N-(2-Acetamido-2-de­oxy-β-D-gluco­pyranos­yl)-N-(3-azido­prop­yl)-O-methyl­hydroxyl­amine

The structure determination of an oxyamine glycoside confirmed that it was obtained in the ring-closed β-pyran­ose configuration with a ⁴C₁ conformation. The mol­ecules are bound by O—H...O(OH) hydrogen bonds, notably in a zigzag C(2) chain along the short b (screw) axis, supplemented with an (12) O—H...O(carbon­yl) link along the a axis and other C(2) links.

Key indicators

• Single-crystal X-ray study
• T = 120 K
• Mean [sigma](C-C) = 0.007 Å
• R factor = 0.059
• wR factor = 0.165
• Data-to-parameter ratio = 10.7

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low .......      0.964 Note
PLAT089_ALERT_3_C Poor Data / Parameter Ratio (Zmax < 18) ........       7.15 Note
PLAT340_ALERT_3_C Low Bond Precision on  C-C Bonds ...............    0.00712 Ang.
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.595         19 Report
PLAT915_ALERT_3_C Low Friedel Pair Coverage ....(No Flack x Check)         63 %

Alert level G
PLAT032_ALERT_4_G Std. Uncertainty on Flack Parameter Value High .      0.400 Report
PLAT072_ALERT_2_G SHELXL First  Parameter in WGHT  Unusually Large       0.12 Report
PLAT484_ALERT_4_G Round D-H..A Angle Rep for O3     ..  O3      to        167 Degree
PLAT791_ALERT_4_G The Model has Chirality at C1      (Chiral SPGR)          R Verify
PLAT791_ALERT_4_G The Model has Chirality at C2      (Chiral SPGR)          R Verify
PLAT791_ALERT_4_G The Model has Chirality at C3      (Chiral SPGR)          R Verify
PLAT791_ALERT_4_G The Model has Chirality at C4      (Chiral SPGR)          S Verify
PLAT791_ALERT_4_G The Model has Chirality at C5      (Chiral SPGR)          R Verify
PLAT909_ALERT_3_G Percentage of Observed Data at Theta(Max) Still          77 %
PLAT910_ALERT_3_G Missing # of FCF Reflection(s) Below Th(Min) ...          3 Report
PLAT955_ALERT_1_G Reported (CIF) and Actual (FCF) Lmax Differ by .          1 Units
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density           1 Note

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   5 ALERT level C = Check. Ensure it is not caused by an omission or oversight
  12 ALERT level G = General information/check it is not something unexpected

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   7 ALERT type 3 Indicator that the structure quality may be low
   7 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Chemical context

Oxyamine glycosides, such as the title compound, can be utilized for the synthesis of a wide variety of complex glycoconjugates (Kwase et al.,2014; Munneke et al., 2015; Wang et al., 2013). In particular, the use of an oxyamine bifunctional linker allows for the conjugation of carbohydrates to a substrate of choice, such as proteins, fluoro­phores and biotin. The crystal structure analysis confirmed that the glycoconjugate was obtained in the ring-closed β-pyran­ose configuration.

S2. Structural commentary

The title compound crystallizes with one independent molecule in the asymmetric unit (Fig. 1) in the C1(R), C2(R), C3(R), C4(S), C5(R) configuration. The absolute configuration was not ambiguously determined but was known from the synthetic chemistry.

S3. Supra­molecular features

The molecules are bound together with a comprehensive net of O—H···O(alcohol) hydrogen bonds, as well as one N—H···O(carbonyl) and one O—H···O(carbonyl) hydrogen bond (Table 1). The basic inter­actions are chain C(2) and C(8) types which combine to form larger chain and rings e.g. R₂²(12), as shown on the right of Fig. 2.

S4. Database survey

The Cambridge Structural Database (CSD, Version 5.36, update 3; Groom & Allen, 2014) was searched for N-alkyl-N-(tetra­hydro-2H-pyran-2-yl)oxyamines, and two structures were found, both of which are N-β-glycosyl­oxyamines, viz. an N-β-gluco­pyran­osyloxyamine (Langenhan et al., 2005) and an N-β-galacto­pyran­osyloxyamine (Renaudet & Dumy, 2002). Inter­estingly, all three structures have a similar conformation around the anomeric linkage, with O6—N1—C1—O1 and C9—O6—N1—C1 torsion angles of 62.9 (8) and 115.6 (2) for the glu­cosyl­oxyamine derivative, 50.8 (1) and 126.3 (8) for the galactosyl­oxyamine and 64.2 (4) and 127.1 (3) for the title compound (Fig. 3). A configuration that allows both the meth­oxy group to adopt a pseudoaxial orientation, and positions the nitro­gen for optimal overlap between the nitro­gen lone pair and the C1—O1 σ* (n → σ* inter­action).

