Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270110042356/gd3361sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270110042356/gd3361Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270110042356/gd3361IIsup3.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270110042356/gd3361IIIsup4.hkl |
CCDC references: 810010; 810011; 810012
The title compounds, (I)–(III), were synthesized by heating together under reflux for 10 min 1 mmol quantities of, respectively, rac-trans-cyclohexane-1,2-dicarboxylic acid [for (I)], benzene-1,3-dicarboxylic acid (isophthalic acid) [for (II)] and benzene-1,4-dicarboxylic acid (terephthalic acid) [for (III)], with guanidine carbonate [1 mmol?] in 50% aqueous propan-2-ol (50 ml). After concentration to ca 30 ml, partial room-temperature evaporation of the hot-filtered solutions gave large colourless plates [(I) and (III)] or small colourless flat prisms [(II)] [Please clarify - block given in CIF tables for (I) and (III), and platelet for (II)] [m.p. 525 K for (I), 474 K for (II) and 505 K for (III)]. For (I) and (III), specimens suitable for X-ray analysis were cleaved from larger crystals.
H atoms involved in hydrogen-bonding interactions were located by difference methods and their positional and isotropic displacement parameters were refined, with the exception of the water H atoms of (III) which were constrained with Uiso(H) = 1.2Ueq(O). Aromatic H atoms were included in the refinement in calculated positions using a riding-model approximation, with C–H = 0.95 Å and with Uiso(H) = 1.2Ueq(C).
Data collection: CrysAlis PRO (Oxford Diffraction, 2009) for (I), (II); CrysAlis CCD (Oxford Diffraction, 2008) for (III). Cell refinement: CrysAlis PRO (Oxford Diffraction, 2009) for (I), (II); CrysAlis RED (Oxford Diffraction, 2008) for (III). Data reduction: CrysAlis PRO (Oxford Diffraction, 2009) for (I), (II); CrysAlis RED (Oxford Diffraction, 2008) for (III). Program(s) used to solve structure: SIR92 (Altomare et al., 1994) for (I), (III); SHELXS97 (Sheldrick, 2008) for (II). Program(s) used to refine structure: SHELXL97 (Sheldrick, 2008) within WinGX (Farrugia, 1999) for (I), (III); SHELXL97 (Sheldrick, 2008) for (II). For all compounds, molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: PLATON (Spek, 2009).
2CH6N3+·C8H10O42− | F(000) = 624 |
Mr = 290.34 | Dx = 1.325 Mg m−3 |
Monoclinic, P21/c | Melting point: 525 K |
Hall symbol: -P 2ybc | Mo Kα radiation, λ = 0.71073 Å |
a = 10.7425 (10) Å | Cell parameters from 4460 reflections |
b = 16.0538 (15) Å | θ = 3.3–27.3° |
c = 8.5067 (8) Å | µ = 0.10 mm−1 |
β = 97.224 (9)° | T = 200 K |
V = 1455.4 (2) Å3 | Block, colourless |
Z = 4 | 0.50 × 0.50 × 0.45 mm |
Oxford Gemini-S CCD area-detector diffractometer | 2858 independent reflections |
Radiation source: Enhance (Mo) X-ray source | 2222 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.026 |
ω scans | θmax = 26.0°, θmin = 3.5° |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009) | h = −13→13 |
Tmin = 0.956, Tmax = 0.980 | k = −19→19 |
10102 measured reflections | l = −10→10 |
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) = 0.089 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0499P)2] where P = (Fo2 + 2Fc2)/3 |
2858 reflections | (Δ/σ)max = 0.001 |
229 parameters | Δρmax = 0.21 e Å−3 |
0 restraints | Δρmin = −0.16 e Å−3 |
2CH6N3+·C8H10O42− | V = 1455.4 (2) Å3 |
Mr = 290.34 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 10.7425 (10) Å | µ = 0.10 mm−1 |
b = 16.0538 (15) Å | T = 200 K |
c = 8.5067 (8) Å | 0.50 × 0.50 × 0.45 mm |
β = 97.224 (9)° |
Oxford Gemini-S CCD area-detector diffractometer | 2858 independent reflections |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009) | 2222 reflections with I > 2σ(I) |
Tmin = 0.956, Tmax = 0.980 | Rint = 0.026 |
10102 measured reflections |
R[F2 > 2σ(F2)] = 0.035 | 0 restraints |
wR(F2) = 0.089 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | Δρmax = 0.21 e Å−3 |
2858 reflections | Δρmin = −0.16 e Å−3 |
229 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 | ||
O11 | 0.28367 (9) | 0.65888 (5) | 0.22616 (10) | 0.0388 (3) | |
O12 | 0.38881 (10) | 0.54439 (6) | 0.18356 (12) | 0.0532 (4) | |
O21 | 0.13764 (9) | 0.46127 (6) | 0.22862 (12) | 0.0467 (3) | |
O22 | 0.23469 (9) | 0.34074 (5) | 0.28527 (10) | 0.0383 (3) | |
C1 | 0.30811 (11) | 0.55434 (8) | 0.43121 (15) | 0.0317 (4) | |
C2 | 0.31330 (12) | 0.45930 (8) | 0.43500 (15) | 0.0326 (4) | |
C3 | 0.29719 (14) | 0.42556 (9) | 0.59977 (16) | 0.0457 (5) | |
C4 | 0.17857 (15) | 0.45842 (10) | 0.65769 (17) | 0.0520 (6) | |
C5 | 0.17851 (15) | 0.55300 (9) | 0.66004 (17) | 0.0504 (5) | |
C6 | 0.19322 (13) | 0.58938 (9) | 0.49817 (15) | 0.0380 (5) | |
C11 | 0.32681 (11) | 0.58714 (8) | 0.26785 (15) | 0.0336 (4) | |
