Crystal structure of diethyl [(4-chloro-anilino)(4-hy-droxy-phen-yl)meth-yl]phospho-nate N,N-di-methyl-formamide monosolvate.

In the title compound, C17H21ClNO4P·C3H7NO, the dihedral angle formed by the aromatic rings is 83.98 (7)°. In the crystal, O-H⋯O, N-H⋯O and C-H⋯O hydrogen bonds link the mol-ecules into double layers parallel to (011).

Related literature

For background to the synthesis and properties of α-amino­phospho­nic acids, see: Puius et al. (1997 ▶); Hum et al. (2002 ▶); Evindar et al. (2009 ▶); Meyer et al. (2004 ▶); Kachkovskyi & Kolodiazhnyi (2007 ▶); Sieńczyk & Oleksyszyn (2009 ▶). For the structures of related compounds, see: Li et al. (2008 ▶); Wang et al. (2012 ▶).

Experimental

Crystal data

C17H21ClNO4P·C3H7NO

M = 442.86

Triclinic,

a = 7.7230 (3) Å

b = 11.6834 (5) Å

c = 13.4582 (5) Å

α = 69.872 (2)°

β = 88.159 (2)°

γ = 83.841 (2)°

V = 1133.58 (8) Å3

Z = 2

Mo Kα radiation

μ = 0.27 mm−1

T = 296 K

0.40 × 0.20 × 0.15 mm

Data collection

Bruker SMART CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2000 ▶) T min = 0.937, T max = 0.960

17340 measured reflections

5126 independent reflections

3982 reflections with I > 2σ(I)

R int = 0.022

Refinement

R[F 2 > 2σ(F 2)] = 0.057

wR(F 2) = 0.174

S = 1.04

5126 reflections

271 parameters

1 restraint

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.41 e Å−3

Δρmin = −0.41 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/S1600536814016626/rz5129sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814016626/rz5129Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S1600536814016626/rz5129Isup3.cml

Click here for additional data file.

. DOI: 10.1107/S1600536814016626/rz5129fig1.tif

The mol­ecular structure of the title compound with displacement ellipsoids drawn at the 30% probability level. An intra­molecular hydrogen bond is shown as a dashed line.

Click here for additional data file.

. DOI: 10.1107/S1600536814016626/rz5129fig2.tif

Partial crystal packing of the title compound showing the intra- and inter­molecular hydrogen bonding network (dashed lines).

CCDC reference: 1014609

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

C17H21ClNO4P·C3H7NO	Z = 2
Mr = 442.86	F(000) = 468
Triclinic, P1	Dx = 1.297 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.7230 (3) Å	Cell parameters from 9970 reflections
b = 11.6834 (5) Å	θ = 2.7–27.5°
c = 13.4582 (5) Å	µ = 0.27 mm−1
α = 69.872 (2)°	T = 296 K
β = 88.159 (2)°	Block, yellow
γ = 83.841 (2)°	0.40 × 0.20 × 0.15 mm
V = 1133.58 (8) Å3

Bruker SMART CCD area-detector diffractometer	5126 independent reflections
Radiation source: fine-focus sealed tube	3982 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.022
phi and ω scans	θmax = 27.6°, θmin = 3.5°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −10→9
Tmin = 0.937, Tmax = 0.960	k = −15→13
17340 measured reflections	l = −17→17

