Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802016501/cv6144sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536802016501/cv61442sup2.hkl |
CCDC reference: 198961
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.004 Å
- R factor = 0.048
- wR factor = 0.130
- Data-to-parameter ratio = 14.5
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry
Alert Level C:
PLAT_353 Alert C Long N-H Bond (0.87A) N(1) - H(1) = 1.06 Ang.
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
1 Alert Level C = Please check
The spectroscopy (1H, 13 C, 31P NMR, IR) and elemental analysis showed that the diphenyl 3,5- dimethyl-1–1pyrazolylphosphonate (1) is formed in the reaction of 3,5-dimethyl pyrazole with diphenyl chlorophosphate in presence of anhydrous pyridine. In the presence of water, compound (1) is rapidly converted into the compound (2).
All H atoms from methyl and phenyl groups were geometrically placed. All methyl H atoms were constrained to their parent atom as a rigid body (C—H = 0.96 Å), and the Uiso values were refined as 1.5 Ueq of the parent C atom. All phenyl H atoms and H4 atom from the pyrazole ring were constrained to their parent atoms as a rigid body (C—H = 0.93 Å), and the Uiso values were refined as 1.2 Ueq of the parent C atom. All other H atoms (H1, H2) were located in the difference map and refined isotropically.
Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1989); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: TEXSAN (Molecular Structure Corporation, 1989); program(s) used to solve structure: SHELXS86 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 1998); software used to prepare material for publication: PARST97 (Nardelli, 1996).
C5H9N2+·C12H10O2P− | F(000) = 728 |
Mr = 346.31 | Dx = 1.332 Mg m−3 |
Monoclinic, P21/n | Cu Kα radiation, λ = 1.54178 Å |
a = 8.890 (1) Å | Cell parameters from 25 reflections |
b = 10.970 (2) Å | θ = 20.2–27.9° |
c = 17.714 (1) Å | µ = 1.62 mm−1 |
β = 90.41 (1)° | T = 293 K |
V = 1727.5 (4) Å3 | Block, colorless |
Z = 4 | 0.6 × 0.4 × 0.3 mm |
AFC-5S Rigaku diffractometer | 2118 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.020 |
Graphite monochromator | θmax = 72.8°, θmin = 4.7° |
ω scan | h = 0→10 |
Absorption correction: analytical (De Meulenaer & Tompa, 1965) | k = 0→13 |
Tmin = 0.507, Tmax = 0.667 | l = −21→21 |
3507 measured reflections | 3 standard reflections every 150 reflections |
3283 independent reflections | intensity decay: <2% |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.048 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.130 | w = 1/[σ2(Fo2) + (0.0891P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.87 | (Δ/σ)max < 0.001 |
3283 reflections | Δρmax = 0.22 e Å−3 |
227 parameters | Δρmin = −0.42 e Å−3 |
0 restraints |
C5H9N2+·C12H10O2P− | V = 1727.5 (4) Å3 |
Mr = 346.31 | Z = 4 |
