(2S)-2-(4-Ethyl-2,3-dioxopiperazine-1-carboxamido)-2-(4-hy-droxy-phen-yl)acetic acid.

There are two mol-ecules in the asymmetric unit of the title compound, C(15)H(17)N(3)O(6). The 2,3-dioxopiperazine ring adopts a half-chair conformation with torsion angles of -7.6 (4) and 35.1 (4)° in one mol-ecule, and 5.3 (4) and 45.4 (4)° in the other mol-ecule. In the crystal structure, the carb-oxy groups are involved in classical inversion-related O-H⋯O hydrogen bonds, which link the mol-ecules into centrosymmetric dimers. These dimers are further linked by inter-molecular O-H⋯O and C-H⋯O hydrogen bonds. Each independent mol-ecule also exhibits an intra-molecular N-H⋯O hydrogen bond. The H atoms of the carb-oxy groups are disordered over two positions, with refined site-occupancy factors of 0.5.

Related literature

For general background to cefoperazone, a third generation cephalosporin anti­biotic, and HO-EPCP [(2R)-2-(4-ethyl-2,3-dioxopiperazine-1-carboxamido)-2-(4-hydroxyphenyl)acetic acid], which has been investigated extensively as a key inter­mediate for the synthesis of cefoperazone, see: Spyker et al. (1985 ▶); Chen et al. (2009 ▶); Murakami et al. (1981 ▶); Albrecht et al. (1991 ▶). For the synthesis of the (2S)-enantiomer of (HO-EPCP), see: De Lorenzi et al. (2001 ▶). For a related structure, see: Lenstra et al. (1998 ▶). For disordered carb­oxy dimers, see: Leiserowitz (1976 ▶); Feeder & Jones (1996 ▶). For helical chains, see: Adachi et al. (2001 ▶); Xu et al.(2003 ▶); Enamullah et al. (2006 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For the synthesis, see: Saikawa et al. (1978 ▶).

Experimental

Crystal data

C15H17N3O6

M = 335.32

Orthorhombic,

a = 11.5899 (19) Å

b = 13.038 (2) Å

c = 20.794 (3) Å

V = 3142.2 (9) Å3

Z = 8

Mo Kα radiation

μ = 0.11 mm−1

T = 298 K

0.51 × 0.15 × 0.09 mm

Data collection

Bruker SMART CCD area-detector diffractometer

16467 measured reflections

3237 independent reflections

2722 reflections with I > 2σ(I)

R int = 0.040

Refinement

R[F 2 > 2σ(F 2)] = 0.044

wR(F 2) = 0.107

S = 1.06

3237 reflections

449 parameters

16 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.18 e Å−3

Δρmin = −0.16 e Å−3

Data collection: SMART (Bruker, 1999 ▶); cell refinement: SAINT (Bruker, 1999 ▶); 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 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810025262/lx2155sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810025262/lx2155Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C15H17N3O6	F(000) = 1408
Mr = 335.32	Dx = 1.418 Mg m−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 3149 reflections
a = 11.5899 (19) Å	θ = 2.5–22.5°
b = 13.038 (2) Å	µ = 0.11 mm−1
c = 20.794 (3) Å	T = 298 K
V = 3142.2 (9) Å3	Bar, colourless
Z = 8	0.51 × 0.15 × 0.09 mm

Bruker SMART CCD area-detector diffractometer	2722 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.040
graphite	θmax = 25.4°, θmin = 1.8°
Detector resolution: 10.0 pixels mm-1	h = −13→13
phi and ω scans	k = −15→15
16467 measured reflections	l = −18→25
3237 independent reflections

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)] = 0.044	Hydrogen site location: difference Fourier map
wR(F2) = 0.107	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ2(Fo2) + (0.0613P)2 + 0.0947P] where P = (Fo2 + 2Fc2)/3
3237 reflections	(Δ/σ)max < 0.001
449 parameters	Δρmax = 0.18 e Å−3
16 restraints	Δρmin = −0.16 e Å−3

