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The first two crystal structures of en­amines derived from 1-n-alkyl-3-methyl-5-pyrazolones, namely 1-(n-hexyl)-3-methyl-4-[1-(phenyl­amino)­propyl­idene]-2-pyrazolin-5-one, C19H27N3O, (I), and N,N'-bis{1-[1-(n-hexyl)-3-methyl-5-oxo-2-pyrazolin-4-yl­idene]­ethyl}hexane-1,6-di­amine, C30H52N6O2, (II), are reported. The mol­ecule of (II) lies about an inversion centre. Both (I) and (II) are stabilized by intramolecular N-H...O hydrogen bonding. This confirms previous results based on spectroscopic evidence alone.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270104018736/ob1196sup1.cif
Contains datablocks global, I, II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270104018736/ob1196Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270104018736/ob1196IIsup3.hkl
Contains datablock II

CCDC references: 251342; 251343

Comment top

Pyrazolones constitute an important group of organic compounds (Wiley & Wiley, 1964; Elguero, 1984; Elguero, 1996; Elnagdi et al., 1985), for both theoretical and practical reasons (Kuznetsov et al., 2001). Their application fields include analgesics and antiinflammatory drugs (Kees et al., 1996; Gürzov et al., 2000), dyes (Venkataraman, 1952), chelating extractants for several ions (Petinari et al., 1999, 2000), etc.

In addition, these compounds exhibit prototropic tautomerism, a subject that has attracted much attention (Elguero et al., 1976; Wolfgang & Reiner, 1981; Nivorozhkin et al., 1985; Uraev et al., 1989, 2000; Gilchrist, 2001). In solution, the situation may become quite complex to analyse, since several equilibria among the different possible tautomers may be established. Such equilibria depend on the structure of the compound, its concentration, the nature of the solvent and the temperature (Kurkovskaya et al., 1973). Further difficulties arise from inherent limitations in the spectroscopic techniques used in the study of these equilibria. In spite of this, 1H, 13C and 15N NMR spectroscopies are still very powerful tools to undertake these studies in solution and thus are the most frequently used. Only in those cases where single crystals can be obtained does X-ray diffraction allow the unambiguous establishment of the structure of the tautomeric form (see, for example, O'Connell et al., 1985; Uzoukwu et al., 1993; Akama et al., 1995; Holzer et al., 2003).

Pyrazolones have been obtained by the same synthetic procedure, a condensation between an acylacetate and a hydrazine, for more than a century (Knorr, 1884; Varvouris et al., 2001). In spite of the many advantages of 1-alkylpyrazolone derivatives (viz. their greater solubility), most literature reports deal with 1-phenylpyrazolones or N-1 unsubstituted pyrazolones, and only recently has research aimed at synthesizing 1-alkylpyrazolones and derivatives been undertaken (Bartulin et al., 1992, 1994; Belmar et al., 1997, 1999), paying particular attention to the study of the tautomerism involved. These efforts finally led to the obtention of the title enamines, (I) and (II), derived from 4-acyl-1-(n-hexyl)-3-methyl-5-pyrazolones (Belmar et al., 2004). \sch

The fact that several tautomers can be envisaged for (I) and (II) left open the question of whether there was one single tautomer or a mixture of them in the solid state. Both situations have been shown to occur in related compounds (Foces-Foces et al., 2000). Based upon 1H, 13C and 15N NMR measurements, it was concluded at the time that, in solution (CDCl3), (I) and (II) exist mainly as enamines stabilized by an intramolecular hydrogen bond (case D in Scheme 2). In addition, IR measurements had also suggested that the same tautomeric species was present in the solid state, though unfortunately no single crystals could be obtained to support this hypothesis further. Furthermore, to our knowledge and to date, not a single-crystal structure of enamines derived from alkylpyrazolones has been reported, in contrast with their 1-aryl homologues, of which a few are known (see, for example, Singh et al., 1995; Malhotra et al., 1997; Wang et al., 2003; Jiang et al., 2004). In this paper, we present the first examples of two such structures, (I) and (II). Scheme 2 here.

Figs. 1 and 2 show molecular diagrams of the two structures, and Tables 1 and 3 give selected bond lengths. From the analysis of the values therein, it can be concluded that C1O1 and C2C5 are well defined double bonds, and that the shortest bond in the heterocycle (and therefore, the one with enhanced double-bond character) is N2C3. All these features point to the enamine character of both compounds. In addition, both structures share an intramolecular medium-strength hydrogen bond (N3—H3N···O1; Tables 2 and 4), all of which fully confirms the hypothesis previously raised on spectroscopic grounds alone.

