(2,4-Dihydroxy­benzyl­idene)dimethyl­ammonium dichloro­phosphinate

Xu, H.-J.; Tan, Q.-Y.; Pang, Y.-J.

doi:10.1107/S1600536809001925

organic compounds

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ISSN: 2056-9890

Volume 65| Part 2| February 2009| Page o353

doi:10.1107/S1600536809001925

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(2,4-Dihydroxybenzylidene)dimethylammonium dichlorophosphinate

Hai-Jun Xu,^a ^* Qing-Yin Tan ^a and Yi-Jie Pang ^a

^aOrdered Matter Science Research Center, College of Chemistry and Chemical, Engineering, Southeast University, Nanjing 210096, People's Republic of China
^*Correspondence e-mail: xuhj@seu.edu.cn

(Received 31 December 2008; accepted 15 January 2009; online 23 January 2009)

In the title compound, C₉H₁₂NO₂⁺·Cl₂PO₂⁻, the molecular skeleton of the cation is nearly planar with an r.m.s. deviation of 0.0336 Å. In the crystal structure, intermolecular O—H⋯O hydrogen bonds link cations and anions into chains running along [1 $[\overline{1}]$ 0].

Related literature

For details of the synthesis, see Ramadas & David Krupadanam (2000 ). For typical values of C=N bond lengths, see Elmah et al. (1999 ).

Experimental

Crystal data

C₉H₁₂NO₂⁺·Cl₂O₂P⁻
M_r = 300.07
Triclinic, $[P \overline 1]$
a = 7.922 (4) Å
b = 8.163 (4) Å
c = 11.035 (9) Å
α = 100.021 (19)°
β = 107.035 (2)°
γ = 103.02 (3)°
V = 642.3 (7) Å³
Z = 2
Mo Kα radiation
μ = 0.63 mm⁻¹
T = 293 (2) K
0.20 × 0.20 × 0.20 mm

Data collection

Rigaku Mercury2 diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.903, T_max = 1.000 (expected range = 0.796–0.881)
6473 measured reflections
2898 independent reflections
2374 reflections with I > 2σ(I)
R_int = 0.020

Refinement

R[F² > 2σ(F²)] = 0.043
wR(F²) = 0.116
S = 1.06
2898 reflections
155 parameters
H-atom parameters constrained
Δρ_max = 0.34 e Å⁻³
Δρ_min = −0.38 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯O4ⁱ	0.82	1.79	2.609 (3)	180
O2—H2⋯O3ⁱⁱ	0.82	1.83	2.635 (3)	167
Symmetry codes: (i) -x, -y+1, -z+1; (ii) -x+1, -y+2, -z+1.

Data collection: CrystalClear (Rigaku, 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: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809001925/cv2507sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809001925/cv2507Isup2.hkl

checkCIF report

Comment top

Vilsmeier conditions are important synthetic tool usually utilized in the synthesis of aldehydes . The title compound is a Vilsmeier intermediate synthesized from resorcinol, DMF and POCl₃ in dry CH₃CN. Here we report its crystal structure.

In the title compound (Fig. 1), all bond lengths are normal. The C7=N1 bond length of 1.288 (3) Å indicates a high degree of double-bond character comparable with the typical values of C=N bond length (Elmah et al., 1999). The two P—O bond lengths are almost equal - 1.4604 (19) and 1.4642 (18) Å, repectively.

In the crystal, the cations and anions are further connected via O–H···O hydrongen bonds into chains running in direction [1-10].

Related literature top

For details of the synthesis, see Ramadas & David Krupadanam (2000). For typical values of C=N bond lengths, see Elmah et al. (1999).

Experimental top

All chemicals were obtained from commercial sources and used without further purification except POCl₃ and DMF, which were distiled under reduced pressure before use. The title compound was prepared according to the literature (Ramadas & David Krupadanam, 2000).

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. A view of the title compound with the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.

(2,4-Dihydroxybenzylidene)dimethylammonium dichlorophosphinate top

Crystal data top

C₉H₁₂NO₂⁺·Cl₂O₂P⁻	Z = 2
M_r = 300.07	F(000) = 308
Triclinic, P1	D_x = 1.552 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.922 (4) Å	Cell parameters from 1854 reflections
b = 8.163 (4) Å	θ = 2.7–27.5°
c = 11.035 (9) Å	µ = 0.63 mm⁻¹
α = 100.021 (19)°	T = 293 K
β = 107.035 (2)°	Prism, colourless
γ = 103.02 (3)°	0.20 × 0.20 × 0.20 mm
V = 642.3 (7) Å³

Data collection top

Rigaku Mercury2 diffractometer	2898 independent reflections
Radiation source: fine-focus sealed tube	2374 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.020
Detector resolution: 13.6612 pixels mm^-1	θ_max = 27.5°, θ_min = 2.7°
ω scans	h = −10→10
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −10→10
T_min = 0.903, T_max = 1.000	l = −14→14
6473 measured reflections

