Benzyl 5-{2-[2-(diethoxy­phosphinoyl)­acetyl]-3-oxo-7-thia-2,4-di­aza­bi­cyclo­[3.3.0]­oct-6-yl}pentanoate, a novel biotin derivative

The title compound, C₂₃H₃₃N₂O₇PS, has its phospho­no­acetate carbonyl group rotated slightly out of the plane of the ureido ring, with a C-N-C-O torsion angle of -6.9 (4)°. The sulfur-containing ring has an envelope conformation, while the ureido ring is nearly planar.

S1. Comment

Biotin, or vitamin H, is found in all animals, plants and bacteria, and functions as a cofactor for a group of enzymes that catalyze carboxylation, transcarboxylation and decarboxylation reactions (Wagner & Folkers, 1964; Wood & Barden, 1977). The reactions catalyzed by biotin-dependent enzymes are involved in diverse but essential metabolic pathways such as gluconeogenesis, fatty acid synthesis and amino acid catabolism (Wood & Barden, 1977). The first step in all biotin-dependent carboxylases involves the carboxylation of biotin at the 1'-N position (Guchhait et al., 1974). This is accomplished by the ATP-dependent phosphorylation of bicarbonate, the source of CO₂, forming a reactive carboxyphosphate intermediate. The carboxyl group is then transferred to biotin to form carboxybiotin. Recently, a novel reaction intermediate analogue of biotin-dependent carboxylases that incorporates the carboxyphosphate intermediate and biotin has been synthesized and found to inhibit biotin carboxylase from Eschericia coli (Knowles, 1989).

We reported recently (Amspacher et al., 1999) the structure of the title compound, (I), at room temperature. It was obtained as a reaction intermediate to the inhibitor, and was obtained via an Arbuzov reaction with triethyl phosphite and biotin acylated with chloroacetyl chloride (Knowles, 1989). The 299 K data were sufficient to establish the connectivity and relative configuration of the molecule, but little else. We report herein a refinement of the structure with high-resolution low-temperature data.

The carbonyl group of the phosphonoacetate moiety of (I) is rotated slightly out of the plane of the ureido ring, with a C3—N2—C18—O4 torsion angle of −6.9 (4)°. This contrasts with 1'-N-methoxycarbonylbiotin methyl ester (Stallings et al., 1980), in which the methoxycarbonyl group and the ureido ring are nearly coplanar, with torson angles in two independent molecules −1.1 and −2.9°. Since the title compound is a reaction intermediate analogue of the carboxylation of biotin, this is consistent with computational studies and host–guest experiments which suggest that the carboxyl group of carboxybiotin is rotated out of the plane of the ureido ring when biotin is carboxylated and decarboxylated (Gregory et al., 1986).

The five atoms of the ureido ring are nearly coplanar, with a maximum deviation of 0.029 (2) Å for N2. The sulfur-containing ring has the envelope conformation with the S atom at the flap position, lying 0.850 (4) Å from the best plane of the four C atoms. These two planes form a dihedral angle of 60.94 (13)°.

S2. Experimental

The title compound was synthesized according to the method of Amspacher et al. (1999). Crystals were obtained from ethyl acetate by evaporation.

S3. Refinement

H atoms were placed in calculated positions with C—H = 0.95–1.00 Å, N—H = 0.88 Å, and U_iso = 1.2U_eq for the bonded atom (1.5 for methyl), and treated as riding. A torsional parameter was refined for the methyl groups.

Computing details

Data collection: CAD-4 EXPRESS (Enraf-Nonius, 1994); cell refinement: CAD-4 EXPRESS; data reduction: PROCESS in MolEN (Fair, 1990); program(s) used to solve structure: direct methods using SIR (Burla et al., 1989); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); software used to prepare material for publication: CIFTAB in SHELXL97.

phenylmethyl 5-(6,8-diaza-6-(2-diethoxyphosphono) acetyl)-7-oxo-3-thiabicyclo [3.3.0] oct-2-yl) pentanoate

Crystal data

C23H33N2O7PS	F(000) = 544
Mr = 512.57	Dx = 1.368 Mg m^−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2y1	Cell parameters from 25 reflections
a = 10.455 (2) Å	θ = 8.9–18.2°
b = 12.410 (2) Å	µ = 0.24 mm^−1
c = 10.592 (2) Å	T = 100 K
β = 115.077 (10)°	Prism, colourless
V = 1244.7 (4) Å^3	0.50 × 0.33 × 0.18 mm
Z = 2

