Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807025408/dn2181sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807025408/dn2181Isup2.hkl |
CCDC reference: 654885
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.003 Å
- R factor = 0.037
- wR factor = 0.112
- Data-to-parameter ratio = 12.9
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for N1
Alert level G PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature 293 K PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature . 293 K
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 1 ALERT level C = Check and explain 2 ALERT level G = General alerts; check 2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 1 ALERT type 2 Indicator that the structure model may be wrong or deficient 0 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
For general background, see: Xiao et al. (2005); Yuan et al. (2006); Wang & Zhang (2006). For related structures, see: Hemissi et al. (2001); Perpétuo & Janczak (2004).
For related literature, see: Spek (2003).
An ethanolic 2,6-xylidinium solution (5 mmol, in 5 ml) was added to an aqueous HNO3 solution (0.5 M, 10 ml). The obtained solution is evaporated during several days in ambient condition until the formation of single crystals of the title compound (I).
All H atoms were positioned geometrically and treated as riding on their parent atoms, [N–H = 0.89, C–H =0.96 Å (CH3 ) with Uiso(H) = 1.5Ueq and C–H =0.96 Å (Ar–H), with Uiso(H) = 1.5Ueq]
Hybrid compounds are widely investigated due to their special relevance in fundamental sciences and in several applied fields such as biomolecular sciences, catalysis and nonlinear optics (Xiao et al., 2005, Yuan et al., 2006). These materials are generally rich in hydrogen bonds which are considered as the most effective tool for constructing sophisticated assemblies from discrete ionic or molecular building blocks due to its strength and directionality (Wang & Zhang, 2006). In this paper, we report the synthesis and structure of a new organic nitrate. Single-crystal X-ray diffraction study of the title compounds shows that the asymmetric unit corresponds to the formula unit (I) which is made of one NO3- anion and one 2,6-xylidinium cation (Fig. 1). As well as electrostatic and van der Walls forces, two types of hydrogen bonds (Table 1) participate to define the crystal packing. The first one, N–H···O bonds links ammonium groups and nitrate anions into infinite layers propagating in the (b, c) plane (Fig. 2, Table 1). The second H-bonds type, C–H···O bonds, identified by PLATON (Spek, 2003), connects the successive layers to form a three-dimensional network (Fig. 3, Table 1). It is noteworthy that two hydrogen atoms of the NH3 groups form bifurcated hydrogen bonds with the nitrate oxygen atoms. Bond lengths and angles observed in this structure agree well with those reported for nitrate or xylidinium compounds (Hemissi et al., 2001, Perpétuo & Janczak, 2004).
