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Reaction of di-tert-butyl ketone with hydrazine hydrate gives di-tert-butyl ketone hydrazone, C9H20N2, which is dimerized by double hydrogen bonding in the solid state. Further reaction of this compound with dibromo­triphenyl­phospho­rane gives di-tert-butyl ketone triphenyl­phosphoranyl­idene­hydrazone, C27H33N2P, in the structure of which double chains parallel to the c axis are formed through weak C—H...π and π–π stacking inter­actions. The hydrazone group is nearly planar in both cases. In the second compound, one of the aromatic rings is nearly coplanar with the hydrazone moiety, indicating possible π-conjugation.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270106008687/hj3003sup1.cif
Contains datablocks I, II, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270106008687/hj3003Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270106008687/hj3003IIsup3.hkl
Contains datablock II

CCDC references: 605703; 605704

Comment top

To date, the highly sterically crowded alkene tetra-tert-butylethylene has not been synthesized, in spite of many attempts using various methods, such as the McMurry coupling reaction (Ephritikhine & Villiers, 2004), Barton's extrusion process (Barton et al., 1974) and reactions exploiting other possible pathways (Sulzbach et al., 1996). During our investigations into the McMurry reaction, we have particularly studied the carbonyl coupling of benzophenone and di-tert-butyl ketone with the MCl4/M'(Hg) system (M/M' = U/Na, U/Li or Ti/Li) (Ephritikhine & Villiers, 2004). During this work, we have prepared di-tert-butyl ketone hydrazone, (I), and the new compound di-tert-butyl ketone (triphenylphosphorane)hydrazone, (II), by analogy with the synthesis reported for the two corresponding benzophenone derivatives (Barton et al., 1974; Bestmann & Fritzsche, 1961). The crystal structure of benzophenone (triphenylphosphorane)hydrazone, (III), has been reported previously (Bethell et al., 1992). Compound (II) could not be transformed into tetra-tert-butylethylene.

The asymmetric unit in (I) contains one hydrazone molecule. The C1N2 and N1—N2 bond lengths (Table 1) are in agreement with the mean values reported for similar hydrazones in the Cambridge Structural Database (CSD, Version 5.27; Allen, 2002), which are 1.282 (11) and 1.38 (3) Å, respectively. The C1—C2 and C1—C6 bond lengths and the C2—C1—C6 angle are also in agreement with the mean values for similar di-tBu-substituted sp2-hybridized C atoms reported in the CSD, which are 1.56 (5) Å and 123 (3)°. The value of the N2—C1—C6 angle is lower by about 11° than those of the other two angles around C1, which is likely due to the minimal crowding in the corresponding sector, atom N1 being on the same side as C2. The five atoms N1, N2, C1, C2 and C6 define a plane with an r.m.s. deviation of 0.005 Å. Centrosymmetric dimers are formed through double hydrogen bonding between the N—NH2 groups of two neighbouring molecules, with the formation of a six-membered ring (Fig. 1 and Table 2).

The asymmetric unit in (II) contains two independent but nearly identical molecules, denoted A and B (molecule A is represented in Fig. 2). These two molecules fit to one another with an overall r.m.s. of 0.143 Å (the largest deviations, up to 0.29 Å, are those of atoms in the tBu groups and aromatic rings) (OFIT in SHELXTL; Bruker, 1999). The C1N2 bond lengths [Table 3; mean value 1.2905 (15) Å], as well as the angles around C1, match those in (I), but the N1—N2 distances [mean value 1.4205 (5) Å] are slightly larger than those in compounds (I) and (III) [1.388 (4) Å] and are also larger than the mean value for N—N bond lengths in (triphenylphosphorane)hydrazone CN—NP(C6H5)3 groups reported in the CSD [1.384 (19) Å]. This may be due to the crowding induced by the simultaneous presence of tBu groups and aromatic rings in (II). However, the mean P1N1 bond length of 1.6017 (9) Å is slightly lower than the mean value of 1.616 (13) Å from the CSD and the value of 1.606 (3) Å in (III). These bond lengths indicate the presence of double bonds between C1 and N2 and between P1 and N1. However, their slight deviation from the values tabulated for single and double bonds has been considered as possible evidence of π-conjugation over the whole of the (triphenylphosphorane)hydrazone moiety (Bethell et al., 1992). This moiety adopts a trans geometry with respect to the central N1—N2 bond in (II), as is usual in such compounds (Bethell et al., 1992; Minutolo et al., 1999).

The group defined by the atoms P1, N1, N2, C1, C2 and C6 is close to planarity in both molecules of (II), with r.m.s. deviations of 0.010 and 0.024 Å and P1—N1—N2—C1 torsion angles of 179.55 (14) and 175.93 (14)° in molecules A and B, respectively. One of the aromatic rings in both molecules (atoms C10–C15) is nearly coplanar with the (triphenylphosphorane)hydrazone mean plane, with dihedral angles of 8.70 (12) and 2.78 (12)° in molecules A and B, respectively (but with, however, out-of-plane displacements as large as 0.4 Å). Such a geometry has previously been observed in a related (triphenylphosphorane)hydrazone compound, (2,4-cyclopentadien-1-ylidenehydrazono)triphenylphosphorane, (IV), and considered as indicative of the possibility of π-conjugation between the two fragments, which was supported by the corresponding P—C bond length being slightly smaller that those of the other two, by about 0.011 Å (Minutolo et al., 1999).

The P1—C10 bonds in (II) are also slightly shorter than P1—C16 and P1—C22, by about 0.01–0.02 Å, which confirms the previous observation. However, the C—N, N—N, P—N and P—C bonds in (II) are all longer, by 0.01–0.05 Å, than their counterparts in (IV) (the largest difference corresponds to N—N), which may partly be due to the data collection temperature difference of 98 K, but also to the presence in (IV) of a Cp ring instead of the two tBu groups in (II), with possible additional conjugation effects. The aromatic C—C bond lengths in (II) are in the usual range in all three rings.

The aromatic rings in (II) are involved in several weak intermolecular interactions. ππ stacking interactions are possibly present between the rings C10–C15 (centroid Cg1) and C16–C21 (centroid Cg2) of molecules related by a glide plane, for both A and B molecules [Cg1A···Cg2Ai = 3.76 Å, dihedral angle 7.0°, centroid offset 1.65 Å and shortest interatomic contact 3.26 Å for A molecules; Cg1B···Cg2Bi 3.64 Å, dihedral angle 6.5°, centroid offset 1.22 Å and shortest interatomic contact 3.36 Å for B molecules; symmetry code: (i) x, 3/2 − y, z − 1/2]. Although the shortest interatomic contacts are shorter than twice the out-of-plane van der Waals radius of C (1.7 Å; Reference?), these interactions are weak at best, due to the large offset values.