Data collection

Enraf-Nonius CAD-4 (with Oxford Cryostreams Cryostream cooler) diffractometer	4521 reflections with I > 2σ(I)
Radiation source: sealed tube	Rint = 0.033
Graphite monochromator	θmax = 30.0°, θmin = 2.5°
θ/2θ scans	h = 0→14
Absorption correction: ψ scan (North et al., 1968)	k = −13→17
Tmin = 0.920, Tmax = 0.959	l = −14→13
5600 measured reflections	3 standard reflections every 60 min
5297 independent reflections	intensity decay: 2.9%

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.040	H-atom parameters constrained
wR(F^2) = 0.101	w = 1/[σ^2(Fo^2) + (0.0378P)^2 + 0.6507P] where P = (Fo^2 + 2Fc^2)/3
S = 1.12	(Δ/σ)max = 0.002
5297 reflections	Δρmax = 0.44 e Å^−3
309 parameters	Δρmin = −0.43 e Å^−3
1 restraint	Absolute structure: Flack (1983)
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.07 (8); 1521 Friedel pairs

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
S	0.15464 (8)	−0.00002 (6)	0.50200 (7)	0.02093 (16)
P	0.56073 (8)	−0.31423 (6)	0.84128 (7)	0.01808 (16)
O1	0.5366 (2)	−0.07268 (17)	0.9157 (2)	0.0216 (4)
O2	0.0933 (3)	0.59257 (17)	0.9411 (2)	0.0261 (5)
O3	−0.0240 (2)	0.4366 (2)	0.9121 (3)	0.0343 (6)
O4	0.5615 (2)	−0.16967 (16)	0.5502 (2)	0.0216 (5)
O5	0.6095 (2)	−0.32900 (18)	0.99252 (19)	0.0268 (5)
O6	0.3987 (2)	−0.28939 (16)	0.7593 (2)	0.0219 (5)
O7	0.5824 (2)	−0.41463 (16)	0.7604 (2)	0.0218 (4)
N1	0.4361 (3)	0.0764 (2)	0.7816 (2)	0.0187 (5)
H1N	0.4262	0.1153	0.8463	0.022*
N2	0.4998 (3)	−0.05748 (19)	0.6824 (2)	0.0165 (5)
C1	0.2299 (3)	0.1324 (2)	0.5644 (3)	0.0179 (6)
H1	0.2099	0.1799	0.4819	0.022*
C2	0.3903 (3)	0.1139 (2)	0.6390 (3)	0.0175 (6)
H2	0.4427	0.1806	0.6363	0.021*
C3	0.4299 (3)	0.0184 (2)	0.5662 (3)	0.0171 (6)
H3	0.4969	0.0429	0.5271	0.021*
C4	0.2950 (3)	−0.0274 (2)	0.4510 (3)	0.0206 (6)
H4A	0.3046	−0.1060	0.4413	0.025*
H4B	0.2757	0.0075	0.3607	0.025*
C5	0.4946 (3)	−0.0219 (2)	0.8069 (3)	0.0177 (6)
C6	0.1605 (3)	0.1812 (2)	0.6508 (3)	0.0184 (5)
H6A	0.1810	0.1347	0.7331	0.022*
H6B	0.0569	0.1810	0.5946	0.022*
C7	0.2068 (3)	0.2955 (2)	0.7011 (3)	0.0188 (6)
H7A	0.1921	0.3426	0.6207	0.023*
