Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270113015783/wq3039sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270113015783/wq3039Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270113015783/wq3039IIsup3.hkl | |
Chemical Markup Language (CML) file https://doi.org/10.1107/S0108270113015783/wq3039Isup4.cml | |
Chemical Markup Language (CML) file https://doi.org/10.1107/S0108270113015783/wq3039IIsup5.cml |
CCDC references: 957035; 957036
For related literature, see: Allen (2002); Aoki et al. (1993); Bai et al. (2009); Bernstein et al. (1995); Blank et al. (1976); Breslow (1958); Cramer et al. (1988); Hu et al. (1999, 2001, 2005); Krampitz (1969); Li & Hu (2010); Nangia (2006); Pletcher & Sax (1972); Pletcher et al. (1977, 1979).
Compound (I) was prepared by mixing thiamine pyrophosphate hydrochloride (0.092 g, 0.2 mmol) and KNO3 (0.020 g, 0.2 mmol) in water–methanol (8 ml, 1:1 v/v). Diffusing acetone into the mixture gave colourless crystals. Compound (II) was obtained by diffusing acetone into a solution of thiamine pyrophosphate hydrochloride (0.092 g, 0.2 mmol) in water–ethyl acetate (8 ml, 1:3 v/v) to afford colourless crystals.
C- and N-bound H atoms were positioned geometrically and refined as riding, with C—H = 0.93 (aromatic), 0.97 (CH2) and 0.96 Å (CH3) and N—H = 0.86 Å, and with Uiso(H) = 1.2(1.5 for methyl)Ueq(C,N). H atoms of the hydroxy groups and water molecules were located in difference Fourier maps and refined as riding, with Uiso(H) = 1.5Ueq(O).
For both compounds, data collection: XSCANS (Siemens, 1996); cell refinement: XSCANS (Siemens, 1996); data reduction: XSCANS (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
C12H18N4O7P2S·2H2O | Z = 2 |
Mr = 460.34 | F(000) = 480 |
Triclinic, P1 | Dx = 1.643 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 7.8778 (12) Å | Cell parameters from 30 reflections |
b = 11.2134 (14) Å | θ = 6.7–20.0° |
c = 11.7613 (14) Å | µ = 0.40 mm−1 |
α = 69.368 (12)° | T = 295 K |
β = 73.893 (12)° | Prism, colourless |
γ = 89.070 (11)° | 0.41 × 0.20 × 0.18 mm |
V = 930.3 (2) Å3 |
Siemens P4 four-circle diffractometer | 2647 reflections with I > 2σ(I) |
Radiation source: sealed tube | Rint = 0.024 |
Graphite monochromator | θmax = 25.0°, θmin = 1.9° |
2θ and ω scans | h = −1→9 |
Absorption correction: ψ scan (XSCANS; Siemens, 1996) | k = −12→12 |
Tmin = 0.852, Tmax = 0.931 | l = −13→13 |
4169 measured reflections | 3 standard reflections every 150 reflections |
3259 independent reflections | intensity decay: 2.0% |
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) = 0.116 | H-atom parameters constrained |
S = 1.05 | w = 1/[σ2(Fo2) + (0.070P)2] where P = (Fo2 + 2Fc2)/3 |
3259 reflections | (Δ/σ)max = 0.001 |
256 parameters | Δρmax = 0.26 e Å−3 |
6 restraints | Δρmin = −0.33 e Å−3 |
C12H18N4O7P2S·2H2O | γ = 89.070 (11)° |
Mr = 460.34 | V = 930.3 (2) Å3 |
Triclinic, P1 | Z = 2 |
a = 7.8778 (12) Å | Mo Kα radiation |
b = 11.2134 (14) Å | µ = 0.40 mm−1 |
c = 11.7613 (14) Å | T = 295 K |
α = 69.368 (12)° | 0.41 × 0.20 × 0.18 mm |
β = 73.893 (12)° |
Siemens P4 four-circle diffractometer | 2647 reflections with I > 2σ(I) |
Absorption correction: ψ scan (XSCANS; Siemens, 1996) | Rint = 0.024 |
Tmin = 0.852, Tmax = 0.931 | 3 standard reflections every 150 reflections |
4169 measured reflections | intensity decay: 2.0% |
3259 independent reflections |
R[F2 > 2σ(F2)] = 0.038 | 6 restraints |
wR(F2) = 0.116 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.26 e Å−3 |
3259 reflections | Δρmin = −0.33 e Å−3 |
256 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
S1 | 0.60227 (8) | 0.62188 (7) | 0.57391 (6) | 0.03270 (19) | |
P1 | 0.92737 (9) | 0.87753 (6) | 0.27302 (6) | 0.02922 (19) | |
P2 | 1.23877 (9) | 0.80004 (6) | 0.12596 (6) | 0.02772 (19) | |
O1 | 0.7447 (2) | 0.78904 (16) | 0.31641 (17) | 0.0343 (4) | |
O2 | 1.0549 (2) | 0.77456 (17) | 0.24144 (18) | 0.0375 (5) | |
O3 | 0.9345 (3) | 0.98886 (19) | 0.15739 (18) | 0.0451 (5) | |
O4 | 0.9537 (3) | 0.8990 (2) | 0.3838 (2) | 0.0543 (6) | |
O5 | 1.1735 (3) | 0.82538 (19) | 0.0060 (2) | 0.0484 (6) | |
H5 | 1.1553 | 0.9009 | −0.0225 | 0.073* | |
O6 | 1.3444 (3) | 0.91110 (17) | 0.12017 (19) | 0.0389 (5) | |
O7 | 1.3120 (2) | 0.67384 (16) | 0.15106 (17) | 0.0342 (4) | |
N1 | 0.3092 (3) | 0.50824 (18) | 0.71860 (18) | 0.0245 (5) | |
N2 | 0.3001 (3) | 0.1603 (2) | 1.0786 (2) | 0.0325 (5) | |