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 F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > σ(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

	x	y	z	Uiso*/Ueq	Occ. (<1)
O5	0.6862 (2)	0.66654 (17)	0.51841 (12)	0.0584 (6)
C1	0.4645 (3)	0.3773 (2)	0.73859 (14)	0.0421 (7)
C2	0.5301 (3)	0.4183 (2)	0.67963 (14)	0.0379 (7)
C3	0.6229 (4)	0.5339 (3)	0.75568 (14)	0.0608 (10)
H3A	0.5614	0.5831	0.7630	0.073*
H3B	0.6960	0.5696	0.7598	0.073*
C4	0.6161 (3)	0.4511 (3)	0.80428 (14)	0.0515 (8)
H4A	0.6815	0.4052	0.7994	0.062*
H4B	0.6191	0.4805	0.8471	0.062*
C5	0.4652 (3)	0.3361 (3)	0.85232 (14)	0.0534 (9)
H5A	0.3841	0.3206	0.8457	0.064*
H5B	0.4717	0.3781	0.8906	0.064*
C6	0.5296 (4)	0.2396 (3)	0.86191 (19)	0.0841 (13)
H6A	0.4973	0.2028	0.8976	0.126*
H6B	0.6091	0.2549	0.8705	0.126*
H6C	0.5242	0.1983	0.8238	0.126*
C7	0.6935 (3)	0.5273 (2)	0.64418 (14)	0.0468 (8)
C8	0.78013 (16)	0.6197 (2)	0.52363 (14)	0.0420 (7)
C9	0.7784 (3)	0.5059 (2)	0.53998 (13)	0.0417 (7)
H9	0.8536	0.4865	0.5578	0.050*
C10	0.7571 (3)	0.4445 (2)	0.47940 (13)	0.0392 (7)
C11	0.8371 (3)	0.3733 (2)	0.45867 (14)	0.0445 (8)
H11	0.9052	0.3646	0.4817	0.053*
C12	0.8176 (3)	0.3146 (2)	0.40408 (15)	0.0474 (8)
H12	0.8723	0.2671	0.3905	0.057*
C13	0.7164 (3)	0.3271 (2)	0.37011 (14)	0.0435 (8)
C14	0.6354 (3)	0.3972 (3)	0.39031 (15)	0.0507 (8)
H14	0.5671	0.4058	0.3674	0.061*
C15	0.6563 (3)	0.4549 (2)	0.44491 (15)	0.0480 (8)
H15	0.6011	0.5018	0.4587	0.058*
C16	0.4769 (4)	1.2845 (3)	0.1574 (2)	0.0929 (15)
H16A	0.4413	1.3066	0.1967	0.139*
H16B	0.4416	1.3192	0.1218	0.139*
H16C	0.5577	1.3003	0.1585	0.139*
C17	0.4611 (3)	1.1708 (3)	0.14984 (15)	0.0552 (9)
H17A	0.3794	1.1548	0.1495	0.066*
H17B	0.4935	1.1492	0.1090	0.066*
C18	0.4657 (3)	1.1091 (2)	0.25917 (14)	0.0415 (7)
C19	0.5391 (3)	1.0779 (2)	0.31764 (13)	0.0379 (7)
C20	0.6653 (3)	0.9982 (3)	0.23883 (13)	0.0564 (9)
H20A	0.6198	0.9381	0.2282	0.068*
H20B	0.7462	0.9806	0.2344	0.068*
