Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270108008275/sk3210sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270108008275/sk3210Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270108008275/sk3210IIsup3.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270108008275/sk3210IIIsup4.hkl |
CCDC references: 690183; 690184; 690185
Compounds (I) and (II) were prepared by similar routes. Anhydrous potassium carbonate (1.0943 g, 0.008 mol) and a solution of ethylamine (1.0805 g, 0.0240 mol; 70% in water) or octylamine (0.7284 g, 0.006 mol) in dimethylacetamide (DMAC) (8 ml) were combined in a three-necked 100 ml round-bottomed flask, fitted with a nitrogen inlet, a thermometer, a magnetic stirring bar and a Dean–Stark trap fitted with a condenser. To the stirred solution, 2,6-difluoronitrobenzene (0.4342 g, 0.0027 mol) in DMAC (5 ml) was added. Additional DMAC (8 ml) was used to wash the transfer container and this was added to the reaction mixture, followed by the addition of toluene (20 ml). The color of the reaction mixture turned bright red when the temperature reached 343 K. The temperature of the reaction mixture was raised to 393 K, and the reaction was allowed to continue at this temperature for 3 h. Water, the by-product of the reaction, was removed via azeotropic distillation with toluene. On completion of the reaction, the reaction mixture was allowed to cool to room temperature and diluted with dichloromethane (30 ml). The resulting heterogeneous mixture was then filtered through Celite at reduced pressure, and the solvents from the dark-red filtrate were removed under high vacuum to yield a bright-red solid residue. The crude product was dissolved in hexane (15 ml), transferred to a separating funnel and washed repeatedly with deionized water. The organic layer was collected, dried over anhydrous magnesium sulfate and filtered, and the filtrate was evaporated using a rotary evaporator to yield a bright-red solid. Crystals suitable for X-ray diffraction were obtained by recrystallization from hexane.
Analysis for compound (I): yield 65%; m.p. 336–338 K; 1H NMR (400 MHz, CDCl3, δ, p.p.m.): 8.6 (s, 2H), 7.1 (m, 1H), 5.9 (d, 2H), 3.2 (m, 3H), 1.3 (t, 6H); 13C NMR (CDCl3, δ, p.p.m.): 148.51, 137.06, 121.01, 98.01, 38.34, 14.42; IR (KBr, ν > 1400 cm-1): 3347, 2980, 2860, 1582, 1515, 1472; MS (m/z) (% base peak): 209 (85), 174 (100), 132 (72.5), 147 (55).
Analysis for compound (II): yield 70%; m.p. 343–345 K; 1H NMR (400 MHz, CDCl3, δ, p.p.m.): 8.7 (t, 2H), 7.1 (t, 1H), 5.8 (d, 2H), 3.2 (m, 4H), 1.7 (m, 4H), 1.3 (m, 20H), 0.9 (t, 6H); 13C NMR (CDCl3, δ, p.p.m.): 148.69, 136.99, 97.88, 43.76, 32.02, 29.51, 29.42, 28.99, 27.40, 22.86, 14.31; IR (KBr, ν > 1400 cm-1): 3343, 2957, 2926, 2850, 1583, 1515, 1471; MS (m/z) (% base peak): 377 (63.2), 342 (97.7), 244 (40.3), 232 (43.7), 134 (100).
Compound (III) was synthesized from (I) (prepared as described above) by taking the red solution obtained after azeoptropic removal of the water and heating it to 433 K for 24 h. During this time, the color gradually turned dark brown. The reaction solution was then diluted with dichloromethane (30 ml). The resulting heterogeneous mixture was filtered through Celite at reduced pressure. Solvents were then removed under high vacuum. The crude product was dissolved in dichloromethane (15 ml), transferred to a separating funnel and washed repeatedly with deionized water. The organic layer was collected, dried over anhydrous magnesium sulfate and filtered, and the filtrate was evaporated using a rotary evaporator to yield a dark-brown solid. The crude product was eluted on a neutral alumina column using dichloromethane–ethyl acetate (70:30 v/v) to obtain the desired compound, (III). The bluish–green solid was recrystallized from hexane.
Analysis for compound (III): yield: 15%; m.p. 432–434 K; 1H NMR (400 MHz, CDCl3, δ, p.p.m.): 7.1 (m, 1H), 6.7 (m, 1H), 6.3 (m, 1H), 3.3 (q, 2H), 2.6 (s, 3H), 1.3 (t, 3H); 13C NMR (CDCl3, δ, p.p.m.): 148.24, 139.90, 134.53, 131.55, 124.02, 101.55, 99.67, 38.39, 30.00, 15.06; IR (KBr, ν > 1400 cm-1): 3366, 2961, 1607, 1540, 1422; MS (m/z) (% base peak): 175 (38), 132 (38), 160 (100).
For all compounds, data collection: SMART (Bruker, 2003); cell refinement: SAINT-Plus (Bruker, 2003); data reduction: SAINT-Plus (Bruker, 2003); program(s) used to solve structure: SHELXTL (Version 6.10; Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Version 6.10; Sheldrick, 2008); molecular graphics: Crystal Maker (Palmer, 2006); software used to prepare material for publication: SHELXTL (Version 6.10; Sheldrick, 2008) and local programs.
