Triethyl­ammonium 1,1′-binaphthyl-2,2′-diyl phosphate

Gowda, R.R.; Ramkumar, V.; Chakraborty, D.

doi:10.1107/S160053681002026X

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 66| Part 7| July 2010| Page o1625

doi:10.1107/S160053681002026X

Open

access

Triethylammonium 1,1′-binaphthyl-2,2′-diyl phosphate

Ravikumar R. Gowda,^a Venkatachalam Ramkumar ^a and Debashis Chakraborty ^a ^*

^aDepartment of Chemistry, IIT Madras, Chennai, TamilNadu, India
^*Correspondence e-mail: dchakraborty@iitm.ac.in

(Received 1 May 2010; accepted 28 May 2010; online 16 June 2010)

In the crystal structure of the title compound, C₆H₁₆N⁺·C₂₀H₁₂O₄P⁻, an N—H⋯O interaction links the cation to the anion. The N atom in the triethylammonium cation exhibits a trigonal-bipyramidal coordination geometry and forms an N—H⋯O interaction with one phosphate O atom of the 1,1′-binaphthyl-2,2′-diyl phosphate ligand. A bifurcated C—H⋯O interaction with the other phosphate O atom links molecules along the a axis. The dihedral angle between the two naphthyl ring systems is 58.92 (3)°. The refined Flack parameter value of 0.50 (10) indicates inversion twinning.

Related literature

For the use of binolphosphoric acid in synthesis, see: Jacques et al. (1971 ); Moreau et al., (2009 ). For the binaphthyl unit in host compounds, see: Kyba et al. (1977 ).

Experimental

Crystal data

C₆H₁₆N⁺·C₂₀H₁₂O₄P⁻
M_r = 449.46
Orthorhombic, P 2₁ 2₁ 2₁
a = 8.4605 (2) Å
b = 13.3603 (4) Å
c = 20.5688 (7) Å
V = 2324.99 (12) Å³
Z = 4
Mo Kα radiation
μ = 0.15 mm⁻¹
T = 298 K
0.32 × 0.27 × 0.22 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1999 ) T_min = 0.953, T_max = 0.968
30327 measured reflections
5561 independent reflections
4823 reflections with I > 2σ(I)
R_int = 0.028

Refinement

R[F² > 2σ(F²)] = 0.043
wR(F²) = 0.121
S = 1.04
5561 reflections
297 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.54 e Å⁻³
Δρ_min = −0.31 e Å⁻³
Absolute structure: Flack (1983 )
Flack parameter: 0.50 (10)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯O4	0.87 (3)	1.83 (3)	2.689 (2)	172 (2)
C24—H24B⋯O3ⁱ	0.97	2.47	3.342 (4)	149
C26—H26A⋯O3ⁱ	0.97	2.47	3.373 (3)	155
Symmetry code: (i) x-1, y, z.

Data collection: APEX2 (Bruker, 2004 ); cell refinement: APEX2 and SAINT-Plus (Bruker, 2004); data reduction: SAINT-Plus and XPREP (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053681002026X/bq2208sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681002026X/bq2208Isup2.hkl

checkCIF report

Comment top

The title compound is a salt of binol phosphoric acid. It represents a useful tool for the resolution of amines. Amines which are unable to resolve using other chiral acids, are resolved using binolphosphoric acid very easily and in high yield (Jacques et al., 1971). Optically active amines are useful as intermediates of medicines, agricultural chemicals, or the like can be produced without special post-treatment in high yield at high optical purity using optically active phosphoric acid derivatives. A recent report depicts phosphoric acid acts as Bronsted acid to catalyze the addition of enolizable β-diketones, β-ketoesters, and vinylogous amides to α,β-unsaturated aldehydes to lead to substituted chromenones, pyranones, and tetra hydroquinolinones in good yields under mild reaction conditions via a formal [3+3] cycloaddition (Moreau et al., 2009).

In the title compound C₂₆H₂₈N O₄P, (I), the 1,1'-binaphthyl-2-2'diyl phosphate ligand coordinates with the triethyl ammonium to form an intra molecular N-H..O interaction with one phosphate O atom and with another phosphate O atom with which a bifurcated C-H..O interaction (Table 1) along the a axis extending into a network (Figure 2). The molecular structure viewed down along the C10-C11 pivot, clearly shows the non co-planar geometry of the two naptha rings system with a dihedral angle of 58.92 (3)°.