C21	0.6363 (3)	1.0832 (3)	0.19387 (14)	0.0535 (9)
H21A	0.6867	1.1412	0.2020	0.064*
H21B	0.6484	1.0608	0.1499	0.064*
C22	0.7251 (3)	1.0017 (2)	0.35317 (14)	0.0413 (7)
C23	0.7895 (3)	1.0151 (2)	0.46270 (13)	0.0400 (7)
H23	0.8671	1.0322	0.4474	0.048*
C24	0.78669 (17)	0.9022 (2)	0.48071 (13)	0.0403 (7)
C25	0.7646 (3)	1.0775 (2)	0.52265 (13)	0.0380 (7)
C26	0.8464 (3)	1.1431 (2)	0.54761 (15)	0.0450 (7)
H26	0.9170	1.1500	0.5268	0.054*
C27	0.8258 (3)	1.1987 (2)	0.60304 (14)	0.0484 (8)
H27	0.8823	1.2423	0.6193	0.058*
C28	0.7214 (3)	1.1894 (2)	0.63420 (14)	0.0441 (8)
C29	0.6382 (3)	1.1250 (3)	0.60949 (15)	0.0540 (9)
H29	0.5673	1.1188	0.6301	0.065*
C30	0.6598 (3)	1.0695 (2)	0.55422 (15)	0.0494 (8)
H30	0.6032	1.0262	0.5380	0.059*
N1	0.5094 (2)	0.39370 (19)	0.79653 (11)	0.0421 (6)
N2	0.6125 (2)	0.49079 (18)	0.69051 (11)	0.0448 (6)
N3	0.6901 (2)	0.48256 (18)	0.58659 (10)	0.0440 (6)
H3	0.6357	0.4402	0.5773	0.053*
N4	0.5174 (2)	1.11428 (19)	0.20220 (11)	0.0412 (6)
N5	0.6415 (2)	1.02945 (18)	0.30565 (10)	0.0402 (6)
N6	0.7073 (2)	1.03845 (17)	0.41218 (10)	0.0421 (6)
H6D	0.6477	1.0756	0.4202	0.051*
O1	0.3770 (2)	0.3277 (2)	0.72961 (11)	0.0663 (7)
O2	0.50699 (18)	0.38196 (17)	0.62759 (9)	0.0482 (6)
O3	0.7594 (2)	0.59548 (19)	0.65771 (11)	0.0759 (9)
O4	0.8770 (2)	0.65925 (18)	0.51346 (13)	0.0615 (7)
H4O	0.900 (8)	0.722 (3)	0.509 (4)	0.092*	0.50
H5O	0.687 (9)	0.726 (3)	0.500 (4)	0.092*	0.50
O6	0.6918 (2)	0.27188 (18)	0.31598 (10)	0.0590 (6)
H6	0.7493	0.2401	0.3046	0.088*
O7	0.3658 (2)	1.1346 (2)	0.26865 (11)	0.0609 (7)
O8	0.50410 (18)	1.10077 (18)	0.37060 (9)	0.0507 (6)
O9	0.8068 (2)	0.94970 (17)	0.33806 (10)	0.0625 (7)
O10	0.8777 (2)	0.86393 (17)	0.50285 (12)	0.0532 (6)
H10O	0.881 (7)	0.798 (2)	0.503 (4)	0.080*	0.50
O11	0.6930 (2)	0.85492 (17)	0.47513 (12)	0.0604 (7)
H11O	0.679 (8)	0.800 (4)	0.496 (4)	0.091*	0.50
O12	0.6966 (2)	1.24064 (19)	0.68955 (10)	0.0615 (7)
H12A	0.7521	1.2758	0.7000	0.092*