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)] = 0.057	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.174	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ2(Fo2) + (0.0923P)2 + 0.5091P] where P = (Fo2 + 2Fc2)/3
5126 reflections	(Δ/σ)max = 0.001
271 parameters	Δρmax = 0.41 e Å−3
1 restraint	Δρmin = −0.41 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	0.3710 (3)	0.80977 (18)	0.82727 (15)	0.0377 (4)
C2	0.3340 (3)	0.93464 (19)	0.77767 (17)	0.0432 (5)
H2	0.4242	0.9847	0.7633	0.052*
C3	0.0306 (3)	0.9130 (2)	0.76955 (17)	0.0449 (5)
C4	0.1652 (3)	0.9867 (2)	0.74897 (18)	0.0473 (5)
H4A	0.1425	1.0710	0.7160	0.057*
C5	0.0659 (3)	0.7874 (2)	0.81811 (19)	0.0486 (5)
H5	−0.0241	0.7373	0.8317	0.058*
C6	0.2337 (3)	0.73708 (19)	0.84612 (18)	0.0456 (5)
H6	0.2561	0.6527	0.8784	0.055*
C7	0.5553 (3)	0.75408 (18)	0.86193 (15)	0.0394 (4)
H7	0.6331	0.8180	0.8305	0.047*
C8	0.6226 (2)	0.66491 (19)	0.72271 (16)	0.0394 (4)
C9	0.6075 (3)	0.5653 (2)	0.69055 (18)	0.0459 (5)
H13	0.5904	0.4897	0.7410	0.055*
C10	0.6176 (3)	0.5765 (2)	0.58476 (19)	0.0508 (5)
H9	0.6067	0.5091	0.5645	0.061*
C11	0.6438 (3)	0.6878 (2)	0.50973 (17)	0.0499 (5)
C12	0.6600 (3)	0.7882 (2)	0.53900 (18)	0.0534 (6)
H11	0.6782	0.8631	0.4879	0.064*
C13	0.6491 (3)	0.7771 (2)	0.64451 (18)	0.0487 (5)
H12	0.6595	0.8452	0.6639	0.058*
C14	0.3741 (5)	0.8376 (4)	1.1019 (2)	0.0828 (9)
H14A	0.3369	0.7573	1.1394	0.099*
H14B	0.4171	0.8685	1.1537	0.099*
C15	0.2261 (5)	0.9194 (3)	1.0463 (3)	0.0879 (10)
H15A	0.2638	0.9978	1.0060	0.132*
H15B	0.1401	0.9292	1.0966	0.132*
H15C	0.1767	0.8853	0.9995	0.132*
C16	0.8504 (6)	0.6584 (6)	1.1231 (3)	0.144 (2)
H16A	0.8621	0.7317	1.1397	0.173*
H16B	0.7723	0.6098	1.1745	0.173*
C17	1.0151 (6)	0.5904 (5)	1.1311 (4)	0.150 (2)
H17A	1.0022	0.5138	1.1219	0.225*
H17B	1.0648	0.5751	1.1995	0.225*
H17C	1.0904	0.6361	1.0772	0.225*
C19	0.8263 (6)	0.1600 (4)	0.4743 (3)	0.0995 (11)
H19A	0.9352	0.1152	0.4677	0.149*
H19B	0.7566	0.1764	0.4122	0.149*
H19C	0.7658	0.1123	0.5355	0.149*
C20	0.8875 (5)	0.3742 (4)	0.3889 (3)	0.0956 (11)
H20A	0.9054	0.4455	0.4057	0.143*
H20B	0.7877	0.3919	0.3433	0.143*
H20C	0.9884	0.3515	0.3537	0.143*
C21	0.8634 (4)	0.2850 (3)	0.5803 (3)	0.0739 (8)
H21	0.8868	0.3608	0.5818	0.089*
Cl1	0.65380 (12)	0.70206 (8)	0.37615 (5)	0.0787 (3)
N1	0.6162 (3)	0.65004 (18)	0.82953 (14)	0.0452 (4)
H1A	0.589 (3)	0.584 (3)	0.862 (2)	0.051 (7)*
N2	0.8584 (3)	0.2738 (2)	0.4857 (2)	0.0673 (6)
O1	0.5143 (2)	0.82636 (17)	1.02988 (14)	0.0611 (5)
O2	0.4857 (3)	0.60211 (17)	1.06464 (14)	0.0713 (6)
O3	0.7772 (3)	0.6924 (2)	1.01916 (15)	0.0798 (6)
O4	−0.1380 (2)	0.95971 (17)	0.74345 (16)	0.0611 (5)
H4	−0.1433	1.0346	0.7171	0.092*
O9	0.8404 (3)	0.2062 (2)	0.66580 (19)	0.0866 (7)
P1	0.57543 (8)	0.70788 (5)	1.00447 (4)	0.04728 (19)