Three significant C—H···π interactions are also present. One of them links molecules A and B in the asymmetric unit [H13A···Cg1B = 2.74 Å and C13A—H13A···Cg1B = 153°] and the other two involve two sets of adjacent A or B molecules [H20A···Cg3Aii = 2.68 Å and C20A—H20A···Cg3Aii = 154°; H20B···Cg3Bii = 2.60 Å and C20B—H20B···Cg3Bii = 147°; Cg3 is the centroid of the C22–C27 ring; symmetry code: (ii) x, 3/2 − y, z + 1/2]. Molecule A thus acts as a hydrogen-bond donor to two neighbouring molecules and as an acceptor from one, whereas molecule B acts as a single donor and double acceptor. These interactions result in double chains of A and B molecules running along the c axis (Fig. 3).

Experimental top

Reaction of di-tert-butyl ketone with hydrazine hydrate in diethylene glycol gave compound (I) in 94% yield. [Please give brief details of quantities used] The 1H NMR spectrum of (I) in CDCl3 is identical to that previously described (Hartzler, 1971). Reaction of (I) with dibromotriphenylphosphorane gave compound (II) in 60% yield. [Please give brief details of quantities used] 1H NMR (200 MHz, CDCl3, δ, p.p.m.): 1.08 (s, 9H, tBu), 1.56 (s, 9H, tBu), 7.33–7.51 (m, 9H, ortho- and para-Ph3P), 7.61–7.74 (m, 6H, meta-Ph3P). Single crystals of both compounds were obtained by slow evaporation of pentane solutions.

Refinement top

The two H atoms bound to N1 in (I) were found in a difference Fourier map and they were refined with Uiso(H) = 1.2Ueq(N1). All other H atoms in both compounds were introduced at calculated positions as riding atoms, with C—H bond lengths of 0.93 (aromatic CH) or 0.96 Å (CH3), and with Uiso(H) = 1.2Ueq(CH) or 1.5Ueq(CH3).

Computing details top

For both compounds, data collection: COLLECT (Nonius, 1998); cell refinement: HKL-2000 (Otwinowski & Minor, 1997); data reduction: HKL-2000; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1999); software used to prepare material for publication: SHELXTL and PLATON (Spek, 2003).

Figures top
[Figure 1] Fig. 1. A view of (I), with the atom-numbering scheme. Hydrogen bonds are shown as dashed lines. Displacement ellipsoids are drawn at the 50% probability level. Primed atoms are related by the symmetry operator (−x, −y, −z).
[Figure 2] Fig. 2. A view of molecule A in (II). with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
[Figure 3] Fig. 3. A view of (II), showing the double chains along the c axis. C—H···π and ππ stacking interactions are represented as dashed and dotted lines, respectively. Displacement ellipsoids are drawn at the 30% probability level.
(I) Di-tert-butyl ketone hydrazone top
Crystal data top
C9H20N2F(000) = 352
Mr = 156.27Dx = 1.040 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 23020 reflections
a = 11.5299 (8) Åθ = 3.1–25.7°
b = 8.0975 (4) ŵ = 0.06 mm1
c = 10.8937 (8) ÅT = 100 K
β = 101.111 (3)°Irregular, colourless
V = 998.01 (11) Å30.23 × 0.19 × 0.16 mm
Z = 4
Data collection top
Nonius KappaCCD area-detector
diffractometer
1717 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.038
Graphite monochromatorθmax = 25.7°, θmin = 3.1°
two ϕ and two ω scans with 2° stepsh = 1413
23020 measured reflectionsk = 90
1884 independent reflectionsl = 013
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)] = 0.039Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.105H atoms treated by a mixture of independent and constrained refinement
S = 1.04 w = 1/[σ2(Fo2) + (0.0544P)2 + 0.3197P]
where P = (Fo2 + 2Fc2)/3
1884 reflections(Δ/σ)max < 0.001
112 parametersΔρmax = 0.27 e Å3
0 restraintsΔρmin = 0.15 e Å3
Crystal data top
C9H20N2V = 998.01 (11) Å3
Mr = 156.27Z = 4
Monoclinic, P21/cMo Kα radiation
a = 11.5299 (8) ŵ = 0.06 mm1
b = 8.0975 (4) ÅT = 100 K
c = 10.8937 (8) Å0.23 × 0.19 × 0.16 mm
β = 101.111 (3)°
Data collection top
Nonius KappaCCD area-detector
diffractometer
1717 reflections with I > 2σ(I)
23020 measured reflectionsRint = 0.038
1884 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0390 restraints
wR(F2) = 0.105H atoms treated by a mixture of independent and constrained refinement
S = 1.04Δρmax = 0.27 e Å3
1884 reflectionsΔρmin = 0.15 e Å3
112 parameters
Special details top

