organic compounds
N,N-Diethyl-5-nitropyridin-2-amine
aChemistry Department, University of Durham, South Road, Durham DH1 3LE, England
*Correspondence e-mail: d.s.yufit@durham.ac.uk
In the title compound, C9H13N3O2, the contains two almost identical but crystallographically independent molecules. The molecules are linked together by pairs of weak C—H⋯O interactions into zigzag chains, which, in turn, form corrugated layers perpendicular to the a axis.
Comment
In continuation of our studies of organic molecules with non-linear optical properties (Yufit et al., 2006), an attempt to grow crystals of 2-adamantylamino-5-nitropyridine (AANP) (Tomaru et al., 1991; Antipin et al., 2001) by has been made. As a result, two types of crystals formed in the reaction vessel. An X-ray study of the small cubic-shaped ones revealed that they are, in fact, crystals of N,N-diethyl-5-nitropyridine-2-amine, (I), which is a side product in the synthesis of AANP. Here, we briefly describe the structural features of this compound.
The contains two virtually identical but crystallographically independent molecules (Fig. 1). These molecules differ slightly in the positions of the terminal C atoms of the ethyl groups (Fig. 2).
of (I)The packing of the molecules of (I) is quite different from that of its benzene analogue N,N-diethyl-p-nitroaniline (Maurin & Krygowski, 1988), in which numerous C—H⋯π interactions are present.
In the i⋯H2(—C2) = 2.74 (1) Å, O2i⋯H3(—C3) = 2.63 (1) Å, O21ii⋯H22(—C22) = 2.67 (1) Å and O22ii⋯H23(—C23) = 2.51 (1) Å; symmetry codes: (i) x, − y, + z, (ii) x, − y, − + z] interactions in zigzag chains parallel to the c axis (Fig. 3); each independent molecule forms separate chains. These chains form corrugated layers perpendicular to a axis (Fig. 4). The pyridine rings of the molecules in adjacent layers are partially overlapped, the shortest interplanar distance being 3.42 Å, which is within the normal range for π–π aromatic interactions (Janiak, 2000).
molecules are linked together by pairs of C—H⋯O [O1Experimental
The title compound, (I), was isolated by from the mixture of products of the reaction between 2-chloronitropyridine (0.948 g, 5.979 mmol) and adamantylamine (0.984 g, 6.594 mmol). The crystals of (I) were formed on heating the powder sample at 343 K for 3 d (yield 0.99 g, 61%; m.p. 440 K).
Crystal data
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Data collection
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Refinement
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H atoms were located in a difference synthesis and refined isotropically [C—H = 0.922 (14)–0.976 (14) for CH, 0.965 (13)–1.007 (14) for CH2 and 0.970 (17)–1.028 (16) Å for CH3].
