Crystal structure of diethyl [(4-nitro-phenyl-amino)(2-hy-droxy-phen-yl)meth-yl]phospho-nate methanol monosolvate.

In the title compound, C17H21N2O6P·CH3OH, the planes of the 4-nitro-aniline and 2-hy-droxy-phenyl groups form a dihedral angle of 84.04 (8)°. The P atom exhibits tetra-hedral geometry involving two O-ethyl groups, a Cα atom and a double-bonded O atom. In the crystal, O-H⋯O, N-H⋯O and C-H⋯O hydrogen bonds link the α-amino-phospho-nic acid and methanol mol-ecules into chains that propagate parallel to the a axis.

Related literature

For background to the synthesis and properties of α-amino­phospho­nic acids, see: Allen et al. (1978 ▶); Arizpe et al. (2011 ▶); Cherkasov & Galkin (1998 ▶); Sieńczyk & Oleksyszyn (2009 ▶). For structures of related compounds, see: Li et al. (2008 ▶); Wang et al. (2012 ▶).

Experimental

Crystal data

C17H21N2O6P·CH4O

M = 412.37

Triclinic,

a = 9.401 (6) Å

b = 10.061 (6) Å

c = 11.963 (7) Å

α = 101.328 (10)°

β = 94.183 (10)°

γ = 104.549 (9)°

V = 1065.0 (12) Å3

Z = 2

Mo Kα radiation

μ = 0.17 mm−1

T = 296 K

0.40 × 0.34 × 0.30 mm

Data collection

Bruker SMART 1K CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 2000 ▶) T min = 0.935, T max = 0.951

14569 measured reflections

5230 independent reflections

2934 reflections with I > 2σ(I)

R int = 0.051

Refinement

R[F 2 > 2σ(F 2)] = 0.054

wR(F 2) = 0.138

S = 1.01

5230 reflections

262 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.31 e Å−3

Δρmin = −0.27 e Å−3

Data collection: SMART (Bruker, 2000 ▶); cell refinement: SAINT (Bruker, 2000 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL/PC (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S1600536814018649/pk2529sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814018649/pk2529Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S1600536814018649/pk2529Isup3.cml

Click here for additional data file.

. DOI: 10.1107/S1600536814018649/pk2529fig1.tif

A view of the structure of the title compound with displacement ellipsoids drawn at the 30% probability level.

Click here for additional data file.

. DOI: 10.1107/S1600536814018649/pk2529fig2.tif

Crystal packing of the title compound, drawn so as to highlight the hydrogen-bonding inter­actions between mol­ecules.

CCDC reference: 1019639

Additional supporting information: crystallographic information; 3D view; checkCIF report

C17H21N2O6P·CH4O	Z = 2
Mr = 412.37	F(000) = 436
Triclinic, P1	Dx = 1.286 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.401 (6) Å	Cell parameters from 1930 reflections
b = 10.061 (6) Å	θ = 1.8–28.3°
c = 11.963 (7) Å	µ = 0.17 mm−1
α = 101.328 (10)°	T = 296 K
β = 94.183 (10)°	Block, yellow
γ = 104.549 (9)°	0.4 × 0.34 × 0.3 mm
V = 1065.0 (12) Å3

Bruker SMART 1K CCD area-detector diffractometer	5230 independent reflections
Radiation source: fine-focus sealed tube	2934 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.051
ω scans	θmax = 28.2°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 2000)	h = −12→12
Tmin = 0.935, Tmax = 0.951	k = −13→13
14569 measured reflections	l = −15→15

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)] = 0.054	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.138	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	w = 1/[σ2(Fo2) + (0.0575P)2 + 0.0659P] where P = (Fo2 + 2Fc2)/3
5230 reflections	(Δ/σ)max < 0.001
262 parameters	Δρmax = 0.31 e Å−3
0 restraints	Δρmin = −0.27 e Å−3