C10H15N3O2 | F(000) = 224 |
Mr = 209.25 | Dx = 1.327 Mg m−3 |
Monoclinic, P2/n | Melting point: 336 K |
Hall symbol: -P 2yac | Mo Kα radiation, λ = 0.71073 Å |
a = 5.0425 (6) Å | Cell parameters from 2623 reflections |
b = 9.2564 (10) Å | θ = 2.8–33.0° |
c = 11.4901 (13) Å | µ = 0.10 mm−1 |
β = 102.492 (2)° | T = 140 K |
V = 523.61 (10) Å3 | Needle, red |
Z = 2 | 0.40 × 0.06 × 0.03 mm |
Bruker SMART 6000 CCD area-detector diffractometer | 1017 independent reflections |
Radiation source: fine-focus sealed tube | 919 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.055 |
ω scans | θmax = 26.0°, θmin = 2.2° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −6→4 |
Tmin = 0.77, Tmax = 1.00 | k = −11→10 |
3016 measured reflections | l = −14→14 |
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)] = 0.046 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.121 | All H-atom parameters refined |
S = 1.15 | w = 1/[σ2(Fo2) + (0.0413P)2 + 0.1845P] where P = (Fo2 + 2Fc2)/3 |
1017 reflections | (Δ/σ)max < 0.001 |
100 parameters | Δρmax = 0.31 e Å−3 |
0 restraints | Δρmin = −0.16 e Å−3 |
C10H15N3O2 | V = 523.61 (10) Å3 |
Mr = 209.25 | Z = 2 |
Monoclinic, P2/n | Mo Kα radiation |
a = 5.0425 (6) Å | µ = 0.10 mm−1 |
b = 9.2564 (10) Å | T = 140 K |
c = 11.4901 (13) Å | 0.40 × 0.06 × 0.03 mm |
β = 102.492 (2)° |
Bruker SMART 6000 CCD area-detector diffractometer | 1017 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 919 reflections with I > 2σ(I) |
Tmin = 0.77, Tmax = 1.00 | Rint = 0.055 |
3016 measured reflections |
R[F2 > 2σ(F2)] = 0.046 | 0 restraints |
wR(F2) = 0.121 | All H-atom parameters refined |
S = 1.15 | Δρmax = 0.31 e Å−3 |
1017 reflections | Δρmin = −0.16 e Å−3 |
100 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 | ||
O1 | 0.9243 (2) | 0.50417 (12) | 0.82181 (10) | 0.0410 (4) | |
N1 | 0.7500 | 0.43516 (19) | 0.7500 | 0.0281 (4) | |
N2 | 1.1793 (2) | 0.27164 (15) | 0.89937 (10) | 0.0268 (4) | |
C1 | 0.7500 | 0.2823 (2) | 0.7500 | 0.0248 (5) | |
C2 | 0.9703 (3) | 0.20475 (16) | 0.82619 (11) | 0.0239 (4) | |
C3 | 0.9629 (3) | 0.05350 (16) | 0.82223 (12) | 0.0257 (4) | |
C4 | 0.7500 | −0.0188 (2) | 0.7500 | 0.0271 (5) | |
C5 | 1.3992 (3) | 0.19564 (16) | 0.97807 (12) | 0.0262 (4) | |
C6 | 1.5899 (3) | 0.30237 (19) | 1.05306 (15) | 0.0340 (4) | |
H2 | 1.176 (3) | 0.363 (2) | 0.9019 (15) | 0.034 (5)* | |
H3 | 1.106 (3) | 0.0036 (17) | 0.8670 (15) | 0.028 (4)* | |
H4 | 0.7500 | −0.120 (3) | 0.7500 | 0.019 (5)* | |
H5A | 1.322 (3) | 0.1303 (19) | 1.0311 (15) | 0.033 (4)* | |
H5B | 1.499 (3) | 0.1344 (18) | 0.9323 (14) | 0.030 (4)* | |
H6C | 1.737 (4) | 0.254 (2) | 1.1045 (17) | 0.043 (5)* | |
H6A | 1.665 (4) | 0.368 (2) | 1.0015 (17) | 0.048 (5)* | |
H6B | 1.497 (4) | 0.357 (2) | 1.1008 (17) | 0.045 (5)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0352 (7) | 0.0268 (7) | 0.0515 (7) | −0.0012 (5) | −0.0113 (5) | −0.0040 (5) |
N1 | 0.0236 (8) | 0.0272 (9) | 0.0322 (9) | 0.000 | 0.0030 (7) | 0.000 |
N2 | 0.0258 (7) | 0.0246 (7) | 0.0296 (7) | 0.0017 (5) | 0.0053 (5) | 0.0004 (5) |
C1 | 0.0255 (10) | 0.0252 (11) | 0.0264 (10) | 0.000 | 0.0113 (8) | 0.000 |
C2 | 0.0229 (7) | 0.0298 (8) | 0.0218 (7) | 0.0002 (6) | 0.0108 (6) | 0.0012 (5) |
C3 | 0.0270 (8) | 0.0278 (8) | 0.0244 (7) | 0.0041 (6) | 0.0100 (6) | 0.0028 (5) |
C4 | 0.0367 (12) | 0.0216 (11) | 0.0272 (10) | 0.000 | 0.0162 (9) | 0.000 |
C5 | 0.0267 (8) | 0.0286 (8) | 0.0244 (7) | 0.0035 (6) | 0.0080 (6) | 0.0023 (6) |
C6 | 0.0322 (9) | 0.0348 (9) | 0.0317 (8) | 0.0064 (7) | −0.0001 (7) | −0.0009 (7) |
O1—N1 | 1.2441 (14) | C3—H3 | 0.915 (17) |
N1—O1i | 1.2441 (14) | C4—C3i | 1.3795 (18) |
N1—C1 | 1.415 (3) | C4—H4 | 0.93 (2) |
N2—C2 | 1.3483 (18) | C5—C6 | 1.511 (2) |
N2—C5 | 1.4520 (18) | C5—H5A | 0.997 (18) |
N2—H2 | 0.85 (2) | C5—H5B | 0.982 (17) |
C1—C2 | 1.4472 (17) | C6—H6C | 0.95 (2) |
C1—C2i | 1.4472 (18) | C6—H6A | 0.98 (2) |
C2—C3 | 1.401 (2) | C6—H6B | 0.94 (2) |
C3—C4 | 1.3795 (18) | ||
O1—N1—O1i | 118.21 (17) | C3—C4—C3i | 122.0 (2) |
O1—N1—C1 | 120.90 (9) | C3—C4—H4 | 119.00 (10) |
O1i—N1—C1 | 120.90 (9) | C3i—C4—H4 | 119.00 (10) |
C2—N2—C5 | 123.68 (14) | N2—C5—C6 | 110.14 (13) |
C2—N2—H2 | 117.3 (11) | N2—C5—H5A | 109.1 (9) |
C5—N2—H2 | 118.9 (11) | C6—C5—H5A | 109.5 (9) |
N1—C1—C2 | 119.72 (10) | N2—C5—H5B | 110.9 (9) |
