2-(3,4-Di­hydroxy­phenyl)­ethyl­ammonium 3,5-di­nitro­benzoate

In the crystal structure of the title salt, C₈H₁₂NO₂⁺·C₇H₃N₂O₆⁻, the di­hydroxy moiety of the cation is connected to the nitro and carboxyl­ate O atoms of the anion via hydrogen bonds, forming a planar two-component assembly of the aromatic rings. Furthermore, the assemblies are linked into a three-dimensional network by N—H...O hydrogen bonds.

Key indicators

• Single-crystal X-ray study
• T = 250 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.037
• wR factor = 0.118
• Data-to-parameter ratio = 11.8

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


 Alert Level C:



REFLT_03
         From the CIF: _diffrn_reflns_theta_max           75.00
         From the CIF: _reflns_number_total               3025
         TEST2: Reflns within _diffrn_reflns_theta_max
         Count of symmetry unique reflns         3196
         Completeness (_total/calc)             94.65%
          Alert C: < 95% complete

PLAT_369  Alert C Long   C(sp2)-C(sp2) Bond  C(20)  -   C(21)  =       1.53 Ang.


 0 Alert Level A = Potentially serious problem

 0 Alert Level B = Potential problem

 2 Alert Level C = Please check

---

S1. Comment

Solid-state photoreactivities of some donor–acceptor crystals have been investigated by one of the authors (YI) (Ito et al., 1998). The structure of the title compound, (I), has been determined to study the packing mode of the molecules in the crystal.

The title crystal consists of ammonium cations and carboxylato anions (Fig. 1 and Table 1). The dihydroxy moiety of the cation (the O1 and O2 atoms) is connected with the nitro O5 and carboxylate O4 atoms of the anion via hydrogen bonds (Table 2), forming a planar two-component assembly of the aromatic rings. Furthermore, the assemblies are linked into a three-dimensional network by N—H···O hydrogen bonds involving the ammonium moiety (Fig. 2). The crystal structure of (I) might be regarded also as the alternative stacking of the cations and anions along c, although the overlap between the aromatic rings is very poor.

S2. Experimental

Crystals of (I) were grown by slow evaporation from an aqueous solution of a mixture of 2-(3,4-dihydroxyphenyl)ethylamine and 3,5-dinitrobenzoic acid (1:1)

S3. Refinement

The relatively low completeness of data collection (0.947 for θ_max = 75°) is a result of the blind region of the low-temperature apparatus. The discrimination of the COO^- against the NO₂ groups was based on the displacement parameters of the C and N atoms. This assignment is rationalized by the longer C—O distances, 1.236 (2) and 1.264 (2) Å, than the nitro N—O distances, 1.218 (2)–1.230 (2) Å. It is reasonable that the carboxylate O atoms (O3 and O4) are both hydrogen-bond acceptors of the ammonium N—H bonds. The hydroxyl and ammonium H atoms were located from difference syntheses and refined isotropically. The O—H bond lengths are 0.88 (3)–0.99 (3) Å, and the N—H lengths 0.93 (2)–0.93 (3) Å. The other H atoms were positioned geometrically and fixed with U_iso(H) = 1.2U_eq(parent atom).

Computing details

Data collection: WinAFC Diffractometer Control Software (Rigaku, 1999); cell refinement: WinAFC Diffractometer Control Software; data reduction: TEXSAN (Molecular Structure Corporation, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: TEXSAN.

Figures

	Fig. 1. The molecular structure of (I), with displacement ellipsoids at the 50% probability level. The broken lines indicate hydrogen bonds.
	Fig. 2. The projection of the crystal structure of (I) along c.

(I)

Crystal data

C8H12NO2^+·C7H3N2O6^−	Z = 2
Mr = 365.30	F(000) = 380
Triclinic, P1	Dx = 1.569 Mg m^−3
a = 11.392 (1) Å	Cu Kα radiation, λ = 1.5418 Å
b = 11.644 (1) Å	Cell parameters from 25 reflections
c = 6.7552 (3) Å	θ = 25.4–29.0°
α = 103.233 (6)°	µ = 1.12 mm^−1
β = 97.756 (7)°	T = 250 K
γ = 113.585 (8)°	Plate, orange
V = 773.2 (1) Å^3	0.3 × 0.25 × 0.1 mm

Data collection

Rigaku AFC-7R diffractometer	Rint = 0.076
θ–2θ scans	θmax = 75.0°, θmin = 2.5°
Absorption correction: integration (Coppens et al., 1965)	h = −14→14
Tmin = 0.740, Tmax = 0.903	k = −14→14
3648 measured reflections	l = 0→8
3025 independent reflections	3 standard reflections every 150 reflections
2625 reflections with I > 2σ(I)	intensity decay: 3.0%

Refinement

Refinement on F^2	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.037	w = 1/[σ^2(Fo^2) + (0.0614P)^2 + 0.2307P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.118	(Δ/σ)max = 0.001
S = 1.12	Δρmax = 0.27 e Å^−3
3025 reflections	Δρmin = −0.19 e Å^−3
256 parameters

Special details

Refinement. Refinement was based on F² against all reflections. The weighted R-factor (wR) and goodness of fit (S) were based on F², and conventional R-factor (R) was calculated on F, with F set to zero for negative F². The threshold expression of I > 2σ(I) was used only for calculating R-factor(gt).

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
O1	−0.3080 (1)	0.1960 (1)	0.1593 (2)	0.0449 (3)
O2	−0.0491 (1)	0.2788 (1)	0.2166 (2)	0.0410 (3)
O3	0.3986 (1)	0.5884 (1)	0.3146 (2)	0.0410 (3)
O4	0.2038 (1)	0.4129 (1)	0.2281 (2)	0.0448 (3)
O5	−0.1896 (1)	0.4887 (1)	0.2509 (3)	0.0584 (4)
O6	−0.1681 (1)	0.6869 (1)	0.3573 (2)	0.0511 (3)
O7	0.2329 (1)	1.0469 (1)	0.3650 (2)	0.0459 (3)
O8	0.4112 (1)	1.0234 (1)	0.3615 (2)	0.0482 (3)
N9	−0.3903 (1)	−0.3153 (1)	−0.3327 (2)	0.0375 (3)
N10	−0.1240 (1)	0.6082 (1)	0.3012 (2)	0.0388 (3)
N11	0.2934 (1)	0.9797 (1)	0.3535 (2)	0.0339 (3)
C12	−0.3439 (1)	−0.0251 (2)	0.1123 (2)	0.0333 (3)
C13	−0.2589 (1)	0.1059 (2)	0.1500 (2)	0.0313 (3)
C14	−0.1228 (1)	0.1473 (1)	0.1793 (2)	0.0310 (3)
C15	−0.0734 (2)	0.0566 (2)	0.1741 (3)	0.0363 (3)
C16	−0.1601 (2)	−0.0761 (2)	0.1312 (3)	0.0374 (4)
C17	−0.2952 (2)	−0.1184 (2)	0.0994 (2)	0.0332 (3)
C18	−0.3895 (2)	−0.2632 (2)	0.0454 (3)	0.0421 (4)
C19	−0.4733 (2)	−0.3237 (2)	−0.1795 (3)	0.0423 (4)
C20	0.2764 (2)	0.5354 (2)	0.2743 (2)	0.0319 (3)
C21	0.2077 (1)	0.6246 (1)	0.2835 (2)	0.0300 (3)
C22	0.0737 (2)	0.5756 (1)	0.2740 (2)	0.0321 (3)
C23	0.0161 (1)	0.6606 (2)	0.2970 (2)	0.0315 (3)
C24	0.0852 (2)	0.7933 (1)	0.3241 (2)	0.0314 (3)
C25	0.2176 (2)	0.8385 (1)	0.3265 (2)	0.0301 (3)
C26	0.2814 (1)	0.7589 (1)	0.3106 (2)	0.0304 (3)
H1	−0.237 (3)	0.279 (3)	0.193 (4)	0.0883 (1)*
H2	0.034 (3)	0.306 (3)	0.214 (4)	0.07530 (10)*