C21 | 0.21998 (11) | 0.41906 (8) | 0.30680 (14) | 0.0307 (4) | |
N1A | −0.14413 (12) | 0.71415 (8) | 0.02360 (15) | 0.0404 (4) | |
N2A | 0.03214 (14) | 0.72334 (9) | 0.20525 (15) | 0.0451 (4) | |
N3A | 0.01995 (12) | 0.62499 (8) | 0.00845 (15) | 0.0410 (4) | |
C1A | −0.03143 (12) | 0.68735 (8) | 0.07946 (14) | 0.0319 (4) | |
N1B | 0.47601 (13) | 0.39190 (8) | 0.04825 (16) | 0.0447 (4) | |
N2B | 0.48434 (14) | 0.29413 (8) | 0.24571 (15) | 0.0443 (4) | |
N3B | 0.63072 (11) | 0.29361 (8) | 0.07093 (15) | 0.0379 (4) | |
C1B | 0.53062 (12) | 0.32699 (8) | 0.12250 (15) | 0.0326 (4) | |
H1 | 0.38110 | 0.57330 | 0.50300 | 0.0380* | |
H2 | 0.39750 | 0.44320 | 0.41330 | 0.0390* | |
H31 | 0.29400 | 0.36520 | 0.59590 | 0.0550* | |
H32 | 0.36920 | 0.44150 | 0.67410 | 0.0550* | |
H41 | 0.17300 | 0.43750 | 0.76350 | 0.0620* | |
H42 | 0.10590 | 0.43860 | 0.58850 | 0.0620* | |
H51 | 0.24670 | 0.57250 | 0.73680 | 0.0610* | |
H52 | 0.10040 | 0.57260 | 0.69310 | 0.0610* | |
H61 | 0.20100 | 0.64940 | 0.50710 | 0.0460* | |
H62 | 0.11850 | 0.57720 | 0.42530 | 0.0460* | |
H11A | −0.1770 (15) | 0.7570 (10) | 0.0751 (17) | 0.057 (5)* | |
H12A | −0.1796 (15) | 0.6929 (9) | −0.0661 (19) | 0.049 (4)* | |
H21A | 0.1066 (17) | 0.7077 (10) | 0.2333 (19) | 0.054 (5)* | |
H22A | −0.0005 (15) | 0.7647 (10) | 0.2435 (18) | 0.056 (5)* | |
H31A | −0.0265 (14) | 0.5966 (10) | −0.0628 (18) | 0.047 (4)* | |
H32A | 0.0840 (16) | 0.6043 (10) | 0.0540 (19) | 0.055 (5)* | |
H11B | 0.5152 (14) | 0.4140 (10) | −0.0279 (18) | 0.051 (4)* | |
H12B | 0.4289 (16) | 0.4197 (11) | 0.094 (2) | 0.062 (5)* | |
H21B | 0.4117 (17) | 0.3086 (10) | 0.2649 (19) | 0.055 (5)* | |
H22B | 0.5235 (15) | 0.2521 (10) | 0.2943 (18) | 0.058 (5)* | |
H31B | 0.6636 (15) | 0.2503 (11) | 0.1179 (18) | 0.054 (5)* | |
H32B | 0.6650 (15) | 0.3180 (10) | −0.0156 (18) | 0.056 (5)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O11 | 0.0442 (6) | 0.0319 (5) | 0.0428 (5) | 0.0016 (4) | 0.0148 (4) | 0.0009 (4) |
O12 | 0.0660 (7) | 0.0424 (6) | 0.0594 (7) | 0.0126 (5) | 0.0396 (6) | 0.0056 (5) |
O21 | 0.0394 (6) | 0.0456 (6) | 0.0507 (6) | 0.0093 (5) | −0.0120 (5) | −0.0135 (5) |
O22 | 0.0477 (6) | 0.0302 (5) | 0.0374 (5) | −0.0040 (4) | 0.0075 (4) | 0.0013 (4) |
C1 | 0.0250 (7) | 0.0364 (8) | 0.0338 (7) | −0.0064 (5) | 0.0039 (5) | −0.0036 (5) |
C2 | 0.0241 (7) | 0.0358 (7) | 0.0371 (7) | −0.0028 (5) | 0.0004 (5) | 0.0019 (5) |
C3 | 0.0522 (9) | 0.0464 (9) | 0.0347 (8) | −0.0104 (7) | −0.0088 (7) | 0.0068 (6) |
C4 | 0.0612 (11) | 0.0621 (10) | 0.0344 (8) | −0.0208 (8) | 0.0123 (7) | 0.0056 (7) |
C5 | 0.0546 (10) | 0.0605 (10) | 0.0395 (8) | −0.0134 (8) | 0.0193 (7) | −0.0070 (7) |
C6 | 0.0370 (8) | 0.0395 (8) | 0.0401 (8) | −0.0054 (6) | 0.0147 (6) | −0.0061 (6) |
C11 | 0.0282 (7) | 0.0329 (7) | 0.0415 (7) | −0.0039 (6) | 0.0113 (6) | −0.0023 (6) |
C21 | 0.0285 (7) | 0.0338 (7) | 0.0311 (7) | −0.0030 (5) | 0.0088 (5) | 0.0001 (5) |
N1A | 0.0447 (8) | 0.0398 (7) | 0.0367 (7) | 0.0112 (5) | 0.0053 (6) | −0.0060 (5) |
N2A | 0.0458 (8) | 0.0473 (8) | 0.0423 (7) | 0.0024 (6) | 0.0056 (6) | −0.0157 (6) |
N3A | 0.0318 (7) | 0.0473 (8) | 0.0428 (7) | 0.0072 (6) | 0.0006 (6) | −0.0166 (6) |
C1A | 0.0353 (7) | 0.0328 (7) | 0.0293 (7) | −0.0020 (6) | 0.0103 (6) | −0.0017 (5) |
N1B | 0.0503 (8) | 0.0420 (7) | 0.0461 (7) | 0.0147 (6) | 0.0231 (6) | 0.0129 (6) |
N2B | 0.0479 (8) | 0.0439 (8) | 0.0436 (7) | 0.0120 (6) | 0.0152 (6) | 0.0145 (6) |
N3B | 0.0405 (7) | 0.0315 (7) | 0.0430 (7) | 0.0064 (5) | 0.0107 (6) | 0.0016 (5) |
C1B | 0.0362 (7) | 0.0284 (7) | 0.0331 (7) | −0.0004 (5) | 0.0041 (6) | −0.0017 (5) |
O11—C11 | 1.2750 (15) | N3B—H32B | 0.948 (16) |
O12—C11 | 1.2445 (16) | N3B—H31B | 0.856 (17) |
O21—C21 | 1.2393 (16) | C1—C6 | 1.5300 (19) |
O22—C21 | 1.2832 (15) | C1—C2 | 1.5270 (18) |
N1A—C1A | 1.3160 (18) | C1—C11 | 1.5228 (18) |
N2A—C1A | 1.3272 (18) | C2—C3 | 1.5326 (19) |
N3A—C1A | 1.3250 (18) | C2—C21 | 1.5286 (18) |
N1A—H12A | 0.878 (16) | C3—C4 | 1.518 (2) |
N1A—H11A | 0.910 (16) | C4—C5 | 1.519 (2) |
N2A—H21A | 0.844 (18) | C5—C6 | 1.522 (2) |
N2A—H22A | 0.836 (16) | C1—H1 | 0.9800 |
N3A—H31A | 0.865 (15) | C2—H2 | 0.9800 |
N3A—H32A | 0.817 (17) | C3—H31 | 0.9700 |
N1B—C1B | 1.3175 (18) | C3—H32 | 0.9700 |
N2B—C1B | 1.3248 (18) | C4—H42 | 0.9700 |
N3B—C1B | 1.3246 (18) | C4—H41 | 0.9700 |
N1B—H11B | 0.890 (15) | C5—H51 | 0.9700 |
N1B—H12B | 0.810 (17) | C5—H52 | 0.9700 |
N2B—H22B | 0.871 (16) | C6—H61 | 0.9700 |
N2B—H21B | 0.850 (18) | C6—H62 | 0.9700 |
C1A—N1A—H12A | 117.8 (10) | O21—C21—C2 | 120.77 (11) |
H11A—N1A—H12A | 124.0 (14) | C11—C1—H1 | 106.00 |
C1A—N1A—H11A | 117.9 (10) | C2—C1—H1 | 106.00 |
C1A—N2A—H21A | 118.2 (11) | C6—C1—H1 | 106.00 |
C1A—N2A—H22A | 117.5 (11) | C21—C2—H2 | 107.00 |
H21A—N2A—H22A | 123.8 (16) | C3—C2—H2 | 107.00 |
C1A—N3A—H31A | 118.8 (10) | C1—C2—H2 | 107.00 |
