Bis(propan-2-yl) [(2S,3S)-2-hydr­oxy-3-nitro­butan-2-yl]phospho­nate

Mandal, T.; Samanta, S.; Broker, G.A.; Zhao, C.-G.; Tiekink, E.R.T.

doi:10.1107/S1600536809052428

organic compounds

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ISSN: 2056-9890

Volume 66| Part 1| January 2010| Page o98

doi:10.1107/S1600536809052428

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Bis(propan-2-yl) [(2S,3S)-2-hydroxy-3-nitrobutan-2-yl]phosphonate

Tanmay Mandal,^a Sampak Samanta,^a Grant A. Broker,^a Cong-Gui Zhao ^a ‡ and Edward R. T. Tiekink ^b ^*

^aDepartment of Chemistry, University of Texas at San Antonio, One UTSA Circle, San Antonio, Texas 78249-0698, USA, and ^bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: edward.tiekink@gmail.com

(Received 4 December 2009; accepted 6 December 2009; online 12 December 2009)

In the title compound, C₁₀H₂₂NO₆P, a staggered conformation is found when the molecule is viewed down the central P—C bond, with the oxo and hydroxy groups gauche to each other. The crystal structure features supramolecular chains of helical topology propagating along the b axis, mediated by O—H⋯O hydrogen bonds.

Related literature

For background to the enantioselective nitroaldol reaction of α-ketophosphonates and nitromethane and for the synthesis, see: Mandal et al. (2007 ).

Experimental

Crystal data

C₁₀H₂₂NO₆P
M_r = 283.26
Orthorhombic, P 2₁ 2₁ 2₁
a = 7.8620 (16) Å
b = 11.369 (2) Å
c = 16.920 (3) Å
V = 1512.4 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.20 mm⁻¹
T = 173 K
0.32 × 0.10 × 0.05 mm

Data collection

Rigaku AFC12/SATURN724 diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.884, T_max = 1
13441 measured reflections
3072 independent reflections
3020 reflections with I > 2σ(I)
R_int = 0.089
Standard reflections: 0

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.105
S = 1.07
3072 reflections
166 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.19 e Å⁻³
Δρ_min = −0.25 e Å⁻³
Absolute structure: Flack (1983 ), 1272 Friedel pairs
Flack parameter: 0.05 (11)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H4o⋯O1ⁱ	0.84	1.90	2.7289 (19)	172
Symmetry code: (i) $[-x+1, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Data collection: CrystalClear (Rigaku/MSC, 2005 ); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2006 ); software used to prepare material for publication: publCIF (Westrip, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809052428/hb5269sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809052428/hb5269Isup2.hkl

checkCIF report

Comment top

The title compound, (I), was investigated as a part of previous studies on the enantioselective nitroaldol reaction of α-ketophosphonates and nitromethane for the synthesis of optically active α-hydroxy-β-nitrophosphonates (Mandal et al., 2007). The crystal structure analysis of (I), Fig. 1, shows a staggered conformation when the molecule is viewed down the P–C7 axis in which the oxo and hydroxy groups are gauche to each other. The presence of O–H···O hydrogen bonding formed between the hydroxy-O4—H and O═P atoms leads to the formation of supramolecular chains along the b axis, Fig. 2 and Table 1.

Related literature top

For background to the enantioselective nitroaldol reaction of α-ketophosphonates and nitromethane and for the synthesis, see: Mandal et al. (2007).

Experimental top

The title compound was prepared as described in the literature (Mandal et al., 2007).

Computing details top

Data collection: CrystalClear (Rigaku/MSC, 2005); cell refinement: CrystalClear (Rigaku/MSC, 2005); data reduction: CrystalClear (Rigaku/MSC, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2009).

Figures top

	Fig. 1. Molecular structure of (I), showing displacement ellipsoids at the 35% probability level.
	Fig. 2. Supramolecular chain along the b axis in (I) mediated by O–H···O (orange dashed lines) hydrogen bonding. Colour scheme: P, olive; O, red; N, blue; C, grey; and H, green.