H2 | 0.3162 | 0.0805 | 1.0959 | 0.039* | |
N3 | 0.3059 (3) | 0.34223 (19) | 1.13225 (19) | 0.0297 (5) | |
N4 | 0.2547 (3) | 0.5357 (2) | 1.0012 (2) | 0.0319 (5) | |
H4A | 0.2735 | 0.5686 | 1.0530 | 0.038* | |
H4B | 0.2290 | 0.5833 | 0.9339 | 0.038* | |
C1 | 0.4783 (3) | 0.5184 (2) | 0.7135 (2) | 0.0298 (6) | |
H1 | 0.5234 | 0.4730 | 0.7800 | 0.036* | |
C2 | 0.2706 (3) | 0.5854 (2) | 0.6088 (2) | 0.0258 (5) | |
C3 | 0.4176 (3) | 0.6555 (2) | 0.5193 (2) | 0.0269 (5) | |
C4 | 0.0860 (4) | 0.5818 (3) | 0.5998 (3) | 0.0379 (7) | |
H4C | 0.0838 | 0.6365 | 0.5165 | 0.057* | |
H4D | 0.0096 | 0.6108 | 0.6621 | 0.057* | |
H4E | 0.0457 | 0.4957 | 0.6149 | 0.057* | |
C5 | 0.4287 (4) | 0.7511 (3) | 0.3891 (2) | 0.0317 (6) | |
H5A | 0.4372 | 0.7054 | 0.3317 | 0.038* | |
H5B | 0.3196 | 0.7929 | 0.3935 | 0.038* | |
C6 | 0.5817 (4) | 0.8512 (3) | 0.3350 (3) | 0.0355 (6) | |
H6A | 0.5753 | 0.9131 | 0.2547 | 0.043* | |
H6B | 0.5784 | 0.8958 | 0.3927 | 0.043* | |
C7 | 0.1683 (3) | 0.4247 (3) | 0.8313 (2) | 0.0299 (6) | |
H7A | 0.1140 | 0.3637 | 0.8074 | 0.036* | |
H7B | 0.0772 | 0.4771 | 0.8568 | 0.036* | |
C8 | 0.2335 (3) | 0.3532 (2) | 0.9420 (2) | 0.0259 (5) | |
C9 | 0.2538 (3) | 0.2258 (2) | 0.9745 (2) | 0.0311 (6) | |
H9 | 0.2349 | 0.1836 | 0.9230 | 0.037* | |
C10 | 0.3217 (3) | 0.2184 (2) | 1.1568 (2) | 0.0316 (6) | |
C11 | 0.2651 (3) | 0.4125 (2) | 1.0249 (2) | 0.0255 (5) | |
C12 | 0.3648 (5) | 0.1384 (3) | 1.2736 (3) | 0.0501 (8) | |
H12A | 0.4907 | 0.1472 | 1.2598 | 0.075* | |
H12B | 0.3264 | 0.0505 | 1.2947 | 0.075* | |
H12C | 0.3055 | 0.1657 | 1.3421 | 0.075* | |
O1W | 0.1593 (4) | 0.7354 (2) | 0.8001 (2) | 0.0619 (7) | |
H1A | 0.1427 | 0.7762 | 0.7276 | 0.093* | |
H1B | 0.1380 | 0.7834 | 0.8445 | 0.093* | |
O2W | 0.8689 (4) | 1.1173 (2) | 0.4343 (2) | 0.0760 (8) | |
H2A | 0.9049 | 1.0533 | 0.4118 | 0.114* | |
H2B | 0.9379 | 1.1301 | 0.4757 | 0.114* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0243 (3) | 0.0375 (4) | 0.0313 (4) | 0.0020 (3) | −0.0077 (3) | −0.0068 (3) |
P1 | 0.0328 (4) | 0.0263 (4) | 0.0304 (4) | 0.0030 (3) | −0.0106 (3) | −0.0113 (3) |
P2 | 0.0298 (4) | 0.0233 (4) | 0.0340 (4) | 0.0045 (3) | −0.0122 (3) | −0.0128 (3) |
O1 | 0.0307 (10) | 0.0276 (10) | 0.0384 (10) | 0.0025 (8) | −0.0032 (8) | −0.0099 (8) |
O2 | 0.0330 (10) | 0.0283 (10) | 0.0496 (12) | 0.0012 (8) | −0.0062 (9) | −0.0165 (9) |
O3 | 0.0460 (12) | 0.0350 (11) | 0.0408 (11) | 0.0012 (9) | −0.0114 (9) | 0.0015 (9) |
O4 | 0.0807 (17) | 0.0496 (13) | 0.0537 (13) | 0.0134 (12) | −0.0364 (13) | −0.0312 (11) |
O5 | 0.0770 (16) | 0.0372 (12) | 0.0476 (12) | 0.0218 (11) | −0.0352 (12) | −0.0225 (10) |
O6 | 0.0365 (11) | 0.0259 (10) | 0.0537 (12) | −0.0013 (8) | −0.0098 (9) | −0.0159 (9) |
O7 | 0.0410 (11) | 0.0258 (10) | 0.0449 (11) | 0.0107 (8) | −0.0204 (9) | −0.0177 (8) |
N1 | 0.0262 (11) | 0.0235 (11) | 0.0266 (11) | 0.0027 (8) | −0.0087 (9) | −0.0118 (9) |
N2 | 0.0417 (13) | 0.0199 (11) | 0.0359 (12) | −0.0010 (9) | −0.0103 (10) | −0.0105 (9) |
N3 | 0.0358 (12) | 0.0257 (11) | 0.0295 (11) | 0.0025 (9) | −0.0117 (10) | −0.0105 (9) |
N4 | 0.0437 (14) | 0.0266 (12) | 0.0303 (11) | 0.0050 (10) | −0.0155 (10) | −0.0127 (9) |
C1 | 0.0279 (13) | 0.0327 (14) | 0.0290 (13) | 0.0044 (11) | −0.0113 (11) | −0.0091 (11) |
C2 | 0.0311 (13) | 0.0248 (13) | 0.0266 (12) | 0.0049 (10) | −0.0109 (11) | −0.0133 (10) |
C3 | 0.0259 (13) | 0.0287 (13) | 0.0284 (13) | 0.0056 (10) | −0.0078 (11) | −0.0133 (11) |
C4 | 0.0310 (15) | 0.0425 (16) | 0.0403 (15) | 0.0017 (12) | −0.0142 (12) | −0.0121 (13) |
C5 | 0.0314 (14) | 0.0363 (15) | 0.0265 (13) | 0.0078 (12) | −0.0093 (11) | −0.0097 (11) |
C6 | 0.0359 (15) | 0.0305 (14) | 0.0355 (15) | 0.0083 (12) | −0.0080 (12) | −0.0083 (12) |
C7 | 0.0275 (13) | 0.0322 (14) | 0.0293 (13) | −0.0032 (11) | −0.0065 (11) | −0.0112 (11) |
C8 | 0.0238 (12) | 0.0272 (13) | 0.0252 (12) | −0.0028 (10) | −0.0033 (10) | −0.0103 (10) |
C9 | 0.0359 (15) | 0.0292 (14) | 0.0298 (13) | −0.0032 (11) | −0.0076 (11) | −0.0139 (11) |
C10 | 0.0333 (14) | 0.0276 (14) | 0.0325 (14) | −0.0012 (11) | −0.0081 (11) | −0.0100 (11) |
C11 | 0.0221 (12) | 0.0250 (13) | 0.0267 (12) | −0.0024 (10) | −0.0027 (10) | −0.0093 (10) |
C12 | 0.078 (2) | 0.0298 (15) | 0.0455 (18) | 0.0058 (16) | −0.0297 (17) | −0.0078 (13) |
O1W | 0.106 (2) | 0.0445 (13) | 0.0482 (13) | 0.0214 (13) | −0.0354 (14) | −0.0233 (11) |
