The title compound, C
12H
19OP
4, with a bulky group, exhibits one-dimensional hydrogen-bonded chains of bifurcated P—OH
O=P interactions. This one-dimensional chain structure with double P—OH
O=P hydrogen bonds is induced by the bulky isopropyl groups.
Supporting information
CCDC reference: 176002
Key indicators
- Single-crystal X-ray study
- T = 296 K
- Mean (C-C) = 0.006 Å
- R factor = 0.035
- wR factor = 0.106
- Data-to-parameter ratio = 14.2
checkCIF results
No syntax errors found
ADDSYM reports no extra symmetry
General Notes
REFLT_03
From the CIF: _diffrn_reflns_theta_max 30.00
From the CIF: _reflns_number_total 2219
Count of symmetry unique reflns 2221
Completeness (_total/calc) 99.91%
TEST3: Check Friedels for noncentro structure
Estimate of Friedel pairs measured 0
Fraction of Friedel pairs measured 0.000
Are heavy atom types Z>Si present yes
WARNING: Large fraction of Friedel related reflns may
be needed to determine absolute structure
The title compound was synthesized according to literature methods (Kosolapoff
et al., 1968). The product was recrystallized from chloroform.
The torsion angles about the PO bonds of the two hydroxyl groups were refined.
Data collection: MSC/AFC Diffractometer Control Software
(Molecular Structure Corporation, 1991); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: TEXSAN (Molecular Structure Corporation, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: TEXSAN; software used to prepare material for publication: TEXSAN.
2,6-Diisopropylbenzene dihydrogen phosphate
top
Crystal data top
C12H19O4P | F(000) = 276 |
Mr = 258.24 | Dx = 1.217 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71069 Å |
a = 10.0298 (15) Å | Cell parameters from 25 reflections |
b = 6.3718 (15) Å | θ = 14.7–15.0° |
c = 11.2238 (14) Å | µ = 0.20 mm−1 |
β = 100.685 (11)° | T = 296 K |
V = 704.9 (2) Å3 | Prismatic, colorless |
Z = 2 | 0.30 × 0.20 × 0.20 mm |
Data collection top
Rigaku AFC-5R diffractometer | Rint = 0.014 |
Radiation source: fine-focus sealed tube | θmax = 30.0°, θmin = 2.5° |
Graphite monochromator | h = 0→14 |
ω–2θ scans | k = −8→0 |
2329 measured reflections | l = −15→15 |
2219 independent reflections | 3 standard reflections every 150 reflections |
1627 reflections with I > 2σ(I) | intensity decay: 0.7% |
Refinement top
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)] = 0.035 | H-atom parameters constrained |
wR(F2) = 0.106 | w = 1/[σ2(Fo2) + (0.0527P)2 + 0.1189P] where P = (Fo2 + 2Fc2)/3 |
