Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802005743/om6082sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536802005743/om60824sup2.hkl |
CCDC reference: 185774
Key indicators
- Single-crystal X-ray study
- T = 193 K
- Mean (C-C) = 0.005 Å
- R factor = 0.043
- wR factor = 0.110
- Data-to-parameter ratio = 11.4
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry
Alert Level C:
PLAT_728 Alert C D-H..A Calc 172(6), Rep 170.90, Dev. 1.10 Deg. O1 -H1 -O1 1.555 1.555 7.545 PLAT_748 Alert C D-H..A Calc 137.5(8), Rep 137.30 .... Missing s.u. N -H1A -O1 1.555 1.555 1.555
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
2 Alert Level C = Please check
3-Methyl-1,2-butadiene-1,1-diphosphonic acid, (3), was treated with aniline to yield the title compound (4). The crude salt, (4), was recrystallized from water to yield colorless crystals [m.p. 450 K; 31P NMR (D2O), p.p.m.: δ(versus. ext. 85% H3PO4) 9.64].
Data for compound (4) were collected at 193 K on a Bruker PLATFORM diffractometer equipped with SMART 1000 CCD area detector. The structure of (4) was solved through use of the direct-methods program SHELXS97 (Sheldrick, 1990). Except for H1, the H atoms were generated in idealized positions (according to the sp2 or sp3 geometries of their parent C, N or O atoms), and then allowed to refine with no restraints on coordinates or isotropic displacement parameters. The hydroxyl H1 atom was located from a difference Fourier map, and found to lie on the crystallographic twofold axis (1/4,y,1/4). It was also allowed to freely refine. Its Ueq value [0.10 (2) e Å-3] is significantly larger than that for its attached oxygen, but attempts to model it as belonging to a rotationally disordered O1—H1···O1'' unit (i.e. by initially inserting H1 between O1 and O1'' approximately 0.8 Å from O1, with an occupancy factor of 1/2, then allowing free refinement) yielded less satisfactory results [Ueq(H1) = 0.009 (15) e Å-3, O1—H1 = 0.72 (4) Å].
Data collection: SMART (Bruker, 1997); cell refinement: SMART; data reduction: SHELXTL (Sheldrick, 1997a); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997b); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2001).
C6H8N+·C5H9O6P2− | Dx = 1.447 Mg m−3 |
Mr = 321.20 | Melting point: 450 K |
Orthorhombic, Cmca | Mo Kα radiation, λ = 0.71073 Å |
a = 9.9331 (14) Å | Cell parameters from 2913 reflections |
b = 20.188 (3) Å | θ = 2.5–26.3° |
c = 14.701 (2) Å | µ = 0.32 mm−1 |
V = 2947.9 (7) Å3 | T = 193 K |
Z = 8 | Plate, colorless |
F(000) = 1344 | 0.47 × 0.15 × 0.04 mm |
Bruker PLATFORM diffractometer/SMART 1000 CCD area-detector | 1604 independent reflections |
Radiation source: fine-focus sealed tube | 1177 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.065 |
Detector resolution: 8.192 pixels mm-1 | θmax = 26.4°, θmin = 2.0° |
ω scans | h = −11→12 |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | k = −24→25 |
Tmin = 0.865, Tmax = 0.987 | l = −16→18 |