The analogies between the two compounds go even further. The group of 17 atoms determined by the heterocyclic ring, the alkyl substituent at N1 and the C atoms bound to atoms C3, C5 and N3 present exactly the same conformation in both structures, with a least-squares fit (SHELXTL/PC; Sheldrick, 1994) of both moieties giving a mean deviation of 0.08 (1) Å (Fig. 3). Regarding their differences, the largest one arises from the sustituents at N3, a phenyl group in (I) and an alkyl C6H12 chain in (II).

In fact, the alkyl chain lies on a symmetry centre in (II), thus defining a dimeric unit, in contrast with the monomeric character of (I). But even here, there is a striking similarity to be found. In (I), the terminal phenyl groups related by the symmetry operation (1 − x, 1 − y, 1 − z) appear connected by a ππ bond, with an interplanar distance of 3.60 (1) Å, a centre-to-centre distance of 3.78 (1) Å and a slippage angle of 17.7 (1)° (Fig. 1; for details, see Janiak, 2000). This second-order interaction also has the effect of defining some sort of dimer in (I), which thus becomes a structural unit fully comparable with that in (II): both are centrosymmetric, and present the terminal alkyl chains in a position trans to each other, at right angles to the line connecting their bases [angles of the lateral chains to the N1···N1' line are 90.2 (2)° in (I) and 92.9 (2)° in (II)].

Both `dimers', however, have different shapes, which also promote different packing interactions. In (I), the two almost-perpendicular aromatic rings [dihedral angle 80.1 (2)°] develop ππ interactions with their respective centrosymmetric counterparts, the first with that at (1/2,1/2,1/2) (the above-mentioned interaction between the phenyl groups which define the `elementary dimers'), and the second with that at (0,0,1/2), connecting the aromatic system composed of the heterocyclic ring plus C1O1 and C2C5 with its (-x, −y, 1 − z) image, 3.50 (3) Å apart and with 4.20 (3) Å between centres, linking the former units together (Fig. 4). Structure (II) instead lacks any particular intermolecular contacts shorter than the usual van der Waals interactions. In spite of these dissimilar interactions, in both structures the terminal alkyl groups arrange in space in a similar way, as centrosymmetric pairs parallel to one another and at a nearest C···C distance of ca 4.20 Å.

Experimental top

4-Acetyl-1-(n-hexyl)-3-methylpyrazol-5-ol and 1-(n-hexyl)-3-methyl-4-propionylpyrazol-5-ol were prepared using the usual methods of Jensen (1959) and Belmar et al. (1997). Each reaction was carried out using a magnetic stirrer in a flask provided with a Dean Stark Something missing? to separate the water produced during the reaction. Acylpyrazolone and the corresponding amine were dissolved in toluene and heated to reflux. The solution was then washed with brine until a neutral pH was achieved and then dried over Na2SO4. After filtration, the solution was concentrated in a rotary evaporator to obtain the crude product of enamines. For the preparation of (I), 1-(n-hexyl)-3-methyl-4-propionylpyrazol-5-ol (1.00 g, 4.2 mmol) and aniline (0.4 ml, 4.2 mmol) in toluene (10 ml) were heated to reflux for 8 h. The crude product of (I) was crystallized from a heptane solution (yield 0.79 g, 60%; m.p. 367 K). Elemental analysis, calculated: C 72.81, H 8.68, N 13.41%; found: C 72.70, H 8.70, N 13.50%. For the preparation of (II), 4-acetyl-1-(n-hexyl)-3-methylpyrazol-5-ol (3.00 g, 13.4 mmol) and 1,6-diaminohexane (0.93 g, 8.0 mmol) in toluene (20 ml) were heated to reflux for 10 h. The crude product of (II) was crystallized from a hexane-ethyl acetate mixture (Ratio?) (yield 1.42 g, 40%; m.p. 389 K). Elemental analysis, calculated: C 68.14, H 9.91, N 15.89%; found: C 68.00, H 10.00, N 16.20%.

Refinement top

Even though all H atoms were clearly seen in difference Fourier maps (in particular those involved in intramolecular N—H···O bonds), for simplicity they were placed in their theoretical positions (C—H = 0.93–0.97 and N—H = 0.86 Å) and allowed to ride on their parent atoms, with Uiso(H) = 1.2Ueq(C,N) [or 1.5Ueq(C) for methyl groups]. The latter were allowed to rotate as well. Full use of the CCDC package was made for searching in the Cambridge Structural Database (Allen, 2002).

Computing details top

For both compounds, data collection: SMART (Bruker, 2001); cell refinement: SMART; data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL/PC (Sheldrick, 1994); software used to prepare material for publication: SHELXTL/PC.

