3-Methyl­anilinium picrate

In 3-methyl­anilinium picrate (3-MAP), C₇H₁₀N⁺·C₆H₂N₃O₇^-, one of the nitro groups in the picrate ion is rotationally disordered with site occupancy factors of 0.80 and 0.20. The expected proton transfer took place between picric acid and 3-methyl­aniline, and the amine group is hydrogen bonded to two of the phenolate O atoms. The ortho-nitro groups deviate greatly from the benzene plane of the picrate ion, facilitating hydrogen-bond formation. While the cations are stacked as columns along the [001] direction, the anions are stacked in an offset fashion.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.055
• wR factor = 0.170
• Data-to-parameter ratio = 11.9

checkCIF/PLATON results

No syntax errors found





Alert level C
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT152_ALERT_1_C Supplied and Calc Volume s.u. Inconsistent .....          ?
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         N1
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         N3
PLAT301_ALERT_3_C Main Residue  Disorder .........................      11.00 Perc.

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

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

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Computing details

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976) and PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97.

3-methylanilinium picrate

Crystal data

C7H10N^+·C6H2N3O7^−	F(000) = 696
Mr = 336.27	Dx = 1.483 Mg m^−3
Monoclinic, P21/c	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: -P 2ybc	Cell parameters from 25 reflections
a = 12.439 (4) Å	θ = 15–30°
b = 16.9472 (18) Å	µ = 1.06 mm^−1
c = 7.4504 (8) Å	T = 293 K
β = 106.437 (18)°	Needle, red
V = 1506.5 (5) Å^3	0.50 × 0.30 × 0.30 mm
Z = 4

Data collection

Enraf–Nonius CAD-4 diffractometer	2574 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.029
Graphite monochromator	θmax = 74.9°, θmin = 3.7°
ω–2θ scans	h = −6→15
Absorption correction: ψ scan (North et al., 1968)	k = −21→8
Tmin = 0.671, Tmax = 0.727	l = −9→8
3596 measured reflections	2 standard reflections every 100 reflections
3096 independent reflections	intensity decay: 1%

