In the crystal structure of the title salt, C
10H
16NO
2+·C
7H
3N
2O
6−, the cations adopt a dimer structure, through a head-to-tail hydrogen-bond between the dimethoxy and the ammonium groups. The cations are further connected to the anions by N—H
O hydrogen bonds, forming a three-dimensional network.
Supporting information
CCDC reference: 185811
Key indicators
- Single-crystal X-ray study
- T = 250 K
- Mean (C-C) = 0.003 Å
- R factor = 0.044
- wR factor = 0.125
- Data-to-parameter ratio = 12.6
checkCIF results
No syntax errors found
ADDSYM reports no extra symmetry
Alert Level B:
REFLT_03
From the CIF: _diffrn_reflns_theta_max 75.00
From the CIF: _reflns_number_total 3362
TEST2: Reflns within _diffrn_reflns_theta_max
Count of symmetry unique reflns 3803
Completeness (_total/calc) 88.40%
Alert B: < 90% complete (theta max?)
| Author response: Please see _publ_section_exptl_refinement
|
Alert Level C:
PLAT_353 Alert C Long N-H Bond (0.87A) N(9) - H(9A) = 1.01 Ang.
0 Alert Level A = Potentially serious problem
1 Alert Level B = Potential problem
1 Alert Level C = Please check
Crystals of (I) were grown by slow evaporation from a methanol solution of a
mixture of 2-(3,4-dimethoxyphenyl)ethylamine and 3,5-dinitrobenzoic acid (1:1)
The relatively low completeness of data collection (0.884 for θmax = 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, 1.243 (2) and 1.245 (2) Å, than the nitro N—O
distances, 1.214 (2)–1.220 (2) Å. It is reasonable that the carboxylato O
atoms (O3 and O4) are both hydrogen-bond acceptors of the ammonium N—H
bonds. The ammonium H atoms were located from difference syntheses and refined
isotropically. The N—H bond lengths are 0.88 (2)–1.01 (2) Å. The other H
atoms were positioned geometrically and fixed with Uiso(H) =
1.2Ueq(parent atom).
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.
Crystal data top
C10H16NO2+·C7H3N2O6− | Z = 2 |
Mr = 393.35 | F(000) = 412 |
Triclinic, P1 | Dx = 1.418 Mg m−3 |
a = 10.0546 (9) Å | Cu Kα radiation, λ = 1.5418 Å |
b = 10.9344 (13) Å | Cell parameters from 25 reflections |
c = 9.0112 (14) Å | θ = 25.2–29.4° |
α = 106.451 (10)° | µ = 0.98 mm−1 |
β = 101.240 (9)° | T = 250 K |
γ = 94.890 (8)° | Block, yellow |
V = 921.5 (2) Å3 | 0.5 × 0.4 × 0.4 mm |
Data collection top
Rigaku AFC-7R diffractometer | Rint = 0.063 |
θ–2θ scans | θmax = 75.0°, θmin = 2.5° |
Absorption correction: integration (Coppens et al., 1965) | h = −12→0 |