Experimental. crystal-to-detector distance 30 mm

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 > 2σ(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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
N10.12987 (9)0.09362 (13)0.01219 (9)0.0245 (2)
H10.0533 (13)0.1035 (17)0.0336 (13)0.029*
H20.1610 (12)0.1948 (19)0.0312 (13)0.029*
N20.12725 (8)0.01011 (11)0.11434 (8)0.0206 (2)
C10.20987 (9)0.01413 (13)0.21226 (10)0.0192 (2)
C20.32112 (9)0.09921 (13)0.23046 (10)0.0218 (3)
C30.28322 (11)0.27995 (14)0.24534 (11)0.0276 (3)
H3A0.35050.35120.25040.041*
H3B0.25160.29030.32030.041*
H3C0.22390.31070.17450.041*
C40.41908 (11)0.06408 (16)0.34566 (11)0.0306 (3)
H4A0.48080.14470.35000.046*
H4B0.45100.04420.33840.046*
H4C0.38640.06990.42020.046*
C50.38405 (10)0.07964 (15)0.11793 (11)0.0282 (3)
H5A0.45090.15250.12820.042*
H5B0.33000.10670.04200.042*
H5C0.41030.03240.11380.042*
C60.18503 (9)0.14007 (14)0.31124 (10)0.0222 (3)
C70.28249 (11)0.27168 (15)0.34220 (13)0.0333 (3)
H7A0.35030.22460.39590.050*
H7B0.30430.30940.26630.050*
H7C0.25370.36310.38380.050*
C80.16816 (11)0.05157 (17)0.43156 (11)0.0321 (3)
H8A0.15090.13150.49060.048*
H8B0.10380.02520.41220.048*
H8C0.23920.00680.46700.048*
C90.06898 (10)0.23344 (15)0.26280 (11)0.0290 (3)
H9A0.07510.29200.18770.044*
H9B0.00480.15610.24530.044*
H9C0.05470.31050.32520.044*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0230 (5)0.0280 (5)0.0210 (5)0.0030 (4)0.0009 (4)0.0050 (4)
N20.0206 (5)0.0218 (5)0.0193 (5)0.0009 (4)0.0038 (4)0.0014 (3)
C10.0184 (5)0.0185 (5)0.0206 (5)0.0013 (4)0.0031 (4)0.0008 (4)
C20.0201 (5)0.0225 (6)0.0221 (5)0.0017 (4)0.0023 (4)0.0002 (4)
C30.0291 (6)0.0233 (6)0.0290 (6)0.0031 (5)0.0028 (5)0.0023 (5)
C40.0241 (6)0.0339 (7)0.0303 (6)0.0044 (5)0.0035 (5)0.0023 (5)
C50.0207 (6)0.0340 (6)0.0303 (6)0.0037 (5)0.0058 (5)0.0022 (5)
C60.0219 (5)0.0219 (6)0.0225 (6)0.0007 (4)0.0036 (4)0.0030 (4)
C70.0304 (6)0.0261 (6)0.0435 (7)0.0047 (5)0.0074 (5)0.0095 (5)
C80.0351 (7)0.0381 (7)0.0240 (6)0.0018 (5)0.0083 (5)0.0006 (5)
C90.0281 (6)0.0306 (6)0.0280 (6)0.0062 (5)0.0047 (5)0.0061 (5)
Geometric parameters (Å, º) top
N1—N21.3992 (13)C5—H5A0.9600
N1—H10.930 (15)C5—H5B0.9600
N1—H20.903 (16)C5—H5C0.9600
C1—N21.2864 (14)C6—C71.5382 (15)
C1—C21.5585 (14)C6—C91.5389 (15)
C1—C61.5504 (15)C6—C81.5387 (16)
C2—C31.5448 (16)C7—H7A0.9600
C2—C41.5444 (15)C7—H7B0.9600
C2—C51.5482 (15)C7—H7C0.9600
C3—H3A0.9600C8—H8A0.9600
C3—H3B0.9600C8—H8B0.9600
C3—H3C0.9600C8—H8C0.9600
C4—H4A0.9600C9—H9A0.9600
C4—H4B0.9600C9—H9B0.9600
C4—H4C0.9600C9—H9C0.9600
N2—N1—H1108.4 (8)C2—C5—H5C109.5
N2—N1—H2115.5 (9)H5A—C5—H5C109.5
H1—N1—H2109.8 (12)H5B—C5—H5C109.5
N1—N2—C1123.28 (9)C7—C6—C9106.56 (10)
N2—C1—C2123.39 (9)C7—C6—C8110.05 (10)
N2—C1—C6112.76 (9)C9—C6—C8106.06 (9)
C2—C1—C6123.83 (9)C7—C6—C1112.53 (9)
C3—C2—C4105.46 (9)C9—C6—C1110.46 (9)
C3—C2—C5111.43 (9)C8—C6—C1110.90 (9)
C4—C2—C5104.10 (9)C6—C7—H7A109.5
C3—C2—C1109.19 (9)C6—C7—H7B109.5
C4—C2—C1116.74 (9)H7A—C7—H7B109.5
C5—C2—C1109.80 (9)C6—C7—H7C109.5
C2—C3—H3A109.5H7A—C7—H7C109.5
C2—C3—H3B109.5H7B—C7—H7C109.5
H3A—C3—H3B109.5C6—C8—H8A109.5
C2—C3—H3C109.5C6—C8—H8B109.5
H3A—C3—H3C109.5H8A—C8—H8B109.5
H3B—C3—H3C109.5C6—C8—H8C109.5
C2—C4—H4A109.5H8A—C8—H8C109.5
C2—C4—H4B109.5H8B—C8—H8C109.5
H4A—C4—H4B109.5C6—C9—H9A109.5
C2—C4—H4C109.5C6—C9—H9B109.5
H4A—C4—H4C109.5H9A—C9—H9B109.5
H4B—C4—H4C109.5C6—C9—H9C109.5
C2—C5—H5A109.5H9A—C9—H9C109.5
C2—C5—H5B109.5H9B—C9—H9C109.5
H5A—C5—H5B109.5
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···N2i0.930 (15)2.230 (15)3.0937 (13)154.1 (12)
Symmetry code: (i) x, y, z.
(II) di-tert-butyl ketone triphenylphosphoranylidenehydrazone top
Crystal data top
C27H33N2PF(000) = 1792
Mr = 416.52Dx = 1.160 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 122758 reflections
a = 29.1768 (16) Åθ = 2.9–25.7°
b = 11.6848 (7) ŵ = 0.13 mm1
c = 14.3768 (6) ÅT = 100 K
β = 103.243 (3)°Platelet, colourless
V = 4771.1 (4) Å30.17 × 0.15 × 0.10 mm
Z = 8
Data collection top
Nonius KappaCCD area-detector
diffractometer
6960 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.036
Graphite monochromatorθmax = 25.7°, θmin = 2.9°
two ϕ and two ω scans with 2° stepsh = 3534
122758 measured reflectionsk = 140
9059 independent reflectionsl = 017
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)] = 0.044Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.118H-atom parameters constrained
S = 0.99 w = 1/[σ2(Fo2) + (0.0646P)2 + 1.2906P]
where P = (Fo2 + 2Fc2)/3
9059 reflections(Δ/σ)max = 0.001
553 parametersΔρmax = 0.18 e Å3
0 restraintsΔρmin = 0.31 e Å3
Crystal data top
C27H33N2PV = 4771.1 (4) Å3
Mr = 416.52Z = 8
Monoclinic, P21/cMo Kα radiation
a = 29.1768 (16) ŵ = 0.13 mm1
b = 11.6848 (7) ÅT = 100 K
c = 14.3768 (6) Å0.17 × 0.15 × 0.10 mm
β = 103.243 (3)°
Data collection top
Nonius KappaCCD area-detector
diffractometer
6960 reflections with I > 2σ(I)
122758 measured reflectionsRint = 0.036
9059 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0440 restraints
wR(F2) = 0.118H-atom parameters constrained
S = 0.99Δρmax = 0.18 e Å3
9059 reflectionsΔρmin = 0.31 e Å3
553 parameters
Special details top

