Reinvestigation of 4-methyl­anilinium dihydrogen phosphite

Fejfarová, K.; Jarošová, M.; Halime, I.; Lachkar, M.; El Bali, B.

doi:10.1107/S1600536810017563

Reinvestigation of 4-methylanilinium dihydrogen phosphite

K. Fejfarová, M. Jarošová, I. Halime, M. Lachkar and B. El Bali

The crystal structure of the title compound, C₇H₁₀N⁺·H₂PO₃⁻, has been reported previously by Sabounchei & Naghipour [Asian J. Chem. (2003), 15, 1677–1686]. A new look at this compound has revealed doubling of the unit cell. The asymmetric unit consists of two 4-methylanilinium cations and two dihydrogen phosphite anions. The crystal structure is built upon alternating layers of organic cations and dihydrogen phosphite anions stacked along c. The organic layer is stabilized by C—H

π interactions. Weak aromatic π–π stacking interactions with centroid–centroid distances of 4.6147 (12), 4.6917 (12), 4.6932 (13) and 4.8366 (13) Å are also observed in the structure. The dihydrogen phosphite anions are linked by O—H

O hydrogen bonds into chains running parallel to the a-axis direction. These chains are connected to the cation layer by N—H

O hydrogen bonds.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536810017563/fk2019sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536810017563/fk2019Isup2.hkl Contains datablock I

CCDC reference: 781367

checkCIF report

Key indicators

Single-crystal X-ray study
T = 120 K
Mean (C-C) = 0.003 Å
R factor = 0.031
wR factor = 0.085
Data-to-parameter ratio = 16.5

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT910_ALERT_3_C Missing # of FCF Reflections Below Th(Min) .....          5
PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L=  0.600          2

Alert level G
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          2

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   2 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

Related literature top

For the previously reported structure determination of the title compound, see: Sabounchei & Naghipour (2003).

Experimental top

Crystals of the title compound were obtained unintentionally in an attempt to prepare a Ni based hybrid organic-inorganic phosphite. In fact, reactants NiCl₂ (0.078 g, 5 mmol), H₃PO₃ (0.0834 g, 1 mmol) and four drops of p-Toluidine were added to 10 ml of distilled water. The solution was heated for 3 hours at 330 K and the resulting greenish solution was left at room temperature. After two weeks, colourless irregular shaped crystals deposited. They were filtered off and washed with a solution of ethanol–water (4:1 v/v). The chemical composition of the reported compound was confirmed by microprobe analysis.

Structure description top

For the previously reported structure determination of the title compound, see: Sabounchei & Naghipour (2003).

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2006); cell refinement: CrysAlis RED (Oxford Diffraction, 2008); data reduction: CrysAlis RED (Oxford Diffraction, 2008); program(s) used to solve structure: SIR2002 (Burla et al., 2003); program(s) used to refine structure: JANA2006 (Petříček et al., 2010); molecular graphics: DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: JANA2006 (Petříček et al., 2010).

Figures top

	Fig. 1. : The molecular structure of C₇H₁₀N⁺ H₂PO₃^-. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. : Crystal packing of title coumpound viewed along the b axis. Hydrogen bonds are displayed as dashed lines. Color code: Grey balls (C), blue balls (N), red balls (O), pink balls (P), black balls (H).

4-methylanilinium dihydrogen phosphite top

Crystal data top

C₇H₁₀N⁺·H₂PO₃⁻	Z = 4
M_r = 189.15	F(000) = 400
Triclinic, P1	D_x = 1.385 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71069 Å
a = 9.3053 (7) Å	Cell parameters from 1617 reflections
b = 9.4087 (7) Å	θ = 3.0–26.5°
c = 11.3432 (8) Å	µ = 0.27 mm⁻¹
α = 70.253 (7)°	T = 120 K
β = 76.304 (6)°	Prism, colorless
γ = 82.771 (6)°	0.54 × 0.20 × 0.10 mm
V = 906.99 (12) Å³

Data collection top

Oxford Diffraction XCalibur 2 with area-detector Sapphire 2 diffractometer	3787 independent reflections
Radiation source: X-ray tube	1948 reflections with I > 3σ(I)
Graphite monochromator	R_int = 0.036
Detector resolution: 8.3438 pixels mm^-1	θ_max = 26.6°, θ_min = 3°
Rotation method data acquisition using ω scans	h = −11→11
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2008)	k = −11→11
T_min = 0.885, T_max = 0.973	l = −14→14
11211 measured reflections