Tmin = 0.582, Tmax = 0.741 | k = −13→13 |
4022 measured reflections | l = −11→11 |
3362 independent reflections | 3 standard reflections every 150 reflections |
3229 reflections with I > 2σ(I) | intensity decay: 1.0% |
Refinement top
Refinement on F2 | w = 1/[σ2(Fo2) + (0.0606P)2 + 0.3459P] where P = (Fo2 + 2Fc2)/3 |
R[F2 > 2σ(F2)] = 0.044 | (Δ/σ)max = 0.001 |
wR(F2) = 0.125 | Δρmax = 0.22 e Å−3 |
S = 1.11 | Δρmin = −0.25 e Å−3 |
3362 reflections | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
266 parameters | Extinction coefficient: 0.0042 (7) |
H atoms treated by a mixture of independent and constrained refinement | |
Crystal data top
C10H16NO2+·C7H3N2O6− | γ = 94.890 (8)° |
Mr = 393.35 | V = 921.5 (2) Å3 |
Triclinic, P1 | Z = 2 |
a = 10.0546 (9) Å | Cu Kα radiation |
b = 10.9344 (13) Å | µ = 0.98 mm−1 |
c = 9.0112 (14) Å | T = 250 K |
α = 106.451 (10)° | 0.5 × 0.4 × 0.4 mm |
β = 101.240 (9)° | |
Data collection top
Rigaku AFC-7R diffractometer | 3229 reflections with I > 2σ(I) |
Absorption correction: integration (Coppens et al., 1965) | Rint = 0.063 |
Tmin = 0.582, Tmax = 0.741 | 3 standard reflections every 150 reflections |
4022 measured reflections | intensity decay: 1.0% |
3362 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.044 | 266 parameters |
wR(F2) = 0.125 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.11 | Δρmax = 0.22 e Å−3 |
3362 reflections | Δρmin = −0.25 e Å−3 |
Special details top
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 (Å2) top | x | y | z | Uiso*/Ueq | |
O1 | 0.4623 (1) | 0.8037 (1) | 0.4684 (1) | 0.0435 (3) | |
O2 | 0.2562 (1) | 0.8307 (1) | 0.2682 (1) | 0.0489 (3) | |
O3 | −0.2269 (1) | 0.4623 (1) | 0.0237 (1) | 0.0562 (4) | |
O4 | −0.3043 (1) | 0.5755 (2) | 0.2288 (2) | 0.0663 (4) | |
O5 | 0.0273 (2) | 0.8190 (2) | 0.7185 (2) | 0.0721 (4) | |
O6 | 0.2259 (2) | 0.7610 (2) | 0.7702 (2) | 0.0637 (4) | |
O7 | 0.3885 (1) | 0.4924 (2) | 0.3193 (2) | 0.0641 (4) | |
O8 | 0.2317 (2) | 0.3369 (2) | 0.1685 (2) | 0.0702 (4) | |
N9 | 0.5257 (1) | 1.3139 (1) | 0.8672 (2) | 0.0420 (3) | |
N10 | 0.1160 (2) | 0.7554 (1) | 0.6806 (2) | 0.0462 (4) | |
N11 | 0.2688 (2) | 0.4435 (2) | 0.2643 (2) | 0.0470 (4) | |
C12 | 0.5666 (2) | 0.7712 (2) | 0.5762 (2) | 0.0499 (4) | |
C13 | 0.1408 (2) | 0.8378 (2) | 0.1529 (2) | 0.0627 (6) | |
C14 | 0.4144 (2) | 0.9718 (2) | 0.6864 (2) | 0.0404 (4) | |
