.8 (14) | N1A—C6A—H62A | 109.00 |
C41A—N41A—H41A | 119.1 (10) | H61A—C6A—H62A | 108.00 |
O42—N4—C4 | 118.21 (11) | C5A—C6A—H61A | 109.00 |
O41—N4—O42 | 123.57 (12) | C5A—C6A—H62A | 109.00 |
O41—N4—C4 | 118.23 (11) | N1A—C6A—H61A | 109.00 |
N1A—C2A—C3A | 110.20 (11) | C2—C1—C6 | 118.92 (11) |
C2A—C3A—C4A | 111.05 (10) | C2—C1—C11 | 119.92 (11) |
C3A—C4A—C41A | 111.78 (10) | C6—C1—C11 | 121.15 (11) |
C5A—C4A—C41A | 110.93 (10) | C1—C2—C3 | 121.00 (12) |
C3A—C4A—C5A | 109.50 (10) | C2—C3—C4 | 118.65 (12) |
C4A—C5A—C6A | 111.21 (10) | N4—C4—C3 | 118.69 (11) |
N1A—C6A—C5A | 111.37 (10) | N4—C4—C5 | 118.90 (11) |
O41A—C41A—C4A | 120.71 (12) | C3—C4—C5 | 122.41 (12) |
O41A—C41A—N41A | 122.57 (13) | C4—C5—C6 | 117.94 (11) |
N41A—C41A—C4A | 116.72 (11) | C1—C6—C5 | 121.07 (11) |
N1A—C2A—H21A | 110.00 | O11—C11—O12 | 125.56 (12) |
H21A—C2A—H22A | 108.00 | O11—C11—C1 | 117.65 (11) |
N1A—C2A—H22A | 110.00 | O12—C11—C1 | 116.79 (11) |
C3A—C2A—H21A | 110.00 | C1—C2—H2 | 120.00 |
C3A—C2A—H22A | 110.00 | C3—C2—H2 | 119.00 |
C2A—C3A—H31A | 109.00 | C2—C3—H3 | 121.00 |
C2A—C3A—H32A | 109.00 | C4—C3—H3 | 121.00 |
C4A—C3A—H31A | 109.00 | C4—C5—H5 | 121.00 |
H31A—C3A—H32A | 108.00 | C6—C5—H5 | 121.00 |
C4A—C3A—H32A | 109.00 | C1—C6—H6 | 119.00 |
C41A—C4A—H4A | 108.00 | C5—C6—H6 | 119.00 |
C6A—N1A—C2A—C3A | 57.56 (14) | C4A—C5A—C6A—N1A | 54.50 (14) |
C2A—N1A—C6A—C5A | −56.10 (14) | C6—C1—C2—C3 | 0.08 (19) |
O41—N4—C4—C3 | −169.40 (12) | C11—C1—C2—C3 | 179.36 (12) |
O41—N4—C4—C5 | 10.16 (18) | C2—C1—C6—C5 | −0.48 (18) |
O42—N4—C4—C3 | 10.14 (18) | C11—C1—C6—C5 | −179.75 (11) |
O42—N4—C4—C5 | −170.29 (12) | C2—C1—C11—O11 | 16.61 (18) |
N1A—C2A—C3A—C4A | −58.22 (14) | C2—C1—C11—O12 | −163.01 (12) |
C2A—C3A—C4A—C5A | 56.72 (14) | C6—C1—C11—O11 | −164.13 (12) |
C2A—C3A—C4A—C41A | −179.93 (12) | C6—C1—C11—O12 | 16.26 (18) |
C5A—C4A—C41A—O41A | 107.96 (14) | C1—C2—C3—C4 | 0.7 (2) |
C5A—C4A—C41A—N41A | −72.89 (15) | C2—C3—C4—N4 | 178.49 (12) |
C3A—C4A—C41A—O41A | −14.57 (17) | C2—C3—C4—C5 | −1.1 (2) |
C3A—C4A—C5A—C6A | −54.70 (13) | N4—C4—C5—C6 | −178.88 (11) |
C41A—C4A—C5A—C6A | −178.55 (10) | C3—C4—C5—C6 | 0.67 (19) |
C3A—C4A—C41A—N41A | 164.58 (12) | C4—C5—C6—C1 | 0.12 (19) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1A—H11A···O11i | 0.938 (15) | 1.933 (15) | 2.8503 (15) | 165.4 (14) |
N1A—H12A···O12 | 0.936 (18) | 1.808 (17) | 2.7278 (15) | 167.0 (14) |
N41A—H41A···O41Aii | 0.949 (19) | 1.940 (19) | 2.8833 (16) | 172.3 (14) |
N41A—H42A···O12iii | 0.882 (16) | 2.078 (16) | 2.9401 (15) | 165.5 (14) |
C3—H3···O42iv | 0.93 | 2.58 | 3.3027 (18) | 135 |
C5—H5···O11v | 0.93 | 2.54 | 3.4407 (16) | 163 |
