Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805040067/is6161sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536805040067/is6161Isup2.hkl |
CCDC reference: 296588
Key indicators
- Single-crystal X-ray study
- T = 296 K
- Mean (C-C) = 0.002 Å
- R factor = 0.035
- wR factor = 0.071
- Data-to-parameter ratio = 16.0
checkCIF/PLATON results
No syntax errors found
Alert level B PLAT230_ALERT_2_B Hirshfeld Test Diff for N2 - C3 .. 8.39 su
Alert level C PLAT230_ALERT_2_C Hirshfeld Test Diff for O1 - N2 .. 5.76 su PLAT230_ALERT_2_C Hirshfeld Test Diff for C5 - C6 .. 5.88 su PLAT420_ALERT_2_C D-H Without Acceptor N1 - H1 ... ?
0 ALERT level A = In general: serious problem 1 ALERT level B = Potentially serious problem 3 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 4 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
The title compound was prepared according to the method reported by Kulka & Manske (1952). To sulfuric acid (75 ml, 96.6%) cooled in a salt-ice bath was added dropwise 1,2,3,4-tetrahydroquinoline (25 ml, 0.2 mol). After 30 min, concomitant addition of nitric acid (9.5 ml, 0.2 mol, 90%) in sulfuric acid (40 ml) was started, keeping the temperature at 278–283 K. The reaction mixture was stirred in the ice bath for 3 h and then poured on to 1.4 kg of ice. The solution was neutralized to pH 8 with sodium carbonate (255 g). The precipitate was then collected, washed with water and recrystallized from methanol (200 ml) to give a dark-orange solid (yield 49%, 35 g). It was recrystallized from acetonitrile, giving red crystals of (I) suitable for X-ray diffraction.
All H atoms were placed in calculated positions, with C—H = 0.93–0.96 Å and N—H = 0.86 Å, and included in the refinement in the riding-model approximation, with Uiso(H) = 1.2Ueq(carrier atom).
Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: CRYSTALS (Betteridge et al., 2003); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: CrystalStructure.
Fig. 1. View of the molecular structure of (I) and the atom-numbering scheme. Displacement ellipsoids are drawn at the 40% probability level. |
C9H10N2O2 | F(000) = 752.00 |
Mr = 178.19 | Dx = 1.415 Mg m−3 |
Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71075 Å |
Hall symbol: -P 2ac 2ab | Cell parameters from 12005 reflections |
a = 7.985 (2) Å | θ = 3.1–27.5° |
b = 10.583 (4) Å | µ = 0.10 mm−1 |
c = 19.790 (5) Å | T = 296 K |
V = 1672.4 (9) Å3 | Block, red |
Z = 8 | 0.28 × 0.15 × 0.14 mm |
Rigaku R-AXIS RAPID diffractometer | Rint = 0.036 |
Detector resolution: 10.00 pixels mm-1 | θmax = 27.5° |
ω scans | h = −9→10 |
15209 measured reflections | k = −13→13 |
1906 independent reflections | l = −25→25 |
1188 reflections with F2 > 2σ(F2) |
Refinement on F2 | w = 1/[0.0001Fo2 + σ(Fo2)]/(4Fo2) |