7136 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)] = 0.043 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.110 | All H-atom parameters refined |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0514P)2 + 4.4604P] where P = (Fo2 + 2Fc2)/3 |
1604 reflections | (Δ/σ)max < 0.001 |
141 parameters | Δρmax = 0.56 e Å−3 |
0 restraints | Δρmin = −0.36 e Å−3 |
C6H8N+·C5H9O6P2− | V = 2947.9 (7) Å3 |
Mr = 321.20 | Z = 8 |
Orthorhombic, Cmca | Mo Kα radiation |
a = 9.9331 (14) Å | µ = 0.32 mm−1 |
b = 20.188 (3) Å | T = 193 K |
c = 14.701 (2) Å | 0.47 × 0.15 × 0.04 mm |
Bruker PLATFORM diffractometer/SMART 1000 CCD area-detector | 1604 independent reflections |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | 1177 reflections with I > 2σ(I) |
Tmin = 0.865, Tmax = 0.987 | Rint = 0.065 |
7136 measured reflections |
R[F2 > 2σ(F2)] = 0.043 | 0 restraints |
wR(F2) = 0.110 | All H-atom parameters refined |
S = 1.02 | Δρmax = 0.56 e Å−3 |
1604 reflections | Δρmin = −0.36 e Å−3 |
141 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. Hydrogen atoms were refined with fixed C—H, N—H or O—H distances and with isotropici displacement parameters 20% (for C—H or N—H) or 50% (for O—H) greater than those for their attached atoms. The close contact (2.414 (3) Å) between O1 and the symmetry-related O1 at (1/2 - x, y, 1/2 - z) suggested a hydrogen-bonded interaction between these atoms, thus the hydroxylic hydrogen H1 was assigned an occupancy factor of 0.5 to allow for the disorder generated by the intervening twofold axis (1/4, y, 1/4). |
x | y | z | Uiso*/Ueq | ||
P | 0.15793 (6) | 0.20007 (3) | 0.10477 (4) | 0.0176 (2) | |
O1 | 0.15184 (17) | 0.17459 (9) | 0.20181 (12) | 0.0258 (4) | |
H1 | 0.2500 | 0.179 (3) | 0.2500 | 0.10 (2)* | |
O2 | 0.16508 (19) | 0.27709 (9) | 0.10995 (14) | 0.0235 (4) | |
H2 | 0.188 (3) | 0.2919 (15) | 0.063 (2) | 0.039 (10)* | |
O3 | 0.27166 (16) | 0.17290 (8) | 0.04932 (11) | 0.0209 (4) | |
C1 | 0.0000 | 0.17891 (17) | 0.0529 (2) | 0.0172 (7) | |
C2 | 0.0000 | 0.15157 (18) | −0.0279 (2) | 0.0225 (8) | |
C3 | 0.0000 | 0.1281 (2) | −0.1100 (3) | 0.0280 (9) | |
C4 | 0.0000 | 0.1753 (3) | −0.1889 (3) | 0.0415 (12) | |
H4A | 0.0000 | 0.223 (2) | −0.166 (3) | 0.048 (14)* | |
H4B | 0.073 (3) | 0.1669 (15) | −0.226 (2) | 0.056 (11)* | |
C5 | 0.0000 | 0.0550 (3) | −0.1293 (4) | 0.0420 (12) | |
H5A | 0.0000 | 0.029 (3) | −0.081 (4) | 0.062 (17)* | |
H5B | 0.072 (4) | 0.0443 (17) | −0.165 (2) | 0.063 (12)* | |
N | 0.0000 | 0.12706 (16) | 0.3615 (2) | 0.0193 (7) | |
H1A | 0.0000 | 0.141 (2) | 0.305 (3) | 0.043 (13)* | |
H1B | 0.074 (3) | 0.1439 (14) | 0.3899 (19) | 0.031 (8)* | |
C6 | 0.0000 | 0.05491 (17) | 0.3675 (2) | 0.0186 (7) | |
C7 | 0.1184 (3) | 0.02160 (16) | 0.3720 (3) | 0.0483 (10) | |
H7 | 0.199 (4) | 0.044 (2) | 0.366 (3) | 0.083 (13)* | |
C8 | 0.1170 (4) | −0.04641 (16) | 0.3820 (3) | 0.0531 (11) | |
H8 | 0.194 (4) | −0.0686 (18) | 0.382 (3) | 0.073 (12)* | |
C9 | 0.0000 | −0.0805 (2) | 0.3867 (3) | 0.0303 (9) | |