N1—C1—C2i | 119.72 (10) | C6—C5—H5B | 110.3 (9) |
C2—C1—C2i | 120.56 (19) | H5A—C5—H5B | 106.9 (14) |
N2—C2—C3 | 119.40 (13) | C5—C6—H6C | 111.0 (11) |
N2—C2—C1 | 122.95 (15) | C5—C6—H6A | 110.1 (11) |
C3—C2—C1 | 117.66 (14) | H6C—C6—H6A | 108.4 (16) |
C4—C3—C2 | 121.05 (14) | C5—C6—H6B | 110.5 (11) |
C4—C3—H3 | 120.6 (10) | H6C—C6—H6B | 108.0 (16) |
C2—C3—H3 | 118.3 (10) | H6A—C6—H6B | 108.7 (17) |
Symmetry code: (i) −x+3/2, y, −z+3/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2···O1 | 0.85 (2) | 1.91 (2) | 2.566 (1) | 133 (2) |
C22H39N3O2 | F(000) = 832 |
Mr = 377.56 | Dx = 1.182 Mg m−3 |
Monoclinic, C2/c | Melting point: 343 K |
Hall symbol: -C 2yc | Mo Kα radiation, λ = 0.71073 Å |
a = 21.5603 (16) Å | Cell parameters from 4172 reflections |
b = 9.1066 (7) Å | θ = 2.2–32.5° |
c = 12.6778 (10) Å | µ = 0.08 mm−1 |
β = 121.560 (2)° | T = 140 K |
V = 2121.0 (3) Å3 | Plate, red |
Z = 4 | 0.38 × 0.19 × 0.03 mm |
Bruker SMART 6000 CCD area-detector diffractometer | 2568 independent reflections |
Radiation source: fine-focus sealed tube | 2012 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.022 |
ω scans | θmax = 28.0°, θmin = 2.2° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −17→28 |
Tmin = 0.841, Tmax = 1.000 | k = −12→12 |
8645 measured reflections | l = −16→14 |
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)] = 0.054 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.149 | All H-atom parameters refined |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0768P)2 + 0.9135P] where P = (Fo2 + 2Fc2)/3 |
2568 reflections | (Δ/σ)max = 0.001 |
202 parameters | Δρmax = 0.43 e Å−3 |
0 restraints | Δρmin = −0.28 e Å−3 |
C22H39N3O2 | V = 2121.0 (3) Å3 |
Mr = 377.56 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 21.5603 (16) Å | µ = 0.08 mm−1 |
b = 9.1066 (7) Å | T = 140 K |
c = 12.6778 (10) Å | 0.38 × 0.19 × 0.03 mm |
β = 121.560 (2)° |
Bruker SMART 6000 CCD area-detector diffractometer | 2568 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2012 reflections with I > 2σ(I) |
Tmin = 0.841, Tmax = 1.000 | Rint = 0.022 |
8645 measured reflections |
R[F2 > 2σ(F2)] = 0.054 | 0 restraints |
wR(F2) = 0.149 | All H-atom parameters refined |
S = 1.06 | Δρmax = 0.43 e Å−3 |
2568 reflections | Δρmin = −0.28 e Å−3 |
202 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 | ||
O1 | 0.03356 (5) | 0.24375 (10) | 0.34884 (7) | 0.0309 (3) | |
N1 | 0.0000 | 0.31326 (15) | 0.2500 | 0.0183 (3) | |
N2 | 0.07516 (5) | 0.48067 (12) | 0.47798 (8) | 0.0192 (3) | |
H2 | 0.0744 (9) | 0.388 (2) | 0.4771 (15) | 0.043 (5)* | |
C1 | 0.0000 | 0.46890 (17) | 0.2500 | 0.0168 (4) | |
C2 | 0.03837 (6) | 0.54746 (13) | 0.36629 (10) | 0.0162 (3) | |
C3 | 0.03701 (6) | 0.70176 (13) | 0.36179 (10) | 0.0193 (3) | |
C4 | 0.0000 | 0.77460 (18) | 0.2500 | 0.0204 (4) | |
C5 | 0.11256 (7) | 0.56209 (13) | 0.59375 (10) | 0.0189 (3) | |
C6 | 0.15100 (7) | 0.45987 (13) | 0.70473 (10) | 0.0192 (3) | |
C7 | 0.19201 (7) | 0.54834 (13) | 0.82471 (10) | 0.0193 (3) | |
C8 | 0.23421 (7) | 0.45336 (13) | 0.94019 (10) | 0.0206 (3) | |
C9 | 0.27633 (7) | 0.54404 (13) | 1.05862 (10) | 0.0204 (3) | |
C10 | 0.31773 (7) | 0.44949 (13) | 1.17500 (10) | 0.0200 (3) | |
C11 | 0.36251 (8) | 0.53845 (14) | 1.29341 (11) | 0.0232 (3) | |
C12 | 0.39927 (8) | 0.44240 (15) | 1.40876 (11) | 0.0252 (3) | |
H3 | 0.0606 (9) | 0.7560 (17) | 0.4368 (15) | 0.038 (4)* | |
H4 | 0.0000 | 0.878 (2) | 0.2500 | 0.022 (5)* | |
H5A | 0.1500 (7) | 0.6286 (15) | 0.5940 (11) | 0.020 (3)* | |
H5B | 0.0762 (7) | 0.6235 (15) | 0.6010 (12) | 0.019 (3)* | |
H6A | 0.1867 (7) | 0.3979 (15) | 0.6959 (12) | 0.021 (3)* | |
H6B | 0.1143 (8) | 0.3944 (16) | 0.7064 (13) | 0.028 (4)* | |
H7A | 0.2281 (8) | 0.6181 (16) | 0.8201 (12) | 0.025 (4)* | |
H7B | 0.1563 (8) | 0.6107 (15) | 0.8325 (12) | 0.023 (3)* | |
H8A | 0.1997 (8) | 0.3874 (17) | 0.9455 (13) | 0.029 (4)* | |
H8B | 0.2701 (8) | 0.3910 (16) | 0.9317 (13) | 0.027 (4)* | |
H9A | 0.2414 (8) | 0.6069 (16) | 1.0651 (13) | 0.027 (4)* | |
H9B | 0.3133 (8) | 0.6065 (16) | 1.0526 (13) | 0.028 (4)* | |
H10A | 0.2827 (8) | 0.3886 (17) | 1.1826 (13) | 0.030 (4)* | |
H10B | 0.3510 (8) | 0.3825 (16) | 1.1654 (13) | 0.028 (4)* | |
H11A | 0.3313 (8) | 0.6086 (19) | 1.3004 (14) | 0.036 (4)* | |
H11B | 0.4004 (8) | 0.5952 (17) | 1.2868 (13) | 0.034 (4)* | |