C15 | 0.3864 (2) | 0.8955 (1) | 0.5301 (2) | 0.0356 (3) | |
C16 | 0.2725 (2) | 0.9086 (2) | 0.4207 (2) | 0.0378 (3) | |
C17 | 0.1878 (2) | 0.9965 (2) | 0.4723 (2) | 0.0445 (4) | |
C18 | 0.2181 (2) | 1.0732 (2) | 0.6301 (2) | 0.0463 (4) | |
C19 | 0.3305 (2) | 1.0631 (2) | 0.7383 (2) | 0.0424 (4) | |
C20 | 0.3617 (2) | 1.1486 (2) | 0.9092 (2) | 0.0553 (5) | |
C21 | 0.5020 (2) | 1.2319 (2) | 0.9674 (2) | 0.0509 (4) | |
C22 | −0.2133 (2) | 0.5296 (2) | 0.1642 (2) | 0.0412 (4) | |
C23 | −0.0695 (2) | 0.5569 (1) | 0.2705 (2) | 0.0346 (3) | |
C24 | −0.0415 (2) | 0.6436 (2) | 0.4225 (2) | 0.0362 (3) | |
C25 | 0.0887 (2) | 0.6651 (1) | 0.5181 (2) | 0.0364 (3) | |
C26 | 0.1936 (2) | 0.6023 (2) | 0.4697 (2) | 0.0387 (4) | |
C27 | 0.1618 (2) | 0.5163 (2) | 0.3185 (2) | 0.0369 (3) | |
C28 | 0.0335 (2) | 0.4923 (2) | 0.2173 (2) | 0.0362 (3) | |
H9A | 0.449 (2) | 1.366 (2) | 0.849 (2) | 0.06064 (7)* | |
H9B | 0.538 (2) | 1.269 (2) | 0.774 (2) | 0.04285 (6)* | |
H9C | 0.612 (2) | 1.372 (2) | 0.918 (3) | 0.06175 (8)* | |
H12A | 0.6342 | 0.8446 | 0.6309 | 0.0599* | |
H12B | 0.5272 | 0.7433 | 0.6511 | 0.0599* | |
H12C | 0.6080 | 0.7037 | 0.5191 | 0.0599* | |
H13A | 0.1454 | 0.9225 | 0.1447 | 0.0755* | |
H13B | 0.1399 | 0.7781 | 0.0530 | 0.0755* | |
H13C | 0.0589 | 0.8170 | 0.1849 | 0.0755* | |
H14 | 0.4915 | 0.9622 | 0.7598 | 0.0484* | |
H17 | 0.1090 | 1.0047 | 0.4000 | 0.0534* | |
H18 | 0.1597 | 1.1340 | 0.6641 | 0.0555* | |
H20A | 0.2941 | 1.2042 | 0.9195 | 0.0664* | |
H20B | 0.3561 | 1.0950 | 0.9749 | 0.0664* | |
H21A | 0.5094 | 1.2858 | 1.0727 | 0.0611* | |
H21B | 0.5704 | 1.1769 | 0.9674 | 0.0611* | |
H24 | −0.1114 | 0.6879 | 0.4604 | 0.0434* | |
H26 | 0.2827 | 0.6177 | 0.5369 | 0.0464* | |
H28 | 0.0162 | 0.4327 | 0.1134 | 0.0433* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.0509 (7) | 0.0421 (6) | 0.0372 (6) | 0.0214 (5) | 0.0092 (5) | 0.0082 (5) |
O2 | 0.0501 (7) | 0.0540 (7) | 0.0336 (6) | 0.0173 (6) | 0.0036 (5) | 0.0006 (5) |
O3 | 0.0414 (7) | 0.0750 (9) | 0.0392 (7) | 0.0012 (6) | −0.0027 (5) | 0.0075 (6) |
O4 | 0.0384 (7) | 0.083 (1) | 0.0647 (9) | 0.0252 (7) | 0.0023 (6) | 0.0034 (7) |
O5 | 0.082 (1) | 0.0706 (10) | 0.0495 (8) | 0.0257 (8) | 0.0147 (7) | −0.0073 (7) |
O6 | 0.0628 (9) | 0.0746 (9) | 0.0370 (7) | −0.0004 (7) | −0.0068 (6) | 0.0065 (6) |
O7 | 0.0357 (7) | 0.0718 (9) | 0.091 (1) | 0.0185 (6) | 0.0177 (7) | 0.0293 (8) |