	U11	U22	U33	U12	U13	U23
O5	0.0529 (15)	0.0450 (13)	0.0772 (16)	0.0050 (12)	0.0103 (13)	0.0107 (12)
C1	0.0428 (19)	0.0438 (17)	0.0398 (17)	−0.0002 (16)	0.0001 (15)	−0.0009 (13)
C2	0.0387 (17)	0.0364 (15)	0.0386 (17)	0.0030 (14)	0.0005 (14)	0.0016 (13)
C3	0.085 (3)	0.059 (2)	0.0387 (18)	−0.026 (2)	0.0137 (18)	−0.0173 (16)
C4	0.057 (2)	0.066 (2)	0.0320 (16)	−0.0083 (18)	0.0017 (15)	−0.0093 (15)
C5	0.057 (2)	0.064 (2)	0.0388 (17)	0.0020 (18)	0.0073 (16)	0.0106 (15)
C6	0.115 (4)	0.065 (3)	0.072 (3)	0.010 (3)	0.007 (3)	0.021 (2)
C7	0.060 (2)	0.0418 (16)	0.0389 (17)	−0.0105 (17)	0.0088 (15)	0.0007 (14)
C8	0.046 (2)	0.0422 (16)	0.0375 (16)	−0.0016 (16)	0.0079 (15)	0.0004 (13)
C9	0.0481 (19)	0.0394 (15)	0.0375 (16)	0.0039 (15)	0.0048 (14)	0.0043 (12)
C10	0.0469 (19)	0.0338 (14)	0.0370 (15)	0.0008 (13)	0.0073 (14)	0.0068 (12)
C11	0.0459 (19)	0.0422 (16)	0.0454 (17)	0.0058 (15)	0.0025 (15)	0.0069 (14)
C12	0.051 (2)	0.0400 (15)	0.0511 (19)	0.0093 (15)	0.0143 (16)	0.0010 (14)
C13	0.055 (2)	0.0370 (15)	0.0383 (16)	−0.0053 (15)	0.0132 (15)	−0.0008 (13)
C14	0.051 (2)	0.0588 (19)	0.0428 (18)	0.0054 (18)	0.0011 (15)	−0.0040 (16)
C15	0.050 (2)	0.0492 (18)	0.0447 (18)	0.0147 (16)	0.0060 (16)	−0.0026 (15)
C16	0.126 (4)	0.071 (3)	0.082 (3)	0.003 (3)	−0.029 (3)	0.025 (2)
C17	0.046 (2)	0.081 (2)	0.0387 (18)	0.0045 (19)	−0.0083 (16)	0.0017 (17)
C18	0.044 (2)	0.0415 (17)	0.0391 (17)	−0.0024 (15)	−0.0020 (15)	−0.0052 (13)
C19	0.0425 (18)	0.0359 (15)	0.0353 (16)	−0.0011 (14)	0.0030 (14)	−0.0010 (12)
C20	0.064 (2)	0.069 (2)	0.0363 (17)	0.026 (2)	−0.0042 (16)	−0.0180 (16)
C21	0.047 (2)	0.080 (2)	0.0333 (17)	0.0110 (19)	0.0011 (14)	−0.0053 (16)
C22	0.0510 (19)	0.0342 (14)	0.0387 (16)	0.0073 (15)	−0.0022 (15)	0.0003 (12)
C23	0.0442 (18)	0.0400 (15)	0.0357 (15)	−0.0017 (14)	−0.0033 (13)	0.0050 (12)
C24	0.0473 (19)	0.0417 (15)	0.0319 (15)	−0.0015 (16)	−0.0054 (14)	−0.0003 (12)
C25	0.0423 (18)	0.0354 (14)	0.0364 (15)	0.0009 (13)	−0.0058 (14)	0.0050 (12)
C26	0.0423 (19)	0.0475 (17)	0.0453 (17)	−0.0079 (15)	0.0012 (14)	0.0069 (14)
C27	0.051 (2)	0.0456 (17)	0.0486 (18)	−0.0088 (16)	−0.0108 (16)	−0.0060 (14)
C28	0.049 (2)	0.0426 (15)	0.0408 (17)	0.0048 (16)	−0.0101 (15)	0.0007 (13)
C29	0.049 (2)	0.065 (2)	0.0489 (19)	−0.0050 (19)	0.0057 (16)	−0.0076 (16)
C30	0.047 (2)	0.0521 (19)	0.0492 (19)	−0.0146 (16)	−0.0025 (16)	−0.0068 (15)
N1	0.0449 (16)	0.0437 (13)	0.0377 (13)	0.0032 (12)	0.0022 (12)	0.0041 (11)
N2	0.0634 (18)	0.0390 (13)	0.0320 (13)	−0.0106 (13)	0.0090 (12)	−0.0028 (11)
N3	0.0565 (17)	0.0417 (13)	0.0339 (13)	−0.0120 (13)	0.0062 (12)	0.0009 (11)
N4	0.0406 (15)	0.0501 (14)	0.0330 (13)	0.0015 (12)	−0.0020 (11)	−0.0019 (11)
N5	0.0478 (16)	0.0409 (13)	0.0318 (12)	0.0108 (12)	−0.0036 (11)	−0.0057 (10)
N6	0.0526 (17)	0.0398 (13)	0.0339 (13)	0.0080 (13)	−0.0028 (12)	0.0020 (11)
O1	0.0525 (16)	0.0900 (18)	0.0564 (15)	−0.0224 (15)	−0.0003 (12)	0.0063 (14)
O2	0.0522 (14)	0.0569 (13)	0.0355 (12)	−0.0080 (11)	−0.0067 (10)	−0.0026 (10)
O3	0.099 (2)	0.0766 (16)	0.0520 (14)	−0.0526 (17)	0.0165 (14)	−0.0137 (13)
O4	0.0525 (16)	0.0522 (14)	0.0799 (17)	−0.0074 (13)	0.0115 (13)	0.0142 (13)
O6	0.0652 (16)	0.0586 (14)	0.0530 (14)	−0.0088 (13)	0.0116 (12)	−0.0176 (11)
O7	0.0371 (14)	0.0910 (18)	0.0545 (14)	0.0106 (13)	0.0005 (11)	−0.0080 (13)
O8	0.0486 (14)	0.0694 (14)	0.0341 (12)	0.0074 (12)	0.0080 (10)	0.0019 (10)
O9	0.0718 (17)	0.0650 (15)	0.0508 (13)	0.0346 (14)	−0.0129 (12)	−0.0133 (11)
O10	0.0516 (14)	0.0462 (12)	0.0619 (14)	0.0026 (12)	−0.0150 (11)	0.0048 (11)
O11	0.0536 (15)	0.0461 (12)	0.0816 (18)	−0.0110 (12)	−0.0200 (14)	0.0137 (12)
O12	0.0635 (17)	0.0705 (16)	0.0504 (13)	0.0077 (14)	−0.0068 (12)	−0.0234 (12)