R[F2 > 2σ(F2)] = 0.035 | (Δ/σ)max < 0.001 |
wR(F2) = 0.071 | Δρmax = 0.25 e Å−3 |
S = 1.01 | Δρmin = −0.17 e Å−3 |
1906 reflections | Extinction correction: Larson (1970) |
119 parameters | Extinction coefficient: 313 (18) |
H-atom parameters constrained |
C9H10N2O2 | V = 1672.4 (9) Å3 |
Mr = 178.19 | Z = 8 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 7.985 (2) Å | µ = 0.10 mm−1 |
b = 10.583 (4) Å | T = 296 K |
c = 19.790 (5) Å | 0.28 × 0.15 × 0.14 mm |
Rigaku R-AXIS RAPID diffractometer | 1188 reflections with F2 > 2σ(F2) |
15209 measured reflections | Rint = 0.036 |
1906 independent reflections |
R[F2 > 2σ(F2)] = 0.035 | 119 parameters |
wR(F2) = 0.071 | H-atom parameters constrained |
S = 1.01 | Δρmax = 0.25 e Å−3 |
1906 reflections | Δρmin = −0.17 e Å−3 |
Geometry. ENTER SPECIAL DETAILS OF THE MOLECULAR GEOMETRY |
Refinement. Refinement using all reflections. The weighted R-factor (wR) and goodness of fit (S) are based on F2. R-factor (gt) are based on F. The threshold expression of F2 > 2.0 σ(F2) is used only for calculating R-factor (gt). |
x | y | z | Uiso*/Ueq | ||
O1 | 0.63457 (13) | 0.46121 (12) | 0.09338 (5) | 0.0803 (3) | |
O2 | 0.56622 (13) | 0.26946 (12) | 0.11683 (4) | 0.0709 (3) | |
N1 | 0.49817 (12) | 0.26484 (11) | 0.36674 (5) | 0.0488 (3) | |
N2 | 0.60753 (12) | 0.37617 (13) | 0.13382 (5) | 0.0533 (3) | |
C1 | 0.56791 (12) | 0.34555 (12) | 0.32053 (5) | 0.0345 (3) | |
C2 | 0.55548 (12) | 0.31988 (12) | 0.25155 (6) | 0.0374 (3) | |
C3 | 0.62554 (13) | 0.40348 (12) | 0.20609 (5) | 0.0386 (3) | |
C4 | 0.70973 (14) | 0.51039 (13) | 0.22548 (6) | 0.0449 (3) | |
C5 | 0.72221 (14) | 0.53368 (12) | 0.29399 (6) | 0.0447 (3) | |
C6 | 0.65336 (13) | 0.45445 (12) | 0.34164 (5) | 0.0377 (3) | |
C7 | 0.66928 (18) | 0.48050 (13) | 0.41660 (6) | 0.0536 (4) | |
C8 | 0.66406 (16) | 0.35882 (13) | 0.45633 (6) | 0.0530 (4) | |
C9 | 0.50867 (16) | 0.28493 (13) | 0.43921 (6) | 0.0524 (4) | |
H1 | 0.4465 | 0.1991 | 0.3520 | 0.059* | |
H2 | 0.5007 | 0.2478 | 0.2363 | 0.044* | |
H4 | 0.7561 | 0.5647 | 0.1936 | 0.054* | |
H5 | 0.7789 | 0.6052 | 0.3089 | 0.053* | |
H72 | 0.7730 | 0.5235 | 0.4252 | 0.064* | |
H71 | 0.5776 | 0.5326 | 0.4310 | 0.064* | |
H82 | 0.7594 | 0.3089 | 0.4436 | 0.063* | |
H81 | 0.6682 | 0.3757 | 0.5040 | 0.063* | |
H91 | 0.4133 | 0.3330 | 0.4537 | 0.062* | |
H92 | 0.5101 | 0.2051 | 0.4622 | 0.063* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0978 (8) | 0.0946 (10) | 0.0487 (5) | 0.0100 (7) | 0.0028 (5) | 0.0272 (5) |
O2 | 0.0827 (7) | 0.0843 (9) | 0.0458 (5) | −0.0039 (7) | −0.0054 (4) | −0.0152 (5) |
N1 | 0.0577 (6) | 0.0464 (7) | 0.0424 (5) | −0.0139 (5) | 0.0069 (4) | −0.0031 (5) |
N2 | 0.0472 (6) | 0.0703 (10) | 0.0423 (5) | 0.0119 (6) | −0.0002 (5) | 0.0043 (6) |
C1 | 0.0306 (5) | 0.0332 (7) | 0.0396 (5) | 0.0035 (5) | 0.0034 (4) | 0.0005 (5) |