Refinement top

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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.116	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0563P)² + 0.2201P] where P = (F_o² + 2F_c²)/3
2898 reflections	(Δ/σ)_max < 0.001
155 parameters	Δρ_max = 0.34 e Å⁻³
0 restraints	Δρ_min = −0.38 e Å⁻³

Crystal data top

C₉H₁₂NO₂⁺·Cl₂O₂P⁻	γ = 103.02 (3)°
M_r = 300.07	V = 642.3 (7) Å³
Triclinic, P1	Z = 2
a = 7.922 (4) Å	Mo Kα radiation
b = 8.163 (4) Å	µ = 0.63 mm⁻¹
c = 11.035 (9) Å	T = 293 K
α = 100.021 (19)°	0.20 × 0.20 × 0.20 mm
β = 107.035 (2)°

Data collection top

Rigaku Mercury2 diffractometer	2898 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	2374 reflections with I > 2σ(I)
T_min = 0.903, T_max = 1.000	R_int = 0.020
6473 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	0 restraints
wR(F²) = 0.116	H-atom parameters constrained
S = 1.06	Δρ_max = 0.34 e Å⁻³
2898 reflections	Δρ_min = −0.38 e Å⁻³
155 parameters

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	0.07808 (7)	0.57775 (7)	0.79425 (5)	0.04024 (16)
Cl2	−0.01734 (10)	0.66505 (10)	0.63397 (6)	0.0665 (2)
O1	0.1067 (2)	0.88448 (19)	0.41735 (15)	0.0469 (4)
H1A	0.0823	0.7961	0.3592	0.070*
O2	0.4455 (2)	1.1302 (2)	0.17313 (15)	0.0556 (4)
H2	0.5384	1.2072	0.1825	0.083*
C1	0.3561 (2)	1.1426 (2)	0.52665 (18)	0.0340 (4)
N1	0.3863 (2)	1.2128 (2)	0.76201 (16)	0.0424 (4)
C6	0.2445 (3)	1.0094 (2)	0.40992 (19)	0.0342 (4)
C5	0.2758 (3)	1.0099 (3)	0.29337 (19)	0.0382 (4)
H5A	0.2007	0.9231	0.2179	0.046*
C7	0.3111 (3)	1.1237 (3)	0.6409 (2)	0.0394 (4)
H7A	0.2087	1.0299	0.6251	0.047*
C3	0.5312 (3)	1.2722 (3)	0.4014 (2)	0.0424 (5)
H3A	0.6267	1.3596	0.3980	0.051*
C4	0.4190 (3)	1.1396 (3)	0.28853 (19)	0.0388 (4)
C2	0.4993 (3)	1.2723 (3)	0.5167 (2)	0.0411 (5)
H2A	0.5746	1.3609	0.5911	0.049*
C8	0.5515 (4)	1.3646 (4)	0.8156 (2)	0.0627 (7)
H8A	0.5790	1.4070	0.9081	0.094*
H8B	0.5293	1.4545	0.7729	0.094*
H8C	0.6541	1.3315	0.8009	0.094*
C9	0.3073 (4)	1.1623 (4)	0.8600 (2)	0.0642 (7)
H9A	0.2007	1.0624	0.8178	0.096*
H9B	0.2720	1.2571	0.8998	0.096*
H9C	0.3977	1.1345	0.9261	0.096*
Cl1	0.00162 (13)	0.72157 (11)	0.92482 (8)	0.0820 (3)
O4	−0.0294 (3)	0.3961 (2)	0.76791 (18)	0.0643 (5)
O3	0.2793 (2)	0.6276 (3)	0.83673 (19)	0.0676 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
P1	0.0420 (3)	0.0381 (3)	0.0372 (3)	0.0040 (2)	0.0153 (2)	0.0083 (2)
Cl2	0.0797 (5)	0.0756 (5)	0.0469 (4)	0.0299 (4)	0.0158 (3)	0.0234 (3)
O1	0.0444 (8)	0.0444 (8)	0.0439 (8)	−0.0018 (6)	0.0192 (7)	0.0040 (6)
O2	0.0622 (11)	0.0637 (11)	0.0367 (8)	0.0029 (8)	0.0235 (7)	0.0116 (7)
C1	0.0336 (9)	0.0374 (10)	0.0300 (9)	0.0116 (8)	0.0087 (7)	0.0087 (7)
N1	0.0439 (10)	0.0527 (11)	0.0315 (9)	0.0174 (8)	0.0129 (7)	0.0091 (7)
C6	0.0322 (9)	0.0349 (9)	0.0357 (10)	0.0108 (7)	0.0110 (7)	0.0096 (7)
C5	0.0402 (10)	0.0382 (10)	0.0320 (10)	0.0094 (8)	0.0104 (8)	0.0047 (8)
C7	0.0376 (10)	0.0439 (11)	0.0362 (10)	0.0121 (8)	0.0121 (8)	0.0098 (8)
C3	0.0410 (11)	0.0408 (11)	0.0406 (11)	0.0031 (8)	0.0132 (9)	0.0121 (9)
C4	0.0427 (11)	0.0439 (11)	0.0323 (10)	0.0138 (8)	0.0137 (8)	0.0133 (8)
C2	0.0402 (11)	0.0395 (10)	0.0349 (10)	0.0050 (8)	0.0074 (8)	0.0067 (8)
C8	0.0578 (15)	0.0714 (17)	0.0398 (13)	0.0026 (12)	0.0120 (11)	−0.0034 (11)
C9	0.0794 (18)	0.0802 (18)	0.0377 (12)	0.0198 (14)	0.0290 (12)	0.0162 (12)
Cl1	0.1114 (7)	0.0773 (5)	0.0594 (4)	0.0271 (4)	0.0444 (4)	−0.0020 (3)
O4	0.0824 (13)	0.0392 (9)	0.0644 (12)	−0.0028 (8)	0.0353 (10)	0.0061 (8)
O3	0.0420 (9)	0.0902 (14)	0.0699 (12)	0.0091 (9)	0.0166 (8)	0.0371 (10)