O2W | 0.130 (3) | 0.0522 (15) | 0.0764 (17) | 0.0467 (16) | −0.0632 (18) | −0.0364 (13) |
S1—C1 | 1.673 (3) | C2—C4 | 1.490 (4) |
S1—C3 | 1.733 (3) | C3—C5 | 1.507 (3) |
P1—O4 | 1.473 (2) | C4—H4C | 0.9600 |
P1—O3 | 1.4746 (19) | C4—H4D | 0.9600 |
P1—O2 | 1.5933 (19) | C4—H4E | 0.9600 |
P1—O1 | 1.6119 (19) | C5—C6 | 1.495 (4) |
P2—O6 | 1.4802 (19) | C5—H5A | 0.9700 |
P2—O7 | 1.4821 (18) | C5—H5B | 0.9700 |
P2—O5 | 1.566 (2) | C6—H6A | 0.9700 |
P2—O2 | 1.635 (2) | C6—H6B | 0.9700 |
O1—C6 | 1.451 (3) | C7—C8 | 1.491 (4) |
O5—H5 | 0.8200 | C7—H7A | 0.9700 |
N1—C1 | 1.322 (3) | C7—H7B | 0.9700 |
N1—C2 | 1.390 (3) | C8—C9 | 1.363 (3) |
N1—C7 | 1.486 (3) | C8—C11 | 1.432 (3) |
N2—C9 | 1.333 (3) | C9—H9 | 0.9300 |
N2—C10 | 1.347 (3) | C10—C12 | 1.479 (4) |
N2—H2 | 0.8600 | C12—H12A | 0.9600 |
N3—C10 | 1.326 (3) | C12—H12B | 0.9600 |
N3—C11 | 1.354 (3) | C12—H12C | 0.9600 |
N4—C11 | 1.315 (3) | O1W—H1A | 0.8598 |
N4—H4A | 0.8600 | O1W—H1B | 0.8586 |
N4—H4B | 0.8600 | O2W—H2A | 0.8664 |
C1—H1 | 0.9300 | O2W—H2B | 0.8667 |
C2—C3 | 1.355 (3) | ||
C1—S1—C3 | 91.14 (12) | H4D—C4—H4E | 109.5 |
O4—P1—O3 | 119.05 (13) | C6—C5—C3 | 114.5 (2) |
O4—P1—O2 | 109.23 (12) | C6—C5—H5A | 108.6 |
O3—P1—O2 | 111.35 (12) | C3—C5—H5A | 108.6 |
O4—P1—O1 | 109.30 (13) | C6—C5—H5B | 108.6 |
O3—P1—O1 | 109.49 (11) | C3—C5—H5B | 108.6 |
O2—P1—O1 | 95.96 (10) | H5A—C5—H5B | 107.6 |
O6—P2—O7 | 119.75 (11) | O1—C6—C5 | 108.4 (2) |
O6—P2—O5 | 113.58 (12) | O1—C6—H6A | 110.0 |
O7—P2—O5 | 105.91 (11) | C5—C6—H6A | 110.0 |
O6—P2—O2 | 107.88 (11) | O1—C6—H6B | 110.0 |
O7—P2—O2 | 104.54 (10) | C5—C6—H6B | 110.0 |
O5—P2—O2 | 103.69 (12) | H6A—C6—H6B | 108.4 |
C6—O1—P1 | 116.73 (16) | N1—C7—C8 | 113.8 (2) |
P1—O2—P2 | 127.76 (12) | N1—C7—H7A | 108.8 |
P2—O5—H5 | 109.5 | C8—C7—H7A | 108.8 |
C1—N1—C2 | 114.2 (2) | N1—C7—H7B | 108.8 |
C1—N1—C7 | 124.3 (2) | C8—C7—H7B | 108.8 |
C2—N1—C7 | 121.5 (2) | H7A—C7—H7B | 107.7 |
C9—N2—C10 | 120.3 (2) | C9—C8—C11 | 116.6 (2) |
C9—N2—H2 | 119.8 | C9—C8—C7 | 121.4 (2) |
C10—N2—H2 | 119.8 | C11—C8—C7 | 121.8 (2) |
C10—N3—C11 | 118.7 (2) | N2—C9—C8 | 121.3 (2) |
C11—N4—H4A | 120.0 | N2—C9—H9 | 119.4 |
C11—N4—H4B | 120.0 | C8—C9—H9 | 119.4 |
H4A—N4—H4B | 120.0 | N3—C10—N2 | 122.5 (2) |
N1—C1—S1 | 112.47 (19) | N3—C10—C12 | 120.2 (2) |
N1—C1—H1 | 123.8 | N2—C10—C12 | 117.3 (2) |
S1—C1—H1 | 123.8 | N4—C11—N3 | 117.4 (2) |
C3—C2—N1 | 111.7 (2) | N4—C11—C8 | 122.0 (2) |
C3—C2—C4 | 128.1 (2) | N3—C11—C8 | 120.6 (2) |
N1—C2—C4 | 120.2 (2) | C10—C12—H12A | 109.5 |
C2—C3—C5 | 127.3 (2) | C10—C12—H12B | 109.5 |
C2—C3—S1 | 110.50 (19) | H12A—C12—H12B | 109.5 |
C5—C3—S1 | 122.20 (18) | C10—C12—H12C | 109.5 |
C2—C4—H4C | 109.5 | H12A—C12—H12C | 109.5 |
C2—C4—H4D | 109.5 | H12B—C12—H12C | 109.5 |
H4C—C4—H4D | 109.5 | H1A—O1W—H1B | 108.7 |
C2—C4—H4E | 109.5 | H2A—O2W—H2B | 107.2 |
H4C—C4—H4E | 109.5 | ||
O4—P1—O1—C6 | 77.5 (2) | C2—C3—C5—C6 | 154.8 (3) |
O3—P1—O1—C6 | −54.5 (2) | S1—C3—C5—C6 | −24.9 (3) |
O2—P1—O1—C6 | −169.68 (18) | P1—O1—C6—C5 | −173.47 (16) |
O4—P1—O2—P2 | −104.39 (18) | C3—C5—C6—O1 | 64.2 (3) |
O3—P1—O2—P2 | 29.1 (2) | C1—N1—C7—C8 | 1.1 (3) |
O1—P1—O2—P2 | 142.77 (15) | C2—N1—C7—C8 | −177.5 (2) |
O6—P2—O2—P1 | 45.00 (19) | N1—C7—C8—C9 | −105.1 (3) |
O7—P2—O2—P1 | 173.48 (14) | N1—C7—C8—C11 | 79.7 (3) |
O5—P2—O2—P1 | −75.74 (17) | C10—N2—C9—C8 | 2.4 (4) |
C2—N1—C1—S1 | −0.5 (3) | C11—C8—C9—N2 | 0.2 (4) |
C7—N1—C1—S1 | −179.20 (18) | C7—C8—C9—N2 | −175.2 (2) |
C3—S1—C1—N1 | 0.7 (2) | C11—N3—C10—N2 | 0.6 (4) |
C1—N1—C2—C3 | −0.1 (3) | C11—N3—C10—C12 | −179.6 (3) |
C7—N1—C2—C3 | 178.7 (2) | C9—N2—C10—N3 | −2.9 (4) |
C1—N1—C2—C4 | 178.6 (2) | C9—N2—C10—C12 | 177.2 (3) |
C7—N1—C2—C4 | −2.7 (3) | C10—N3—C11—N4 | −178.3 (2) |
N1—C2—C3—C5 | −179.1 (2) | C10—N3—C11—C8 | 2.2 (4) |
C4—C2—C3—C5 | 2.4 (4) | C9—C8—C11—N4 | 178.0 (2) |
N1—C2—C3—S1 | 0.6 (3) | C7—C8—C11—N4 | −6.6 (4) |
C4—C2—C3—S1 | −177.9 (2) | C9—C8—C11—N3 | −2.5 (3) |
C1—S1—C3—C2 | −0.8 (2) | C7—C8—C11—N3 | 172.9 (2) |
C1—S1—C3—C5 | 179.0 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
C1—H1···O7i | 0.93 | 2.15 | 2.972 (3) | 147 |
N2—H2···O6ii | 0.86 | 1.84 | 2.696 (3) | 175 |
N4—H4A···O7iii | 0.86 | 2.00 | 2.846 (3) | 170 |
N4—H4B···O1W | 0.86 | 2.06 | 2.893 (3) | 163 |
O5—H5···O3iv | 0.82 | 1.94 | 2.605 (3) | 138 |
O1W—H1A···O2Wv | 0.86 | 1.88 | 2.738 (3) | 172 |
O1W—H1B···O5iii | 0.86 | 2.20 | 2.962 (3) | 148 |
O2W—H2A···O4 | 0.87 | 1.89 | 2.746 (3) | 171 |
O2W—H2B···O4vi | 0.87 | 1.99 | 2.818 (3) | 159 |
Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) x−1, y−1, z+1; (iii) x−1, y, z+1; (iv) −x+2, −y+2, −z; (v) −x+1, −y+2, −z+1; (vi) −x+2, −y+2, −z+1. |
C12H18N4O7P2S·3H2O | Z = 2 |
Mr = 478.35 | F(000) = 500 |
Triclinic, P1 | Dx = 1.550 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 8.3776 (12) Å | Cell parameters from 30 reflections |
b = 9.2397 (13) Å | θ = 9.7–19.9° |
c = 14.208 (2) Å | µ = 0.37 mm−1 |
α = 87.896 (11)° | T = 295 K |
β = 74.324 (13)° | Plate, colourless |
γ = 75.559 (11)° | 0.47 × 0.38 × 0.13 mm |
V = 1024.8 (3) Å3 |
Siemens P4 four-circle diffractometer | 2953 reflections with I > 2σ(I) |
Radiation source: sealed tube | Rint = 0.017 |
Graphite monochromator | θmax = 25.0°, θmin = 1.5° |
2θ and ω scans | h = −1→9 |
Absorption correction: ψ scan (XSCANS; Siemens, 1996) | k = −10→10 |
Tmin = 0.844, Tmax = 0.953 | l = −16→16 |
4473 measured reflections | 3 standard reflections every 150 reflections |
3593 independent reflections | intensity decay: 2.5% |
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) = 0.111 | H-atom parameters constrained |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0566P)2 + 0.4384P] where P = (Fo2 + 2Fc2)/3 |
3593 reflections | (Δ/σ)max = 0.001 |
265 parameters | Δρmax = 0.45 e Å−3 |
0 restraints | Δρmin = −0.38 e Å−3 |
C12H18N4O7P2S·3H2O | γ = 75.559 (11)° |
Mr = 478.35 | V = 1024.8 (3) Å3 |
Triclinic, P1 | Z = 2 |
a = 8.3776 (12) Å | Mo Kα radiation |
b = 9.2397 (13) Å | µ = 0.37 mm−1 |
c = 14.208 (2) Å | T = 295 K |
α = 87.896 (11)° | 0.47 × 0.38 × 0.13 mm |
β = 74.324 (13)° |
Siemens P4 four-circle diffractometer | 2953 reflections with I > 2σ(I) |
Absorption correction: ψ scan (XSCANS; Siemens, 1996) | Rint = 0.017 |
Tmin = 0.844, Tmax = 0.953 | 3 standard reflections every 150 reflections |
4473 measured reflections | intensity decay: 2.5% |
3593 independent reflections |
R[F2 > 2σ(F2)] = 0.040 | 0 restraints |
wR(F2) = 0.111 | H-atom parameters constrained |
S = 1.06 | Δρmax = 0.45 e Å−3 |
3593 reflections | Δρmin = −0.38 e Å−3 |
265 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
S1 | 0.56965 (10) | 0.68932 (9) | 0.88403 (5) | 0.0446 (2) | |
P1 | 0.45328 (8) | 0.76825 (7) | 1.17304 (4) | 0.02809 (17) | |
P2 | 0.72596 (8) | 0.51133 (7) | 1.20239 (4) | 0.02943 (18) | |
O1 | 0.5264 (2) | 0.8371 (3) | 1.07179 (13) | 0.0469 (5) | |
O2 | 0.5695 (3) | 0.6016 (2) | 1.16260 (17) | 0.0574 (6) | |
O3 | 0.4726 (2) | 0.8499 (2) | 1.25489 (13) | 0.0395 (4) | |
O4 | 0.2808 (2) | 0.7564 (2) | 1.17169 (14) | 0.0466 (5) | |
O5 | 0.7733 (2) | 0.3606 (2) | 1.14276 (13) | 0.0375 (4) | |
H5 | 0.7955 | 0.3769 | 1.0841 | 0.056* | |
O6 | 0.6629 (3) | 0.4770 (2) | 1.30680 (13) | 0.0526 (6) | |
O7 | 0.8613 (3) | 0.5935 (3) | 1.17575 (16) | 0.0586 (6) | |
N1 | 0.6884 (2) | 0.7951 (2) | 0.72405 (13) | 0.0258 (4) | |
N2 | 0.5270 (3) | 0.6725 (2) | 0.45746 (14) | 0.0364 (5) | |
H2 | 0.5614 | 0.6032 | 0.4125 | 0.044* | |
N3 | 0.3039 (3) | 0.8628 (2) | 0.54785 (14) | 0.0326 (5) | |
N4 | 0.3484 (3) | 1.0109 (2) | 0.65830 (15) | 0.0339 (5) | |
H4A | 0.2430 | 1.0593 | 0.6686 | 0.041* | |
H4B | 0.4122 | 1.0367 | 0.6896 | 0.041* | |
C1 | 0.5710 (3) | 0.7256 (3) | 0.76771 (17) | 0.0341 (6) | |
H1 | 0.4965 | 0.6994 | 0.7372 | 0.041* | |
C2 | 0.7878 (3) | 0.8217 (3) | 0.78318 (17) | 0.0278 (5) | |
C3 | 0.7374 (3) | 0.7706 (3) | 0.87406 (17) | 0.0314 (5) | |
C4 | 0.9316 (3) | 0.8927 (3) | 0.7429 (2) | 0.0400 (6) | |
H4C | 0.9900 | 0.8970 | 0.7919 | 0.060* | |
H4D | 0.8878 | 0.9922 | 0.7236 | 0.060* | |
H4E | 1.0101 | 0.8349 | 0.6870 | 0.060* | |
C5 | 0.8092 (3) | 0.7750 (3) | 0.96008 (18) | 0.0366 (6) | |
H5A | 0.9139 | 0.8084 | 0.9384 | 0.044* | |
H5B | 0.8384 | 0.6745 | 0.9835 | 0.044* | |
C6 | 0.6873 (3) | 0.8767 (3) | 1.04385 (18) | 0.0364 (6) | |
H6A | 0.7359 | 0.8676 | 1.0992 | 0.044* | |
H6B | 0.6701 | 0.9798 | 1.0241 | 0.044* | |
C7 | 0.7134 (3) | 0.8448 (3) | 0.62156 (17) | 0.0297 (5) | |
H7A | 0.8280 | 0.7952 | 0.5837 | 0.036* | |
H7B | 0.7043 | 0.9516 | 0.6210 | 0.036* | |
C8 | 0.5868 (3) | 0.8125 (3) | 0.57386 (16) | 0.0280 (5) | |
C9 | 0.6374 (3) | 0.7029 (3) | 0.50307 (17) | 0.0338 (6) | |
H9 | 0.7508 | 0.6476 | 0.4856 | 0.041* | |
C10 | 0.3627 (3) | 0.7515 (3) | 0.48273 (17) | 0.0338 (6) | |
C11 | 0.4122 (3) | 0.8973 (3) | 0.59463 (16) | 0.0272 (5) | |
C12 | 0.2417 (4) | 0.7084 (4) | 0.4354 (2) | 0.0477 (7) | |