Related literature top

For the use of binolphosphoric acid in synthesis, see: Jacques et al. (1971); Moreau et al., (2009). For the binaphthyl unit in host compounds, see: Kyba et al. (1977).

Experimental top

To a stirred ice cold solution of 0.2 g (0.69 mole) binol (Evan et. al, 1977) in 20 mL of dichloromethane under nitrogen atmosphere was added 0.07 mL (0.69 mmol) POCl₃ drop wise followed by addition of 0.5 mL (3.5 mmol) triethylamine. White fumes of HCl were observed upon addition, reaction mixture was stirred at 0 °C for 30 minutes. Then 0.13 mL (6.9 mmol) H₂O was added slowly at 0 °C. Reaction mixture was stirred at 0 °C for 1 h and warmed up to room temperature and stirred for 40 h. The reaction was monitored using thin layer chromatography. The product was extracted using dichloromethane and purified by crystallization in dichloromethane. Yield is found to be 0.26 g (83.9 %).

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: APEX2 and SAINT-Plus (Bruker, 2004); data reduction: SAINT-Plus and XPREP (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The ORTEP drawing of the molecule with atoms represented as 30% probability ellipsoids.
	Fig. 2. The Packing diagram showing the N-H···O (blue dashed line) and the bifurcated C-H···O interactions (red dashed line)

Triethylammonium 1,1'-binaphthyl-2,2'-diyl phosphate top

Crystal data top

C₆H₁₆N⁺·C₂₀H₁₂O₄P⁻	F(000) = 952
M_r = 449.46	D_x = 1.284 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 7503 reflections
a = 8.4605 (2) Å	θ = 2.5–27.9°
b = 13.3603 (4) Å	µ = 0.15 mm⁻¹
c = 20.5688 (7) Å	T = 298 K
V = 2324.99 (12) Å³	Block, white
Z = 4	0.32 × 0.27 × 0.22 mm

Data collection top

Bruker APEXII CCD area-detector diffractometer	5561 independent reflections
Radiation source: fine-focus sealed tube	4823 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.028
phi and ω scans	θ_max = 28.3°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 1999)	h = −10→10
T_min = 0.953, T_max = 0.968	k = −17→15
30327 measured reflections	l = −27→27

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.043	w = 1/[σ²(F_o²) + (0.0768P)² + 0.3083P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.121	(Δ/σ)_max < 0.001
S = 1.04	Δρ_max = 0.54 e Å⁻³
5561 reflections	Δρ_min = −0.31 e Å⁻³
297 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.000
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983)
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0.50 (10)

Crystal data top

C₆H₁₆N⁺·C₂₀H₁₂O₄P⁻	V = 2324.99 (12) Å³
M_r = 449.46	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 8.4605 (2) Å	µ = 0.15 mm⁻¹
b = 13.3603 (4) Å	T = 298 K
c = 20.5688 (7) Å	0.32 × 0.27 × 0.22 mm

Data collection top

Bruker APEXII CCD area-detector diffractometer	5561 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1999)	4823 reflections with I > 2σ(I)
T_min = 0.953, T_max = 0.968	R_int = 0.028
30327 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.121	Δρ_max = 0.54 e Å⁻³
S = 1.04	Δρ_min = −0.31 e Å⁻³
5561 reflections	Absolute structure: Flack (1983)
297 parameters	Absolute structure parameter: 0.50 (10)
0 restraints

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes)

are estimated using the full covariance matrix. The cell esds are taken

into account individually in the estimation of esds in distances, angles

and torsion angles; correlations between esds in cell parameters are only

used when they are defined by crystal symmetry. An approximate (isotropic)