H12A | 0.3631 (9) | 0.3891 (19) | 1.4164 (14) | 0.043 (5)* | |
H12B | 0.4281 (9) | 0.4950 (18) | 1.4860 (16) | 0.039 (4)* | |
H12C | 0.4332 (8) | 0.3747 (18) | 1.4050 (14) | 0.036 (4)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0443 (6) | 0.0206 (5) | 0.0118 (4) | 0.0014 (4) | 0.0036 (4) | 0.0029 (3) |
N1 | 0.0202 (7) | 0.0196 (7) | 0.0125 (6) | 0.000 | 0.0068 (5) | 0.000 |
N2 | 0.0219 (6) | 0.0206 (5) | 0.0088 (5) | −0.0012 (4) | 0.0035 (4) | −0.0017 (4) |
C1 | 0.0162 (8) | 0.0195 (8) | 0.0120 (7) | 0.000 | 0.0055 (6) | 0.000 |
C2 | 0.0136 (6) | 0.0216 (6) | 0.0122 (6) | −0.0007 (4) | 0.0059 (5) | −0.0010 (4) |
C3 | 0.0178 (6) | 0.0215 (6) | 0.0158 (6) | −0.0023 (4) | 0.0068 (5) | −0.0034 (4) |
C4 | 0.0201 (8) | 0.0161 (7) | 0.0234 (8) | 0.000 | 0.0102 (7) | 0.000 |
C5 | 0.0197 (6) | 0.0223 (6) | 0.0108 (5) | −0.0023 (5) | 0.0053 (5) | −0.0023 (4) |
C6 | 0.0198 (6) | 0.0233 (6) | 0.0111 (6) | −0.0006 (5) | 0.0058 (5) | −0.0010 (4) |
C7 | 0.0205 (6) | 0.0235 (6) | 0.0112 (6) | −0.0016 (5) | 0.0063 (5) | −0.0014 (4) |
C8 | 0.0222 (7) | 0.0233 (6) | 0.0121 (6) | −0.0009 (5) | 0.0061 (5) | −0.0005 (4) |
C9 | 0.0228 (7) | 0.0237 (6) | 0.0120 (6) | −0.0001 (5) | 0.0073 (5) | −0.0003 (4) |
C10 | 0.0205 (6) | 0.0224 (6) | 0.0129 (6) | −0.0007 (5) | 0.0057 (5) | −0.0012 (4) |
C11 | 0.0258 (7) | 0.0235 (6) | 0.0131 (6) | −0.0010 (5) | 0.0053 (5) | −0.0016 (4) |
C12 | 0.0249 (7) | 0.0297 (7) | 0.0136 (6) | 0.0003 (5) | 0.0050 (5) | −0.0014 (5) |
O1—N1 | 1.2431 (10) | C7—C8 | 1.5247 (15) |
N1—O1i | 1.2431 (10) | C7—H7A | 1.030 (14) |
N1—C1 | 1.417 (2) | C7—H7B | 1.002 (14) |
N2—C2 | 1.3522 (14) | C8—C9 | 1.5276 (16) |
N2—C5 | 1.4544 (14) | C8—H8A | 0.986 (15) |
N2—H2 | 0.844 (18) | C8—H8B | 1.009 (15) |
C1—C2i | 1.4467 (13) | C9—C10 | 1.5285 (15) |
C1—C2 | 1.4467 (13) | C9—H9A | 0.983 (15) |
C2—C3 | 1.4060 (16) | C9—H9B | 1.014 (15) |
C3—C4 | 1.3789 (14) | C10—C11 | 1.5247 (16) |
C3—H3 | 0.949 (16) | C10—H10A | 0.981 (15) |
C4—C3i | 1.3790 (14) | C10—H10B | 0.997 (15) |
C4—H4 | 0.94 (2) | C11—C12 | 1.5227 (16) |
C5—C6 | 1.5206 (15) | C11—H11A | 0.966 (17) |
C5—H5A | 1.008 (14) | C11—H11B | 1.006 (16) |
C5—H5B | 1.006 (14) | C12—H12A | 0.966 (18) |
C6—C7 | 1.5287 (15) | C12—H12B | 0.968 (17) |
C6—H6A | 1.006 (14) | C12—H12C | 0.976 (16) |
C6—H6B | 1.000 (15) | ||
O1i—N1—O1 | 118.77 (13) | C8—C7—H7B | 109.3 (8) |
O1i—N1—C1 | 120.61 (7) | C6—C7—H7B | 108.8 (8) |
O1—N1—C1 | 120.61 (7) | H7A—C7—H7B | 107.4 (12) |
C2—N2—C5 | 122.61 (10) | C7—C8—C9 | 112.71 (10) |
C2—N2—H2 | 116.1 (11) | C7—C8—H8A | 108.6 (9) |
C5—N2—H2 | 121.3 (11) | C9—C8—H8A | 110.1 (8) |
N1—C1—C2i | 119.64 (7) | C7—C8—H8B | 108.8 (8) |
N1—C1—C2 | 119.64 (7) | C9—C8—H8B | 108.3 (8) |
C2i—C1—C2 | 120.73 (14) | H8A—C8—H8B | 108.2 (13) |
N2—C2—C3 | 118.71 (10) | C8—C9—C10 | 112.99 (10) |
N2—C2—C1 | 123.63 (11) | C8—C9—H9A | 108.1 (9) |
C3—C2—C1 | 117.66 (11) | C10—C9—H9A | 109.4 (8) |
C4—C3—C2 | 120.73 (11) | C8—C9—H9B | 108.4 (8) |
C4—C3—H3 | 119.9 (9) | C10—C9—H9B | 107.7 (8) |
C2—C3—H3 | 119.4 (9) | H9A—C9—H9B | 110.2 (12) |
C3—C4—C3i | 122.50 (15) | C11—C10—C9 | 113.58 (10) |
C3—C4—H4 | 118.75 (8) | C11—C10—H10A | 109.1 (8) |
C3i—C4—H4 | 118.75 (8) | C9—C10—H10A | 108.8 (9) |
N2—C5—C6 | 111.56 (10) | C11—C10—H10B | 108.7 (8) |
N2—C5—H5A | 109.3 (7) | C9—C10—H10B | 108.7 (8) |
C6—C5—H5A | 108.5 (7) | H10A—C10—H10B | 107.9 (12) |
N2—C5—H5B | 109.2 (7) | C12—C11—C10 | 112.55 (11) |
C6—C5—H5B | 109.2 (7) | C12—C11—H11A | 109.2 (9) |
H5A—C5—H5B | 109.1 (11) | C10—C11—H11A | 109.2 (9) |
C5—C6—C7 | 110.45 (10) | C12—C11—H11B | 109.8 (9) |
C5—C6—H6A | 108.6 (7) | C10—C11—H11B | 108.3 (9) |
C7—C6—H6A | 109.2 (8) | H11A—C11—H11B | 107.7 (13) |
C5—C6—H6B | 109.3 (8) | C11—C12—H12A | 110.1 (10) |
C7—C6—H6B | 110.2 (8) | C11—C12—H12B | 115.0 (9) |
H6A—C6—H6B | 109.1 (12) | H12A—C12—H12B | 105.7 (13) |
C8—C7—C6 | 113.59 (10) | C11—C12—H12C | 110.1 (9) |
C8—C7—H7A | 108.4 (8) | H12A—C12—H12C | 110.6 (14) |
C6—C7—H7A | 109.2 (8) | H12B—C12—H12C | 105.2 (13) |
Symmetry code: (i) −x, y, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2···O1 | 0.844 (18) | 1.910 (18) | 2.570 (1) | 134 (2) |
C10H13N3 | F(000) = 752 |
Mr = 175.23 | Dx = 1.234 Mg m−3 |
Monoclinic, P21/n | Melting point: 432 K |
Hall symbol: -P 2yn | Mo Kα radiation, λ = 0.71073 Å |
a = 9.6166 (3) Å | Cell parameters from 8542 reflections |