H7B	0.3085	0.2963	0.7651	0.023*
C8	0.1212 (3)	0.3375 (2)	0.7765 (3)	0.0192 (6)
H8A	0.0195	0.3317	0.7131	0.023*
H8B	0.1393	0.2909	0.8582	0.023*
C9	0.1536 (3)	0.4534 (2)	0.8257 (3)	0.0180 (6)
H9A	0.2544	0.4595	0.8915	0.022*
H9B	0.1368	0.5006	0.7448	0.022*
C10	0.0640 (3)	0.4900 (3)	0.8958 (3)	0.0206 (6)
C11	0.0151 (4)	0.6351 (3)	1.0157 (3)	0.0281 (7)
H11A	−0.0822	0.6060	0.9739	0.034*
H11B	0.0091	0.7145	1.0062	0.034*
C12	0.0853 (3)	0.6056 (2)	1.1682 (3)	0.0212 (6)
C13	0.0476 (3)	0.5115 (3)	1.2166 (3)	0.0245 (6)
H13	−0.0217	0.4647	1.1529	0.029*
C14	0.1109 (3)	0.4863 (3)	1.3571 (3)	0.0267 (7)
H14	0.0850	0.4220	1.3892	0.032*
C15	0.2113 (3)	0.5536 (3)	1.4510 (3)	0.0249 (7)
H15	0.2543	0.5357	1.5473	0.030*
C16	0.2487 (4)	0.6466 (3)	1.4046 (3)	0.0294 (7)
H16	0.3173	0.6935	1.4689	0.035*
C17	0.1861 (3)	0.6722 (3)	1.2635 (3)	0.0260 (7)
H17	0.2130	0.7364	1.2321	0.031*
C18	0.5688 (3)	−0.1469 (2)	0.6651 (3)	0.0168 (6)
C19	0.6567 (3)	−0.2129 (2)	0.7933 (3)	0.0198 (6)
H19A	0.7020	−0.1631	0.8730	0.024*
H19B	0.7329	−0.2490	0.7772	0.024*
C20	0.3089 (4)	−0.2659 (3)	0.8308 (4)	0.0351 (9)
H20A	0.3432	−0.2005	0.8890	0.042*
H20B	0.3112	−0.3268	0.8920	0.042*
C21	0.1624 (4)	−0.2487 (3)	0.7230 (5)	0.0451 (11)
H21A	0.1617	−0.1897	0.6612	0.068*
H21B	0.1009	−0.2302	0.7684	0.068*
H21C	0.1280	−0.3147	0.6683	0.068*
C22	0.5271 (3)	−0.5193 (2)	0.7756 (3)	0.0252 (7)
H22A	0.4858	−0.5564	0.6843	0.030*
H22B	0.4514	−0.5091	0.8073	0.030*
C23	0.6414 (4)	−0.5870 (3)	0.8784 (4)	0.0296 (7)
H23A	0.7192	−0.5930	0.8502	0.044*
H23B	0.6044	−0.6590	0.8818	0.044*
H23C	0.6760	−0.5536	0.9708	0.044*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S	0.0222 (4)	0.0185 (4)	0.0202 (3)	−0.0019 (3)	0.0072 (3)	−0.0044 (3)
P	0.0254 (4)	0.0153 (3)	0.0144 (3)	−0.0009 (3)	0.0092 (3)	0.0010 (3)
O1	0.0262 (11)	0.0238 (11)	0.0147 (9)	0.0020 (9)	0.0087 (8)	0.0036 (8)
O2	0.0454 (14)	0.0147 (10)	0.0268 (11)	0.0005 (10)	0.0235 (11)	−0.0002 (9)
O3	0.0325 (13)	0.0332 (14)	0.0466 (14)	−0.0091 (11)	0.0260 (11)	−0.0167 (11)
O4	0.0320 (12)	0.0162 (10)	0.0205 (10)	0.0034 (9)	0.0149 (9)	−0.0004 (8)