treatment of cell esds is used for estimating esds 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 > 2sigma(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
C1	0.9569 (2)	−0.09228 (15)	0.66118 (9)	0.0337 (4)
C2	1.0264 (3)	−0.18489 (16)	0.67555 (11)	0.0431 (5)
H2	0.9953	−0.2203	0.7123	0.052*
C3	1.1397 (3)	−0.22298 (15)	0.63547 (12)	0.0475 (5)
H3	1.1837	−0.2853	0.6444	0.057*
C4	1.1909 (3)	−0.16849 (15)	0.58042 (10)	0.0423 (5)
C5	1.3154 (3)	−0.2041 (2)	0.54033 (13)	0.0600 (7)
H5	1.3603	−0.2662	0.5489	0.072*
C6	1.3702 (4)	−0.1483 (2)	0.48930 (14)	0.0677 (8)
H6	1.4518	−0.1728	0.4635	0.081*
C7	1.3040 (3)	−0.0549 (2)	0.47599 (11)	0.0546 (6)
H7	1.3435	−0.0165	0.4419	0.065*
C8	1.1824 (3)	−0.01962 (17)	0.51244 (9)	0.0410 (5)
H8	1.1381	0.0421	0.5021	0.049*
C9	1.1211 (2)	−0.07409 (14)	0.56575 (9)	0.0323 (4)
C10	0.9960 (2)	−0.03785 (14)	0.60657 (8)	0.0298 (4)
C11	0.9160 (2)	0.05934 (13)	0.59444 (8)	0.0283 (4)
C12	0.8330 (2)	0.07958 (14)	0.53500 (8)	0.0309 (4)
C13	0.8099 (3)	0.00551 (16)	0.48651 (10)	0.0408 (5)
H13	0.8506	−0.0584	0.4928	0.049*
C14	0.7289 (3)	0.0268 (2)	0.43082 (10)	0.0518 (6)
H14	0.7143	−0.0229	0.3997	0.062*
C15	0.6676 (3)	0.1229 (2)	0.42019 (11)	0.0576 (7)
H15	0.6153	0.1371	0.3815	0.069*
C16	0.6841 (3)	0.19519 (19)	0.46587 (11)	0.0506 (6)
H16	0.6415	0.2583	0.4585	0.061*
C17	0.7658 (3)	0.17582 (15)	0.52499 (9)	0.0368 (4)
C18	0.7767 (3)	0.24789 (15)	0.57516 (10)	0.0432 (5)
H18	0.7358	0.3116	0.5684	0.052*
C19	0.8456 (2)	0.22598 (15)	0.63296 (10)	0.0368 (4)
H19	0.8485	0.2734	0.6660	0.044*
C20	0.9126 (2)	0.13082 (14)	0.64237 (8)	0.0291 (4)
C21	0.4505 (5)	0.0741 (4)	0.64124 (17)	0.1067 (15)
H21A	0.5583	0.0913	0.6504	0.160*
H21B	0.3883	0.1340	0.6381	0.160*
H21C	0.4454	0.0383	0.6008	0.160*
C22	0.3853 (4)	0.0076 (3)	0.69635 (16)	0.0853 (10)
H22A	0.2711	0.0039	0.6928	0.102*
H22B	0.4271	−0.0597	0.6917	0.102*
C23	0.4903 (4)	−0.1247 (2)	0.8033 (2)	0.0832 (10)
H23A	0.5959	−0.1078	0.7903	0.125*
H23B	0.4408	−0.1636	0.7698	0.125*
H23C	0.4936	−0.1629	0.8428	0.125*
C24	0.3995 (4)	−0.0330 (2)	0.81405 (17)	0.0715 (8)
H24A	0.4278	−0.0052	0.8560	0.086*
H24B	0.2879	−0.0494	0.8152	0.086*
C25	0.4079 (4)	0.1960 (3)	0.83499 (17)	0.0788 (9)
H25A	0.5187	0.2078	0.8285	0.118*
H25B	0.3927	0.1586	0.8744	0.118*
H25C	0.3536	0.2589	0.8382	0.118*
C26	0.3437 (3)	0.1379 (3)	0.77885 (19)	0.0791 (9)
H26A	0.2352	0.1200	0.7887	0.095*
H26B	0.3415	0.1816	0.7412	0.095*
N1	0.4281 (2)	0.04695 (16)	0.76106 (11)	0.0490 (5)
O1	0.84192 (17)	−0.05577 (10)	0.70278 (6)	0.0372 (3)
O2	0.98292 (15)	0.11072 (10)	0.70184 (6)	0.0308 (3)
O3	1.01033 (17)	0.00302 (13)	0.79917 (7)	0.0491 (4)