H9 | 0.0000 | −0.128 (2) | 0.394 (3) | 0.025 (10)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
P | 0.0130 (3) | 0.0249 (4) | 0.0149 (3) | −0.0002 (3) | 0.0002 (2) | 0.0018 (3) |
O1 | 0.0182 (9) | 0.0427 (11) | 0.0167 (9) | −0.0046 (8) | −0.0032 (7) | 0.0079 (8) |
O2 | 0.0212 (9) | 0.0275 (11) | 0.0218 (10) | −0.0018 (8) | 0.0054 (8) | −0.0033 (8) |
O3 | 0.0162 (8) | 0.0261 (10) | 0.0205 (9) | 0.0035 (7) | 0.0025 (7) | 0.0019 (7) |
C1 | 0.0144 (16) | 0.0226 (19) | 0.0146 (17) | 0.000 | 0.000 | 0.0029 (14) |
C2 | 0.0172 (17) | 0.027 (2) | 0.024 (2) | 0.000 | 0.000 | 0.0018 (16) |
C3 | 0.0254 (19) | 0.039 (2) | 0.0196 (19) | 0.000 | 0.000 | −0.0037 (17) |
C4 | 0.050 (3) | 0.056 (3) | 0.019 (2) | 0.000 | 0.000 | −0.001 (2) |
C5 | 0.051 (3) | 0.039 (3) | 0.035 (3) | 0.000 | 0.000 | −0.010 (2) |
N | 0.0157 (15) | 0.0236 (18) | 0.0187 (16) | 0.000 | 0.000 | 0.0021 (13) |
C6 | 0.0205 (17) | 0.0195 (19) | 0.0159 (17) | 0.000 | 0.000 | −0.0020 (14) |
C7 | 0.0200 (15) | 0.0275 (18) | 0.097 (3) | −0.0013 (12) | −0.0071 (16) | −0.0009 (18) |
C8 | 0.0305 (17) | 0.0238 (17) | 0.105 (3) | 0.0069 (14) | −0.0134 (19) | −0.0009 (19) |
C9 | 0.040 (2) | 0.021 (2) | 0.030 (2) | 0.000 | 0.000 | −0.0028 (17) |
P—O1 | 1.5177 (18) | C5—H5A | 0.88 (5) |
P—O2 | 1.558 (2) | C5—H5B | 0.91 (3) |
P—O3 | 1.4972 (17) | N—C6 | 1.459 (5) |
P—C1 | 1.7959 (18) | N—H1A | 0.88 (5) |
O1—H1 | 1.209 (5) | N—H1B | 0.91 (3) |
O2—H2 | 0.78 (3) | C6—C7 | 1.356 (3) |
C1—C2 | 1.309 (5) | C6—C7i | 1.356 (3) |
C2—C3 | 1.296 (5) | C7—C8 | 1.381 (5) |
C3—C4 | 1.501 (6) | C7—H7 | 0.92 (4) |
C3—C5 | 1.504 (6) | C8—C9 | 1.352 (4) |
C4—H4A | 1.03 (5) | C8—H8 | 0.89 (4) |
C4—H4B | 0.93 (3) | C9—H9 | 0.96 (4) |
O1—P—O2 | 107.10 (11) | C3—C5—H5A | 116 (3) |
O1—P—O3 | 114.69 (10) | C3—C5—H5B | 110 (2) |
O1—P—C1 | 106.49 (12) | H5A—C5—H5B | 109 (3) |
O2—P—O3 | 110.96 (10) | C6—N—H1A | 113 (3) |
O2—P—C1 | 107.33 (13) | C6—N—H1B | 110.1 (18) |
O3—P—C1 | 109.92 (12) | H1A—N—H1B | 108 (2) |
P—O1—H1 | 119.5 (12) | C7—C6—C7i | 120.2 (4) |
P—O2—H2 | 111 (2) | N—C6—C7 | 119.87 (19) |
P—C1—Pi | 121.74 (19) | C6—C7—C8 | 119.3 (3) |
P—C1—C2 | 119.04 (10) | C6—C7—H7 | 120 (3) |
C1—C2—C3 | 176.5 (4) | C8—C7—H7 | 120 (3) |
C2—C3—C4 | 119.2 (4) | C7—C8—C9 | 121.3 (3) |
C2—C3—C5 | 122.3 (4) | C7—C8—H8 | 120 (2) |
C4—C3—C5 | 118.5 (4) | C9—C8—H8 | 119 (2) |
C3—C4—H4A | 110 (3) | C8—C9—C8i | 118.5 (4) |
C3—C4—H4B | 110 (2) | C8—C9—H9 | 120.7 (2) |
H4A—C4—H4B | 112 (2) | ||
O1—P—C1—Pi | 51.9 (2) | O3—P—C1—C2 | −8.2 (3) |
O1—P—C1—C2 | −133.0 (3) | N—C6—C7—C8 | 176.9 (4) |
O2—P—C1—Pi | −62.5 (2) | C7i—C6—C7—C8 | −0.5 (7) |
O2—P—C1—C2 | 112.6 (3) | C6—C7—C8—C9 | 0.4 (6) |
O3—P—C1—Pi | 176.72 (16) | C7—C8—C9—C8i | −0.3 (8) |
Symmetry code: (i) −x, y, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O1ii | 1.21 (1) | 1.21 (1) | 2.411 (3) | 171 |
O2—H2···O3iii | 0.78 (3) | 1.85 (3) | 2.626 (3) | 175.6 |
N—H1A···O1 | 0.88 (5) | 2.24 (4) | 2.951 (3) | 137 |