S = 1.02 | (Δ/σ)max < 0.001 |
2219 reflections | Δρmax = 0.24 e Å−3 |
156 parameters | Δρmin = −0.25 e Å−3 |
1 restraint | Absolute structure: Flack (1983) |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.11 (15) |
Crystal data top
C12H19O4P | V = 704.9 (2) Å3 |
Mr = 258.24 | Z = 2 |
Monoclinic, P21 | Mo Kα radiation |
a = 10.0298 (15) Å | µ = 0.20 mm−1 |
b = 6.3718 (15) Å | T = 296 K |
c = 11.2238 (14) Å | 0.30 × 0.20 × 0.20 mm |
β = 100.685 (11)° | |
Data collection top
Rigaku AFC-5R diffractometer | Rint = 0.014 |
2329 measured reflections | 3 standard reflections every 150 reflections |
2219 independent reflections | intensity decay: 0.7% |
1627 reflections with I > 2σ(I) | |
Refinement top
R[F2 > 2σ(F2)] = 0.035 | H-atom parameters constrained |
wR(F2) = 0.106 | Δρmax = 0.24 e Å−3 |
S = 1.02 | Δρmin = −0.25 e Å−3 |
2219 reflections | Absolute structure: Flack (1983) |
156 parameters | Absolute structure parameter: 0.11 (15) |
1 restraint | |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
P1 | 0.12980 (6) | 0.50000 (10) | 0.02135 (6) | 0.03514 (14) | |
O1 | 0.24004 (17) | 0.3911 (3) | 0.11897 (16) | 0.0402 (4) | |
O2 | 0.1299 (2) | 0.3641 (4) | −0.09264 (16) | 0.0459 (5) | |
H1 | 0.0922 | 0.2520 | −0.0853 | 0.055* | |
O3 | −0.00615 (15) | 0.5133 (4) | 0.05675 (15) | 0.0393 (4) | |
O4 | 0.18713 (18) | 0.7165 (3) | −0.0045 (2) | 0.0495 (5) | |
H2 | 0.1243 | 0.7980 | −0.0272 | 0.059* | |
C1 | 0.2765 (3) | 0.4642 (5) | 0.2409 (2) | 0.0426 (7) | |
C2 | 0.3916 (3) | 0.5918 (6) | 0.2681 (3) | 0.0534 (7) | |
C3 | 0.4267 (4) | 0.6547 (7) | 0.3889 (3) | 0.0722 (11) | |
H3 | 0.5032 | 0.7382 | 0.4123 | 0.087* | |
C4 | 0.3524 (4) | 0.5976 (9) | 0.4740 (3) | 0.0772 (12) | |
H4 | 0.3760 | 0.6477 | 0.5529 | 0.093* | |
C5 | 0.2430 (4) | 0.4666 (8) | 0.4432 (3) | 0.0683 (11) | |
H5 | 0.1947 | 0.4265 | 0.5026 | 0.082* | |
C6 | 0.2021 (3) | 0.3919 (5) | 0.3256 (3) | 0.0489 (7) | |
C7 | 0.0894 (3) | 0.2318 (6) | 0.2952 (3) | 0.0557 (8) | |
H6 | 0.0696 | 0.2165 | 0.2068 | 0.067* | |
C8 | 0.1357 (5) | 0.0171 (9) | 0.3487 (4) | 0.0913 (13) | |
H7 | 0.2126 | −0.0294 | 0.3160 | 0.110* | |
H8 | 0.0631 | −0.0821 | 0.3283 | 0.110* | |
H9 | 0.1605 | 0.0283 | 0.4353 | 0.110* | |
C9 | −0.0412 (4) | 0.3002 (11) | 0.3344 (4) | 0.0979 (17) | |
H10 | −0.0244 | 0.3225 | 0.4205 | 0.117* | |
H11 | −0.1088 | 0.1930 | 0.3138 | 0.117* | |
H12 | −0.0730 | 0.4283 | 0.2938 | 0.117* | |
C10 | 0.4776 (3) | 0.6500 (7) | 0.1756 (4) | 0.0652 (9) | |
H13 | 0.4275 | 0.6074 | 0.0959 | 0.078* | |