Data collection: SMART (Bruker, 2003); cell SAINT (Bruker, 2003); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Bruker, 2003); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
Supporting information
https://doi.org/10.1107/S160053680600729X/hk2006sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S160053680600729X/hk2006Isup2.hkl
Data collection: SMART (Bruker, 2003); cell
SAINT (Bruker, 2003); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Bruker, 2003); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.C9H13N3O2 | F(000) = 832 |
Mr = 195.22 | Dx = 1.340 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 4483 reflections |
a = 14.6723 (7) Å | θ = 2.4–30.4° |
b = 10.6920 (5) Å | µ = 0.10 mm−1 |
c = 12.4224 (5) Å | T = 120 K |
β = 96.820 (1)° | Block, yellow |
V = 1934.99 (15) Å3 | 0.26 × 0.14 × 0.12 mm |
Z = 8 |
Bruker SMART CCD 6000 diffractometer | 3536 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.048 |
Graphite monochromator | θmax = 29.5°, θmin = 1.4° |
ω scans | h = −20→20 |
19597 measured reflections | k = −14→14 |
5389 independent reflections | l = −17→17 |
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)] = 0.040 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.112 | All H-atom parameters refined |
S = 0.97 | w = 1/[σ2(Fo2) + (0.06P)2] where P = (Fo2 + 2Fc2)/3 |
5389 reflections | (Δ/σ)max = 0.001 |
357 parameters | Δρmax = 0.29 e Å−3 |
0 restraints | Δρmin = −0.19 e Å−3 |
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 | 0.88641 (7) | 1.16690 (10) | −0.20267 (7) | 0.0395 (3) | |
O2 | 0.85357 (7) | 1.31005 (9) | −0.08920 (8) | 0.0394 (2) | |
O21 | 0.35252 (8) | 1.16353 (10) | 1.18822 (7) | 0.0408 (3) | |
O22 | 0.34599 (7) | 1.31229 (9) | 1.06912 (7) | 0.0336 (2) | |
N1 | 0.86987 (8) | 1.20006 (11) | −0.11143 (9) | 0.0296 (2) | |
N2 | 0.88886 (7) | 0.89231 (10) | 0.02259 (8) | 0.0268 (2) | |
N3 | 0.87939 (7) | 0.83105 (9) | 0.19895 (8) | 0.0236 (2) | |
N21 | 0.35337 (7) | 1.20055 (10) | 1.09402 (8) | 0.0273 (2) | |
N22 | 0.39111 (7) | 0.89809 (9) | 0.96485 (9) | 0.0262 (2) | |
N23 | 0.38857 (7) | 0.83972 (9) | 0.78584 (8) | 0.0260 (2) | |
C1 | 0.86994 (8) | 1.10729 (12) | −0.02779 (10) | 0.0244 (3) | |
C2 | 0.85663 (8) | 1.14175 (12) | 0.07749 (10) | 0.0251 (3) | |
C3 | 0.85941 (8) | 1.05069 (11) | 0.15475 (10) | 0.0234 (3) | |
C4 | 0.87580 (8) | 0.92429 (11) | 0.12583 (10) | 0.0223 (2) | |
C5 | 0.88623 (9) | 0.98302 (12) | −0.05055 (10) | 0.0268 (3) | |
C6 | 0.90970 (9) | 0.70469 (12) | 0.17327 (11) | 0.0262 (3) | |
C7 | 0.83026 (10) | 0.61517 (13) | 0.14346 (12) | 0.0309 (3) | |
C8 | 0.86461 (9) | 0.85407 (13) | 0.31190 (10) | 0.0260 (3) | |
C9 | 0.95032 (10) | 0.89981 (14) | 0.38086 (11) | 0.0328 (3) | |
C21 | 0.36342 (8) | 1.11063 (11) | 1.01067 (9) | 0.0229 (3) | |
C22 | 0.35764 (8) | 1.14762 (11) | 0.90234 (10) | 0.0224 (2) | |