Bis(propan-2-yl) [(2S,3S)-2-hydroxy-3-nitrobutan-2-yl]phosphonate top

Crystal data top

C₁₀H₂₂NO₆P	F(000) = 608
M_r = 283.26	D_x = 1.244 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 2308 reflections
a = 7.8620 (16) Å	θ = 4.0–30.1°
b = 11.369 (2) Å	µ = 0.20 mm⁻¹
c = 16.920 (3) Å	T = 173 K
V = 1512.4 (5) Å³	Block, pale-yellow
Z = 4	0.32 × 0.10 × 0.05 mm

Data collection top

Rigaku AFC12K/SATURN724 diffractometer	3072 independent reflections
Radiation source: fine-focus sealed tube	3020 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.089
ω scans	θ_max = 26.5°, θ_min = 4.0°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −9→8
T_min = 0.884, T_max = 1	k = −13→14
13441 measured reflections	l = −21→20

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)] = 0.040	H-atom parameters constrained
wR(F²) = 0.105	w = 1/[σ²(F_o²) + (0.0497P)² + 0.2822P] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max = 0.001
3072 reflections	Δρ_max = 0.19 e Å⁻³
166 parameters	Δρ_min = −0.25 e Å⁻³
1 restraint	Absolute structure: Flack (1983), 1272 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.05 (11)

Crystal data top

C₁₀H₂₂NO₆P	V = 1512.4 (5) Å³
M_r = 283.26	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 7.8620 (16) Å	µ = 0.20 mm⁻¹
b = 11.369 (2) Å	T = 173 K
c = 16.920 (3) Å	0.32 × 0.10 × 0.05 mm