C1A—N3A—H32A | 117.7 (11) | C2—C3—H32 | 109.00 |
H31A—N3A—H32A | 119.7 (15) | C4—C3—H31 | 109.00 |
C1B—N1B—H12B | 118.2 (12) | C4—C3—H32 | 109.00 |
H11B—N1B—H12B | 120.8 (16) | H31—C3—H32 | 108.00 |
C1B—N1B—H11B | 116.2 (10) | C2—C3—H31 | 109.00 |
C1B—N2B—H22B | 118.5 (10) | C3—C4—H42 | 109.00 |
H21B—N2B—H22B | 121.4 (15) | C3—C4—H41 | 109.00 |
C1B—N2B—H21B | 119.2 (11) | C5—C4—H42 | 110.00 |
H31B—N3B—H32B | 121.4 (14) | H41—C4—H42 | 108.00 |
C1B—N3B—H32B | 120.1 (10) | C5—C4—H41 | 110.00 |
C1B—N3B—H31B | 118.6 (11) | C6—C5—H52 | 109.00 |
C6—C1—C11 | 114.69 (10) | H51—C5—H52 | 108.00 |
C2—C1—C11 | 110.86 (10) | C6—C5—H51 | 109.00 |
C2—C1—C6 | 112.86 (11) | C4—C5—H51 | 109.00 |
C3—C2—C21 | 111.33 (11) | C4—C5—H52 | 109.00 |
C1—C2—C3 | 111.37 (11) | C1—C6—H61 | 109.00 |
C1—C2—C21 | 112.85 (10) | C5—C6—H61 | 109.00 |
C2—C3—C4 | 111.72 (12) | C5—C6—H62 | 109.00 |
C3—C4—C5 | 110.71 (13) | H61—C6—H62 | 108.00 |
C4—C5—C6 | 111.81 (12) | C1—C6—H62 | 109.00 |
C1—C6—C5 | 112.09 (12) | N2A—C1A—N3A | 119.66 (13) |
O11—C11—O12 | 122.68 (12) | N1A—C1A—N2A | 120.37 (13) |
O12—C11—C1 | 118.47 (11) | N1A—C1A—N3A | 119.96 (12) |
O11—C11—C1 | 118.76 (11) | N2B—C1B—N3B | 120.13 (13) |
O21—C21—O22 | 123.47 (11) | N1B—C1B—N2B | 120.36 (13) |
O22—C21—C2 | 115.75 (11) | N1B—C1B—N3B | 119.49 (13) |
C6—C1—C2—C3 | −50.89 (14) | C1—C2—C3—C4 | 54.26 (15) |
C6—C1—C2—C21 | 75.18 (13) | C21—C2—C3—C4 | −72.64 (14) |
C11—C1—C2—C3 | 178.88 (11) | C1—C2—C21—O21 | −10.73 (17) |
C11—C1—C2—C21 | −55.05 (13) | C1—C2—C21—O22 | 168.09 (10) |
C2—C1—C6—C5 | 50.69 (15) | C3—C2—C21—O21 | 115.36 (13) |
C11—C1—C6—C5 | 178.95 (11) | C3—C2—C21—O22 | −65.82 (14) |
C2—C1—C11—O11 | 155.96 (11) | C2—C3—C4—C5 | −57.11 (15) |
C2—C1—C11—O12 | −27.39 (16) | C3—C4—C5—C6 | 56.55 (16) |
C6—C1—C11—O11 | 26.70 (16) | C4—C5—C6—C1 | −53.32 (16) |
C6—C1—C11—O12 | −156.65 (12) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1A—H11A···O22i | 0.910 (16) | 1.946 (15) | 2.8492 (16) | 171.2 (13) |
N1A—H12A···O22ii | 0.878 (16) | 1.960 (16) | 2.8255 (15) | 168.6 (14) |
N2A—H21A···O11 | 0.844 (18) | 2.065 (18) | 2.8780 (18) | 161.6 (15) |
N3A—H31A···O21ii | 0.865 (15) | 1.963 (15) | 2.8270 (16) | 176.4 (16) |
N3A—H32A···O11 | 0.817 (17) | 2.593 (17) | 3.2299 (16) | 135.9 (14) |
N1B—H11B···O12iii | 0.890 (15) | 1.899 (15) | 2.7863 (17) | 175.0 (15) |
N1B—H12B···O12 | 0.810 (17) | 2.204 (18) | 2.9097 (17) | 145.9 (16) |
N2B—H21B···O22 | 0.850 (18) | 1.999 (18) | 2.8447 (18) | 173.8 (16) |
N2B—H22B···O11iv | 0.871 (16) | 2.579 (16) | 3.2913 (17) | 139.6 (13) |
N2B—H22B···N3Bv | 0.871 (16) | 2.593 (15) | 3.3191 (18) | 141.5 (13) |
N3B—H31B···O11iv | 0.856 (17) | 2.011 (17) | 2.8468 (15) | 165.1 (15) |
N3B—H32B···O11iii | 0.948 (16) | 1.975 (15) | 2.8981 (15) | 164.2 (14) |
Symmetry codes: (i) −x, y+1/2, −z+1/2; (ii) −x, −y+1, −z; (iii) −x+1, −y+1, −z; (iv) −x+1, y−1/2, −z+1/2; (v) x, −y+1/2, z+1/2. |
CH6N3+·C8H5O4−·H2O | F(000) = 1024 |
Mr = 243.22 | Dx = 1.413 Mg m−3 |
Monoclinic, C2/c | Melting point: 474 K |
Hall symbol: -C 2yc | Mo Kα radiation, λ = 0.71073 Å |
a = 20.970 (3) Å | Cell parameters from 1819 reflections |
b = 5.1421 (6) Å | θ = 3.8–28.8° |
c = 22.241 (2) Å | µ = 0.12 mm−1 |
β = 107.577 (14)° | T = 297 K |
V = 2286.3 (5) Å3 | Platelet, colourless |
Z = 8 | 0.40 × 0.30 × 0.16 mm |
Oxford Gemini-S CCD area-detector diffractometer | 2239 independent reflections |
Radiation source: Enhance (Mo) X-ray source | 1694 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.013 |
ω scans | θmax = 26.0°, θmin = 3.8° |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009) | h = −25→24 |
Tmin = 0.907, Tmax = 0.987 | k = −5→6 |
3906 measured reflections | l = −27→16 |
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)] = 0.052 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.156 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0881P)2 + 1.4498P] where P = (Fo2 + 2Fc2)/3 |
2239 reflections | (Δ/σ)max = 0.002 |
181 parameters | Δρmax = 0.58 e Å−3 |
0 restraints | Δρmin = −0.50 e Å−3 |
CH6N3+·C8H5O4−·H2O | V = 2286.3 (5) Å3 |
Mr = 243.22 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 20.970 (3) Å | µ = 0.12 mm−1 |
b = 5.1421 (6) Å | T = 297 K |
c = 22.241 (2) Å | 0.40 × 0.30 × 0.16 mm |
β = 107.577 (14)° |
Oxford Gemini-S CCD area-detector diffractometer | 2239 independent reflections |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009) | 1694 reflections with I > 2σ(I) |
Tmin = 0.907, Tmax = 0.987 | Rint = 0.013 |
3906 measured reflections |
R[F2 > 2σ(F2)] = 0.052 | 0 restraints |
wR(F2) = 0.156 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | Δρmax = 0.58 e Å−3 |
2239 reflections | Δρmin = −0.50 e Å−3 |
181 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 | ||
O11 | 0.66357 (7) | 0.4840 (3) | 0.52173 (7) | 0.0458 (5) | |