Experimental. crystal-to-detector distance 30 mm

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 > 2σ(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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
P1A0.126578 (16)0.87567 (4)0.35509 (3)0.02327 (12)
N1A0.14460 (5)0.98479 (14)0.42084 (11)0.0266 (4)
N2A0.11641 (5)0.99813 (14)0.48864 (10)0.0263 (3)
C1A0.12476 (6)1.08194 (17)0.54874 (12)0.0259 (4)
C2A0.16387 (7)1.17240 (17)0.55023 (13)0.0287 (4)
C3A0.15162 (8)1.23777 (18)0.45438 (14)0.0365 (5)
H3A0.14621.18410.40250.055*
H3B0.17731.28730.44990.055*
H3C0.12371.28260.45120.055*
C4A0.21186 (7)1.11266 (19)0.56231 (16)0.0363 (5)
H4A0.21181.06640.50710.055*
H4B0.21751.06510.61820.055*
H4C0.23631.16930.56910.055*
C5A0.17153 (8)1.26305 (18)0.63071 (14)0.0353 (5)
H5A0.19281.32070.61850.053*
H5B0.18461.22690.69090.053*
H5C0.14191.29770.63260.053*
C6A0.09036 (7)1.08489 (18)0.61627 (13)0.0304 (4)
C7A0.05684 (8)1.1888 (2)0.59358 (15)0.0399 (5)
H7A0.07491.25820.60360.060*
H7B0.03521.18780.63490.060*
H7C0.03961.18490.52820.060*
C8A0.05893 (7)0.97765 (19)0.60192 (14)0.0349 (5)
H8A0.03690.98230.64220.052*
H8B0.07820.91070.61830.052*
H8C0.04210.97300.53630.052*
C9A0.11642 (8)1.0856 (2)0.72279 (14)0.0387 (5)
H9A0.12711.16180.74120.058*
H9B0.14301.03490.73220.058*
H9C0.09541.06070.76120.058*
C10A0.16748 (6)0.86014 (17)0.27903 (12)0.0244 (4)
C11A0.19999 (6)0.94665 (18)0.27593 (13)0.0270 (4)
H11A0.20081.01180.31350.032*
C12A0.23112 (7)0.93504 (19)0.21645 (13)0.0313 (4)
H12A0.25280.99270.21420.038*
C13A0.23009 (7)0.83822 (19)0.16058 (13)0.0326 (5)
H13A0.25140.83080.12170.039*
C14A0.19749 (7)0.75200 (18)0.16222 (13)0.0309 (4)
H14A0.19680.68710.12460.037*
C15A0.16587 (7)0.76371 (18)0.22069 (13)0.0285 (4)
H15A0.14350.70710.22100.034*
C16A0.12308 (6)0.74199 (17)0.41682 (12)0.0250 (4)
C17A0.15670 (7)0.65539 (17)0.42471 (13)0.0282 (4)
H17A0.18120.66260.39370.034*
C18A0.15360 (7)0.55865 (18)0.47878 (14)0.0326 (5)
H18A0.17580.50060.48300.039*
C19A0.11766 (7)0.54793 (18)0.52643 (14)0.0334 (5)
H19A0.11580.48300.56280.040*
C20A0.08434 (7)0.63420 (18)0.51988 (13)0.0323 (5)
H20A0.06040.62750.55260.039*
C21A0.08671 (7)0.73002 (17)0.46483 (13)0.0280 (4)
H21A0.06400.78690.45970.034*
C22A0.06880 (6)0.88968 (17)0.27444 (12)0.0252 (4)
C23A0.05362 (7)0.99840 (18)0.24230 (13)0.0298 (4)
H23A0.07201.06190.26510.036*
C24A0.01105 (7)1.01247 (19)0.17608 (14)0.0349 (5)
H24A0.00121.08530.15410.042*
C25A0.01659 (7)0.9182 (2)0.14286 (14)0.0358 (5)
H25A0.04520.92810.09900.043*
C26A0.00201 (7)0.8095 (2)0.17439 (13)0.0328 (5)
H26A0.02070.74640.15180.039*
C27A0.04077 (7)0.79520 (18)0.24010 (13)0.0280 (4)
H27A0.05070.72220.26120.034*
P1B0.378096 (16)0.63657 (4)0.23986 (3)0.02313 (12)
N1B0.35412 (6)0.52716 (14)0.27612 (11)0.0278 (4)
N2B0.38056 (5)0.49398 (14)0.36776 (10)0.0268 (4)
C1B0.36555 (7)0.41133 (17)0.41229 (13)0.0271 (4)
C2B0.31963 (8)0.34335 (18)0.37059 (14)0.0344 (5)
C3B0.32498 (9)0.2847 (2)0.27700 (15)0.0422 (5)
H3D0.35030.23040.29120.063*
H3E0.33170.34150.23370.063*
H3F0.29620.24600.24800.063*
C4B0.30603 (9)0.2474 (2)0.43339 (17)0.0494 (6)
H4D0.29900.28040.48970.074*
H4E0.33180.19470.45150.074*
H4F0.27880.20740.39790.074*
C5B0.27741 (7)0.4265 (2)0.35038 (16)0.0416 (5)
H5D0.24930.38550.32100.062*
H5E0.28290.48600.30820.062*
H5F0.27380.45970.40930.062*
C6B0.39857 (7)0.38686 (18)0.51135 (13)0.0319 (5)
C7B0.42194 (10)0.2684 (2)0.51370 (18)0.0564 (7)
H7D0.44350.25760.57440.085*
H7E0.43870.26380.46360.085*
H7F0.39820.21000.50460.085*
C8B0.37278 (8)0.3972 (2)0.59324 (14)0.0421 (5)
H8D0.35390.33020.59440.063*
H8E0.35290.46370.58330.063*
H8F0.39550.40410.65300.063*
C9B0.43916 (7)0.4743 (2)0.53285 (14)0.0385 (5)
H9D0.46000.45620.59300.058*
H9E0.42660.54970.53570.058*
H9F0.45620.47140.48320.058*
C10B0.33994 (6)0.67597 (17)0.12737 (12)0.0244 (4)
C11B0.29963 (6)0.61255 (17)0.08934 (13)0.0272 (4)
H11B0.29190.54970.12230.033*
C12B0.27094 (7)0.64374 (18)0.00143 (13)0.0295 (4)
H12B0.24370.60220.02380.035*
C13B0.28284 (7)0.73639 (17)0.04838 (13)0.0277 (4)