C2A—H22A···O41vi | 0.97 | 2.45 | 3.4064 (17) | 167 |
C6A—H61A···O41Avii | 0.97 | 2.47 | 3.3027 (16) | 144 |
Symmetry codes: (i) −x, −y+2, −z+1; (ii) −x, −y+2, −z; (iii) x, −y+3/2, z−1/2; (iv) −x+1, −y+2, −z+2; (v) −x+1, y−1/2, −z+3/2; (vi) −x+1, y+1/2, −z+3/2; (vii) −x, y−1/2, −z+1/2. |
C6H13N2O+·C7H3N2O6− | Z = 2 |
Mr = 340.30 | F(000) = 356 |
Triclinic, P1 | Dx = 1.473 Mg m−3 |
Hall symbol: -P 1 | Melting point = 473–475 K |
a = 5.7159 (5) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 11.9970 (12) Å | Cell parameters from 3824 reflections |
c = 12.6447 (10) Å | θ = 3.1–28.7° |
α = 111.370 (8)° | µ = 0.12 mm−1 |
β = 99.504 (7)° | T = 200 K |
γ = 100.772 (8)° | Plate, yellow |
V = 767.04 (14) Å3 | 0.30 × 0.25 × 0.15 mm |
Oxford Gemini-S Ultra CCD area-detector diffractometer | 2996 independent reflections |
Radiation source: Enhance (Mo) X-ray source | 2279 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.029 |
ω scans | θmax = 26.0°, θmin = 3.1° |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009) | h = −7→7 |
Tmin = 0.967, Tmax = 0.980 | k = −14→14 |
9445 measured reflections | l = −15→15 |
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)] = 0.040 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.092 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0464P)2 + 0.0623P] where P = (Fo2 + 2Fc2)/3 |
2996 reflections | (Δ/σ)max < 0.001 |
233 parameters | Δρmax = 0.16 e Å−3 |
0 restraints | Δρmin = −0.21 e Å−3 |
C6H13N2O+·C7H3N2O6− | γ = 100.772 (8)° |
Mr = 340.30 | V = 767.04 (14) Å3 |
Triclinic, P1 | Z = 2 |
a = 5.7159 (5) Å | Mo Kα radiation |
b = 11.9970 (12) Å | µ = 0.12 mm−1 |
c = 12.6447 (10) Å | T = 200 K |
α = 111.370 (8)° | 0.30 × 0.25 × 0.15 mm |
β = 99.504 (7)° |
Oxford Gemini-S Ultra CCD area-detector diffractometer | 2996 independent reflections |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009) | 2279 reflections with I > 2σ(I) |
Tmin = 0.967, Tmax = 0.980 | Rint = 0.029 |
9445 measured reflections |
R[F2 > 2σ(F2)] = 0.040 | 0 restraints |
wR(F2) = 0.092 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | Δρmax = 0.16 e Å−3 |
2996 reflections | Δρmin = −0.21 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 | 0.0238 (2) | 0.94674 (11) | 0.12385 (10) | 0.0368 (4) | |
N1A | 0.4414 (3) | 0.69533 (13) | 0.25966 (12) | 0.0313 (5) | |
N41A | 0.2169 (3) | 0.91229 (13) | −0.02221 (12) | 0.0304 (4) | |
C2A | 0.4128 (3) | 0.64556 (16) | 0.13017 (14) | 0.0359 (6) | |
C3A | 0.2496 (3) | 0.70614 (15) | 0.07572 (14) | 0.0304 (5) | |
C4A | 0.3521 (3) | 0.84774 (14) | 0.13217 (13) | 0.0273 (5) | |