Refinement top

Refinement on F²	84 constraints
R[F > 3σ(F)] = 0.031	H atoms treated by a mixture of independent and constrained refinement
wR(F) = 0.085	Weighting scheme based on measured s.u.'s w = 1/[σ²(I) + 0.0016I²]
S = 0.94	(Δ/σ)_max = 0.006
3787 reflections	Δρ_max = 0.18 e Å⁻³
229 parameters	Δρ_min = −0.21 e Å⁻³
2 restraints

Crystal data top

C₇H₁₀N⁺·H₂PO₃⁻	γ = 82.771 (6)°
M_r = 189.15	V = 906.99 (12) Å³
Triclinic, P1	Z = 4
a = 9.3053 (7) Å	Mo Kα radiation
b = 9.4087 (7) Å	µ = 0.27 mm⁻¹
c = 11.3432 (8) Å	T = 120 K
α = 70.253 (7)°	0.54 × 0.20 × 0.10 mm
β = 76.304 (6)°

Data collection top

Oxford Diffraction XCalibur 2 with area-detector Sapphire 2 diffractometer	3787 independent reflections
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2008)	1948 reflections with I > 3σ(I)
T_min = 0.885, T_max = 0.973	R_int = 0.036
11211 measured reflections

Refinement top

R[F > 3σ(F)] = 0.031	2 restraints
wR(F) = 0.085	H atoms treated by a mixture of independent and constrained refinement
S = 0.94	Δρ_max = 0.18 e Å⁻³
3787 reflections	Δρ_min = −0.21 e Å⁻³
229 parameters

Special details top

Experimental. CrysAlis RED, Oxford Diffraction (2008). Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

Refinement. The refinement was carried out against all reflections. The conventional R-factor is always based on F. The goodness of fit as well as the weighted R-factor are based on F and F² for refinement carried out on F and F², respectively. The threshold expression is used only for calculating R-factors etc. and it is not relevant to the choice of reflections for refinement.