C23 | 0.36722 (8) | 1.05862 (11) | 0.82571 (10) | 0.0226 (2) | |
C24 | 0.38215 (8) | 0.93229 (11) | 0.85857 (10) | 0.0230 (3) | |
C25 | 0.38127 (8) | 0.98655 (12) | 1.03757 (10) | 0.0262 (3) | |
C26 | 0.41529 (9) | 0.71269 (12) | 0.82107 (12) | 0.0283 (3) | |
C27 | 0.33357 (10) | 0.62959 (14) | 0.83556 (14) | 0.0362 (3) | |
C28 | 0.37213 (10) | 0.86210 (13) | 0.66905 (10) | 0.0287 (3) | |
C29 | 0.45757 (11) | 0.90510 (15) | 0.62215 (12) | 0.0361 (3) | |
H2 | 0.8458 (9) | 1.2287 (13) | 0.0962 (11) | 0.025 (3)* | |
H3 | 0.8547 (10) | 1.0713 (13) | 0.2259 (11) | 0.029 (4)* | |
H5 | 0.8977 (9) | 0.9588 (14) | −0.1233 (12) | 0.035 (4)* | |
H61 | 0.9503 (10) | 0.6739 (13) | 0.2380 (12) | 0.034 (4)* | |
H62 | 0.9477 (9) | 0.7122 (12) | 0.1149 (11) | 0.025 (3)* | |
H71 | 0.7969 (11) | 0.6413 (14) | 0.0736 (13) | 0.040 (4)* | |
H72 | 0.8559 (10) | 0.5284 (15) | 0.1329 (12) | 0.042 (4)* | |
H73 | 0.7881 (10) | 0.6140 (13) | 0.1993 (12) | 0.036 (4)* | |
H81 | 0.8431 (9) | 0.7764 (13) | 0.3393 (10) | 0.023 (3)* | |
H82 | 0.8137 (9) | 0.9168 (13) | 0.3140 (10) | 0.027 (4)* | |
H91 | 0.9978 (12) | 0.8369 (16) | 0.3803 (13) | 0.052 (5)* | |
H92 | 0.9758 (10) | 0.9807 (15) | 0.3509 (12) | 0.041 (4)* | |
H93 | 0.9373 (11) | 0.9131 (15) | 0.4526 (14) | 0.048 (5)* | |
H22 | 0.3491 (9) | 1.2342 (12) | 0.8839 (10) | 0.019 (3)* | |
H23 | 0.3659 (9) | 1.0812 (13) | 0.7504 (11) | 0.029 (4)* | |
H25 | 0.3891 (9) | 0.9642 (13) | 1.1136 (11) | 0.030 (4)* | |
H261 | 0.4578 (10) | 0.7189 (13) | 0.8895 (11) | 0.028 (4)* | |
H262 | 0.4534 (10) | 0.6804 (13) | 0.7657 (12) | 0.031 (4)* | |
H271 | 0.3047 (11) | 0.6582 (15) | 0.8981 (13) | 0.045 (5)* | |
H272 | 0.3546 (11) | 0.5419 (17) | 0.8529 (13) | 0.050 (5)* | |
H273 | 0.2913 (11) | 0.6265 (15) | 0.7689 (13) | 0.044 (4)* | |
H281 | 0.3220 (10) | 0.9221 (13) | 0.6533 (11) | 0.030 (4)* | |
H282 | 0.3488 (10) | 0.7821 (14) | 0.6362 (11) | 0.030 (4)* | |
H291 | 0.5053 (12) | 0.8409 (16) | 0.6329 (13) | 0.052 (5)* | |
H292 | 0.4821 (11) | 0.9817 (16) | 0.6565 (12) | 0.044 (4)* | |
H293 | 0.4438 (10) | 0.9218 (14) | 0.5436 (13) | 0.038 (4)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0501 (6) | 0.0455 (6) | 0.0230 (5) | −0.0122 (5) | 0.0038 (4) | 0.0050 (4) |
O2 | 0.0465 (6) | 0.0308 (5) | 0.0411 (6) | 0.0025 (4) | 0.0057 (5) | 0.0107 (5) |
O21 | 0.0614 (7) | 0.0411 (6) | 0.0210 (5) | 0.0002 (5) | 0.0086 (5) | −0.0017 (4) |
O22 | 0.0426 (6) | 0.0275 (5) | 0.0300 (5) | 0.0021 (4) | 0.0020 (4) | −0.0050 (4) |
N1 | 0.0276 (6) | 0.0330 (6) | 0.0274 (6) | −0.0054 (5) | −0.0001 (4) | 0.0061 (5) |
N2 | 0.0316 (6) | 0.0256 (5) | 0.0235 (5) | −0.0018 (4) | 0.0051 (4) | −0.0023 (4) |
N3 | 0.0273 (5) | 0.0211 (5) | 0.0228 (5) | 0.0006 (4) | 0.0041 (4) | 0.0002 (4) |