H12A | 0.1805 | 0.7954 | 0.4093 | 0.072* | |
H12B | 0.1621 | 0.6661 | 0.4830 | 0.072* | |
H12C | 0.3048 | 0.6359 | 0.3834 | 0.072* | |
O1W | 0.9665 (2) | 0.7524 (2) | 1.29550 (15) | 0.0498 (5) | |
H1A | 1.0652 | 0.7622 | 1.2606 | 0.075* | |
H1B | 0.9246 | 0.7084 | 1.2587 | 0.075* | |
O2W | 0.8420 (3) | 0.3743 (3) | 0.95506 (14) | 0.0632 (7) | |
H2A | 0.8023 | 0.3276 | 0.9197 | 0.095* | |
H2B | 0.9399 | 0.3861 | 0.9237 | 0.095* | |
O3W | 0.9915 (3) | 0.4591 (3) | 1.37667 (17) | 0.0718 (7) | |
H3A | 1.0225 | 0.5385 | 1.3511 | 0.108* | |
H3B | 0.9124 | 0.4475 | 1.3507 | 0.108* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0507 (4) | 0.0698 (5) | 0.0282 (3) | −0.0382 (4) | −0.0159 (3) | 0.0142 (3) |
P1 | 0.0252 (3) | 0.0359 (3) | 0.0233 (3) | −0.0069 (3) | −0.0063 (2) | −0.0072 (2) |
P2 | 0.0273 (3) | 0.0336 (3) | 0.0287 (3) | −0.0099 (3) | −0.0067 (3) | −0.0056 (3) |
O1 | 0.0374 (11) | 0.0802 (15) | 0.0284 (10) | −0.0222 (10) | −0.0112 (8) | 0.0057 (9) |
O2 | 0.0645 (14) | 0.0364 (11) | 0.0809 (16) | −0.0014 (10) | −0.0435 (13) | −0.0151 (10) |
O3 | 0.0422 (10) | 0.0472 (11) | 0.0309 (9) | −0.0146 (9) | −0.0078 (8) | −0.0139 (8) |
O4 | 0.0317 (10) | 0.0694 (14) | 0.0415 (11) | −0.0178 (9) | −0.0075 (8) | −0.0146 (10) |
O5 | 0.0387 (10) | 0.0391 (10) | 0.0309 (9) | −0.0057 (8) | −0.0053 (8) | −0.0086 (8) |
O6 | 0.0810 (16) | 0.0443 (11) | 0.0269 (10) | −0.0178 (11) | −0.0022 (10) | −0.0067 (8) |
O7 | 0.0468 (12) | 0.0752 (15) | 0.0612 (14) | −0.0339 (11) | −0.0075 (11) | −0.0137 (12) |
N1 | 0.0261 (10) | 0.0294 (10) | 0.0215 (9) | −0.0072 (8) | −0.0053 (8) | 0.0002 (8) |
N2 | 0.0511 (14) | 0.0360 (12) | 0.0204 (10) | −0.0127 (10) | −0.0043 (9) | −0.0065 (9) |
N3 | 0.0346 (11) | 0.0402 (12) | 0.0254 (10) | −0.0140 (9) | −0.0080 (9) | −0.0002 (9) |
N4 | 0.0279 (11) | 0.0386 (12) | 0.0341 (11) | −0.0029 (9) | −0.0098 (9) | −0.0111 (9) |
C1 | 0.0381 (14) | 0.0437 (14) | 0.0283 (13) | −0.0204 (12) | −0.0133 (11) | 0.0051 (11) |
C2 | 0.0233 (12) | 0.0294 (12) | 0.0300 (12) | −0.0048 (9) | −0.0071 (10) | −0.0028 (10) |
C3 | 0.0283 (13) | 0.0384 (13) | 0.0289 (12) | −0.0099 (10) | −0.0084 (10) | −0.0004 (10) |
C4 | 0.0305 (14) | 0.0491 (16) | 0.0431 (15) | −0.0151 (12) | −0.0100 (12) | 0.0046 (12) |
C5 | 0.0296 (13) | 0.0506 (16) | 0.0320 (13) | −0.0094 (12) | −0.0129 (11) | 0.0023 (12) |
C6 | 0.0395 (14) | 0.0441 (15) | 0.0296 (13) | −0.0139 (12) | −0.0131 (11) | 0.0020 (11) |
C7 | 0.0277 (12) | 0.0346 (13) | 0.0239 (11) | −0.0069 (10) | −0.0032 (10) | 0.0023 (9) |
C8 | 0.0315 (13) | 0.0310 (12) | 0.0191 (11) | −0.0072 (10) | −0.0035 (9) | 0.0011 (9) |
C9 | 0.0391 (14) | 0.0329 (13) | 0.0240 (12) | −0.0052 (11) | −0.0027 (11) | −0.0006 (10) |
C10 | 0.0473 (16) | 0.0398 (14) | 0.0180 (11) | −0.0200 (12) | −0.0069 (11) | 0.0022 (10) |
C11 | 0.0319 (12) | 0.0317 (12) | 0.0184 (11) | −0.0101 (10) | −0.0055 (9) | 0.0011 (9) |
C12 | 0.0597 (19) | 0.0611 (19) | 0.0329 (14) | −0.0333 (16) | −0.0128 (13) | −0.0023 (13) |
O1W | 0.0370 (11) | 0.0633 (13) | 0.0491 (12) | −0.0172 (10) | −0.0050 (9) | −0.0147 (10) |
O2W | 0.0565 (14) | 0.113 (2) | 0.0310 (11) | −0.0417 (14) | −0.0082 (10) | −0.0129 (12) |
O3W | 0.0761 (17) | 0.0641 (15) | 0.0636 (15) | 0.0021 (13) | −0.0180 (13) | 0.0050 (12) |
S1—C1 | 1.672 (2) | C3—C5 | 1.507 (3) |
S1—C3 | 1.723 (2) | C4—H4C | 0.9600 |
P1—O3 | 1.4746 (17) | C4—H4D | 0.9600 |
P1—O4 | 1.4812 (19) | C4—H4E | 0.9600 |
P1—O1 | 1.5813 (19) | C5—C6 | 1.513 (4) |
P1—O2 | 1.591 (2) | C5—H5A | 0.9700 |
P2—O7 | 1.477 (2) | C5—H5B | 0.9700 |
P2—O6 | 1.485 (2) | C6—H6A | 0.9700 |
P2—O5 | 1.5633 (18) | C6—H6B | 0.9700 |
P2—O2 | 1.598 (2) | C7—C8 | 1.496 (3) |
O1—C6 | 1.433 (3) | C7—H7A | 0.9700 |
O5—H5 | 0.8200 | C7—H7B | 0.9700 |
N1—C1 | 1.311 (3) | C8—C9 | 1.359 (3) |
N1—C2 | 1.398 (3) | C8—C11 | 1.433 (3) |
N1—C7 | 1.486 (3) | C9—H9 | 0.9300 |
N2—C10 | 1.344 (4) | C10—C12 | 1.492 (4) |
N2—C9 | 1.350 (3) | C12—H12A | 0.9600 |
N2—H2 | 0.8600 | C12—H12B | 0.9600 |
N3—C10 | 1.314 (3) | C12—H12C | 0.9600 |
N3—C11 | 1.361 (3) | O1W—H1A | 0.8665 |
N4—C11 | 1.317 (3) | O1W—H1B | 0.8645 |
N4—H4A | 0.8600 | O2W—H2A | 0.8523 |
N4—H4B | 0.8600 | O2W—H2B | 0.8522 |
C1—H1 | 0.9300 | O3W—H3A | 0.8736 |
C2—C3 | 1.353 (3) | O3W—H3B | 0.8700 |
C2—C4 | 1.485 (3) | ||
C1—S1—C3 | 91.07 (12) | H4D—C4—H4E | 109.5 |
O3—P1—O4 | 119.48 (11) | C3—C5—C6 | 113.5 (2) |
O3—P1—O1 | 111.00 (11) | C3—C5—H5A | 108.9 |
O4—P1—O1 | 105.10 (11) | C6—C5—H5A | 108.9 |