O12 | 0.77147 (7) | 0.5771 (3) | 0.53995 (7) | 0.0453 (5) | |
O31 | 0.94195 (8) | 0.1767 (4) | 0.71504 (8) | 0.0632 (7) | |
O32 | 0.91247 (10) | −0.0160 (4) | 0.79184 (8) | 0.0717 (7) | |
C1 | 0.74351 (9) | 0.2626 (4) | 0.60568 (8) | 0.0309 (6) | |
C2 | 0.80914 (9) | 0.2562 (4) | 0.64532 (9) | 0.0320 (6) | |
C3 | 0.82785 (10) | 0.0833 (4) | 0.69596 (9) | 0.0346 (6) | |
C4 | 0.78025 (11) | −0.0864 (4) | 0.70603 (10) | 0.0408 (7) | |
C5 | 0.71536 (11) | −0.0851 (4) | 0.66614 (10) | 0.0426 (7) | |
C6 | 0.69681 (10) | 0.0894 (4) | 0.61645 (9) | 0.0376 (6) | |
C11 | 0.72328 (9) | 0.4525 (4) | 0.55200 (9) | 0.0330 (6) | |
C31 | 0.89860 (11) | 0.0781 (5) | 0.73853 (10) | 0.0433 (7) | |
N1A | 0.92726 (17) | 0.4335 (6) | 0.55135 (12) | 0.0725 (10) | |
N2A | 1.01868 (12) | 0.5649 (5) | 0.63160 (13) | 0.0645 (9) | |
N3A | 0.92136 (13) | 0.8032 (5) | 0.60519 (13) | 0.0604 (8) | |
C1A | 0.95621 (11) | 0.6008 (5) | 0.59668 (10) | 0.0419 (7) | |
O1W | 0.55885 (14) | 0.6030 (5) | 0.57132 (16) | 0.1076 (13) | |
H2 | 0.84080 | 0.36830 | 0.63800 | 0.0380* | |
H4 | 0.79230 | −0.20140 | 0.73990 | 0.0490* | |
H5 | 0.68410 | −0.20140 | 0.67270 | 0.0510* | |
H6 | 0.65290 | 0.09120 | 0.59010 | 0.0450* | |
H12 | 0.75000 | 0.75000 | 0.50000 | 0.102 (16)* | |
H31 | 1.00000 | 0.146 (11) | 0.75000 | 0.112 (17)* | |
H11A | 0.882 (2) | 0.434 (8) | 0.5312 (19) | 0.107 (13)* | |
H12A | 0.952 (2) | 0.330 (10) | 0.539 (2) | 0.121 (18)* | |
H21A | 1.0371 (18) | 0.437 (7) | 0.6227 (17) | 0.088 (12)* | |
H22A | 1.0417 (16) | 0.679 (7) | 0.6666 (16) | 0.084 (10)* | |
H31A | 0.877 (3) | 0.841 (11) | 0.578 (3) | 0.16 (2)* | |
H32A | 0.9406 (15) | 0.897 (6) | 0.6354 (15) | 0.059 (9)* | |
H11W | 0.57800 | 0.56590 | 0.61220 | 0.1290* | |
H12W | 0.59240 | 0.58380 | 0.54880 | 0.1290* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O11 | 0.0298 (8) | 0.0580 (10) | 0.0419 (8) | 0.0015 (7) | −0.0006 (6) | 0.0120 (7) |
O12 | 0.0309 (8) | 0.0531 (10) | 0.0472 (9) | 0.0006 (7) | 0.0049 (6) | 0.0235 (7) |
O31 | 0.0357 (9) | 0.1032 (15) | 0.0400 (9) | −0.0126 (9) | −0.0047 (7) | 0.0184 (9) |
O32 | 0.0632 (11) | 0.1043 (16) | 0.0400 (9) | 0.0143 (11) | 0.0041 (8) | 0.0312 (10) |
C1 | 0.0315 (10) | 0.0327 (10) | 0.0278 (9) | −0.0002 (8) | 0.0081 (8) | −0.0007 (8) |
C2 | 0.0311 (10) | 0.0347 (10) | 0.0302 (9) | −0.0012 (8) | 0.0092 (8) | 0.0044 (8) |
C3 | 0.0385 (11) | 0.0376 (11) | 0.0278 (9) | 0.0042 (9) | 0.0101 (8) | 0.0019 (8) |
C4 | 0.0538 (13) | 0.0360 (12) | 0.0346 (10) | 0.0017 (10) | 0.0163 (9) | 0.0080 (9) |
C5 | 0.0473 (12) | 0.0403 (12) | 0.0431 (12) | −0.0119 (10) | 0.0179 (10) | 0.0020 (10) |
C6 | 0.0317 (10) | 0.0422 (12) | 0.0374 (10) | −0.0053 (9) | 0.0080 (8) | −0.0029 (9) |
C11 | 0.0309 (10) | 0.0359 (11) | 0.0291 (9) | 0.0011 (8) | 0.0043 (8) | −0.0004 (8) |
C31 | 0.0448 (12) | 0.0493 (13) | 0.0313 (10) | 0.0082 (10) | 0.0049 (9) | 0.0053 (10) |
N1A | 0.0739 (18) | 0.0752 (19) | 0.0587 (15) | −0.0258 (16) | 0.0056 (13) | −0.0193 (13) |
N2A | 0.0437 (12) | 0.0649 (16) | 0.0723 (16) | 0.0022 (12) | −0.0012 (11) | −0.0088 (13) |
N3A | 0.0558 (14) | 0.0620 (15) | 0.0601 (14) | 0.0054 (12) | 0.0124 (11) | −0.0059 (12) |
C1A | 0.0401 (11) | 0.0448 (12) | 0.0371 (11) | −0.0091 (10) | 0.0061 (9) | −0.0013 (10) |
O1W | 0.1022 (18) | 0.0861 (17) | 0.166 (3) | 0.0114 (15) | 0.0878 (18) | 0.0111 (18) |
O11—C11 | 1.240 (2) | N3A—H31A | 0.96 (6) |
O12—C11 | 1.291 (3) | N3A—H32A | 0.83 (3) |
O31—C31 | 1.282 (3) | C1—C2 | 1.393 (3) |
O32—C31 | 1.231 (3) | C1—C11 | 1.501 (3) |
O12—H12 | 1.2400 | C1—C6 | 1.397 (3) |
O31—H31 | 1.241 (6) | C2—C3 | 1.395 (3) |
O1W—H12W | 0.9800 | C3—C4 | 1.394 (3) |
O1W—H11W | 0.9000 | C3—C31 | 1.500 (3) |
N1A—C1A | 1.325 (4) | C4—C5 | 1.382 (3) |
N2A—C1A | 1.319 (4) | C5—C6 | 1.385 (3) |
N3A—C1A | 1.318 (4) | C2—H2 | 0.9300 |
N1A—H12A | 0.85 (5) | C4—H4 | 0.9300 |
N1A—H11A | 0.92 (4) | C5—H5 | 0.9300 |
N2A—H22A | 0.98 (4) | C6—H6 | 0.9300 |
N2A—H21A | 0.82 (4) | ||
C11—O12—H12 | 112.00 | C4—C5—C6 | 120.0 (2) |
C31—O31—H31 | 112.1 (12) | C1—C6—C5 | 120.49 (19) |
H11W—O1W—H12W | 109.00 | O12—C11—C1 | 115.91 (17) |
H11A—N1A—H12A | 119 (4) | O11—C11—O12 | 123.21 (19) |
C1A—N1A—H12A | 118 (3) | O11—C11—C1 | 120.88 (18) |
C1A—N1A—H11A | 123 (3) | O31—C31—O32 | 123.9 (2) |
H21A—N2A—H22A | 121 (3) | O31—C31—C3 | 115.07 (19) |
C1A—N2A—H21A | 115 (3) | O32—C31—C3 | 121.1 (2) |
C1A—N2A—H22A | 123 (2) | C1—C2—H2 | 120.00 |
H31A—N3A—H32A | 122 (4) | C3—C2—H2 | 120.00 |
C1A—N3A—H31A | 123 (4) | C3—C4—H4 | 120.00 |
C1A—N3A—H32A | 115 (2) | C5—C4—H4 | 120.00 |
C2—C1—C11 | 120.45 (18) | C6—C5—H5 | 120.00 |
C6—C1—C11 | 120.45 (17) | C4—C5—H5 | 120.00 |
C2—C1—C6 | 119.10 (18) | C5—C6—H6 | 120.00 |
C1—C2—C3 | 120.62 (19) | C1—C6—H6 | 120.00 |
C2—C3—C4 | 119.23 (19) | N1A—C1A—N2A | 120.2 (3) |
C4—C3—C31 | 120.48 (19) | N1A—C1A—N3A | 118.4 (3) |
C2—C3—C31 | 120.29 (19) | N2A—C1A—N3A | 121.4 (2) |
