Dimethyl hydrazine-1,2-dicarboxyl­ate–triphenyl­phosphine oxide (1/1)

Doboszewski, B.; McGarrah, J.; Nazarenko, A.Y.; Paixao Soares, F. da

doi:10.1107/S160053681101991X

organic compounds

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ISSN: 2056-9890

Volume 67| Part 7| July 2011| Page o1565

doi:10.1107/S160053681101991X

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Dimethyl hydrazine-1,2-dicarboxylate–triphenylphosphine oxide (1/1)

Bogdan Doboszewski,^a James McGarrah,^b Alexander Y. Nazarenko ^c ^* and Fabio da Paixao Soares ^a

^aDepartamento de Química, Universidade Federal Rural de Pernambuco, 52171-900 Recife, PE, Brazil, ^bDepartment of Chemistry, State University of New York, College at Geneseo, 1 College Circle, Geneseo, NY 14454, USA, and ^cChemistry Department, State University of New York, College at Buffalo, 1300 Elmwood Ave, Buffalo, NY 14222-1095, USA
^*Correspondence e-mail: nazareay@buffalostate.edu

(Received 11 May 2011; accepted 25 May 2011; online 4 June 2011)

In the crystal structure of the title compound, C₄H₈N₂O₄·C₁₈H₁₅OP, two triphenylphosphine oxide molecules and two dimethyl hydrazine-1,2-dicarboxylate molecules are connected via N—H⋯O hydrogen bonds of moderate strength and are related via a twofold rotational axis. Weak C_ar—H⋯ O contacts strengthen the crystal structure.

Related literature

For the Mitsunobu reaction, see: Mitsunobu (1981 ); Hughes (1992 ), Swamy et al. (2009 ). For the structures of analogous compounds, see: Anderson et al. (1996 ); Héroux & Brisse (1997 ); Wang et al. (2007 ). For the synthesis of this and related compounds, see Doboszewski (1997 , 2009 ).

Experimental

Crystal data

C₄H₈N₂O₄·C₁₈H₁₅OP
M_r = 426.39
Monoclinic, C 2/c
a = 26.494 (3) Å
b = 8.5545 (9) Å
c = 20.4426 (19) Å
β = 109.090 (3)°
V = 4378.3 (8) Å³
Z = 8
Mo Kα radiation
μ = 0.16 mm⁻¹
T = 200 K
0.8 × 0.7 × 0.4 mm

Data collection

Bruker SMART X2S diffractometer
Absorption correction: multi-scan (SADABS (Sheldrick, 2008a ) T_min = 0.84, T_max = 0.93
20468 measured reflections
3862 independent reflections
2956 reflections with I > 2σ(I)
R_int = 0.036

Refinement

R[F² > 2σ(F²)] = 0.036
wR(F²) = 0.095
S = 1.03
3862 reflections
298 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.30 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O5ⁱ	0.85 (2)	2.05 (2)	2.899 (2)	174.2 (19)
N2—H2⋯O5	0.83 (2)	2.05 (2)	2.833 (2)	155.9 (17)
C13—H13A⋯O2ⁱⁱ	0.92	2.53	3.310 (3)	143
C35—H35A⋯O3ⁱⁱⁱ	0.98	2.54	3.270 (3)	131
Symmetry codes: (i) $[-x, y, -z+{\script{3\over 2}}]$ ; (ii) $[x, -y+1, z+{\script{1\over 2}}]$ ; (iii) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Data collection: GIS (Bruker, 2010 ); cell refinement: APEX2 (Bruker, 2010) and SAINT (Bruker, 2009 ); data reduction: SAINT and XPREP (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008b ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008b); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ) and Mercury (Macrae et al., 2008 ); software used to prepare material for publication: PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053681101991X/mw2011sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681101991X/mw2011Isup2.hkl

Supporting information file. DOI: 10.1107/S160053681101991X/mw2011Isup3.cml

checkCIF report

Comment top

The two main by-products of the Mitsunobu reaction are bis-substituted hydrazines RO₂CNHNHCO₂R and phosphine oxides O=PR₃. Both types of compounds can interfere with the isolation of the desired products as in our work using N3-benzoylthymine. In such cases it was necessary to skip isolation of the initially formed product and to perform debenzoylation in basic medium and eventually isolate the much more polar deprotected final compound. We recently alkylated N3-benzoylthymine and uracil with allyl and propargyl alcohol, Ph₃P and iPrO₂CNNCO₂iPr in dioxane or tetrahydrofuran for further transformations. After treatment of the crude reaction mixture with sodium methoxide in methanol, we isolated a crystalline compound identified by the present study as a 2:2 complex of the substituted hydrazine with triphenylphosphine oxide. Evidently, a transesterification occurred during the sodium methoxide treatment.