b = 16.2072 (5) Å | θ = 2.5–33.5° |
c = 12.1236 (3) Å | µ = 0.08 mm−1 |
β = 93.278 (1)° | T = 140 K |
V = 1886.47 (10) Å3 | Pyramidal, blue |
Z = 8 | 0.36 × 0.30 × 0.30 mm |
Bruker SMART 6000 CCD area-detector diffractometer | 4120 independent reflections |
Radiation source: fine-focus sealed tube | 3759 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.019 |
ω scans | θmax = 27.0°, θmin = 2.1° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −12→12 |
Tmin = 0.893, Tmax = 1.000 | k = −20→20 |
19605 measured reflections | l = −15→15 |
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)] = 0.044 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.118 | All H-atom parameters refined |
S = 1.09 | w = 1/[σ2(Fo2) + (0.0528P)2 + 0.7046P] where P = (Fo2 + 2Fc2)/3 |
4120 reflections | (Δ/σ)max < 0.001 |
339 parameters | Δρmax = 0.30 e Å−3 |
0 restraints | Δρmin = −0.24 e Å−3 |
C10H13N3 | V = 1886.47 (10) Å3 |
Mr = 175.23 | Z = 8 |
Monoclinic, P21/n | Mo Kα radiation |
a = 9.6166 (3) Å | µ = 0.08 mm−1 |
b = 16.2072 (5) Å | T = 140 K |
c = 12.1236 (3) Å | 0.36 × 0.30 × 0.30 mm |
β = 93.278 (1)° |
Bruker SMART 6000 CCD area-detector diffractometer | 4120 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 3759 reflections with I > 2σ(I) |
Tmin = 0.893, Tmax = 1.000 | Rint = 0.019 |
19605 measured reflections |
R[F2 > 2σ(F2)] = 0.044 | 0 restraints |
wR(F2) = 0.118 | All H-atom parameters refined |
S = 1.09 | Δρmax = 0.30 e Å−3 |
4120 reflections | Δρmin = −0.24 e Å−3 |
339 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 | ||
N11 | 0.28781 (10) | 0.15867 (6) | 0.29060 (9) | 0.0238 (2) | |
H11 | 0.3717 (18) | 0.1303 (11) | 0.2798 (13) | 0.037 (4)* | |
N12 | −0.06234 (11) | 0.33365 (7) | 0.38748 (10) | 0.0281 (3) | |
H12 | −0.1062 (19) | 0.3112 (11) | 0.3307 (15) | 0.042 (5)* | |
N13 | 0.05966 (10) | 0.18629 (6) | 0.28385 (8) | 0.0228 (2) | |
N21 | 0.78283 (11) | 0.11946 (7) | 0.28668 (9) | 0.0242 (2) | |
H21 | 0.8672 (18) | 0.1489 (10) | 0.2790 (13) | 0.036 (4)* | |
N22 | 0.43596 (12) | −0.06583 (7) | 0.36301 (9) | 0.0274 (2) | |
H22 | 0.381 (2) | −0.0246 (13) | 0.3567 (16) | 0.056 (6)* | |
N23 | 0.55596 (10) | 0.08952 (6) | 0.27404 (8) | 0.0227 (2) | |
C10 | 0.13212 (15) | 0.05655 (9) | 0.19189 (12) | 0.0301 (3) | |
H10C | 0.120 (3) | 0.0126 (16) | 0.240 (2) | 0.087 (8)* | |
H10B | 0.209 (3) | 0.0412 (17) | 0.153 (2) | 0.097 (8)* | |
H10A | 0.051 (3) | 0.0598 (17) | 0.148 (2) | 0.095 (8)* | |
C12 | 0.15746 (12) | 0.13444 (7) | 0.25537 (10) | 0.0232 (3) | |
C14 | 0.08000 (13) | 0.32040 (7) | 0.39062 (10) | 0.0236 (3) | |
C15 | 0.17802 (14) | 0.37286 (8) | 0.44329 (11) | 0.0275 (3) | |
H15 | 0.1485 (16) | 0.4238 (10) | 0.4790 (12) | 0.030 (4)* | |
C16 | 0.32104 (14) | 0.35398 (8) | 0.44841 (11) | 0.0293 (3) | |
H16 | 0.3847 (18) | 0.3916 (11) | 0.4876 (13) | 0.039 (4)* | |
C17 | 0.37337 (13) | 0.28372 (8) | 0.40120 (11) | 0.0270 (3) | |
H17 | 0.4711 (17) | 0.2693 (10) | 0.4066 (13) | 0.033 (4)* | |
C18 | 0.27474 (12) | 0.23198 (7) | 0.34712 (10) | 0.0228 (3) | |
C19 | 0.13236 (12) | 0.24868 (7) | 0.34190 (9) | 0.0217 (2) | |
C20 | 0.62661 (15) | 0.22327 (8) | 0.19147 (12) | 0.0284 (3) | |
H20C | 0.543 (2) | 0.2216 (13) | 0.1467 (17) | 0.060 (6)* | |
H20B | 0.702 (2) | 0.2358 (13) | 0.1444 (17) | 0.063 (6)* | |
H20A | 0.620 (2) | 0.2670 (13) | 0.2453 (17) | 0.062 (6)* | |
C22 | 0.65275 (12) | 0.14355 (7) | 0.25029 (10) | 0.0234 (3) | |
C24 | 0.57654 (12) | −0.04809 (7) | 0.37341 (10) | 0.0233 (3) | |
C25 | 0.67585 (14) | −0.10095 (8) | 0.42394 (10) | 0.0266 (3) | |
H25 | 0.6482 (16) | −0.1527 (10) | 0.4554 (13) | 0.029 (4)* | |
C26 | 0.81814 (14) | −0.08090 (8) | 0.43200 (11) | 0.0284 (3) | |
H26 | 0.8834 (17) | −0.1203 (10) | 0.4683 (13) | 0.035 (4)* | |
C27 | 0.86935 (13) | −0.00864 (8) | 0.38980 (10) | 0.0265 (3) | |
H27 | 0.9654 (17) | 0.0059 (10) | 0.3960 (12) | 0.029 (4)* | |
C28 | 0.77014 (13) | 0.04390 (7) | 0.33833 (10) | 0.0231 (3) | |
C29 | 0.62820 (12) | 0.02590 (7) | 0.32974 (9) | 0.0219 (2) | |
C32 | −0.11810 (14) | 0.41224 (8) | 0.42203 (11) | 0.0278 (3) | |
H32B | −0.0730 (16) | 0.4589 (10) | 0.3851 (12) | 0.030 (4)* | |
H32A | −0.0946 (15) | 0.4178 (9) | 0.5033 (13) | 0.030 (4)* | |
C33 | −0.27458 (15) | 0.41379 (9) | 0.39849 (13) | 0.0333 (3) | |
H33C | −0.3133 (18) | 0.4655 (12) | 0.4224 (14) | 0.045 (5)* | |