C2 | 0.0344 (6) | 0.0342 (7) | 0.0437 (5) | 0.0014 (5) | −0.0007 (5) | −0.0053 (5) |
C3 | 0.0349 (6) | 0.0441 (8) | 0.0369 (5) | 0.0097 (5) | −0.0012 (5) | 0.0017 (5) |
C4 | 0.0417 (7) | 0.0390 (8) | 0.0540 (7) | 0.0050 (6) | 0.0033 (5) | 0.0127 (6) |
C5 | 0.0426 (6) | 0.0312 (8) | 0.0603 (7) | −0.0013 (6) | −0.0041 (5) | −0.0010 (6) |
C6 | 0.0355 (5) | 0.0333 (7) | 0.0442 (6) | 0.0043 (5) | −0.0007 (5) | −0.0031 (5) |
C7 | 0.0570 (8) | 0.0533 (10) | 0.0504 (7) | −0.0017 (7) | −0.0013 (6) | −0.0151 (6) |
C8 | 0.0526 (7) | 0.0693 (11) | 0.0372 (5) | 0.0074 (7) | −0.0009 (5) | −0.0032 (6) |
C9 | 0.0540 (7) | 0.0627 (11) | 0.0405 (6) | 0.0041 (7) | 0.0085 (5) | 0.0019 (6) |
O1—N2 | 1.2236 (17) | C7—C8 | 1.5094 (19) |
O2—N2 | 1.2236 (19) | C8—C9 | 1.5053 (18) |
N1—C1 | 1.3697 (15) | N1—H1 | 0.860 |
N1—C9 | 1.4523 (15) | C2—H2 | 0.930 |
N2—C3 | 1.4662 (14) | C4—H4 | 0.930 |
C1—C2 | 1.3954 (15) | C5—H5 | 0.930 |
C1—C6 | 1.4030 (17) | C7—H72 | 0.960 |
C2—C3 | 1.3803 (16) | C7—H71 | 0.960 |
C3—C4 | 1.3709 (19) | C8—H82 | 0.960 |
C4—C5 | 1.3816 (16) | C8—H81 | 0.960 |
C5—C6 | 1.3764 (16) | C9—H91 | 0.960 |
C6—C7 | 1.5142 (15) | C9—H92 | 0.960 |
O1···N1i | 3.4745 (16) | H2···C4iv | 3.116 |
O1···C9ii | 3.5805 (17) | H2···C5viii | 3.367 |
O2···N1ii | 3.4648 (14) | H2···C5iv | 2.943 |
O2···C8iii | 3.5415 (15) | H2···H4viii | 2.870 |
O2···C9iii | 3.5914 (14) | H2···H4iv | 3.145 |
N1···O1iv | 3.4745 (16) | H2···H5viii | 2.727 |
N1···O2v | 3.4648 (14) | H2···H5iv | 2.838 |
N1···N2v | 3.3345 (14) | H4···O2ix | 3.003 |
N2···N1ii | 3.3345 (14) | H4···N1i | 3.168 |
C1···C4v | 3.4717 (16) | H4···C1ii | 3.414 |
C2···C4v | 3.4488 (17) | H4···C2ix | 3.297 |
C3···C5v | 3.5031 (16) | H4···C6ii | 3.451 |
C4···C1ii | 3.4717 (16) | H4···H1i | 2.336 |
C4···C2ii | 3.4488 (17) | H4···H2ix | 2.870 |
C5···C3ii | 3.5031 (16) | H4···H2i | 3.145 |
C8···O2vi | 3.5415 (15) | H4···H71ii | 3.576 |
C9···O1v | 3.5805 (17) | H5···O2i | 3.574 |
C9···O2vi | 3.5914 (14) | H5···N1ix | 2.708 |
O1···H1i | 2.816 | H5···C1ix | 2.832 |
O1···H72vii | 3.413 | H5···C2ix | 2.863 |
O1···H72v | 2.984 | H5···C3ii | 3.509 |
O1···H82v | 3.480 | H5···H1ix | 2.555 |
O1···H81vii | 2.931 | H5···H2ix | 2.727 |
O1···H91ii | 2.769 | H5···H2i | 2.838 |
O1···H92iii | 3.290 | H5···H82ix | 3.442 |
O1···H92i | 3.035 | H72···O1xiii | 3.413 |
O2···H1ii | 3.187 | H72···O1ii | 2.984 |
O2···H4viii | 3.003 | H72···N1ix | 3.347 |
O2···H5iv | 3.574 | H72···N2ii | 3.306 |
O2···H71iv | 2.915 | H72···C9ix | 3.282 |
O2···H82v | 2.758 | H72···H1ix | 3.252 |
O2···H81iii | 2.831 | H72···H82ix | 3.054 |
O2···H91ii | 3.176 | H72···H91x | 3.203 |
O2···H92iii | 3.104 | H72···H92ix | 2.690 |
N1···H4iv | 3.168 | H71···O2i | 2.915 |
N1···H5viii | 2.708 | H71···C8x | 3.164 |
N1···H72viii | 3.347 | H71···C9x | 3.286 |