C3—C4—C5 | 120.52 (19) | ||
C6—C1—C2—C3 | −1.4 (3) | C1—C2—C3—C31 | −179.85 (19) |
C11—C1—C2—C3 | 178.81 (18) | C2—C3—C4—C5 | 0.5 (3) |
C2—C1—C6—C5 | 0.5 (3) | C31—C3—C4—C5 | −178.8 (2) |
C11—C1—C6—C5 | −179.71 (19) | C2—C3—C31—O31 | −20.3 (3) |
C2—C1—C11—O11 | −170.30 (19) | C2—C3—C31—O32 | 159.9 (2) |
C2—C1—C11—O12 | 9.8 (3) | C4—C3—C31—O31 | 159.0 (2) |
C6—C1—C11—O11 | 9.9 (3) | C4—C3—C31—O32 | −20.9 (3) |
C6—C1—C11—O12 | −170.02 (18) | C3—C4—C5—C6 | −1.4 (3) |
C1—C2—C3—C4 | 0.9 (3) | C4—C5—C6—C1 | 0.9 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1A—H11A···O12 | 0.92 (4) | 2.50 (4) | 3.284 (4) | 144 (3) |
N1A—H12A···O1Wi | 0.85 (5) | 2.44 (5) | 3.156 (5) | 144 (4) |
N2A—H21A···O1Wi | 0.82 (4) | 2.19 (4) | 2.972 (4) | 161 (4) |
N2A—H22A···O32ii | 0.98 (4) | 1.92 (4) | 2.854 (3) | 158 (3) |
N3A—H31A···O12 | 0.96 (6) | 2.52 (6) | 3.253 (3) | 133 (4) |
N3A—H31A···O11iii | 0.96 (6) | 2.31 (6) | 3.050 (3) | 134 (5) |
N3A—H32A···O31iv | 0.83 (3) | 2.28 (3) | 3.034 (3) | 153 (3) |
O1W—H11W···O32v | 0.90 | 2.12 | 2.982 (4) | 160 |
O1W—H12W···O11 | 0.98 | 1.84 | 2.806 (4) | 166 |
O12—H12···O12iii | 1.24 | 1.24 | 2.483 (2) | 180 |
O31—H31···O31vi | 1.241 (6) | 1.241 (6) | 2.462 (2) | 165 (5) |
Symmetry codes: (i) x+1/2, y−1/2, z; (ii) −x+2, y+1, −z+3/2; (iii) −x+3/2, −y+3/2, −z+1; (iv) x, y+1, z; (v) −x+3/2, y+1/2, −z+3/2; (vi) −x+2, y, −z+3/2. |
2CH6N3+·C8H4O42−·3H2O | F(000) = 720 |
Mr = 338.34 | Dx = 1.423 Mg m−3 |
Monoclinic, C2/c | Melting point: 505 K |
Hall symbol: -C 2yc | Mo Kα radiation, λ = 0.71073 Å |
a = 18.0402 (7) Å | Cell parameters from 1952 reflections |
b = 5.1420 (2) Å | θ = 3.0–28.6° |
c = 18.1496 (7) Å | µ = 0.12 mm−1 |
β = 110.297 (4)° | T = 297 K |
V = 1579.07 (11) Å3 | Block, colourless |
Z = 4 | 0.25 × 0.25 × 0.25 mm |
Oxford Gemini-S Ultra CCD area-detector diffractometer | 1546 independent reflections |
Radiation source: Enhance (Mo) X-ray source | 1177 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.020 |
Detector resolution: 16.0774 pixels mm-1 | θmax = 26.0°, θmin = 3.9° |
ω scans | h = −21→22 |
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2008) | k = −6→6 |
Tmin = 0.98, Tmax = 0.99 | l = −22→11 |
3988 measured reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.039 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.114 | w = 1/[σ2(Fo2) + (0.0724P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.04 | (Δ/σ)max = 0.001 |
1546 reflections | Δρmax = 0.23 e Å−3 |
130 parameters | Δρmin = −0.48 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.014 (2) |
2CH6N3+·C8H4O42−·3H2O | V = 1579.07 (11) Å3 |
Mr = 338.34 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 18.0402 (7) Å | µ = 0.12 mm−1 |
b = 5.1420 (2) Å | T = 297 K |
c = 18.1496 (7) Å | 0.25 × 0.25 × 0.25 mm |
β = 110.297 (4)° |
Oxford Gemini-S Ultra CCD area-detector diffractometer | 1546 independent reflections |
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2008) | 1177 reflections with I > 2σ(I) |
Tmin = 0.98, Tmax = 0.99 | Rint = 0.020 |
3988 measured reflections |
R[F2 > 2σ(F2)] = 0.039 | 0 restraints |
wR(F2) = 0.114 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | Δρmax = 0.23 e Å−3 |
1546 reflections | Δρmin = −0.48 e Å−3 |
130 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 | ||
O11 | 0.91167 (6) | 0.6439 (2) | 0.62864 (7) | 0.0362 (4) | |
O12 | 0.80638 (7) | 0.7267 (2) | 0.66117 (7) | 0.0379 (4) | |
C1 | 0.79313 (9) | 0.4245 (3) | 0.55846 (9) | 0.0267 (5) | |
C2 | 0.83110 (10) | 0.2372 (3) | 0.52989 (10) | 0.0320 (5) | |
C6 | 0.71103 (9) | 0.4345 (3) | 0.52779 (10) | 0.0318 (5) | |
C11 | 0.84013 (9) | 0.6122 (3) | 0.62100 (9) | 0.0280 (5) | |
N1A | 0.67652 (9) | 0.6121 (3) | 0.71264 (10) | 0.0414 (6) | |
N2A | 0.55815 (9) | 0.8196 (4) | 0.68312 (11) | 0.0446 (5) | |
N3A | 0.65240 (11) | 0.9751 (3) | 0.63647 (10) | 0.0411 (5) | |
C1A | 0.62841 (9) | 0.8024 (3) | 0.67693 (9) | 0.0303 (5) | |
O1W | 0.50000 | 0.4250 (3) | 0.75000 | 0.0414 (6) | |
O2W | 1.00186 (8) | 0.7514 (3) | 0.53680 (9) | 0.0513 (5) | |
H2 | 0.88600 | 0.22690 | 0.54990 | 0.0380* | |
H6 | 0.68430 | 0.55830 | 0.54640 | 0.0380* | |
H11A | 0.7265 (13) | 0.600 (4) | 0.7065 (13) | 0.051 (6)* | |
H12A | 0.6644 (12) | 0.506 (5) | 0.7446 (14) | 0.052 (6)* | |
H21A | 0.5402 (13) | 0.686 (5) | 0.7100 (15) | 0.064 (7)* | |
H22A | 0.5261 (14) | 0.955 (5) | 0.6619 (15) | 0.075 (8)* | |
H31A | 0.6211 (15) | 1.082 (4) | 0.6093 (15) | 0.058 (7)* | |
H32A | 0.7004 (12) | 0.959 (4) | 0.6331 (12) | 0.042 (5)* | |
H11W | 0.46660 | 0.32690 | 0.70930 | 0.0500* | |
H21W | 0.96610 | 0.73390 | 0.55720 | 0.0620* | |
H22W | 0.97120 | 0.81500 | 0.48360 | 0.0620* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O11 | 0.0248 (6) | 0.0458 (7) | 0.0392 (7) | −0.0037 (5) | 0.0125 (5) | −0.0077 (6) |