	U11	U22	U33	U12	U13	U23
C1	0.0417 (10)	0.0406 (10)	0.0315 (9)	−0.0111 (8)	0.0061 (7)	−0.0118 (8)
C2	0.0443 (11)	0.0399 (10)	0.0437 (11)	−0.0144 (8)	0.0053 (8)	−0.0094 (9)
C3	0.0425 (11)	0.0519 (12)	0.0413 (11)	−0.0078 (9)	0.0032 (8)	−0.0167 (9)
C4	0.0526 (12)	0.0361 (10)	0.0484 (12)	−0.0072 (9)	0.0033 (9)	−0.0078 (9)
C5	0.0446 (12)	0.0495 (12)	0.0526 (12)	−0.0193 (9)	0.0080 (9)	−0.0150 (10)
C6	0.0527 (12)	0.0344 (10)	0.0473 (12)	−0.0129 (9)	0.0071 (9)	−0.0092 (9)
C7	0.0430 (11)	0.0397 (10)	0.0319 (9)	−0.0105 (8)	0.0056 (8)	−0.0064 (8)
C8	0.0341 (10)	0.0431 (11)	0.0374 (10)	−0.0031 (8)	0.0043 (7)	−0.0096 (8)
C9	0.0459 (11)	0.0419 (11)	0.0443 (11)	−0.0073 (9)	0.0040 (9)	−0.0073 (9)
C10	0.0540 (13)	0.0508 (13)	0.0513 (13)	−0.0111 (10)	0.0028 (10)	−0.0208 (10)
C11	0.0511 (12)	0.0614 (14)	0.0377 (11)	−0.0103 (10)	0.0040 (9)	−0.0165 (10)
C12	0.0669 (15)	0.0486 (12)	0.0400 (11)	−0.0150 (11)	0.0088 (10)	−0.0073 (9)
C13	0.0624 (14)	0.0416 (11)	0.0415 (11)	−0.0117 (10)	0.0084 (10)	−0.0122 (9)
C14	0.094 (2)	0.101 (2)	0.0568 (16)	0.0018 (19)	0.0125 (15)	−0.0368 (17)
C15	0.093 (2)	0.089 (2)	0.083 (2)	0.0007 (19)	0.0159 (19)	−0.0359 (19)
C16	0.090 (3)	0.240 (6)	0.073 (3)	0.012 (3)	−0.026 (2)	−0.021 (3)
C17	0.089 (3)	0.175 (5)	0.120 (4)	−0.013 (3)	−0.028 (3)	0.036 (3)
C19	0.126 (3)	0.098 (3)	0.082 (2)	−0.023 (2)	−0.005 (2)	−0.035 (2)
C20	0.089 (2)	0.089 (2)	0.083 (2)	−0.0010 (19)	0.0005 (19)	0.0003 (19)
C21	0.0759 (19)	0.0589 (16)	0.084 (2)	0.0154 (14)	−0.0077 (16)	−0.0272 (16)
Cl1	0.1139 (6)	0.0865 (5)	0.0423 (3)	−0.0296 (4)	0.0097 (3)	−0.0257 (3)
N1	0.0548 (11)	0.0377 (10)	0.0362 (9)	−0.0040 (8)	0.0068 (8)	−0.0046 (7)
N2	0.0594 (13)	0.0660 (14)	0.0676 (15)	0.0037 (10)	0.0001 (11)	−0.0146 (12)
O1	0.0711 (11)	0.0623 (11)	0.0590 (10)	−0.0183 (9)	0.0095 (8)	−0.0298 (9)
O2	0.1158 (16)	0.0534 (10)	0.0411 (9)	−0.0282 (10)	0.0133 (9)	−0.0070 (8)
O3	0.0603 (12)	0.1195 (18)	0.0472 (10)	0.0072 (11)	−0.0112 (8)	−0.0166 (11)
O4	0.0439 (9)	0.0629 (11)	0.0720 (12)	−0.0056 (7)	−0.0031 (8)	−0.0172 (9)
O9	0.1075 (17)	0.0732 (14)	0.0685 (14)	0.0198 (12)	0.0008 (12)	−0.0195 (11)
P1	0.0558 (4)	0.0495 (3)	0.0333 (3)	−0.0099 (3)	0.0030 (2)	−0.0090 (2)