For general background, see: Xiao et al. (2005); Yuan et al. (2006); Wang & Zhang (2006). For related structures, see: Hemissi et al. (2001); Perpétuo & Janczak (2004).
For related literature, see: Spek (2003).
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, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
C8H12N+·NO3− | F(000) = 392 |
Mr = 184.20 | Dx = 1.367 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 25 reflections |
a = 7.891 (2) Å | θ = 8.3–9.7° |
b = 8.328 (3) Å | µ = 0.11 mm−1 |
c = 13.628 (2) Å | T = 293 K |
β = 91.47 (2)° | Parallelepiped, colourless |
V = 895.2 (4) Å3 | 0.20 × 0.19 × 0.17 mm |
Z = 4 |
Enraf–Nonius TurboCAD-4 diffractometer | Rint = 0.018 |
Radiation source: X-ray tube | θmax = 25.0°, θmin = 2.6° |
Graphite monochromator | h = −9→9 |
non–profiled ω scans | k = 0→9 |
3131 measured reflections | l = −16→16 |
1568 independent reflections | 2 standard reflections every 120 min |
1181 reflections with I > 2σ(I) | intensity decay: 5% |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.037 | H-atom parameters constrained |
wR(F2) = 0.112 | w = 1/[σ2(Fo2) + (0.0537P)2 + 0.2838P] where P = (Fo2 + 2Fc2)/3 |
S = 1.06 | (Δ/σ)max = 0.005 |
1568 reflections | Δρmax = 0.17 e Å−3 |
122 parameters | Δρmin = −0.16 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.014 (3) |
C8H12N+·NO3− | V = 895.2 (4) Å3 |
Mr = 184.20 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 7.891 (2) Å | µ = 0.11 mm−1 |
b = 8.328 (3) Å | T = 293 K |
c = 13.628 (2) Å | 0.20 × 0.19 × 0.17 mm |
β = 91.47 (2)° |
Enraf–Nonius TurboCAD-4 diffractometer | Rint = 0.018 |
3131 measured reflections | 2 standard reflections every 120 min |
1568 independent reflections | intensity decay: 5% |
1181 reflections with I > 2σ(I) |
R[F2 > 2σ(F2)] = 0.037 | 0 restraints |
wR(F2) = 0.112 | H-atom parameters constrained |
S = 1.06 | Δρmax = 0.17 e Å−3 |
1568 reflections | Δρmin = −0.16 e Å−3 |
122 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
N1 | 0.05197 (19) | 0.23434 (19) | 0.13088 (12) | 0.0375 (4) | |
O1 | −0.01610 (19) | 0.19181 (19) | 0.20863 (10) | 0.0535 (4) | |
O2 | 0.0066 (2) | 0.16522 (19) | 0.05302 (10) | 0.0548 (4) | |
O3 | 0.1585 (2) | 0.3402 (2) | 0.13256 (13) | 0.0701 (5) | |
N2 | 0.16555 (19) | 0.37350 (19) | 0.36594 (11) | 0.0379 (4) | |
C1 | 0.3441 (2) | 0.3220 (2) | 0.37321 (12) | 0.0318 (4) | |
C2 | 0.4727 (2) | 0.4356 (2) | 0.37051 (12) | 0.0366 (5) | |
C3 | 0.6386 (3) | 0.3782 (3) | 0.37620 (14) | 0.0465 (5) | |
C4 | 0.6726 (3) | 0.2168 (3) | 0.38574 (15) | 0.0465 (5) | |
C5 | 0.5416 (2) | 0.1077 (3) | 0.38996 (13) | 0.0418 (5) | |
C6 | 0.3738 (2) | 0.1575 (2) | 0.38346 (12) | 0.0341 (4) | |
C7 | 0.4382 (3) | 0.6136 (3) | 0.36478 (15) | 0.0487 (5) | |
C8 | 0.2319 (3) | 0.0377 (2) | 0.38770 (16) | 0.0466 (5) | |
H2A | 0.1609 | 0.4793 | 0.3569 | 0.057* | |
H2B | 0.1138 | 0.3482 | 0.4211 | 0.057* | |
H2C | 0.1142 | 0.3241 | 0.3155 | 0.057* | |
H3 | 0.7282 | 0.4505 | 0.3735 | 0.056* | |
H4 | 0.7843 | 0.1812 | 0.3894 | 0.056* | |
H5 | 0.5660 | −0.0010 | 0.3973 | 0.050* | |
