The crystal structure of a second monoclinic polymorph of anilinium picrate (C
6H
8N
+·C
6H
2N
3O
7−) shows a three-dimensional hydrogen-bonded polymer with strong primary interspecies interactions involving the proximal phenolate and adjacent nitro group O-atom acceptors and separate anilinium H-atom donors in two cyclic
(6) associations. Other nitro-O–anilinium-H hydrogen bonds together with heteromolecular π–π interactions are also present.
Supporting information
CCDC reference: 253006
Key indicators
- Single-crystal X-ray study
- T = 298 K
- Mean (C-C) = 0.005 Å
- R factor = 0.053
- wR factor = 0.209
- Data-to-parameter ratio = 14.3
checkCIF/PLATON results
No syntax errors found
Alert level C
PLAT026_ALERT_3_C Ratio Observed / Unique Reflections too Low .... 45 Perc.
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ?
PLAT340_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ... 5
0 ALERT level A = In general: serious problem
0 ALERT level B = Potentially serious problem
3 ALERT level C = Check and explain
0 ALERT level G = General alerts; check
1 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
0 ALERT type 4 Improvement, methodology, query or suggestion
Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure
Corporation, 1999); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: TEXSAN for Windows (Molecular Structure Corporation, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON for Windows (Spek, 1999); software used to prepare material for publication: PLATON for Windows.
anilinium 2,4,6-trinitrophenate
top
Crystal data top
C6H8N+·C6H2N3O7− | F(000) = 664 |
Mr = 322.24 | Dx = 1.554 Mg m−3 |
Monoclinic, P21/c | Melting point: 452.1–454.5 (dec.) K |
Hall symbol: -P 2ybc | Mo Kα radiation, λ = 0.71069 Å |
a = 13.064 (7) Å | Cell parameters from 25 reflections |
b = 7.1007 (17) Å | θ = 13.0–17.0° |
c = 14.863 (8) Å | µ = 0.13 mm−1 |
β = 92.96 (3)° | T = 298 K |
V = 1376.9 (11) Å3 | Block, yellow–brown |
Z = 4 | 0.40 × 0.34 × 0.30 mm |
Data collection top
Rigaku AFC 7R diffractometer | Rint = 0.023 |
Radiation source: Rigaku rotating anode | θmax = 27.5°, θmin = 2.7° |
Graphite monochromator | h = −16→16 |
ω–2θ scans | k = −9→0 |
3420 measured reflections | l = −7→19 |
3160 independent reflections | 3 standard reflections every 150 min |
1417 reflections with I > 2σ(I) | intensity decay: 0.6% |
Refinement top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.053 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.209 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.92 | w = 1/[σ2(Fo2) + (0.1P)2 + 1.0338P] where P = (Fo2 + 2Fc2)/3 |
3160 reflections | (Δ/σ)max = 0.023 |