N—H1A···O1i | 0.88 (5) | 2.24 (4) | 2.951 (3) | 137 |
N—H1B···O3ii | 0.91 (3) | 1.87 (3) | 2.778 (3) | 176.4 |
Symmetry codes: (i) −x, y, z; (ii) −x+1/2, y, −z+1/2; (iii) −x+1/2, −y+1/2, −z. |
Experimental details
Crystal data | |
Chemical formula | C6H8N+·C5H9O6P2− |
Mr | 321.20 |
Crystal system, space group | Orthorhombic, Cmca |
Temperature (K) | 193 |
a, b, c (Å) | 9.9331 (14), 20.188 (3), 14.701 (2) |
V (Å3) | 2947.9 (7) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.32 |
Crystal size (mm) | 0.47 × 0.15 × 0.04 |
Data collection | |
Diffractometer | Bruker PLATFORM diffractometer/SMART 1000 CCD area-detector |
Absorption correction | Empirical (using intensity measurements) (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.865, 0.987 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7136, 1604, 1177 |
Rint | 0.065 |
(sin θ/λ)max (Å−1) | 0.626 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.043, 0.110, 1.02 |
No. of reflections | 1604 |
No. of parameters | 141 |
H-atom treatment | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 0.56, −0.36 |
Computer programs: SMART (Bruker, 1997), SMART, SHELXTL (Sheldrick, 1997a), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997b), SHELXTL and PLATON (Spek, 2001).
P—O1 | 1.5177 (18) | C3—C5 | 1.504 (6) |
P—O2 | 1.558 (2) | N—C6 | 1.459 (5) |
P—O3 | 1.4972 (17) | N—H1A | 0.88 (5) |
P—C1 | 1.7959 (18) | N—H1B | 0.91 (3) |
O1—H1 | 1.209 (5) | C6—C7 | 1.356 (3) |
O2—H2 | 0.78 (3) | C6—C7i | 1.356 (3) |
C1—C2 | 1.309 (5) | C7—C8 | 1.381 (5) |
C2—C3 | 1.296 (5) | C8—C9 | 1.352 (4) |
C3—C4 | 1.501 (6) | ||
O1—P—O2 | 107.10 (11) | C2—C3—C4 | 119.2 (4) |
O1—P—O3 | 114.69 (10) | C2—C3—C5 | 122.3 (4) |
O1—P—C1 | 106.49 (12) | C4—C3—C5 | 118.5 (4) |
O2—P—O3 | 110.96 (10) | C6—N—H1A | 113 (3) |
O2—P—C1 | 107.33 (13) | C6—N—H1B | 110.1 (18) |
O3—P—C1 | 109.92 (12) | H1A—N—H1B | 108 (2) |
P—O1—H1 | 119.5 (12) | C7—C6—C7i | 120.2 (4) |
P—O2—H2 | 111 (2) | N—C6—C7 | 119.87 (19) |
P—C1—Pi | 121.74 (19) | C6—C7—C8 | 119.3 (3) |
P—C1—C2 | 119.04 (10) | C7—C8—C9 | 121.3 (3) |
C1—C2—C3 | 176.5 (4) | C8—C9—C8i | 118.5 (4) |
Symmetry code: (i) −x, y, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O1ii | 1.209 (3) | 1.209 (3) | 2.411 (3) | 170.9 |
O2—H2···O3iii | 0.78 (3) | 1.85 (3) | 2.626 (3) | 175.6 |
N—H1A···O1 | 0.88 (5) | 2.24 (4) | 2.951 (3) | 137.3 |
N—H1A···O1i | 0.88 (5) | 2.24 (4) | 2.951 (3) | 137.3 |
N—H1B···O3ii | 0.91 (3) | 1.87 (3) | 2.778 (3) | 176.4 |
Symmetry codes: (i) −x, y, z; (ii) −x+1/2, y, −z+1/2; (iii) −x+1/2, −y+1/2, −z. |