Monoclinic, P21/n | Cu Kα radiation |
a = 8.890 (1) Å | µ = 1.62 mm−1 |
b = 10.970 (2) Å | T = 293 K |
c = 17.714 (1) Å | 0.6 × 0.4 × 0.3 mm |
β = 90.41 (1)° |
AFC-5S Rigaku diffractometer | 2118 reflections with I > 2σ(I) |
Absorption correction: analytical (De Meulenaer & Tompa, 1965) | Rint = 0.020 |
Tmin = 0.507, Tmax = 0.667 | 3 standard reflections every 150 reflections |
3507 measured reflections | intensity decay: <2% |
3283 independent reflections |
R[F2 > 2σ(F2)] = 0.048 | 0 restraints |
wR(F2) = 0.130 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.87 | Δρmax = 0.22 e Å−3 |
3283 reflections | Δρmin = −0.42 e Å−3 |
227 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 | ||
P1 | 0.13145 (7) | 0.72841 (6) | 0.25491 (3) | 0.05600 (19) | |
O1 | 0.11587 (18) | 0.77752 (17) | 0.17762 (8) | 0.0675 (5) | |
O2 | 0.14138 (19) | 0.59602 (15) | 0.26744 (10) | 0.0685 (5) | |
O3 | −0.00381 (17) | 0.77317 (15) | 0.30720 (8) | 0.0611 (4) | |
C31 | −0.0760 (3) | 0.8856 (2) | 0.30381 (12) | 0.0555 (5) | |
C32 | −0.0012 (3) | 0.9940 (2) | 0.29080 (13) | 0.0622 (6) | |
H32 | 0.1010 | 0.9939 | 0.2800 | 0.075* | |
C33 | −0.0803 (3) | 1.1027 (2) | 0.29405 (14) | 0.0693 (7) | |
H33 | −0.0304 | 1.1760 | 0.2858 | 0.083* | |
C34 | −0.2324 (3) | 1.1033 (3) | 0.30947 (15) | 0.0764 (7) | |
H34 | −0.2848 | 1.1765 | 0.3121 | 0.092* | |
C35 | −0.3056 (3) | 0.9942 (3) | 0.32098 (15) | 0.0748 (7) | |
H35 | −0.4081 | 0.9940 | 0.3312 | 0.090* | |
C36 | −0.2288 (3) | 0.8858 (3) | 0.31746 (14) | 0.0667 (6) | |
H36 | −0.2795 | 0.8126 | 0.3243 | 0.080* | |
O4 | 0.27701 (17) | 0.79599 (14) | 0.28854 (8) | 0.0600 (4) | |
C41 | 0.3277 (3) | 0.7833 (2) | 0.36324 (13) | 0.0582 (6) | |
C42 | 0.3927 (3) | 0.6778 (3) | 0.38754 (16) | 0.0768 (8) | |
H42 | 0.3997 | 0.6100 | 0.3562 | 0.092* | |
C43 | 0.4493 (3) | 0.6756 (3) | 0.46241 (19) | 0.0918 (10) | |
H43 | 0.4958 | 0.6056 | 0.4808 | 0.110* | |
C44 | 0.4358 (3) | 0.7761 (4) | 0.50814 (17) | 0.0904 (10) | |
H44 | 0.4725 | 0.7738 | 0.5574 | 0.109* | |
C45 | 0.3696 (4) | 0.8779 (3) | 0.48164 (17) | 0.0933 (10) | |
H45 | 0.3605 | 0.9454 | 0.5130 | 0.112* | |
C46 | 0.3157 (3) | 0.8834 (3) | 0.40929 (15) | 0.0774 (8) | |
H46 | 0.2710 | 0.9545 | 0.3914 | 0.093* | |
N2 | 0.0494 (2) | 0.4359 (2) | 0.36779 (12) | 0.0635 (5) | |
H2 | 0.077 (3) | 0.497 (3) | 0.3375 (16) | 0.089 (9)* | |
N1 | 0.1395 (2) | 0.34567 (19) | 0.39204 (11) | 0.0622 (5) | |
H1 | 0.238 (4) | 0.317 (3) | 0.3639 (18) | 0.117 (11)* | |
C5 | 0.0695 (3) | 0.2850 (2) | 0.44690 (13) | 0.0640 (6) | |
C501 | 0.1367 (4) | 0.1732 (3) | 0.48168 (18) | 0.0907 (9) | |
H501 | 0.1004 | 0.1642 | 0.5323 | 0.136* | |
H502 | 0.2443 | 0.1806 | 0.4827 | 0.136* | |
H503 | 0.1086 | 0.1031 | 0.4524 | 0.136* | |
C4 | −0.0674 (3) | 0.3404 (2) | 0.45804 (14) | 0.0683 (7) | |
H4 | −0.1394 | 0.3178 | 0.4932 | 0.082* | |
C3 | −0.0782 (3) | 0.4351 (2) | 0.40766 (14) | 0.0652 (6) | |