S5. Synthesis and crystallization

\ N-(2-Acetamido-2-de­oxy-β-D-gluco­pyran­osyl)-N-(3-\ azido­propyl) -O-methyl­hydroxyl­amine was prepared as described in Munneke et al. (2015) from 3-azido-1-meth­oxy­amino­propane and commercially available N-acetyl­glucosamine. The title compound was recrystallized from freshly distilled MeOH–Et₂O (1:8 v/v).

S6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. A l l me thyl H atoms were constrained to an ideal geometry (C—H = 0.98 Å) with U_iso(H) = 1.5U_eq(C), but were allowed to rotate freely about the adjacent C—C bond. All other O,C-bound H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms with C—H distances of 0.99 (methyl­ene) and 1.0 (tertiary) Å, O—H = 0.84 Å and with U_iso(H) = 1.2U_eq(C,O). The nitro­gen H atom was located in a difference Fourier map and refined with U_iso(H) = 1.2U_eq(N).

Related literature

For related structures, see N-β-glucopyranosyloxyamine (Langenhan et al., 2005) and N-β-galactopyranosyloxyamine (Renaudet & Dumy, 2002)

Structure description

Oxyamine glycosides, such as the title compound, can be utilized for the synthesis of a wide variety of complex glycoconjugates (Kwase et al.,2014; Munneke et al., 2015; Wang et al., 2013). In particular, the use of an oxyamine bifunctional linker allows for the conjugation of carbohydrates to a substrate of choice, such as proteins, fluoro­phores and biotin. The crystal structure analysis confirmed that the glycoconjugate was obtained in the ring-closed β-pyran­ose configuration.

The title compound crystallizes with one independent molecule in the asymmetric unit (Fig. 1) in the C1(R), C2(R), C3(R), C4(S), C5(R) configuration. The absolute configuration was not ambiguously determined but was known from the synthetic chemistry.

The molecules are bound together with a comprehensive net of O—H···O(alcohol) hydrogen bonds, as well as one N—H···O(carbonyl) and one O—H···O(carbonyl) hydrogen bond (Table 1). The basic inter­actions are chain C(2) and C(8) types which combine to form larger chain and rings e.g. R₂²(12), as shown on the right of Fig. 2.

The Cambridge Structural Database (CSD, Version 5.36, update 3; Groom & Allen, 2014) was searched for N-alkyl-N-(tetra­hydro-2H-pyran-2-yl)oxyamines, and two structures were found, both of which are N-β-glycosyl­oxyamines, viz. an N-β-gluco­pyran­osyloxyamine (Langenhan et al., 2005) and an N-β-galacto­pyran­osyloxyamine (Renaudet & Dumy, 2002). Inter­estingly, all three structures have a similar conformation around the anomeric linkage, with O6—N1—C1—O1 and C9—O6—N1—C1 torsion angles of 62.9 (8) and 115.6 (2) for the glu­cosyl­oxyamine derivative, 50.8 (1) and 126.3 (8) for the galactosyl­oxyamine and 64.2 (4) and 127.1 (3) for the title compound (Fig. 3). A configuration that allows both the meth­oxy group to adopt a pseudoaxial orientation, and positions the nitro­gen for optimal overlap between the nitro­gen lone pair and the C1—O1 σ* (n → σ* inter­action).

For related structures, see N-β-glucopyranosyloxyamine (Langenhan et al., 2005) and N-β-galactopyranosyloxyamine (Renaudet & Dumy, 2002)

Synthesis and crystallization

\ N-(2-Acetamido-2-de­oxy-β-D-gluco­pyran­osyl)-N-(3-\ azido­propyl) -O-methyl­hydroxyl­amine was prepared as described in Munneke et al. (2015) from 3-azido-1-meth­oxy­amino­propane and commercially available N-acetyl­glucosamine. The title compound was recrystallized from freshly distilled MeOH–Et₂O (1:8 v/v).