O4	0.74028 (17)	0.08038 (13)	0.77268 (7)	0.0451 (4)
P1	0.89188 (6)	0.03523 (4)	0.75172 (2)	0.03329 (13)
H1N	0.529 (4)	0.0593 (18)	0.7609 (12)	0.044 (7)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0328 (10)	0.0342 (10)	0.0342 (9)	−0.0053 (8)	−0.0050 (8)	−0.0002 (7)
C2	0.0506 (13)	0.0361 (10)	0.0424 (10)	−0.0078 (10)	−0.0115 (10)	0.0096 (9)
C3	0.0560 (15)	0.0293 (10)	0.0573 (12)	0.0071 (10)	−0.0186 (11)	0.0003 (9)
C4	0.0451 (13)	0.0371 (11)	0.0446 (11)	0.0090 (9)	−0.0150 (10)	−0.0086 (8)
C5	0.0611 (17)	0.0540 (14)	0.0649 (16)	0.0286 (13)	−0.0112 (13)	−0.0187 (12)
C6	0.0567 (18)	0.090 (2)	0.0565 (15)	0.0292 (15)	0.0067 (13)	−0.0209 (14)
C7	0.0493 (14)	0.0724 (17)	0.0421 (12)	0.0084 (12)	0.0076 (10)	−0.0062 (10)
C8	0.0397 (12)	0.0492 (12)	0.0341 (9)	0.0076 (9)	0.0003 (8)	−0.0012 (8)
C9	0.0336 (10)	0.0330 (9)	0.0303 (8)	0.0042 (8)	−0.0060 (7)	−0.0057 (7)
C10	0.0314 (10)	0.0295 (8)	0.0285 (8)	−0.0011 (8)	−0.0059 (7)	−0.0013 (7)
C11	0.0272 (9)	0.0312 (9)	0.0266 (8)	0.0016 (7)	0.0007 (7)	−0.0001 (6)
C12	0.0300 (10)	0.0345 (9)	0.0281 (8)	0.0037 (8)	−0.0001 (7)	−0.0002 (7)
C13	0.0452 (13)	0.0416 (11)	0.0355 (10)	0.0086 (9)	−0.0082 (9)	−0.0055 (8)
C14	0.0579 (15)	0.0613 (14)	0.0363 (10)	0.0111 (12)	−0.0154 (10)	−0.0122 (10)
C15	0.0617 (16)	0.0760 (17)	0.0351 (11)	0.0244 (14)	−0.0169 (11)	−0.0014 (11)
C16	0.0550 (15)	0.0526 (13)	0.0443 (12)	0.0177 (11)	−0.0136 (11)	0.0031 (10)
C17	0.0364 (11)	0.0393 (10)	0.0347 (9)	0.0072 (9)	−0.0023 (8)	0.0025 (8)
C18	0.0501 (13)	0.0339 (10)	0.0456 (11)	0.0124 (9)	0.0008 (10)	0.0005 (8)
C19	0.0387 (11)	0.0341 (9)	0.0375 (9)	0.0034 (8)	0.0028 (8)	−0.0092 (8)
C20	0.0251 (9)	0.0348 (9)	0.0275 (8)	−0.0043 (7)	0.0019 (7)	−0.0002 (7)
C21	0.106 (3)	0.148 (4)	0.066 (2)	−0.055 (3)	−0.031 (2)	0.016 (2)
C22	0.0621 (19)	0.124 (3)	0.0700 (19)	−0.028 (2)	−0.0083 (16)	−0.0116 (19)
C23	0.066 (2)	0.0684 (19)	0.115 (3)	−0.0038 (17)	0.019 (2)	0.0201 (19)
C24	0.0518 (16)	0.081 (2)	0.0814 (19)	−0.0096 (16)	0.0100 (15)	0.0077 (16)
C25	0.067 (2)	0.080 (2)	0.090 (2)	−0.0061 (17)	0.0116 (18)	−0.0214 (18)
C26	0.0399 (14)	0.0747 (19)	0.123 (3)	−0.0043 (14)	−0.0115 (17)	−0.0150 (19)
N1	0.0287 (10)	0.0563 (11)	0.0620 (12)	−0.0120 (8)	−0.0041 (8)	−0.0065 (9)
O1	0.0352 (7)	0.0421 (8)	0.0344 (7)	−0.0118 (6)	0.0018 (6)	0.0011 (5)
O2	0.0270 (7)	0.0402 (7)	0.0253 (6)	−0.0071 (6)	−0.0016 (5)	−0.0022 (5)
O3	0.0333 (8)	0.0790 (11)	0.0349 (7)	−0.0104 (8)	−0.0052 (6)	0.0127 (7)
O4	0.0269 (7)	0.0676 (10)	0.0408 (7)	−0.0058 (7)	0.0043 (6)	−0.0114 (7)
P1	0.0237 (2)	0.0516 (3)	0.0245 (2)	−0.0080 (2)	0.00039 (18)	−0.0002 (2)