O12 | 0.0333 (7) | 0.0453 (8) | 0.0389 (7) | −0.0039 (5) | 0.0175 (5) | −0.0146 (6) |
C1 | 0.0264 (8) | 0.0295 (9) | 0.0256 (7) | −0.0003 (6) | 0.0109 (6) | 0.0018 (6) |
C2 | 0.0218 (7) | 0.0377 (9) | 0.0362 (9) | 0.0024 (7) | 0.0098 (7) | −0.0016 (8) |
C6 | 0.0282 (8) | 0.0326 (9) | 0.0356 (9) | 0.0042 (7) | 0.0124 (7) | −0.0053 (7) |
C11 | 0.0269 (8) | 0.0311 (9) | 0.0259 (8) | 0.0023 (7) | 0.0092 (6) | 0.0029 (7) |
N1A | 0.0352 (9) | 0.0433 (10) | 0.0500 (10) | 0.0094 (7) | 0.0202 (7) | 0.0155 (8) |
N2A | 0.0350 (8) | 0.0476 (10) | 0.0560 (10) | 0.0109 (8) | 0.0217 (7) | 0.0100 (9) |
N3A | 0.0391 (9) | 0.0392 (9) | 0.0457 (9) | 0.0046 (8) | 0.0157 (8) | 0.0105 (8) |
C1A | 0.0300 (9) | 0.0305 (9) | 0.0304 (8) | 0.0007 (7) | 0.0104 (7) | −0.0010 (7) |
O1W | 0.0388 (10) | 0.0383 (10) | 0.0396 (10) | 0.0000 | 0.0041 (8) | 0.0000 |
O2W | 0.0493 (8) | 0.0595 (10) | 0.0532 (8) | 0.0110 (7) | 0.0282 (7) | 0.0136 (7) |
O11—C11 | 1.260 (2) | N2A—H22A | 0.90 (3) |
O12—C11 | 1.248 (2) | N2A—H21A | 0.96 (3) |
O1W—H11W | 0.9200 | N3A—H32A | 0.89 (2) |
O1W—H11Wi | 0.9200 | N3A—H31A | 0.82 (2) |
O2W—H21W | 0.8500 | C1—C2 | 1.383 (2) |
O2W—H22W | 0.9900 | C1—C11 | 1.507 (2) |
N1A—C1A | 1.319 (2) | C1—C6 | 1.391 (2) |
N2A—C1A | 1.314 (2) | C2—C6ii | 1.379 (2) |
N3A—C1A | 1.317 (2) | C2—H2 | 0.9300 |
N1A—H12A | 0.88 (2) | C6—H6 | 0.9300 |
N1A—H11A | 0.95 (2) | ||
H11W—O1W—H11Wi | 114.00 | C2—C1—C11 | 120.40 (15) |
H21W—O2W—H22W | 102.00 | C1—C2—C6ii | 121.09 (17) |
C1A—N1A—H12A | 120.9 (16) | C1—C6—C2ii | 120.68 (16) |
C1A—N1A—H11A | 118.8 (13) | O11—C11—O12 | 124.30 (15) |
H11A—N1A—H12A | 120 (2) | O11—C11—C1 | 116.94 (14) |
C1A—N2A—H22A | 120.7 (17) | O12—C11—C1 | 118.76 (15) |
H21A—N2A—H22A | 119 (2) | C6ii—C2—H2 | 119.00 |
C1A—N2A—H21A | 120.0 (15) | C1—C2—H2 | 119.00 |
H31A—N3A—H32A | 120 (2) | C2ii—C6—H6 | 120.00 |
C1A—N3A—H31A | 120 (2) | C1—C6—H6 | 120.00 |
C1A—N3A—H32A | 119.3 (13) | N1A—C1A—N3A | 119.11 (17) |
C6—C1—C11 | 121.37 (14) | N2A—C1A—N3A | 121.03 (17) |
C2—C1—C6 | 118.23 (15) | N1A—C1A—N2A | 119.85 (17) |
C6—C1—C2—C6ii | 0.4 (2) | C2—C1—C11—O12 | −159.86 (15) |
C11—C1—C2—C6ii | −179.45 (15) | C6—C1—C11—O11 | −159.19 (15) |
C2—C1—C6—C2ii | −0.4 (2) | C6—C1—C11—O12 | 20.3 (2) |
C11—C1—C6—C2ii | 179.45 (15) | C1—C2—C6ii—C1ii | −0.4 (3) |
C2—C1—C11—O11 | 20.6 (2) |
Symmetry codes: (i) −x+1, y, −z+3/2; (ii) −x+3/2, −y+1/2, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1A—H11A···O12 | 0.95 (2) | 2.00 (2) | 2.868 (2) | 151.3 (19) |
N1A—H12A···O12iii | 0.88 (2) | 2.15 (2) | 2.963 (2) | 153 (2) |
N2A—H21A···O1W | 0.96 (3) | 1.79 (3) | 2.752 (2) | 174 (2) |
N2A—H22A···O11iv | 0.90 (3) | 2.17 (3) | 2.988 (2) | 151 (2) |
N3A—H31A···O2Wiv | 0.82 (2) | 2.27 (3) | 3.043 (2) | 157 (2) |
N3A—H32A···O12 | 0.89 (2) | 2.16 (2) | 2.947 (2) | 146.6 (18) |
O1W—H11W···O11v | 0.92 | 1.73 | 2.6542 (14) | 174 |
O2W—H21W···O11 | 0.85 | 1.93 | 2.7591 (19) | 162 |
O2W—H22W···O2Wvi | 0.99 | 2.34 | 2.875 (2) | 113 |
Symmetry codes: (iii) −x+3/2, y−1/2, −z+3/2; (iv) x−1/2, y+1/2, z; (v) x−1/2, y−1/2, z; (vi) −x+2, −y+2, −z+1. |
Experimental details
(I) | (II) | (III) | |
Crystal data | |||
Chemical formula | 2CH6N3+·C8H10O42− | CH6N3+·C8H5O4−·H2O | 2CH6N3+·C8H4O42−·3H2O |
Mr | 290.34 | 243.22 | 338.34 |
Crystal system, space group | Monoclinic, P21/c | Monoclinic, C2/c | Monoclinic, C2/c |
Temperature (K) | 200 | 297 | 297 |
a, b, c (Å) | 10.7425 (10), 16.0538 (15), 8.5067 (8) | 20.970 (3), 5.1421 (6), 22.241 (2) | 18.0402 (7), 5.1420 (2), 18.1496 (7) |
β (°) | 97.224 (9) | 107.577 (14) | 110.297 (4) |
V (Å3) | 1455.4 (2) | 2286.3 (5) | 1579.07 (11) |
Z | 4 | 8 | 4 |
Radiation type | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.10 | 0.12 | 0.12 |
Crystal size (mm) | 0.50 × 0.50 × 0.45 | 0.40 × 0.30 × 0.16 | 0.25 × 0.25 × 0.25 |
Data collection | |||
Diffractometer | Oxford Gemini-S CCD area-detector diffractometer | Oxford Gemini-S 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 RED; Oxford Diffraction, 2008) |
Tmin, Tmax | 0.956, 0.980 | 0.907, 0.987 | 0.98, 0.99 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 10102, 2858, 2222 | 3906, 2239, 1694 | 3988, 1546, 1177 |
Rint | 0.026 | 0.013 | 0.020 |
(sin θ/λ)max (Å−1) | 0.617 | 0.617 | 0.616 |
Refinement | |||
R[F2 > 2σ(F2)], wR(F2), S | 0.035, 0.089, 1.05 | 0.052, 0.156, 1.06 | 0.039, 0.114, 1.04 |
No. of reflections | 2858 | 2239 | 1546 |
No. of parameters | 229 | 181 | 130 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.21, −0.16 | 0.58, −0.50 | 0.23, −0.48 |
Computer programs: CrysAlis PRO (Oxford Diffraction, 2009), CrysAlis CCD (Oxford Diffraction, 2008), CrysAlis RED (Oxford Diffraction, 2008), SIR92 (Altomare et al., 1994), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008) within WinGX (Farrugia, 1999), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009).