Even though the Mitsunobu reaction has been known for over 40 years, only in 1996 has an X-ray structure of a similar complex (Anderson et al., 1996, Héroux & Brisse, 1997) been published and its stability was attributed to strong association via hydrogen bonding. The present communication shows a second compound of this kind.

In the adduct the bond lengths of the hydrazine molecule are the same within 0.01 Å as in the crystal structure of pure dimethyl hydrazine-1,2-dicarboxylate (Wang et al., 2007) while the H—N—N—H torsion angle increases from 95 to 105° with adduct formation. This value is almost identical to that in the di(isopropyl) hydrazine-1,2-dicarboxylate adduct (Héroux & Brisse, 1997).

That there is little or no change in component geometry with adduct formation suggests that the hydrogen bonds formed are of only moderate strength (Table 1). This is also supported by the modest shift of the P=O stretching frequency from 1190 cm^-1 in pure triphenylphosphine oxide to 1166 cm^-1 in the adduct which is one property expected to be sensitive to the strength of the hydrogen bonding.

Related literature top

For the Mitsunobu reaction, see: Mitsunobu (1981); Hughes (1992), Swamy et al. (2009). For the structures of analogous compounds, see: Anderson et al. (1996); Héroux & Brisse (1997); Wang et al. (2007). For the synthesis of this and related compounds, see Doboszewski (1997, 2009).

Experimental top

The compound is a by-product of the Mitsunobu reaction: allyl alcohol was employed for alkylation of thymine using Ph₃P and iPrO₂CNNCO₂iPr in dioxane. After treatment of the crude reaction mixture with sodium methoxide in methanol, a crystalline compound was isolated (m.p. 127–129° C). Parent peaks at 148 and 278 were clearly visible in a mass spectrum of the crystal dissolved in dichloromethane. Evidently, a transesterification occurred during a sodium methoxide treatment.

FTIR (Nicolet Nexus 470, Diamond ATR): 3229 and shoulder at 3180 (N—H), 3023 and 2952 (C—H), 1731 (C=O), 1535, 1434,1362,1263, 1225, 1165 and 1153, 116, 1068, 996,869,718, 694, 538 cm^-1.

Raman (Raman Systems 2.0, 785 nm laser): 1737 (C=O), 1590, 1442, 1169, 997 (very strong), 871, 689, 618,531, 437, 300, 266 and 206 cm^-1.

A comparatively large block was cut for the data collection due to the relatively low sensitivity of the CCD detector. Data collection was limited to θ=25° because of the geometry of the instrument.

Computing details top

Data collection: GIS (Bruker, 2010); cell refinement: APEX2 (Bruker, 2010) and SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009) and XPREP (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008b); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008b); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and Mercury (Macrae et al., 2008); software used to prepare material for publication: PLATON (Spek, 2009).

Figures top

	Fig. 1. Perspective view of the dimethyl hydrazine-1,2-dicarboxylate - triphenylphosphine oxide adduct with displacement ellipsoids drawn at the 50% probability level.
	Fig. 2. Two of the adducts connected via N—H···O hydrogen bonds.
	Fig. 3. View of the title compound showing displacement ellipsoids at the 50% probability level.

Dimethyl hydrazine-1,2-dicarboxylate–triphenylphosphine oxide (1/1) top

Crystal data top

C₄H₈N₂O₄·C₁₈H₁₅OP	F(000) = 1792
M_r = 426.39	D_x = 1.294 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 3730 reflections
a = 26.494 (3) Å	θ = 2.5–24.4°
b = 8.5545 (9) Å	µ = 0.16 mm⁻¹
c = 20.4426 (19) Å	T = 200 K
β = 109.090 (3)°	Prism, colourless
V = 4378.3 (8) Å³	0.8 × 0.7 × 0.4 mm
Z = 8

Data collection top

Bruker SMART X2S diffractometer	3862 independent reflections
Radiation source: XOS X-beam microfocus source	2956 reflections with I > 2σ(I)
Doubly curved silicon crystal monochromator	R_int = 0.036
ω scans	θ_max = 25.1°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS (Sheldrick, 2008a)	h = −31→31
T_min = 0.84, T_max = 0.93	k = −10→10
20468 measured reflections	l = −24→24

Refinement top

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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.095	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ²(F_o²) + (0.0533P)²] where P = (F_o² + 2F_c²)/3
3862 reflections	(Δ/σ)_max = 0.001
298 parameters	Δρ_max = 0.26 e Å⁻³
0 restraints	Δρ_min = −0.30 e Å⁻³

Crystal data top

C₄H₈N₂O₄·C₁₈H₁₅OP	V = 4378.3 (8) Å³
M_r = 426.39	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 26.494 (3) Å	µ = 0.16 mm⁻¹
b = 8.5545 (9) Å	T = 200 K
c = 20.4426 (19) Å	0.8 × 0.7 × 0.4 mm
β = 109.090 (3)°

Data collection top

Bruker SMART X2S diffractometer	3862 independent reflections
Absorption correction: multi-scan (SADABS (Sheldrick, 2008a)	2956 reflections with I > 2σ(I)
T_min = 0.84, T_max = 0.93	R_int = 0.036
20468 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.036	0 restraints
wR(F²) = 0.095	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	Δρ_max = 0.26 e Å⁻³
3862 reflections	Δρ_min = −0.30 e Å⁻³
298 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.

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
P1	0.149303 (17)	0.57905 (5)	0.87467 (2)	0.02544 (14)
O1	−0.00845 (5)	0.79421 (15)	0.65671 (7)	0.0488 (4)
O2	0.07350 (5)	0.70178 (15)	0.66494 (6)	0.0447 (3)
O3	0.08693 (5)	0.23349 (15)	0.65300 (7)	0.0476 (4)
O4	0.01686 (5)	0.35822 (15)	0.57612 (6)	0.0451 (3)
O5	0.10118 (4)	0.50237 (13)	0.82537 (5)	0.0294 (3)
N1	0.00680 (6)	0.54291 (18)	0.67207 (8)	0.0378 (4)
H1	−0.0244 (8)	0.535 (2)	0.6754 (10)	0.048 (6)*
N2	0.03969 (6)	0.41275 (18)	0.68918 (8)	0.0372 (4)
H2	0.0640 (7)	0.419 (2)	0.7272 (10)	0.036 (5)*
C1	0.00936 (10)	0.9500 (2)	0.65050 (13)	0.0638 (7)
H1C	−0.0205 (4)	1.0138 (9)	0.6276 (8)	0.096*
H1B	0.0332 (6)	0.9482 (3)	0.6246 (8)	0.096*
H1A	0.0271 (6)	0.9911 (9)	0.6953 (6)	0.096*
C2	0.02861 (7)	0.6822 (2)	0.66519 (8)	0.0351 (4)
C3	0.05118 (7)	0.3283 (2)	0.63982 (9)	0.0349 (4)
C4	0.02347 (10)	0.2626 (3)	0.52124 (11)	0.0646 (7)
H4C	0.0053 (6)	0.3099 (11)	0.4776 (6)	0.097*
H4B	0.0089 (6)	0.1613 (14)	0.5229 (5)	0.097*
H4A	0.0606 (5)	0.2535 (15)	0.5269 (5)	0.097*
C11	0.16370 (7)	0.50014 (18)	0.96079 (8)	0.0281 (4)
C12	0.12062 (8)	0.4739 (2)	0.98395 (10)	0.0405 (5)
H12A	0.0857 (7)	0.4938 (5)	0.9542 (6)	0.049*
C13	0.12841 (9)	0.4190 (2)	1.04989 (10)	0.0486 (5)
H13A	0.0996 (6)	0.4028 (4)	1.0647 (3)	0.058*
C14	0.17909 (9)	0.3886 (2)	1.09350 (11)	0.0517 (6)
H14A	0.18455 (16)	0.3523 (9)	1.1397 (11)	0.062*
C15	0.22194 (9)	0.4102 (3)	1.07079 (11)	0.0575 (6)
H15A	0.2541 (8)	0.3883 (6)	1.0982 (7)	0.069*
C16	0.21459 (8)	0.4665 (2)	1.00490 (9)	0.0425 (5)
H16A	0.2438 (6)	0.4818 (4)	0.9902 (3)	0.051*
C21	0.14139 (6)	0.78746 (18)	0.88138 (8)	0.0268 (4)
C22	0.13023 (7)	0.8756 (2)	0.82090 (10)	0.0350 (4)
H22A	0.12774 (8)	0.8242 (10)	0.7772 (8)	0.042*
C23	0.12265 (8)	1.0355 (2)	0.82236 (11)	0.0422 (5)
H23A	0.11515 (17)	1.0970 (12)	0.7799 (9)	0.051*
C24	0.12570 (8)	1.1079 (2)	0.88404 (11)	0.0473 (5)
H24A	0.12009 (15)	1.216 (2)	0.88489 (11)	0.057*
C25	0.13689 (8)	1.0227 (2)	0.94401 (11)	0.0457 (5)
H25A	0.13925 (9)	1.0737 (11)	0.9865 (9)	0.055*
C26	0.14479 (7)	0.8620 (2)	0.94297 (10)	0.0352 (4)
H26A	0.15250 (16)	0.8033 (11)	0.9845 (8)	0.042*
C31	0.20790 (7)	0.55624 (18)	0.84924 (8)	0.0276 (4)
C32	0.20893 (8)	0.4427 (2)	0.80066 (9)	0.0392 (5)
H32A	0.1776 (6)	0.3766 (13)	0.7795 (4)	0.047*
C33	0.25459 (8)	0.4243 (3)	0.78255 (11)	0.0515 (6)
H33A	0.25523 (9)	0.3520 (18)	0.7511 (8)	0.062*
C34	0.29896 (8)	0.5155 (3)	0.81221 (10)	0.0477 (5)
H34A	0.3296 (7)	0.5006 (4)	0.8003 (3)	0.057*
C35	0.29792 (8)	0.6288 (2)	0.85965 (10)	0.0423 (5)
H35A	0.3295 (6)	0.6949 (14)	0.8805 (4)	0.051*
C36	0.25267 (7)	0.6494 (2)	0.87778 (9)	0.0352 (4)
H36A	0.25208 (7)	0.7255 (16)	0.9091 (6)	0.042*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
P1	0.0270 (2)	0.0250 (2)	0.0231 (3)	−0.00232 (18)	0.00640 (19)	−0.00216 (18)
O1	0.0400 (8)	0.0444 (8)	0.0621 (9)	0.0031 (6)	0.0167 (7)	0.0007 (7)
O2	0.0374 (8)	0.0594 (9)	0.0420 (8)	−0.0045 (6)	0.0192 (6)	−0.0049 (6)
O3	0.0497 (8)	0.0438 (8)	0.0514 (9)	0.0081 (7)	0.0195 (7)	0.0000 (6)
O4	0.0513 (8)	0.0565 (9)	0.0254 (7)	0.0014 (7)	0.0097 (6)	−0.0057 (6)
O5	0.0281 (6)	0.0295 (6)	0.0275 (6)	−0.0044 (5)	0.0049 (5)	−0.0050 (5)
N1	0.0282 (9)	0.0469 (10)	0.0385 (10)	0.0018 (7)	0.0113 (7)	−0.0041 (7)
N2	0.0327 (9)	0.0480 (10)	0.0259 (9)	0.0065 (7)	0.0026 (8)	−0.0050 (7)
C1	0.0649 (16)	0.0467 (14)	0.0768 (17)	−0.0003 (11)	0.0192 (13)	0.0018 (12)
C2	0.0311 (10)	0.0512 (12)	0.0218 (10)	0.0021 (9)	0.0070 (8)	−0.0043 (8)
C3	0.0353 (10)	0.0372 (11)	0.0337 (11)	−0.0056 (9)	0.0132 (9)	−0.0016 (8)
C4	0.0955 (19)	0.0660 (15)	0.0359 (13)	−0.0054 (13)	0.0262 (12)	−0.0144 (11)
C11	0.0327 (10)	0.0237 (9)	0.0267 (10)	−0.0028 (7)	0.0082 (8)	−0.0032 (7)
C12	0.0400 (11)	0.0510 (12)	0.0321 (11)	0.0040 (9)	0.0139 (9)	0.0054 (9)
C13	0.0553 (14)	0.0582 (14)	0.0403 (13)	0.0019 (10)	0.0267 (11)	0.0055 (10)
C14	0.0726 (17)	0.0516 (13)	0.0304 (12)	−0.0028 (11)	0.0164 (11)	0.0101 (9)
C15	0.0484 (13)	0.0737 (16)	0.0383 (13)	0.0008 (11)	−0.0024 (10)	0.0208 (11)
C16	0.0356 (11)	0.0528 (13)	0.0358 (12)	−0.0052 (9)	0.0072 (9)	0.0093 (9)
C21	0.0253 (9)	0.0258 (9)	0.0281 (10)	−0.0024 (7)	0.0069 (7)	−0.0027 (7)
C22	0.0389 (11)	0.0325 (10)	0.0332 (11)	−0.0022 (8)	0.0111 (8)	0.0003 (8)
C23	0.0470 (12)	0.0315 (10)	0.0449 (12)	−0.0027 (8)	0.0107 (9)	0.0071 (9)
C24	0.0483 (13)	0.0252 (10)	0.0635 (15)	−0.0010 (8)	0.0114 (11)	−0.0041 (10)
C25	0.0508 (13)	0.0366 (11)	0.0453 (12)	−0.0017 (9)	0.0096 (10)	−0.0170 (10)
C26	0.0385 (10)	0.0324 (10)	0.0310 (10)	−0.0018 (8)	0.0064 (8)	−0.0052 (8)
C31	0.0301 (9)	0.0279 (9)	0.0234 (9)	0.0005 (7)	0.0071 (7)	0.0016 (7)
C32	0.0411 (11)	0.0403 (11)	0.0368 (11)	−0.0021 (9)	0.0136 (9)	−0.0076 (9)
C33	0.0575 (14)	0.0564 (14)	0.0464 (13)	0.0051 (11)	0.0251 (11)	−0.0156 (10)
C34	0.0407 (12)	0.0643 (14)	0.0453 (13)	0.0059 (10)	0.0241 (10)	0.0021 (11)
C35	0.0348 (11)	0.0546 (12)	0.0391 (12)	−0.0064 (9)	0.0142 (9)	0.0012 (10)
C36	0.0375 (11)	0.0391 (10)	0.0306 (10)	−0.0042 (8)	0.0131 (8)	−0.0052 (8)

Geometric parameters (Å, º) top

P1—O5	1.4938 (11)	C14—C15	1.373 (3)
P1—C31	1.8017 (17)	C14—H14A	0.9582
P1—C21	1.8056 (16)	C15—C16	1.383 (3)
P1—C11	1.8058 (17)	C15—H15A	0.8729
O1—C2	1.342 (2)	C16—H16A	0.9271
O1—C1	1.433 (2)	C21—C26	1.388 (2)
O2—C2	1.203 (2)	C21—C22	1.395 (2)
O3—C3	1.209 (2)	C22—C23	1.384 (2)
O4—C3	1.347 (2)	C22—H22A	0.9782
O4—C4	1.445 (2)	C23—C24	1.383 (3)
N1—C2	1.352 (2)	C23—H23A	0.9780
N1—N2	1.386 (2)	C24—C25	1.373 (3)
N1—H1	0.85 (2)	C24—H24A	0.9379
N2—C3	1.354 (2)	C25—C26	1.391 (2)
N2—H2	0.832 (18)	C25—H25A	0.9546
C1—H1C	0.9492	C26—H26A	0.9485
C1—H1B	0.9492	C31—C36	1.389 (2)
C1—H1A	0.9492	C31—C32	1.396 (2)
C4—H4C	0.9539	C32—C33	1.385 (3)
C4—H4B	0.9539	C32—H32A	0.9810
C4—H4A	0.9539	C33—C34	1.375 (3)
C11—C16	1.385 (2)	C33—H33A	0.8962
C11—C12	1.389 (2)	C34—C35	1.378 (3)
C12—C13	1.378 (3)	C34—H34A	0.9307
C12—H12A	0.9422	C35—C36	1.377 (2)
C13—C14	1.372 (3)	C35—H35A	0.9830
C13—H13A	0.9187	C36—H36A	0.9161

O5—P1—C31	112.56 (7)	C15—C14—H14A	120.1
O5—P1—C21	112.97 (7)	C14—C15—C16	120.5 (2)
C31—P1—C21	105.14 (7)	C14—C15—H15A	119.7
O5—P1—C11	110.80 (7)	C16—C15—H15A	119.7
C31—P1—C11	108.28 (8)	C15—C16—C11	120.22 (19)
C21—P1—C11	106.73 (8)	C15—C16—H16A	119.9
C2—O1—C1	115.29 (16)	C11—C16—H16A	119.9
C3—O4—C4	115.36 (16)	C26—C21—C22	119.19 (16)
C2—N1—N2	118.65 (16)	C26—C21—P1	123.23 (13)
C2—N1—H1	122.3 (13)	C22—C21—P1	117.57 (13)
N2—N1—H1	117.6 (13)	C23—C22—C21	120.35 (18)
C3—N2—N1	121.10 (16)	C23—C22—H22A	119.8
C3—N2—H2	115.9 (12)	C21—C22—H22A	119.8
N1—N2—H2	114.3 (12)	C24—C23—C22	119.80 (19)
O1—C1—H1C	109.5	C24—C23—H23A	120.1
O1—C1—H1B	109.5	C22—C23—H23A	120.1
H1C—C1—H1B	109.5	C25—C24—C23	120.46 (19)
O1—C1—H1A	109.5	C25—C24—H24A	119.8
H1C—C1—H1A	109.5	C23—C24—H24A	119.8
H1B—C1—H1A	109.5	C24—C25—C26	120.04 (19)
O2—C2—O1	125.67 (18)	C24—C25—H25A	120.0
O2—C2—N1	125.44 (18)	C26—C25—H25A	120.0
O1—C2—N1	108.86 (15)	C21—C26—C25	120.16 (18)
O3—C3—O4	125.12 (17)	C21—C26—H26A	119.9
O3—C3—N2	122.87 (17)	C25—C26—H26A	119.9
O4—C3—N2	111.95 (16)	C36—C31—C32	119.02 (17)
O4—C4—H4C	109.5	C36—C31—P1	120.98 (13)
O4—C4—H4B	109.5	C32—C31—P1	120.00 (13)
H4C—C4—H4B	109.5	C33—C32—C31	119.46 (18)
O4—C4—H4A	109.5	C33—C32—H32A	120.3
H4C—C4—H4A	109.5	C31—C32—H32A	120.3
H4B—C4—H4A	109.5	C34—C33—C32	120.84 (19)
C16—C11—C12	118.54 (16)	C34—C33—H33A	119.6
C16—C11—P1	124.23 (14)	C32—C33—H33A	119.6
C12—C11—P1	117.23 (13)	C33—C34—C35	119.90 (19)
C13—C12—C11	120.77 (19)	C33—C34—H34A	120.0
C13—C12—H12A	119.6	C35—C34—H34A	120.0
C11—C12—H12A	119.6	C36—C35—C34	119.92 (19)
C14—C13—C12	120.1 (2)	C36—C35—H35A	120.0
C14—C13—H13A	119.9	C34—C35—H35A	120.0
C12—C13—H13A	119.9	C35—C36—C31	120.85 (18)
C13—C14—C15	119.8 (2)	C35—C36—H36A	119.6
C13—C14—H14A	120.1	C31—C36—H36A	119.6

C2—N1—N2—C3	−85.2 (2)	O5—P1—C21—C22	−58.38 (15)
C1—O1—C2—O2	−3.3 (3)	C31—P1—C21—C22	64.74 (15)
C1—O1—C2—N1	178.43 (16)	C11—P1—C21—C22	179.61 (13)
N2—N1—C2—O2	8.9 (3)	C26—C21—C22—C23	0.0 (3)
N2—N1—C2—O1	−172.85 (14)	P1—C21—C22—C23	178.68 (14)
C4—O4—C3—O3	2.5 (3)	C21—C22—C23—C24	−0.6 (3)
C4—O4—C3—N2	−174.72 (16)	C22—C23—C24—C25	0.8 (3)
N1—N2—C3—O3	165.73 (17)	C23—C24—C25—C26	−0.6 (3)
N1—N2—C3—O4	−17.0 (2)	C22—C21—C26—C25	0.3 (3)
O5—P1—C11—C16	138.93 (15)	P1—C21—C26—C25	−178.33 (14)
C31—P1—C11—C16	15.04 (17)	C24—C25—C26—C21	0.0 (3)
C21—P1—C11—C16	−97.70 (16)	O5—P1—C31—C36	163.98 (13)
O5—P1—C11—C12	−41.92 (15)	C21—P1—C31—C36	40.60 (16)
C31—P1—C11—C12	−165.81 (13)	C11—P1—C31—C36	−73.19 (15)
C21—P1—C11—C12	81.45 (14)	O5—P1—C31—C32	−16.60 (16)
C16—C11—C12—C13	1.5 (3)	C21—P1—C31—C32	−139.98 (14)
P1—C11—C12—C13	−177.73 (15)	C11—P1—C31—C32	106.23 (15)
C11—C12—C13—C14	−0.4 (3)	C36—C31—C32—C33	0.7 (3)
C12—C13—C14—C15	−1.2 (3)	P1—C31—C32—C33	−178.72 (14)
C13—C14—C15—C16	1.7 (3)	C31—C32—C33—C34	0.5 (3)
C14—C15—C16—C11	−0.7 (3)	C32—C33—C34—C35	−1.2 (3)
C12—C11—C16—C15	−0.9 (3)	C33—C34—C35—C36	0.7 (3)
P1—C11—C16—C15	178.22 (16)	C34—C35—C36—C31	0.5 (3)
O5—P1—C21—C26	120.24 (14)	C32—C31—C36—C35	−1.2 (3)
C31—P1—C21—C26	−116.65 (14)	P1—C31—C36—C35	178.21 (13)
C11—P1—C21—C26	−1.77 (16)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O5ⁱ	0.85 (2)	2.05 (2)	2.899 (2)	174.2 (19)
N2—H2···O5	0.83 (2)	2.05 (2)	2.833 (2)	155.9 (17)
C13—H13A···O2ⁱⁱ	0.92	2.53	3.310 (3)	143
C35—H35A···O3ⁱⁱⁱ	0.98	2.54	3.270 (3)	131

Symmetry codes: (i) −x, y, −z+3/2; (ii) x, −y+1, z+1/2; (iii) −x+1/2, y+1/2, −z+3/2.

Experimental details

Crystal data
Chemical formula	C₄H₈N₂O₄·C₁₈H₁₅OP
M_r	426.39
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	200
a, b, c (Å)	26.494 (3), 8.5545 (9), 20.4426 (19)
β (°)	109.090 (3)
V (Å³)	4378.3 (8)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.16
Crystal size (mm)	0.8 × 0.7 × 0.4

Data collection
Diffractometer	Bruker SMART X2S diffractometer
Absorption correction	Multi-scan (SADABS (Sheldrick, 2008a)
T_min, T_max	0.84, 0.93
No. of measured, independent and observed [I > 2σ(I)] reflections	20468, 3862, 2956
R_int	0.036
(sin θ/λ)_max (Å⁻¹)	0.596

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.095, 1.03
No. of reflections	3862
No. of parameters	298
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.30

Computer programs: GIS (Bruker, 2010), APEX2 (Bruker, 2010) and SAINT (Bruker, 2009), SAINT (Bruker, 2009) and XPREP (Bruker, 2009), SHELXS97 (Sheldrick, 2008b), SHELXL97 (Sheldrick, 2008b), ORTEP-3 for Windows (Farrugia, 1997) and Mercury (Macrae et al., 2008), PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O5ⁱ	0.85 (2)	2.05 (2)	2.899 (2)	174.2 (19)
N2—H2···O5	0.83 (2)	2.05 (2)	2.833 (2)	155.9 (17)
C13—H13A···O2ⁱⁱ	0.92	2.53	3.310 (3)	143
C35—H35A···O3ⁱⁱⁱ	0.984	2.54	3.270 (3)	131

Symmetry codes: (i) −x, y, −z+3/2; (ii) x, −y+1, z+1/2; (iii) −x+1/2, y+1/2, −z+3/2.

Acknowledgements

This study was supported a by grant for the X-ray diffractometer and SUNY grant No. 1073053. AYN thanks Dr Bruce Noll (Bruker AXS) for useful advice on operating the X2S diffractometer and Dr David Geiger (SUNY Geneseo) for help with the experiment.

References

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