Data collection top

Rigaku AFC12K/SATURN724 diffractometer	3072 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	3020 reflections with I > 2σ(I)
T_min = 0.884, T_max = 1	R_int = 0.089
13441 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	H-atom parameters constrained
wR(F²) = 0.105	Δρ_max = 0.19 e Å⁻³
S = 1.07	Δρ_min = −0.25 e Å⁻³
3072 reflections	Absolute structure: Flack (1983), 1272 Friedel pairs
166 parameters	Absolute structure parameter: 0.05 (11)
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	U_iso*/U_eq
P1	0.63065 (6)	0.29509 (4)	0.74005 (3)	0.03236 (14)
O1	0.51586 (18)	0.19464 (11)	0.75316 (9)	0.0416 (3)
O2	0.80539 (18)	0.26553 (13)	0.70112 (9)	0.0415 (3)
O3	0.67933 (17)	0.36408 (13)	0.81677 (8)	0.0383 (3)
O4	0.41385 (17)	0.46364 (12)	0.71762 (9)	0.0400 (3)
H4O	0.4448	0.5337	0.7241	0.060*
O5	0.3878 (4)	0.49342 (19)	0.51776 (13)	0.0848 (7)
O6	0.1751 (3)	0.4227 (2)	0.58457 (14)	0.0861 (7)
N1	0.3262 (3)	0.4256 (2)	0.56573 (14)	0.0608 (6)
C1	0.9313 (3)	0.18894 (18)	0.74033 (13)	0.0438 (5)
H1	0.8736	0.1412	0.7821	0.053*
C2	0.9985 (4)	0.1089 (3)	0.67718 (17)	0.0706 (8)
H2A	0.9051	0.0617	0.6556	0.106*
H2B	1.0849	0.0567	0.6998	0.106*
H2C	1.0495	0.1560	0.6348	0.106*
C3	1.0653 (3)	0.2668 (2)	0.7782 (2)	0.0656 (8)
H3A	1.0121	0.3162	0.8187	0.098*
H3B	1.1173	0.3168	0.7377	0.098*
H3C	1.1530	0.2175	0.8026	0.098*
C4	0.5800 (3)	0.3614 (2)	0.89018 (13)	0.0551 (6)
H4	0.4659	0.3254	0.8803	0.066*
C5	0.5601 (6)	0.4848 (3)	0.91703 (18)	0.0879 (11)
H5A	0.4970	0.5295	0.8771	0.132*
H5B	0.6726	0.5202	0.9246	0.132*
H5C	0.4976	0.4862	0.9671	0.132*
C6	0.6764 (7)	0.2898 (3)	0.94900 (18)	0.1056 (15)
H6A	0.6874	0.2089	0.9296	0.158*
H6B	0.6152	0.2896	0.9995	0.158*
H6C	0.7897	0.3238	0.9565	0.158*
C7	0.5409 (2)	0.40550 (16)	0.67209 (11)	0.0336 (4)
C8	0.4436 (3)	0.33911 (18)	0.60636 (12)	0.0419 (5)
H8	0.3722	0.2770	0.6318	0.050*
C9	0.5556 (4)	0.2804 (2)	0.54440 (13)	0.0558 (6)
H9A	0.4838	0.2406	0.5053	0.084*
H9B	0.6299	0.2227	0.5700	0.084*
H9C	0.6251	0.3401	0.5179	0.084*
C10	0.6767 (3)	0.49079 (18)	0.64308 (14)	0.0430 (5)
H10A	0.7312	0.5287	0.6885	0.065*
H10B	0.6239	0.5509	0.6095	0.065*
H10C	0.7623	0.4477	0.6125	0.065*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
P1	0.0303 (2)	0.0284 (2)	0.0384 (2)	0.00159 (18)	0.00078 (17)	0.00062 (19)
O1	0.0432 (7)	0.0284 (6)	0.0532 (8)	−0.0023 (5)	−0.0002 (6)	0.0044 (7)
O2	0.0357 (7)	0.0454 (8)	0.0435 (7)	0.0140 (6)	0.0051 (6)	0.0031 (6)
O3	0.0365 (7)	0.0426 (7)	0.0359 (7)	−0.0048 (6)	0.0024 (5)	−0.0017 (6)
O4	0.0342 (7)	0.0316 (7)	0.0541 (8)	0.0031 (6)	0.0021 (6)	−0.0080 (6)
O5	0.1205 (19)	0.0631 (12)	0.0708 (13)	0.0063 (14)	−0.0288 (14)	0.0171 (10)
O6	0.0593 (13)	0.1078 (17)	0.0912 (16)	0.0212 (13)	−0.0342 (12)	−0.0093 (14)
N1	0.0736 (16)	0.0513 (12)	0.0576 (12)	0.0103 (11)	−0.0261 (11)	−0.0073 (11)
C1	0.0408 (10)	0.0399 (11)	0.0507 (11)	0.0124 (8)	−0.0022 (9)	0.0007 (10)
C2	0.0768 (19)	0.0698 (17)	0.0650 (16)	0.0410 (16)	−0.0121 (14)	−0.0150 (14)
C3	0.0423 (12)	0.0584 (15)	0.096 (2)	0.0113 (11)	−0.0130 (13)	−0.0103 (14)
C4	0.0576 (14)	0.0725 (16)	0.0351 (10)	−0.0157 (12)	0.0104 (9)	−0.0010 (10)
C5	0.128 (3)	0.085 (2)	0.0507 (15)	0.038 (2)	0.0216 (17)	−0.0070 (15)
C6	0.189 (5)	0.081 (2)	0.0471 (15)	0.029 (3)	0.004 (2)	0.0180 (16)
C7	0.0344 (9)	0.0283 (8)	0.0383 (9)	0.0022 (7)	−0.0010 (8)	−0.0021 (8)
C8	0.0498 (12)	0.0332 (9)	0.0428 (10)	0.0031 (9)	−0.0088 (9)	−0.0032 (9)
C9	0.0772 (17)	0.0502 (13)	0.0399 (11)	0.0049 (13)	0.0000 (11)	−0.0097 (10)
C10	0.0451 (11)	0.0334 (10)	0.0506 (12)	−0.0024 (9)	0.0042 (9)	0.0032 (9)