O5	0.0410 (13)	0.0226 (11)	0.0156 (10)	−0.0041 (10)	0.0110 (9)	0.0019 (9)
O6	0.0260 (11)	0.0223 (11)	0.0216 (10)	0.0001 (9)	0.0143 (9)	−0.0028 (8)
O7	0.0307 (12)	0.0128 (10)	0.0251 (11)	0.0002 (9)	0.0151 (10)	0.0009 (8)
N1	0.0239 (13)	0.0178 (12)	0.0147 (11)	0.0026 (10)	0.0086 (10)	−0.0031 (9)
N2	0.0230 (12)	0.0135 (11)	0.0145 (11)	0.0015 (10)	0.0093 (10)	0.0004 (9)
C1	0.0231 (15)	0.0141 (13)	0.0163 (13)	0.0006 (12)	0.0080 (12)	−0.0006 (11)
C2	0.0228 (14)	0.0144 (13)	0.0163 (13)	0.0000 (11)	0.0094 (11)	−0.0015 (11)
C3	0.0232 (14)	0.0141 (13)	0.0155 (12)	0.0021 (11)	0.0097 (11)	0.0018 (10)
C4	0.0242 (15)	0.0209 (15)	0.0176 (13)	0.0034 (12)	0.0097 (12)	−0.0007 (11)
C5	0.0194 (14)	0.0202 (15)	0.0111 (12)	−0.0020 (11)	0.0043 (11)	−0.0022 (11)
C6	0.0203 (13)	0.0138 (12)	0.0202 (13)	0.0026 (12)	0.0078 (11)	−0.0009 (12)
C7	0.0240 (15)	0.0151 (14)	0.0182 (14)	0.0031 (12)	0.0097 (12)	0.0010 (11)
C8	0.0238 (15)	0.0140 (13)	0.0215 (14)	0.0033 (11)	0.0112 (13)	0.0035 (11)
C9	0.0185 (14)	0.0173 (14)	0.0168 (13)	−0.0001 (11)	0.0061 (11)	0.0011 (11)
C10	0.0217 (14)	0.0213 (15)	0.0171 (13)	0.0013 (13)	0.0067 (11)	−0.0008 (12)
C11	0.045 (2)	0.0191 (15)	0.0251 (16)	0.0125 (15)	0.0200 (15)	0.0003 (13)
C12	0.0279 (16)	0.0163 (14)	0.0257 (15)	0.0041 (12)	0.0173 (13)	0.0002 (12)
C13	0.0286 (16)	0.0189 (15)	0.0260 (15)	−0.0007 (13)	0.0115 (13)	−0.0002 (13)
C14	0.0309 (16)	0.0228 (16)	0.0276 (15)	−0.0012 (14)	0.0136 (13)	0.0047 (13)
C15	0.0265 (17)	0.0264 (17)	0.0221 (15)	0.0028 (13)	0.0105 (13)	0.0015 (13)
C16	0.0252 (16)	0.0274 (17)	0.0301 (17)	0.0004 (13)	0.0063 (14)	−0.0061 (13)
C17	0.0324 (17)	0.0154 (15)	0.0349 (17)	−0.0002 (13)	0.0188 (14)	−0.0006 (13)
C18	0.0191 (14)	0.0142 (13)	0.0188 (13)	−0.0011 (11)	0.0098 (12)	0.0006 (11)
C19	0.0203 (15)	0.0191 (15)	0.0210 (14)	−0.0008 (12)	0.0097 (12)	0.0027 (11)
C20	0.038 (2)	0.0321 (19)	0.052 (2)	−0.0130 (16)	0.0354 (19)	−0.0178 (17)
C21	0.044 (2)	0.034 (2)	0.076 (3)	0.0155 (18)	0.044 (2)	0.025 (2)
C22	0.0318 (17)	0.0149 (15)	0.0305 (16)	−0.0031 (12)	0.0149 (14)	−0.0028 (12)
C23	0.0355 (18)	0.0186 (16)	0.0382 (19)	0.0010 (14)	0.0190 (16)	0.0056 (14)