The program used for refinement, Jana2006, uses the weighting scheme based on the experimental expectations, see _refine_ls_weighting_details, that does not force S to be one. Therefore the values of S are usually larger then the ones from the SHELX program.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
P1	0.44268 (6)	0.24716 (7)	0.46676 (6)	0.0165 (2)
P2	0.94726 (6)	0.25421 (7)	0.47260 (6)	0.0167 (2)
O1	0.54591 (17)	0.17576 (19)	0.56371 (16)	0.0298 (7)
O2	0.51328 (15)	0.37070 (16)	0.35039 (13)	0.0195 (6)
O3	0.29515 (15)	0.29375 (16)	0.53675 (13)	0.0195 (6)
O4	1.03762 (17)	0.2061 (2)	0.58040 (15)	0.0308 (7)
O5	1.01622 (15)	0.37753 (16)	0.35577 (13)	0.0184 (6)
O6	0.78923 (15)	0.28969 (16)	0.53163 (13)	0.0190 (6)
N1	0.74334 (19)	0.44279 (19)	0.70739 (16)	0.0171 (7)
N2	0.25053 (18)	0.4549 (2)	0.70792 (16)	0.0168 (7)
C1	0.7462 (2)	0.3513 (2)	0.8403 (2)	0.0159 (9)
C2	0.8748 (2)	0.2693 (2)	0.8666 (2)	0.0194 (8)
C3	0.8833 (2)	0.1901 (2)	0.9927 (2)	0.0203 (9)
C4	0.7635 (3)	0.1912 (3)	1.0925 (2)	0.0194 (9)
C5	0.6343 (2)	0.2725 (2)	1.0629 (2)	0.0206 (9)
C6	0.6246 (2)	0.3533 (2)	0.93645 (19)	0.0179 (8)
C7	0.7744 (3)	0.1095 (3)	1.2295 (2)	0.0330 (11)
C8	0.2503 (2)	0.3567 (2)	0.8389 (2)	0.0144 (9)
C9	0.3142 (2)	0.2119 (2)	0.86021 (19)	0.0173 (8)
C10	0.3151 (2)	0.1208 (2)	0.98476 (19)	0.0187 (8)
C11	0.2530 (2)	0.1712 (3)	1.0889 (2)	0.0193 (9)
C12	0.1901 (2)	0.3180 (2)	1.0644 (2)	0.0193 (8)
C13	0.1881 (2)	0.4110 (2)	0.94022 (19)	0.0190 (8)
C14	0.2534 (3)	0.0697 (3)	1.2231 (2)	0.0309 (10)
H1o	0.6230 (17)	0.219 (3)	0.549 (2)	0.0358*
H4o	1.1189 (15)	0.242 (3)	0.560 (2)	0.037*
H1a	0.750815	0.383602	0.661368	0.0205*
H1b	0.660389	0.496818	0.704816	0.0205*
H1c	0.817088	0.502228	0.677138	0.0205*
H2a	0.163763	0.500864	0.70399	0.0202*
H2b	0.317161	0.52158	0.685108	0.0202*
H2c	0.270786	0.400831	0.656644	0.0202*
H2	0.957885	0.267015	0.798343	0.0233*
H3	0.973162	0.133701	1.011183	0.0244*
H5	0.550038	0.273093	1.130628	0.0247*
H6	0.534789	0.409164	0.916969	0.0215*
H7a	0.864717	0.047813	1.231763	0.0396*
H7b	0.773841	0.181898	1.27231	0.0396*
H7c	0.691539	0.046706	1.271737	0.0396*
H9	0.35734	0.175038	0.789684	0.0207*
H10	0.3597	0.020317	0.999763	0.0225*
H12	0.147349	0.355424	1.134695	0.0232*
H13	0.144188	0.511853	0.924573	0.0228*
H14a	0.240884	0.129949	1.278716	0.0371*
H14b	0.173647	0.002559	1.251293	0.0371*
H14c	0.345892	0.011813	1.225366	0.0371*
H1p	0.415 (2)	0.132 (2)	0.4315 (18)	0.0198*
H2p	0.940 (2)	0.131 (2)	0.4421 (18)	0.02*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
P1	0.0147 (3)	0.0167 (3)	0.0165 (3)	−0.0020 (3)	−0.0049 (3)	−0.0019 (3)
P2	0.0155 (3)	0.0169 (3)	0.0157 (3)	−0.0013 (3)	−0.0045 (3)	−0.0017 (3)
O1	0.0185 (9)	0.0311 (11)	0.0295 (10)	−0.0094 (8)	−0.0128 (8)	0.0118 (8)
O2	0.0173 (8)	0.0213 (9)	0.0168 (9)	−0.0009 (7)	−0.0046 (7)	−0.0014 (7)
O3	0.0157 (8)	0.0246 (9)	0.0170 (8)	−0.0036 (7)	−0.0025 (7)	−0.0048 (7)
O4	0.0165 (9)	0.0450 (12)	0.0203 (9)	−0.0103 (8)	−0.0072 (8)	0.0086 (9)
O5	0.0173 (8)	0.0204 (9)	0.0144 (8)	−0.0019 (7)	−0.0037 (7)	−0.0011 (7)
O6	0.0148 (8)	0.0219 (9)	0.0178 (8)	−0.0034 (7)	−0.0043 (7)	−0.0017 (7)
N1	0.0156 (10)	0.0174 (10)	0.0163 (10)	−0.0015 (9)	−0.0038 (8)	−0.0024 (9)
N2	0.0153 (10)	0.0174 (10)	0.0154 (10)	−0.0007 (9)	−0.0033 (8)	−0.0021 (8)
C1	0.0195 (13)	0.0138 (13)	0.0145 (12)	−0.0040 (11)	−0.0057 (10)	−0.0019 (11)
C2	0.0164 (12)	0.0218 (12)	0.0198 (12)	−0.0034 (10)	−0.0022 (9)	−0.0064 (10)
C3	0.0198 (12)	0.0158 (12)	0.0269 (13)	0.0013 (10)	−0.0118 (10)	−0.0048 (10)
C4	0.0260 (13)	0.0152 (12)	0.0193 (13)	−0.0042 (10)	−0.0097 (11)	−0.0039 (10)
C5	0.0223 (13)	0.0227 (12)	0.0160 (12)	−0.0044 (10)	0.0001 (10)	−0.0065 (10)
C6	0.0164 (11)	0.0169 (11)	0.0214 (12)	−0.0007 (10)	−0.0071 (9)	−0.0051 (10)
C7	0.0473 (17)	0.0282 (15)	0.0243 (14)	0.0008 (13)	−0.0142 (13)	−0.0059 (12)
C8	0.0131 (12)	0.0159 (13)	0.0130 (12)	−0.0035 (10)	−0.0042 (10)	−0.0011 (10)
C9	0.0175 (12)	0.0193 (12)	0.0166 (11)	−0.0014 (10)	−0.0047 (9)	−0.0067 (9)
C10	0.0181 (12)	0.0131 (11)	0.0243 (12)	0.0006 (9)	−0.0084 (10)	−0.0028 (10)
C11	0.0185 (12)	0.0208 (13)	0.0174 (12)	−0.0078 (11)	−0.0059 (10)	−0.0005 (10)
C12	0.0217 (12)	0.0230 (13)	0.0149 (11)	−0.0057 (10)	−0.0029 (9)	−0.0074 (10)
C13	0.0190 (12)	0.0132 (11)	0.0245 (12)	−0.0019 (9)	−0.0050 (10)	−0.0050 (10)
C14	0.0360 (16)	0.0311 (15)	0.0209 (13)	−0.0043 (12)	−0.0088 (12)	0.0006 (12)