C1—C2	1.381 (3)	C14—H14A	0.9700
C1—C6	1.392 (3)	C14—H14B	0.9700
C1—C7	1.517 (3)	C15—H15A	0.9600
C2—C4	1.386 (3)	C15—H15B	0.9600
C2—H2	0.9300	C15—H15C	0.9600
C3—O4	1.365 (3)	C16—C17	1.412 (6)
C3—C4	1.381 (3)	C16—O3	1.434 (4)
C3—C5	1.386 (3)	C16—H16A	0.9700
C4—H4A	0.9300	C16—H16B	0.9700
C5—C6	1.372 (3)	C17—H17A	0.9600
C5—H5	0.9300	C17—H17B	0.9600
C6—H6	0.9300	C17—H17C	0.9600
C7—N1	1.455 (3)	C19—N2	1.438 (4)
C7—P1	1.812 (2)	C19—H19A	0.9600
C7—H7	0.9800	C19—H19B	0.9600
C8—N1	1.387 (3)	C19—H19C	0.9600
C8—C9	1.391 (3)	C20—N2	1.453 (4)
C8—C13	1.401 (3)	C20—H20A	0.9600
C9—C10	1.384 (3)	C20—H20B	0.9600
C9—H13	0.9300	C20—H20C	0.9600
C10—C11	1.375 (3)	C21—O9	1.222 (4)
C10—H9	0.9300	C21—N2	1.326 (4)
C11—C12	1.379 (3)	C21—H21	0.9300
C11—Cl1	1.747 (2)	N1—H1A	0.79 (3)
C12—C13	1.381 (3)	O1—P1	1.5592 (18)
C12—H11	0.9300	O2—P1	1.4568 (18)
C13—H12	0.9300	O3—P1	1.560 (2)
C14—C15	1.452 (5)	O4—H4	0.8200
C14—O1	1.455 (3)
C2—C1—C6	117.98 (19)	C14—C15—H15A	109.5
C2—C1—C7	120.88 (17)	C14—C15—H15B	109.5
C6—C1—C7	121.12 (18)	H15A—C15—H15B	109.5
C1—C2—C4	121.24 (19)	C14—C15—H15C	109.5
C1—C2—H2	119.4	H15A—C15—H15C	109.5
C4—C2—H2	119.4	H15B—C15—H15C	109.5
O4—C3—C4	122.1 (2)	C17—C16—O3	111.6 (4)
O4—C3—C5	118.2 (2)	C17—C16—H16A	109.3
C4—C3—C5	119.7 (2)	O3—C16—H16A	109.3
C3—C4—C2	119.8 (2)	C17—C16—H16B	109.3
C3—C4—H4A	120.1	O3—C16—H16B	109.3
C2—C4—H4A	120.1	H16A—C16—H16B	108.0
C6—C5—C3	119.93 (19)	C16—C17—H17A	109.5
C6—C5—H5	120.0	C16—C17—H17B	109.5
C3—C5—H5	120.0	H17A—C17—H17B	109.5
C5—C6—C1	121.4 (2)	C16—C17—H17C	109.5
C5—C6—H6	119.3	H17A—C17—H17C	109.5
C1—C6—H6	119.3	H17B—C17—H17C	109.5
N1—C7—C1	114.86 (17)	N2—C19—H19A	109.5
N1—C7—P1	108.79 (13)	N2—C19—H19B	109.5
C1—C7—P1	110.17 (13)	H19A—C19—H19B	109.5
N1—C7—H7	107.6	N2—C19—H19C	109.5
C1—C7—H7	107.6	H19A—C19—H19C	109.5
P1—C7—H7	107.6	H19B—C19—H19C	109.5
N1—C8—C9	119.85 (19)	N2—C20—H20A	109.5
N1—C8—C13	122.3 (2)	N2—C20—H20B	109.5
C9—C8—C13	117.79 (19)	H20A—C20—H20B	109.5
C10—C9—C8	121.2 (2)	N2—C20—H20C	109.5
C10—C9—H13	119.4	H20A—C20—H20C	109.5
C8—C9—H13	119.4	H20B—C20—H20C	109.5
C11—C10—C9	119.7 (2)	O9—C21—N2	126.9 (3)
C11—C10—H9	120.1	O9—C21—H21	116.5