H13B0.26380.75620.10730.033*
C14B0.32301 (6)0.79976 (17)0.01077 (13)0.0265 (4)
H14B0.33080.86230.04410.032*
C15B0.35146 (6)0.76939 (17)0.07655 (13)0.0262 (4)
H15B0.37850.81150.10160.031*
C16B0.38592 (6)0.76161 (16)0.31634 (12)0.0238 (4)
C17B0.35309 (7)0.85021 (17)0.30093 (14)0.0283 (4)
H17B0.32850.84950.24680.034*
C18B0.35692 (7)0.93974 (18)0.36592 (14)0.0318 (4)
H18B0.33480.99850.35550.038*
C19B0.39361 (7)0.94128 (18)0.44607 (13)0.0316 (4)
H19B0.39611.00100.48970.038*
C20B0.42681 (7)0.85385 (17)0.46162 (13)0.0302 (4)
H20B0.45170.85580.51520.036*
C21B0.42292 (6)0.76391 (17)0.39751 (12)0.0260 (4)
H21B0.44500.70500.40850.031*
C22B0.43638 (6)0.61407 (17)0.21741 (12)0.0262 (4)
C23B0.46780 (7)0.70383 (19)0.21720 (13)0.0294 (4)
H23B0.45950.77780.23080.035*
C24B0.51144 (7)0.6836 (2)0.19675 (13)0.0362 (5)
H24B0.53260.74350.19800.043*
C25B0.52328 (7)0.5733 (2)0.17451 (14)0.0400 (5)
H25B0.55240.55940.16070.048*
C26B0.49195 (7)0.4842 (2)0.17275 (14)0.0374 (5)
H26B0.49980.41090.15650.045*
C27B0.44870 (7)0.50368 (18)0.19527 (13)0.0319 (4)
H27B0.42800.44320.19560.038*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
P1A0.0242 (2)0.0232 (3)0.0227 (2)0.00044 (19)0.00580 (19)0.00069 (19)
N1A0.0292 (8)0.0260 (9)0.0258 (8)0.0013 (7)0.0089 (7)0.0024 (6)
N2A0.0279 (8)0.0279 (9)0.0238 (8)0.0031 (7)0.0073 (7)0.0006 (7)
C1A0.0274 (10)0.0262 (11)0.0228 (9)0.0055 (8)0.0031 (8)0.0005 (7)
C2A0.0310 (10)0.0244 (11)0.0302 (10)0.0020 (8)0.0059 (8)0.0020 (8)
C3A0.0488 (13)0.0254 (12)0.0354 (11)0.0026 (10)0.0102 (10)0.0009 (9)
C4A0.0304 (11)0.0324 (12)0.0447 (12)0.0018 (9)0.0055 (9)0.0077 (9)
C5A0.0405 (12)0.0279 (12)0.0350 (11)0.0007 (9)0.0035 (9)0.0060 (9)
C6A0.0317 (10)0.0335 (12)0.0270 (10)0.0046 (9)0.0088 (8)0.0012 (8)
C7A0.0397 (12)0.0421 (14)0.0411 (12)0.0106 (10)0.0160 (10)0.0003 (10)
C8A0.0342 (11)0.0401 (13)0.0332 (10)0.0014 (9)0.0137 (9)0.0023 (9)
C9A0.0433 (12)0.0472 (14)0.0263 (10)0.0028 (11)0.0095 (9)0.0005 (9)
C10A0.0231 (9)0.0267 (11)0.0223 (9)0.0040 (8)0.0029 (7)0.0010 (7)
C11A0.0273 (10)0.0297 (11)0.0236 (9)0.0018 (8)0.0049 (8)0.0004 (8)
C12A0.0259 (10)0.0401 (13)0.0279 (10)0.0005 (9)0.0063 (8)0.0043 (9)
C13A0.0276 (10)0.0442 (13)0.0270 (10)0.0080 (9)0.0080 (8)0.0024 (9)
C14A0.0315 (10)0.0348 (12)0.0257 (9)0.0075 (9)0.0054 (8)0.0029 (8)
C15A0.0278 (10)0.0289 (11)0.0278 (9)0.0017 (8)0.0043 (8)0.0011 (8)
C16A0.0279 (10)0.0248 (10)0.0207 (8)0.0020 (8)0.0022 (7)0.0018 (7)
C17A0.0287 (10)0.0268 (11)0.0277 (9)0.0010 (8)0.0035 (8)0.0029 (8)
C18A0.0372 (11)0.0241 (11)0.0329 (10)0.0020 (9)0.0003 (9)0.0002 (8)
C19A0.0422 (12)0.0280 (12)0.0277 (10)0.0057 (9)0.0030 (9)0.0026 (8)
C20A0.0367 (11)0.0331 (12)0.0264 (10)0.0075 (9)0.0062 (8)0.0018 (8)
C21A0.0288 (10)0.0302 (11)0.0243 (9)0.0002 (8)0.0047 (8)0.0016 (8)
C22A0.0263 (9)0.0287 (11)0.0221 (9)0.0025 (8)0.0088 (7)0.0001 (7)
C23A0.0311 (10)0.0295 (11)0.0302 (10)0.0042 (9)0.0096 (8)0.0013 (8)
C24A0.0355 (11)0.0369 (13)0.0332 (10)0.0132 (10)0.0097 (9)0.0047 (9)
C25A0.0272 (10)0.0501 (15)0.0295 (10)0.0061 (10)0.0051 (8)0.0026 (9)
C26A0.0280 (10)0.0412 (13)0.0288 (10)0.0055 (9)0.0058 (8)0.0004 (9)
C27A0.0308 (10)0.0291 (11)0.0248 (9)0.0004 (8)0.0077 (8)0.0018 (8)
P1B0.0238 (2)0.0233 (3)0.0222 (2)0.0006 (2)0.00493 (18)0.00040 (18)
N1B0.0315 (9)0.0267 (9)0.0238 (8)0.0012 (7)0.0035 (7)0.0018 (6)
N2B0.0309 (8)0.0265 (9)0.0231 (8)0.0027 (7)0.0066 (7)0.0010 (6)
C1B0.0324 (10)0.0236 (10)0.0268 (9)0.0010 (8)0.0098 (8)0.0002 (8)
C2B0.0414 (12)0.0294 (12)0.0326 (10)0.0079 (9)0.0090 (9)0.0006 (8)
C3B0.0605 (15)0.0312 (13)0.0356 (11)0.0096 (11)0.0122 (10)0.0055 (9)
C4B0.0634 (16)0.0429 (15)0.0435 (13)0.0207 (12)0.0152 (12)0.0044 (11)
C5B0.0354 (12)0.0457 (14)0.0426 (12)0.0116 (10)0.0069 (10)0.0035 (10)
C6B0.0400 (11)0.0297 (12)0.0259 (10)0.0045 (9)0.0075 (9)0.0040 (8)
C7B0.0692 (17)0.0388 (15)0.0550 (15)0.0204 (13)0.0013 (13)0.0039 (12)
C8B0.0488 (13)0.0509 (15)0.0266 (10)0.0051 (11)0.0088 (10)0.0053 (9)
C9B0.0356 (11)0.0469 (14)0.0302 (10)0.0007 (10)0.0017 (9)0.0056 (9)