C301 | −0.2005 (3) | 0.5242 (3) | 0.39294 (17) | 0.0903 (9) | |
H301 | −0.2437 | 0.5493 | 0.4400 | 0.135* | |
H302 | −0.2767 | 0.4869 | 0.3620 | 0.135* | |
H303 | −0.1603 | 0.5939 | 0.3673 | 0.135* |
U11 | U22 | U33 | U12 | U13 | U23 | |
P1 | 0.0488 (3) | 0.0632 (4) | 0.0562 (3) | −0.0053 (3) | 0.0112 (2) | 0.0005 (3) |
O1 | 0.0612 (10) | 0.0891 (12) | 0.0522 (8) | −0.0130 (9) | 0.0063 (7) | 0.0060 (8) |
O2 | 0.0639 (10) | 0.0600 (10) | 0.0819 (11) | −0.0046 (8) | 0.0184 (8) | −0.0008 (8) |
O3 | 0.0548 (9) | 0.0644 (10) | 0.0642 (9) | 0.0043 (8) | 0.0192 (7) | 0.0081 (8) |
C31 | 0.0522 (13) | 0.0656 (14) | 0.0489 (11) | 0.0024 (11) | 0.0057 (9) | 0.0044 (10) |
C32 | 0.0534 (13) | 0.0699 (15) | 0.0633 (13) | −0.0003 (12) | 0.0039 (10) | 0.0075 (12) |
C33 | 0.0733 (17) | 0.0647 (16) | 0.0700 (15) | −0.0001 (13) | 0.0001 (13) | 0.0057 (12) |
C34 | 0.0760 (19) | 0.0784 (19) | 0.0748 (17) | 0.0189 (15) | 0.0056 (14) | 0.0014 (14) |
C35 | 0.0564 (15) | 0.092 (2) | 0.0757 (16) | 0.0112 (15) | 0.0123 (12) | 0.0053 (15) |
C36 | 0.0542 (14) | 0.0791 (17) | 0.0671 (14) | −0.0048 (13) | 0.0105 (11) | 0.0071 (13) |
O4 | 0.0539 (9) | 0.0707 (11) | 0.0555 (8) | −0.0075 (8) | 0.0048 (7) | 0.0051 (7) |
C41 | 0.0454 (12) | 0.0707 (15) | 0.0586 (12) | −0.0024 (12) | 0.0029 (10) | 0.0089 (12) |
C42 | 0.0706 (17) | 0.0829 (19) | 0.0772 (17) | 0.0189 (15) | 0.0163 (14) | 0.0120 (14) |
C43 | 0.0642 (18) | 0.123 (3) | 0.089 (2) | 0.0294 (18) | 0.0110 (15) | 0.040 (2) |
C44 | 0.0622 (17) | 0.142 (3) | 0.0674 (16) | −0.007 (2) | −0.0042 (14) | 0.011 (2) |
C45 | 0.103 (3) | 0.104 (3) | 0.0725 (18) | −0.012 (2) | −0.0144 (17) | −0.0045 (17) |
C46 | 0.089 (2) | 0.0737 (17) | 0.0695 (16) | −0.0011 (15) | −0.0126 (14) | −0.0028 (13) |
N2 | 0.0613 (13) | 0.0657 (13) | 0.0637 (12) | 0.0019 (11) | 0.0147 (10) | 0.0044 (10) |
N1 | 0.0586 (12) | 0.0683 (13) | 0.0599 (11) | 0.0034 (10) | 0.0102 (9) | −0.0004 (10) |
C5 | 0.0669 (15) | 0.0680 (16) | 0.0573 (13) | −0.0013 (13) | 0.0079 (11) | 0.0037 (11) |
C501 | 0.093 (2) | 0.094 (2) | 0.085 (2) | 0.0132 (18) | 0.0089 (16) | 0.0184 (17) |
C4 | 0.0585 (14) | 0.0821 (18) | 0.0645 (14) | 0.0013 (13) | 0.0193 (11) | 0.0043 (13) |
C3 | 0.0574 (14) | 0.0712 (16) | 0.0673 (14) | 0.0031 (12) | 0.0136 (11) | −0.0030 (12) |
C301 | 0.0763 (19) | 0.097 (2) | 0.098 (2) | 0.0194 (17) | 0.0211 (16) | 0.0135 (17) |
P1—O2 | 1.4717 (18) | C43—H43 | 0.9300 |
P1—O1 | 1.4770 (16) | C44—C45 | 1.345 (4) |
P1—O3 | 1.6003 (15) | C44—H44 | 0.9300 |
P1—O4 | 1.6025 (16) | C45—C46 | 1.367 (4) |
O3—C31 | 1.392 (3) | C45—H45 | 0.9300 |
C31—C36 | 1.381 (3) | C46—H46 | 0.9300 |
C31—C32 | 1.382 (3) | N2—C3 | 1.340 (3) |
C32—C33 | 1.385 (3) | N2—N1 | 1.342 (3) |
C32—H32 | 0.9300 | N2—H2 | 0.89 (3) |
C33—C34 | 1.381 (4) | N1—C5 | 1.335 (3) |
C33—H33 | 0.9300 | N1—H1 | 1.06 (4) |
C34—C35 | 1.379 (4) | C5—C4 | 1.376 (4) |