221 parameters | Δρmax = 0.24 e Å−3 |
0 restraints | Δρmin = −0.27 e Å−3 |
Special details top
Geometry. Bond distances, angles etc. have been calculated using the rounded
fractional coordinates. All e.s.d.'s are estimated from the variances of the
(full) variance-covariance matrix. The cell e.s.d.'s are taken into account in
the estimation of distances, angles and torsion angles |
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 (Å2) top | x | y | z | Uiso*/Ueq | |
O1 | 0.61340 (18) | −0.1336 (4) | 0.03204 (16) | 0.0420 (9) | |
O21 | 0.7103 (2) | −0.1255 (5) | −0.12369 (18) | 0.0621 (13) | |
O22 | 0.8459 (3) | −0.2973 (5) | −0.1071 (2) | 0.0734 (14) | |
O41 | 1.0813 (2) | −0.1194 (6) | 0.1366 (2) | 0.0738 (13) | |
O42 | 1.0232 (2) | −0.0121 (7) | 0.2594 (2) | 0.0835 (16) | |
O61 | 0.6681 (2) | 0.0615 (5) | 0.29062 (18) | 0.0566 (10) | |
O62 | 0.5608 (2) | −0.0869 (6) | 0.2035 (2) | 0.0758 (13) | |
N2 | 0.7816 (3) | −0.1928 (5) | −0.0776 (2) | 0.0473 (11) | |
N4 | 1.0108 (3) | −0.0707 (6) | 0.1828 (2) | 0.0554 (13) | |
N6 | 0.6466 (2) | −0.0278 (5) | 0.2216 (2) | 0.0407 (10) | |
C1 | 0.7022 (3) | −0.1152 (5) | 0.0678 (2) | 0.0304 (11) | |
C2 | 0.7925 (3) | −0.1445 (5) | 0.0176 (2) | 0.0349 (11) | |
C3 | 0.8910 (3) | −0.1356 (6) | 0.0543 (2) | 0.0375 (11) | |
C4 | 0.9065 (3) | −0.0822 (6) | 0.1434 (2) | 0.0390 (13) | |
C5 | 0.8261 (3) | −0.0435 (6) | 0.1960 (2) | 0.0350 (11) | |
C6 | 0.7272 (3) | −0.0636 (5) | 0.1603 (2) | 0.0313 (10) | |
N11 | 0.5818 (2) | 0.2897 (5) | 0.4279 (2) | 0.0434 (10) | |
C11 | 0.6347 (3) | 0.1973 (6) | 0.5058 (2) | 0.0370 (11) | |
C21 | 0.5804 (3) | 0.1503 (6) | 0.5790 (3) | 0.0426 (14) | |
C31 | 0.6333 (3) | 0.0723 (6) | 0.6534 (3) | 0.0458 (14) | |
C41 | 0.7385 (3) | 0.0503 (6) | 0.6544 (3) | 0.0484 (14) | |
C51 | 0.7914 (3) | 0.0986 (6) | 0.5800 (3) | 0.0459 (15) | |
C61 | 0.7392 (3) | 0.1715 (6) | 0.5045 (3) | 0.0406 (11) | |
H3 | 0.947500 | −0.165400 | 0.019100 | 0.0460* | |
H5 | 0.838100 | −0.002500 | 0.256500 | 0.0440* | |
H11A | 0.587 (5) | 0.213 (9) | 0.376 (4) | 0.090 (18)* | |
H11B | 0.614 (4) | 0.408 (8) | 0.414 (3) | 0.072 (17)* | |
H11C | 0.513 (5) | 0.301 (9) | 0.438 (4) | 0.086 (19)* | |
H21 | 0.508400 | 0.169800 | 0.578600 | 0.0520* | |
H31 | 0.596900 | 0.034400 | 0.704200 | 0.0570* | |
H41 | 0.774800 | 0.001800 | 0.706800 | 0.0600* | |
H51 | 0.863800 | 0.082400 | 0.580400 | 0.0560* | |
H61 | 0.774900 | 0.202900 | 0.452300 | 0.0500* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.0305 (13) | 0.0610 (18) | 0.0341 (14) | −0.0085 (13) | −0.0016 (10) | 0.0037 (13) |
O21 | 0.0572 (19) | 0.102 (3) | 0.0268 (14) | −0.0029 (19) | −0.0007 (13) | −0.0043 (16) |