C10B0.0248 (9)0.0262 (11)0.0229 (9)0.0011 (8)0.0069 (7)0.0012 (7)
C11B0.0289 (10)0.0259 (11)0.0272 (9)0.0028 (8)0.0070 (8)0.0004 (8)
C12B0.0271 (10)0.0338 (12)0.0265 (9)0.0025 (8)0.0041 (8)0.0025 (8)
C13B0.0295 (10)0.0303 (11)0.0232 (9)0.0042 (8)0.0055 (8)0.0003 (8)
C14B0.0287 (10)0.0257 (11)0.0269 (9)0.0024 (8)0.0103 (8)0.0023 (8)
C15B0.0230 (9)0.0262 (11)0.0296 (10)0.0020 (8)0.0063 (8)0.0002 (8)
C16B0.0257 (9)0.0247 (10)0.0227 (9)0.0027 (8)0.0089 (7)0.0010 (7)
C17B0.0277 (10)0.0286 (11)0.0285 (9)0.0010 (8)0.0061 (8)0.0011 (8)
C18B0.0361 (11)0.0261 (11)0.0350 (10)0.0041 (9)0.0121 (9)0.0007 (8)
C19B0.0437 (12)0.0250 (11)0.0286 (10)0.0066 (9)0.0137 (9)0.0041 (8)
C20B0.0353 (11)0.0325 (12)0.0228 (9)0.0080 (9)0.0066 (8)0.0003 (8)
C21B0.0273 (9)0.0280 (11)0.0242 (9)0.0016 (8)0.0086 (8)0.0016 (8)
C22B0.0268 (10)0.0311 (11)0.0197 (8)0.0037 (8)0.0032 (7)0.0010 (8)
C23B0.0280 (10)0.0351 (12)0.0252 (9)0.0006 (9)0.0060 (8)0.0038 (8)
C24B0.0252 (10)0.0545 (15)0.0287 (10)0.0025 (10)0.0056 (8)0.0066 (9)
C25B0.0292 (11)0.0629 (16)0.0270 (10)0.0139 (11)0.0048 (8)0.0007 (10)
C26B0.0404 (12)0.0413 (14)0.0300 (10)0.0179 (10)0.0072 (9)0.0026 (9)
C27B0.0373 (11)0.0320 (12)0.0255 (9)0.0072 (9)0.0058 (8)0.0031 (8)
Geometric parameters (Å, º) top
P1A—N1A1.6025 (16)P1B—N1B1.6008 (16)
P1A—C10A1.8030 (18)P1B—C10B1.8006 (18)
P1A—C16A1.811 (2)P1B—C16B1.8114 (19)
P1A—C22A1.8214 (19)P1B—C22B1.8212 (19)
N1A—N2A1.421 (2)N1B—N2B1.420 (2)
C1A—N2A1.292 (2)C1B—N2B1.289 (2)
C1A—C2A1.552 (3)C1B—C2B1.555 (3)
C1A—C6A1.548 (3)C1B—C6B1.552 (3)
C2A—C4A1.538 (3)C2B—C5B1.543 (3)
C2A—C3A1.544 (3)C2B—C4B1.548 (3)
C2A—C5A1.547 (3)C2B—C3B1.549 (3)
C3A—H3A0.9600C3B—H3D0.9600
C3A—H3B0.9600C3B—H3E0.9600
C3A—H3C0.9600C3B—H3F0.9600
C4A—H4A0.9600C4B—H4D0.9600
C4A—H4B0.9600C4B—H4E0.9600
C4A—H4C0.9600C4B—H4F0.9600
C5A—H5A0.9600C5B—H5D0.9600
C5A—H5B0.9600C5B—H5E0.9600
C5A—H5C0.9600C5B—H5F0.9600
C6A—C8A1.538 (3)C6B—C7B1.540 (3)
C6A—C9A1.546 (3)C6B—C8B1.540 (3)
C6A—C7A1.546 (3)C6B—C9B1.541 (3)
C7A—H7A0.9600C7B—H7D0.9600
C7A—H7B0.9600C7B—H7E0.9600
C7A—H7C0.9600C7B—H7F0.9600
C8A—H8A0.9600C8B—H8D0.9600
C8A—H8B0.9600C8B—H8E0.9600
C8A—H8C0.9600C8B—H8F0.9600
C9A—H9A0.9600C9B—H9D0.9600
C9A—H9B0.9600C9B—H9E0.9600
C9A—H9C0.9600C9B—H9F0.9600
C10A—C11A1.394 (3)C10B—C11B1.392 (3)
C10A—C15A1.399 (3)C10B—C15B1.397 (3)
C11A—C12A1.389 (3)C11B—C12B1.395 (3)
C11A—H11A0.9300C11B—H11B0.9300
C12A—C13A1.384 (3)C12B—C13B1.385 (3)
C12A—H12A0.9300C12B—H12B0.9300
C13A—C14A1.389 (3)C13B—C14B1.387 (3)
C13A—H13A0.9300C13B—H13B0.9300
C14A—C15A1.390 (3)C14B—C15B1.383 (3)
C14A—H14A0.9300C14B—H14B0.9300
C15A—H15A0.9300C15B—H15B0.9300
C16A—C17A1.396 (3)C16B—C17B1.393 (3)
C16A—C21A1.399 (3)C16B—C21B1.397 (3)
C17A—C18A1.387 (3)C17B—C18B1.390 (3)
C17A—H17A0.9300C17B—H17B0.9300
C18A—C19A1.383 (3)C18B—C19B1.382 (3)
C18A—H18A0.9300C18B—H18B0.9300
C19A—C20A1.389 (3)C19B—C20B1.390 (3)
C19A—H19A0.9300C19B—H19B0.9300
C20A—C21A1.382 (3)C20B—C21B1.385 (3)
C20A—H20A0.9300C20B—H20B0.9300
C21A—H21A0.9300C21B—H21B0.9300
C22A—C23A1.389 (3)C22B—C23B1.393 (3)
C22A—C27A1.395 (3)C22B—C27B1.395 (3)
C23A—C24A1.391 (3)C23B—C24B1.391 (3)
C23A—H23A0.9300C23B—H23B0.9300
C24A—C25A1.384 (3)C24B—C25B1.390 (3)
C24A—H24A0.9300C24B—H24B0.9300
C25A—C26A1.382 (3)C25B—C26B1.382 (3)
C25A—H25A0.9300C25B—H25B0.9300
C26A—C27A1.392 (3)C26B—C27B1.391 (3)
C26A—H26A0.9300C26B—H26B0.9300
C27A—H27A0.9300C27B—H27B0.9300
P1A—N1A—N2A109.19 (12)N1B—P1B—C10B105.68 (9)
N1A—N2A—C1A119.47 (16)N1B—P1B—C16B116.75 (8)
N2A—C1A—C2A123.44 (17)C10B—P1B—C16B107.76 (9)
N2A—C1A—C6A112.72 (17)N1B—P1B—C22B115.97 (9)
C2A—C1A—C6A123.80 (16)C10B—P1B—C22B106.74 (8)
N1A—P1A—C10A105.33 (8)C16B—P1B—C22B103.36 (9)
N1A—P1A—C16A116.42 (8)P1B—N1B—N2B109.58 (12)
C10A—P1A—C16A109.26 (9)N1B—N2B—C1B119.41 (16)
N1A—P1A—C22A115.77 (9)N2B—C1B—C2B123.49 (17)
C10A—P1A—C22A105.52 (8)N2B—C1B—C6B112.55 (17)
C16A—P1A—C22A103.98 (9)C2B—C1B—C6B123.95 (16)
C4A—C2A—C3A110.10 (16)C5B—C2B—C4B105.42 (18)
C4A—C2A—C5A104.74 (16)C5B—C2B—C3B110.48 (18)
C3A—C2A—C5A107.04 (17)C4B—C2B—C3B106.06 (18)