C11 | 0.6099 (4) | 0.5235 (14) | 0.2002 (5) | 0.123 (2) | |
H14 | 0.6618 | 0.5532 | 0.1383 | 0.147* | |
H15 | 0.5893 | 0.3764 | 0.1997 | 0.147* | |
H16 | 0.6617 | 0.5618 | 0.2779 | 0.147* | |
C12 | 0.5022 (6) | 0.8825 (10) | 0.1704 (5) | 0.1106 (19) | |
H17 | 0.5508 | 0.9298 | 0.2476 | 0.133* | |
H18 | 0.4169 | 0.9546 | 0.1514 | 0.133* | |
H19 | 0.5548 | 0.9115 | 0.1090 | 0.133* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
P1 | 0.0326 (2) | 0.0288 (2) | 0.0447 (3) | 0.0002 (3) | 0.0091 (2) | 0.0030 (3) |
O1 | 0.0358 (8) | 0.0375 (10) | 0.0473 (10) | 0.0068 (8) | 0.0076 (7) | 0.0016 (8) |
O2 | 0.0539 (11) | 0.0419 (11) | 0.0453 (10) | −0.0028 (10) | 0.0182 (8) | 0.0003 (9) |
O3 | 0.0332 (7) | 0.0328 (8) | 0.0533 (9) | 0.0009 (10) | 0.0117 (6) | 0.0017 (10) |
O4 | 0.0357 (9) | 0.0335 (10) | 0.0795 (14) | −0.0028 (8) | 0.0114 (9) | 0.0118 (10) |
C1 | 0.0434 (12) | 0.0427 (19) | 0.0402 (12) | 0.0122 (11) | 0.0041 (9) | 0.0031 (11) |
C2 | 0.0433 (15) | 0.0496 (16) | 0.0622 (18) | 0.0025 (13) | −0.0033 (13) | 0.0018 (16) |
C3 | 0.069 (2) | 0.067 (3) | 0.069 (2) | 0.000 (2) | −0.0191 (18) | −0.006 (2) |
C4 | 0.102 (3) | 0.075 (3) | 0.0442 (17) | 0.012 (2) | −0.0115 (19) | −0.0050 (18) |
C5 | 0.086 (2) | 0.074 (3) | 0.0443 (15) | 0.021 (2) | 0.0106 (15) | 0.0085 (17) |
C6 | 0.0535 (15) | 0.0461 (17) | 0.0482 (14) | 0.0161 (14) | 0.0121 (12) | 0.0120 (14) |
C7 | 0.0588 (18) | 0.0551 (18) | 0.0564 (17) | 0.0039 (16) | 0.0189 (14) | 0.0158 (16) |
C8 | 0.112 (3) | 0.067 (3) | 0.093 (3) | 0.004 (3) | 0.014 (2) | 0.028 (3) |
C9 | 0.068 (2) | 0.122 (5) | 0.113 (3) | 0.007 (3) | 0.041 (2) | 0.007 (4) |
C10 | 0.0419 (15) | 0.069 (2) | 0.081 (2) | −0.0087 (17) | 0.0026 (15) | 0.001 (2) |
C11 | 0.058 (2) | 0.131 (6) | 0.186 (5) | 0.019 (4) | 0.039 (3) | 0.037 (5) |
C12 | 0.131 (5) | 0.085 (4) | 0.117 (4) | −0.022 (4) | 0.029 (4) | 0.017 (3) |
Geometric parameters (Å, º) top
P1—O3 | 1.4917 (16) | C7—C9 | 1.521 (5) |
P1—O4 | 1.543 (2) | C7—C8 | 1.531 (6) |
P1—O2 | 1.545 (2) | C7—H6 | 0.9800 |
P1—O1 | 1.5668 (18) | C8—H7 | 0.9600 |
O1—C1 | 1.427 (3) | C8—H8 | 0.9600 |
O2—H1 | 0.8200 | C8—H9 | 0.9600 |
O4—H2 | 0.8200 | C9—H10 | 0.9600 |
C1—C6 | 1.392 (4) | C9—H11 | 0.9600 |
C1—C2 | 1.399 (4) | C9—H12 | 0.9600 |
C2—C3 | 1.395 (5) | C10—C12 | 1.505 (8) |
C2—C10 | 1.513 (5) | C10—C11 | 1.534 (7) |
C3—C4 | 1.365 (6) | C10—H13 | 0.9800 |
C3—H3 | 0.9300 | C11—H14 | 0.9600 |
C4—C5 | 1.371 (6) | C11—H15 | 0.9600 |
C4—H4 | 0.9300 | C11—H16 | 0.9600 |
C5—C6 | 1.391 (5) | C12—H17 | 0.9600 |