D—H···A | D—H | H···A | D···A | D—H···A |
N1A—H11A···O22i | 0.910 (16) | 1.946 (15) | 2.8492 (16) | 171.2 (13) |
N1A—H12A···O22ii | 0.878 (16) | 1.960 (16) | 2.8255 (15) | 168.6 (14) |
N2A—H21A···O11 | 0.844 (18) | 2.065 (18) | 2.8780 (18) | 161.6 (15) |
N3A—H31A···O21ii | 0.865 (15) | 1.963 (15) | 2.8270 (16) | 176.4 (16) |
N3A—H32A···O11 | 0.817 (17) | 2.593 (17) | 3.2299 (16) | 135.9 (14) |
N1B—H11B···O12iii | 0.890 (15) | 1.899 (15) | 2.7863 (17) | 175.0 (15) |
N1B—H12B···O12 | 0.810 (17) | 2.204 (18) | 2.9097 (17) | 145.9 (16) |
N2B—H21B···O22 | 0.850 (18) | 1.999 (18) | 2.8447 (18) | 173.8 (16) |
N2B—H22B···O11iv | 0.871 (16) | 2.579 (16) | 3.2913 (17) | 139.6 (13) |
N2B—H22B···N3Bv | 0.871 (16) | 2.593 (15) | 3.3191 (18) | 141.5 (13) |
N3B—H31B···O11iv | 0.856 (17) | 2.011 (17) | 2.8468 (15) | 165.1 (15) |
N3B—H32B···O11iii | 0.948 (16) | 1.975 (15) | 2.8981 (15) | 164.2 (14) |
Symmetry codes: (i) −x, y+1/2, −z+1/2; (ii) −x, −y+1, −z; (iii) −x+1, −y+1, −z; (iv) −x+1, y−1/2, −z+1/2; (v) x, −y+1/2, z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1A—H11A···O12 | 0.92 (4) | 2.50 (4) | 3.284 (4) | 144 (3) |
N1A—H12A···O1Wi | 0.85 (5) | 2.44 (5) | 3.156 (5) | 144 (4) |
N2A—H21A···O1Wi | 0.82 (4) | 2.19 (4) | 2.972 (4) | 161 (4) |
N2A—H22A···O32ii | 0.98 (4) | 1.92 (4) | 2.854 (3) | 158 (3) |
N3A—H31A···O12 | 0.96 (6) | 2.52 (6) | 3.253 (3) | 133 (4) |
N3A—H31A···O11iii | 0.96 (6) | 2.31 (6) | 3.050 (3) | 134 (5) |
N3A—H32A···O31iv | 0.83 (3) | 2.28 (3) | 3.034 (3) | 153 (3) |
O1W—H11W···O32v | 0.90 | 2.12 | 2.982 (4) | 160 |
O1W—H12W···O11 | 0.98 | 1.84 | 2.806 (4) | 166 |
O12—H12···O12iii | 1.24 | 1.24 | 2.483 (2) | 180 |
O31—H31···O31vi | 1.241 (6) | 1.241 (6) | 2.462 (2) | 165 (5) |
Symmetry codes: (i) x+1/2, y−1/2, z; (ii) −x+2, y+1, −z+3/2; (iii) −x+3/2, −y+3/2, −z+1; (iv) x, y+1, z; (v) −x+3/2, y+1/2, −z+3/2; (vi) −x+2, y, −z+3/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1A—H11A···O12 | 0.95 (2) | 2.00 (2) | 2.868 (2) | 151.3 (19) |
N1A—H12A···O12i | 0.88 (2) | 2.15 (2) | 2.963 (2) | 153 (2) |
N2A—H21A···O1W | 0.96 (3) | 1.79 (3) | 2.752 (2) | 174 (2) |
N2A—H22A···O11ii | 0.90 (3) | 2.17 (3) | 2.988 (2) | 151 (2) |
N3A—H31A···O2Wii | 0.82 (2) | 2.27 (3) | 3.043 (2) | 157 (2) |
N3A—H32A···O12 | 0.89 (2) | 2.16 (2) | 2.947 (2) | 146.6 (18) |
O1W—H11W···O11iii | 0.92 | 1.73 | 2.6542 (14) | 174 |
O2W—H21W···O11 | 0.85 | 1.9300 | 2.7591 (19) | 162 |
Symmetry codes: (i) −x+3/2, y−1/2, −z+3/2; (ii) x−1/2, y+1/2, z; (iii) x−1/2, y−1/2, z. |
The structures of the guanidinium salts of aromatic and heteroaromatic polyfunctional carboxylic acids are not numerous in the crystallographic literature, but they are of interest because of the the capacity of the guanidinium cation to generate stable supramolecular framework structures through hydrogen-bonding associations, largely cyclic, such as those found in the structures of guanidinium carbonate (Adams & Small, 1974) and guanidinium bicarbonate (Baldwin et al., 1986). Among the known aromatic and heteroaromatic carboxylate examples are the monoguanidinium salts of the dicarboxylic acids 4-hydroxypyridine-2,6-dicarboxylic acid (an unusual anhydrous compound in which the pyridine N atom and one of the carboxylic acid groups exist as a zwitterion; Moghimi et al., 2005) and 3-nitrophthalic acid (a monohydrate; Smith, Wermuth & Healy, 2007). Other bifunctional acid salts are those with 4-chloro-3-nitrobenzoic acid (a monohydrate; Najafpour et al., 2007), 4-amino-2,4,6-trichloropicolinic acid (Parthasarathi et al., 1984), 4-nitroanthranilic acid (Smith, Wermuth, Healy & White, 2007), 3-nitrobenzoic acid (Smith & Wermuth, 2010), 4-nitrobenzoic acid (Schurmann et al., 1998), 4-aminobenzoic acid (Pereira Silva et al., 2010) and 3,5-dinitrobenzoic acid (Smith, Wermuth & White, 2007) (all anhydrates). The known bis(guanidinium) salts are those with phthalic acid (anhydrous; Krumbe & Haussuhl, 1987) and pyrazine-2,3-dicarboxylic acid (a trihydrate; Smith et al., 2006). Another bis(guanidinium) example but with a tetracarboxylic acid is that with 1,2,4,5-benzenetetracarboxylic acid (pyromellitic acid; Sun et al., 2002). However, the most spectacular examples have been found in the supramolecular ribbon structures of the guanidinium bicarbonate tert-butylammonium salts of terephthalic acid (Mak & Xue, 2000). Among these examples, high-dimensional hydrogen-bonded structures are predominant, with the guanidinium cation forming multiple cyclic hydrogen-bonding associations with carboxylate O-acceptors, most commonly those defined by graph sets R22(8) and R21(6) and, to a lesser extent, R21(4) (Etter et al., 1990). In the hydrated examples, the water molecules are usually incorporated in expanded cyclic associations.