Figures top
[Figure 1] Fig. 1. A molecular diagram for (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 40% probability level and H atoms have been omitted, apart from those involved in hydrogen bonds, which are shown as small spheres of arbitrary radii. Full ellipsoids denote the independent molecule and open ones the symmetry-related moiety, and double broken lines denote the ππ intaraction linking them. Single dashed lines denote the hydrogen bonds.
[Figure 2] Fig. 2. A molecular diagram for (II), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 40% probability level and H atoms have been omitted, apart from those involved in hydrogen bonds, which are shown as small spheres of arbitrary radii. Full ellipsoids denote the independent molecule and open ones the symmetry-related moiety. Single dashed lines denote the hydrogen bonds.
[Figure 3] Fig. 3. A superposition diagram, showing the similarities between the two nuclei of (I) and (II). All H atoms except H3N have been omitted for clarity.
[Figure 4] Fig. 4. A packing diagram for (I), showing the leading interactions. For clarity, only H atoms involved in hydrogen bonding have been included.
(I) 1-(n-hexyl)-3-methyl-4-(1-phenylaminopropylidene)-2-pyrazolin-5-one top
Crystal data top
C19H27N3OZ = 2
Mr = 313.44F(000) = 340
Triclinic, P1Dx = 1.158 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 9.0221 (14) ÅCell parameters from 2388 reflections
b = 9.1427 (14) Åθ = 4.5–50.1°
c = 11.9077 (18) ŵ = 0.07 mm1
α = 85.111 (2)°T = 300 K
β = 68.812 (2)°Prisms, yellow
γ = 78.911 (2)°0.32 × 0.14 × 0.12 mm
V = 898.6 (2) Å3
Data collection top
Bruker SMART CCD area-detector
diffractometer
2155 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.020
Graphite monochromatorθmax = 25.0°, θmin = 1.8°
ϕ and ω scansh = 1010
5601 measured reflectionsk = 1010
3132 independent reflectionsl = 1414
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.049Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.158H-atom parameters constrained
S = 1.07 w = 1/[σ2(Fo2) + (0.0865P)2]
where P = (Fo2 + 2Fc2)/3
3132 reflections(Δ/σ)max = 0.004
211 parametersΔρmax = 0.25 e Å3
0 restraintsΔρmin = 0.28 e Å3
Crystal data top
C19H27N3Oγ = 78.911 (2)°
Mr = 313.44V = 898.6 (2) Å3
Triclinic, P1Z = 2
a = 9.0221 (14) ÅMo Kα radiation
b = 9.1427 (14) ŵ = 0.07 mm1
c = 11.9077 (18) ÅT = 300 K
α = 85.111 (2)°0.32 × 0.14 × 0.12 mm
β = 68.812 (2)°
Data collection top
Bruker SMART CCD area-detector
diffractometer
2155 reflections with I > 2σ(I)
5601 measured reflectionsRint = 0.020
3132 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0490 restraints
wR(F2) = 0.158H-atom parameters constrained
S = 1.07Δρmax = 0.25 e Å3
3132 reflectionsΔρmin = 0.28 e Å3
211 parameters
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O10.33453 (18)0.88340 (16)0.28489 (13)0.0709 (4)
N10.20236 (19)1.12682 (18)0.28119 (15)0.0631 (5)
N20.11541 (18)1.24112 (18)0.36057 (16)0.0641 (5)
N30.31692 (18)0.80665 (16)0.51385 (14)0.0571 (4)
H3N0.34990.78870.43820.068*
C10.2555 (2)1.0027 (2)0.33617 (18)0.0561 (5)
C20.1989 (2)1.03999 (19)0.46136 (17)0.0502 (5)