N21 | 0.0286 (6) | 0.0303 (6) | 0.0230 (5) | −0.0007 (4) | 0.0030 (4) | −0.0028 (5) |
N22 | 0.0293 (6) | 0.0239 (5) | 0.0253 (5) | 0.0002 (4) | 0.0029 (4) | 0.0024 (4) |
N23 | 0.0304 (6) | 0.0212 (5) | 0.0260 (5) | 0.0019 (4) | 0.0018 (4) | −0.0005 (4) |
C1 | 0.0232 (6) | 0.0273 (6) | 0.0224 (6) | −0.0033 (5) | 0.0018 (5) | 0.0047 (5) |
C2 | 0.0227 (6) | 0.0233 (6) | 0.0294 (7) | −0.0002 (5) | 0.0027 (5) | −0.0009 (5) |
C3 | 0.0262 (6) | 0.0238 (6) | 0.0205 (6) | −0.0001 (5) | 0.0041 (5) | −0.0022 (5) |
C4 | 0.0212 (6) | 0.0229 (6) | 0.0226 (6) | −0.0015 (5) | 0.0019 (5) | −0.0010 (5) |
C5 | 0.0299 (7) | 0.0296 (7) | 0.0209 (6) | −0.0045 (5) | 0.0038 (5) | −0.0016 (5) |
C6 | 0.0268 (6) | 0.0222 (6) | 0.0296 (7) | 0.0019 (5) | 0.0031 (5) | 0.0001 (5) |
C7 | 0.0308 (7) | 0.0252 (7) | 0.0361 (8) | −0.0012 (5) | 0.0019 (6) | −0.0005 (6) |
C8 | 0.0300 (7) | 0.0257 (6) | 0.0227 (6) | −0.0004 (5) | 0.0051 (5) | 0.0033 (5) |
C9 | 0.0347 (8) | 0.0377 (8) | 0.0252 (7) | −0.0005 (6) | 0.0000 (6) | 0.0011 (6) |
C21 | 0.0229 (6) | 0.0246 (6) | 0.0212 (6) | −0.0017 (5) | 0.0029 (5) | −0.0025 (5) |
C22 | 0.0213 (6) | 0.0214 (6) | 0.0245 (6) | −0.0006 (5) | 0.0026 (5) | 0.0011 (5) |
C23 | 0.0235 (6) | 0.0235 (6) | 0.0209 (6) | 0.0006 (5) | 0.0028 (5) | 0.0019 (5) |
C24 | 0.0207 (6) | 0.0235 (6) | 0.0248 (6) | −0.0008 (5) | 0.0030 (5) | −0.0002 (5) |
C25 | 0.0280 (7) | 0.0272 (6) | 0.0234 (6) | −0.0015 (5) | 0.0025 (5) | 0.0032 (5) |
C26 | 0.0288 (7) | 0.0209 (6) | 0.0354 (7) | 0.0013 (5) | 0.0041 (6) | −0.0007 (6) |
C27 | 0.0317 (8) | 0.0271 (7) | 0.0493 (9) | −0.0018 (6) | 0.0034 (7) | 0.0003 (7) |
C28 | 0.0327 (7) | 0.0280 (7) | 0.0250 (6) | 0.0014 (6) | 0.0016 (5) | −0.0047 (5) |
C29 | 0.0405 (8) | 0.0386 (8) | 0.0304 (8) | 0.0005 (7) | 0.0097 (6) | −0.0023 (7) |
O1—N1 | 1.2387 (14) | C7—H72 | 1.015 (16) |
O2—N1 | 1.2378 (15) | C7—H73 | 0.983 (15) |
O21—N21 | 1.2368 (14) | C8—C9 | 1.516 (2) |
O22—N21 | 1.2356 (14) | C8—H81 | 0.965 (13) |
N1—C1 | 1.4365 (16) | C8—H82 | 1.007 (14) |
N2—C5 | 1.3263 (16) | C9—H91 | 0.970 (17) |
N2—C4 | 1.3626 (15) | C9—H92 | 1.028 (16) |
N3—C4 | 1.3455 (15) | C9—H93 | 0.944 (17) |
N3—C8 | 1.4658 (15) | C21—C25 | 1.3855 (17) |
N3—C6 | 1.4692 (16) | C21—C22 | 1.3955 (16) |
N21—C21 | 1.4333 (15) | C22—C23 | 1.3650 (17) |
N22—C25 | 1.3276 (17) | C22—H22 | 0.958 (13) |
N22—C24 | 1.3612 (16) | C23—C24 | 1.4205 (17) |
N23—C24 | 1.3509 (15) | C23—H23 | 0.964 (14) |
N23—C28 | 1.4620 (17) | C25—H25 | 0.968 (14) |
N23—C26 | 1.4660 (16) | C26—C27 | 1.5201 (19) |
C1—C5 | 1.3851 (18) | C26—H261 | 0.995 (14) |
C1—C2 | 1.3946 (18) | C26—H262 | 0.997 (14) |
C2—C3 | 1.3644 (18) | C27—H271 | 0.977 (16) |
C2—H2 | 0.976 (14) | C27—H272 | 1.003 (17) |
C3—C4 | 1.4261 (17) | C27—H273 | 0.974 (17) |
C3—H3 | 0.922 (14) | C28—C29 | 1.515 (2) |