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
C1	0.4255 (3)	0.3224 (2)	0.17400 (19)	0.0408 (5)
C2	0.4364 (3)	0.2362 (3)	0.2493 (2)	0.0538 (7)
H2	0.5292	0.2347	0.2808	0.065*
C3	0.3111 (4)	0.1532 (3)	0.2778 (2)	0.0655 (8)
H3	0.3192	0.0962	0.3291	0.079*
C4	0.1720 (4)	0.1538 (3)	0.2302 (3)	0.0692 (8)
H4	0.0868	0.0979	0.2497	0.083*
C5	0.1618 (3)	0.2385 (3)	0.1535 (2)	0.0538 (7)
H5	0.0688	0.2379	0.1207	0.065*
C6	0.2871 (3)	0.3241 (2)	0.12431 (18)	0.0378 (5)
C7	0.2760 (2)	0.4232 (2)	0.04485 (17)	0.0348 (5)
H7	0.3749	0.4597	0.0239	0.042*
C8	0.2056 (2)	0.2631 (2)	−0.14895 (19)	0.0372 (5)
C9	0.1083 (3)	0.2150 (2)	−0.2517 (2)	0.0467 (6)
H9	0.0257	0.2492	−0.2595	0.056*
C10	0.1327 (3)	0.1185 (3)	−0.3410 (2)	0.0526 (7)
H10	0.0681	0.0884	−0.4092	0.063*
C11	0.2548 (3)	0.0660 (2)	−0.3287 (2)	0.0449 (6)
C12	0.3527 (3)	0.1124 (3)	−0.2294 (2)	0.0472 (6)
H12	0.4347	0.0772	−0.2227	0.057*
C13	0.3303 (3)	0.2105 (2)	−0.1397 (2)	0.0428 (6)
H13	0.3976	0.2422	−0.0729	0.051*
C14	0.3182 (4)	0.6256 (4)	0.3468 (2)	0.0941 (12)
H14A	0.2782	0.7004	0.3841	0.113*
H14B	0.2476	0.5363	0.3455	0.113*
C15	0.4561 (4)	0.6334 (4)	0.4116 (3)	0.0989 (12)
H15A	0.5020	0.5674	0.3700	0.148*
H15B	0.4377	0.6111	0.4846	0.148*
H15C	0.5206	0.7269	0.4237	0.148*
C16	0.2262 (3)	0.8152 (3)	0.0724 (2)	0.0600 (7)
H16A	0.2731	0.8615	0.1500	0.072*
H16B	0.1208	0.8069	0.0696	0.072*
C17	0.2894 (4)	0.8987 (3)	−0.0089 (3)	0.0853 (10)
H17A	0.3945	0.9110	−0.0026	0.128*
H17B	0.2697	0.9891	0.0087	0.128*
H17C	0.2453	0.8505	−0.0858	0.128*
C18	0.8676 (5)	0.4263 (6)	0.3596 (3)	0.154 (2)
H18A	0.9379	0.3743	0.3716	0.232*
H18B	0.7854	0.3987	0.4010	0.232*
H18C	0.9143	0.5253	0.3868	0.232*
N1	0.1748 (2)	0.3567 (2)	−0.06050 (16)	0.0415 (5)
N2	0.2802 (3)	−0.0373 (3)	−0.4225 (2)	0.0650 (7)
O1	0.54719 (18)	0.4078 (2)	0.14493 (15)	0.0566 (5)
H1	0.6220	0.4018	0.1811	0.085*
O2	0.33759 (18)	0.63846 (17)	0.22920 (13)	0.0518 (4)
O3	0.25022 (19)	0.67641 (16)	0.04156 (14)	0.0525 (5)
O4	0.06458 (17)	0.53339 (17)	0.14848 (13)	0.0478 (4)
O5	0.1927 (3)	−0.0771 (3)	−0.51111 (19)	0.1029 (9)
O6	0.3885 (3)	−0.0818 (2)	−0.41134 (17)	0.0919 (8)
O7	0.8177 (2)	0.3987 (3)	0.24407 (17)	0.0785 (6)
H7A	0.8843	0.4359	0.2104	0.118*
P1	0.21847 (7)	0.57045 (6)	0.12230 (5)	0.03809 (18)
H1A	0.107 (3)	0.391 (2)	−0.077 (2)	0.045 (7)*