H33B | −0.3159 (18) | 0.3691 (11) | 0.4380 (14) | 0.039 (4)* | |
H33A | −0.2990 (17) | 0.4063 (10) | 0.3209 (15) | 0.039 (4)* | |
C42 | 0.37983 (14) | −0.13834 (8) | 0.41501 (11) | 0.0274 (3) | |
H42B | 0.4236 (16) | −0.1875 (10) | 0.3846 (12) | 0.030 (4)* | |
H42A | 0.4069 (16) | −0.1373 (10) | 0.4959 (13) | 0.031 (4)* | |
C43 | 0.22287 (15) | −0.14141 (10) | 0.39529 (13) | 0.0344 (3) | |
H43C | 0.188 (2) | −0.1904 (13) | 0.4301 (16) | 0.057 (6)* | |
H43B | 0.1813 (18) | −0.0918 (11) | 0.4256 (14) | 0.039 (4)* | |
H43A | 0.1961 (17) | −0.1428 (10) | 0.3164 (15) | 0.040 (4)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N11 | 0.0196 (5) | 0.0219 (5) | 0.0299 (5) | 0.0015 (4) | 0.0021 (4) | 0.0017 (4) |
N12 | 0.0234 (5) | 0.0227 (5) | 0.0383 (6) | 0.0013 (4) | 0.0020 (4) | −0.0068 (5) |
N13 | 0.0210 (5) | 0.0203 (5) | 0.0271 (5) | 0.0006 (4) | 0.0017 (4) | −0.0001 (4) |
N21 | 0.0199 (5) | 0.0221 (5) | 0.0305 (5) | −0.0001 (4) | 0.0009 (4) | −0.0009 (4) |
N22 | 0.0246 (5) | 0.0232 (5) | 0.0343 (6) | −0.0010 (4) | 0.0009 (4) | 0.0032 (4) |
N23 | 0.0209 (5) | 0.0197 (5) | 0.0275 (5) | 0.0019 (4) | 0.0011 (4) | 0.0005 (4) |
C10 | 0.0295 (7) | 0.0257 (7) | 0.0351 (7) | 0.0021 (5) | 0.0024 (6) | −0.0061 (6) |
C12 | 0.0221 (6) | 0.0218 (6) | 0.0258 (6) | 0.0008 (5) | 0.0022 (4) | 0.0018 (5) |
C14 | 0.0251 (6) | 0.0193 (6) | 0.0264 (6) | −0.0003 (5) | 0.0026 (5) | 0.0030 (4) |
C15 | 0.0299 (6) | 0.0213 (6) | 0.0312 (6) | −0.0021 (5) | 0.0007 (5) | −0.0013 (5) |
C16 | 0.0284 (6) | 0.0256 (6) | 0.0333 (7) | −0.0066 (5) | −0.0040 (5) | 0.0007 (5) |
C17 | 0.0211 (6) | 0.0255 (6) | 0.0339 (7) | −0.0018 (5) | −0.0023 (5) | 0.0048 (5) |
C18 | 0.0224 (6) | 0.0208 (6) | 0.0253 (6) | 0.0009 (4) | 0.0023 (4) | 0.0048 (4) |
C19 | 0.0219 (6) | 0.0197 (6) | 0.0234 (5) | −0.0016 (4) | 0.0014 (4) | 0.0031 (4) |
C20 | 0.0284 (6) | 0.0221 (6) | 0.0347 (7) | 0.0017 (5) | 0.0039 (5) | 0.0030 (5) |
C22 | 0.0220 (6) | 0.0212 (6) | 0.0272 (6) | 0.0018 (5) | 0.0024 (4) | −0.0018 (5) |
C24 | 0.0257 (6) | 0.0211 (6) | 0.0229 (6) | −0.0001 (5) | 0.0007 (4) | −0.0025 (4) |
C25 | 0.0311 (7) | 0.0212 (6) | 0.0272 (6) | 0.0018 (5) | −0.0001 (5) | 0.0008 (5) |
C26 | 0.0300 (7) | 0.0267 (6) | 0.0276 (6) | 0.0071 (5) | −0.0049 (5) | −0.0012 (5) |
C27 | 0.0217 (6) | 0.0278 (6) | 0.0294 (6) | 0.0035 (5) | −0.0039 (5) | −0.0034 (5) |
C28 | 0.0244 (6) | 0.0208 (6) | 0.0239 (6) | 0.0002 (5) | −0.0001 (4) | −0.0029 (4) |
C29 | 0.0219 (6) | 0.0208 (6) | 0.0229 (5) | 0.0022 (4) | −0.0002 (4) | −0.0022 (4) |
C32 | 0.0300 (7) | 0.0222 (6) | 0.0312 (7) | 0.0035 (5) | 0.0022 (5) | −0.0035 (5) |
C33 | 0.0300 (7) | 0.0304 (7) | 0.0393 (8) | 0.0076 (6) | 0.0012 (6) | −0.0066 (6) |
C42 | 0.0314 (7) | 0.0225 (6) | 0.0288 (6) | −0.0026 (5) | 0.0052 (5) | −0.0018 (5) |
C43 | 0.0324 (7) | 0.0333 (7) | 0.0379 (8) | −0.0073 (6) | 0.0069 (6) | −0.0045 (6) |
N11—C12 | 1.3589 (16) | C17—H17 | 0.967 (16) |
N11—C18 | 1.3810 (16) | C18—C19 | 1.3936 (16) |
N11—H11 | 0.945 (17) | C20—C22 | 1.4902 (17) |
N12—C14 | 1.3839 (16) | C20—H20C | 0.94 (2) |
N12—C32 | 1.4529 (16) | C20—H20B | 0.97 (2) |
N12—H12 | 0.867 (19) | C20—H20A | 0.97 (2) |
N13—C12 | 1.3218 (16) | C24—C25 | 1.3980 (17) |
N13—C19 | 1.3964 (15) | C24—C29 | 1.4126 (17) |
N21—C22 | 1.3597 (15) | C25—C26 | 1.4044 (19) |
N21—C28 | 1.3840 (16) | C25—H25 | 0.965 (16) |
N21—H21 | 0.950 (17) | C26—C27 | 1.3801 (19) |
N22—C24 | 1.3807 (16) | C26—H26 | 0.982 (17) |
N22—C42 | 1.4522 (17) | C27—C28 | 1.3988 (17) |
N22—H22 | 0.85 (2) | C27—H27 | 0.952 (16) |
N23—C22 | 1.3216 (16) | C28—C29 | 1.3938 (17) |
N23—C29 | 1.3957 (15) | C32—C33 | 1.5158 (19) |
C10—C12 | 1.4912 (18) | C32—H32B | 0.992 (16) |
C10—H10C | 0.94 (3) | C32—H32A | 1.003 (15) |
C10—H10B | 0.94 (3) | C33—H33C | 0.968 (19) |
C10—H10A | 0.92 (3) | C33—H33B | 0.966 (18) |
C14—C15 | 1.3965 (18) | C33—H33A | 0.964 (17) |
C14—C19 | 1.4099 (17) | C42—C43 | 1.5155 (19) |
C15—C16 | 1.4069 (19) | C42—H42B | 0.982 (16) |
C15—H15 | 0.981 (16) | C42—H42A | 1.000 (16) |
C16—C17 | 1.3823 (19) | C43—H43C | 0.97 (2) |
C16—H16 | 0.969 (17) | C43—H43B | 0.979 (18) |
C17—C18 | 1.4005 (17) | C43—H43A | 0.976 (18) |
C12—N11—C18 | 107.22 (10) | H20B—C20—H20A | 108.8 (17) |
C12—N11—H11 | 126.5 (10) | N23—C22—N21 | 112.67 (11) |
C18—N11—H11 | 126.2 (10) | N23—C22—C20 | 125.25 (11) |
C14—N12—C32 | 120.59 (11) | N21—C22—C20 | 122.08 (11) |