C5A | 0.3880 (3) | 0.89615 (15) | 0.26500 (13) | 0.0334 (5) | |
C6A | 0.5495 (3) | 0.83224 (16) | 0.31662 (14) | 0.0356 (6) | |
C41A | 0.1842 (3) | 0.90734 (14) | 0.07838 (13) | 0.0269 (5) | |
O11 | 0.9403 (2) | 0.58841 (12) | 0.23351 (11) | 0.0435 (4) | |
O12 | 0.6878 (2) | 0.56279 (11) | 0.34513 (10) | 0.0371 (4) | |
O31 | 0.7183 (2) | 0.25715 (13) | 0.50782 (12) | 0.0527 (5) | |
O32 | 0.9621 (3) | 0.13842 (13) | 0.47058 (13) | 0.0593 (6) | |
O51 | 1.4706 (2) | 0.16989 (12) | 0.20496 (12) | 0.0534 (5) | |
O52 | 1.4018 (2) | 0.28118 (15) | 0.10752 (12) | 0.0605 (5) | |
N3 | 0.8779 (3) | 0.22183 (14) | 0.46136 (12) | 0.0393 (5) | |
N5 | 1.3703 (2) | 0.24465 (14) | 0.18419 (13) | 0.0416 (5) | |
C1 | 0.9562 (3) | 0.43419 (14) | 0.30805 (12) | 0.0259 (4) | |
C2 | 0.8795 (3) | 0.37918 (14) | 0.38042 (12) | 0.0263 (5) | |
C3 | 0.9707 (3) | 0.28290 (15) | 0.38908 (13) | 0.0284 (5) | |
C4 | 1.1348 (3) | 0.23763 (15) | 0.32766 (14) | 0.0319 (5) | |
C5 | 1.2050 (3) | 0.29341 (15) | 0.25593 (13) | 0.0307 (5) | |
C6 | 1.1204 (3) | 0.39006 (15) | 0.24469 (13) | 0.0294 (5) | |
C11 | 0.8538 (3) | 0.53762 (15) | 0.29406 (14) | 0.0296 (5) | |
H4A | 0.51320 | 0.86850 | 0.11650 | 0.0330* | |
H11A | 0.283 (3) | 0.6745 (16) | 0.2719 (14) | 0.034 (4)* | |
H12A | 0.542 (4) | 0.652 (2) | 0.2898 (18) | 0.062 (6)* | |
H21A | 0.34100 | 0.55630 | 0.09560 | 0.0430* | |
H22A | 0.57320 | 0.66170 | 0.11430 | 0.0430* | |
H31A | 0.08530 | 0.68400 | 0.08590 | 0.0370* | |
H32A | 0.23790 | 0.67560 | −0.00790 | 0.0370* | |
H41A | 0.332 (4) | 0.8823 (18) | −0.0494 (17) | 0.049 (6)* | |
H42A | 0.135 (3) | 0.9531 (17) | −0.0548 (15) | 0.038 (5)* | |
H51A | 0.46370 | 0.98510 | 0.30060 | 0.0400* | |
H52A | 0.22910 | 0.88140 | 0.28250 | 0.0400* | |
H61A | 0.71290 | 0.85250 | 0.30480 | 0.0430* | |
H62A | 0.56460 | 0.86170 | 0.40040 | 0.0430* | |
H2 | 0.76780 | 0.40680 | 0.42270 | 0.0320* | |
H4 | 1.19480 | 0.17290 | 0.33430 | 0.0380* | |
H6 | 1.17280 | 0.42520 | 0.19520 | 0.0350* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O41A | 0.0379 (6) | 0.0498 (8) | 0.0405 (7) | 0.0247 (6) | 0.0186 (5) | 0.0282 (6) |
N1A | 0.0300 (8) | 0.0401 (9) | 0.0389 (8) | 0.0169 (7) | 0.0140 (6) | 0.0271 (7) |
N41A | 0.0344 (8) | 0.0368 (8) | 0.0295 (7) | 0.0181 (7) | 0.0109 (6) | 0.0188 (6) |
C2A | 0.0423 (10) | 0.0375 (10) | 0.0397 (9) | 0.0194 (8) | 0.0189 (8) | 0.0210 (8) |
C3A | 0.0342 (9) | 0.0319 (9) | 0.0302 (8) | 0.0118 (7) | 0.0105 (7) | 0.0158 (7) |
C4A | 0.0237 (8) | 0.0314 (9) | 0.0337 (9) | 0.0096 (7) | 0.0096 (6) | 0.0190 (7) |
C5A | 0.0365 (9) | 0.0328 (9) | 0.0323 (9) | 0.0112 (7) | 0.0042 (7) | 0.0160 (7) |