O22 | 0.074 (2) | 0.090 (3) | 0.058 (2) | 0.008 (2) | 0.0207 (17) | −0.0298 (19) |
O41 | 0.0332 (15) | 0.117 (3) | 0.072 (2) | 0.0042 (18) | 0.0114 (15) | 0.003 (2) |
O42 | 0.0496 (19) | 0.144 (4) | 0.055 (2) | −0.006 (2) | −0.0161 (15) | −0.010 (2) |
O61 | 0.0520 (16) | 0.080 (2) | 0.0380 (15) | 0.0123 (16) | 0.0044 (13) | −0.0171 (16) |
O62 | 0.0373 (16) | 0.142 (3) | 0.0495 (18) | −0.021 (2) | 0.0152 (14) | −0.026 (2) |
N2 | 0.050 (2) | 0.062 (2) | 0.0306 (17) | −0.0100 (19) | 0.0088 (15) | −0.0105 (17) |
N4 | 0.0360 (18) | 0.082 (3) | 0.048 (2) | −0.0040 (19) | −0.0009 (16) | 0.007 (2) |
N6 | 0.0373 (17) | 0.055 (2) | 0.0298 (16) | 0.0044 (16) | 0.0024 (13) | −0.0021 (15) |
C1 | 0.0339 (18) | 0.0296 (19) | 0.0277 (18) | −0.0013 (16) | 0.0011 (14) | 0.0032 (15) |
C2 | 0.042 (2) | 0.040 (2) | 0.0230 (17) | −0.0045 (17) | 0.0033 (14) | −0.0016 (16) |
C3 | 0.0343 (19) | 0.043 (2) | 0.036 (2) | 0.0006 (17) | 0.0095 (15) | 0.0005 (17) |
C4 | 0.0267 (17) | 0.052 (3) | 0.038 (2) | −0.0016 (17) | −0.0021 (15) | 0.0044 (18) |
C5 | 0.0394 (19) | 0.042 (2) | 0.0235 (16) | −0.0017 (18) | 0.0007 (14) | 0.0026 (16) |
C6 | 0.0319 (17) | 0.035 (2) | 0.0271 (17) | 0.0021 (16) | 0.0038 (14) | 0.0005 (15) |
N11 | 0.0332 (16) | 0.060 (2) | 0.0369 (17) | 0.0078 (16) | 0.0016 (13) | −0.0073 (16) |
C11 | 0.0345 (19) | 0.037 (2) | 0.039 (2) | 0.0057 (17) | −0.0025 (15) | −0.0072 (17) |
C21 | 0.0322 (19) | 0.051 (3) | 0.045 (2) | 0.0019 (18) | 0.0050 (17) | −0.008 (2) |
C31 | 0.050 (2) | 0.051 (3) | 0.037 (2) | −0.004 (2) | 0.0071 (17) | −0.0020 (19) |
C41 | 0.048 (2) | 0.046 (3) | 0.050 (2) | 0.003 (2) | −0.0103 (19) | 0.000 (2) |
C51 | 0.0318 (19) | 0.046 (3) | 0.059 (3) | 0.0094 (18) | −0.0067 (18) | −0.009 (2) |
C61 | 0.0343 (19) | 0.043 (2) | 0.045 (2) | 0.0038 (17) | 0.0076 (17) | −0.0079 (19) |
Geometric parameters (Å, º) top
O1—C1 | 1.258 (5) | C3—C4 | 1.382 (4) |
O21—N2 | 1.224 (5) | C4—C5 | 1.369 (5) |
O22—N2 | 1.219 (5) | C5—C6 | 1.379 (5) |
O41—N4 | 1.227 (5) | C3—H3 | 0.9504 |
O42—N4 | 1.215 (5) | C5—H5 | 0.9504 |
O61—N6 | 1.226 (4) | C11—C61 | 1.379 (6) |
O62—N6 | 1.214 (4) | C11—C21 | 1.370 (6) |
N2—C2 | 1.456 (4) | C21—C31 | 1.389 (6) |
N4—C4 | 1.457 (5) | C31—C41 | 1.382 (6) |
N6—C6 | 1.450 (5) | C41—C51 | 1.377 (6) |
N11—C11 | 1.472 (5) | C51—C61 | 1.383 (6) |
N11—H11A | 0.95 (6) | C21—H21 | 0.9505 |
N11—H11C | 0.92 (7) | C31—H31 | 0.9517 |
N11—H11B | 0.97 (6) | C41—H41 | 0.9549 |
C1—C6 | 1.444 (4) | C51—H51 | 0.9525 |
C1—C2 | 1.443 (5) | C61—H61 | 0.9521 |
C2—C3 | 1.373 (5) | | |
| | | |
O21—N2—O22 | 123.7 (3) | N6—C6—C5 | 115.9 (3) |
O21—N2—C2 | 119.0 (3) | C1—C6—C5 | 123.7 (3) |