C30.1115 (2)1.1902 (2)0.46784 (18)0.0557 (5)
C40.0217 (3)1.2879 (2)0.5722 (2)0.0735 (6)
H4A0.02481.38140.54540.110*
H4B0.09401.30470.61040.110*
H4C0.06261.24090.62870.110*
C50.2296 (2)0.94039 (19)0.54886 (16)0.0496 (5)
C60.1784 (2)0.9790 (2)0.67776 (17)0.0580 (5)
H6A0.16340.88920.72720.070*
H6B0.07581.04670.70070.070*
C70.3026 (3)1.0515 (2)0.7010 (2)0.0765 (7)
H7A0.26781.07190.78530.115*
H7B0.31351.14310.65530.115*
H7C0.40470.98540.67710.115*
C80.3616 (2)0.68928 (19)0.58946 (16)0.0515 (5)
C90.2538 (2)0.5986 (2)0.65451 (18)0.0618 (5)
H9A0.15000.61500.65210.074*
C100.3010 (3)0.4830 (2)0.72332 (19)0.0701 (6)
H10A0.22840.42150.76770.084*
C110.4541 (3)0.4578 (2)0.72692 (19)0.0701 (6)
H11A0.48530.37960.77340.084*
C120.5602 (3)0.5480 (2)0.6620 (2)0.0734 (6)
H12A0.66430.53060.66380.088*
C130.5143 (2)0.6649 (2)0.59368 (19)0.0639 (6)
H13A0.58680.72700.55050.077*
C140.2228 (3)1.1460 (3)0.15446 (19)0.0770 (7)
H14A0.11901.18760.14760.092*
H14B0.25831.04900.11730.092*
C150.3426 (3)1.2461 (3)0.0859 (2)0.0824 (7)
H15A0.34671.25600.00320.099*
H15B0.30461.34440.12090.099*
C160.5102 (3)1.1905 (2)0.0865 (2)0.0753 (6)
H16A0.54361.08830.05930.090*
H16B0.50751.19000.16860.090*
C170.6347 (3)1.2811 (3)0.0084 (2)0.0798 (7)
H17A0.64401.27470.07480.096*
H17B0.59721.38480.03120.096*
C180.7992 (3)1.2321 (3)0.0173 (2)0.0925 (8)
H18A0.78891.23580.10100.111*
H18B0.83741.12900.00720.111*
C190.9231 (3)1.3219 (4)0.0564 (3)0.1162 (10)
H19A1.02301.28460.04390.174*
H19B0.88721.42420.03280.174*
H19C0.93891.31480.14010.174*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0852 (10)0.0624 (9)0.0647 (9)0.0039 (8)0.0312 (8)0.0031 (7)
N10.0625 (10)0.0637 (11)0.0643 (11)0.0100 (8)0.0283 (8)0.0178 (9)
N20.0543 (10)0.0604 (10)0.0764 (12)0.0104 (8)0.0261 (9)0.0211 (9)
N30.0646 (10)0.0498 (9)0.0557 (10)0.0031 (8)0.0251 (8)0.0073 (7)
C10.0533 (11)0.0548 (12)0.0657 (13)0.0146 (9)0.0280 (10)0.0134 (10)
C20.0445 (10)0.0480 (10)0.0615 (12)0.0123 (8)0.0234 (8)0.0121 (8)
C30.0449 (10)0.0532 (11)0.0699 (13)0.0134 (9)0.0224 (9)0.0149 (10)
C40.0718 (14)0.0540 (12)0.0889 (16)0.0023 (10)0.0279 (12)0.0084 (11)
C50.0427 (10)0.0471 (10)0.0605 (12)0.0129 (8)0.0196 (8)0.0090 (8)
C60.0591 (12)0.0498 (11)0.0608 (13)0.0069 (9)0.0198 (10)0.0100 (9)
C70.0900 (16)0.0735 (14)0.0780 (15)0.0166 (12)0.0435 (13)0.0016 (12)
C80.0566 (11)0.0442 (10)0.0540 (11)0.0041 (8)0.0235 (9)0.0042 (8)
C90.0595 (12)0.0577 (12)0.0709 (13)0.0121 (10)0.0271 (10)0.0078 (10)
C100.0855 (16)0.0537 (12)0.0679 (14)0.0167 (11)0.0244 (12)0.0152 (10)
C110.0896 (17)0.0537 (12)0.0615 (13)0.0075 (11)0.0320 (12)0.0061 (10)
C120.0636 (13)0.0782 (15)0.0785 (15)0.0054 (12)0.0354 (12)0.0045 (12)
C130.0536 (12)0.0637 (13)0.0735 (14)0.0095 (10)0.0242 (10)0.0106 (10)
C140.0746 (14)0.0952 (17)0.0686 (15)0.0194 (13)0.0374 (12)0.0248 (12)
C150.0816 (16)0.0932 (17)0.0718 (15)0.0159 (13)0.0328 (12)0.0295 (13)
C160.0785 (15)0.0766 (15)0.0712 (15)0.0143 (12)0.0285 (12)0.0079 (12)
C170.0848 (16)0.0916 (16)0.0627 (14)0.0204 (13)0.0255 (12)0.0096 (12)
C180.0914 (18)0.1036 (19)0.0853 (18)0.0243 (16)0.0325 (15)0.0056 (15)