O3—P1—O2 | 110.61 (11) | C3—C5—H5B | 108.9 |
O4—P1—O2 | 106.06 (12) | C6—C5—H5B | 108.9 |
O1—P1—O2 | 103.23 (13) | H5A—C5—H5B | 107.7 |
O7—P2—O6 | 118.21 (13) | O1—C6—C5 | 109.9 (2) |
O7—P2—O5 | 113.21 (12) | O1—C6—H6A | 109.7 |
O6—P2—O5 | 106.48 (11) | C5—C6—H6A | 109.7 |
O7—P2—O2 | 107.72 (13) | O1—C6—H6B | 109.7 |
O6—P2—O2 | 109.95 (14) | C5—C6—H6B | 109.7 |
O5—P2—O2 | 99.71 (10) | H6A—C6—H6B | 108.2 |
C6—O1—P1 | 124.44 (16) | N1—C7—C8 | 113.11 (19) |
P1—O2—P2 | 136.32 (13) | N1—C7—H7A | 109.0 |
P2—O5—H5 | 109.5 | C8—C7—H7A | 109.0 |
C1—N1—C2 | 114.1 (2) | N1—C7—H7B | 109.0 |
C1—N1—C7 | 123.8 (2) | C8—C7—H7B | 109.0 |
C2—N1—C7 | 122.14 (19) | H7A—C7—H7B | 107.8 |
C10—N2—C9 | 119.5 (2) | C9—C8—C11 | 116.5 (2) |
C10—N2—H2 | 120.2 | C9—C8—C7 | 120.0 (2) |
C9—N2—H2 | 120.2 | C11—C8—C7 | 123.4 (2) |
C10—N3—C11 | 118.9 (2) | N2—C9—C8 | 121.5 (2) |
C11—N4—H4A | 120.0 | N2—C9—H9 | 119.3 |
C11—N4—H4B | 120.0 | C8—C9—H9 | 119.3 |
H4A—N4—H4B | 120.0 | N3—C10—N2 | 123.1 (2) |
N1—C1—S1 | 112.75 (18) | N3—C10—C12 | 118.9 (2) |
N1—C1—H1 | 123.6 | N2—C10—C12 | 118.1 (2) |
S1—C1—H1 | 123.6 | N4—C11—N3 | 116.8 (2) |
C3—C2—N1 | 111.2 (2) | N4—C11—C8 | 122.8 (2) |
C3—C2—C4 | 128.2 (2) | N3—C11—C8 | 120.4 (2) |
N1—C2—C4 | 120.5 (2) | C10—C12—H12A | 109.5 |
C2—C3—C5 | 128.9 (2) | C10—C12—H12B | 109.5 |
C2—C3—S1 | 110.89 (18) | H12A—C12—H12B | 109.5 |
C5—C3—S1 | 120.16 (18) | C10—C12—H12C | 109.5 |
C2—C4—H4C | 109.5 | H12A—C12—H12C | 109.5 |
C2—C4—H4D | 109.5 | H12B—C12—H12C | 109.5 |
H4C—C4—H4D | 109.5 | H1A—O1W—H1B | 107.4 |
C2—C4—H4E | 109.5 | H2A—O2W—H2B | 111.0 |
H4C—C4—H4E | 109.5 | H3A—O3W—H3B | 106.4 |
O3—P1—O1—C6 | 45.5 (2) | C2—C3—C5—C6 | 112.7 (3) |
O4—P1—O1—C6 | 176.1 (2) | S1—C3—C5—C6 | −68.3 (3) |
O2—P1—O1—C6 | −73.0 (2) | P1—O1—C6—C5 | 113.0 (2) |
O3—P1—O2—P2 | −15.2 (3) | C3—C5—C6—O1 | 53.9 (3) |
O4—P1—O2—P2 | −146.1 (2) | C1—N1—C7—C8 | 2.0 (3) |
O1—P1—O2—P2 | 103.6 (2) | C2—N1—C7—C8 | −176.7 (2) |
O7—P2—O2—P1 | −54.2 (3) | N1—C7—C8—C9 | −108.1 (2) |
O6—P2—O2—P1 | 75.9 (3) | N1—C7—C8—C11 | 75.5 (3) |
O5—P2—O2—P1 | −172.5 (2) | C10—N2—C9—C8 | −0.4 (4) |
C2—N1—C1—S1 | 0.8 (3) | C11—C8—C9—N2 | −2.3 (3) |
C7—N1—C1—S1 | −177.98 (17) | C7—C8—C9—N2 | −178.9 (2) |
C3—S1—C1—N1 | −0.4 (2) | C11—N3—C10—N2 | −2.3 (4) |
C1—N1—C2—C3 | −0.9 (3) | C11—N3—C10—C12 | 176.7 (2) |
C7—N1—C2—C3 | 178.0 (2) | C9—N2—C10—N3 | 2.9 (4) |
C1—N1—C2—C4 | 177.0 (2) | C9—N2—C10—C12 | −176.1 (2) |
C7—N1—C2—C4 | −4.2 (3) | C10—N3—C11—N4 | 179.1 (2) |
N1—C2—C3—C5 | 179.5 (2) | C10—N3—C11—C8 | −0.7 (3) |
C4—C2—C3—C5 | 1.9 (4) | C9—C8—C11—N4 | −176.9 (2) |
N1—C2—C3—S1 | 0.5 (3) | C7—C8—C11—N4 | −0.4 (4) |
C4—C2—C3—S1 | −177.1 (2) | C9—C8—C11—N3 | 2.9 (3) |
C1—S1—C3—C2 | −0.1 (2) | C7—C8—C11—N3 | 179.4 (2) |
C1—S1—C3—C5 | −179.2 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
C1—H1···O6i | 0.93 | 2.54 | 3.400 (3) | 154 |
N2—H2···O6ii | 0.86 | 1.81 | 2.662 (3) | 169 |
N4—H4A···O1Wiii | 0.86 | 2.10 | 2.910 (3) | 156 |
N4—H4B···O3iii | 0.86 | 1.90 | 2.739 (3) | 163 |
O5—H5···O2W | 0.82 | 1.77 | 2.577 (3) | 169 |
O1W—H1A···O4iv | 0.87 | 1.89 | 2.751 (3) | 171 |
O1W—H1B···O7 | 0.86 | 1.87 | 2.733 (3) | 172 |
O2W—H2A···O4i | 0.85 | 1.90 | 2.746 (3) | 172 |
O2W—H2B···O7v | 0.85 | 1.92 | 2.748 (3) | 165 |
O3W—H3A···O1W | 0.87 | 2.09 | 2.888 (3) | 151 |
O3W—H3B···O6 | 0.87 | 2.29 | 3.135 (4) | 164 |
Symmetry codes: (i) −x+1, −y+1, −z+2; (ii) x, y, z−1; (iii) −x+1, −y+2, −z+2; (iv) x+1, y, z; (v) −x+2, −y+1, −z+2. |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | C12H18N4O7P2S·2H2O | C12H18N4O7P2S·3H2O |
Mr | 460.34 | 478.35 |
Crystal system, space group | Triclinic, P1 | Triclinic, P1 |
Temperature (K) | 295 | 295 |
a, b, c (Å) | 7.8778 (12), 11.2134 (14), 11.7613 (14) | 8.3776 (12), 9.2397 (13), 14.208 (2) |
α, β, γ (°) | 69.368 (12), 73.893 (12), 89.070 (11) | 87.896 (11), 74.324 (13), 75.559 (11) |
V (Å3) | 930.3 (2) | 1024.8 (3) |
Z | 2 | 2 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.40 | 0.37 |
Crystal size (mm) | 0.41 × 0.20 × 0.18 | 0.47 × 0.38 × 0.13 |
Data collection | ||
Diffractometer | Siemens P4 four-circle diffractometer | Siemens P4 four-circle diffractometer |
Absorption correction | ψ scan (XSCANS; Siemens, 1996) | ψ scan (XSCANS; Siemens, 1996) |
Tmin, Tmax | 0.852, 0.931 | 0.844, 0.953 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4169, 3259, 2647 | 4473, 3593, 2953 |
Rint | 0.024 | 0.017 |