C9—C10—H9	120.1	N2—C21—H21	116.5
C10—C11—C12	120.5 (2)	C8—N1—C7	119.49 (17)
C10—C11—Cl1	119.60 (19)	C8—N1—H1A	109 (2)
C12—C11—Cl1	119.88 (18)	C7—N1—H1A	120.2 (19)
C11—C12—C13	119.8 (2)	C21—N2—C19	121.2 (3)
C11—C12—H11	120.1	C21—N2—C20	122.2 (3)
C13—C12—H11	120.1	C19—N2—C20	116.6 (3)
C12—C13—C8	121.0 (2)	C14—O1—P1	125.2 (2)
C12—C13—H12	119.5	C16—O3—P1	119.8 (2)
C8—C13—H12	119.5	C3—O4—H4	109.5
C15—C14—O1	111.8 (3)	O2—P1—O1	114.07 (11)
C15—C14—H14A	109.2	O2—P1—O3	115.77 (13)
O1—C14—H14A	109.2	O1—P1—O3	104.04 (12)
C15—C14—H14B	109.2	O2—P1—C7	115.27 (11)
O1—C14—H14B	109.2	O1—P1—C7	104.53 (10)
H14A—C14—H14B	107.9	O3—P1—C7	101.57 (10)
C6—C1—C2—C4	1.1 (3)	N1—C8—C13—C12	178.1 (2)
C7—C1—C2—C4	−177.80 (19)	C9—C8—C13—C12	−0.1 (3)
O4—C3—C4—C2	179.6 (2)	C9—C8—N1—C7	−152.9 (2)
C5—C3—C4—C2	−0.5 (3)	C13—C8—N1—C7	29.0 (3)
C1—C2—C4—C3	−0.3 (3)	C1—C7—N1—C8	59.6 (2)
O4—C3—C5—C6	−179.6 (2)	P1—C7—N1—C8	−176.39 (16)
C4—C3—C5—C6	0.5 (3)	O9—C21—N2—C19	−1.1 (5)
C3—C5—C6—C1	0.3 (3)	O9—C21—N2—C20	179.8 (3)
C2—C1—C6—C5	−1.1 (3)	C15—C14—O1—P1	−112.5 (3)
C7—C1—C6—C5	177.8 (2)	C17—C16—O3—P1	150.0 (4)
C2—C1—C7—N1	−130.6 (2)	C14—O1—P1—O2	−3.4 (3)
C6—C1—C7—N1	50.6 (2)	C14—O1—P1—O3	−130.5 (2)
C2—C1—C7—P1	106.19 (19)	C14—O1—P1—C7	123.4 (2)
C6—C1—C7—P1	−72.6 (2)	C16—O3—P1—O2	−55.8 (4)
N1—C8—C9—C10	−178.4 (2)	C16—O3—P1—O1	70.2 (4)
C13—C8—C9—C10	−0.3 (3)	C16—O3—P1—C7	178.5 (4)
C8—C9—C10—C11	0.3 (3)	N1—C7—P1—O2	−56.14 (19)
C9—C10—C11—C12	0.0 (4)	C1—C7—P1—O2	70.60 (18)
C9—C10—C11—Cl1	−179.24 (18)	N1—C7—P1—O1	177.83 (14)
C10—C11—C12—C13	−0.3 (4)	C1—C7—P1—O1	−55.43 (16)
Cl1—C11—C12—C13	178.91 (19)	N1—C7—P1—O3	69.84 (17)
C11—C12—C13—C8	0.3 (4)	C1—C7—P1—O3	−163.43 (15)

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4···O9i	0.82	1.87	2.693 (3)	176
N1—H1A···O2ii	0.79 (3)	2.19 (3)	2.977 (3)	174 (3)
C7—H7···O4iii	0.98	2.53	3.502 (3)	172
C9—H13···O2ii	0.93	2.54	3.304 (3)	140

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H4⋯O9i	0.82	1.87	2.693 (3)	176
N1—H1A⋯O2ii	0.79 (3)	2.19 (3)	2.977 (3)	174 (3)
C7—H7⋯O4iii	0.98	2.53	3.502 (3)	172
C9—H13⋯O2ii	0.93	2.54	3.304 (3)	140

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