C190.097 (2)0.149 (3)0.102 (2)0.045 (2)0.0274 (17)0.0189 (19)
Geometric parameters (Å, º) top
O1—C11.253 (2)C10—C111.372 (3)
N1—C11.355 (2)C10—H10A0.9300
N1—N21.385 (2)C11—C121.361 (3)
N1—C141.452 (3)C11—H11A0.9300
N2—C31.312 (2)C12—C131.378 (3)
N3—C51.330 (2)C12—H12A0.9300
N3—C81.434 (2)C13—H13A0.9300
N3—H3N0.8600C14—C151.512 (3)
C1—C21.438 (3)C14—H14A0.9700
C2—C51.394 (2)C14—H14B0.9700
C2—C31.439 (2)C15—C161.501 (3)
C3—C41.477 (3)C15—H15A0.9700
C4—H4A0.9600C15—H15B0.9700
C4—H4B0.9600C16—C171.512 (3)
C4—H4C0.9600C16—H16A0.9700
C5—C61.487 (3)C16—H16B0.9700
C6—C71.521 (3)C17—C181.504 (3)
C6—H6A0.9700C17—H17A0.9700
C6—H6B0.9700C17—H17B0.9700
C7—H7A0.9600C18—C191.488 (3)
C7—H7B0.9600C18—H18A0.9700
C7—H7C0.9600C18—H18B0.9700
C8—C131.372 (3)C19—H19A0.9600
C8—C91.375 (2)C19—H19B0.9600
C9—C101.379 (3)C19—H19C0.9600
C9—H9A0.9300
C1—N1—N2112.89 (16)C12—C11—C10119.61 (18)
C1—N1—C14127.03 (19)C12—C11—H11A120.2
N2—N1—C14120.04 (16)C10—C11—H11A120.2
C3—N2—N1106.42 (15)C11—C12—C13120.49 (19)
C5—N3—C8126.59 (16)C11—C12—H12A119.8
C5—N3—H3N116.7C13—C12—H12A119.8
C8—N3—H3N116.7C8—C13—C12119.86 (18)
O1—C1—N1125.42 (19)C8—C13—H13A120.1
O1—C1—C2129.71 (17)C12—C13—H13A120.1
N1—C1—C2104.86 (17)N1—C14—C15113.81 (18)
C5—C2—C1122.63 (16)N1—C14—H14A108.8
C5—C2—C3132.34 (18)C15—C14—H14A108.8
C1—C2—C3105.03 (15)N1—C14—H14B108.8
N2—C3—C2110.79 (18)C15—C14—H14B108.8
N2—C3—C4118.51 (18)H14A—C14—H14B107.7
C2—C3—C4130.70 (18)C16—C15—C14113.80 (18)
C3—C4—H4A109.5C16—C15—H15A108.8
C3—C4—H4B109.5C14—C15—H15A108.8
H4A—C4—H4B109.5C16—C15—H15B108.8
C3—C4—H4C109.5C14—C15—H15B108.8
H4A—C4—H4C109.5H15A—C15—H15B107.7
H4B—C4—H4C109.5C15—C16—C17114.42 (18)
N3—C5—C2118.10 (17)C15—C16—H16A108.7
N3—C5—C6118.36 (15)C17—C16—H16A108.7
C2—C5—C6123.43 (16)C15—C16—H16B108.7
C5—C6—C7111.51 (15)C17—C16—H16B108.7
C5—C6—H6A109.3H16A—C16—H16B107.6
C7—C6—H6A109.3C18—C17—C16114.03 (19)
C5—C6—H6B109.3C18—C17—H17A108.7
C7—C6—H6B109.3C16—C17—H17A108.7
H6A—C6—H6B108.0C18—C17—H17B108.7
C6—C7—H7A109.5C16—C17—H17B108.7
C6—C7—H7B109.5H17A—C17—H17B107.6
H7A—C7—H7B109.5C19—C18—C17115.1 (2)
C6—C7—H7C109.5C19—C18—H18A108.5
H7A—C7—H7C109.5C17—C18—H18A108.5
H7B—C7—H7C109.5C19—C18—H18B108.5
C13—C8—C9120.04 (17)C17—C18—H18B108.5
C13—C8—N3119.64 (17)H18A—C18—H18B107.5
C9—C8—N3120.29 (16)C18—C19—H19A109.5
C8—C9—C10119.42 (19)C18—C19—H19B109.5
C8—C9—H9A120.3H19A—C19—H19B109.5
C10—C9—H9A120.3C18—C19—H19C109.5
C11—C10—C9120.6 (2)H19A—C19—H19C109.5
C11—C10—H10A119.7H19B—C19—H19C109.5
C9—C10—H10A119.7
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N3—H3N···O10.861.992.712 (2)141
(II) N,N'-bis{1-[1-(n-hexyl)-3-methyl-5-oxo-2-pyrazolin-4-ylidene]ethyl}hexane- 1,6-diamine top
Crystal data top
C30H52N6O2Z = 1
Mr = 528.78F(000) = 290
Triclinic, P1Dx = 1.141 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 8.0168 (13) ÅCell parameters from 1755 reflections
b = 9.5029 (15) Åθ = 5.0–47.1°
c = 10.7032 (17) ŵ = 0.07 mm1
α = 71.357 (2)°T = 293 K
β = 86.811 (2)°Prisms, yellow
γ = 85.112 (3)°0.28 × 0.16 × 0.10 mm
V = 769.5 (2) Å3
Data collection top
Bruker SMART CCD area-detector
diffractometer
1477 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.056