C5—H5 | 0.974 (14) | C28—H281 | 0.978 (14) |
C6—C7 | 1.5197 (19) | C28—H282 | 0.991 (15) |
C6—H61 | 0.997 (15) | C29—H291 | 0.978 (18) |
C6—H62 | 0.970 (13) | C29—H292 | 0.973 (17) |
C7—H71 | 0.985 (16) | C29—H293 | 0.989 (15) |
O2—N1—O1 | 122.69 (11) | H81—C8—H82 | 106.9 (11) |
O2—N1—C1 | 118.57 (11) | C8—C9—H91 | 108.7 (10) |
O1—N1—C1 | 118.74 (11) | C8—C9—H92 | 112.3 (8) |
C5—N2—C4 | 117.73 (11) | H91—C9—H92 | 106.8 (13) |
C4—N3—C8 | 121.56 (10) | C8—C9—H93 | 109.6 (10) |
C4—N3—C6 | 121.56 (10) | H91—C9—H93 | 109.7 (13) |
C8—N3—C6 | 116.44 (10) | H92—C9—H93 | 109.7 (13) |
O22—N21—O21 | 122.40 (11) | C25—C21—C22 | 119.48 (11) |
O22—N21—C21 | 118.76 (10) | C25—C21—N21 | 120.05 (11) |
O21—N21—C21 | 118.83 (11) | C22—C21—N21 | 120.45 (11) |
C25—N22—C24 | 117.57 (11) | C23—C22—C21 | 118.39 (11) |
C24—N23—C28 | 121.83 (10) | C23—C22—H22 | 121.9 (8) |
C24—N23—C26 | 121.11 (11) | C21—C22—H22 | 119.7 (8) |
C28—N23—C26 | 117.04 (10) | C22—C23—C24 | 119.18 (11) |
C5—C1—C2 | 119.45 (11) | C22—C23—H23 | 120.7 (8) |
C5—C1—N1 | 120.00 (11) | C24—C23—H23 | 120.1 (8) |
C2—C1—N1 | 120.51 (11) | N23—C24—N22 | 116.45 (11) |
C3—C2—C1 | 118.38 (12) | N23—C24—C23 | 121.68 (11) |
C3—C2—H2 | 120.3 (8) | N22—C24—C23 | 121.87 (11) |
C1—C2—H2 | 121.3 (8) | N22—C25—C21 | 123.42 (12) |
C2—C3—C4 | 119.40 (11) | N22—C25—H25 | 118.6 (8) |
C2—C3—H3 | 120.3 (9) | C21—C25—H25 | 118.0 (8) |
C4—C3—H3 | 120.1 (9) | N23—C26—C27 | 112.96 (11) |
N3—C4—N2 | 116.80 (11) | N23—C26—H261 | 108.2 (8) |
N3—C4—C3 | 121.76 (11) | C27—C26—H261 | 111.1 (8) |
N2—C4—C3 | 121.44 (11) | N23—C26—H262 | 105.5 (8) |
N2—C5—C1 | 123.59 (11) | C27—C26—H262 | 113.1 (8) |
N2—C5—H5 | 116.6 (9) | H261—C26—H262 | 105.5 (11) |
C1—C5—H5 | 119.8 (9) | C26—C27—H271 | 109.5 (9) |
N3—C6—C7 | 112.89 (11) | C26—C27—H272 | 110.2 (10) |
N3—C6—H61 | 107.2 (8) | H271—C27—H272 | 105.9 (13) |
C7—C6—H61 | 110.9 (8) | C26—C27—H273 | 110.5 (10) |
N3—C6—H62 | 107.6 (8) | H271—C27—H273 | 113.2 (13) |
C7—C6—H62 | 111.3 (8) | H272—C27—H273 | 107.5 (13) |
H61—C6—H62 | 106.8 (12) | N23—C28—C29 | 112.63 (12) |
C6—C7—H71 | 108.8 (9) | N23—C28—H281 | 109.7 (8) |
C6—C7—H72 | 108.8 (9) | C29—C28—H281 | 111.2 (8) |
H71—C7—H72 | 107.4 (12) | N23—C28—H282 | 106.0 (8) |
C6—C7—H73 | 111.4 (9) | C29—C28—H282 | 111.4 (8) |
H71—C7—H73 | 109.8 (12) | H281—C28—H282 | 105.6 (11) |
H72—C7—H73 | 110.7 (12) | C28—C29—H291 | 110.2 (10) |
N3—C8—C9 | 112.83 (11) | C28—C29—H292 | 111.5 (9) |
N3—C8—H81 | 106.5 (8) | H291—C29—H292 | 108.0 (14) |
C9—C8—H81 | 111.2 (8) | C28—C29—H293 | 110.7 (9) |
N3—C8—H82 | 109.4 (7) | H291—C29—H293 | 108.7 (12) |
C9—C8—H82 | 109.8 (8) | H292—C29—H293 | 107.6 (12) |
Acknowledgements
We thank the EPSRC (UK) for financial support.
References
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