H7A | 0.3797 | 0.6471 | 0.4222 | 0.073* | |
H7B | 0.3693 | 0.6363 | 0.3074 | 0.073* | |
H7C | 0.5436 | 0.6706 | 0.3611 | 0.073* | |
H8A | 0.2780 | −0.0678 | 0.3983 | 0.070* | |
H8B | 0.1677 | 0.0395 | 0.3269 | 0.070* | |
H8C | 0.1592 | 0.0647 | 0.4407 | 0.070* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0347 (8) | 0.0315 (9) | 0.0462 (10) | 0.0017 (7) | −0.0007 (7) | 0.0007 (7) |
O1 | 0.0636 (10) | 0.0570 (10) | 0.0401 (8) | −0.0097 (8) | 0.0044 (7) | 0.0044 (7) |
O2 | 0.0665 (10) | 0.0575 (10) | 0.0406 (8) | −0.0133 (8) | 0.0043 (7) | −0.0105 (7) |
O3 | 0.0585 (10) | 0.0629 (11) | 0.0889 (13) | −0.0317 (9) | 0.0005 (8) | −0.0011 (9) |
N2 | 0.0408 (9) | 0.0321 (9) | 0.0406 (8) | 0.0074 (7) | −0.0005 (7) | −0.0025 (7) |
C1 | 0.0351 (9) | 0.0334 (10) | 0.0268 (8) | 0.0049 (8) | 0.0003 (7) | −0.0013 (7) |
C2 | 0.0457 (12) | 0.0355 (11) | 0.0285 (9) | −0.0019 (8) | 0.0010 (7) | 0.0000 (8) |
C3 | 0.0408 (11) | 0.0530 (13) | 0.0456 (11) | −0.0093 (10) | 0.0021 (9) | 0.0011 (10) |
C4 | 0.0355 (11) | 0.0572 (14) | 0.0470 (12) | 0.0085 (10) | 0.0015 (8) | 0.0018 (10) |
C5 | 0.0473 (12) | 0.0388 (11) | 0.0393 (10) | 0.0132 (10) | 0.0006 (8) | 0.0007 (9) |
C6 | 0.0397 (10) | 0.0318 (10) | 0.0307 (9) | 0.0043 (8) | 0.0005 (7) | −0.0014 (7) |
C8 | 0.0510 (13) | 0.0319 (11) | 0.0565 (12) | −0.0003 (9) | −0.0046 (9) | 0.0006 (9) |
C7 | 0.0655 (14) | 0.0348 (11) | 0.0457 (11) | −0.0052 (11) | 0.0014 (10) | 0.0026 (9) |
O1—N1 | 1.251 (2) | C6—C8 | 1.502 (3) |
O2—N1 | 1.251 (2) | C1—C2 | 1.389 (3) |
N1—O3 | 1.218 (2) | C2—C7 | 1.508 (3) |
N2—C1 | 1.473 (2) | C8—H8A | 0.9600 |
N2—H2A | 0.8900 | C8—H8B | 0.9600 |
N2—H2B | 0.8900 | C8—H8C | 0.9600 |
N2—H2C | 0.8900 | C4—C5 | 1.379 (3) |
C3—C4 | 1.376 (3) | C4—H4 | 0.9300 |
C3—C2 | 1.394 (3) | C5—H5 | 0.9300 |
C3—H3 | 0.9300 | C7—H7A | 0.9600 |
C6—C5 | 1.388 (3) | C7—H7B | 0.9600 |
C6—C1 | 1.396 (3) | C7—H7C | 0.9600 |
O3—N1—O1 | 120.00 (17) | C3—C2—C7 | 120.52 (19) |
O3—N1—O2 | 122.10 (17) | C6—C8—H8A | 109.5 |
O1—N1—O2 | 117.90 (16) | C6—C8—H8B | 109.5 |
C1—N2—H2A | 109.5 | H8A—C8—H8B | 109.5 |
C1—N2—H2B | 109.5 | C6—C8—H8C | 109.5 |
H2A—N2—H2B | 109.5 | H8A—C8—H8C | 109.5 |
C1—N2—H2C | 109.5 | H8B—C8—H8C | 109.5 |
H2A—N2—H2C | 109.5 | C3—C4—C5 | 120.22 (19) |
H2B—N2—H2C | 109.5 | C3—C4—H4 | 119.9 |
C4—C3—C2 | 121.37 (19) | C5—C4—H4 | 119.9 |
C4—C3—H3 | 119.3 | C4—C5—C6 | 121.0 (2) |
C2—C3—H3 | 119.3 | C4—C5—H5 | 119.5 |
C5—C6—C1 | 117.22 (18) | C6—C5—H5 | 119.5 |
C5—C6—C8 | 120.64 (18) | C2—C7—H7A | 109.5 |
C1—C6—C8 | 122.14 (17) | C2—C7—H7B | 109.5 |
C2—C1—C6 | 123.39 (17) | H7A—C7—H7B | 109.5 |
C2—C1—N2 | 119.84 (17) | C2—C7—H7C | 109.5 |
C6—C1—N2 | 116.77 (16) | H7A—C7—H7C | 109.5 |
C1—C2—C3 | 116.78 (18) | H7B—C7—H7C | 109.5 |
C1—C2—C7 | 122.68 (18) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2A···O1i | 0.89 | 2.28 | 3.064 (2) | 147 |
N2—H2A···O2i | 0.89 | 2.40 | 3.007 (2) | 126 |
N2—H2B···O2ii | 0.89 | 2.01 | 2.888 (2) | 169 |
N2—H2C···O1 | 0.89 | 2.08 | 2.964 (2) | 174 |