Refinement details

Crystal data, data collection and structure refinement details are summarized in Table 2. A l l me thyl H atoms were constrained to an ideal geometry (C—H = 0.98 Å) with U_iso(H) = 1.5U_eq(C), but were allowed to rotate freely about the adjacent C—C bond. All other O,C-bound H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms with C—H distances of 0.99 (methyl­ene) and 1.0 (tertiary) Å, O—H = 0.84 Å and with U_iso(H) = 1.2U_eq(C,O). The nitro­gen H atom was located in a difference Fourier map and refined with U_iso(H) = 1.2U_eq(N).

Computing details

Data collection: CrysAlis PRO (Agilent, 2014); cell refinement: CrysAlis PRO (Agilent, 2014); data reduction: CrysAlis PRO (Agilent, 2014); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL2012 (Sheldrick, 2015) and PLATON (Spek, 2009).

Figures

	Fig. 1. View of the title molecule, drawn with 25% probability displacement ellipsoids.
	Fig. 2. The unit-cell contents viewed along approximately the b axis. Some intermolecular binding contacts are shown as blue dotted lines. [Symmetry codes: (i) −x, y + 1/2, 1 − z; (ii) 1 − x, y − 1/2, 1 − z; (iii) 1 − x, y + 1/2, 1 − z.]
	Fig. 3. The O6—N1—C1—O1 and C9—O6—N1—C1 torsion angles of N-glycosyloxyamines.

N-(2-Acetamido-2-deoxy-β-D-glucopyranosyl)-N-(3-azidopropyl)-O-methylhydroxylamine

Crystal data

C12H23N5O6	F(000) = 356
Mr = 333.35	Dx = 1.382 Mg m^−3
Monoclinic, P21	Cu Kα radiation, λ = 1.54184 Å
a = 13.5605 (18) Å	Cell parameters from 2327 reflections
b = 4.7386 (3) Å	θ = 3.7–75.3°
c = 14.140 (2) Å	µ = 0.95 mm^−1
β = 118.181 (19)°	T = 120 K
V = 800.9 (2) Å^3	Needle, colourless
Z = 2	0.57 × 0.14 × 0.02 mm

Data collection

Agilent SuperNova Dual Source diffractometer with an Atlas detector	2355 independent reflections
Radiation source: sealed X-ray tube, SuperNova (Cu) X-ray Source	2073 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.053
Detector resolution: 10.6501 pixels mm^-1	θmax = 66.6°, θmin = 3.6°
ω scans	h = −16→16
Absorption correction: gaussian (CrysAlis PRO; Agilent, 2014)	k = −5→5
Tmin = 0.792, Tmax = 0.985	l = −17→16
6061 measured reflections

Refinement

Refinement on F^2	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.059	w = 1/[σ^2(Fo^2) + (0.1194P)^2] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.165	(Δ/σ)max < 0.001
S = 1.03	Δρmax = 0.39 e Å^−3
2355 reflections	Δρmin = −0.31 e Å^−3
221 parameters	Absolute structure: Flack x determined using 619 quotients [(I^+)-(I^-)]/[(I^+)+(I^-)] (Parsons & Flack, 2004)
1 restraint	Absolute structure parameter: 0.2 (4)