(sin θ/λ)max (Å−1) | 0.595 | 0.595 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.038, 0.116, 1.05 | 0.040, 0.111, 1.06 |
No. of reflections | 3259 | 3593 |
No. of parameters | 256 | 265 |
No. of restraints | 6 | 0 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.26, −0.33 | 0.45, −0.38 |
Computer programs: XSCANS (Siemens, 1996), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XP in SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2008), SHELXTL (Sheldrick, 2008).
D—H···A | D—H | H···A | D···A | D—H···A |
C1—H1···O7i | 0.93 | 2.15 | 2.972 (3) | 147 |
N2—H2···O6ii | 0.86 | 1.84 | 2.696 (3) | 175 |
N4—H4A···O7iii | 0.86 | 2.00 | 2.846 (3) | 170 |
N4—H4B···O1W | 0.86 | 2.06 | 2.893 (3) | 163 |
O5—H5···O3iv | 0.82 | 1.94 | 2.605 (3) | 138 |
O1W—H1A···O2Wv | 0.86 | 1.88 | 2.738 (3) | 172 |
O1W—H1B···O5iii | 0.86 | 2.20 | 2.962 (3) | 148 |
O2W—H2A···O4 | 0.87 | 1.89 | 2.746 (3) | 171 |
O2W—H2B···O4vi | 0.87 | 1.99 | 2.818 (3) | 159 |
Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) x−1, y−1, z+1; (iii) x−1, y, z+1; (iv) −x+2, −y+2, −z; (v) −x+1, −y+2, −z+1; (vi) −x+2, −y+2, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
C1—H1···O6i | 0.93 | 2.54 | 3.400 (3) | 154 |
N2—H2···O6ii | 0.86 | 1.81 | 2.662 (3) | 169 |
N4—H4A···O1Wiii | 0.86 | 2.10 | 2.910 (3) | 156 |
N4—H4B···O3iii | 0.86 | 1.90 | 2.739 (3) | 163 |
O5—H5···O2W | 0.82 | 1.77 | 2.577 (3) | 169 |
O1W—H1A···O4iv | 0.87 | 1.89 | 2.751 (3) | 171 |
O1W—H1B···O7 | 0.86 | 1.87 | 2.733 (3) | 172 |
O2W—H2A···O4i | 0.85 | 1.90 | 2.746 (3) | 172 |
O2W—H2B···O7v | 0.85 | 1.92 | 2.748 (3) | 165 |
O3W—H3A···O1W | 0.87 | 2.09 | 2.888 (3) | 151 |
O3W—H3B···O6 | 0.87 | 2.29 | 3.135 (4) | 164 |
Symmetry codes: (i) −x+1, −y+1, −z+2; (ii) x, y, z−1; (iii) −x+1, −y+2, −z+2; (iv) x+1, y, z; (v) −x+2, −y+1, −z+2. |
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Pseudopolymorphs are solvated forms of a compound which differ in the nature or stoichiometry of the included solvent molecules (Nangia, 2006). Like polymorphs, pseudopolymorphs are of importance in pharmaceutical science and solid-state chemistry because physical properties and bioavailability can be critically dependent on crystal forms. Thiamine (vitamin B1) in its pyrophosphate form (thiamine pyrophosphate, TPP) is a coenzyme for a number of enzyme systems which catalyse a number of important metabolic reactions, including the transfer of aldehyde groups and the oxidative and non-oxidative decarboxylation of α-keto acids (Breslow, 1958; Krampitz, 1969). The catalytic processes involve the recognition and reaction of a substrate electrophile such as pyruvate at nucleophilic site C1 of the deprotonated thiazolium group (see Fig. 1 for atomic numbering). Thiamine and TPP are not only biologically important molecules but potential building blocks for constructing hydrogen-bonded supramolecular arrays, on which anionic or electronegative guests are adsorbed (Aoki et al., 1993; Hu et al., 2001; Li & Hu, 2010), as they provide multiple sites that serve as hydrogen-bond donors and acceptors. A large number of crystal structures of thiamine compounds have been reported as models of host–guest interactions [65 hits from the Cambridge Structural Database (CSD), Version 5.33; Allen, 2002], including thiamine–anion salt compounds (43 hits) and thiamine–metal complexes (22 hits). However, only limited structural studies can be found for TPP (six hits from the CSD). In three of these compounds, TPP exists as a monovalent cation with a protonated pyrimidine ring and a deprotonated phosphate group (Bai et al., 2009; Pletcher & Sax, 1972), and in the others TPP acts as a neutral zwitterion with a doubly deprotonated pyrophosphate group. The structure of neutral TPP has been determined in its tetrahydrate form, (III) (CSD refcode THPPTH01; Pletcher et al., 1977), and 4.5-hydrate form, (IV) (THPPTI; Pletcher et al., 1979). Interestingly, both pseudopolymorphs (III) and (IV) show a two-dimensional hydrogen-bonded network, with similar N—H···O hydrogen-bonding interactions between the pyrimidine and pyrophosphate groups but different O—H···O hydrogen-bonding interactions between the pyrophosphate groups. This prompted us to examine the supramolecular structures in different hydrate pseudopolymorphs of TPP. We report here the crystal structures of a dihydrate form, (I), and a trihydrate form, (II).