O5—C8	1.2534 (17)	C16—H16C	0.9600
O5—O10	3.414 (3)	C17—N4	1.468 (4)
O5—H5O	0.86 (3)	C17—H17A	0.9700
C1—O1	1.217 (4)	C17—H17B	0.9700
C1—N1	1.330 (4)	C18—O7	1.221 (4)
C1—C2	1.539 (4)	C18—N4	1.329 (4)
C2—O2	1.211 (3)	C18—C19	1.539 (4)
C2—N2	1.362 (4)	C19—O8	1.211 (3)
C3—N2	1.472 (4)	C19—N5	1.367 (4)
C3—C4	1.482 (5)	C20—N5	1.474 (3)
C3—H3A	0.9700	C20—C21	1.488 (4)
C3—H3B	0.9700	C20—H20A	0.9700
C4—N1	1.454 (4)	C20—H20B	0.9700
C4—H4A	0.9700	C21—N4	1.447 (4)
C4—H4B	0.9700	C21—H21A	0.9700
C5—N1	1.474 (4)	C21—H21B	0.9700
C5—C6	1.476 (5)	C22—O9	1.206 (4)
C5—H5A	0.9700	C22—N6	1.333 (3)
C5—H5B	0.9700	C22—N5	1.431 (4)
C6—H6A	0.9600	C23—N6	1.450 (4)
C6—H6B	0.9600	C23—C25	1.516 (4)
C6—H6C	0.9600	C23—C24	1.520 (4)
C7—O3	1.206 (4)	C23—H23	0.9800
C7—N3	1.332 (4)	C24—O10	1.2537 (17)
C7—N2	1.427 (4)	C24—O11	1.2538 (17)
C8—O4	1.2538 (17)	C25—C26	1.378 (4)
C8—C9	1.523 (4)	C25—C30	1.384 (4)
C9—N3	1.442 (4)	C26—C27	1.383 (4)
C9—C10	1.513 (4)	C26—H26	0.9300
C9—H9	0.9800	C27—C28	1.378 (5)
C10—C15	1.378 (4)	C27—H27	0.9300
C10—C11	1.381 (4)	C28—O12	1.362 (3)
C11—C12	1.388 (4)	C28—C29	1.379 (4)
C11—H11	0.9300	C29—C30	1.381 (4)
C12—C13	1.379 (5)	C29—H29	0.9300
C12—H12	0.9300	C30—H30	0.9300
C13—O6	1.367 (3)	N3—H3	0.8600
C13—C14	1.376 (4)	N6—H6D	0.8600
C14—C15	1.383 (4)	O4—H4O	0.86 (3)
C14—H14	0.9300	O6—H6	0.8200
C15—H15	0.9300	O10—H10O	0.86 (3)
C16—C17	1.501 (6)	O11—H11O	0.86 (3)
C16—H16A	0.9600	O12—H12A	0.8200
C16—H16B	0.9600
C8—O5—O10	79.07 (15)	H17A—C17—H17B	108.0
C8—O5—H5O	117 (7)	O7—C18—N4	123.9 (3)
O10—O5—H5O	43 (7)	O7—C18—C19	118.0 (3)
O1—C1—N1	123.4 (3)	N4—C18—C19	117.9 (3)
O1—C1—C2	118.3 (3)	O8—C19—N5	124.8 (3)
N1—C1—C2	118.2 (3)	O8—C19—C18	117.9 (3)
O2—C2—N2	125.1 (3)	N5—C19—C18	117.3 (2)
O2—C2—C1	117.8 (3)	N5—C20—C21	110.1 (3)
N2—C2—C1	117.1 (3)	N5—C20—H20A	109.6
N2—C3—C4	110.2 (3)	C21—C20—H20A	109.6
N2—C3—H3A	109.6	N5—C20—H20B	109.6
C4—C3—H3A	109.6	C21—C20—H20B	109.6
N2—C3—H3B	109.6	H20A—C20—H20B	108.1
C4—C3—H3B	109.6	N4—C21—C20	110.4 (3)
H3A—C3—H3B	108.1	N4—C21—H21A	109.6
N1—C4—C3	110.2 (3)	C20—C21—H21A	109.6
N1—C4—H4A	109.6	N4—C21—H21B	109.6
C3—C4—H4A	109.6	C20—C21—H21B	109.6
N1—C4—H4B	109.6	H21A—C21—H21B	108.1
C3—C4—H4B	109.6	O9—C22—N6	124.3 (3)