C6A | 0.0329 (9) | 0.0422 (11) | 0.0346 (9) | 0.0088 (8) | 0.0037 (7) | 0.0217 (8) |
C41A | 0.0263 (8) | 0.0256 (8) | 0.0299 (8) | 0.0063 (7) | 0.0061 (6) | 0.0133 (7) |
O11 | 0.0359 (7) | 0.0550 (8) | 0.0597 (8) | 0.0151 (6) | 0.0160 (6) | 0.0426 (7) |
O12 | 0.0362 (6) | 0.0428 (7) | 0.0473 (7) | 0.0214 (6) | 0.0174 (5) | 0.0270 (6) |
O31 | 0.0591 (8) | 0.0658 (10) | 0.0547 (8) | 0.0227 (7) | 0.0310 (7) | 0.0386 (7) |
O32 | 0.0791 (10) | 0.0515 (9) | 0.0692 (10) | 0.0283 (8) | 0.0210 (8) | 0.0429 (8) |
O51 | 0.0371 (7) | 0.0352 (8) | 0.0740 (10) | 0.0143 (6) | 0.0190 (6) | 0.0025 (7) |
O52 | 0.0528 (8) | 0.0812 (11) | 0.0462 (8) | 0.0190 (8) | 0.0292 (7) | 0.0171 (8) |
N3 | 0.0452 (9) | 0.0401 (9) | 0.0371 (8) | 0.0107 (7) | 0.0097 (7) | 0.0213 (7) |
N5 | 0.0262 (8) | 0.0396 (9) | 0.0385 (9) | 0.0022 (7) | 0.0094 (6) | −0.0039 (7) |
C1 | 0.0223 (8) | 0.0278 (8) | 0.0236 (7) | 0.0044 (6) | 0.0020 (6) | 0.0087 (6) |
C2 | 0.0240 (8) | 0.0284 (9) | 0.0238 (8) | 0.0066 (7) | 0.0058 (6) | 0.0080 (6) |
C3 | 0.0304 (8) | 0.0278 (9) | 0.0249 (8) | 0.0066 (7) | 0.0041 (6) | 0.0103 (7) |
C4 | 0.0306 (9) | 0.0255 (9) | 0.0337 (9) | 0.0098 (7) | 0.0017 (7) | 0.0074 (7) |
C5 | 0.0239 (8) | 0.0317 (9) | 0.0278 (8) | 0.0066 (7) | 0.0065 (6) | 0.0030 (7) |
C6 | 0.0252 (8) | 0.0342 (9) | 0.0243 (8) | 0.0018 (7) | 0.0054 (6) | 0.0104 (7) |
C11 | 0.0247 (8) | 0.0333 (9) | 0.0331 (9) | 0.0066 (7) | 0.0033 (7) | 0.0184 (7) |
O41A—C41A | 1.238 (2) | C5A—C6A | 1.515 (3) |
O11—C11 | 1.247 (2) | C2A—H21A | 0.9700 |
O12—C11 | 1.255 (2) | C2A—H22A | 0.9700 |
O31—N3 | 1.224 (2) | C3A—H32A | 0.9700 |
O32—N3 | 1.222 (2) | C3A—H31A | 0.9700 |
O51—N5 | 1.231 (2) | C4A—H4A | 0.9800 |
O52—N5 | 1.226 (2) | C5A—H51A | 0.9700 |
N1A—C6A | 1.487 (3) | C5A—H52A | 0.9700 |
N1A—C2A | 1.492 (2) | C6A—H61A | 0.9700 |
N41A—C41A | 1.336 (2) | C6A—H62A | 0.9700 |
N1A—H12A | 0.96 (2) | C1—C2 | 1.389 (2) |
N1A—H11A | 0.947 (18) | C1—C6 | 1.389 (2) |
N41A—H42A | 0.89 (2) | C1—C11 | 1.520 (3) |
N41A—H41A | 0.87 (2) | C2—C3 | 1.384 (3) |
N3—C3 | 1.468 (2) | C3—C4 | 1.379 (2) |
N5—C5 | 1.470 (2) | C4—C5 | 1.376 (3) |
C2A—C3A | 1.509 (3) | C5—C6 | 1.380 (3) |
C3A—C4A | 1.531 (3) | C2—H2 | 0.9300 |
C4A—C41A | 1.513 (2) | C4—H4 | 0.9300 |
C4A—C5A | 1.527 (2) | C6—H6 | 0.9300 |
C2A—N1A—C6A | 111.66 (14) | C3A—C4A—H4A | 108.00 |
H11A—N1A—H12A | 108.3 (18) | C41A—C4A—H4A | 108.00 |
C2A—N1A—H12A | 107.0 (12) | C5A—C4A—H4A | 108.00 |
C6A—N1A—H11A | 110.2 (12) | C6A—C5A—H51A | 109.00 |
C2A—N1A—H11A | 107.3 (10) | C4A—C5A—H52A | 109.00 |
C6A—N1A—H12A | 112.1 (14) | C4A—C5A—H51A | 109.00 |
C41A—N41A—H42A | 120.4 (11) | C6A—C5A—H52A | 109.00 |