	U11	U22	U33	U12	U13	U23
C1	0.0458 (14)	0.0433 (14)	0.0362 (12)	0.0202 (11)	0.0041 (11)	0.0060 (11)
C2	0.0633 (18)	0.0542 (16)	0.0482 (15)	0.0253 (14)	−0.0009 (13)	0.0122 (13)
C3	0.092 (2)	0.0552 (18)	0.0595 (18)	0.0284 (17)	0.0110 (17)	0.0260 (14)
C4	0.073 (2)	0.0569 (18)	0.081 (2)	0.0077 (16)	0.0271 (17)	0.0307 (16)
C5	0.0478 (16)	0.0494 (16)	0.0677 (18)	0.0133 (12)	0.0112 (13)	0.0202 (14)
C6	0.0427 (13)	0.0345 (12)	0.0383 (12)	0.0170 (10)	0.0074 (10)	0.0043 (10)
C7	0.0304 (12)	0.0384 (12)	0.0371 (12)	0.0127 (10)	0.0051 (10)	0.0069 (10)
C8	0.0386 (13)	0.0356 (12)	0.0384 (12)	0.0127 (10)	0.0057 (10)	0.0070 (10)
C9	0.0420 (14)	0.0532 (15)	0.0473 (14)	0.0244 (12)	−0.0002 (11)	0.0041 (12)
C10	0.0521 (16)	0.0589 (16)	0.0433 (14)	0.0201 (13)	−0.0072 (12)	0.0010 (12)
C11	0.0521 (15)	0.0439 (14)	0.0401 (13)	0.0229 (12)	0.0043 (11)	0.0008 (11)
C12	0.0491 (15)	0.0530 (15)	0.0478 (15)	0.0301 (12)	0.0070 (12)	0.0093 (12)
C13	0.0401 (13)	0.0476 (14)	0.0421 (13)	0.0196 (11)	0.0015 (11)	0.0047 (11)
C14	0.077 (2)	0.154 (4)	0.0440 (17)	0.040 (2)	0.0036 (17)	−0.005 (2)
C15	0.131 (3)	0.117 (3)	0.0546 (19)	0.058 (3)	−0.007 (2)	0.008 (2)
C16	0.0649 (18)	0.0428 (15)	0.0774 (19)	0.0221 (14)	0.0101 (15)	0.0153 (14)
C17	0.102 (3)	0.0560 (19)	0.106 (3)	0.0203 (18)	0.030 (2)	0.0333 (19)
C18	0.090 (3)	0.273 (6)	0.081 (3)	−0.008 (3)	−0.006 (2)	0.074 (4)
N1	0.0372 (11)	0.0475 (12)	0.0416 (11)	0.0229 (10)	−0.0020 (9)	0.0017 (9)
N2	0.0834 (18)	0.0676 (16)	0.0481 (14)	0.0422 (14)	−0.0002 (13)	−0.0021 (12)
O1	0.0382 (10)	0.0749 (13)	0.0640 (12)	0.0186 (9)	0.0022 (9)	0.0298 (10)
O2	0.0484 (10)	0.0560 (11)	0.0440 (10)	0.0116 (8)	−0.0047 (8)	0.0020 (8)
O3	0.0708 (12)	0.0400 (9)	0.0556 (11)	0.0256 (9)	0.0171 (9)	0.0143 (8)
O4	0.0395 (9)	0.0560 (10)	0.0531 (10)	0.0234 (8)	0.0092 (8)	0.0094 (8)
O5	0.1169 (19)	0.120 (2)	0.0634 (14)	0.0713 (16)	−0.0256 (14)	−0.0358 (13)
O6	0.1136 (18)	0.1124 (18)	0.0664 (14)	0.0860 (16)	−0.0014 (13)	−0.0079 (12)
O7	0.0485 (12)	0.1205 (19)	0.0717 (14)	0.0160 (12)	0.0039 (10)	0.0441 (13)
P1	0.0382 (3)	0.0382 (3)	0.0402 (3)	0.0168 (3)	0.0047 (3)	0.0059 (3)