H4A—C4—H4B	108.1	O9—C22—N5	119.6 (3)
N1—C5—C6	111.4 (3)	N6—C22—N5	116.1 (3)
N1—C5—H5A	109.3	N6—C23—C25	111.0 (2)
C6—C5—H5A	109.3	N6—C23—C24	111.6 (2)
N1—C5—H5B	109.3	C25—C23—C24	108.3 (2)
C6—C5—H5B	109.3	N6—C23—H23	108.7
H5A—C5—H5B	108.0	C25—C23—H23	108.7
C5—C6—H6A	109.5	C24—C23—H23	108.7
C5—C6—H6B	109.5	O10—C24—O11	124.5 (3)
H6A—C6—H6B	109.5	O10—C24—C23	117.2 (2)
C5—C6—H6C	109.5	O11—C24—C23	118.2 (2)
H6A—C6—H6C	109.5	C26—C25—C30	118.2 (3)
H6B—C6—H6C	109.5	C26—C25—C23	120.7 (3)
O3—C7—N3	123.5 (3)	C30—C25—C23	121.1 (3)
O3—C7—N2	120.3 (3)	C25—C26—C27	121.3 (3)
N3—C7—N2	116.2 (3)	C25—C26—H26	119.3
O5—C8—O4	124.3 (3)	C27—C26—H26	119.3
O5—C8—C9	118.9 (2)	C28—C27—C26	119.8 (3)
O4—C8—C9	116.8 (2)	C28—C27—H27	120.1
N3—C9—C10	109.4 (2)	C26—C27—H27	120.1
N3—C9—C8	111.4 (2)	O12—C28—C27	122.7 (3)
C10—C9—C8	109.4 (2)	O12—C28—C29	117.8 (3)
N3—C9—H9	108.9	C27—C28—C29	119.5 (3)
C10—C9—H9	108.9	C28—C29—C30	120.1 (3)
C8—C9—H9	108.9	C28—C29—H29	119.9
C15—C10—C11	118.2 (3)	C30—C29—H29	119.9
C15—C10—C9	121.3 (3)	C29—C30—C25	121.0 (3)
C11—C10—C9	120.4 (3)	C29—C30—H30	119.5
C10—C11—C12	121.1 (3)	C25—C30—H30	119.5
C10—C11—H11	119.4	C1—N1—C4	121.1 (3)
C12—C11—H11	119.4	C1—N1—C5	119.7 (3)
C13—C12—C11	119.5 (3)	C4—N1—C5	118.1 (2)
C13—C12—H12	120.3	C2—N2—C7	125.5 (2)
C11—C12—H12	120.3	C2—N2—C3	118.4 (2)
O6—C13—C14	117.3 (3)	C7—N2—C3	116.1 (3)
O6—C13—C12	122.5 (3)	C7—N3—C9	119.4 (3)
C14—C13—C12	120.2 (3)	C7—N3—H3	120.3
C13—C14—C15	119.5 (3)	C9—N3—H3	120.3
C13—C14—H14	120.3	C18—N4—C21	121.4 (3)
C15—C14—H14	120.3	C18—N4—C17	119.1 (3)
C10—C15—C14	121.5 (3)	C21—N4—C17	118.4 (2)
C10—C15—H15	119.3	C19—N5—C22	125.4 (2)
C14—C15—H15	119.3	C19—N5—C20	117.5 (2)
C17—C16—H16A	109.5	C22—N5—C20	117.0 (2)
C17—C16—H16B	109.5	C22—N6—C23	119.3 (3)
H16A—C16—H16B	109.5	C22—N6—H6D	120.4
C17—C16—H16C	109.5	C23—N6—H6D	120.4
H16A—C16—H16C	109.5	C8—O4—H4O	133 (6)
H16B—C16—H16C	109.5	C13—O6—H6	109.5
N4—C17—C16	111.3 (3)	C24—O10—O5	77.75 (16)
N4—C17—H17A	109.4	C24—O10—H10O	116 (6)
C16—C17—H17A	109.4	O5—O10—H10O	44 (6)
N4—C17—H17B	109.4	C24—O11—H11O	122 (6)
C16—C17—H17B	109.4	C28—O12—H12A	109.5
O1—C1—C2—O2	−15.5 (4)	O1—C1—N1—C4	178.2 (3)
N1—C1—C2—O2	161.3 (3)	C2—C1—N1—C4	1.6 (4)