C4A—C2A—C1A109.86 (16)C5B—C2B—C1B109.33 (17)
C3A—C2A—C1A107.79 (16)C4B—C2B—C1B117.31 (17)
C5A—C2A—C1A117.17 (16)C3B—C2B—C1B108.14 (16)
C2A—C3A—H3A109.5C2B—C3B—H3D109.5
C2A—C3A—H3B109.5C2B—C3B—H3E109.5
H3A—C3A—H3B109.5H3D—C3B—H3E109.5
C2A—C3A—H3C109.5C2B—C3B—H3F109.5
H3A—C3A—H3C109.5H3D—C3B—H3F109.5
H3B—C3A—H3C109.5H3E—C3B—H3F109.5
C2A—C4A—H4A109.5C2B—C4B—H4D109.5
C2A—C4A—H4B109.5C2B—C4B—H4E109.5
H4A—C4A—H4B109.5H4D—C4B—H4E109.5
C2A—C4A—H4C109.5C2B—C4B—H4F109.5
H4A—C4A—H4C109.5H4D—C4B—H4F109.5
H4B—C4A—H4C109.5H4E—C4B—H4F109.5
C2A—C5A—H5A109.5C2B—C5B—H5D109.5
C2A—C5A—H5B109.5C2B—C5B—H5E109.5
H5A—C5A—H5B109.5H5D—C5B—H5E109.5
C2A—C5A—H5C109.5C2B—C5B—H5F109.5
H5A—C5A—H5C109.5H5D—C5B—H5F109.5
H5B—C5A—H5C109.5H5E—C5B—H5F109.5
C8A—C6A—C9A106.27 (17)C7B—C6B—C8B110.18 (19)
C8A—C6A—C7A106.41 (17)C7B—C6B—C9B105.97 (19)
C9A—C6A—C7A110.38 (17)C8B—C6B—C9B106.40 (17)
C8A—C6A—C1A110.48 (16)C7B—C6B—C1B111.37 (17)
C9A—C6A—C1A112.26 (16)C8B—C6B—C1B112.19 (17)
C7A—C6A—C1A110.78 (16)C9B—C6B—C1B110.42 (16)
C6A—C7A—H7A109.5C6B—C7B—H7D109.5
C6A—C7A—H7B109.5C6B—C7B—H7E109.5
H7A—C7A—H7B109.5H7D—C7B—H7E109.5
C6A—C7A—H7C109.5C6B—C7B—H7F109.5
H7A—C7A—H7C109.5H7D—C7B—H7F109.5
H7B—C7A—H7C109.5H7E—C7B—H7F109.5
C6A—C8A—H8A109.5C6B—C8B—H8D109.5
C6A—C8A—H8B109.5C6B—C8B—H8E109.5
H8A—C8A—H8B109.5H8D—C8B—H8E109.5
C6A—C8A—H8C109.5C6B—C8B—H8F109.5
H8A—C8A—H8C109.5H8D—C8B—H8F109.5
H8B—C8A—H8C109.5H8E—C8B—H8F109.5
C6A—C9A—H9A109.5C6B—C9B—H9D109.5
C6A—C9A—H9B109.5C6B—C9B—H9E109.5
H9A—C9A—H9B109.5H9D—C9B—H9E109.5
C6A—C9A—H9C109.5C6B—C9B—H9F109.5
H9A—C9A—H9C109.5H9D—C9B—H9F109.5
H9B—C9A—H9C109.5H9E—C9B—H9F109.5
C11A—C10A—C15A119.64 (17)C11B—C10B—C15B119.59 (17)
C11A—C10A—P1A119.75 (15)C11B—C10B—P1B120.64 (14)
C15A—C10A—P1A120.58 (15)C15B—C10B—P1B119.75 (14)
C12A—C11A—C10A119.63 (19)C10B—C11B—C12B119.64 (18)
C12A—C11A—H11A120.2C10B—C11B—H11B120.2
C10A—C11A—H11A120.2C12B—C11B—H11B120.2
C13A—C12A—C11A120.45 (19)C13B—C12B—C11B120.20 (18)
C13A—C12A—H12A119.8C13B—C12B—H12B119.9
C11A—C12A—H12A119.8C11B—C12B—H12B119.9
C12A—C13A—C14A120.45 (18)C12B—C13B—C14B120.33 (17)
C12A—C13A—H13A119.8C12B—C13B—H13B119.8
C14A—C13A—H13A119.8C14B—C13B—H13B119.8
C15A—C14A—C13A119.39 (19)C15B—C14B—C13B119.65 (18)
C15A—C14A—H14A120.3C15B—C14B—H14B120.2
C13A—C14A—H14A120.3C13B—C14B—H14B120.2
C14A—C15A—C10A120.40 (19)C14B—C15B—C10B120.59 (18)
C14A—C15A—H15A119.8C14B—C15B—H15B119.7
C10A—C15A—H15A119.8C10B—C15B—H15B119.7
C17A—C16A—C21A119.07 (18)C17B—C16B—C21B119.36 (17)
C17A—C16A—P1A123.20 (14)C17B—C16B—P1B121.09 (14)
C21A—C16A—P1A117.53 (15)C21B—C16B—P1B119.24 (15)
C18A—C17A—C16A120.11 (18)C18B—C17B—C16B120.39 (18)
C18A—C17A—H17A119.9C18B—C17B—H17B119.8
C16A—C17A—H17A119.9C16B—C17B—H17B119.8
C19A—C18A—C17A120.38 (19)C19B—C18B—C17B119.87 (19)
C19A—C18A—H18A119.8C19B—C18B—H18B120.1
C17A—C18A—H18A119.8C17B—C18B—H18B120.1
C18A—C19A—C20A119.93 (19)C18B—C19B—C20B120.18 (18)
C18A—C19A—H19A120.0C18B—C19B—H19B119.9
C20A—C19A—H19A120.0C20B—C19B—H19B119.9
C21A—C20A—C19A120.06 (19)C21B—C20B—C19B120.17 (18)
C21A—C20A—H20A120.0C21B—C20B—H20B119.9
C19A—C20A—H20A120.0C19B—C20B—H20B119.9
C20A—C21A—C16A120.44 (19)C20B—C21B—C16B120.02 (18)
C20A—C21A—H21A119.8C20B—C21B—H21B120.0
C16A—C21A—H21A119.8C16B—C21B—H21B120.0
C23A—C22A—C27A119.31 (18)C23B—C22B—C27B119.43 (18)
C23A—C22A—P1A118.16 (15)C23B—C22B—P1B122.23 (15)
C27A—C22A—P1A122.43 (15)C27B—C22B—P1B118.27 (15)
C22A—C23A—C24A120.2 (2)C24B—C23B—C22B120.5 (2)
C22A—C23A—H23A119.9C24B—C23B—H23B119.8
C24A—C23A—H23A119.9C22B—C23B—H23B119.8
C25A—C24A—C23A120.0 (2)C25B—C24B—C23B119.6 (2)
C25A—C24A—H24A120.0C25B—C24B—H24B120.2
C23A—C24A—H24A120.0C23B—C24B—H24B120.2
C26A—C25A—C24A120.45 (19)C26B—C25B—C24B120.31 (19)
C26A—C25A—H25A119.8C26B—C25B—H25B119.8
C24A—C25A—H25A119.8C24B—C25B—H25B119.8
C25A—C26A—C27A119.6 (2)C25B—C26B—C27B120.2 (2)
C25A—C26A—H26A120.2C25B—C26B—H26B119.9
C27A—C26A—H26A120.2C27B—C26B—H26B119.9
C26A—C27A—C22A120.44 (19)C26B—C27B—C22B119.9 (2)
C26A—C27A—H27A119.8C26B—C27B—H27B120.0
C22A—C27A—H27A119.8C22B—C27B—H27B120.0