H41A—N41A—H42A | 121.8 (18) | H51A—C5A—H52A | 108.00 |
C41A—N41A—H41A | 117.4 (14) | H61A—C6A—H62A | 108.00 |
O32—N3—C3 | 118.39 (16) | N1A—C6A—H61A | 110.00 |
O31—N3—O32 | 124.01 (17) | N1A—C6A—H62A | 110.00 |
O31—N3—C3 | 117.60 (16) | C5A—C6A—H61A | 110.00 |
O51—N5—C5 | 118.14 (15) | C5A—C6A—H62A | 110.00 |
O52—N5—C5 | 118.22 (15) | C2—C1—C6 | 119.13 (16) |
O51—N5—O52 | 123.64 (14) | C2—C1—C11 | 120.61 (15) |
N1A—C2A—C3A | 110.18 (14) | C6—C1—C11 | 120.21 (15) |
C2A—C3A—C4A | 110.96 (14) | C1—C2—C3 | 119.41 (16) |
C5A—C4A—C41A | 111.63 (14) | N3—C3—C2 | 118.55 (15) |
C3A—C4A—C41A | 110.39 (14) | N3—C3—C4 | 118.65 (17) |
C3A—C4A—C5A | 110.00 (14) | C2—C3—C4 | 122.70 (16) |
C4A—C5A—C6A | 110.83 (14) | C3—C4—C5 | 116.36 (17) |
N1A—C6A—C5A | 110.25 (14) | N5—C5—C4 | 118.51 (16) |
O41A—C41A—N41A | 122.33 (16) | N5—C5—C6 | 118.27 (15) |
O41A—C41A—C4A | 121.88 (14) | C4—C5—C6 | 123.17 (16) |
N41A—C41A—C4A | 115.78 (15) | C1—C6—C5 | 119.23 (16) |
N1A—C2A—H21A | 110.00 | O11—C11—O12 | 126.51 (18) |
C3A—C2A—H22A | 110.00 | O11—C11—C1 | 117.67 (15) |
N1A—C2A—H22A | 110.00 | O12—C11—C1 | 115.82 (16) |
C3A—C2A—H21A | 110.00 | C1—C2—H2 | 120.00 |
H21A—C2A—H22A | 108.00 | C3—C2—H2 | 120.00 |
C4A—C3A—H31A | 109.00 | C3—C4—H4 | 122.00 |
C2A—C3A—H31A | 109.00 | C5—C4—H4 | 122.00 |
C2A—C3A—H32A | 109.00 | C1—C6—H6 | 120.00 |
H31A—C3A—H32A | 108.00 | C5—C6—H6 | 120.00 |
C4A—C3A—H32A | 109.00 | ||
C6A—N1A—C2A—C3A | −58.9 (2) | C3A—C4A—C5A—C6A | 55.18 (19) |
C2A—N1A—C6A—C5A | 58.87 (19) | C4A—C5A—C6A—N1A | −56.93 (19) |
O31—N3—C3—C2 | 2.1 (2) | C6—C1—C2—C3 | 0.9 (2) |
O31—N3—C3—C4 | −174.46 (16) | C11—C1—C2—C3 | 178.26 (15) |
O32—N3—C3—C2 | −178.67 (16) | C2—C1—C6—C5 | −0.6 (2) |
O32—N3—C3—C4 | 4.8 (2) | C11—C1—C6—C5 | −177.95 (15) |
O52—N5—C5—C4 | 168.85 (16) | C2—C1—C11—O11 | 175.83 (15) |
O52—N5—C5—C6 | −8.8 (2) | C2—C1—C11—O12 | −4.5 (2) |
O51—N5—C5—C6 | 170.81 (15) | C6—C1—C11—O11 | −6.8 (2) |
O51—N5—C5—C4 | −11.6 (2) | C6—C1—C11—O12 | 172.89 (15) |
N1A—C2A—C3A—C4A | 56.79 (19) | C1—C2—C3—N3 | −176.96 (14) |
C2A—C3A—C4A—C5A | −55.30 (18) | C1—C2—C3—C4 | −0.6 (2) |
C2A—C3A—C4A—C41A | −178.92 (14) | N3—C3—C4—C5 | 176.32 (15) |
C41A—C4A—C5A—C6A | 178.08 (15) | C2—C3—C4—C5 | −0.1 (2) |
C3A—C4A—C41A—O41A | 95.34 (18) | C3—C4—C5—N5 | −177.09 (15) |
C3A—C4A—C41A—N41A | −83.34 (19) | C3—C4—C5—C6 | 0.4 (3) |
C5A—C4A—C41A—O41A | −27.3 (2) | N5—C5—C6—C1 | 177.41 (14) |
C5A—C4A—C41A—N41A | 153.99 (16) | C4—C5—C6—C1 | −0.1 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1A—H11A···O11i | 0.947 (18) | 1.925 (18) | 2.822 (2) | 157.4 (15) |