Graphite monochromatorθmax = 25.0°, θmin = 2.0°
ϕ and ω scansh = 99
5582 measured reflectionsk = 1111
2689 independent reflectionsl = 1212
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.048Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.152H-atom parameters constrained
S = 0.93 w = 1/[σ2(Fo2) + (0.0659P)2]
where P = (Fo2 + 2Fc2)/3
2689 reflections(Δ/σ)max = 0.007
174 parametersΔρmax = 0.25 e Å3
0 restraintsΔρmin = 0.27 e Å3
Crystal data top
C30H52N6O2γ = 85.112 (3)°
Mr = 528.78V = 769.5 (2) Å3
Triclinic, P1Z = 1
a = 8.0168 (13) ÅMo Kα radiation
b = 9.5029 (15) ŵ = 0.07 mm1
c = 10.7032 (17) ÅT = 293 K
α = 71.357 (2)°0.28 × 0.16 × 0.10 mm
β = 86.811 (2)°
Data collection top
Bruker SMART CCD area-detector
diffractometer
1477 reflections with I > 2σ(I)
5582 measured reflectionsRint = 0.056
2689 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0480 restraints
wR(F2) = 0.152H-atom parameters constrained
S = 0.93Δρmax = 0.25 e Å3
2689 reflectionsΔρmin = 0.27 e Å3
174 parameters
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O10.2199 (2)0.0708 (2)0.27772 (17)0.0680 (6)
N10.1036 (3)0.1523 (2)0.3047 (2)0.0535 (6)
N20.0615 (2)0.2787 (2)0.4054 (2)0.0549 (6)
N30.2937 (2)0.0847 (2)0.5155 (2)0.0535 (6)
H3N0.28750.12020.43110.064*
C10.1729 (3)0.0519 (3)0.3489 (2)0.0496 (6)
C20.1765 (3)0.1196 (3)0.4894 (2)0.0447 (6)
C30.1037 (3)0.2591 (3)0.5151 (2)0.0475 (6)
C40.0703 (4)0.3769 (3)0.6427 (3)0.0687 (8)
H4A0.02290.45840.62600.103*
H4B0.00680.33650.69640.103*
H4C0.17340.41180.68790.103*
C50.2395 (3)0.0484 (3)0.5709 (2)0.0475 (6)
C60.2512 (4)0.1164 (3)0.7164 (2)0.0673 (8)
H6A0.29660.04790.75240.101*
H6B0.32290.20650.73600.101*
H6C0.14160.13880.75480.101*
C70.3632 (3)0.1790 (3)0.5803 (3)0.0579 (7)
H7A0.46550.12960.62310.069*
H7B0.28420.19380.64770.069*
C80.4003 (3)0.3272 (3)0.4837 (3)0.0612 (8)
H8A0.29670.37840.44470.073*
H8B0.47370.31160.41340.073*
C90.4823 (3)0.4246 (2)0.5468 (3)0.0576 (7)
H9A0.41000.43750.61860.069*
H9B0.58690.37370.58420.069*
C100.0750 (3)0.1397 (3)0.1691 (3)0.0654 (8)
H10A0.08790.03770.11420.078*
H10B0.03940.16180.16230.078*
C110.1929 (4)0.2426 (3)0.1171 (3)0.0703 (8)
H11A0.18970.34290.17810.084*
H11B0.15290.24310.03340.084*
C120.3716 (4)0.2011 (3)0.0977 (3)0.0671 (8)
H12A0.40870.19210.17930.081*
H12B0.37630.10440.03080.081*
C130.4907 (3)0.3114 (3)0.0569 (3)0.0694 (8)
H13A0.48280.40860.12260.083*
H13B0.45470.31820.02590.083*
C140.6687 (4)0.2757 (4)0.0408 (3)0.0848 (10)
H14A0.70660.27450.12490.102*
H14B0.67580.17620.02120.102*
C150.7860 (4)0.3816 (4)0.0071 (3)0.0920 (11)
H15A0.89790.35040.01490.138*
H15B0.75180.38180.09160.138*
H15C0.78280.48020.05470.138*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0953 (15)0.0570 (12)0.0530 (12)0.0228 (11)0.0011 (10)0.0151 (10)
N10.0629 (14)0.0567 (14)0.0472 (13)0.0125 (11)0.0026 (10)0.0230 (12)
N20.0559 (14)0.0554 (14)0.0605 (15)0.0110 (11)0.0026 (11)0.0274 (12)
N30.0593 (14)0.0543 (14)0.0541 (14)0.0115 (11)0.0045 (10)0.0248 (12)
C10.0520 (16)0.0481 (16)0.0531 (17)0.0080 (13)0.0005 (12)0.0213 (14)
C20.0473 (15)0.0441 (15)0.0464 (15)0.0040 (12)0.0004 (11)0.0192 (12)