O1—C1—C2—N2	166.5 (3)	O1—C1—N1—C5	10.9 (5)
N1—C1—C2—N2	−16.8 (4)	C2—C1—N1—C5	−165.7 (3)
N2—C3—C4—N1	−56.5 (4)	C3—C4—N1—C1	35.1 (4)
O10—O5—C8—O4	−8.8 (3)	C3—C4—N1—C5	−157.4 (3)
O10—O5—C8—C9	174.5 (3)	C6—C5—N1—C1	90.2 (4)
O5—C8—C9—N3	−39.2 (4)	C6—C5—N1—C4	−77.4 (4)
O4—C8—C9—N3	143.9 (3)	O2—C2—N2—C7	−7.5 (5)
O5—C8—C9—C10	81.9 (3)	C1—C2—N2—C7	170.4 (3)
O4—C8—C9—C10	−95.0 (3)	O2—C2—N2—C3	174.5 (3)
N3—C9—C10—C15	59.9 (3)	C1—C2—N2—C3	−7.6 (4)
C8—C9—C10—C15	−62.4 (3)	O3—C7—N2—C2	176.3 (3)
N3—C9—C10—C11	−117.6 (3)	N3—C7—N2—C2	−3.0 (4)
C8—C9—C10—C11	120.1 (3)	O3—C7—N2—C3	−5.7 (5)
C15—C10—C11—C12	0.8 (4)	N3—C7—N2—C3	175.0 (3)
C9—C10—C11—C12	178.4 (3)	C4—C3—N2—C2	44.0 (4)
C10—C11—C12—C13	−0.3 (4)	C4—C3—N2—C7	−134.1 (3)
C11—C12—C13—O6	180.0 (3)	O3—C7—N3—C9	8.6 (5)
C11—C12—C13—C14	−0.1 (4)	N2—C7—N3—C9	−172.2 (3)
O6—C13—C14—C15	179.9 (3)	C10—C9—N3—C7	178.9 (3)
C12—C13—C14—C15	0.0 (5)	C8—C9—N3—C7	−60.1 (3)
C11—C10—C15—C14	−1.0 (4)	O7—C18—N4—C21	179.8 (3)
C9—C10—C15—C14	−178.5 (3)	C19—C18—N4—C21	5.3 (4)
C13—C14—C15—C10	0.6 (5)	O7—C18—N4—C17	11.8 (5)
O7—C18—C19—O8	−15.6 (4)	C19—C18—N4—C17	−162.6 (3)
N4—C18—C19—O8	159.2 (3)	C20—C21—N4—C18	32.0 (4)
O7—C18—C19—N5	166.6 (3)	C20—C21—N4—C17	−159.9 (3)
N4—C18—C19—N5	−18.6 (4)	C16—C17—N4—C18	78.3 (4)
N5—C20—C21—N4	−56.3 (4)	C16—C17—N4—C21	−90.0 (4)
N6—C23—C24—O10	152.5 (3)	O8—C19—N5—C22	−2.6 (5)
C25—C23—C24—O10	−85.1 (3)	C18—C19—N5—C22	175.0 (3)
N6—C23—C24—O11	−30.5 (4)	O8—C19—N5—C20	174.1 (3)
C25—C23—C24—O11	91.8 (3)	C18—C19—N5—C20	−8.4 (4)
N6—C23—C25—C26	−120.9 (3)	O9—C22—N5—C19	172.3 (3)
C24—C23—C25—C26	116.4 (3)	N6—C22—N5—C19	−9.2 (4)
N6—C23—C25—C30	59.8 (3)	O9—C22—N5—C20	−4.4 (4)
C24—C23—C25—C30	−62.9 (3)	N6—C22—N5—C20	174.2 (3)
C30—C25—C26—C27	0.7 (4)	C21—C20—N5—C19	45.4 (4)
C23—C25—C26—C27	−178.5 (3)	C21—C20—N5—C22	−137.7 (3)
C25—C26—C27—C28	−0.3 (5)	O9—C22—N6—C23	−0.4 (5)
C26—C27—C28—O12	178.8 (3)	N5—C22—N6—C23	−178.9 (2)
C26—C27—C28—C29	−0.4 (5)	C25—C23—N6—C22	170.7 (2)
O12—C28—C29—C30	−178.6 (3)	C24—C23—N6—C22	−68.5 (3)
C27—C28—C29—C30	0.6 (5)	O11—C24—O10—O5	−2.3 (3)
C28—C29—C30—C25	−0.1 (5)	C23—C24—O10—O5	174.5 (3)
C26—C25—C30—C29	−0.5 (5)	C8—O5—O10—C24	162.7 (3)
C23—C25—C30—C29	178.7 (3)