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.055	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.170	w = 1/[σ^2(Fo^2) + (0.0957P)^2 + 0.4692P] where P = (Fo^2 + 2Fc^2)/3
S = 1.07	(Δ/σ)max < 0.001
3096 reflections	Δρmax = 0.42 e Å^−3
261 parameters	Δρmin = −0.34 e Å^−3
30 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0050 (7)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
O1	0.84233 (11)	0.18218 (8)	0.1108 (2)	0.0502 (4)
O2	0.77378 (16)	0.04098 (10)	−0.0698 (2)	0.0732 (5)
O3	0.79351 (18)	−0.04020 (11)	0.1598 (3)	0.0846 (6)
O4	1.19741 (15)	−0.07305 (10)	0.4768 (2)	0.0674 (5)
O5	1.30528 (14)	0.02926 (12)	0.5075 (3)	0.0821 (6)
O6	1.1440 (2)	0.28205 (15)	0.2866 (7)	0.1122 (13)	0.80
O6'	1.1256 (7)	0.2811 (6)	0.4363 (10)	0.1122 (13)	0.20
O7	0.97716 (19)	0.30139 (14)	0.3080 (4)	0.0737 (8)	0.80
O7'	0.9770 (8)	0.3009 (6)	0.2141 (15)	0.0737 (8)	0.20
N1	0.82385 (15)	0.01656 (10)	0.0861 (3)	0.0502 (4)
N2	1.21302 (16)	−0.00207 (12)	0.4572 (3)	0.0563 (5)
N3	1.05347 (11)	0.25763 (11)	0.2981 (3)	0.0602 (5)
C1	0.92812 (15)	0.14137 (11)	0.1887 (2)	0.0395 (4)
C2	0.92723 (15)	0.05637 (11)	0.1874 (3)	0.0412 (4)
C3	1.01592 (17)	0.00937 (12)	0.2769 (3)	0.0451 (4)
C4	1.11660 (16)	0.04588 (12)	0.3677 (3)	0.0462 (5)
C5	1.12783 (16)	0.12697 (12)	0.3716 (3)	0.0486 (5)
C6	1.03541 (16)	0.17259 (11)	0.2878 (3)	0.0445 (4)
N4	0.73321 (14)	0.30361 (10)	0.2358 (3)	0.0451 (4)
C7	0.61968 (15)	0.27817 (12)	0.2327 (3)	0.0437 (4)
C8	0.5405 (2)	0.33429 (18)	0.2402 (3)	0.0632 (6)
C9	0.4344 (2)	0.3069 (3)	0.2410 (4)	0.0835 (10)
C10	0.4115 (2)	0.2274 (2)	0.2347 (4)	0.0803 (9)
C11	0.49084 (19)	0.17229 (18)	0.2265 (3)	0.0663 (7)
C12	0.59711 (16)	0.19883 (13)	0.2272 (3)	0.0497 (5)
C13	0.4659 (3)	0.0852 (2)	0.2153 (5)	0.1036 (12)
H13A	0.3879	0.0770	0.1529	0.155*
H13B	0.4834	0.0636	0.3393	0.155*
H13C	0.5105	0.0595	0.1465	0.155*
H3	1.008 (2)	−0.0439 (15)	0.271 (3)	0.054 (6)*
H5	1.198 (2)	0.1501 (16)	0.436 (4)	0.068 (7)*
H1N	0.772 (2)	0.2607 (17)	0.199 (4)	0.065 (7)*
H2N	0.777 (2)	0.3168 (16)	0.353 (5)	0.072 (8)*
H3N	0.733 (2)	0.3464 (18)	0.164 (4)	0.069 (8)*