O8 | 0.0677 (9) | 0.0612 (9) | 0.0731 (10) | 0.0268 (7) | 0.0217 (8) | −0.0018 (8) |
N9 | 0.0357 (7) | 0.0467 (8) | 0.0328 (7) | 0.0115 (6) | 0.0041 (5) | −0.0036 (6) |
N10 | 0.0559 (9) | 0.0434 (8) | 0.0337 (7) | 0.0015 (7) | 0.0067 (6) | 0.0072 (6) |
N11 | 0.0452 (9) | 0.0502 (9) | 0.0518 (8) | 0.0199 (7) | 0.0168 (7) | 0.0179 (7) |
C12 | 0.0481 (10) | 0.0499 (10) | 0.052 (1) | 0.0181 (8) | 0.0057 (8) | 0.0165 (8) |
C13 | 0.059 (1) | 0.076 (1) | 0.0395 (9) | 0.019 (1) | −0.0029 (8) | 0.0041 (9) |
C14 | 0.0421 (9) | 0.0436 (9) | 0.0339 (8) | 0.0070 (7) | 0.0086 (6) | 0.0094 (7) |
C15 | 0.0402 (8) | 0.0322 (7) | 0.0359 (8) | 0.0090 (6) | 0.0128 (6) | 0.0089 (6) |
C16 | 0.0408 (8) | 0.0359 (8) | 0.0346 (8) | 0.0070 (6) | 0.0100 (6) | 0.0065 (6) |
C17 | 0.0394 (9) | 0.0450 (9) | 0.0461 (9) | 0.0123 (7) | 0.0080 (7) | 0.0089 (7) |
C18 | 0.0433 (9) | 0.0428 (9) | 0.0511 (10) | 0.0125 (7) | 0.0187 (7) | 0.0046 (7) |
C19 | 0.0455 (9) | 0.0411 (9) | 0.0373 (8) | 0.0033 (7) | 0.0156 (7) | 0.0035 (7) |
C20 | 0.060 (1) | 0.059 (1) | 0.0406 (9) | 0.0054 (9) | 0.0203 (8) | 0.0005 (8) |
C21 | 0.054 (1) | 0.058 (1) | 0.0302 (8) | 0.0120 (8) | 0.0050 (7) | −0.0005 (7) |
C22 | 0.0356 (8) | 0.0446 (9) | 0.0410 (9) | 0.0071 (7) | 0.0018 (7) | 0.0138 (7) |
C23 | 0.0336 (8) | 0.0361 (8) | 0.0338 (8) | 0.0065 (6) | 0.0058 (6) | 0.0112 (6) |
C24 | 0.0365 (8) | 0.0355 (8) | 0.0377 (8) | 0.0097 (6) | 0.0104 (6) | 0.0105 (6) |
C25 | 0.0415 (8) | 0.0354 (8) | 0.0298 (7) | 0.0036 (6) | 0.0059 (6) | 0.0082 (6) |
C26 | 0.0324 (8) | 0.0435 (9) | 0.0391 (8) | 0.0034 (6) | 0.0029 (6) | 0.0150 (7) |
C27 | 0.0340 (8) | 0.0401 (8) | 0.0399 (8) | 0.0109 (6) | 0.0112 (6) | 0.0139 (7) |
C28 | 0.0390 (8) | 0.0361 (8) | 0.0316 (7) | 0.0063 (6) | 0.0078 (6) | 0.0073 (6) |
Geometric parameters (Å, º) top
O1—C12 | 1.426 (2) | C14—H14 | 0.950 |
O1—C15 | 1.370 (2) | C15—C16 | 1.404 (2) |
O2—C13 | 1.422 (2) | C16—C17 | 1.381 (3) |
O2—C16 | 1.367 (2) | C17—C18 | 1.389 (2) |
O3—C22 | 1.245 (2) | C17—H17 | 0.950 |
O4—C22 | 1.243 (2) | C18—C19 | 1.376 (3) |
O5—N10 | 1.219 (2) | C18—H18 | 0.950 |
O6—N10 | 1.220 (2) | C19—C20 | 1.513 (2) |
O7—N11 | 1.220 (2) | C20—C21 | 1.522 (3) |
O8—N11 | 1.214 (2) | C20—H20A | 0.950 |
N9—C21 | 1.478 (3) | C20—H20B | 0.950 |
N9—H9A | 1.01 (2) | C21—H21A | 0.950 |
N9—H9B | 0.88 (2) | C21—H21B | 0.951 |
N9—H9C | 0.97 (2) | C22—C23 | 1.524 (2) |
N10—C25 | 1.474 (2) | C23—C24 | 1.387 (2) |