N2···H1i | 3.456 | H71···H4v | 3.576 |
N2···H1ii | 3.304 | H71···H71x | 3.076 |
N2···H72v | 3.306 | H71···H82ix | 3.211 |
N2···H82v | 3.253 | H71···H81x | 2.540 |
N2···H91ii | 3.029 | H71···H91x | 2.689 |
N2···H92iii | 3.588 | H71···H92x | 3.558 |
C1···H4v | 3.414 | H82···O1ii | 3.480 |
C1···H5viii | 2.832 | H82···O2ii | 2.758 |
C2···H4viii | 3.297 | H82···N2ii | 3.253 |
C2···H5viii | 2.863 | H82···C7viii | 3.563 |
C3···H1i | 3.382 | H82···C9xi | 3.214 |
C3···H1ii | 3.545 | H82···H5viii | 3.442 |
C3···H5v | 3.509 | H82···H72viii | 3.054 |
C4···H1i | 2.810 | H82···H71viii | 3.211 |
C4···H2ix | 3.421 | H82···H91xi | 2.810 |
C4···H2i | 3.116 | H82···H92xi | 2.739 |
C5···H1ix | 3.374 | H81···O1xiii | 2.931 |
C5···H2ix | 3.367 | H81···O2vi | 2.831 |
C5···H2i | 2.943 | H81···C7x | 3.471 |
C6···H4v | 3.451 | H81···H71x | 2.540 |
C7···H82ix | 3.563 | H81···H91x | 3.260 |
C7···H81x | 3.471 | H81···H91xi | 3.067 |
C7···H91x | 3.304 | H81···H92xi | 2.938 |
C8···H71x | 3.164 | H91···O1v | 2.769 |
C8···H91xi | 3.354 | H91···O2v | 3.176 |
C8···H92xi | 3.269 | H91···N2v | 3.029 |
C9···H72viii | 3.282 | H91···C7x | 3.304 |
C9···H71x | 3.286 | H91···C8xii | 3.354 |
C9···H82xii | 3.214 | H91···H72x | 3.203 |
C9···H81xii | 3.398 | H91···H71x | 2.689 |
H1···O1iv | 2.816 | H91···H82xii | 2.810 |
H1···O2v | 3.187 | H91···H81x | 3.260 |
H1···N2iv | 3.456 | H91···H81xii | 3.067 |
H1···N2v | 3.304 | H92···O1vi | 3.290 |
H1···C3iv | 3.382 | H92···O1iv | 3.035 |
H1···C3v | 3.545 | H92···O2vi | 3.104 |
H1···C4iv | 2.810 | H92···N2vi | 3.588 |
H1···C5viii | 3.374 | H92···C8xii | 3.269 |
H1···H4iv | 2.336 | H92···H72viii | 2.690 |
H1···H5viii | 2.555 | H92···H71x | 3.558 |
H1···H72viii | 3.252 | H92···H82xii | 2.739 |
H2···C4viii | 3.421 | H92···H81xii | 2.938 |
C1—N1—C9 | 123.00 (10) | C1—C2—H2 | 120.8 |
O1—N2—O2 | 123.14 (10) | C3—C2—H2 | 120.3 |
O1—N2—C3 | 118.41 (12) | C3—C4—H4 | 121.0 |
O2—N2—C3 | 118.45 (11) | C5—C4—H4 | 121.8 |
N1—C1—C2 | 120.19 (10) | C4—C5—H5 | 119.4 |
N1—C1—C6 | 120.75 (9) | C6—C5—H5 | 118.3 |
C2—C1—C6 | 119.07 (10) | C6—C7—H72 | 109.4 |
C1—C2—C3 | 118.95 (11) | C6—C7—H71 | 109.4 |
N2—C3—C2 | 118.01 (11) | C8—C7—H72 | 109.6 |
N2—C3—C4 | 118.94 (10) | C8—C7—H71 | 108.3 |
C2—C3—C4 | 123.05 (10) | H72—C7—H71 | 109.5 |
C3—C4—C5 | 117.21 (11) | C7—C8—H82 | 108.1 |
C4—C5—C6 | 122.33 (12) | C7—C8—H81 | 110.6 |
C1—C6—C5 | 119.39 (9) | C9—C8—H82 | 108.0 |
C1—C6—C7 | 118.82 (10) | C9—C8—H81 | 110.3 |
C5—C6—C7 | 121.78 (11) | H82—C8—H81 | 109.5 |
C6—C7—C8 | 110.65 (11) | N1—C9—H91 | 109.1 |
C7—C8—C9 | 110.41 (10) | N1—C9—H92 | 109.9 |
N1—C9—C8 | 110.24 (10) | C8—C9—H91 | 108.1 |
C1—N1—H1 | 118.2 | C8—C9—H92 | 109.9 |
C9—N1—H1 | 118.8 | H91—C9—H92 | 109.5 |
C1—N1—C9—C8 | −27.63 (16) | C6—C1—C2—C3 | −0.96 (16) |
C9—N1—C1—C2 | 179.06 (10) | C1—C2—C3—N2 | −178.58 (10) |