Geometric parameters (Å, º)

S—C4	1.799 (3)	C8—H8A	0.9900
S—C1	1.822 (3)	C8—H8B	0.9900
P—O5	1.472 (2)	C9—C10	1.492 (4)
P—O6	1.572 (2)	C9—H9A	0.9900
P—O7	1.582 (2)	C9—H9B	0.9900
P—C19	1.811 (3)	C11—C12	1.509 (4)
O1—C5	1.221 (3)	C11—H11A	0.9900
O2—C10	1.349 (4)	C11—H11B	0.9900
O2—C11	1.456 (4)	C12—C17	1.382 (4)
O3—C10	1.205 (4)	C12—C13	1.398 (4)
O4—C18	1.220 (3)	C13—C14	1.384 (4)
O6—C20	1.464 (4)	C13—H13	0.9500
O7—C22	1.459 (4)	C14—C15	1.379 (4)
N1—C5	1.339 (4)	C14—H14	0.9500
N1—C2	1.454 (4)	C15—C16	1.376 (5)
N1—H1N	0.8800	C15—H15	0.9500
N2—C18	1.377 (4)	C16—C17	1.391 (4)
N2—C5	1.413 (3)	C16—H16	0.9500
N2—C3	1.474 (4)	C17—H17	0.9500
C1—C6	1.515 (4)	C18—C19	1.517 (4)
C1—C2	1.538 (4)	C19—H19A	0.9900
C1—H1	1.0000	C19—H19B	0.9900
C2—C3	1.562 (4)	C20—C21	1.488 (5)
C2—H2	1.0000	C20—H20A	0.9900
C3—C4	1.531 (4)	C20—H20B	0.9900
C3—H3	1.0000	C21—H21A	0.9800
C4—H4A	0.9900	C21—H21B	0.9800
C4—H4B	0.9900	C21—H21C	0.9800
C6—C7	1.520 (4)	C22—C23	1.489 (4)
C6—H6A	0.9900	C22—H22A	0.9900
C6—H6B	0.9900	C22—H22B	0.9900
C7—C8	1.521 (4)	C23—H23A	0.9800
C7—H7A	0.9900	C23—H23B	0.9800
C7—H7B	0.9900	C23—H23C	0.9800
C8—C9	1.518 (4)
C4—S—C1	89.86 (14)	C10—C9—H9B	109.4
O5—P—O6	114.87 (12)	C8—C9—H9B	109.4
O5—P—O7	115.35 (13)	H9A—C9—H9B	108.0
O6—P—O7	102.91 (12)	O3—C10—O2	122.7 (3)
O5—P—C19	114.48 (14)	O3—C10—C9	125.6 (3)
O6—P—C19	107.70 (13)	O2—C10—C9	111.7 (3)
O7—P—C19	99.88 (13)	O2—C11—C12	111.2 (3)
C10—O2—C11	116.1 (2)	O2—C11—H11A	109.4
C20—O6—P	122.0 (2)	C12—C11—H11A	109.4
C22—O7—P	119.15 (19)	O2—C11—H11B	109.4
C5—N1—C2	114.9 (2)	C12—C11—H11B	109.4
C5—N1—H1N	122.6	H11A—C11—H11B	108.0
C2—N1—H1N	122.6	C17—C12—C13	118.6 (3)
C18—N2—C5	127.2 (2)	C17—C12—C11	120.7 (3)
C18—N2—C3	120.4 (2)	C13—C12—C11	120.7 (3)
C5—N2—C3	112.2 (2)	C14—C13—C12	120.1 (3)
C6—C1—C2	116.6 (2)	C14—C13—H13	119.9
C6—C1—S	109.6 (2)	C12—C13—H13	119.9
C2—C1—S	105.10 (19)	C15—C14—C13	120.7 (3)
C6—C1—H1	108.4	C15—C14—H14	119.7
C2—C1—H1	108.4	C13—C14—H14	119.7
S—C1—H1	108.4	C16—C15—C14	119.7 (3)
N1—C2—C1	112.9 (2)	C16—C15—H15	120.2
N1—C2—C3	103.3 (2)	C14—C15—H15	120.2
C1—C2—C3	108.6 (2)	C15—C16—C17	120.0 (3)
N1—C2—H2	110.6	C15—C16—H16	120.0
C1—C2—H2	110.6	C17—C16—H16	120.0
C3—C2—H2	110.6	C12—C17—C16	120.9 (3)
N2—C3—C4	113.0 (2)	C12—C17—H17	119.5
N2—C3—C2	102.4 (2)	C16—C17—H17	119.5
C4—C3—C2	109.2 (2)	O4—C18—N2	120.3 (3)
N2—C3—H3	110.7	O4—C18—C19	121.7 (3)
C4—C3—H3	110.7	N2—C18—C19	118.0 (2)
C2—C3—H3	110.7	C18—C19—P	115.4 (2)
C3—C4—S	106.46 (19)	C18—C19—H19A	108.4
C3—C4—H4A	110.4	P—C19—H19A	108.4
S—C4—H4A	110.4	C18—C19—H19B	108.4