Diphosphonate compounds are of interest to us due to their known biological activity, particularly their ability to reduce tumour-induced bone resorption (Fleisch, 1998). Their affinity for bone and other calcified tissues (Wingen & Schmähl, 1985) has led others to demonstrate the utility of functionalized organic diphosphonates to facilitate site-preferential delivery of antiosteosarcomic agents (Klenner et al., 1990). Recently, we have studied the reactivity of polyfunctional electrophilic and nucleophilic reagents with 1,2-alkadiene mono- and diphosphonates. These compounds are relatively easy to prepare by acetylene–allene rearrangement of acetylene phosphines, which are obtained by the reaction of phosphorus trichloride (or chlorophosphines) with α-acetylenic alcohols under mild conditions to afford 1,2-alkadiene mono- and diphosphonates (Ignat'ev et al., 1967; Mark, 1969).
In this communication, we wish to describe the preparation of the previously unknown 3-methyl-1,2-butadiene-1,1-diphosphonic acid, (3), and its structural elucidation. We used 3-methyl-1,2-butadiene-1,1-diphosphonic tetraethyl ester, (1), as a convenient precursor for the synthesis of the acid (3) by a procedure recently developed in our laboratory (Angelov, 2002). By replacing the ethyl groups in (I) with trimethylsilyl groups, we were able to prepare 3-methyl-1,2-butadiene-1,1-diphosphonic tetrakis(trimethylsilyl) ester, (2). Hydrolysis of (2) [31P NMR (CDCl3), p.p.m.: δ (versus. ext. 85% H3PO4) -7.90] with methanol afforded the acid (3). Compound (3) [31P NMR (CDCl3), p.p.m.: δ(versus. ext. 85% H3PO4) 3.42] is a colorless hygroscopic powder which quickly absorbs moisture and becomes an oil. We stabilized (3) by treatment with one molar equivalent of aniline, and were able to prepare a stable anilinium salt (4).
In the solid-state structure of (4), both the Me2C═C═ C{PO(OH)2}{PO2(OH)}- ion and the associated anilinium ion are situated upon a crystallographic mirror plane (0,y,z) (primed atoms are related to unprimed ones via this plane). As shown in Fig. 1, this mirror plane contains atoms C1–C5 of the anion and N/C6/C9 of the PhNH3+ ion. The allenic unit is essentially linear [C1—C2—C3 = 176.5 (4)°], with the C1—C2 [1.308 (5) Å] and C2—C3 [1.298 (5) Å] distances approximately equal. Despite the mirror plane, atom O1' is drawn without a hydroxylic H atom. This is due to a hydrogen-bonded interaction with an adjacent twofold-related molecule (see below).
Fig. 2 illustrates the interactions between adjacent anilinium and diphosphonate ions (the relevant hydrogen-bond parameters are given in Table 2). Adjacent diphosphonate ions form hydrogen-bonded interactions in two different manners. A chain interaction is observed between O1—H1 and the O1 atom (indicated as O1'') related by the (1/4,y,1/4) twofold axis, in which the O1—H1 and O1*···H1 distances are equal [1.209(3 Å], due to the location of H1 upon the twofold axis. A cyclic interaction is also formed about the inversion center (1/4,1/4,0) by O2—H2 and the inversion-generated O3 atom (indicated as O3*), with O3 being hydrogen bonded to O2*-H2*. As might be seen in Fig. 1, one of the ammonium H atoms of the anilinium ion is within 2.24 (4) Å of both O1 and O1', forming a cyclic C(—P═O···)2H unit. A closer [1.87 (3) Å], more linear interaction is formed between the anilinium H1B atom and O3''.