D—H···A	D—H	H···A	D···A	D—H···A
O11—H11O···O5	0.86 (3)	1.80 (4)	2.617 (3)	159 (9)
O10—H10O···O4	0.86 (3)	1.82 (3)	2.678 (3)	171 (9)
O5—H5O···O11	0.86 (3)	1.76 (3)	2.617 (3)	171 (8)
O4—H4O···O10	0.86 (3)	1.88 (5)	2.678 (3)	154 (9)
N6—H6D···O8	0.86	1.98	2.637 (3)	132
N3—H3···O2	0.86	1.97	2.636 (3)	133
O6—H6···O1i	0.82	1.87	2.682 (3)	174
C12—H12···O2i	0.93	2.52	3.438 (4)	169
O12—H12A···O7ii	0.82	1.88	2.692 (3)	172
C27—H27···O8ii	0.93	2.50	3.378 (4)	158

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O11—H11O⋯O5	0.86 (3)	1.80 (4)	2.617 (3)	159 (9)
O10—H10O⋯O4	0.86 (3)	1.82 (3)	2.678 (3)	171 (9)
O5—H5O⋯O11	0.86 (3)	1.76 (3)	2.617 (3)	171 (8)
O4—H4O⋯O10	0.86 (3)	1.88 (5)	2.678 (3)	154 (9)
N6—H6D⋯O8	0.86	1.98	2.637 (3)	132
N3—H3⋯O2	0.86	1.97	2.636 (3)	133
O6—H6⋯O1i	0.82	1.87	2.682 (3)	174
C12—H12⋯O2i	0.93	2.52	3.438 (4)	169
O12—H12A⋯O7ii	0.82	1.88	2.692 (3)	172
C27—H27⋯O8ii	0.93	2.50	3.378 (4)	158

Symmetry codes: (i) ; (ii) .