C34—H34 | 0.9300 | C5—C501 | 1.495 (4) |
C35—C36 | 1.373 (4) | C501—H501 | 0.9600 |
C35—H35 | 0.9300 | C501—H502 | 0.9600 |
C36—H36 | 0.9300 | C501—H503 | 0.9600 |
O4—C41 | 1.402 (3) | C4—C3 | 1.372 (3) |
C41—C42 | 1.363 (3) | C4—H4 | 0.9300 |
C41—C46 | 1.372 (3) | C3—C301 | 1.484 (4) |
C42—C43 | 1.415 (4) | C301—H301 | 0.9600 |
C42—H42 | 0.9300 | C301—H302 | 0.9600 |
C43—C44 | 1.374 (4) | C301—H303 | 0.9600 |
O2—P1—O1 | 120.33 (11) | C45—C44—H44 | 120.0 |
O2—P1—O3 | 105.07 (9) | C43—C44—H44 | 120.0 |
O1—P1—O3 | 111.02 (10) | C44—C45—C46 | 120.9 (3) |
O2—P1—O4 | 110.67 (10) | C44—C45—H45 | 119.5 |
O1—P1—O4 | 104.25 (9) | C46—C45—H45 | 119.5 |
O3—P1—O4 | 104.53 (9) | C45—C46—C41 | 119.6 (3) |
C31—O3—P1 | 126.53 (13) | C45—C46—H46 | 120.2 |
C36—C31—C32 | 120.2 (2) | C41—C46—H46 | 120.2 |
C36—C31—O3 | 116.6 (2) | C3—N2—N1 | 109.4 (2) |
C32—C31—O3 | 123.2 (2) | C3—N2—H2 | 123.9 (18) |
C31—C32—C33 | 119.2 (2) | N1—N2—H2 | 125.4 (18) |
C31—C32—H32 | 120.4 | C5—N1—N2 | 108.7 (2) |
C33—C32—H32 | 120.4 | C5—N1—H1 | 125.6 (17) |
C34—C33—C32 | 120.7 (3) | N2—N1—H1 | 124.4 (17) |
C34—C33—H33 | 119.7 | N1—C5—C4 | 107.5 (2) |
C32—C33—H33 | 119.7 | N1—C5—C501 | 121.5 (2) |
C35—C34—C33 | 119.3 (3) | C4—C5—C501 | 130.9 (2) |
C35—C34—H34 | 120.4 | C5—C501—H501 | 109.5 |
C33—C34—H34 | 120.4 | C5—C501—H502 | 109.5 |
C36—C35—C34 | 120.6 (2) | H501—C501—H502 | 109.5 |
C36—C35—H35 | 119.7 | C5—C501—H503 | 109.5 |
C34—C35—H35 | 119.7 | H501—C501—H503 | 109.5 |
C35—C36—C31 | 120.0 (3) | H502—C501—H503 | 109.5 |
C35—C36—H36 | 120.0 | C3—C4—C5 | 107.4 (2) |
C31—C36—H36 | 120.0 | C3—C4—H4 | 126.3 |
C41—O4—P1 | 123.96 (14) | C5—C4—H4 | 126.3 |
C42—C41—C46 | 121.8 (2) | N2—C3—C4 | 107.0 (2) |
C42—C41—O4 | 121.0 (2) | N2—C3—C301 | 121.6 (2) |
C46—C41—O4 | 117.1 (2) | C4—C3—C301 | 131.3 (2) |
C41—C42—C43 | 117.2 (3) | C3—C301—H301 | 109.5 |
C41—C42—H42 | 121.4 | C3—C301—H302 | 109.5 |
C43—C42—H42 | 121.4 | H301—C301—H302 | 109.5 |
C44—C43—C42 | 120.5 (3) | C3—C301—H303 | 109.5 |
C44—C43—H43 | 119.8 | H301—C301—H303 | 109.5 |
C42—C43—H43 | 119.8 | H302—C301—H303 | 109.5 |
C45—C44—C43 | 120.0 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1i | 1.06 (3) | 1.56 (3) | 2.617 (3) | 178 (3) |
N2—H2···O2 | 0.90 (3) | 1.75 (3) | 2.633 (3) | 170 (3) |
Symmetry code: (i) −x+1/2, y−1/2, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C5H9N2+·C12H10O2P− |
Mr | 346.31 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 293 |
a, b, c (Å) | 8.890 (1), 10.970 (2), 17.714 (1) |
β (°) | 90.41 (1) |
V (Å3) | 1727.5 (4) |
Z | 4 |
Radiation type | Cu Kα |
µ (mm−1) | 1.62 |
Crystal size (mm) | 0.6 × 0.4 × 0.3 |
Data collection | |
Diffractometer | AFC-5S Rigaku diffractometer |
Absorption correction | Analytical (De Meulenaer & Tompa, 1965) |
Tmin, Tmax | 0.507, 0.667 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3507, 3283, 2118 |
Rint | 0.020 |