N1A—H12A···O12 | 0.96 (2) | 1.74 (2) | 2.696 (2) | 173 (2) |
N41A—H41A···O51ii | 0.87 (2) | 2.37 (2) | 3.141 (2) | 147.5 (18) |
N41A—H42A···O41Aiii | 0.89 (2) | 1.99 (2) | 2.877 (2) | 175.8 (17) |
Symmetry codes: (i) x−1, y, z; (ii) −x+2, −y+1, −z; (iii) −x, −y+2, −z. |
Experimental details
(I) | (II) | (III) | (IV) | |
Crystal data | ||||
Chemical formula | C6H13N2O+·C7H4NO4− | C6H13N2O+·C7H4NO4− | C6H13N2O+·C7H4NO4− | C6H13N2O+·C7H3N2O6− |
Mr | 295.30 | 295.30 | 295.30 | 340.30 |
Crystal system, space group | Monoclinic, C2/c | Monoclinic, P21/c | Monoclinic, P21/c | Triclinic, P1 |
Temperature (K) | 200 | 200 | 200 | 200 |
a, b, c (Å) | 29.035 (3), 9.7660 (9), 10.5779 (12) | 14.2504 (15), 6.8276 (5), 15.4580 (17) | 7.5371 (6), 12.4216 (12), 15.0911 (13) | 5.7159 (5), 11.9970 (12), 12.6447 (10) |
α, β, γ (°) | 90, 105.020 (12), 90 | 90, 115.410 (13), 90 | 90, 99.848 (7), 90 | 111.370 (8), 99.504 (7), 100.772 (8) |
V (Å3) | 2897.0 (5) | 1358.5 (2) | 1392.1 (2) | 767.04 (14) |
Z | 8 | 4 | 4 | 2 |
Radiation type | Mo Kα | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.11 | 0.11 | 0.11 | 0.12 |
Crystal size (mm) | 0.50 × 0.26 × 0.12 | 0.30 × 0.20 × 0.15 | 0.30 × 0.18 × 0.15 | 0.30 × 0.25 × 0.15 |
Data collection | ||||
Diffractometer | Oxford Gemini-S Ultra CCD area-detector diffractometer | Oxford Gemini S Ultra CCD area-detector diffractometer | Oxford Gemini-S Ultra CCD area-detector diffractometer | Oxford Gemini-S Ultra CCD area-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 | 0.940, 0.980 | 0.948, 0.980 | 0.952, 0.980 | 0.967, 0.980 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9784, 2832, 2076 | 9250, 2669, 1982 | 14612, 2727, 2279 | 9445, 2996, 2279 |
Rint | 0.029 | 0.026 | 0.042 | 0.029 |
(sin θ/λ)max (Å−1) | 0.617 | 0.617 | 0.617 | 0.617 |
Refinement | ||||
R[F2 > 2σ(F2)], wR(F2), S | 0.035, 0.087, 0.93 | 0.038, 0.093, 1.04 | 0.035, 0.095, 1.14 | 0.040, 0.092, 1.05 |
No. of reflections | 2832 | 2669 | 2727 | 2996 |
No. of parameters | 206 | 206 | 206 | 233 |
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) | 0.15, −0.17 | 0.21, −0.20 | 0.21, −0.19 | 0.16, −0.21 |
Computer programs: CrysAlis PRO (Oxford Diffraction, 2009), 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···O11i | 0.941 (17) | 1.848 (17) | 2.7759 (17) | 168.3 (17) |
N1A—H12A···O12 | 0.951 (18) | 1.792 (17) | 2.7380 (17) | 172.5 (13) |
N41A—H41A···O41Aii | 0.90 (2) | 2.00 (2) | 2.8978 (19) | 174.6 (15) |
N41A—H42A···O41Aiii | 0.878 (16) | 2.313 (16) | 3.0914 (17) | 147.8 (13) |
Symmetry codes: (i) −x+1/2, −y+3/2, −z; (ii) −x, −y+1, −z; (iii) x, −y+1, z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1A—H11A···O41Ai | 0.97 (2) | 1.88 (2) | 2.7933 (19) | 157 (2) |