N11—C27 | 1.469 (2) | C23—C28 | 1.388 (2) |
C12—H12A | 0.950 | C24—C25 | 1.380 (2) |
C12—H12B | 0.951 | C24—H24 | 0.950 |
C12—H12C | 0.951 | C25—C26 | 1.381 (2) |
C13—H13A | 0.948 | C26—C27 | 1.377 (2) |
C13—H13B | 0.948 | C26—H26 | 0.951 |
C13—H13C | 0.954 | C27—C28 | 1.384 (2) |
C14—C15 | 1.378 (2) | C28—H28 | 0.951 |
C14—C19 | 1.400 (3) | | |
| | | |
C12—O1—C15 | 118.0 (1) | C17—C18—H18 | 119.1 |
C13—O2—C16 | 117.7 (1) | C19—C18—H18 | 119.2 |
C21—N9—H9A | 113 (1) | C14—C19—C18 | 118.4 (1) |
C21—N9—H9B | 112 (2) | C14—C19—C20 | 121.2 (2) |
C21—N9—H9C | 109 (2) | C18—C19—C20 | 120.5 (2) |
H9A—N9—H9B | 108 (2) | C19—C20—C21 | 115.0 (2) |
H9A—N9—H9C | 109 (2) | C19—C20—H20A | 108.0 |
H9B—N9—H9C | 105 (2) | C19—C20—H20B | 108.1 |
O5—N10—O6 | 123.7 (1) | C21—C20—H20A | 108.1 |
O5—N10—C25 | 118.3 (1) | C21—C20—H20B | 108.1 |
O6—N10—C25 | 117.9 (1) | H20A—C20—H20B | 109.5 |
O7—N11—O8 | 124.1 (2) | N9—C21—C20 | 112.9 (1) |
O7—N11—C27 | 118.5 (1) | N9—C21—H21A | 108.6 |
O8—N11—C27 | 117.4 (1) | N9—C21—H21B | 108.6 |
O1—C12—H12A | 109.6 | C20—C21—H21A | 108.6 |
O1—C12—H12B | 109.5 | C20—C21—H21B | 108.6 |
O1—C12—H12C | 109.6 | H21A—C21—H21B | 109.4 |
H12A—C12—H12B | 109.3 | O3—C22—O4 | 127.4 (1) |
H12A—C12—H12C | 109.4 | O3—C22—C23 | 116.5 (1) |
H12B—C12—H12C | 109.3 | O4—C22—C23 | 116.1 (1) |
O2—C13—H13A | 109.7 | C22—C23—C24 | 120.3 (1) |
O2—C13—H13B | 109.6 | C22—C23—C28 | 120.2 (1) |
O2—C13—H13C | 109.2 | C24—C23—C28 | 119.6 (1) |
H13A—C13—H13B | 109.8 | C23—C24—C25 | 119.4 (1) |
H13A—C13—H13C | 109.3 | C23—C24—H24 | 120.3 |
H13B—C13—H13C | 109.2 | C25—C24—H24 | 120.3 |
C15—C14—C19 | 120.8 (1) | N10—C25—C24 | 118.8 (1) |
C15—C14—H14 | 119.6 | N10—C25—C26 | 118.5 (1) |
C19—C14—H14 | 119.6 | C24—C25—C26 | 122.7 (1) |
O1—C15—C14 | 125.0 (1) | C25—C26—C27 | 116.3 (1) |
O1—C15—C16 | 115.0 (1) | C25—C26—H26 | 121.9 |
C14—C15—C16 | 120.1 (2) | C27—C26—H26 | 121.9 |
O2—C16—C15 | 115.3 (1) | N11—C27—C26 | 118.1 (1) |
O2—C16—C17 | 125.4 (1) | N11—C27—C28 | 118.5 (1) |
C15—C16—C17 | 119.3 (1) | C26—C27—C28 | 123.3 (2) |
C16—C17—C18 | 119.8 (2) | C23—C28—C27 | 118.7 (1) |
C16—C17—H17 | 120.1 | C23—C28—H28 | 120.7 |
C18—C17—H17 | 120.1 | C27—C28—H28 | 120.6 |
C17—C18—C19 | 121.6 (2) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N9—H9A···O4i | 1.01 (2) | 1.74 (2) | 2.733 (2) | 165 (2) |
N9—H9B···O1ii | 0.88 (2) | 2.10 (2) | 2.963 (2) | 164 (2) |