Geometric parameters (Å, º) top

P1—O1	1.4723 (14)	C4—C5	1.483 (4)
P1—O2	1.5602 (14)	C4—C6	1.492 (4)
P1—O3	1.5643 (15)	C4—H4	1.0000
P1—C7	1.8428 (19)	C5—H5A	0.9800
O2—C1	1.476 (2)	C5—H5B	0.9800
O3—C4	1.467 (2)	C5—H5C	0.9800
O4—C7	1.424 (2)	C6—H6A	0.9800
O4—H4O	0.8400	C6—H6B	0.9800
O5—N1	1.219 (3)	C6—H6C	0.9800
O6—N1	1.230 (4)	C7—C10	1.524 (3)
N1—C8	1.514 (3)	C7—C8	1.546 (3)
C1—C2	1.500 (3)	C8—C9	1.523 (3)
C1—C3	1.517 (3)	C8—H8	1.0000
C1—H1	1.0000	C9—H9A	0.9800
C2—H2A	0.9800	C9—H9B	0.9800
C2—H2B	0.9800	C9—H9C	0.9800
C2—H2C	0.9800	C10—H10A	0.9800
C3—H3A	0.9800	C10—H10B	0.9800
C3—H3B	0.9800	C10—H10C	0.9800
C3—H3C	0.9800

O1—P1—O2	115.86 (9)	C4—C5—H5A	109.5
O1—P1—O3	114.44 (9)	C4—C5—H5B	109.5
O2—P1—O3	104.06 (8)	H5A—C5—H5B	109.5
O1—P1—C7	112.80 (9)	C4—C5—H5C	109.5
O2—P1—C7	102.75 (8)	H5A—C5—H5C	109.5
O3—P1—C7	105.67 (8)	H5B—C5—H5C	109.5
C1—O2—P1	121.86 (13)	C4—C6—H6A	109.5
C4—O3—P1	124.17 (14)	C4—C6—H6B	109.5
C7—O4—H4O	108.0	H6A—C6—H6B	109.5
O5—N1—O6	124.9 (3)	C4—C6—H6C	109.5
O5—N1—C8	118.1 (2)	H6A—C6—H6C	109.5
O6—N1—C8	117.0 (2)	H6B—C6—H6C	109.5
O2—C1—C2	105.91 (18)	O4—C7—C10	111.74 (15)
O2—C1—C3	108.14 (17)	O4—C7—C8	105.60 (16)
C2—C1—C3	114.2 (2)	C10—C7—C8	115.18 (18)
O2—C1—H1	109.5	O4—C7—P1	104.31 (12)
C2—C1—H1	109.5	C10—C7—P1	111.47 (14)
C3—C1—H1	109.5	C8—C7—P1	107.80 (13)
C1—C2—H2A	109.5	N1—C8—C9	108.94 (19)
C1—C2—H2B	109.5	N1—C8—C7	108.11 (16)
H2A—C2—H2B	109.5	C9—C8—C7	115.0 (2)
C1—C2—H2C	109.5	N1—C8—H8	108.2
H2A—C2—H2C	109.5	C9—C8—H8	108.2
H2B—C2—H2C	109.5	C7—C8—H8	108.2
C1—C3—H3A	109.5	C8—C9—H9A	109.5
C1—C3—H3B	109.5	C8—C9—H9B	109.5
H3A—C3—H3B	109.5	H9A—C9—H9B	109.5
C1—C3—H3C	109.5	C8—C9—H9C	109.5
H3A—C3—H3C	109.5	H9A—C9—H9C	109.5
H3B—C3—H3C	109.5	H9B—C9—H9C	109.5
O3—C4—C5	107.2 (2)	C7—C10—H10A	109.5
O3—C4—C6	107.8 (2)	C7—C10—H10B	109.5
C5—C4—C6	111.4 (3)	H10A—C10—H10B	109.5
O3—C4—H4	110.1	C7—C10—H10C	109.5
C5—C4—H4	110.1	H10A—C10—H10C	109.5
C6—C4—H4	110.1	H10B—C10—H10C	109.5