Geometric parameters (Å, º) top

P1—O1	1.5563 (18)	C3—H3	0.96
P1—O2	1.5066 (13)	C4—C5	1.389 (3)
P1—O3	1.5082 (14)	C4—C7	1.504 (3)
P1—H1p	1.35 (2)	C5—C6	1.397 (3)
P2—O4	1.5570 (19)	C5—H5	0.96
P2—O5	1.5033 (13)	C6—H6	0.96
P2—O6	1.5111 (14)	C7—H7a	0.96
P2—H2p	1.33 (2)	C7—H7b	0.96
O1—H1o	0.82 (2)	C7—H7c	0.96
O4—H4o	0.817 (17)	C8—C9	1.382 (3)
N1—C1	1.467 (3)	C8—C13	1.387 (3)
N1—H1a	0.87	C9—C10	1.384 (3)
N1—H1b	0.87	C9—H9	0.96
N1—H1c	0.87	C10—C11	1.393 (3)
N2—C8	1.461 (3)	C10—H10	0.96
N2—H2a	0.87	C11—C12	1.394 (3)
N2—H2b	0.87	C11—C14	1.500 (3)
N2—H2c	0.87	C12—C13	1.388 (3)
C1—C2	1.377 (3)	C12—H12	0.96
C1—C6	1.377 (3)	C13—H13	0.96
C2—C3	1.387 (3)	C14—H14a	0.96
C2—H2	0.96	C14—H14b	0.96
C3—C4	1.390 (3)	C14—H14c	0.96

O1—P1—O2	112.94 (9)	C5—C4—C7	120.72 (19)
O1—P1—O3	109.03 (9)	C4—C5—C6	121.28 (19)
O1—P1—H1p	105.0 (8)	C4—C5—H5	119.3623
O2—P1—O3	114.33 (8)	C6—C5—H5	119.3618
O2—P1—H1p	109.7 (7)	C1—C6—C5	118.73 (19)
O3—P1—H1p	105.2 (8)	C1—C6—H6	120.6345
O4—P2—O5	113.03 (9)	C5—C6—H6	120.6348
O4—P2—O6	107.47 (9)	C4—C7—H7a	109.4716
O4—P2—H2p	106.5 (8)	C4—C7—H7b	109.4709
O5—P2—O6	114.87 (8)	C4—C7—H7c	109.4717
O5—P2—H2p	109.9 (7)	H7a—C7—H7b	109.4704
O6—P2—H2p	104.4 (8)	H7a—C7—H7c	109.4711
P1—O1—H1o	115.9 (15)	H7b—C7—H7c	109.4716
P2—O4—H4o	114.8 (16)	N2—C8—C9	119.6 (2)
C1—N1—H1a	109.4712	N2—C8—C13	119.48 (18)
C1—N1—H1b	109.4716	C9—C8—C13	120.91 (19)
C1—N1—H1c	109.4717	C8—C9—C10	119.0 (2)
H1a—N1—H1b	109.4701	C8—C9—H9	120.5149
H1a—N1—H1c	109.4712	C10—C9—H9	120.5151
H1b—N1—H1c	109.4716	C9—C10—C11	121.74 (19)
C8—N2—H2a	109.471	C9—C10—H10	119.1322
C8—N2—H2b	109.4707	C11—C10—H10	119.1326
C8—N2—H2c	109.4708	C10—C11—C12	118.00 (19)
H2a—N2—H2b	109.4716	C10—C11—C14	120.8 (2)
H2a—N2—H2c	109.4717	C12—C11—C14	121.2 (2)
H2b—N2—H2c	109.4715	C11—C12—C13	121.1 (2)
N1—C1—C2	118.50 (17)	C11—C12—H12	119.4449
N1—C1—C6	120.20 (18)	C13—C12—H12	119.4445
C2—C1—C6	121.24 (19)	C8—C13—C12	119.27 (19)
C1—C2—C3	119.45 (19)	C8—C13—H13	120.366
C1—C2—H2	120.2763	C12—C13—H13	120.3658
C3—C2—H2	120.2765	C11—C14—H14a	109.4716
C2—C3—C4	121.0 (2)	C11—C14—H14b	109.4705
C2—C3—H3	119.5091	C11—C14—H14c	109.471
C4—C3—H3	119.5082	H14a—C14—H14b	109.4714
C3—C4—C5	118.3 (2)	H14a—C14—H14c	109.4717
C3—C4—C7	121.0 (2)	H14b—C14—H14c	109.4711