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
O1	0.3682 (2)	0.2828 (6)	0.5792 (2)	0.0314 (7)
O2	0.1361 (3)	0.5357 (7)	0.7397 (3)	0.0378 (8)
O3	0.0442 (2)	0.1637 (7)	0.5080 (3)	0.0368 (8)
H3O	0.007 (4)	0.017 (14)	0.498 (6)	0.055*
O4	0.1155 (3)	0.0380 (8)	0.3491 (3)	0.0426 (8)
H4O	0.050 (6)	0.058 (17)	0.328 (5)	0.064*
O5	0.4546 (3)	0.2456 (8)	0.4382 (3)	0.0401 (8)
H5O	0.486 (6)	0.385 (16)	0.486 (6)	0.060*
O6	0.4312 (3)	0.5384 (7)	0.7784 (3)	0.0369 (7)
N1	0.4434 (3)	0.2390 (8)	0.7677 (3)	0.0329 (8)
N2	0.2088 (3)	0.1158 (8)	0.7250 (3)	0.0326 (8)
H2N	0.205 (4)	−0.077 (14)	0.732 (4)	0.039*
N3	0.7789 (3)	−0.1042 (10)	0.8833 (4)	0.0480 (11)
N4	0.8722 (3)	−0.1684 (10)	0.8948 (4)	0.0451 (10)
N5	0.9545 (4)	−0.2571 (12)	0.9039 (4)	0.0566 (12)
C1	0.3557 (3)	0.1498 (10)	0.6645 (4)	0.0308 (9)
H1	0.3616	−0.0591	0.6585	0.037*
C2	0.2369 (3)	0.2191 (9)	0.6435 (3)	0.0304 (9)
H2	0.2276	0.4289	0.6387	0.036*
C3	0.1552 (3)	0.0914 (9)	0.5340 (4)	0.0318 (9)
H3	0.1626	−0.1187	0.5392	0.038*
C4	0.1797 (3)	0.1921 (9)	0.4452 (4)	0.0320 (9)
H4	0.1613	0.3974	0.4317	0.038*
C5	0.3030 (3)	0.1481 (10)	0.4789 (4)	0.0338 (10)
H5	0.3197	−0.0587	0.4869	0.041*
C6	0.3382 (4)	0.2715 (11)	0.4006 (4)	0.0349 (9)
H6A	0.2977	0.1734	0.3308	0.042*
H6B	0.3172	0.4735	0.3890	0.042*
C7	0.1536 (3)	0.2815 (10)	0.7623 (4)	0.0324 (9)
C8	0.1154 (4)	0.1435 (11)	0.8351 (4)	0.0436 (11)
H8A	0.1627	0.2070	0.9090	0.065*
H8B	0.1212	−0.0619	0.8313	0.065*
H8C	0.0375	0.1955	0.8123	0.065*
C9	0.4282 (4)	0.5914 (10)	0.8765 (4)	0.0395 (11)
H9A	0.4977	0.5240	0.9370	0.059*
H9B	0.3644	0.4919	0.8757	0.059*
H9C	0.4203	0.7945	0.8842	0.059*
C10	0.5538 (3)	0.1952 (11)	0.7742 (4)	0.0389 (11)
H10A	0.5617	0.3227	0.7227	0.047*
H10B	0.5589	−0.0014	0.7532	0.047*
C11	0.6489 (4)	0.2502 (12)	0.8862 (4)	0.0443 (11)
H11A	0.6441	0.4474	0.9068	0.053*
H11B	0.6405	0.1240	0.9378	0.053*
C12	0.7623 (4)	0.2026 (12)	0.8934 (4)	0.0451 (12)
H12A	0.7675	0.3074	0.8353	0.054*
H12B	0.8216	0.2735	0.9630	0.054*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0257 (13)	0.0269 (16)	0.0409 (16)	−0.0022 (12)	0.0150 (12)	0.0014 (13)
O2	0.0370 (16)	0.0236 (16)	0.056 (2)	0.0021 (13)	0.0245 (15)	0.0010 (15)
O3	0.0235 (13)	0.0265 (16)	0.060 (2)	−0.0025 (12)	0.0190 (14)	−0.0003 (15)
O4	0.0270 (15)	0.047 (2)	0.0476 (19)	−0.0046 (16)	0.0129 (14)	−0.0117 (17)
O5	0.0322 (15)	0.0397 (19)	0.0533 (19)	−0.0004 (14)	0.0243 (14)	−0.0017 (17)
O6	0.0412 (17)	0.0222 (15)	0.0421 (17)	−0.0018 (14)	0.0152 (14)	0.0019 (14)
N1	0.0277 (17)	0.0250 (19)	0.042 (2)	0.0011 (14)	0.0130 (15)	0.0004 (15)
N2	0.0313 (17)	0.0212 (18)	0.049 (2)	0.0013 (14)	0.0223 (16)	0.0030 (15)
N3	0.033 (2)	0.042 (2)	0.066 (3)	−0.0007 (19)	0.021 (2)	0.001 (2)
N4	0.038 (2)	0.042 (2)	0.051 (2)	−0.0025 (18)	0.0174 (19)	0.0016 (19)
N5	0.036 (2)	0.055 (3)	0.079 (3)	0.003 (2)	0.027 (2)	−0.002 (3)
C1	0.0266 (19)	0.027 (2)	0.037 (2)	0.0008 (17)	0.0136 (17)	0.0035 (17)
C2	0.0266 (19)	0.022 (2)	0.045 (2)	0.0031 (16)	0.0187 (18)	0.0052 (18)
C3	0.0256 (19)	0.021 (2)	0.047 (2)	0.0000 (16)	0.0160 (18)	0.0006 (18)
C4	0.027 (2)	0.026 (2)	0.041 (2)	0.0014 (17)	0.0143 (18)	0.0008 (19)
C5	0.0249 (19)	0.033 (2)	0.042 (2)	0.0018 (18)	0.0146 (17)	0.0022 (19)
C6	0.033 (2)	0.034 (2)	0.039 (2)	−0.002 (2)	0.0172 (18)	0.000 (2)
C7	0.0297 (19)	0.022 (2)	0.045 (2)	−0.0016 (17)	0.0173 (18)	−0.0012 (18)
C8	0.056 (3)	0.028 (2)	0.061 (3)	0.000 (2)	0.039 (2)	0.003 (2)
C9	0.042 (2)	0.030 (2)	0.041 (2)	−0.0021 (19)	0.016 (2)	−0.004 (2)
C10	0.027 (2)	0.040 (3)	0.044 (3)	0.0000 (19)	0.0112 (19)	0.001 (2)
C11	0.034 (2)	0.044 (3)	0.046 (3)	0.001 (2)	0.012 (2)	−0.001 (2)
C12	0.033 (2)	0.040 (3)	0.048 (3)	−0.002 (2)	0.007 (2)	0.000 (2)