Geometric parameters (Å, º) top

C1—C10	1.378 (3)	C18—C19	1.356 (3)
C1—O1	1.385 (2)	C18—H18	0.9300
C1—C2	1.401 (3)	C19—C20	1.405 (3)
C2—C3	1.363 (4)	C19—H19	0.9300
C2—H2	0.9300	C20—O2	1.386 (2)
C3—C4	1.414 (3)	C21—C22	1.542 (5)
C3—H3	0.9300	C21—H21A	0.9600
C4—C5	1.419 (3)	C21—H21B	0.9600
C4—C9	1.425 (3)	C21—H21C	0.9600
C5—C6	1.368 (4)	C22—N1	1.476 (4)
C5—H5	0.9300	C22—H22A	0.9700
C6—C7	1.396 (4)	C22—H22B	0.9700
C6—H6	0.9300	C23—C24	1.463 (4)
C7—C8	1.358 (3)	C23—H23A	0.9600
C7—H7	0.9300	C23—H23B	0.9600
C8—C9	1.415 (3)	C23—H23C	0.9600
C8—H8	0.9300	C24—N1	1.545 (4)
C9—C10	1.435 (3)	C24—H24A	0.9700
C10—C11	1.485 (3)	C24—H24B	0.9700
C11—C20	1.373 (2)	C25—C26	1.494 (4)
C11—C12	1.436 (2)	C25—H25A	0.9600
C12—C13	1.418 (3)	C25—H25B	0.9600
C12—C17	1.421 (3)	C25—H25C	0.9600
C13—C14	1.365 (3)	C26—N1	1.456 (4)
C13—H13	0.9300	C26—H26A	0.9700
C14—C15	1.402 (3)	C26—H26B	0.9700
C14—H14	0.9300	N1—H1N	0.87 (3)
C15—C16	1.355 (3)	O1—P1	1.6340 (14)
C15—H15	0.9300	O2—P1	1.6319 (13)
C16—C17	1.422 (3)	O3—P1	1.4636 (15)
C16—H16	0.9300	O4—P1	1.4815 (16)
C17—C18	1.414 (3)