N2—H2C···O3 | 0.89 | 2.53 | 3.192 (3) | 132 |
C5—H5···O3iii | 0.93 | 2.59 | 3.270 (3) | 131 |
C8—H8B···O1 | 0.96 | 2.49 | 3.345 (3) | 149 |
Symmetry codes: (i) −x, y+1/2, −z+1/2; (ii) x, −y+1/2, z+1/2; (iii) −x+1, y−1/2, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C8H12N+·NO3− |
Mr | 184.20 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 7.891 (2), 8.328 (3), 13.628 (2) |
β (°) | 91.47 (2) |
V (Å3) | 895.2 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.11 |
Crystal size (mm) | 0.20 × 0.19 × 0.17 |
Data collection | |
Diffractometer | Enraf–Nonius TurboCAD-4 |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3131, 1568, 1181 |
Rint | 0.018 |
(sin θ/λ)max (Å−1) | 0.594 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.037, 0.112, 1.06 |
No. of reflections | 1568 |
No. of parameters | 122 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.17, −0.16 |
Computer programs: CAD-4 EXPRESS (Enraf–Nonius, 1994), CAD-4 EXPRESS, XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2A···O1i | 0.8900 | 2.2800 | 3.064 (2) | 147.00 |
N2—H2A···O2i | 0.8900 | 2.4000 | 3.007 (2) | 126.00 |
N2—H2B···O2ii | 0.8900 | 2.0100 | 2.888 (2) | 169.00 |
N2—H2C···O1 | 0.8900 | 2.0800 | 2.964 (2) | 174.00 |
N2—H2C···O3 | 0.8900 | 2.5300 | 3.192 (3) | 132.00 |
C5—H5···O3iii | 0.9300 | 2.5900 | 3.270 (3) | 131.00 |
C8—H8B···O1 | 0.9600 | 2.4900 | 3.345 (3) | 149.00 |
Symmetry codes: (i) −x, y+1/2, −z+1/2; (ii) x, −y+1/2, z+1/2; (iii) −x+1, y−1/2, −z+1/2. |
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Hybrid compounds are widely investigated due to their special relevance in fundamental sciences and in several applied fields such as biomolecular sciences, catalysis and nonlinear optics (Xiao et al., 2005, Yuan et al., 2006). These materials are generally rich in hydrogen bonds which are considered as the most effective tool for constructing sophisticated assemblies from discrete ionic or molecular building blocks due to its strength and directionality (Wang & Zhang, 2006). In this paper, we report the synthesis and structure of a new organic nitrate. Single-crystal X-ray diffraction study of the title compounds shows that the asymmetric unit corresponds to the formula unit (I) which is made of one NO3- anion and one 2,6-xylidinium cation (Fig. 1). As well as electrostatic and van der Walls forces, two types of hydrogen bonds (Table 1) participate to define the crystal packing. The first one, N–H···O bonds links ammonium groups and nitrate anions into infinite layers propagating in the (b, c) plane (Fig. 2, Table 1). The second H-bonds type, C–H···O bonds, identified by PLATON (Spek, 2003), connects the successive layers to form a three-dimensional network (Fig. 3, Table 1). It is noteworthy that two hydrogen atoms of the NH3 groups form bifurcated hydrogen bonds with the nitrate oxygen atoms. Bond lengths and angles observed in this structure agree well with those reported for nitrate or xylidinium compounds (Hemissi et al., 2001, Perpétuo & Janczak, 2004).