Geometric parameters (Å, º)

O1—C5	1.420 (6)	C3—C4	1.520 (6)
O1—C1	1.441 (5)	C3—H3	1.0000
O2—C7	1.240 (6)	C4—C5	1.521 (5)
O3—C3	1.413 (5)	C4—H4	1.0000
O3—H3O	0.84 (8)	C5—C6	1.515 (6)
O4—C4	1.421 (6)	C5—H5	1.0000
O4—H4O	0.80 (7)	C6—H6A	0.9900
O5—C6	1.413 (5)	C6—H6B	0.9900
O5—H5O	0.90 (8)	C7—C8	1.502 (6)
O6—C9	1.430 (6)	C8—H8A	0.9800
O6—N1	1.445 (5)	C8—H8B	0.9800
N1—C1	1.443 (6)	C8—H8C	0.9800
N1—C10	1.470 (5)	C9—H9A	0.9800
N2—C7	1.352 (6)	C9—H9B	0.9800
N2—C2	1.459 (5)	C9—H9C	0.9800
N2—H2N	0.93 (7)	C10—C11	1.520 (6)
N3—N4	1.235 (6)	C10—H10A	0.9900
N3—C12	1.488 (7)	C10—H10B	0.9900
N4—N5	1.141 (6)	C11—C12	1.510 (7)
C1—C2	1.529 (5)	C11—H11A	0.9900
C1—H1	1.0000	C11—H11B	0.9900
C2—C3	1.539 (6)	C12—H12A	0.9900
C2—H2	1.0000	C12—H12B	0.9900
C5—O1—C1	112.0 (3)	C6—C5—H5	109.1
C3—O3—H3O	109.5	C4—C5—H5	109.1
C4—O4—H4O	112 (5)	O5—C6—C5	111.9 (3)
C6—O5—H5O	106 (5)	O5—C6—H6A	109.2
C9—O6—N1	109.4 (3)	C5—C6—H6A	109.2
C1—N1—O6	108.2 (3)	O5—C6—H6B	109.2
C1—N1—C10	110.6 (3)	C5—C6—H6B	109.2
O6—N1—C10	107.2 (3)	H6A—C6—H6B	107.9
C7—N2—C2	120.9 (4)	O2—C7—N2	122.5 (4)
C7—N2—H2N	118 (3)	O2—C7—C8	120.9 (4)
C2—N2—H2N	118 (3)	N2—C7—C8	116.6 (4)
N4—N3—C12	114.8 (4)	C7—C8—H8A	109.5
N5—N4—N3	172.6 (6)	C7—C8—H8B	109.5
O1—C1—N1	110.6 (3)	H8A—C8—H8B	109.5
O1—C1—C2	105.9 (3)	C7—C8—H8C	109.5
N1—C1—C2	115.1 (4)	H8A—C8—H8C	109.5
O1—C1—H1	108.4	H8B—C8—H8C	109.5
N1—C1—H1	108.4	O6—C9—H9A	109.5
C2—C1—H1	108.4	O6—C9—H9B	109.5
N2—C2—C1	114.7 (3)	H9A—C9—H9B	109.5
N2—C2—C3	109.3 (3)	O6—C9—H9C	109.5
C1—C2—C3	107.6 (3)	H9A—C9—H9C	109.5
N2—C2—H2	108.4	H9B—C9—H9C	109.5
C1—C2—H2	108.4	N1—C10—C11	112.2 (4)
C3—C2—H2	108.4	N1—C10—H10A	109.2
O3—C3—C4	109.3 (4)	C11—C10—H10A	109.2