C10—C1—O1	119.10 (18)	C18—C19—H19	120.3
C10—C1—C2	122.5 (2)	C20—C19—H19	120.3
O1—C1—C2	118.39 (18)	C11—C20—O2	119.33 (16)
C3—C2—C1	119.8 (2)	C11—C20—C19	122.59 (17)
C3—C2—H2	120.1	O2—C20—C19	118.03 (16)
C1—C2—H2	120.1	C22—C21—H21A	109.5
C2—C3—C4	120.50 (19)	C22—C21—H21B	109.5
C2—C3—H3	119.7	H21A—C21—H21B	109.5
C4—C3—H3	119.7	C22—C21—H21C	109.5
C3—C4—C5	121.3 (2)	H21A—C21—H21C	109.5
C3—C4—C9	119.9 (2)	H21B—C21—H21C	109.5
C5—C4—C9	118.8 (2)	N1—C22—C21	111.7 (3)
C6—C5—C4	121.0 (2)	N1—C22—H22A	109.3
C6—C5—H5	119.5	C21—C22—H22A	109.3
C4—C5—H5	119.5	N1—C22—H22B	109.3
C5—C6—C7	120.1 (2)	C21—C22—H22B	109.3
C5—C6—H6	120.0	H22A—C22—H22B	107.9
C7—C6—H6	120.0	C24—C23—H23A	109.5
C8—C7—C6	120.4 (3)	C24—C23—H23B	109.5
C8—C7—H7	119.8	H23A—C23—H23B	109.5
C6—C7—H7	119.8	C24—C23—H23C	109.5
C7—C8—C9	121.8 (2)	H23A—C23—H23C	109.5
C7—C8—H8	119.1	H23B—C23—H23C	109.5
C9—C8—H8	119.1	C23—C24—N1	113.0 (2)
C8—C9—C4	117.86 (19)	C23—C24—H24A	109.0
C8—C9—C10	123.39 (17)	N1—C24—H24A	109.0
C4—C9—C10	118.73 (18)	C23—C24—H24B	109.0
C1—C10—C9	118.40 (17)	N1—C24—H24B	109.0
C1—C10—C11	119.26 (17)	H24A—C24—H24B	107.8
C9—C10—C11	122.20 (16)	C26—C25—H25A	109.5
C20—C11—C12	118.06 (16)	C26—C25—H25B	109.5
C20—C11—C10	119.80 (15)	H25A—C25—H25B	109.5
C12—C11—C10	122.05 (16)	C26—C25—H25C	109.5
C13—C12—C17	118.33 (17)	H25A—C25—H25C	109.5
C13—C12—C11	122.32 (17)	H25B—C25—H25C	109.5
C17—C12—C11	119.31 (17)	N1—C26—C25	116.7 (3)
C14—C13—C12	120.9 (2)	N1—C26—H26A	108.1
C14—C13—H13	119.5	C25—C26—H26A	108.1
C12—C13—H13	119.5	N1—C26—H26B	108.1
C13—C14—C15	120.5 (2)	C25—C26—H26B	108.1
C13—C14—H14	119.8	H26A—C26—H26B	107.3
C15—C14—H14	119.8	C26—N1—C22	113.8 (3)
C16—C15—C14	120.4 (2)	C26—N1—C24	108.8 (2)
C16—C15—H15	119.8	C22—N1—C24	110.6 (2)
C14—C15—H15	119.8	C26—N1—H1N	108.9 (16)
C15—C16—C17	120.9 (2)	C22—N1—H1N	107.8 (17)
C15—C16—H16	119.6	C24—N1—H1N	106.7 (16)
C17—C16—H16	119.6	C1—O1—P1	117.46 (12)
C18—C17—C12	118.96 (17)	C20—O2—P1	118.16 (11)
C18—C17—C16	122.1 (2)	O3—P1—O4	121.23 (9)
C12—C17—C16	118.87 (19)	O3—P1—O2	106.13 (8)
C19—C18—C17	121.39 (18)	O4—P1—O2	109.87 (9)
C19—C18—H18	119.3	O3—P1—O1	111.67 (9)
C17—C18—H18	119.3	O4—P1—O1	104.96 (8)
C18—C19—C20	119.30 (18)	O2—P1—O1	101.22 (7)