C1—O1	1.360 (3)	C14—C15	1.438 (4)
C1—C2	1.382 (3)	C14—O2	1.458 (3)
C1—C6	1.396 (3)	C14—H14A	0.9700
C2—C3	1.370 (4)	C14—H14B	0.9700
C2—H2	0.9300	C15—H15A	0.9600
C3—C4	1.390 (4)	C15—H15B	0.9600
C3—H3	0.9300	C15—H15C	0.9600
C4—C5	1.383 (4)	C16—O3	1.451 (3)
C4—H4	0.9300	C16—C17	1.469 (4)
C5—C6	1.386 (3)	C16—H16A	0.9700
C5—H5	0.9300	C16—H16B	0.9700
C6—C7	1.522 (3)	C17—H17A	0.9600
C7—N1	1.454 (3)	C17—H17B	0.9600
C7—P1	1.812 (2)	C17—H17C	0.9600
C7—H7	0.9800	C18—O7	1.377 (4)
C8—N1	1.371 (3)	C18—H18A	0.9600
C8—C9	1.401 (3)	C18—H18B	0.9600
C8—C13	1.407 (3)	C18—H18C	0.9600
C9—C10	1.371 (3)	N1—H1A	0.82 (2)
C9—H9	0.9300	N2—O6	1.219 (3)
C10—C11	1.389 (3)	N2—O5	1.225 (3)
C10—H10	0.9300	O1—H1	0.8200
C11—C12	1.372 (3)	O2—P1	1.5557 (18)
C11—N2	1.450 (3)	O3—P1	1.5638 (18)
C12—C13	1.376 (3)	O4—P1	1.4734 (18)
C12—H12	0.9300	O7—H7A	0.8200
C13—H13	0.9300
O1—C1—C2	122.1 (2)	O2—C14—H14A	109.3
O1—C1—C6	117.4 (2)	C15—C14—H14B	109.3
C2—C1—C6	120.6 (2)	O2—C14—H14B	109.3
C3—C2—C1	120.4 (3)	H14A—C14—H14B	108.0
C3—C2—H2	119.8	C14—C15—H15A	109.5
C1—C2—H2	119.8	C14—C15—H15B	109.5
C2—C3—C4	120.2 (3)	H15A—C15—H15B	109.5
C2—C3—H3	119.9	C14—C15—H15C	109.5
C4—C3—H3	119.9	H15A—C15—H15C	109.5
C5—C4—C3	119.2 (3)	H15B—C15—H15C	109.5
C5—C4—H4	120.4	O3—C16—C17	109.0 (2)
C3—C4—H4	120.4	O3—C16—H16A	109.9
C4—C5—C6	121.5 (3)	C17—C16—H16A	109.9
C4—C5—H5	119.3	O3—C16—H16B	109.9
C6—C5—H5	119.3	C17—C16—H16B	109.9
C5—C6—C1	118.2 (2)	H16A—C16—H16B	108.3
C5—C6—C7	121.6 (2)	C16—C17—H17A	109.5
C1—C6—C7	120.2 (2)	C16—C17—H17B	109.5
N1—C7—C6	113.91 (19)	H17A—C17—H17B	109.5
N1—C7—P1	109.45 (15)	C16—C17—H17C	109.5
C6—C7—P1	108.85 (14)	H17A—C17—H17C	109.5
N1—C7—H7	108.2	H17B—C17—H17C	109.5
C6—C7—H7	108.2	O7—C18—H18A	109.5
P1—C7—H7	108.2	O7—C18—H18B	109.5
N1—C8—C9	119.2 (2)	H18A—C18—H18B	109.5
N1—C8—C13	122.4 (2)	O7—C18—H18C	109.5
C9—C8—C13	118.4 (2)	H18A—C18—H18C	109.5
C10—C9—C8	121.1 (2)	H18B—C18—H18C	109.5
C10—C9—H9	119.5	C8—N1—C7	123.21 (19)
C8—C9—H9	119.5	C8—N1—H1A	115.2 (17)
C9—C10—C11	119.4 (2)	C7—N1—H1A	119.4 (17)