C5—H5 | 0.9300 | C12—H18 | 0.9600 |
C6—C7 | 1.514 (5) | C12—H19 | 0.9600 |
| | | |
O3—P1—O4 | 112.98 (12) | C8—C7—H6 | 107.3 |
O3—P1—O2 | 113.17 (11) | C7—C8—H7 | 109.5 |
O4—P1—O2 | 106.75 (12) | C7—C8—H8 | 109.5 |
O3—P1—O1 | 113.60 (10) | H7—C8—H8 | 109.5 |
O4—P1—O1 | 106.74 (11) | C7—C8—H9 | 109.5 |
O2—P1—O1 | 102.83 (11) | H7—C8—H9 | 109.5 |
C1—O1—P1 | 123.23 (16) | H8—C8—H9 | 109.5 |
P1—O2—H1 | 109.5 | C7—C9—H10 | 109.5 |
P1—O4—H2 | 109.5 | C7—C9—H11 | 109.5 |
C6—C1—C2 | 124.6 (3) | H10—C9—H11 | 109.5 |
C6—C1—O1 | 118.2 (3) | C7—C9—H12 | 109.5 |
C2—C1—O1 | 117.0 (2) | H10—C9—H12 | 109.5 |
C3—C2—C1 | 115.4 (3) | H11—C9—H12 | 109.5 |
C3—C2—C10 | 121.5 (3) | C12—C10—C2 | 112.7 (4) |
C1—C2—C10 | 123.0 (3) | C12—C10—C11 | 112.4 (5) |
C4—C3—C2 | 122.1 (4) | C2—C10—C11 | 109.4 (4) |
C4—C3—H3 | 119.0 | C12—C10—H13 | 107.3 |
C2—C3—H3 | 119.0 | C2—C10—H13 | 107.3 |
C3—C4—C5 | 120.1 (3) | C11—C10—H13 | 107.3 |
C3—C4—H4 | 119.9 | C10—C11—H14 | 109.5 |
C5—C4—H4 | 119.9 | C10—C11—H15 | 109.5 |
C4—C5—C6 | 121.9 (3) | H14—C11—H15 | 109.5 |
C4—C5—H5 | 119.1 | C10—C11—H16 | 109.5 |
C6—C5—H5 | 119.1 | H14—C11—H16 | 109.5 |
C5—C6—C1 | 115.7 (3) | H15—C11—H16 | 109.5 |
C5—C6—C7 | 121.4 (3) | C10—C12—H17 | 109.5 |
C1—C6—C7 | 122.8 (3) | C10—C12—H18 | 109.5 |
C6—C7—C9 | 112.9 (4) | H17—C12—H18 | 109.5 |
C6—C7—C8 | 110.7 (3) | C10—C12—H19 | 109.5 |
C9—C7—C8 | 111.0 (4) | H17—C12—H19 | 109.5 |
C6—C7—H6 | 107.3 | H18—C12—H19 | 109.5 |
C9—C7—H6 | 107.3 | | |
| | | |
O3—P1—O1—C1 | −57.8 (2) | C4—C5—C6—C7 | 174.3 (4) |
O4—P1—O1—C1 | 67.4 (2) | C2—C1—C6—C5 | 4.4 (5) |
O2—P1—O1—C1 | 179.56 (19) | O1—C1—C6—C5 | 179.4 (3) |
P1—O1—C1—C6 | 87.5 (3) | C2—C1—C6—C7 | −171.9 (3) |
P1—O1—C1—C2 | −97.2 (3) | O1—C1—C6—C7 | 3.0 (4) |
C6—C1—C2—C3 | −3.0 (5) | C5—C6—C7—C9 | 54.5 (4) |
O1—C1—C2—C3 | −178.0 (3) | C1—C6—C7—C9 | −129.4 (3) |
C6—C1—C2—C10 | 173.9 (3) | C5—C6—C7—C8 | −70.6 (4) |
O1—C1—C2—C10 | −1.1 (5) | C1—C6—C7—C8 | 105.5 (4) |
C1—C2—C3—C4 | −0.9 (6) | C3—C2—C10—C12 | −54.1 (5) |
C10—C2—C3—C4 | −177.9 (4) | C1—C2—C10—C12 | 129.1 (4) |
C2—C3—C4—C5 | 3.1 (7) | C3—C2—C10—C11 | 71.8 (5) |
C3—C4—C5—C6 | −1.5 (7) | C1—C2—C10—C11 | −105.0 (5) |
C4—C5—C6—C1 | −2.1 (5) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H1···O3i | 0.82 | 1.81 | 2.624 (3) | 175 |
O4—H2···O3ii | 0.82 | 1.80 | 2.611 (3) | 169 |
Symmetry codes: (i) −x, y−1/2, −z; (ii) −x, y+1/2, −z. |
Experimental details
Crystal data |
Chemical formula | C12H19O4P |
Mr | 258.24 |
Crystal system, space group | Monoclinic, P21 |