C30.0467 (15)0.0428 (15)0.0544 (17)0.0036 (12)0.0047 (12)0.0183 (13)
C40.082 (2)0.0574 (18)0.069 (2)0.0165 (15)0.0057 (16)0.0212 (16)
C50.0454 (15)0.0481 (16)0.0519 (16)0.0002 (12)0.0010 (12)0.0208 (13)
C60.086 (2)0.0651 (19)0.0568 (18)0.0072 (16)0.0075 (15)0.0258 (15)
C70.0577 (17)0.0606 (18)0.0685 (19)0.0121 (14)0.0026 (13)0.0366 (16)
C80.0580 (17)0.0572 (17)0.078 (2)0.0076 (14)0.0072 (14)0.0326 (16)
C90.0525 (16)0.0560 (16)0.074 (2)0.0076 (14)0.0059 (14)0.0330 (14)
C100.0650 (18)0.088 (2)0.0553 (18)0.0113 (16)0.0072 (14)0.0367 (16)
C110.081 (2)0.080 (2)0.0641 (19)0.0147 (17)0.0014 (15)0.0406 (17)
C120.079 (2)0.0671 (19)0.0619 (19)0.0147 (16)0.0031 (15)0.0279 (16)
C130.078 (2)0.073 (2)0.0649 (19)0.0134 (17)0.0001 (15)0.0309 (16)
C140.081 (2)0.091 (2)0.093 (2)0.0233 (19)0.0142 (18)0.041 (2)
C150.077 (2)0.099 (3)0.106 (3)0.003 (2)0.0066 (19)0.042 (2)
Geometric parameters (Å, º) top
O1—C11.248 (3)C8—H8A0.9700
N1—C11.360 (3)C8—H8B0.9700
N1—N21.385 (3)C9—C9i1.502 (5)
N1—C101.447 (3)C9—H9A0.9700
N2—C31.312 (3)C9—H9B0.9700
N3—C51.313 (3)C10—C111.514 (3)
N3—C71.456 (3)C10—H10A0.9700
N3—H3N0.8600C10—H10B0.9700
C1—C21.435 (3)C11—C121.503 (4)
C2—C51.399 (3)C11—H11A0.9700
C2—C31.433 (3)C11—H11B0.9700
C3—C41.492 (3)C12—C131.509 (4)
C4—H4A0.9600C12—H12A0.9700
C4—H4B0.9600C12—H12B0.9700
C4—H4C0.9600C13—C141.483 (4)
C5—C61.488 (3)C13—H13A0.9700
C6—H6A0.9600C13—H13B0.9700
C6—H6B0.9600C14—C151.509 (4)
C6—H6C0.9600C14—H14A0.9700
C7—C81.499 (3)C14—H14B0.9700
C7—H7A0.9700C15—H15A0.9600
C7—H7B0.9700C15—H15B0.9600
C8—C91.516 (3)C15—H15C0.9600
C1—N1—N2112.98 (19)C9i—C9—C8114.0 (3)
C1—N1—C10127.1 (2)C9i—C9—H9A108.8
N2—N1—C10119.9 (2)C8—C9—H9A108.8
C3—N2—N1105.94 (19)C9i—C9—H9B108.8
C5—N3—C7127.6 (2)C8—C9—H9B108.8
C5—N3—H3N116.2H9A—C9—H9B107.7
C7—N3—H3N116.2N1—C10—C11113.3 (2)
O1—C1—N1125.2 (2)N1—C10—H10A108.9
O1—C1—C2130.2 (2)C11—C10—H10A108.9
N1—C1—C2104.7 (2)N1—C10—H10B108.9
C5—C2—C3133.3 (2)C11—C10—H10B108.9
C5—C2—C1121.7 (2)H10A—C10—H10B107.7
C3—C2—C1105.1 (2)C12—C11—C10114.3 (2)
N2—C3—C2111.3 (2)C12—C11—H11A108.7
N2—C3—C4118.6 (2)C10—C11—H11A108.7
C2—C3—C4130.1 (2)C12—C11—H11B108.7
C3—C4—H4A109.5C10—C11—H11B108.7
C3—C4—H4B109.5H11A—C11—H11B107.6
H4A—C4—H4B109.5C11—C12—C13113.9 (2)
C3—C4—H4C109.5C11—C12—H12A108.8
H4A—C4—H4C109.5C13—C12—H12A108.8
H4B—C4—H4C109.5C11—C12—H12B108.8
N3—C5—C2118.2 (2)C13—C12—H12B108.8
N3—C5—C6118.3 (2)H12A—C12—H12B107.7
C2—C5—C6123.5 (2)C14—C13—C12115.1 (2)
C5—C6—H6A109.5C14—C13—H13A108.5
C5—C6—H6B109.5C12—C13—H13A108.5
H6A—C6—H6B109.5C14—C13—H13B108.5
C5—C6—H6C109.5C12—C13—H13B108.5
H6A—C6—H6C109.5H13A—C13—H13B107.5
H6B—C6—H6C109.5C13—C14—C15114.9 (3)
N3—C7—C8111.4 (2)C13—C14—H14A108.5
N3—C7—H7A109.4C15—C14—H14A108.5
C8—C7—H7A109.4C13—C14—H14B108.5
N3—C7—H7B109.4C15—C14—H14B108.5
C8—C7—H7B109.4H14A—C14—H14B107.5
H7A—C7—H7B108.0C14—C15—H15A109.5
C7—C8—C9112.6 (2)C14—C15—H15B109.5
C7—C8—H8A109.1H15A—C15—H15B109.5
C9—C8—H8A109.1C14—C15—H15C109.5
C7—C8—H8B109.1H15A—C15—H15C109.5
C9—C8—H8B109.1H15B—C15—H15C109.5
H8A—C8—H8B107.8
Symmetry code: (i) x+1, y+1, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N3—H3N···O10.861.962.691 (3)142