N9—H9B···O2ii | 0.88 (2) | 2.47 (2) | 3.056 (2) | 125 (2) |
N9—H9C···O3iii | 0.97 (2) | 1.76 (2) | 2.731 (2) | 172 (2) |
Symmetry codes: (i) −x, −y+2, −z+1; (ii) −x+1, −y+2, −z+1; (iii) x+1, y+1, z+1. |
Experimental details
Crystal data |
Chemical formula | C10H16NO2+·C7H3N2O6− |
Mr | 393.35 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 250 |
a, b, c (Å) | 10.0546 (9), 10.9344 (13), 9.0112 (14) |
α, β, γ (°) | 106.451 (10), 101.240 (9), 94.890 (8) |
V (Å3) | 921.5 (2) |
Z | 2 |
Radiation type | Cu Kα |
µ (mm−1) | 0.98 |
Crystal size (mm) | 0.5 × 0.4 × 0.4 |
|
Data collection |
Diffractometer | Rigaku AFC-7R diffractometer |
Absorption correction | Integration (Coppens et al., 1965) |
Tmin, Tmax | 0.582, 0.741 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4022, 3362, 3229 |
Rint | 0.063 |
(sin θ/λ)max (Å−1) | 0.626 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.044, 0.125, 1.11 |
No. of reflections | 3362 |
No. of parameters | 266 |
No. of restraints | ? |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.22, −0.25 |
Selected geometric parameters (Å, º) topO3—C22 | 1.245 (2) | O6—N10 | 1.220 (2) |
O4—C22 | 1.243 (2) | O7—N11 | 1.220 (2) |
O5—N10 | 1.219 (2) | O8—N11 | 1.214 (2) |
| | | |
O5—N10—O6 | 123.7 (1) | O3—C22—O4 | 127.4 (1) |
O7—N11—O8 | 124.1 (2) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N9—H9A···O4i | 1.01 (2) | 1.74 (2) | 2.733 (2) | 165 (2) |
N9—H9B···O1ii | 0.88 (2) | 2.10 (2) | 2.963 (2) | 164 (2) |
N9—H9B···O2ii | 0.88 (2) | 2.47 (2) | 3.056 (2) | 125 (2) |
N9—H9C···O3iii | 0.97 (2) | 1.76 (2) | 2.731 (2) | 172 (2) |
Symmetry codes: (i) −x, −y+2, −z+1; (ii) −x+1, −y+2, −z+1; (iii) x+1, y+1, z+1. |
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 carboxylate anions (Fig. 1 and Table 1). In Fig. 1, the benzene rings of the cation (C14–C19) and that of the anion (C23–C28) are nearly parallel, and the dihedral angle is 18.52 (6)°. One of the nitro groups (N10) of the anion is above the benzene ring of the cation, and methoxy O2 atom of the cation is below the centre of the benzene ring of the anion. A close contact is observed for C14···O6, 3.205 (3) Å. The cations adopt a dimer structure through a head-to-tail hydrogen-bond between the dimethoxy and ammonium groups (Fig. 2 and Table 2). The cations are further connected to the anions by N—H···O hydrogen bonds involving the carboxylate moiety, forming a three-dimensional network.