H8	0.560 (2)	0.3883 (17)	0.256 (4)	0.068 (8)*
H9	0.383 (3)	0.346 (2)	0.242 (5)	0.106 (12)*
H10	0.330 (4)	0.214 (2)	0.225 (6)	0.129 (14)*
H12	0.664 (2)	0.1591 (15)	0.216 (4)	0.062 (7)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0430 (7)	0.0471 (7)	0.0540 (8)	0.0114 (6)	0.0033 (6)	−0.0051 (6)
O2	0.0779 (12)	0.0658 (10)	0.0575 (10)	−0.0148 (8)	−0.0109 (8)	0.0046 (8)
O3	0.0868 (13)	0.0659 (11)	0.0860 (13)	−0.0295 (10)	−0.0001 (10)	0.0154 (9)
O4	0.0766 (11)	0.0552 (9)	0.0671 (10)	0.0257 (8)	0.0152 (8)	0.0079 (8)
O5	0.0439 (9)	0.0906 (14)	0.1015 (15)	0.0145 (9)	0.0038 (9)	0.0146 (11)
O6	0.0580 (14)	0.0589 (13)	0.230 (4)	−0.0144 (10)	0.0585 (19)	0.0002 (19)
O6'	0.0580 (14)	0.0589 (13)	0.230 (4)	−0.0144 (10)	0.0585 (19)	0.0002 (19)
O7	0.0570 (11)	0.0436 (9)	0.123 (2)	0.0017 (8)	0.0296 (15)	−0.0158 (15)
O7'	0.0570 (11)	0.0436 (9)	0.123 (2)	0.0017 (8)	0.0296 (15)	−0.0158 (15)
N1	0.0503 (9)	0.0420 (9)	0.0530 (10)	−0.0034 (7)	0.0057 (7)	−0.0021 (7)
N2	0.0531 (11)	0.0598 (11)	0.0537 (10)	0.0190 (8)	0.0113 (8)	0.0044 (8)
N3	0.0452 (10)	0.0429 (9)	0.0850 (14)	−0.0033 (7)	0.0062 (9)	−0.0014 (9)
C1	0.0377 (9)	0.0401 (9)	0.0405 (9)	0.0044 (7)	0.0107 (7)	−0.0002 (7)
C2	0.0402 (9)	0.0405 (9)	0.0420 (9)	0.0005 (7)	0.0101 (7)	−0.0024 (7)
C3	0.0513 (11)	0.0381 (10)	0.0463 (10)	0.0051 (8)	0.0145 (8)	0.0016 (7)
C4	0.0406 (10)	0.0484 (10)	0.0478 (10)	0.0116 (8)	0.0094 (8)	0.0031 (8)
C5	0.0379 (10)	0.0504 (11)	0.0547 (11)	0.0020 (8)	0.0086 (8)	0.0002 (9)
C6	0.0401 (9)	0.0397 (10)	0.0520 (11)	0.0017 (7)	0.0104 (8)	−0.0004 (8)
N4	0.0430 (9)	0.0410 (8)	0.0507 (9)	−0.0028 (7)	0.0126 (7)	−0.0036 (7)
C7	0.0357 (9)	0.0565 (11)	0.0365 (9)	0.0035 (7)	0.0065 (7)	0.0002 (7)
C8	0.0562 (13)	0.0776 (17)	0.0534 (12)	0.0213 (12)	0.0117 (10)	−0.0011 (11)
C9	0.0499 (14)	0.139 (3)	0.0598 (15)	0.0358 (17)	0.0134 (11)	0.0048 (17)
C10	0.0387 (12)	0.141 (3)	0.0595 (15)	−0.0028 (15)	0.0111 (10)	0.0138 (16)
C11	0.0444 (12)	0.0965 (19)	0.0528 (12)	−0.0209 (11)	0.0051 (9)	0.0091 (12)
C12	0.0380 (9)	0.0618 (12)	0.0458 (10)	−0.0071 (8)	0.0062 (8)	0.0019 (9)
C13	0.080 (2)	0.106 (3)	0.112 (3)	−0.0488 (19)	0.0073 (18)	0.015 (2)