O22—N2—C2 | 117.3 (3) | N6—C6—C1 | 120.5 (3) |
O41—N4—O42 | 123.6 (4) | C4—C3—H3 | 120.59 |
O41—N4—C4 | 118.2 (3) | C2—C3—H3 | 120.64 |
O42—N4—C4 | 118.2 (3) | C4—C5—H5 | 120.51 |
O61—N6—O62 | 122.2 (3) | C6—C5—H5 | 120.09 |
O61—N6—C6 | 118.3 (3) | N11—C11—C21 | 119.5 (3) |
O62—N6—C6 | 119.5 (3) | N11—C11—C61 | 118.3 (3) |
H11B—N11—H11C | 113 (5) | C21—C11—C61 | 122.2 (4) |
H11A—N11—H11C | 107 (5) | C11—C21—C31 | 118.2 (4) |
C11—N11—H11B | 111 (3) | C21—C31—C41 | 120.5 (4) |
C11—N11—H11C | 109 (4) | C31—C41—C51 | 120.2 (4) |
C11—N11—H11A | 109 (4) | C41—C51—C61 | 119.9 (4) |
H11A—N11—H11B | 106 (5) | C11—C61—C51 | 119.0 (4) |
C2—C1—C6 | 112.2 (3) | C11—C21—H21 | 120.81 |
O1—C1—C2 | 121.8 (3) | C31—C21—H21 | 120.98 |
O1—C1—C6 | 126.0 (3) | C21—C31—H31 | 119.74 |
N2—C2—C1 | 119.7 (3) | C41—C31—H31 | 119.78 |
N2—C2—C3 | 116.1 (3) | C31—C41—H41 | 120.07 |
C1—C2—C3 | 124.2 (3) | C51—C41—H41 | 119.73 |
C2—C3—C4 | 118.8 (3) | C41—C51—H51 | 120.28 |
C3—C4—C5 | 121.6 (4) | C61—C51—H51 | 119.87 |
N4—C4—C3 | 119.2 (3) | C11—C61—H61 | 120.49 |
N4—C4—C5 | 119.2 (3) | C51—C61—H61 | 120.46 |
C4—C5—C6 | 119.4 (3) | | |
| | | |
O21—N2—C2—C1 | 34.6 (5) | O1—C1—C6—N6 | 0.1 (6) |
O21—N2—C2—C3 | −147.4 (4) | O1—C1—C6—C5 | −179.3 (4) |
O22—N2—C2—C1 | −146.4 (4) | C1—C2—C3—C4 | −4.9 (6) |
O22—N2—C2—C3 | 31.6 (5) | N2—C2—C3—C4 | 177.2 (4) |
O41—N4—C4—C3 | −4.1 (6) | C2—C3—C4—N4 | −179.5 (4) |
O41—N4—C4—C5 | 174.7 (4) | C2—C3—C4—C5 | 1.9 (6) |
O42—N4—C4—C3 | 175.4 (4) | N4—C4—C5—C6 | −176.7 (4) |
O42—N4—C4—C5 | −5.9 (6) | C3—C4—C5—C6 | 2.0 (6) |
O61—N6—C6—C1 | −161.2 (3) | C4—C5—C6—C1 | −3.1 (6) |
O61—N6—C6—C5 | 18.3 (5) | C4—C5—C6—N6 | 177.4 (4) |
O62—N6—C6—C1 | 19.1 (5) | N11—C11—C21—C31 | −176.7 (4) |
O62—N6—C6—C5 | −161.5 (4) | C21—C11—C61—C51 | −1.1 (6) |
O1—C1—C2—N2 | 1.3 (5) | C61—C11—C21—C31 | −0.7 (6) |
C2—C1—C6—C5 | 0.4 (5) | N11—C11—C61—C51 | 174.9 (4) |
C2—C1—C6—N6 | 179.9 (4) | C11—C21—C31—C41 | 2.6 (6) |
C6—C1—C2—C3 | 3.6 (5) | C21—C31—C41—C51 | −2.6 (7) |
O1—C1—C2—C3 | −176.6 (4) | C31—C41—C51—C61 | 0.8 (7) |
C6—C1—C2—N2 | −178.4 (3) | C41—C51—C61—C11 | 1.0 (6) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N11—H11A···O61 | 0.95 (6) | 2.01 (6) | 2.881 (5) | 152 (6) |
N11—H11B···O1i | 0.97 (6) | 2.38 (5) | 2.909 (5) | 114 (3) |
N11—H11B···O21i | 0.97 (6) | 2.09 (5) | 3.037 (5) | 167 (5) |
N11—H11C···O1ii | 0.92 (7) | 1.79 (7) | 2.704 (4) | 169 (6) |
N11—H11C···O62ii | 0.92 (7) | 2.40 (6) | 2.771 (4) | 104 (4) |
C5—H5···O22iii | 0.95 | 2.47 | 3.135 (5) | 127 |
C31—H31···O62iv | 0.95 | 2.56 | 3.394 (5) | 146 |
Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) −x+1, y+1/2, −z+1/2; (iii) x, −y−1/2, z+1/2; (iv) −x+1, −y, −z+1. |