Our 1:1 stoichiometric reactions of a number of monocyclic dicarboxylic acids, including rac-trans-cyclohexane-1,2-dicarboxylic acid, isophthalic acid and terephthalic acid, with guanidinium carbonate in aqueous propan-2-ol gave relatively hard chemically stable crystals of the anhydrous salt bis(guanidinium) rac-trans-cyclohexane-1,2-dicarboxylate, (I), guanidinium 3-carboxybenzoate monohydrate, (II), and bis(guanidinium) benzene-1,4-dicarboxylate trihydrate, (III), respectively. The structures and hydrogen-bonding patterns for (I)–(III) are reported here. The molecular contents of the asymmetric units of these three compounds and their atom-numbering schemes are shown in Figs. 1–3.
In the anhydrous 2:1 guanidinium salt, (I), both cations (A and B) give classic cyclic R22(8) N—H···Ocarboxyl hydrogen-bonding interactions with, respectively, O21ii/O22ii and O11iii/O12iii (Fig. 4) (for symmetry code, see Table 1). Each cation is also involved in asymmetric cyclic R21(6) interactions with carboxyl O-atom acceptors. Additionally, cation B gives an unusual enlarged cyclic interaction [graph set R22(11)] with acceptors O12 and O22 of the two adjacent cis-related carboxyl groups. Further hydrogen-bonding extensions, including a centrosymmetric cyclic bis(cation–anion) association [graph set R22(8)] (Fig. 4), give the three-dimensional framework structure. The structure also contains a relatively long intermolecular N2B–H···N3Bv interaction [3.3191 (18) Å; for symmetry code see Table 1], and there is one potential guanidinium donor (H22A) for which there is no reasonable acceptor.
The structure of the hydrated 1:1 guanidinium hydrogen isophthalate salt, (II) (Fig. 2), is unusual in that each of the carboxyl groups gives short interanion O—H—O contacts, one across a crystallographic inversion centre [O12···O12iii = 2.483 (2) Å] and the other about a twofold axis of rotation [O31···O31vi = 2.462 (2) Å] (Fig. 5) (for symmetry codes, see Table 2). H atoms were located on these symmetry elements and therefore represent half-occupancy delocalized H atoms. These interactions effectively give anion–anion associated ribbon structures, which extend across the approximate ac diagonal in the cell (Fig. 6) and accommodate both the cations and the water molecules. The cation gives two separate cyclic R21(6) interactions, one with a carboxyl O-atom acceptor (involving atoms N1A and N3A) and the other with the solvent water molecule (involving atoms N1A and N2A), and [these?] are interlinked by the water molecules and further expanded down the b axis into a three-dimensional framework structure (Fig. 7).
In guanidinium terephthalate trihydrate, (III), the formula unit comprises a benzene-1,4-dicarboxylate dianion which lies across a crystallographic inversion centre, two guanidinium cations and two solvent water molecules (both pairs related by twofold rotational symmetry), and a third water molecule (O1W) lying on a crystallographic twofold axis (Fig. 3). The guanidinium cations and the dianion give two types of cyclic hydrogen-bonding motifs, one the common guanidinium R21(6) association (with atoms N1A and N3A) and the others incorporating the two water molecules: (a) atom O1W with atoms N1A and N2A [graph set R33(10)] and (b) atom O2W with atoms N2A and N3A [graph set R32(8)] (Table 3) (Figs. 8, 9), giving the three-dimensional framework structure. Present also in the structure of (III) are unusual inversion-related water–water interactions involving atoms O2W and O2Wvi [2.875 (2) Å; symmetry code: (vi) −x + 2, −y + 2, −z + 1, giving discrete cyclic dimers. Although the O2W–H22W···O2Wvi `bond' angle (113°) is less than would normally be accepted for a conventional hydrogen bond, this unusual R22(4) association must be recognized as such in the assembly of the structure of (III).
In the hydrogen isophthalate anion of (II), one of the carboxyl groups is close to coplanar with the benzene ring [torsion angle C2—C1—C11—O11 = −170.30 (19)°], while the other is twisted out of the plane [torsion angle C2—C3—C31—O32 = 159.9 (2)°]. This latter value is comparable with that for the C2—C1—C11—O12 torsion angle in both carboxyl groups in (III) [−159.86 (15)°].
The three-dimensional structures of (I)–(III) reported here show not only classic guanidinium cyclic R22(8) N—H···Ocarboxyl and R21(6) hydrogen-bonding motifs but, in addition, various expanded cyclic associations involving the solvent water molecules, and in the case of anhydrous (I), an unusual R22(11) cyclic guanidinium–carboxylate interaction. In addition, with (II), the 1:1 guanidinium salt appears to be preferred over the 2:1 salt as expected and found in (I) and (III), considering the identical 2:1 stoichiometric reaction conditions employed in all three preparations [1:1 stoichiometry stated above - please clarify].