Experimental details

(I)(II)
Crystal data
Chemical formulaC9H20N2C27H33N2P
Mr156.27416.52
Crystal system, space groupMonoclinic, P21/cMonoclinic, P21/c
Temperature (K)100100
a, b, c (Å)11.5299 (8), 8.0975 (4), 10.8937 (8)29.1768 (16), 11.6848 (7), 14.3768 (6)
β (°) 101.111 (3) 103.243 (3)
V3)998.01 (11)4771.1 (4)
Z48
Radiation typeMo KαMo Kα
µ (mm1)0.060.13
Crystal size (mm)0.23 × 0.19 × 0.160.17 × 0.15 × 0.10
Data collection
DiffractometerNonius KappaCCD area-detector
diffractometer
Nonius KappaCCD area-detector
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
23020, 1884, 1717 122758, 9059, 6960
Rint0.0380.036
(sin θ/λ)max1)0.6090.610
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.039, 0.105, 1.04 0.044, 0.118, 0.99
No. of reflections18849059
No. of parameters112553
H-atom treatmentH atoms treated by a mixture of independent and constrained refinementH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.27, 0.150.18, 0.31

Computer programs: COLLECT (Nonius, 1998), HKL-2000 (Otwinowski & Minor, 1997), HKL-2000, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1999), SHELXTL and PLATON (Spek, 2003).

Selected geometric parameters (Å, º) for (I) top
N1—N21.3992 (13)C1—C21.5585 (14)
C1—N21.2864 (14)C1—C61.5504 (15)
N1—N2—C1123.28 (9)N2—C1—C6112.76 (9)
N2—C1—C2123.39 (9)C2—C1—C6123.83 (9)
Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
N1—H1···N2i0.930 (15)2.230 (15)3.0937 (13)154.1 (12)
Symmetry code: (i) x, y, z.
Selected geometric parameters (Å, º) for (II) top
P1A—N1A1.6025 (16)P1B—N1B1.6008 (16)
P1A—C10A1.8030 (18)P1B—C10B1.8006 (18)
P1A—C16A1.811 (2)P1B—C16B1.8114 (19)
P1A—C22A1.8214 (19)P1B—C22B1.8212 (19)
N1A—N2A1.421 (2)N1B—N2B1.420 (2)
C1A—N2A1.292 (2)C1B—N2B1.289 (2)
C1A—C2A1.552 (3)C1B—C2B1.555 (3)
C1A—C6A1.548 (3)C1B—C6B1.552 (3)
P1A—N1A—N2A109.19 (12)P1B—N1B—N2B109.58 (12)
N1A—N2A—C1A119.47 (16)N1B—N2B—C1B119.41 (16)
N2A—C1A—C2A123.44 (17)N2B—C1B—C2B123.49 (17)
N2A—C1A—C6A112.72 (17)N2B—C1B—C6B112.55 (17)
C2A—C1A—C6A123.80 (16)C2B—C1B—C6B123.95 (16)
 

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