C14—N12—H12 | 113.1 (12) | N22—C24—C25 | 123.58 (11) |
C32—N12—H12 | 115.2 (12) | N22—C24—C29 | 120.40 (11) |
C12—N13—C19 | 104.41 (10) | C25—C24—C29 | 116.00 (11) |
C22—N21—C28 | 107.31 (10) | C24—C25—C26 | 121.82 (12) |
C22—N21—H21 | 126.8 (10) | C24—C25—H25 | 120.6 (9) |
C28—N21—H21 | 125.9 (10) | C26—C25—H25 | 117.6 (9) |
C24—N22—C42 | 121.01 (11) | C27—C26—C25 | 122.51 (12) |
C24—N22—H22 | 116.5 (14) | C27—C26—H26 | 119.1 (10) |
C42—N22—H22 | 115.3 (13) | C25—C26—H26 | 118.4 (10) |
C22—N23—C29 | 104.93 (10) | C26—C27—C28 | 115.67 (12) |
C12—C10—H10C | 110.0 (15) | C26—C27—H27 | 123.1 (9) |
C12—C10—H10B | 112.0 (16) | C28—C27—H27 | 121.2 (9) |
H10C—C10—H10B | 105 (2) | N21—C28—C29 | 105.23 (10) |
C12—C10—H10A | 111.0 (17) | N21—C28—C27 | 131.68 (12) |
H10C—C10—H10A | 106 (2) | C29—C28—C27 | 123.09 (12) |
H10B—C10—H10A | 113 (2) | C28—C29—N23 | 109.86 (11) |
N13—C12—N11 | 113.05 (11) | C28—C29—C24 | 120.90 (11) |
N13—C12—C10 | 125.12 (11) | N23—C29—C24 | 129.23 (11) |
N11—C12—C10 | 121.83 (11) | N12—C32—C33 | 109.82 (11) |
N12—C14—C15 | 123.97 (12) | N12—C32—H32B | 111.1 (9) |
N12—C14—C19 | 119.52 (11) | C33—C32—H32B | 111.0 (9) |
C15—C14—C19 | 116.47 (11) | N12—C32—H32A | 107.2 (9) |
C14—C15—C16 | 121.36 (12) | C33—C32—H32A | 110.4 (9) |
C14—C15—H15 | 120.6 (9) | H32B—C32—H32A | 107.2 (12) |
C16—C15—H15 | 118.0 (9) | C32—C33—H33C | 110.6 (11) |
C17—C16—C15 | 122.61 (12) | C32—C33—H33B | 109.0 (10) |
C17—C16—H16 | 119.1 (10) | H33C—C33—H33B | 109.0 (14) |
C15—C16—H16 | 118.3 (10) | C32—C33—H33A | 111.4 (10) |
C16—C17—C18 | 115.74 (11) | H33C—C33—H33A | 108.9 (14) |
C16—C17—H17 | 123.1 (10) | H33B—C33—H33A | 107.8 (14) |
C18—C17—H17 | 121.1 (10) | N22—C42—C43 | 110.46 (11) |
N11—C18—C19 | 105.16 (10) | N22—C42—H42B | 108.3 (9) |
N11—C18—C17 | 131.99 (11) | C43—C42—H42B | 111.0 (9) |
C19—C18—C17 | 122.85 (11) | N22—C42—H42A | 109.2 (9) |
C18—C19—N13 | 110.16 (10) | C43—C42—H42A | 110.9 (9) |
C18—C19—C14 | 120.96 (11) | H42B—C42—H42A | 106.8 (12) |
N13—C19—C14 | 128.88 (11) | C42—C43—H43C | 109.2 (12) |
C22—C20—H20C | 111.4 (13) | C42—C43—H43B | 109.7 (10) |
C22—C20—H20B | 110.6 (12) | H43C—C43—H43B | 110.4 (15) |
H20C—C20—H20B | 107.9 (17) | C42—C43—H43A | 111.1 (10) |
C22—C20—H20A | 109.1 (12) | H43C—C43—H43A | 109.1 (15) |
H20C—C20—H20A | 108.9 (17) | H43B—C43—H43A | 107.3 (14) |
D—H···A | D—H | H···A | D···A | D—H···A |
N11—H11···N23 | 0.945 (17) | 1.896 (18) | 2.8293 (14) | 169.2 (15) |
N21—H21···N13i | 0.950 (17) | 1.946 (17) | 2.8761 (15) | 165.9 (15) |
Symmetry code: (i) x+1, y, z. |
Experimental details
(I) | (II) | (III) | |
Crystal data | |||
Chemical formula | C10H15N3O2 | C22H39N3O2 | C10H13N3 |
Mr | 209.25 | 377.56 | 175.23 |
Crystal system, space group | Monoclinic, P2/n | Monoclinic, C2/c | Monoclinic, P21/n |
Temperature (K) | 140 | 140 | 140 |
a, b, c (Å) | 5.0425 (6), 9.2564 (10), 11.4901 (13) | 21.5603 (16), 9.1066 (7), 12.6778 (10) | 9.6166 (3), 16.2072 (5), 12.1236 (3) |
β (°) | 102.492 (2) | 121.560 (2) | 93.278 (1) |
V (Å3) | 523.61 (10) | 2121.0 (3) | 1886.47 (10) |
Z | 2 | 4 | 8 |
Radiation type | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.10 | 0.08 | 0.08 |
Crystal size (mm) | 0.40 × 0.06 × 0.03 | 0.38 × 0.19 × 0.03 | 0.36 × 0.30 × 0.30 |
Data collection | |||
Diffractometer | Bruker SMART 6000 CCD area-detector diffractometer | Bruker SMART 6000 CCD area-detector diffractometer | Bruker SMART 6000 CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) | Multi-scan (SADABS; Sheldrick, 1996) | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.77, 1.00 | 0.841, 1.000 | 0.893, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3016, 1017, 919 | 8645, 2568, 2012 | 19605, 4120, 3759 |
Rint | 0.055 | 0.022 | 0.019 |
(sin θ/λ)max (Å−1) | 0.617 | 0.661 | 0.639 |
Refinement | |||
R[F2 > 2σ(F2)], wR(F2), S | 0.046, 0.121, 1.15 | 0.054, 0.149, 1.06 | 0.044, 0.118, 1.09 |
No. of reflections | 1017 | 2568 | 4120 |
No. of parameters | 100 | 202 | 339 |
H-atom treatment | All H-atom parameters refined | All H-atom parameters refined | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 0.31, −0.16 | 0.43, −0.28 | 0.30, −0.24 |
Computer programs: SMART (Bruker, 2003), SAINT-Plus (Bruker, 2003), Crystal Maker (Palmer, 2006), SHELXTL (Version 6.10; Sheldrick, 2008) and local programs.