The molecular dimensions in (I) (Fig. 1) and (II) (Fig. 2) are in agreement with each other. The C9—N2—C10 angles of the pyrimidinium ring are 120.3 (2) and 119.5 (2)°, respectively, for the two compounds, which are comparable with the reported value for a protonated pyrimidine ring (Hu et al., 2005; Pletcher & Sax, 1972) but larger than in derivatives in which the pyriminine ring is not protonated [115.8 (6) and 115.0 (7)°; Li & Hu, 2010]. It is evident from the P—O bond lengths and the location of the H atoms that both the inner and terminal phosphate groups are deprotonated, and thus the TPP molecule is a neutral zwitterion in both (I) and (II). As is usually observed in thiamine compounds, the TPP molecules adopt an F conformation in terms of the torsion angles: ϕT = 1.1 (3)° and ϕP = 79.7 (3)° for (I), with corresponding values of 2.0 (3) and 75.5 (3)° for (II) (ϕT = C8—C7—N1—C1 ≈ 0° and ϕP = N1—C7—C8—C11 ≈ ±90° for the F conformation; Blank et al., 1976). It has been shown that the manner in which thiamine is associated with anions or electronegative atoms is closely related to the molecular conformation (Aoki et al., 1993; Cramer et al., 1988). Two distinct types of anion-bridging interactions are observed, which link the thiazolium and pyrimidine rings of a thiamine molecule via hydrogen bonds and electrostatic contacts. They have been defined as type I and type II anion bridges, respectively (Hu et al., 1999). In (I), phosphate atom O7i (symmetry code as in Table 1) acts as a type-I anion bridge to link the two aromatic rings by accepting a hydrogen bond from atom C1 (Table 1) and making a close contact with the pyrimidine ring [O7i···centroid distance = 3.354 (3) Å] (Fig. 1). Water molecule O1W occupies the site of a type-II anion bridge to accept a hydrogen bond from atom N4 and making a close contact with the thiazolium ring [O1W···centroid distance = 3.389 (3) Å].
These two anion bridges also occur in (II) (Fig. 2 and Table 2). The role of type-I anion bridge is performed by a phosphate O atom, being of the form C1—H···O6i···pyrimidinium ring [O6i···centroid distance = 3.485 (3) Å; symmetry code as in Table 2], and the type-II anion bridge is another phosphate O atom, not a water molecule, being of the form N4—H···O3iii···thiazolium ring [O3iii···centroid distance = 3.653 (3) Å; symmetry code as in Table 2]. These two types of interaction stabilize the molecular conformation and the type-I anion bridge is characteristic of a thiamine molecule in the F conformation. Our results confirm that TPP hydrates follow this rule.
The conformations of the pyrophosphate groups differ significantly in (I) and (II). From the P1—O1—C6—C5 and O2—P1—O1—C6 torsion angles [-173.5 (2) and -169.7 (2)° in (I), and 113.0 (2) and -73.0 (2)° in (II), respectively], (I) has a more extended pyrophosphate side chain than (II). We note that the role of type-II anion bridge played by a water molecule is also present in tetrahydrate (III) and 4.5-hydrate (IV), similar to that in (I) but different from that played by a phosphate O atom in (II). This may lead to the difference in hydrogen-bonded supramolecular structures between these compounds, a two-dimensional network in (I), (III) and (IV) and a one-dimensional tape in (II), as described below.
The crystal packing in (I) and (II) is dominated by intermolecular hydrogen bonds involving TPP and water molecules. As shown in Fig. 3, the TPP molecules in (I) are self-assembled into a two-dimensional network which is stabilized by three types of hydrogen bonds, Ot—H···Oi, Np—H···Ot and Na—H···Ot (Ot is an O atom of the terminal phosphate, Oi is an O atom of the inner phosphate, Np is the protonated N atom of the pyrimidine ring and Na is the N atom of the amino group). Firstly, a dimer is formed through a pair of O5—H···O3iv hydrogen bonds between two pyrophosphate groups across an inversion centre in an R22(12) motif (Bernstein et al., 1995). N2—H···O6ii and N4—H···O7iii hydrogen bonds then link the dimers to complete a sheet parallel to (101) (symmetry codes as in Table 1). The sheet is further stabilized by π–π interactions between the thiazolium rings [centroid-to-centroid distance = 3.8877 (14) Å]. These sheets are packed with the meshes aligned, thus forming channels along [100]. The solvent water molecules lie in the channels and act as both hydrogen-bond donors and acceptors to interact with the TPP molecules (Table 1). In (II), two TPP molecules form a centrosymmetric cyclic dimer by a pair of N4—H···O3iii hydrogen bonds in an R22(26) motif. The dimers are further connected by a pair of N2—H···O6ii hydrogen bonds (symmetry codes as in Table 2), leading to a one-dimensional tape structure along [001] (Fig. 4). The tapes are linked by water molecules through hydrogen bonds (Table 2).
We examined the structural details of the previously reported pseudopolymorphs (III) and (IV) in order to make a comparison of the supramolecular structures in the TPP hydrates. It is interesting to note that (III) and (IV) also exhibit two-dimensional networks built by three types of hydrogen bond, similar to the case of (I). The structure of (III), containing two crystallographically independent molecules A and B, is composed of two different molecular sheets. Two molecules A are linked by a pair of Ot—H···Ot hydrogen bonds in an R22(8) motif, forming a phosphate-pairing dimer. Np—H···Ot and Na—H···Oi hydrogen bonds connect the dimers into a sheet. Molecules B are self-assembled into a second sheet in a similar way, except the phosphate-pairing dimer is formed by a single Ot—H···Ot hydrogen bond in a D motif. Compound (IV) displays a sheet structure constructed in a similar way to molecules A in (III); a pair of Ot—H···Ot hydrogen bonds results in an R22(8) dimer, and Np—H···Ot and Na—H···Oi hydrogen bonds complete the sheet. Altogether, (I), (III) and (IV) show three kinds of phosphate-pairing dimer, as illustrated in Fig. 5. Despite the differences in these dimers, sheet structures are present in all three pseudopolymorphs. In contrast, there are no phosphate-pairing interactions in (II) and a tape structure is observed.
In summary, two types of anion bridge that have been frequently observed in thiamine compounds are present in the title TPP hydrates (I) and (II). The results could be helpful for understanding the interactions between the TPP coenzyme and substrate. The formation of two-dimensional networks in the neutral TPP zwitterion hydrates is closely related to the existence of hydrogen-bonded phosphate-pairing dimers exhibiting R22(12), R22(8) and D motifs. In the TPP systems, several phosphate O atoms can serve as hydrogen-bond acceptors from water donors, as it is observed that three O(water)—H···O(phosphate) hydrogen bonds are formed in (I) and five in (II). At the same time, a water molecule in (II) competes for the acceptor site on a phosphate group, thus interrupting the self-assembly of a phosphate-pairing dimer. However, from the four neutral TPP hydrates available at present, supramolecular synthons between the pyrophosphate groups are obviously predominant in the crystal packing of two-dimensional networks. Further work is needed to understand the factors that govern the crystal packing in TPP systems.