C9—C10—H10	120.3	O6—N2—O5	121.8 (2)
C11—C10—H10	120.3	O6—N2—C11	119.1 (2)
C12—C11—C10	120.7 (2)	O5—N2—C11	119.1 (2)
C12—C11—N2	119.7 (2)	C1—O1—H1	109.5
C10—C11—N2	119.6 (2)	C14—O2—P1	125.58 (18)
C11—C12—C13	120.4 (2)	C16—O3—P1	121.48 (16)
C11—C12—H12	119.8	C18—O7—H7A	109.5
C13—C12—H12	119.8	O4—P1—O2	114.76 (10)
C12—C13—C8	120.0 (2)	O4—P1—O3	114.66 (10)
C12—C13—H13	120.0	O2—P1—O3	104.51 (10)
C8—C13—H13	120.0	O4—P1—C7	114.21 (10)
C15—C14—O2	111.4 (3)	O2—P1—C7	105.37 (10)
C15—C14—H14A	109.3	O3—P1—C7	101.94 (10)
O1—C1—C2—C3	179.0 (2)	C9—C8—C13—C12	−1.3 (3)
C6—C1—C2—C3	−1.2 (4)	C9—C8—N1—C7	−173.7 (2)
C1—C2—C3—C4	0.7 (4)	C13—C8—N1—C7	7.8 (3)
C2—C3—C4—C5	0.4 (4)	C6—C7—N1—C8	−72.5 (3)
C3—C4—C5—C6	−0.9 (4)	P1—C7—N1—C8	165.39 (18)
C4—C5—C6—C1	0.4 (4)	C12—C11—N2—O6	0.2 (4)
C4—C5—C6—C7	−176.7 (2)	C10—C11—N2—O6	179.3 (3)
O1—C1—C6—C5	−179.6 (2)	C12—C11—N2—O5	−179.4 (3)
C2—C1—C6—C5	0.6 (3)	C10—C11—N2—O5	−0.3 (4)
O1—C1—C6—C7	−2.4 (3)	C15—C14—O2—P1	150.2 (2)
C2—C1—C6—C7	177.8 (2)	C17—C16—O3—P1	170.2 (2)
C5—C6—C7—N1	−49.0 (3)	C14—O2—P1—O4	21.6 (3)
C1—C6—C7—N1	133.9 (2)	C14—O2—P1—O3	148.0 (2)
C5—C6—C7—P1	73.4 (2)	C14—O2—P1—C7	−104.9 (2)
C1—C6—C7—P1	−103.7 (2)	C16—O3—P1—O4	58.8 (2)
N1—C8—C9—C10	−178.1 (2)	C16—O3—P1—O2	−67.7 (2)
C13—C8—C9—C10	0.5 (4)	C16—O3—P1—C7	−177.30 (19)
C8—C9—C10—C11	0.9 (4)	N1—C7—P1—O4	56.04 (18)
C9—C10—C11—C12	−1.6 (4)	C6—C7—P1—O4	−69.04 (17)
C9—C10—C11—N2	179.3 (2)	N1—C7—P1—O2	−177.09 (14)
C10—C11—C12—C13	0.8 (4)	C6—C7—P1—O2	57.82 (17)
N2—C11—C12—C13	179.9 (2)	N1—C7—P1—O3	−68.20 (17)
C11—C12—C13—C8	0.6 (4)	C6—C7—P1—O3	166.71 (15)
N1—C8—C13—C12	177.3 (2)

D—H···A	D—H	H···A	D···A	D—H···A
O7—H7A···O4i	0.82	2.00	2.819 (3)	172
O1—H1···O7	0.82	1.95	2.757 (3)	170
C10—H10···O5ii	0.93	2.53	3.308 (4)	141
N1—H1A···O4iii	0.82 (2)	2.14 (2)	2.959 (3)	171 (2)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O7—H7A⋯O4i	0.82	2.00	2.819 (3)	172
O1—H1⋯O7	0.82	1.95	2.757 (3)	170
C10—H10⋯O5ii	0.93	2.53	3.308 (4)	141
N1—H1A⋯O4iii	0.82 (2)	2.14 (2)	2.959 (3)	171 (2)

Symmetry codes: (i) ; (ii) ; (iii) .