(sin θ/λ)max (Å−1) | 0.620 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.048, 0.130, 0.87 |
No. of reflections | 3283 |
No. of parameters | 227 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.22, −0.42 |
Computer programs: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1989), MSC/AFC Diffractometer Control Software, TEXSAN (Molecular Structure Corporation, 1989), SHELXS86 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), PLATON (Spek, 1998), PARST97 (Nardelli, 1996).
P1—O2 | 1.4717 (18) | P1—O4 | 1.6025 (16) |
P1—O1 | 1.4770 (16) | O3—C31 | 1.392 (3) |
P1—O3 | 1.6003 (15) | O4—C41 | 1.402 (3) |
O2—P1—O1 | 120.33 (11) | O1—P1—O4 | 104.25 (9) |
O2—P1—O3 | 105.07 (9) | O3—P1—O4 | 104.53 (9) |
O1—P1—O3 | 111.02 (10) | C31—O3—P1 | 126.53 (13) |
O2—P1—O4 | 110.67 (10) | C41—O4—P1 | 123.96 (14) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1i | 1.06 (3) | 1.56 (3) | 2.617 (3) | 178 (3) |
N2—H2···O2 | 0.90 (3) | 1.75 (3) | 2.633 (3) | 170 (3) |
Symmetry code: (i) −x+1/2, y−1/2, −z+1/2. |
Anticancer chemotherapy is very important issue in both medicinal chemistry and pharmacology (Lippert, 1999). The aim of this work was the synthesis and investigation of the chemical properties and biological activity of the novel compounds phosphonate esters of diazole: the development of the synthesis method for these compounds, determinations of the structure by means of spectroscopic as well as X-ray methods, and the evaluation of their bio-active properties (Okada et al., 2001; Rinke et al., 2001; Boduszek, 1996). Knowledge of the structure will help to design and sythesize new ligands for Pt complexes.
The X-ray studies confirm that the title compound, (2), exists in the crystal state in the ionic form. The C5N2H9+ cation and (OC6H5)2PO2− anion are linked by N—H···O hydrogen bonds (Table 2, Fig. 2). The combination of two hydrogen bonds provides a second level motif of type C22(7) (Bernstein et al., 1995). Finally, the molecules form chains along the b axis (Fig. 3).
Moreover, aromatic π-π-stacking interactions between pyrazole rings were found, which additionally stabilize the molecular arrangement of the structure. The distance between the centroids of the pyrazole rings Cg···Cgi [symmetry code (i): −x, 1 − y, 1 − z] is 4.21 (1) Å. The perpendicular distance between rings is 3.64 (1) Å.
The bonds and angles around the P atom indicate a slight distortion of the tetrahedron, with the angles varying from 104.24 (9) to 120.31 (11)° (see table 1). The two bond distances P1–O1 and P1–O2 are almost equal in length [1.471 (2) and 1.477 (2) Å, respectively], thus confirming the delocalized bonds in the solid state.
The benzene and pyrazole rings are planar within experimental error. The dihedral angle between benzene rings is 83.2 (1)°. Bond distances and angles are in a good agreement with expected values (Allen et al., 1987).