H9A	−0.337 (2)	−0.228 (2)	−0.322 (3)	0.05061 (7)*
H9B	−0.335 (2)	−0.355 (2)	−0.312 (3)	0.04893 (7)*
H9C	−0.448 (2)	−0.359 (2)	−0.466 (3)	0.04571 (7)*
H12	−0.4361	−0.0520	0.0951	0.0399*
H15	0.0193	0.0843	0.1997	0.0435*
H16	−0.1258	−0.1387	0.1237	0.0449*
H18A	−0.4468	−0.2723	0.1369	0.0506*
H18B	−0.3392	−0.3096	0.0665	0.0506*
H19A	−0.5307	−0.4137	−0.2020	0.0508*
H19B	−0.5244	−0.2781	−0.2013	0.0508*
H22	0.0217	0.4843	0.2519	0.0385*
H24	0.0441	0.8504	0.3402	0.0376*
H26	0.3735	0.7946	0.3178	0.0365*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0348 (6)	0.0343 (6)	0.0658 (8)	0.0195 (5)	0.0113 (6)	0.0095 (6)
O2	0.0296 (6)	0.0288 (6)	0.0573 (7)	0.0096 (5)	0.0113 (5)	0.0066 (5)
O3	0.0290 (6)	0.0381 (6)	0.0555 (7)	0.0158 (5)	0.0076 (5)	0.0139 (5)
O4	0.0338 (6)	0.0282 (6)	0.0765 (9)	0.0168 (5)	0.0175 (6)	0.0164 (6)
O5	0.0342 (6)	0.0374 (7)	0.099 (1)	0.0115 (5)	0.0196 (7)	0.0193 (7)
O6	0.0432 (7)	0.0516 (8)	0.0785 (9)	0.0328 (6)	0.0235 (6)	0.0295 (7)
O7	0.0543 (7)	0.0287 (6)	0.0589 (8)	0.0217 (5)	0.0157 (6)	0.0150 (5)
O8	0.0351 (6)	0.0347 (6)	0.0636 (8)	0.0066 (5)	0.0004 (5)	0.0187 (6)
N9	0.0333 (7)	0.0245 (6)	0.0504 (9)	0.0129 (6)	0.0030 (6)	0.0084 (6)
N10	0.0322 (7)	0.0374 (7)	0.0516 (8)	0.0177 (6)	0.0106 (6)	0.0181 (6)
N11	0.0385 (7)	0.0255 (6)	0.0316 (7)	0.0109 (5)	0.0016 (5)	0.0084 (5)
C12	0.0275 (7)	0.0353 (8)	0.0360 (8)	0.0137 (6)	0.0085 (6)	0.0095 (6)
C13	0.0311 (7)	0.0326 (8)	0.0311 (7)	0.0172 (6)	0.0078 (6)	0.0063 (6)
C14	0.0301 (7)	0.0294 (7)	0.0286 (7)	0.0113 (6)	0.0066 (5)	0.0045 (6)
C15	0.0272 (7)	0.0387 (8)	0.0416 (9)	0.0155 (6)	0.0068 (6)	0.0099 (7)
C16	0.0375 (8)	0.0379 (8)	0.0441 (9)	0.0225 (7)	0.0106 (7)	0.0149 (7)
C17	0.0356 (8)	0.0324 (8)	0.0327 (8)	0.0148 (6)	0.0097 (6)	0.0123 (6)
C18	0.0401 (9)	0.0342 (8)	0.056 (1)	0.0160 (7)	0.0176 (8)	0.0195 (7)
C19	0.0258 (7)	0.0282 (8)	0.067 (1)	0.0104 (6)	0.0088 (7)	0.0091 (7)
C20	0.0304 (7)	0.0304 (7)	0.0370 (8)	0.0149 (6)	0.0094 (6)	0.0115 (6)
C21	0.0313 (7)	0.0282 (7)	0.0299 (7)	0.0143 (6)	0.0054 (6)	0.0078 (6)
C22	0.0317 (7)	0.0239 (7)	0.0382 (8)	0.0110 (6)	0.0066 (6)	0.0094 (6)
C23	0.0285 (7)	0.0323 (7)	0.0347 (8)	0.0143 (6)	0.0067 (6)	0.0114 (6)
C24	0.0371 (8)	0.0296 (7)	0.0307 (7)	0.0182 (6)	0.0064 (6)	0.0101 (6)
C25	0.0345 (7)	0.0238 (7)	0.0267 (7)	0.0101 (6)	0.0029 (5)	0.0068 (5)
C26	0.0289 (7)	0.0282 (7)	0.0313 (7)	0.0110 (6)	0.0049 (5)	0.0090 (6)

Geometric parameters (Å, º)