Geometric parameters (Å, º)

O1—C1	1.266 (2)	C5—H5	0.96 (3)
O2—N1	1.224 (2)	N4—C7	1.471 (2)
O3—N1	1.219 (2)	N4—H1N	0.95 (3)
O4—N2	1.234 (3)	N4—H2N	0.92 (3)
O5—N2	1.223 (3)	N4—H3N	0.90 (3)
O6—N3	1.2259 (17)	C7—C12	1.372 (3)
O6'—N3	1.2247 (19)	C7—C8	1.381 (3)
O7—N3	1.2232 (17)	C8—C9	1.402 (4)
O7'—N3	1.2243 (19)	C8—H8	0.94 (3)
N1—C2	1.459 (2)	C9—C10	1.375 (5)
N2—C4	1.446 (2)	C9—H9	0.92 (4)
N3—C6	1.457 (3)	C10—C11	1.373 (5)
C1—C6	1.431 (3)	C10—H10	1.02 (4)
C1—C2	1.440 (3)	C11—C12	1.395 (3)
C2—C3	1.371 (3)	C11—C13	1.506 (4)
C3—C4	1.389 (3)	C12—H12	1.09 (3)
C3—H3	0.91 (3)	C13—H13A	0.9600
C4—C5	1.381 (3)	C13—H13B	0.9600
C5—C6	1.380 (3)	C13—H13C	0.9600
O3—N1—O2	123.69 (19)	C1—C6—N3	120.01 (16)
O3—N1—C2	118.14 (18)	C7—N4—H1N	109.3 (16)
O2—N1—C2	118.14 (17)	C7—N4—H2N	113.3 (18)
O5—N2—O4	123.54 (19)	H1N—N4—H2N	104 (2)
O5—N2—C4	118.8 (2)	C7—N4—H3N	112.6 (17)
O4—N2—C4	117.69 (19)	H1N—N4—H3N	111 (2)
O7—N3—O6'	98.5 (6)	H2N—N4—H3N	106 (2)
O7'—N3—O6'	120.9 (8)	C12—C7—C8	122.3 (2)
O7—N3—O6	122.9 (2)	C12—C7—N4	118.37 (17)
O7'—N3—O6	111.0 (7)	C8—C7—N4	119.3 (2)
O7—N3—C6	119.48 (18)	C7—C8—C9	117.1 (3)
O7'—N3—C6	118.7 (6)	C7—C8—H8	121.0 (18)
O6'—N3—C6	115.5 (5)	C9—C8—H8	121.6 (17)
O6—N3—C6	117.46 (18)	C10—C9—C8	120.7 (3)
O1—C1—C6	125.19 (17)	C10—C9—H9	124 (2)
O1—C1—C2	122.63 (17)	C8—C9—H9	115 (2)
C6—C1—C2	112.17 (15)	C9—C10—C11	121.6 (2)
C3—C2—C1	125.03 (17)	C9—C10—H10	114 (2)
C3—C2—N1	116.94 (17)	C11—C10—H10	124 (2)
C1—C2—N1	118.02 (16)	C10—C11—C12	118.2 (3)
C2—C3—C4	117.95 (18)	C10—C11—C13	122.0 (3)
C2—C3—H3	119.4 (15)	C12—C11—C13	119.8 (3)
C4—C3—H3	122.6 (15)	C7—C12—C11	120.1 (2)
C5—C4—C3	121.70 (17)	C7—C12—H12	117.1 (14)
C5—C4—N2	118.94 (18)	C11—C12—H12	122.7 (14)
C3—C4—N2	119.36 (19)	C11—C13—H13A	109.5
C6—C5—C4	118.81 (18)	C11—C13—H13B	109.5
C6—C5—H5	121.6 (16)	H13A—C13—H13B	109.5
C4—C5—H5	119.5 (17)	C11—C13—H13C	109.5
C5—C6—C1	124.21 (18)	H13A—C13—H13C	109.5
C5—C6—N3	115.73 (17)	H13B—C13—H13C	109.5
O1—C1—C2—C3	−176.65 (18)	C2—C1—C6—C5	0.4 (3)
C6—C1—C2—C3	2.9 (3)	O1—C1—C6—N3	−2.7 (3)
O1—C1—C2—N1	2.2 (3)	C2—C1—C6—N3	177.77 (17)
C6—C1—C2—N1	−178.19 (16)	O7—N3—C6—C5	−147.4 (3)
O3—N1—C2—C3	42.2 (3)	O7'—N3—C6—C5	174.5 (7)
O2—N1—C2—C3	−136.2 (2)	O6'—N3—C6—C5	−30.1 (6)
O3—N1—C2—C1	−136.8 (2)	O6—N3—C6—C5	36.3 (4)
O2—N1—C2—C1	44.8 (3)	O7—N3—C6—C1	35.1 (3)
C1—C2—C3—C4	−3.7 (3)	O7'—N3—C6—C1	−3.1 (7)
N1—C2—C3—C4	177.38 (17)	O6'—N3—C6—C1	152.4 (6)
C2—C3—C4—C5	1.1 (3)	O6—N3—C6—C1	−141.2 (3)
C2—C3—C4—N2	−177.56 (18)	C12—C7—C8—C9	−0.3 (3)
O5—N2—C4—C5	−11.4 (3)	N4—C7—C8—C9	−178.6 (2)
O4—N2—C4—C5	169.32 (19)	C7—C8—C9—C10	0.0 (4)
O5—N2—C4—C3	167.2 (2)	C8—C9—C10—C11	−0.3 (4)
O4—N2—C4—C3	−12.0 (3)	C9—C10—C11—C12	0.8 (4)
C3—C4—C5—C6	2.1 (3)	C9—C10—C11—C13	−178.6 (3)
N2—C4—C5—C6	−179.32 (19)	C8—C7—C12—C11	0.8 (3)
C4—C5—C6—C1	−2.8 (3)	N4—C7—C12—C11	179.20 (19)
C4—C5—C6—N3	179.74 (19)	C10—C11—C12—C7	−1.1 (3)
O1—C1—C6—C5	−179.98 (19)	C13—C11—C12—C7	178.4 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N4—H1N···O1	0.95 (3)	1.82 (3)	2.767 (2)	175 (2)
N4—H2N···O1^i	0.92 (3)	1.86 (3)	2.750 (2)	162 (3)
N4—H3N···O4^ii	0.90 (3)	2.05 (3)	2.898 (2)	155 (2)

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