C9—N1—C1—C6 | −0.59 (17) | C1—C2—C3—C4 | 1.06 (17) |
O1—N2—C3—C2 | 163.85 (11) | N2—C3—C4—C5 | 179.20 (11) |
O1—N2—C3—C4 | −15.80 (17) | C2—C3—C4—C5 | −0.44 (18) |
O2—N2—C3—C2 | −16.16 (16) | C3—C4—C5—C6 | −0.27 (18) |
O2—N2—C3—C4 | 164.19 (11) | C4—C5—C6—C1 | 0.33 (18) |
N1—C1—C2—C3 | 179.38 (10) | C4—C5—C6—C7 | 179.45 (12) |
N1—C1—C6—C5 | 179.95 (10) | C1—C6—C7—C8 | 27.19 (15) |
N1—C1—C6—C7 | 0.80 (16) | C5—C6—C7—C8 | −151.93 (11) |
C2—C1—C6—C5 | 0.30 (16) | C6—C7—C8—C9 | −54.66 (14) |
C2—C1—C6—C7 | −178.85 (10) | C7—C8—C9—N1 | 54.67 (14) |
Symmetry codes: (i) −x+1, y+1/2, −z+1/2; (ii) x+1/2, y, −z+1/2; (iii) x, −y+1/2, z−1/2; (iv) −x+1, y−1/2, −z+1/2; (v) x−1/2, y, −z+1/2; (vi) x, −y+1/2, z+1/2; (vii) −x+3/2, −y+1, z−1/2; (viii) −x+3/2, y−1/2, z; (ix) −x+3/2, y+1/2, z; (x) −x+1, −y+1, −z+1; (xi) x+1/2, −y+1/2, −z+1; (xii) x−1/2, −y+1/2, −z+1; (xiii) −x+3/2, −y+1, z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C9H10N2O2 |
Mr | 178.19 |
Crystal system, space group | Orthorhombic, Pbca |
Temperature (K) | 296 |
a, b, c (Å) | 7.985 (2), 10.583 (4), 19.790 (5) |
V (Å3) | 1672.4 (9) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.10 |
Crystal size (mm) | 0.28 × 0.15 × 0.14 |
Data collection | |
Diffractometer | Rigaku R-AXIS RAPID diffractometer |
Absorption correction | – |
No. of measured, independent and observed [F2 > 2σ(F2)] reflections | 15209, 1906, 1188 |
Rint | 0.036 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.035, 0.071, 1.01 |
No. of reflections | 1906 |
No. of parameters | 119 |
No. of restraints | ? |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.25, −0.17 |
Computer programs: PROCESS-AUTO (Rigaku, 1998), PROCESS-AUTO, CrystalStructure (Rigaku/MSC, 2004), SHELXS97 (Sheldrick, 1997), CRYSTALS (Betteridge et al., 2003), ORTEP-3 for Windows (Farrugia, 1997), CrystalStructure.
7-Nitro-1,2,3,4-tetrahydroquinoline, (I), is a versatile intermediate in the preparation of 7-hydroxy-1,2,3,4-tetrahydroquinoline, which is widely used in the efficient synthesis of laser dyes of the rhodamine class (Field et al., 1994). Bond lengths and angles in the title compound agree with those reported for related structures (Jasinski & Woudenberg, 1993; Sivaraman et al., 1996; Smith et al., 2002; Sankaranarayanan et al., 2003). The tetrahydropyridine ring adopts an envelope conformation, with atom C8 deviating by 0.659 (2) Å from the mean plane through the other five atoms (Fig. 1). This mean plane is almost planar with the benzene ring, forming a dihedral angle of 0.46 (5)°. The NO2 group is slightly twisted out of the benzene ring plane, the angle between the nitro group and the benzene ring being 16.16 (3)°. The nitro group is, therefore, not conjugated with benzene, resulting in a longer C3—N2 bond length.