N1A—H12A···O11 | 0.93 (2) | 1.88 (3) | 2.7587 (19) | 156 (2) |
N1A—H12A···O12 | 0.93 (2) | 2.36 (2) | 3.0599 (19) | 132 (2) |
N41A—H41A···O32ii | 0.863 (19) | 2.213 (19) | 3.068 (2) | 171.1 (13) |
N41A—H42A···O12iii | 0.91 (2) | 1.98 (2) | 2.844 (2) | 159 (2) |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x, −y, −z; (iii) x, −y−1/2, z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1A—H11A···O11i | 0.938 (15) | 1.933 (15) | 2.8503 (15) | 165.4 (14) |
N1A—H12A···O12 | 0.936 (18) | 1.808 (17) | 2.7278 (15) | 167.0 (14) |
N41A—H41A···O41Aii | 0.949 (19) | 1.940 (19) | 2.8833 (16) | 172.3 (14) |
N41A—H42A···O12iii | 0.882 (16) | 2.078 (16) | 2.9401 (15) | 165.5 (14) |
Symmetry codes: (i) −x, −y+2, −z+1; (ii) −x, −y+2, −z; (iii) x, −y+3/2, z−1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1A—H11A···O11i | 0.947 (18) | 1.925 (18) | 2.822 (2) | 157.4 (15) |
N1A—H12A···O12 | 0.96 (2) | 1.74 (2) | 2.696 (2) | 173 (2) |
N41A—H41A···O51ii | 0.87 (2) | 2.37 (2) | 3.141 (2) | 147.5 (18) |
N41A—H42A···O41Aiii | 0.89 (2) | 1.99 (2) | 2.877 (2) | 175.8 (17) |
Symmetry codes: (i) x−1, y, z; (ii) −x+2, −y+1, −z; (iii) −x, −y+2, −z. |
The alicyclic amide 4-carbamoylpiperidine (isonipecotamide, INIPA) (O'Neil, 2001) or any of its compounds previously had no structural representation in the crystallographic literature, prompting our investigation of the possible use of this Lewis base for the formation of crystalline proton-transfer compounds with organic acids. We have recently reported the crystal structures and hydrogen-bonding features of the anhydrous 1:1 salts with both picric acid and 3,5-dinitrosalicylic acid (two polymorphs, both picrates) (Smith & Wermuth, 2010b), as well the acetate (Smith & Wermuth, 2010a) and the 2:1 salt with biphenyl-4,4'-disulfonic acid (Smith et al., 2010).
Among a number of 1:1 stoichiometric reactions of INIPA with aromatic acids in 50% aqueous ethanol, we also obtained good crystals of the anhydrous salts with the three isomeric mononitro-substituted benzoic acids and with 3,5-dinitrobenzoic acid, namely 4-carbamoylpiperidinium 2-nitrobenzoate, (I), 4-carbamoylpiperidinium 3-nitrobenzoate, (II), 4-carbamoylpiperidinium 4-nitrobenzoate, (III), and 4-carbamoylpiperidinium 3,5-dinitrobenzoate, (IV), and their structures and hydrogen-bonding modes are reported here. We have also recently determined the structures of a number of 1:1 proton-transfer salts of INIPA with aromatic dicarboxylic acids and heteroaromatic carboxylic acids (Smith & Wermuth, 2010c).