C3—C4—H4B	110.4	P—C19—H19B	108.4
S—C4—H4B	110.4	H19A—C19—H19B	107.5
H4A—C4—H4B	108.6	O6—C20—C21	108.0 (3)
O1—C5—N1	127.6 (3)	O6—C20—H20A	110.1
O1—C5—N2	125.4 (3)	C21—C20—H20A	110.1
N1—C5—N2	107.0 (2)	O6—C20—H20B	110.1
C1—C6—C7	114.9 (2)	C21—C20—H20B	110.1
C1—C6—H6A	108.5	H20A—C20—H20B	108.4
C7—C6—H6A	108.5	C20—C21—H21A	109.5
C1—C6—H6B	108.5	C20—C21—H21B	109.5
C7—C6—H6B	108.5	H21A—C21—H21B	109.5
H6A—C6—H6B	107.5	C20—C21—H21C	109.5
C6—C7—C8	109.4 (2)	H21A—C21—H21C	109.5
C6—C7—H7A	109.8	H21B—C21—H21C	109.5
C8—C7—H7A	109.8	O7—C22—C23	110.5 (3)
C6—C7—H7B	109.8	O7—C22—H22A	109.6
C8—C7—H7B	109.8	C23—C22—H22A	109.6
H7A—C7—H7B	108.2	O7—C22—H22B	109.6
C9—C8—C7	114.1 (2)	C23—C22—H22B	109.6
C9—C8—H8A	108.7	H22A—C22—H22B	108.1
C7—C8—H8A	108.7	C22—C23—H23A	109.5
C9—C8—H8B	108.7	C22—C23—H23B	109.5
C7—C8—H8B	108.7	H23A—C23—H23B	109.5
H8A—C8—H8B	107.6	C22—C23—H23C	109.5
C10—C9—C8	111.3 (2)	H23A—C23—H23C	109.5
C10—C9—H9A	109.4	H23B—C23—H23C	109.5
C8—C9—H9A	109.4
O5—P—O6—C20	9.3 (3)	C2—C1—C6—C7	64.9 (3)
O7—P—O6—C20	135.5 (2)	S—C1—C6—C7	−176.0 (2)
C19—P—O6—C20	−119.6 (2)	C1—C6—C7—C8	175.7 (2)
O5—P—O7—C22	53.5 (2)	C6—C7—C8—C9	−177.3 (2)
O6—P—O7—C22	−72.4 (2)	C7—C8—C9—C10	178.8 (2)
C19—P—O7—C22	176.8 (2)	C11—O2—C10—O3	1.8 (4)
C4—S—C1—C6	−167.4 (2)	C11—O2—C10—C9	−177.9 (2)
C4—S—C1—C2	−41.40 (19)	C8—C9—C10—O3	−0.3 (4)
C5—N1—C2—C1	117.1 (3)	C8—C9—C10—O2	179.3 (2)
C5—N1—C2—C3	0.0 (3)	C10—O2—C11—C12	85.0 (3)
C6—C1—C2—N1	38.8 (3)	O2—C11—C12—C17	89.9 (3)
S—C1—C2—N1	−82.8 (2)	O2—C11—C12—C13	−91.5 (4)
C6—C1—C2—C3	152.8 (2)	C17—C12—C13—C14	−0.2 (5)
S—C1—C2—C3	31.2 (3)	C11—C12—C13—C14	−178.8 (3)
C18—N2—C3—C4	71.9 (3)	C12—C13—C14—C15	0.3 (5)
C5—N2—C3—C4	−112.5 (3)	C13—C14—C15—C16	0.0 (5)
C18—N2—C3—C2	−170.8 (2)	C14—C15—C16—C17	−0.4 (5)
C5—N2—C3—C2	4.8 (3)	C13—C12—C17—C16	−0.2 (5)
N1—C2—C3—N2	−2.8 (3)	C11—C12—C17—C16	178.5 (3)
C1—C2—C3—N2	−122.9 (2)	C15—C16—C17—C12	0.4 (5)
N1—C2—C3—C4	117.2 (2)	C5—N2—C18—O4	178.2 (3)
C1—C2—C3—C4	−2.9 (3)	C3—N2—C18—O4	−6.9 (4)
N2—C3—C4—S	86.0 (2)	C5—N2—C18—C19	−3.7 (4)
C2—C3—C4—S	−27.2 (3)	C3—N2—C18—C19	171.2 (2)
C1—S—C4—C3	40.0 (2)	O4—C18—C19—P	−96.4 (3)
C2—N1—C5—O1	−177.2 (3)	N2—C18—C19—P	85.5 (3)
C2—N1—C5—N2	3.0 (3)	O5—P—C19—C18	−143.7 (2)
C18—N2—C5—O1	−9.6 (5)	O6—P—C19—C18	−14.6 (3)
C3—N2—C5—O1	175.2 (3)	O7—P—C19—C18	92.5 (2)
C18—N2—C5—N1	170.2 (3)	P—O6—C20—C21	−178.8 (2)
C3—N2—C5—N1	−5.0 (3)	P—O7—C22—C23	−99.4 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O5^i	0.88	2.02	2.881 (3)	167

Symmetry code: (i) −x+1, y+1/2, −z+2.