Temperature (K) | 296 |
a, b, c (Å) | 10.0298 (15), 6.3718 (15), 11.2238 (14) |
β (°) | 100.685 (11) |
V (Å3) | 704.9 (2) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.20 |
Crystal size (mm) | 0.30 × 0.20 × 0.20 |
|
Data collection |
Diffractometer | Rigaku AFC-5R diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2329, 2219, 1627 |
Rint | 0.014 |
(sin θ/λ)max (Å−1) | 0.704 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.035, 0.106, 1.02 |
No. of reflections | 2219 |
No. of parameters | 156 |
No. of restraints | 1 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.24, −0.25 |
Absolute structure | Flack (1983) |
Absolute structure parameter | 0.11 (15) |
Selected geometric parameters (Å, º) topP1—O3 | 1.4917 (16) | P1—O2 | 1.545 (2) |
P1—O4 | 1.543 (2) | P1—O1 | 1.5668 (18) |
| | | |
O3—P1—O4 | 112.98 (12) | O4—P1—O1 | 106.74 (11) |
O3—P1—O2 | 113.17 (11) | O2—P1—O1 | 102.83 (11) |
O4—P1—O2 | 106.75 (12) | C1—O1—P1 | 123.23 (16) |
O3—P1—O1 | 113.60 (10) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H1···O3i | 0.82 | 1.81 | 2.624 (3) | 175.1 |
O4—H2···O3ii | 0.82 | 1.80 | 2.611 (3) | 168.6 |
Symmetry codes: (i) −x, y−1/2, −z; (ii) −x, y+1/2, −z. |
Phosphate groups are attractive molecular building blocks in crystal engineering to form hydrogen-bond networks (Krishnamohan Sharma & Clearfield, 2000). Our attention has been focused on the control of crystal structures through the P—OH···O═P hydrogen bond using a bulky phosphate compound. The title compound (Kosolapoff et al., 1968), (I), has a P1—O1—C1—C2 torsion angle of -97.2 (2)°. The O3 and O4 atoms form P—OH···O═P hydrogen bonds with O2, which is an acceptor of bifurcated hydrogen bonds formed by the two neighbouring ligands. Thus, the title compound forms a one-dimensional chain.
Most of the reported hydrogen-bond networks in the dihydrogen phosphate or phosphonate state are characterized by single P—OH···O═P hydrogen bonds (Weakly, 1976; Calvo & Berg, 1984; Tkachev et al., 1986). Only a few double P—OH···O═P hydrogen-bond structures have been reported: o-hydroxyphenoxymethylphosphonic acid (Choi et al., 1994) and N-phenyl-1-methylamido-benzylphosphonic acid (Ignat'eva et al., 1989). The bulky isopropyl groups interrupt the formation of inter-column hydrogen bonds. Both of the P—OH atoms interact with intra-column phosphate O atoms. Thus, a one-dimensional chain structure with double P—OH···O═P hydrogen bonds is induced by the bulky isopropyl groups.