O1—C13	1.366 (3)	C15—C16	1.394 (2)
O1—H1	0.93 (3)	C15—H15	0.950
O2—C14	1.360 (2)	C16—C17	1.383 (2)
O2—H2	0.88 (3)	C16—H16	0.950
O3—C20	1.236 (2)	C17—C18	1.514 (2)
O4—C20	1.264 (2)	C18—C19	1.515 (3)
O5—N10	1.222 (2)	C18—H18A	0.950
O6—N10	1.223 (2)	C18—H18B	0.950
O7—N11	1.230 (2)	C19—H19A	0.950
O8—N11	1.218 (2)	C19—H19B	0.950
N9—C19	1.487 (3)	C20—C21	1.526 (3)
N9—H9A	0.93 (2)	C21—C22	1.386 (2)
N9—H9B	0.93 (3)	C21—C26	1.401 (2)
N9—H9C	0.93 (2)	C22—C23	1.382 (3)
N10—C23	1.470 (2)	C22—H22	0.950
N11—C25	1.472 (2)	C23—C24	1.378 (2)
C12—C13	1.380 (2)	C24—C25	1.380 (2)
C12—C17	1.396 (3)	C24—H24	0.950
C12—H12	0.950	C25—C26	1.384 (3)
C13—C14	1.396 (2)	C26—H26	0.950
C14—C15	1.378 (3)
C13—O1—H1	108 (2)	C17—C18—H18A	108.5
C14—O2—H2	117 (2)	C17—C18—H18B	108.5
C19—N9—H9A	111 (2)	C19—C18—H18A	108.5
C19—N9—H9B	112 (1)	C19—C18—H18B	108.5
C19—N9—H9C	107 (1)	H18A—C18—H18B	109.5
H9A—N9—H9B	108 (2)	N9—C19—C18	111.7 (1)
H9A—N9—H9C	110 (2)	N9—C19—H19A	108.9
H9B—N9—H9C	110 (2)	N9—C19—H19B	108.9
O5—N10—O6	123.6 (1)	C18—C19—H19A	108.9
O5—N10—C23	118.3 (2)	C18—C19—H19B	108.9
O6—N10—C23	118.1 (1)	H19A—C19—H19B	109.5
O7—N11—O8	123.7 (1)	O3—C20—O4	125.0 (2)
O7—N11—C25	117.5 (1)	O3—C20—C21	117.6 (1)
O8—N11—C25	118.9 (2)	O4—C20—C21	117.4 (1)
C13—C12—C17	120.4 (1)	C20—C21—C22	120.9 (1)
C13—C12—H12	119.8	C20—C21—C26	119.9 (1)
C17—C12—H12	119.8	C22—C21—C26	119.2 (2)
O1—C13—C12	119.8 (1)	C21—C22—C23	119.5 (1)
O1—C13—C14	119.7 (1)	C21—C22—H22	120.3
C12—C13—C14	120.5 (2)	C23—C22—H22	120.2
O2—C14—C13	115.1 (2)	N10—C23—C22	118.5 (1)
O2—C14—C15	125.4 (1)	N10—C23—C24	118.4 (2)
C13—C14—C15	119.5 (1)	C22—C23—C24	123.0 (1)
C14—C15—C16	119.7 (2)	C23—C24—C25	116.2 (2)
C14—C15—H15	120.2	C23—C24—H24	121.9
C16—C15—H15	120.1	C25—C24—H24	121.9
C15—C16—C17	121.2 (2)	N11—C25—C24	117.2 (2)
C15—C16—H16	119.4	N11—C25—C26	119.4 (1)
C17—C16—H16	119.4	C24—C25—C26	123.3 (1)
C12—C17—C16	118.6 (1)	C21—C26—C25	118.7 (1)
C12—C17—C18	120.2 (1)	C21—C26—H26	120.7
C16—C17—C18	121.1 (2)	C25—C26—H26	120.6
C17—C18—C19	113.3 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2	0.93 (3)	2.13 (4)	2.650 (2)	114 (3)
O1—H1···O5	0.93 (3)	2.20 (3)	2.991 (2)	142 (3)
O2—H2···O4	0.88 (3)	1.81 (3)	2.652 (2)	161 (3)
N9—H9C···O3^i	0.93 (2)	1.91 (2)	2.791 (2)	157 (2)
N9—H9B···O4^ii	0.93 (3)	1.94 (3)	2.863 (2)	171 (2)
N9—H9A···O7^iii	0.93 (2)	2.08 (2)	2.994 (2)	168 (2)

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