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2···O1 | 0.85 (2) | 1.91 (2) | 2.566 (1) | 133 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2···O1 | 0.844 (18) | 1.910 (18) | 2.570 (1) | 134 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
N11—H11···N23 | 0.945 (17) | 1.896 (18) | 2.8293 (14) | 169.2 (15) |
N21—H21···N13i | 0.950 (17) | 1.946 (17) | 2.8761 (15) | 165.9 (15) |
Symmetry code: (i) x+1, y, z. |
This report is part of our continuing work on polyamines. In our earlier studies (Teng et al., 2006), polyamines were synthesized by the reactions of homologous aliphatic diamines with 1,5-difluoro-2,4-dinitrobenzene. These polymers are only soluble in concentrated mineral acids including sulfuric, nitric and perchloric acids at room temperature. This excellent solvent resistance is believed to be due to the existence of strong inter- and intra-chain hydrogen-bonding interactions, which arise from the presence of secondary amine moieties ortho to an aryl nitro group in the polymer repeat unit. As an extension of this study, we have prepared two more series of polyamines by the reactions of homologous aliphatic diamines with 2,6-difluoronitrobenzene and 2,4-difluoronitrobenzene, respectively, details of which will be published elsewhere. As a precursor to the polymer syntheses, model compounds were synthesized from aliphatic diamines and the isomeric difluorides mentioned above. We report herein the detailed structural characterization of the two title secondary diamines, (I) and (II), derived from 2,6-difluoronitrobenzene. These compounds could be synthesized successfully at a reaction temperature of 393 K in dimethylacetamide (DMAC), in the presence of excess anhydrous potassium carbonate and toluene. These reactions failed to yield the desired compounds when the reaction temperature exceeded 403 K. In order to understand this, the reaction mixture was analyzed periodically by gas chromatography and mass spectroscopy (GC/MS) with increasing reaction temperatures. These studies suggest that the desired diamines, which form quantitatively at or below 403 K, undergo further transformations as the temperature is gradually increased. Compound (III) is obtained from (I) during this process. The benzimidazole derivative (III) is the only product that could be unequivocally identified by GC/MS analyses. However, the presence of a number of other organic products, probably oligomeric in nature, was evident during the purification of (III) using column chromatography. Compound (II) underwent a similar reaction to yield 7-N-octyl-2-heptylbenzimidazole. However, in spite of our repeated attempts, we were unable to obtain crystals of appropriate quality.
Molecules of (I) are bisected by a twofold rotation axis that contains atoms N1, C1, C4 and H4 (Fig. 1). The H atoms on the N atoms of the N-ethylamino groups participate in strong intramolecular hydrogen bonds with the O atoms of the adjacent nitro group (Table 1). This pattern has been observed previously in molecules with primary amine groups on both sides of a nitro group (Ammon et al., 1982). A search of the Cambridge Structural Database (CSD, Version 5.29 plus update of January 2008; Allen, 2002) revealed no prior reports of 1,3-bis(N-alkylamino)-2-nitrobenzene structures, so this would appear to be the first example involving secondary amines. The ethyl groups adopt an anti conformation (C2—N2—C5—C6 torsion angle ca 180°), with the result that the molecules are essentially planar. The molecules pack into flat layers parallel to (103) (Fig. 2). Of note, there are no intermolecular hydrogen bonds involving the amine H atoms. The packing is thus dominated by hydrophobic interactions. Interestingly, although the interlayer spacing (ca 3.4 Å) is short enough for strong π–π interactions, the layers are actually shifted so that the rings are not over one another.
Molecules of (II) are very similar to those of (I), being also bisected through the nitro group and ring by a twofold axis (Fig. 3) and displaying the same intramolecular N—H···O hydrogen bonding (Table 2). The n-octyl groups are in the zigzag anti conformation and the essentially planar molecules pack in flat layers parallel to (301) with no intermolecular N—H···O hydrogen bonding (Fig. 4). Similar to (I), the layers are separated by about 3.4 Å, but the rings are not face-to-face. Rather, the dominant interaction is between the hydrophobic octyl chains. This preference for interactions between long alkyl chains over those between phenyl rings has also been noted in N-(n-decyl)-4-nitroaniline (Yonkey et al., 2008). The absence of intermolecular hydrogen bonding between the amine and nitro groups in the monomers, though understandable given the strong intramolecular interactions, does raise questions about what may be taking place in the polymers. We do note, however, that there are examples of aryl nitro compounds with ortho secondary amines in which the amine participates in simultaneous intra- and intermolecular N—H···O hydrogen bonds (Panunto et al., 1987).
Compound (III) is formed from (I) by an internal cyclization in which a new bond is formed between the α C atom of one of the ethyl groups and the nitro N atom. In the process, the two α H atoms and both nitro O atoms are lost. The presence of a peak of 34 amu in the mass spectrum suggests the possibility of hydrogen peroxide as the decomposition product. Structurally, (III) occurs as two independent molecules that occupy general positions and do not differ significantly in conformation (Fig. 5). The molecules are essentially planar, with a dihedral angle of 57.25 (1)° between them. In both, the amine N atom is most displaced from the least-squares plane of the non-H atoms, by 0.124 (1) Å for atom N12 and 0.057 (1) Å for atom N22. Similar to what is found in benzimidazole itself (Vijayan et al., 2006), the molecules in (III) are linked by N—H···N hydrogen bonds between the protonated and unprotonated N atoms of the imidazole rings of adjacent molecules into chains running parallel to the a axis. The amine groups do not participate in any N—H···N hydrogen bonds. Benzimidazole crystallizes in a non-centrosymmetric space group and is of interest as a potential nonlinear optical material (Vijayan et al., 2006). However, in spite of the similar hydrogen bonding, (III) crystallizes in a centrosymmetric space group. The presence of intermolecular hydrogen bonds in (III) is reflected in the significantly higher melting point compared with (I) and (II). A search of the CSD found no benzimidazole derivatives with N-alkyl groups in the 7-position and an R group in the 2-position, making this the first structurally characterized example.