With the structures of (I)–(IV) (Figs. 1–4), proton transfer occurs to the hetero-N atom of the piperidine ring, and the resulting group is subsequently involved in both hydrogen-bonded cation–anion interactions [single in (I), (III) and (IV), but asymmetric bidentate in (III)]. Featured in the hydrogen bonding of three of these [(I), (II) and (IV)] is the head-to-head cyclic amide–amide homodimer motif [graph set R22(8) (Etter et al., 1990)], formed through a duplex N—H···O hydrogen-bonding association. Hydrogen-bonding extensions (Tables 1–4) result in structures which are three-dimensional in (I), two-dimensional in (II) and (III), and one-dimensional in (IV) (Figs. 5–8). The head-to-head amide hydrogen-bonding motif [the `cyclic amide motif' (motif 23) (Allen et al., 1998)] has a surprisingly low probability of formation among the total set of known amide structures, but when restricted to primary amides which have no competing functional substituent groups or other associative companion species such as molecules of solvation the probability is much higher. No amide–amide dimers were found in any of the phenolate structures (Smith & Wermuth, 2010c), but in the biphenyl-4,4'-disulfonate salt there are two separate examples of the dimer involving the three independent INIPA cations, one centrosymmetric and the other noncentrosymmetric (Smith et al., 2010).
In the structure of (I) (Fig. 1), the 2-nitrobenzoate salt, the centrosymmetric R22(8) INIPA cation amide–amide homodimers are extended laterally through N—H···O hydrogen bonds (Table 1). giving cyclic R42(8) interactions which are centred on crystallographic twofold rotation axes, forming ribbons which extend along the c cell direction at a = 0, 1/2 (Fig. 5). These ribbons incorporate the cations through centrosymmetric cyclic piperidine–carboxylate N—H···O associations [graph set R44(12)], giving interconnected sheets in the three-dimensional structure. The nitro group of the anion is unassociated, and both it and the carboxylate group are significantly rotated out of the plane of the benzene ring [torsion angles C1—C2—N2—O22 = -131.60 (13)° and C2—C1—C11—O11 = -138.95 (14)°].
With the structure of the 3-nitrobenzoate salt, (II) (Fig. 2), in which no INIPA amide–amide dimer is present, a different homomolecular head-to-tail cyclic dimer is present involving the R22(14) duplex piperidinium N—H···Oamide hydrogen-bonding association (Fig. 6). This dimer has precedence in a single example among the known INIPA structures in the picrate (Smith & Wermuth, 2010b). In (II), structure extension occurs through hydrogen-bonding associations between both amide H-atom donors and the carboxylate and nitro O-atom acceptors, and between the second piperidinium H-atom donor and the carboxylate O-atom acceptors of the anion, in an asymmetric three-centre cyclic R12(4) mode (Table 2). This results in the two-dimensional structure, which also features large cyclic rings [R44(30)]. The carboxylate group of the anion is approximately coplanar with the benzene ring, while the nitro group is rotated slightly out of the plane [torsion angles C2—C1—C11—O11 = -174.27 (16)° and C2—C3—N3—O32 = -167.65 (16)°].
In the structure of the 4-nitrobenzoate salt, (III) (Fig. 3), the centrosymmetric R22(8) amide–amide dimers are linked through the two carboxylate O-atom acceptors of the anions via bridging amide–carboxylate N—H···O and piperidinium–carboxylate N—H..O hydrogen bonds, giving the two-dimensional sheet structure. Within this structure are centrosymmetric R44(12) associations (Fig. 7). The nitro group is unassociated. Both the carboxylate and nitro groups of the anion in (III) are rotated slightly out of the plane of the benzene ring [torsion angles C2—C1—C11—O12 = -163.01 (12)° and C3—C4—N4—O41 = 169.40 (12)°].
In the 3,5-dinitrobenzoate salt, (IV), the amide–amide dimer is also centrosymmetric but with the dimers linked to the anions through amide N—H···Onitro interactions (Table 4), the second nitro group (at C3) being unassociated. The piperidinium groups extend the structure into one-dimensional ribbons via N—H···Ocarboxylate hydrogen bonds (Fig. 8). The carboxylate group of the anion in (IV) is approximately coplanar with the benzene ring [torsion angle C2—C1—C11—O11 = 175.83 (15)°], while the nitro groups are either close to coplanar [C2—C3—N3—O32 = -178.67 (16)°] or rotated slightly out of the plane [C4—C5—N5—O52 = 168.85 (16)°].
With the INIPA cations in (I)–(IV), the conformation of the amide group is variable [minimum torsion angle C3A/C5A—C4A—C41A—O41A = -15.24 (19)° in (I), 35.9 (2)° in (II), 14.2 (3)° in (III) and -27.3 (2)° in (IV)]. However, the largest value is associated with the structure of (II), where no amide–amide homodimer is formed.
The structures reported here demonstrate the utility of the INIPA cation as a synthon with previously unrecognized potential for structure-assembly applications, in many cases facilitated through the formation of the robust cyclic head-to-head amide–amide hydrogen-bonded dimer association.