Experimental details

(I)(II)
Crystal data
Chemical formulaC19H27N3OC30H52N6O2
Mr313.44528.78
Crystal system, space groupTriclinic, P1Triclinic, P1
Temperature (K)300293
a, b, c (Å)9.0221 (14), 9.1427 (14), 11.9077 (18)8.0168 (13), 9.5029 (15), 10.7032 (17)
α, β, γ (°)85.111 (2), 68.812 (2), 78.911 (2)71.357 (2), 86.811 (2), 85.112 (3)
V3)898.6 (2)769.5 (2)
Z21
Radiation typeMo KαMo Kα
µ (mm1)0.070.07
Crystal size (mm)0.32 × 0.14 × 0.120.28 × 0.16 × 0.10
Data collection
DiffractometerBruker SMART CCD area-detector
diffractometer
Bruker SMART CCD area-detector
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
5601, 3132, 2155 5582, 2689, 1477
Rint0.0200.056
(sin θ/λ)max1)0.5950.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.049, 0.158, 1.07 0.048, 0.152, 0.93
No. of reflections31322689
No. of parameters211174
H-atom treatmentH-atom parameters constrainedH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.25, 0.280.25, 0.27

Computer programs: SMART (Bruker, 2001), SMART, SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL/PC (Sheldrick, 1994), SHELXTL/PC.

Selected bond lengths (Å) for (I) top
O1—C11.253 (2)N3—C81.434 (2)
N1—C11.355 (2)C1—C21.438 (3)
N1—N21.385 (2)C2—C51.394 (2)
N1—C141.452 (3)C2—C31.439 (2)
N2—C31.312 (2)C3—C41.477 (3)
N3—C51.330 (2)
Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
N3—H3N···O10.861.992.712 (2)141
Selected bond lengths (Å) for (II) top
O1—C11.248 (3)N3—C51.313 (3)
N1—C11.360 (3)N3—C71.456 (3)
N1—N21.385 (3)C1—C21.435 (3)
N1—C101.447 (3)C2—C51.399 (3)
N2—C31.312 (3)C2—C31.433 (3)
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
N3—H3N···O10.861.962.691 (3)142
 

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