Geometric parameters (Å, º) top

P1—O3	1.4598 (19)	C6—C5	1.380 (3)
P1—O4	1.4641 (18)	C5—C4	1.387 (3)
P1—Cl1	2.0160 (13)	C5—H5A	0.9300
P1—Cl2	2.0262 (15)	C7—H7A	0.9300
O1—C6	1.349 (2)	C3—C2	1.367 (3)
O1—H1A	0.8200	C3—C4	1.401 (3)
O2—C4	1.342 (3)	C3—H3A	0.9300
O2—H2	0.8200	C2—H2A	0.9300
C1—C2	1.412 (3)	C8—H8A	0.9600
C1—C6	1.426 (3)	C8—H8B	0.9600
C1—C7	1.431 (3)	C8—H8C	0.9600
N1—C7	1.292 (3)	C9—H9A	0.9600
N1—C8	1.470 (3)	C9—H9B	0.9600
N1—C9	1.471 (3)	C9—H9C	0.9600

O3—P1—O4	120.75 (12)	C1—C7—H7A	114.0
O3—P1—Cl1	109.16 (10)	C2—C3—C4	119.5 (2)
O4—P1—Cl1	107.38 (8)	C2—C3—H3A	120.2
O3—P1—Cl2	108.40 (8)	C4—C3—H3A	120.2
O4—P1—Cl2	108.48 (9)	O2—C4—C5	117.32 (18)
Cl1—P1—Cl2	100.85 (7)	O2—C4—C3	122.41 (19)
C6—O1—H1A	109.5	C5—C4—C3	120.26 (19)
C4—O2—H2	109.5	C3—C2—C1	122.27 (18)
C2—C1—C6	116.78 (18)	C3—C2—H2A	118.9
C2—C1—C7	128.16 (18)	C1—C2—H2A	118.9
C6—C1—C7	115.03 (18)	N1—C8—H8A	109.5
C7—N1—C8	125.83 (19)	N1—C8—H8B	109.5
C7—N1—C9	119.8 (2)	H8A—C8—H8B	109.5
C8—N1—C9	114.33 (19)	N1—C8—H8C	109.5
O1—C6—C5	121.34 (17)	H8A—C8—H8C	109.5
O1—C6—C1	117.69 (17)	H8B—C8—H8C	109.5
C5—C6—C1	120.97 (18)	N1—C9—H9A	109.5
C6—C5—C4	120.18 (18)	N1—C9—H9B	109.5
C6—C5—H5A	119.9	H9A—C9—H9B	109.5
C4—C5—H5A	119.9	N1—C9—H9C	109.5
N1—C7—C1	131.9 (2)	H9A—C9—H9C	109.5
N1—C7—H7A	114.0	H9B—C9—H9C	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O4ⁱ	0.82	1.79	2.609 (3)	180
O2—H2···O3ⁱⁱ	0.82	1.83	2.635 (3)	167

Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x+1, −y+2, −z+1.

Experimental details

Crystal data
Chemical formula	C₉H₁₂NO₂⁺·Cl₂O₂P⁻
M_r	300.07
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	7.922 (4), 8.163 (4), 11.035 (9)
α, β, γ (°)	100.021 (19), 107.035 (2), 103.02 (3)
V (Å³)	642.3 (7)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.63
Crystal size (mm)	0.20 × 0.20 × 0.20

Data collection
Diffractometer	Rigaku Mercury2 diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.903, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	6473, 2898, 2374
R_int	0.020
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.116, 1.06
No. of reflections	2898
No. of parameters	155
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.34, −0.38

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O4ⁱ	0.82	1.79	2.609 (3)	179.8
O2—H2···O3ⁱⁱ	0.82	1.83	2.635 (3)	166.9

Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x+1, −y+2, −z+1.

Acknowledgements

HJX acknowledges a Start-up Grant from Southeast University, People's Republic of China.

References

Elmah, A., Kabak, M. & Elerman, Y. (1999). J. Mol. Struct. 484, 229–234. Google Scholar
Ramadas, S. & David Krupadanam, G. L. (2000). Tetrahedron Asymmetry, 11, 3375–3393. Web of Science CrossRef CAS Google Scholar
Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar