A second monoclinic polymorph of N-[bis­(morpholin-4-yl)phosphino­yl]-4-fluoro­benzamide with the P21/n space group

Tarahhomi, A.; Pourayoubi, M.; Keikha, M.; Rheingold, A.L.; Golen, J.A.

doi:10.1107/S1600536812031418

organic compounds

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ISSN: 2056-9890

Volume 68| Part 8| August 2012| Page o2444

https://doi.org/10.1107/S1600536812031418

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A second monoclinic polymorph of N-[bis(morpholin-4-yl)phosphinoyl]-4-fluorobenzamide with the P2₁/n space group

Atekeh Tarahhomi,^a ^* Mehrdad Pourayoubi,^a Mojtaba Keikha,^a Arnold L. Rheingold ^b and James A. Golen ^b

^aDepartment of Chemistry, Ferdowsi University of Mashhad, Mashhad, Iran, and ^bDepartment of Chemistry, University of California, San Diego, 9500 Gilman Drive, La Jolla, CA 92093, USA
^*Correspondence e-mail: tarahhomi_at@yahoo.com

(Received 18 June 2012; accepted 10 July 2012; online 14 July 2012)

A second monoclinic polymorph of the title molecule, C₁₅H₂₁FN₃O₄P, is reported in the space group P2₁/n and compared to the previously reported C2/c space group [Gholivand et al. (2006 ). Polyhedron, 25, 711–721]. The asymmetric unit of the title compound consists of two independent molecules. The P atoms adopt a distorted tetrahedral environment. In the C(O)NHP(O) fragment, the P=O and the N—H groups are in a syn conformation with respect to each other and in the crystal, intermolecular N—H⋯O=P hydrogen bonds form dimeric aggregates.

Related literature

For the monoclinic polymorph of the title molecule, in a C2/c space group, for bond lengths and angles and for preparation of the starting compound 4-F—C₆H₄C(O)NHP(O)Cl₂, see: Gholivand et al. (2006). For related phosphoramidates, see: Pourayoubi, Nečas & Negari (2012 ); Pourayoubi, Tarahhomi et al. (2012 ).

Experimental

Crystal data

C₁₅H₂₁FN₃O₄P
M_r = 357.32
Monoclinic, P 2₁ /n
a = 15.6093 (6) Å
b = 10.7114 (4) Å
c = 21.0045 (9) Å
β = 106.896 (2)°
V = 3360.3 (2) Å³
Z = 8
Mo Kα radiation
μ = 0.20 mm⁻¹
T = 100 K
0.18 × 0.15 × 0.10 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2004 ) T_min = 0.965, T_max = 0.980
25230 measured reflections
6912 independent reflections
5355 reflections with I > 2σ(I)
R_int = 0.037

Refinement

R[F² > 2σ(F²)] = 0.056
wR(F²) = 0.160
S = 1.03
6912 reflections
439 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 1.45 e Å⁻³
Δρ_min = −0.73 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H4N⋯O2ⁱ	0.85 (2)	2.01 (2)	2.855 (3)	176 (3)
N1—H1N⋯O6ⁱⁱ	0.87 (2)	2.04 (2)	2.870 (3)	159 (3)
Symmetry codes: (i) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2005 ); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2008 ); software used to prepare material for publication: SHELXTL and enCIFer (Allen et al., 2004 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536812031418/jj2145sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812031418/jj2145Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536812031418/jj2145Isup3.cml

checkCIF report

Comment top

The structure determination of a monoclinic polymorph of the title molecule, [4-F—C₆H₄C(O)NH]P(O)[NC₄H₈O]₂ (Fig. 1), in a C2/c space group with Z = 8 was investigated in ambient temperature, Gholivand et al. (2006). Here, we report on a second monoclinic polymorph in a space group P2₁/n with Z = 8. Cell parameters for both polymorphs exhibit similar dimensions. The C2/c structure at 293 K has cell parameters of 15.732 (3), 10.740 (2), 21.553 (4) Å with β of 106.93 (3)° while those of P2₁/n at 100 K have smaller cell dimensions indicative of a possible phase change.

The asymmetric unit consists of two independent molecules; in each molecule, the phosphoryl group adopts a syn orientation with respect to the N—H unit. In the first monoclinic modification of this compound (Gholivand et al., 2006), the asymmetric unit is composed of one molecule involving disorder in one morpholin-4-yl moiety. The P atom is in a distorted tetrahedral environment as has been noted for other phosphoramides (Pourayoubi, Nečas & Negari, 2012 and Pourayoubi, Tarahhomi et al., 2012).

The P═O, C═O and P—N bond lengths and P—N—C bond angles are within the expected values (Gholivand et al., 2006).

In the crystal, two different intermolecular N—H···O(P) hydrogen bonds make dimeric aggregates. So, each hydrogen-bonded dimer is built of two symmetrically independent molecules (Fig. 2).

Related literature top

Experimental top

4-F—C₆H₄C(O)NHP(O)Cl₂ was prepared according to the literature method reported by Gholivand et al. (2006).

To a solution of 4-F—C₆H₄C(O)NHP(O)Cl₂ (0.723 g, 2.825 mmol) in dry acetonitrile (25 ml), a solution of morpholine (0.984 g, 11.300 mmol) in dry acetonitrile (5 ml) was added at 273 K. After 4 h stirring, the solvent was removed and the product was washed with distilled water and the resulting precipitate of 4-F—C₆H₄C(O)NHP(O)(NC₄H₈O)₂ was collected. Single crystals were obtained in a try on a reaction between 4-F—C₆H₄C(O)NHP(O)(NC₄H₈O)₂ and Sn(CH₃)₂Cl₂ in CH₃OH under reflux, followed by slow evaporation of the filtered solution at room temperature.

Structure description top

The P═O, C═O and P—N bond lengths and P—N—C bond angles are within the expected values (Gholivand et al., 2006).

In the crystal, two different intermolecular N—H···O(P) hydrogen bonds make dimeric aggregates. So, each hydrogen-bonded dimer is built of two symmetrically independent molecules (Fig. 2).

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and enCIFer (Allen et al., 2004).

Figures top

	Fig. 1. An ORTEP-style plot and atom labeling scheme for the asymmetric unit of the title molecule. Displacement ellipsoids are given at 50% probability level and H atoms are drawn as small spheres of arbitrary radii.
	Fig. 2. Crystal packing view showing N—H···O(P) hydrogen bond which are shown as dotted lines. The symmetrically independent molecules are shown as different colors and the H atoms not involved in hydrogen bonding have been omitted for the sake of clarity.

N-[Bis(morpholin-4-yl)phosphinoyl]-4-fluorobenzamide top

Crystal data top

C₁₅H₂₁FN₃O₄P	F(000) = 1504
M_r = 357.32	D_x = 1.413 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 7455 reflections
a = 15.6093 (6) Å	θ = 2.3–26.4°
b = 10.7114 (4) Å	µ = 0.20 mm⁻¹
c = 21.0045 (9) Å	T = 100 K
β = 106.896 (2)°	Block, colourless
V = 3360.3 (2) Å³	0.18 × 0.15 × 0.10 mm
Z = 8

Data collection top

Bruker APEXII CCD diffractometer	6912 independent reflections
Radiation source: fine-focus sealed tube	5355 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.037
Detector resolution: 8.33 pixels mm^-1	θ_max = 26.4°, θ_min = 1.4°
φ and ω scans	h = −19→19
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	k = −13→13
T_min = 0.965, T_max = 0.980	l = −22→26
25230 measured reflections

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)] = 0.056	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.160	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ²(F_o²) + (0.0816P)² + 4.9555P] where P = (F_o² + 2F_c²)/3
6912 reflections	(Δ/σ)_max < 0.001
439 parameters	Δρ_max = 1.45 e Å⁻³
2 restraints	Δρ_min = −0.73 e Å⁻³

Crystal data top

C₁₅H₂₁FN₃O₄P	V = 3360.3 (2) Å³
M_r = 357.32	Z = 8
Monoclinic, P2₁/n	Mo Kα radiation
a = 15.6093 (6) Å	µ = 0.20 mm⁻¹
b = 10.7114 (4) Å	T = 100 K
c = 21.0045 (9) Å	0.18 × 0.15 × 0.10 mm
β = 106.896 (2)°

Data collection top

Bruker APEXII CCD diffractometer	6912 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	5355 reflections with I > 2σ(I)
T_min = 0.965, T_max = 0.980	R_int = 0.037
25230 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.056	2 restraints
wR(F²) = 0.160	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	Δρ_max = 1.45 e Å⁻³
6912 reflections	Δρ_min = −0.73 e Å⁻³
439 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	0.47360 (4)	0.87432 (6)	0.15573 (3)	0.01350 (17)
P2	0.93848 (4)	0.36293 (6)	0.12376 (3)	0.01408 (17)
F1	0.07031 (11)	0.82774 (16)	0.31748 (9)	0.0255 (4)
F2	0.58872 (11)	0.32224 (15)	0.33946 (9)	0.0239 (4)
O1	0.30622 (14)	0.71437 (19)	0.12959 (10)	0.0250 (5)
O2	0.54401 (12)	0.95376 (17)	0.19942 (9)	0.0170 (4)
O3	0.26441 (14)	1.08121 (18)	0.01350 (10)	0.0263 (5)
O4	0.59087 (13)	0.54123 (18)	0.08540 (10)	0.0238 (5)
O5	0.76002 (14)	0.22559 (19)	0.10808 (10)	0.0246 (5)
O6	1.01711 (12)	0.43300 (18)	0.16535 (10)	0.0192 (4)
O7	0.74106 (13)	0.59113 (17)	−0.00982 (10)	0.0228 (4)
O8	1.08127 (14)	0.03799 (19)	0.09330 (11)	0.0294 (5)
N1	0.40849 (14)	0.8319 (2)	0.20362 (11)	0.0149 (5)
H1N	0.417 (2)	0.872 (3)	0.2410 (11)	0.018*
N2	0.41816 (15)	0.9499 (2)	0.08931 (11)	0.0165 (5)
N3	0.50455 (15)	0.7452 (2)	0.12658 (11)	0.0176 (5)
N4	0.87238 (15)	0.3430 (2)	0.17412 (11)	0.0157 (5)
H4N	0.8948 (19)	0.374 (3)	0.2123 (10)	0.019*
N5	0.88937 (14)	0.4404 (2)	0.05651 (11)	0.0164 (5)
N6	0.95166 (15)	0.2234 (2)	0.09645 (11)	0.0179 (5)
C1	0.27337 (18)	0.8749 (3)	0.27251 (14)	0.0186 (6)
H1A	0.3255	0.9257	0.2849	0.022*
C2	0.20861 (18)	0.8881 (3)	0.30509 (14)	0.0199 (6)
H2A	0.2152	0.9479	0.3396	0.024*
C3	0.13450 (17)	0.8125 (2)	0.28632 (14)	0.0172 (6)
C4	0.12203 (18)	0.7231 (3)	0.23765 (14)	0.0198 (6)
H4A	0.0707	0.6706	0.2269	0.024*
C5	0.18645 (17)	0.7119 (2)	0.20477 (14)	0.0173 (5)
H5A	0.1788	0.6520	0.1702	0.021*
C6	0.26243 (17)	0.7873 (2)	0.22151 (13)	0.0152 (5)
C7	0.32636 (18)	0.7737 (2)	0.18122 (13)	0.0168 (5)
C8	0.35807 (18)	0.8961 (3)	0.02858 (14)	0.0199 (6)
H8A	0.3567	0.8041	0.0330	0.024*
H8B	0.3805	0.9159	−0.0098	0.024*
C9	0.2642 (2)	0.9483 (3)	0.01647 (15)	0.0232 (6)
H9A	0.2249	0.9147	−0.0259	0.028*
H9B	0.2397	0.9213	0.0528	0.028*
C10	0.3181 (2)	1.1302 (3)	0.07509 (15)	0.0242 (6)
H10A	0.2939	1.1023	0.1114	0.029*
H10B	0.3160	1.2225	0.0735	0.029*
C11	0.4140 (2)	1.0871 (2)	0.08929 (15)	0.0226 (6)
H11A	0.4398	1.1206	0.0550	0.027*
H11B	0.4498	1.1193	0.1331	0.027*
C12	0.56485 (19)	0.7619 (3)	0.08400 (15)	0.0225 (6)
H12A	0.6268	0.7770	0.1122	0.027*
H12B	0.5454	0.8351	0.0546	0.027*
C13	0.5620 (2)	0.6472 (3)	0.04299 (15)	0.0249 (6)
H13A	0.5002	0.6333	0.0141	0.030*
H13B	0.6015	0.6582	0.0141	0.030*
C14	0.53270 (19)	0.5219 (3)	0.12520 (15)	0.0226 (6)
H14A	0.5529	0.4478	0.1538	0.027*
H14B	0.4715	0.5049	0.0960	0.027*
C15	0.53018 (19)	0.6333 (2)	0.16835 (14)	0.0204 (6)
H15A	0.4864	0.6186	0.1935	0.024*
H15B	0.5898	0.6459	0.2007	0.024*
C16	0.75142 (17)	0.3982 (2)	0.25373 (14)	0.0173 (5)
H16A	0.7956	0.4597	0.2545	0.021*
C17	0.70067 (17)	0.4068 (2)	0.29795 (14)	0.0177 (6)
H17A	0.7088	0.4741	0.3286	0.021*
C18	0.63820 (17)	0.3150 (2)	0.29609 (13)	0.0159 (5)
C19	0.62334 (16)	0.2167 (2)	0.25214 (14)	0.0158 (5)
H19A	0.5800	0.1546	0.2524	0.019*
C20	0.67331 (16)	0.2109 (2)	0.20749 (13)	0.0131 (5)
H20A	0.6630	0.1450	0.1759	0.016*
C21	0.73824 (17)	0.3000 (2)	0.20819 (13)	0.0142 (5)
C22	0.78981 (17)	0.2861 (2)	0.15893 (14)	0.0161 (5)
C23	0.81724 (17)	0.3917 (2)	0.00028 (13)	0.0171 (5)
H23A	0.8097	0.3012	0.0065	0.021*
H23B	0.8334	0.4033	−0.0415	0.021*
C24	0.73018 (18)	0.4588 (2)	−0.00470 (15)	0.0190 (6)
H24A	0.6832	0.4286	−0.0443	0.023*
H24B	0.7108	0.4401	0.0352	0.023*
C25	0.8061 (2)	0.6370 (3)	0.04805 (16)	0.0262 (7)
H25A	0.7871	0.6179	0.0880	0.031*
H25B	0.8112	0.7288	0.0449	0.031*
C26	0.89630 (19)	0.5771 (2)	0.05444 (16)	0.0244 (6)
H26A	0.9174	0.6018	0.0161	0.029*
H26B	0.9406	0.6070	0.0956	0.029*
C27	0.98143 (19)	0.2023 (3)	0.03698 (15)	0.0229 (6)
H27A	0.9799	0.2821	0.0129	0.027*
H27B	0.9401	0.1432	0.0068	0.027*
C28	1.0750 (2)	0.1502 (3)	0.05604 (18)	0.0305 (7)
H28A	1.0927	0.1334	0.0153	0.037*
H28B	1.1169	0.2127	0.0828	0.037*
C29	1.0563 (2)	0.0604 (3)	0.15248 (16)	0.0280 (7)
H29A	1.0983	0.1214	0.1806	0.034*
H29B	1.0610	−0.0184	0.1779	0.034*
C30	0.9619 (2)	0.1102 (3)	0.13704 (15)	0.0221 (6)
H30A	0.9191	0.0459	0.1129	0.027*
H30B	0.9479	0.1291	0.1791	0.027*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
P1	0.0156 (3)	0.0121 (3)	0.0144 (3)	0.0020 (2)	0.0069 (3)	0.0010 (3)
P2	0.0130 (3)	0.0138 (3)	0.0165 (4)	0.0014 (2)	0.0060 (3)	0.0030 (3)
F1	0.0196 (8)	0.0309 (9)	0.0323 (10)	0.0007 (7)	0.0173 (7)	−0.0010 (8)
F2	0.0236 (8)	0.0232 (8)	0.0321 (10)	−0.0011 (7)	0.0194 (7)	−0.0030 (7)
O1	0.0283 (11)	0.0296 (11)	0.0193 (11)	−0.0100 (9)	0.0104 (9)	−0.0112 (9)
O2	0.0146 (9)	0.0176 (9)	0.0180 (10)	0.0000 (7)	0.0034 (7)	0.0024 (8)
O3	0.0328 (11)	0.0195 (10)	0.0199 (11)	0.0081 (9)	−0.0026 (9)	−0.0024 (8)
O4	0.0260 (11)	0.0196 (10)	0.0305 (12)	0.0071 (8)	0.0155 (9)	0.0017 (9)
O5	0.0287 (11)	0.0272 (11)	0.0211 (11)	−0.0105 (9)	0.0124 (9)	−0.0097 (9)
O6	0.0142 (9)	0.0230 (10)	0.0201 (10)	−0.0004 (8)	0.0045 (8)	0.0065 (8)
O7	0.0235 (10)	0.0166 (9)	0.0240 (11)	0.0052 (8)	0.0002 (8)	0.0008 (8)
O8	0.0281 (11)	0.0238 (11)	0.0389 (13)	0.0130 (9)	0.0140 (10)	0.0058 (10)
N1	0.0151 (11)	0.0159 (10)	0.0157 (11)	−0.0010 (9)	0.0077 (9)	−0.0041 (9)
N2	0.0214 (11)	0.0114 (10)	0.0158 (11)	0.0024 (9)	0.0041 (9)	0.0001 (9)
N3	0.0260 (12)	0.0144 (11)	0.0162 (12)	0.0057 (9)	0.0120 (10)	0.0037 (9)
N4	0.0168 (11)	0.0171 (11)	0.0151 (11)	−0.0028 (9)	0.0075 (9)	−0.0033 (9)
N5	0.0145 (11)	0.0133 (10)	0.0198 (12)	0.0004 (8)	0.0026 (9)	0.0028 (9)
N6	0.0235 (12)	0.0165 (11)	0.0163 (11)	0.0052 (9)	0.0102 (9)	0.0030 (9)
C1	0.0153 (13)	0.0222 (14)	0.0196 (14)	−0.0039 (10)	0.0073 (11)	−0.0049 (11)
C2	0.0168 (13)	0.0239 (14)	0.0191 (14)	0.0007 (11)	0.0054 (11)	−0.0060 (11)
C3	0.0121 (12)	0.0205 (13)	0.0211 (14)	0.0046 (10)	0.0081 (11)	0.0060 (11)
C4	0.0133 (12)	0.0200 (13)	0.0259 (15)	−0.0025 (10)	0.0055 (11)	0.0016 (11)
C5	0.0154 (13)	0.0177 (13)	0.0169 (13)	−0.0003 (10)	0.0018 (10)	−0.0017 (11)
C6	0.0135 (12)	0.0150 (12)	0.0164 (13)	0.0011 (10)	0.0036 (10)	0.0008 (10)
C7	0.0205 (13)	0.0134 (12)	0.0168 (14)	−0.0010 (10)	0.0057 (11)	−0.0006 (10)
C8	0.0252 (14)	0.0183 (13)	0.0162 (14)	0.0028 (11)	0.0061 (11)	−0.0019 (11)
C9	0.0289 (15)	0.0178 (13)	0.0202 (15)	0.0035 (11)	0.0026 (12)	−0.0035 (11)
C10	0.0327 (16)	0.0163 (13)	0.0193 (15)	0.0074 (12)	0.0008 (12)	−0.0024 (11)
C11	0.0305 (16)	0.0130 (13)	0.0228 (15)	0.0008 (11)	0.0055 (12)	0.0020 (11)
C12	0.0262 (15)	0.0214 (14)	0.0241 (15)	0.0034 (12)	0.0140 (12)	0.0021 (12)
C13	0.0324 (16)	0.0238 (15)	0.0238 (16)	0.0070 (12)	0.0165 (13)	0.0015 (12)
C14	0.0240 (14)	0.0189 (13)	0.0280 (16)	0.0028 (11)	0.0122 (12)	0.0024 (12)
C15	0.0251 (14)	0.0175 (13)	0.0208 (14)	0.0038 (11)	0.0101 (12)	0.0047 (11)
C16	0.0127 (12)	0.0171 (13)	0.0229 (14)	−0.0039 (10)	0.0064 (10)	−0.0043 (11)
C17	0.0156 (13)	0.0187 (13)	0.0183 (14)	−0.0011 (10)	0.0042 (11)	−0.0068 (11)
C18	0.0124 (12)	0.0186 (13)	0.0190 (14)	0.0043 (10)	0.0084 (10)	0.0027 (11)
C19	0.0113 (12)	0.0129 (12)	0.0228 (14)	−0.0009 (9)	0.0043 (10)	0.0016 (10)
C20	0.0095 (11)	0.0120 (11)	0.0155 (13)	0.0020 (9)	−0.0002 (10)	0.0014 (10)
C21	0.0145 (12)	0.0131 (12)	0.0151 (13)	0.0003 (9)	0.0045 (10)	0.0017 (10)
C22	0.0180 (13)	0.0122 (12)	0.0187 (14)	−0.0033 (10)	0.0061 (11)	−0.0004 (10)
C23	0.0183 (13)	0.0167 (12)	0.0156 (13)	0.0021 (10)	0.0036 (11)	−0.0009 (10)
C24	0.0179 (13)	0.0159 (13)	0.0221 (14)	0.0012 (10)	0.0041 (11)	−0.0016 (11)
C25	0.0281 (15)	0.0127 (13)	0.0316 (17)	0.0043 (11)	−0.0010 (13)	−0.0011 (12)
C26	0.0226 (14)	0.0143 (13)	0.0307 (16)	−0.0031 (11)	−0.0011 (12)	0.0069 (12)
C27	0.0268 (15)	0.0242 (14)	0.0215 (15)	0.0043 (12)	0.0130 (12)	0.0026 (12)
C28	0.0291 (16)	0.0278 (16)	0.0419 (19)	0.0094 (13)	0.0221 (15)	0.0092 (14)
C29	0.0309 (16)	0.0234 (15)	0.0260 (16)	0.0081 (12)	0.0022 (13)	0.0091 (13)
C30	0.0296 (15)	0.0168 (13)	0.0210 (15)	0.0021 (11)	0.0091 (12)	0.0034 (11)

Geometric parameters (Å, º) top

P1—O2	1.4791 (19)	C9—H9B	0.9900
P1—N2	1.628 (2)	C10—C11	1.511 (4)
P1—N3	1.641 (2)	C10—H10A	0.9900
P1—N1	1.687 (2)	C10—H10B	0.9900
P2—O6	1.4866 (19)	C11—H11A	0.9900
P2—N5	1.626 (2)	C11—H11B	0.9900
P2—N6	1.635 (2)	C12—C13	1.495 (4)
P2—N4	1.692 (2)	C12—H12A	0.9900
F1—C3	1.356 (3)	C12—H12B	0.9900
F2—C18	1.357 (3)	C13—H13A	0.9900
O1—C7	1.217 (3)	C13—H13B	0.9900
O3—C10	1.422 (3)	C14—C15	1.505 (4)
O3—C9	1.425 (3)	C14—H14A	0.9900
O4—C14	1.417 (3)	C14—H14B	0.9900
O4—C13	1.432 (3)	C15—H15A	0.9900
O5—C22	1.220 (3)	C15—H15B	0.9900
O7—C25	1.426 (3)	C16—C17	1.388 (4)
O7—C24	1.435 (3)	C16—C21	1.396 (4)
O8—C28	1.422 (4)	C16—H16A	0.9500
O8—C29	1.427 (4)	C17—C18	1.378 (4)
N1—C7	1.380 (3)	C17—H17A	0.9500
N1—H1N	0.869 (17)	C18—C19	1.375 (4)
N2—C8	1.464 (3)	C19—C20	1.385 (4)
N2—C11	1.471 (3)	C19—H19A	0.9500
N3—C15	1.471 (3)	C20—C21	1.389 (3)
N3—C12	1.486 (3)	C20—H20A	0.9500
N4—C22	1.377 (3)	C21—C22	1.491 (4)
N4—H4N	0.846 (18)	C23—C24	1.514 (4)
N5—C26	1.470 (3)	C23—H23A	0.9900
N5—C23	1.470 (3)	C23—H23B	0.9900
N6—C30	1.465 (3)	C24—H24A	0.9900
N6—C27	1.471 (3)	C24—H24B	0.9900
C1—C2	1.383 (4)	C25—C26	1.517 (4)
C1—C6	1.397 (4)	C25—H25A	0.9900
C1—H1A	0.9500	C25—H25B	0.9900
C2—C3	1.373 (4)	C26—H26A	0.9900
C2—H2A	0.9500	C26—H26B	0.9900
C3—C4	1.373 (4)	C27—C28	1.504 (4)
C4—C5	1.381 (4)	C27—H27A	0.9900
C4—H4A	0.9500	C27—H27B	0.9900
C5—C6	1.392 (4)	C28—H28A	0.9900
C5—H5A	0.9500	C28—H28B	0.9900
C6—C7	1.491 (4)	C29—C30	1.512 (4)
C8—C9	1.519 (4)	C29—H29A	0.9900
C8—H8A	0.9900	C29—H29B	0.9900
C8—H8B	0.9900	C30—H30A	0.9900
C9—H9A	0.9900	C30—H30B	0.9900

O2—P1—N2	111.08 (11)	O4—C13—H13A	109.7
O2—P1—N3	118.04 (11)	C12—C13—H13A	109.7
N2—P1—N3	103.92 (11)	O4—C13—H13B	109.7
O2—P1—N1	104.63 (11)	C12—C13—H13B	109.7
N2—P1—N1	112.50 (12)	H13A—C13—H13B	108.2
N3—P1—N1	106.82 (11)	O4—C14—C15	111.9 (2)
O6—P2—N5	110.68 (11)	O4—C14—H14A	109.2
O6—P2—N6	120.07 (12)	C15—C14—H14A	109.2
N5—P2—N6	103.74 (12)	O4—C14—H14B	109.2
O6—P2—N4	104.22 (11)	C15—C14—H14B	109.2
N5—P2—N4	112.86 (12)	H14A—C14—H14B	107.9
N6—P2—N4	105.41 (11)	N3—C15—C14	109.7 (2)
C10—O3—C9	109.7 (2)	N3—C15—H15A	109.7
C14—O4—C13	110.1 (2)	C14—C15—H15A	109.7
C25—O7—C24	110.3 (2)	N3—C15—H15B	109.7
C28—O8—C29	110.2 (2)	C14—C15—H15B	109.7
C7—N1—P1	125.42 (19)	H15A—C15—H15B	108.2
C7—N1—H1N	115 (2)	C17—C16—C21	120.6 (2)
P1—N1—H1N	116 (2)	C17—C16—H16A	119.7
C8—N2—C11	112.1 (2)	C21—C16—H16A	119.7
C8—N2—P1	126.66 (18)	C18—C17—C16	118.1 (2)
C11—N2—P1	120.65 (19)	C18—C17—H17A	121.0
C15—N3—C12	110.3 (2)	C16—C17—H17A	121.0
C15—N3—P1	121.53 (18)	F2—C18—C19	118.5 (2)
C12—N3—P1	115.43 (18)	F2—C18—C17	118.5 (2)
C22—N4—P2	127.66 (19)	C19—C18—C17	123.1 (2)
C22—N4—H4N	120 (2)	C18—C19—C20	118.1 (2)
P2—N4—H4N	113 (2)	C18—C19—H19A	121.0
C26—N5—C23	112.1 (2)	C20—C19—H19A	120.9
C26—N5—P2	120.94 (19)	C19—C20—C21	121.0 (2)
C23—N5—P2	125.07 (18)	C19—C20—H20A	119.5
C30—N6—C27	111.0 (2)	C21—C20—H20A	119.5
C30—N6—P2	123.80 (19)	C20—C21—C16	119.1 (2)
C27—N6—P2	122.78 (19)	C20—C21—C22	117.6 (2)
C2—C1—C6	120.3 (2)	C16—C21—C22	123.3 (2)
C2—C1—H1A	119.9	O5—C22—N4	122.1 (2)
C6—C1—H1A	119.9	O5—C22—C21	121.0 (2)
C3—C2—C1	118.3 (3)	N4—C22—C21	116.9 (2)
C3—C2—H2A	120.9	N5—C23—C24	110.5 (2)
C1—C2—H2A	120.9	N5—C23—H23A	109.6
F1—C3—C2	118.0 (2)	C24—C23—H23A	109.6
F1—C3—C4	118.6 (2)	N5—C23—H23B	109.6
C2—C3—C4	123.4 (2)	C24—C23—H23B	109.6
C3—C4—C5	117.8 (2)	H23A—C23—H23B	108.1
C3—C4—H4A	121.1	O7—C24—C23	110.5 (2)
C5—C4—H4A	121.1	O7—C24—H24A	109.5
C4—C5—C6	120.9 (3)	C23—C24—H24A	109.5
C4—C5—H5A	119.5	O7—C24—H24B	109.5
C6—C5—H5A	119.5	C23—C24—H24B	109.5
C5—C6—C1	119.2 (2)	H24A—C24—H24B	108.1
C5—C6—C7	117.5 (2)	O7—C25—C26	110.0 (2)
C1—C6—C7	123.2 (2)	O7—C25—H25A	109.7
O1—C7—N1	120.9 (2)	C26—C25—H25A	109.7
O1—C7—C6	121.0 (2)	O7—C25—H25B	109.7
N1—C7—C6	118.1 (2)	C26—C25—H25B	109.7
N2—C8—C9	110.1 (2)	H25A—C25—H25B	108.2
N2—C8—H8A	109.6	N5—C26—C25	110.5 (2)
C9—C8—H8A	109.6	N5—C26—H26A	109.6
N2—C8—H8B	109.6	C25—C26—H26A	109.6
C9—C8—H8B	109.6	N5—C26—H26B	109.6
H8A—C8—H8B	108.2	C25—C26—H26B	109.6
O3—C9—C8	111.1 (2)	H26A—C26—H26B	108.1
O3—C9—H9A	109.4	N6—C27—C28	110.7 (2)
C8—C9—H9A	109.4	N6—C27—H27A	109.5
O3—C9—H9B	109.4	C28—C27—H27A	109.5
C8—C9—H9B	109.4	N6—C27—H27B	109.5
H9A—C9—H9B	108.0	C28—C27—H27B	109.5
O3—C10—C11	110.8 (2)	H27A—C27—H27B	108.1
O3—C10—H10A	109.5	O8—C28—C27	111.5 (2)
C11—C10—H10A	109.5	O8—C28—H28A	109.3
O3—C10—H10B	109.5	C27—C28—H28A	109.3
C11—C10—H10B	109.5	O8—C28—H28B	109.3
H10A—C10—H10B	108.1	C27—C28—H28B	109.3
N2—C11—C10	110.3 (2)	H28A—C28—H28B	108.0
N2—C11—H11A	109.6	O8—C29—C30	111.6 (2)
C10—C11—H11A	109.6	O8—C29—H29A	109.3
N2—C11—H11B	109.6	C30—C29—H29A	109.3
C10—C11—H11B	109.6	O8—C29—H29B	109.3
H11A—C11—H11B	108.1	C30—C29—H29B	109.3
N3—C12—C13	109.3 (2)	H29A—C29—H29B	108.0
N3—C12—H12A	109.8	N6—C30—C29	110.6 (2)
C13—C12—H12A	109.8	N6—C30—H30A	109.5
N3—C12—H12B	109.8	C29—C30—H30A	109.5
C13—C12—H12B	109.8	N6—C30—H30B	109.5
H12A—C12—H12B	108.3	C29—C30—H30B	109.5
O4—C13—C12	110.0 (2)	H30A—C30—H30B	108.1

O2—P1—N1—C7	169.2 (2)	P1—N2—C8—C9	119.3 (2)
N2—P1—N1—C7	48.5 (2)	C10—O3—C9—C8	−61.2 (3)
N3—P1—N1—C7	−64.9 (2)	N2—C8—C9—O3	56.1 (3)
O2—P1—N2—C8	165.5 (2)	C9—O3—C10—C11	61.6 (3)
N3—P1—N2—C8	37.6 (2)	C8—N2—C11—C10	52.5 (3)
N1—P1—N2—C8	−77.6 (2)	P1—N2—C11—C10	−119.2 (2)
O2—P1—N2—C11	−24.1 (2)	O3—C10—C11—N2	−57.0 (3)
N3—P1—N2—C11	−152.0 (2)	C15—N3—C12—C13	56.9 (3)
N1—P1—N2—C11	92.9 (2)	P1—N3—C12—C13	−160.6 (2)
O2—P1—N3—C15	76.8 (2)	C14—O4—C13—C12	61.5 (3)
N2—P1—N3—C15	−159.7 (2)	N3—C12—C13—O4	−60.0 (3)
N1—P1—N3—C15	−40.6 (2)	C13—O4—C14—C15	−59.7 (3)
O2—P1—N3—C12	−61.2 (2)	C12—N3—C15—C14	−54.3 (3)
N2—P1—N3—C12	62.3 (2)	P1—N3—C15—C14	165.87 (19)
N1—P1—N3—C12	−178.56 (19)	O4—C14—C15—N3	56.1 (3)
O6—P2—N4—C22	178.2 (2)	C21—C16—C17—C18	0.9 (4)
N5—P2—N4—C22	58.0 (3)	C16—C17—C18—F2	179.5 (2)
N6—P2—N4—C22	−54.5 (2)	C16—C17—C18—C19	−0.8 (4)
O6—P2—N5—C26	−25.8 (2)	F2—C18—C19—C20	179.2 (2)
N6—P2—N5—C26	−155.8 (2)	C17—C18—C19—C20	−0.5 (4)
N4—P2—N5—C26	90.6 (2)	C18—C19—C20—C21	1.6 (4)
O6—P2—N5—C23	171.3 (2)	C19—C20—C21—C16	−1.5 (4)
N6—P2—N5—C23	41.3 (2)	C19—C20—C21—C22	179.3 (2)
N4—P2—N5—C23	−72.3 (2)	C17—C16—C21—C20	0.2 (4)
O6—P2—N6—C30	79.2 (2)	C17—C16—C21—C22	179.3 (2)
N5—P2—N6—C30	−156.6 (2)	P2—N4—C22—O5	11.3 (4)
N4—P2—N6—C30	−37.8 (2)	P2—N4—C22—C21	−169.64 (19)
O6—P2—N6—C27	−81.7 (2)	C20—C21—C22—O5	22.0 (4)
N5—P2—N6—C27	42.5 (2)	C16—C21—C22—O5	−157.1 (3)
N4—P2—N6—C27	161.3 (2)	C20—C21—C22—N4	−157.1 (2)
C6—C1—C2—C3	0.5 (4)	C16—C21—C22—N4	23.8 (4)
C1—C2—C3—F1	−178.6 (2)	C26—N5—C23—C24	−52.1 (3)
C1—C2—C3—C4	1.1 (4)	P2—N5—C23—C24	112.1 (2)
F1—C3—C4—C5	177.7 (2)	C25—O7—C24—C23	−61.5 (3)
C2—C3—C4—C5	−2.0 (4)	N5—C23—C24—O7	55.9 (3)
C3—C4—C5—C6	1.3 (4)	C24—O7—C25—C26	61.8 (3)
C4—C5—C6—C1	0.2 (4)	C23—N5—C26—C25	52.7 (3)
C4—C5—C6—C7	−176.9 (2)	P2—N5—C26—C25	−112.2 (2)
C2—C1—C6—C5	−1.2 (4)	O7—C25—C26—N5	−57.1 (3)
C2—C1—C6—C7	175.8 (3)	C30—N6—C27—C28	−53.3 (3)
P1—N1—C7—O1	22.8 (4)	P2—N6—C27—C28	109.8 (3)
P1—N1—C7—C6	−156.19 (19)	C29—O8—C28—C27	−59.2 (3)
C5—C6—C7—O1	11.5 (4)	N6—C27—C28—O8	56.7 (3)
C1—C6—C7—O1	−165.6 (3)	C28—O8—C29—C30	58.9 (3)
C5—C6—C7—N1	−169.6 (2)	C27—N6—C30—C29	52.9 (3)
C1—C6—C7—N1	13.4 (4)	P2—N6—C30—C29	−110.0 (3)
C11—N2—C8—C9	−51.9 (3)	O8—C29—C30—N6	−56.0 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4N···O2ⁱ	0.85 (2)	2.01 (2)	2.855 (3)	176 (3)
N1—H1N···O6ⁱⁱ	0.87 (2)	2.04 (2)	2.870 (3)	159 (3)

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

Experimental details

Crystal data
Chemical formula	C₁₅H₂₁FN₃O₄P
M_r	357.32
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	100
a, b, c (Å)	15.6093 (6), 10.7114 (4), 21.0045 (9)
β (°)	106.896 (2)
V (Å³)	3360.3 (2)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.20
Crystal size (mm)	0.18 × 0.15 × 0.10

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Sheldrick, 2004)
T_min, T_max	0.965, 0.980
No. of measured, independent and observed [I > 2σ(I)] reflections	25230, 6912, 5355
R_int	0.037
(sin θ/λ)_max (Å⁻¹)	0.626

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.056, 0.160, 1.03
No. of reflections	6912
No. of parameters	439
No. of restraints	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	1.45, −0.73

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2008), SHELXTL (Sheldrick, 2008) and enCIFer (Allen et al., 2004).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4N···O2ⁱ	0.846 (18)	2.011 (18)	2.855 (3)	176 (3)
N1—H1N···O6ⁱⁱ	0.869 (17)	2.04 (2)	2.870 (3)	159 (3)

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

Acknowledgements

Support of this investigation by Ferdowsi University of Mashhad is gratefully acknowledged.

References

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