N1—C1—C2—C3	175.68 (18)	N2—C8—C9—C10	179.07 (18)
C6—C1—C2—C3	−1.6 (3)	C13—C8—C9—C10	0.2 (3)
N1—C1—C6—C5	−175.96 (18)	N2—C8—C13—C12	−179.06 (18)
C2—C1—C6—C5	1.3 (3)	C9—C8—C13—C12	−0.2 (3)
C1—C2—C3—C4	0.7 (3)	C8—C9—C10—C11	0.2 (3)
C2—C3—C4—C5	0.6 (4)	C9—C10—C11—C12	−0.5 (3)
C2—C3—C4—C7	−178.0 (2)	C9—C10—C11—C14	179.1 (2)
C3—C4—C5—C6	−0.9 (4)	C10—C11—C12—C13	0.5 (3)
C7—C4—C5—C6	177.7 (2)	C14—C11—C12—C13	−179.1 (2)
C4—C5—C6—C1	0.0 (3)	C11—C12—C13—C8	−0.2 (3)

Hydrogen-bond geometry (Å, º) top

Cg1 and Cg2 are the centroids of the C1–C6 and C8–C13 rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1a···O6	0.87	1.90	2.760 (2)	167
N1—H1b···O2ⁱ	0.87	2.00	2.850 (2)	165
N1—H1c···O5ⁱⁱ	0.87	1.93	2.784 (2)	169
O1—H1o···O6	0.82 (2)	1.703 (19)	2.523 (2)	173 (3)
N2—H2a···O5ⁱ	0.87	2.03	2.875 (2)	165
N2—H2b···O2ⁱ	0.87	1.87	2.729 (2)	168
N2—H2c···O3	0.87	1.91	2.773 (2)	173
O4—H4o···O3ⁱⁱⁱ	0.818 (18)	1.704 (17)	2.516 (2)	171 (2)
C3—H3···Cg2ⁱⁱⁱ	0.96	2.87	3.502 (2)	125
C6—H6···Cg2	0.96	2.97	3.589 (2)	123
C10—H10···Cg1^iv	0.96	2.93	3.655 (2)	133

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

Experimental details

Crystal data
Chemical formula	C₇H₁₀N⁺·H₂PO₃⁻
M_r	189.15
Crystal system, space group	Triclinic, P1
Temperature (K)	120
a, b, c (Å)	9.3053 (7), 9.4087 (7), 11.3432 (8)
α, β, γ (°)	70.253 (7), 76.304 (6), 82.771 (6)
V (Å³)	906.99 (12)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.27
Crystal size (mm)	0.54 × 0.20 × 0.10

Data collection
Diffractometer	Oxford Diffraction XCalibur 2 with area-detector Sapphire 2
Absorption correction	Multi-scan (CrysAlis RED; Oxford Diffraction, 2008)
T_min, T_max	0.885, 0.973
No. of measured, independent and observed [I > 3σ(I)] reflections	11211, 3787, 1948
R_int	0.036
(sin θ/λ)_max (Å⁻¹)	0.630

Refinement
R[F > 3σ(F)], wR(F), S	0.031, 0.085, 0.94
No. of reflections	3787
No. of parameters	229
No. of restraints	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.18, −0.21

Computer programs: CrysAlis CCD (Oxford Diffraction, 2006), CrysAlis RED (Oxford Diffraction, 2008), SIR2002 (Burla et al., 2003), JANA2006 (Petříček et al., 2010), DIAMOND (Brandenburg & Putz, 2005).