O1—P1—O2—C1	−63.20 (17)	O3—P1—C7—C10	68.93 (15)
O3—P1—O2—C1	63.34 (17)	O1—P1—C7—C8	−37.99 (17)
C7—P1—O2—C1	173.35 (15)	O2—P1—C7—C8	87.48 (15)
O1—P1—O3—C4	−21.1 (2)	O3—P1—C7—C8	−163.73 (13)
O2—P1—O3—C4	−148.58 (17)	O5—N1—C8—C9	−47.5 (3)
C7—P1—O3—C4	103.58 (19)	O6—N1—C8—C9	133.2 (2)
P1—O2—C1—C2	136.98 (19)	O5—N1—C8—C7	78.1 (3)
P1—O2—C1—C3	−100.2 (2)	O6—N1—C8—C7	−101.1 (3)
P1—O3—C4—C5	−132.8 (2)	O4—C7—C8—N1	51.7 (2)
P1—O3—C4—C6	107.1 (3)	C10—C7—C8—N1	−72.1 (2)
O1—P1—C7—O4	73.94 (14)	P1—C7—C8—N1	162.77 (16)
O2—P1—C7—O4	−160.59 (12)	O4—C7—C8—C9	173.70 (17)
O3—P1—C7—O4	−51.80 (13)	C10—C7—C8—C9	49.9 (2)
O1—P1—C7—C10	−165.33 (14)	P1—C7—C8—C9	−75.2 (2)
O2—P1—C7—C10	−39.85 (16)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4o···O1ⁱ	0.84	1.90	2.7289 (19)	172

Symmetry code: (i) −x+1, y+1/2, −z+3/2.

Experimental details

Crystal data
Chemical formula	C₁₀H₂₂NO₆P
M_r	283.26
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	173
a, b, c (Å)	7.8620 (16), 11.369 (2), 16.920 (3)
V (Å³)	1512.4 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.20
Crystal size (mm)	0.32 × 0.10 × 0.05

Data collection
Diffractometer	Rigaku AFC12K/SATURN724 diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.884, 1
No. of measured, independent and observed [I > 2σ(I)] reflections	13441, 3072, 3020
R_int	0.089
(sin θ/λ)_max (Å⁻¹)	0.628

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.105, 1.07
No. of reflections	3072
No. of parameters	166
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.19, −0.25
Absolute structure	Flack (1983), 1272 Friedel pairs
Absolute structure parameter	0.05 (11)

Computer programs: CrystalClear (Rigaku/MSC, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 2006), publCIF (Westrip, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4o···O1ⁱ	0.84	1.90	2.7289 (19)	172

Symmetry code: (i) −x+1, y+1/2, −z+3/2.

Footnotes

‡Additional correspondence author, e-mail: cong.zhao@utsa.edu.

Acknowledgements

CGZ thanks the Welch Foundation (grant No. AX-1593) and the NIH-MBRS program (S06 GM08194) for support.

References

Brandenburg, K. (2006). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan. Google Scholar
Mandal, T., Samanta, S. & Zhao, C.-G. (2007). Org. Lett. 9, 943–945. Web of Science CrossRef PubMed CAS Google Scholar
Rigaku/MSC (2005). CrystalClear. Rigaku/MSC Inc., The Woodlands, Texas, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Westrip, S. P. (2009). publCIF. In preparation. Google Scholar