O3—C3—C2	109.8 (3)	N1—C10—H10B	109.2
C4—C3—C2	111.9 (3)	C11—C10—H10B	109.2
O3—C3—H3	108.6	H10A—C10—H10B	107.9
C4—C3—H3	108.6	C12—C11—C10	112.3 (4)
C2—C3—H3	108.6	C12—C11—H11A	109.1
O4—C4—C3	110.8 (4)	C10—C11—H11A	109.1
O4—C4—C5	108.4 (3)	C12—C11—H11B	109.1
C3—C4—C5	109.5 (3)	C10—C11—H11B	109.1
O4—C4—H4	109.4	H11A—C11—H11B	107.9
C3—C4—H4	109.4	N3—C12—C11	109.5 (4)
C5—C4—H4	109.4	N3—C12—H12A	109.8
O1—C5—C6	107.1 (3)	C11—C12—H12A	109.8
O1—C5—C4	109.0 (3)	N3—C12—H12B	109.8
C6—C5—C4	113.4 (4)	C11—C12—H12B	109.8
O1—C5—H5	109.1	H12A—C12—H12B	108.2
C9—O6—N1—C1	127.1 (3)	C2—C3—C4—O4	170.7 (3)
C9—O6—N1—C10	−113.6 (4)	O3—C3—C4—C5	173.0 (4)
C5—O1—C1—N1	164.6 (3)	C2—C3—C4—C5	51.1 (5)
C5—O1—C1—C2	−70.2 (4)	C1—O1—C5—C6	−170.3 (3)
O6—N1—C1—O1	64.2 (4)	C1—O1—C5—C4	66.7 (4)
C10—N1—C1—O1	−52.9 (5)	O4—C4—C5—O1	−175.5 (3)
O6—N1—C1—C2	−55.6 (4)	C3—C4—C5—O1	−54.5 (5)
C10—N1—C1—C2	−172.8 (4)	O4—C4—C5—C6	65.3 (5)
C7—N2—C2—C1	136.0 (4)	C3—C4—C5—C6	−173.7 (4)
C7—N2—C2—C3	−103.1 (4)	O1—C5—C6—O5	55.3 (5)
O1—C1—C2—N2	−176.8 (3)	C4—C5—C6—O5	175.6 (4)
N1—C1—C2—N2	−54.4 (5)	C2—N2—C7—O2	−8.8 (7)
O1—C1—C2—C3	61.4 (4)	C2—N2—C7—C8	172.2 (4)
N1—C1—C2—C3	−176.2 (3)	C1—N1—C10—C11	−172.5 (4)
N2—C2—C3—O3	58.2 (4)	O6—N1—C10—C11	69.7 (5)
C1—C2—C3—O3	−176.7 (3)	N1—C10—C11—C12	179.5 (4)
N2—C2—C3—C4	179.7 (3)	N4—N3—C12—C11	−175.7 (4)
C1—C2—C3—C4	−55.1 (4)	C10—C11—C12—N3	−69.7 (6)
O3—C3—C4—O4	−67.5 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3O···O3^i	0.84	1.79	2.616 (5)	167
O4—H4O···O2^i	0.80 (7)	2.23 (7)	3.027 (4)	170 (8)
O5—H5O···O5^ii	0.90 (8)	1.98 (8)	2.855 (4)	167 (7)
N2—H2N···O2^iii	0.93 (7)	2.08 (6)	2.961 (5)	158 (5)

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