C10—C1—C2—C3	1.5 (3)	C12—C13—C14—C15	0.5 (4)
O1—C1—C2—C3	179.86 (19)	C13—C14—C15—C16	−1.8 (4)
C1—C2—C3—C4	1.8 (3)	C14—C15—C16—C17	1.0 (4)
C2—C3—C4—C5	176.2 (2)	C13—C12—C17—C18	174.9 (2)
C2—C3—C4—C9	−1.5 (3)	C11—C12—C17—C18	−2.7 (3)
C3—C4—C5—C6	−176.3 (2)	C13—C12—C17—C16	−2.6 (3)
C9—C4—C5—C6	1.4 (4)	C11—C12—C17—C16	179.8 (2)
C4—C5—C6—C7	0.1 (4)	C15—C16—C17—C18	−176.1 (3)
C5—C6—C7—C8	−1.6 (4)	C15—C16—C17—C12	1.3 (4)
C6—C7—C8—C9	1.7 (4)	C12—C17—C18—C19	−2.0 (3)
C7—C8—C9—C4	−0.2 (3)	C16—C17—C18—C19	175.4 (2)
C7—C8—C9—C10	178.0 (2)	C17—C18—C19—C20	2.3 (3)
C3—C4—C9—C8	176.4 (2)	C12—C11—C20—O2	175.82 (16)
C5—C4—C9—C8	−1.3 (3)	C10—C11—C20—O2	−0.6 (3)
C3—C4—C9—C10	−1.9 (3)	C12—C11—C20—C19	−6.7 (3)
C5—C4—C9—C10	−179.6 (2)	C10—C11—C20—C19	176.85 (18)
O1—C1—C10—C9	176.82 (16)	C18—C19—C20—C11	2.2 (3)
C2—C1—C10—C9	−4.8 (3)	C18—C19—C20—O2	179.68 (19)
O1—C1—C10—C11	1.1 (3)	C25—C26—N1—C22	−165.1 (3)
C2—C1—C10—C11	179.47 (18)	C25—C26—N1—C24	71.1 (3)
C8—C9—C10—C1	−173.24 (18)	C21—C22—N1—C26	71.5 (4)
C4—C9—C10—C1	4.9 (3)	C21—C22—N1—C24	−165.7 (3)
C8—C9—C10—C11	2.3 (3)	C23—C24—N1—C26	−175.3 (3)
C4—C9—C10—C11	−179.53 (17)	C23—C24—N1—C22	59.1 (4)
C1—C10—C11—C20	52.0 (3)	C10—C1—O1—P1	−76.8 (2)
C9—C10—C11—C20	−123.5 (2)	C2—C1—O1—P1	104.78 (18)
C1—C10—C11—C12	−124.3 (2)	C11—C20—O2—P1	−74.93 (19)
C9—C10—C11—C12	60.2 (3)	C19—C20—O2—P1	107.47 (18)
C20—C11—C12—C13	−170.67 (19)	C20—O2—P1—O3	162.56 (13)
C10—C11—C12—C13	5.7 (3)	C20—O2—P1—O4	−64.72 (14)
C20—C11—C12—C17	6.8 (3)	C20—O2—P1—O1	45.86 (14)
C10—C11—C12—C17	−176.80 (18)	C1—O1—P1—O3	−65.43 (15)
C17—C12—C13—C14	1.7 (3)	C1—O1—P1—O4	161.44 (14)
C11—C12—C13—C14	179.3 (2)	C1—O1—P1—O2	47.12 (14)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O4	0.87 (3)	1.83 (3)	2.689 (2)	172 (2)
C24—H24B···O3ⁱ	0.97	2.47	3.342 (4)	149
C26—H26A···O3ⁱ	0.97	2.47	3.373 (3)	155

Symmetry code: (i) x−1, y, z.

Experimental details

Crystal data
Chemical formula	C₆H₁₆N⁺·C₂₀H₁₂O₄P⁻
M_r	449.46
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	298
a, b, c (Å)	8.4605 (2), 13.3603 (4), 20.5688 (7)
V (Å³)	2324.99 (12)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.15
Crystal size (mm)	0.32 × 0.27 × 0.22

Data collection
Diffractometer	Bruker APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 1999)
T_min, T_max	0.953, 0.968
No. of measured, independent and observed [I > 2σ(I)] reflections	30327, 5561, 4823
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.666

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.121, 1.04
No. of reflections	5561
No. of parameters	297
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.54, −0.31
Absolute structure	Flack (1983)
Absolute structure parameter	0.50 (10)

Computer programs: APEX2 (Bruker, 2004), APEX2 and SAINT-Plus (Bruker, 2004), SAINT-Plus and XPREP (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O4	0.87 (3)	1.83 (3)	2.689 (2)	172 (2)
C24—H24B···O3ⁱ	0.97	2.47	3.342 (4)	149
C26—H26A···O3ⁱ	0.97	2.47	3.373 (3)	155

Symmetry code: (i) x−1, y, z.

Acknowledgements

The authors acknowledge the Department of Chemistry, IIT Madras, for the X-ray data collection.

References

Bruker (1999). SADABS, Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2004). APEX2, SAINT-Plus and XPREP, Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Jacques, J., Fouquet, C. & Viterbo, R. (1971). Tetrahedron Lett. 48, 4617–4620. CrossRef Google Scholar
Kyba, E. P., Gokel, G. W., De Jong, F., Koga, K., Sousa, L. R., Siegel, M. G., Kaplan, L., Sogah, G. D. Y. & Cram, D. J. (1977). J. Org. Chem. 42, 4173–4184. CrossRef CAS Web of Science Google Scholar
Moreau, J., Hubert, C., Batany, J., Toupet, L., Roisnel, T., Hurvois, J.-P. & Renaud, J.-L. (2009). J. Org. Chem. 74, 8963–8973. Web of Science CSD CrossRef PubMed CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar