The oxidized form of nicotin­amide adenine dinucleotide

The crystal structure of the free acid form of NAD⁺ tetrahydrate (nicotin­amide adenine dinucleotide tetrahydrate or 3-carbamoyl-1-β-D-ribo­furan­osyl­pyridinium hydro­xide 5′-ester with adenosine 5′-pyrophosphate inner salt tetrahydrate, C₂₁H₂₇N₇O₁₄P₂·4H₂O) has been determined at 100 K. NAD⁺ is the coenzyme of several protein families and plays a dominant role in biological redox processes. In this study, the mol­ecule shows a different conformation from the one usually found in holoenzyme complexes.

Computing details

Data collection: COLLECT (Nonius, 1998); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

β-Nicotinamide Adenine Dinucleotide

Crystal data

C21H27N7O4P2·4(H2O)	Z = 1
Mr = 735.50	F(000) = 384
Triclinic, P1	Dx = 1.579 Mg m^−3
a = 8.592 (10) Å	Mo Kα radiation, λ = 0.70900 Å
b = 8.845 (10) Å	Cell parameters from 141 reflections
c = 11.192 (10) Å	θ = 3.0–19.0°
α = 109.64 (5)°	µ = 0.23 mm^−1
β = 90.56 (5)°	T = 100 K
γ = 103.92 (5)°	Irregular, colourless
V = 773.7 (14) Å^3	0.41 × 0.35 × 0.3 mm

Data collection

Nonius KappaCCD diffractometer	7439 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.026
Graphite monochromator	θmax = 36.3°, θmin = 2.5°
oscillation scans	h = 0→14
15736 measured reflections	k = −14→14
7459 independent reflections	l = −18→18

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.019	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.052	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	Calculated w = 1/[σ^2(Fo^2) + (0.0371P)^2 + 0.0533P] where P = (Fo^2 + 2Fc^2)/3
7459 reflections	(Δ/σ)max = 0.001
573 parameters	Δρmax = 0.32 e Å^−3
15 restraints	Δρmin = −0.25 e Å^−3

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.

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 (Ų)

	x	y	z	Uiso*/Ueq
O1	0.09222 (7)	−0.20496 (7)	0.23359 (6)	0.01127 (9)
P1	0.22886 (2)	−0.29706 (2)	0.187743 (17)	0.00871 (3)
O2	0.16635 (8)	−0.48234 (8)	0.14639 (6)	0.01377 (9)
O3	0.31006 (7)	−0.23175 (8)	0.09062 (6)	0.01284 (9)
O4	0.34589 (7)	−0.22830 (8)	0.31680 (5)	0.01148 (9)
C1	0.49237 (9)	−0.28327 (10)	0.30853 (7)	0.01192 (11)
HC1A	0.578 (2)	−0.205 (2)	0.2914 (18)	0.021 (4)*
HC1B	0.476 (3)	−0.382 (3)	0.246 (2)	0.028 (5)*
C2	0.53848 (8)	−0.29898 (9)	0.43348 (7)	0.00979 (10)
HC2	0.633 (2)	−0.337 (2)	0.4226 (19)	0.021 (4)*
C3	0.40805 (8)	−0.41017 (9)	0.48088 (7)	0.00971 (10)
HC3	0.334 (2)	−0.494 (2)	0.4130 (19)	0.022 (4)*
O6	0.48866 (7)	−0.48042 (7)	0.55255 (6)	0.01263 (9)
HO6	0.425 (2)	−0.563 (2)	0.5603 (16)	0.015 (3)*
C4	0.32408 (8)	−0.28576 (9)	0.56760 (7)	0.00957 (10)
HC4	0.251 (2)	−0.268 (2)	0.5181 (17)	0.013 (3)*
O7	0.24503 (7)	−0.34097 (8)	0.66095 (6)	0.01364 (9)
HO7	0.154 (3)	−0.315 (3)	0.674 (2)	0.034 (5)*
C5	0.46680 (9)	−0.13013 (9)	0.62506 (7)	0.00988 (10)
HC5	0.512 (2)	−0.128 (2)	0.7019 (19)	0.020 (4)*
O5	0.57844 (7)	−0.13590 (7)	0.53335 (6)	0.01170 (9)
N1	0.42122 (8)	0.02677 (8)	0.65298 (6)	0.01029 (9)
C6	0.38847 (9)	0.12487 (9)	0.76831 (7)	0.01057 (10)
N2	0.39494 (9)	0.09973 (9)	0.88112 (7)	0.01350 (11)
C7	0.35170 (11)	0.21523 (10)	0.97369 (7)	0.01379 (12)
HC7	0.340 (2)	0.208 (3)	1.0502 (19)	0.021 (4)*
N3	0.30738 (9)	0.34757 (9)	0.96171 (6)	0.01252 (10)
HN3	0.274 (2)	0.412 (2)	1.0344 (18)	0.020 (4)*
C8	0.30890 (9)	0.38055 (9)	0.85082 (7)	0.01079 (10)
N5	0.27135 (9)	0.51567 (9)	0.84829 (7)	0.01393 (11)
HN5A	0.266 (2)	0.592 (3)	0.919 (2)	0.022 (4)*
HN5B	0.270 (3)	0.539 (3)	0.777 (2)	0.028 (5)*
C9	0.35083 (9)	0.25872 (9)	0.74704 (7)	0.01035 (10)
N4	0.36277 (8)	0.24590 (8)	0.62154 (6)	0.01088 (9)
C10	0.40470 (9)	0.10543 (9)	0.56878 (7)	0.01111 (11)
HC10	0.422 (2)	0.061 (2)	0.4802 (18)	0.017 (4)*
P2	−0.067929 (19)	−0.24839 (2)	0.305121 (16)	0.00809 (3)
O8	−0.02441 (8)	−0.30033 (8)	0.41150 (6)	0.01280 (9)
O9	−0.20305 (7)	−0.35642 (7)	0.20699 (6)	0.01254 (9)
O10	−0.09903 (7)	−0.06741 (7)	0.35813 (6)	0.01092 (9)
C11	0.01603 (10)	0.05681 (10)	0.45951 (8)	0.01462 (12)
H11A	0.125 (2)	0.061 (2)	0.4381 (19)	0.023 (4)*
H11B	0.002 (3)	0.030 (3)	0.543 (2)	0.032 (5)*
C12	−0.01570 (9)	0.22370 (9)	0.48058 (7)	0.01104 (10)
HC12	0.054 (2)	0.301 (2)	0.5567 (16)	0.014 (3)*
C13	−0.19323 (9)	0.22439 (9)	0.49128 (7)	0.01091 (11)
HC13	−0.256 (2)	0.130 (2)	0.5133 (18)	0.016 (3)*
O12	−0.21141 (9)	0.37699 (8)	0.57863 (6)	0.01525 (10)
HO12	−0.222 (3)	0.357 (3)	0.648 (2)	0.034 (5)*
C14	−0.25174 (9)	0.21269 (9)	0.35781 (7)	0.01027 (10)
HC14	−0.285 (2)	0.102 (2)	0.3040 (18)	0.018 (4)*
O13	−0.37894 (8)	0.28780 (9)	0.35705 (6)	0.01635 (11)
HO13	−0.372 (3)	0.357 (3)	0.434 (2)	0.028 (5)*
C15	−0.09715 (9)	0.29943 (9)	0.31379 (7)	0.01056 (10)
HC15	−0.079 (2)	0.414 (2)	0.3340 (16)	0.012 (3)*
O11	0.03325 (7)	0.27523 (8)	0.37342 (6)	0.01362 (9)
N6	−0.09383 (8)	0.22511 (8)	0.17216 (6)	0.01059 (9)
C16	−0.03118 (10)	0.09397 (10)	0.12053 (7)	0.01339 (11)
HC16	0.011 (2)	0.062 (3)	0.1804 (19)	0.023 (4)*
C17	−0.03108 (11)	0.02816 (11)	−0.01045 (8)	0.01503 (12)
HC17	0.018 (3)	−0.059 (3)	−0.040 (2)	0.028 (5)*
C18	−0.09276 (10)	0.09956 (10)	−0.08761 (7)	0.01397 (12)
HC18	−0.090 (3)	0.061 (3)	−0.180 (2)	0.026 (4)*
C19	−0.15467 (9)	0.23635 (9)	−0.03126 (7)	0.01146 (11)
C21	−0.21200 (10)	0.31981 (10)	−0.11383 (7)	0.01391 (12)
O14	−0.22790 (11)	0.24830 (10)	−0.23135 (6)	0.02096 (13)
N7	−0.24234 (11)	0.46731 (10)	−0.05732 (7)	0.01766 (13)
HN7A	−0.268 (3)	0.524 (3)	−0.107 (2)	0.033 (5)*
HN7B	−0.218 (2)	0.526 (3)	0.0270 (19)	0.023 (4)*
C20	−0.15538 (9)	0.29574 (9)	0.10009 (7)	0.01118 (10)
HC20	−0.190 (2)	0.386 (2)	0.1476 (16)	0.015 (3)*
OW1	0.56459 (9)	−0.10609 (9)	−0.03125 (8)	0.01913 (12)
HW1B	0.514 (2)	−0.042 (2)	−0.0627 (18)	0.024 (4)*
HW1A	0.492 (3)	−0.158 (3)	0.015 (2)	0.048 (7)*
OW2	−0.30386 (9)	−0.33492 (9)	0.78751 (7)	0.01745 (11)
HW2A	−0.353 (3)	−0.260 (3)	0.846 (2)	0.056 (8)*
HW2B	−0.374 (2)	−0.377 (2)	0.7138 (13)	0.024 (4)*
OW3	−0.01426 (8)	−0.21778 (9)	0.67140 (6)	0.01693 (11)
HW3A	−0.1068 (19)	−0.270 (3)	0.701 (2)	0.035 (5)*
HW3B	−0.033 (2)	−0.253 (2)	0.5821 (9)	0.022 (4)*
OW4	0.32682 (9)	0.11814 (10)	0.21374 (8)	0.02130 (12)
HW4A	0.326 (3)	0.0036 (14)	0.179 (2)	0.044 (6)*
HW4B	0.434 (2)	0.170 (4)	0.258 (4)	0.095 (13)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0102 (2)	0.0129 (2)	0.0139 (2)	0.00574 (17)	0.00464 (16)	0.00665 (18)
P1	0.00939 (6)	0.00918 (7)	0.00797 (6)	0.00338 (5)	0.00286 (5)	0.00277 (5)
O2	0.0150 (2)	0.0093 (2)	0.0157 (2)	0.00289 (17)	0.00514 (18)	0.00267 (18)
O3	0.0146 (2)	0.0145 (2)	0.0102 (2)	0.00347 (18)	0.00536 (17)	0.00531 (18)
O4	0.0113 (2)	0.0149 (2)	0.0092 (2)	0.00720 (17)	0.00166 (16)	0.00280 (17)
C1	0.0113 (2)	0.0161 (3)	0.0110 (3)	0.0074 (2)	0.0034 (2)	0.0053 (2)
C2	0.0103 (2)	0.0095 (2)	0.0105 (2)	0.00427 (19)	0.00205 (19)	0.0033 (2)
C3	0.0103 (2)	0.0084 (2)	0.0109 (2)	0.00356 (19)	0.00152 (19)	0.00315 (19)
O6	0.0137 (2)	0.0107 (2)	0.0170 (2)	0.00564 (17)	0.00253 (18)	0.00752 (18)
C4	0.0102 (2)	0.0098 (2)	0.0104 (2)	0.00381 (19)	0.00276 (19)	0.0048 (2)
O7	0.0142 (2)	0.0171 (2)	0.0152 (2)	0.00719 (19)	0.00654 (18)	0.0105 (2)
C5	0.0120 (2)	0.0084 (2)	0.0099 (2)	0.0048 (2)	0.00145 (19)	0.0027 (2)
O5	0.0110 (2)	0.0094 (2)	0.0127 (2)	0.00214 (16)	0.00365 (17)	0.00165 (17)
N1	0.0141 (2)	0.0084 (2)	0.0093 (2)	0.00527 (18)	0.00211 (18)	0.00263 (18)
C6	0.0142 (3)	0.0091 (2)	0.0096 (2)	0.0050 (2)	0.0028 (2)	0.0035 (2)
N2	0.0201 (3)	0.0123 (2)	0.0110 (2)	0.0077 (2)	0.0044 (2)	0.0053 (2)
C7	0.0204 (3)	0.0127 (3)	0.0109 (3)	0.0077 (2)	0.0045 (2)	0.0049 (2)
N3	0.0180 (3)	0.0113 (2)	0.0104 (2)	0.0070 (2)	0.0043 (2)	0.00425 (19)
C8	0.0136 (3)	0.0093 (2)	0.0099 (2)	0.0045 (2)	0.0021 (2)	0.0027 (2)
N5	0.0224 (3)	0.0106 (2)	0.0112 (2)	0.0089 (2)	0.0035 (2)	0.0035 (2)
C9	0.0136 (3)	0.0087 (2)	0.0093 (2)	0.0048 (2)	0.0020 (2)	0.0026 (2)
N4	0.0147 (2)	0.0093 (2)	0.0092 (2)	0.00473 (19)	0.00139 (18)	0.00280 (18)
C10	0.0149 (3)	0.0100 (3)	0.0092 (2)	0.0050 (2)	0.0011 (2)	0.0032 (2)
P2	0.00893 (6)	0.00745 (6)	0.00837 (6)	0.00350 (5)	0.00186 (5)	0.00238 (5)
O8	0.0176 (2)	0.0127 (2)	0.0113 (2)	0.00630 (18)	0.00307 (17)	0.00651 (18)
O9	0.0114 (2)	0.0109 (2)	0.0122 (2)	0.00306 (17)	−0.00031 (17)	0.00005 (17)
O10	0.0121 (2)	0.00812 (19)	0.0116 (2)	0.00513 (16)	−0.00118 (16)	0.00048 (16)
C11	0.0180 (3)	0.0100 (3)	0.0138 (3)	0.0063 (2)	−0.0054 (2)	−0.0001 (2)
C12	0.0148 (3)	0.0090 (2)	0.0088 (2)	0.0039 (2)	−0.0007 (2)	0.0020 (2)
C13	0.0156 (3)	0.0095 (2)	0.0089 (2)	0.0053 (2)	0.0028 (2)	0.0034 (2)
O12	0.0248 (3)	0.0132 (2)	0.0093 (2)	0.0105 (2)	0.00389 (19)	0.00196 (18)
C14	0.0123 (2)	0.0098 (2)	0.0091 (2)	0.0048 (2)	0.00157 (19)	0.0026 (2)
O13	0.0167 (2)	0.0198 (3)	0.0140 (2)	0.0115 (2)	0.00120 (19)	0.0031 (2)
C15	0.0147 (3)	0.0086 (2)	0.0082 (2)	0.0030 (2)	0.0011 (2)	0.00268 (19)
O11	0.0120 (2)	0.0176 (2)	0.0117 (2)	0.00262 (18)	0.00028 (17)	0.00651 (19)
N6	0.0142 (2)	0.0090 (2)	0.0087 (2)	0.00324 (19)	0.00212 (18)	0.00317 (18)
C16	0.0174 (3)	0.0122 (3)	0.0120 (3)	0.0066 (2)	0.0031 (2)	0.0040 (2)
C17	0.0198 (3)	0.0144 (3)	0.0118 (3)	0.0082 (2)	0.0040 (2)	0.0030 (2)
C18	0.0179 (3)	0.0131 (3)	0.0100 (3)	0.0049 (2)	0.0029 (2)	0.0023 (2)
C19	0.0152 (3)	0.0103 (3)	0.0082 (2)	0.0025 (2)	0.0012 (2)	0.0029 (2)
C21	0.0189 (3)	0.0132 (3)	0.0092 (3)	0.0032 (2)	0.0001 (2)	0.0040 (2)
O14	0.0358 (4)	0.0190 (3)	0.0080 (2)	0.0093 (3)	0.0002 (2)	0.0030 (2)
N7	0.0292 (4)	0.0148 (3)	0.0101 (2)	0.0090 (3)	−0.0011 (2)	0.0035 (2)
C20	0.0157 (3)	0.0096 (2)	0.0087 (2)	0.0037 (2)	0.0017 (2)	0.0034 (2)
OW1	0.0176 (3)	0.0203 (3)	0.0251 (3)	0.0078 (2)	0.0093 (2)	0.0129 (2)
OW2	0.0193 (3)	0.0194 (3)	0.0152 (2)	0.0092 (2)	0.0008 (2)	0.0052 (2)
OW3	0.0162 (2)	0.0207 (3)	0.0143 (2)	0.0064 (2)	0.00351 (19)	0.0053 (2)
OW4	0.0199 (3)	0.0199 (3)	0.0244 (3)	0.0045 (2)	−0.0003 (2)	0.0088 (3)

Geometric parameters (Å, º)

O1—P1	1.580 (2)	O10—C11	1.4453 (18)
O1—P2	1.630 (2)	C11—C12	1.507 (2)
P1—O3	1.498 (1)	C11—H11A	0.96 (2)
P1—O2	1.500 (2)	C11—H11B	1.03 (2)
P1—O4	1.598 (2)	C12—O11	1.4520 (15)
O4—C1	1.448 (2)	C12—C13	1.533 (2)
C1—C2	1.509 (2)	C12—HC12	0.98 (2)
C1—HC1A	0.95 (2)	C13—O12	1.4210 (17)
C1—HC1B	0.90 (2)	C13—C14	1.5333 (17)
C2—O5	1.4553 (18)	C13—HC13	0.99 (2)
C2—C3	1.5286 (16)	O12—HO12	0.86 (2)
C2—HC2	0.94 (2)	C14—O13	1.4102 (16)
C3—O6	1.4285 (14)	C14—C15	1.5403 (18)
C3—C4	1.5333 (16)	C14—HC14	0.93 (2)
C3—HC3	0.96 (2)	O13—HO13	0.86 (2)
O6—HO6	0.83 (2)	C15—O11	1.3940 (16)
C4—O7	1.4103 (14)	C15—N6	1.502 (2)
C4—C5	1.5457 (19)	C15—HC15	0.93 (2)
C4—HC4	0.91 (2)	N6—C20	1.345 (1)
O7—HO7	0.86 (2)	N6—C16	1.351 (2)
C5—O5	1.4085 (15)	C16—C17	1.384 (2)
C5—N1	1.466 (2)	C16—HC16	0.91 (2)
C5—HC5	0.93 (2)	C17—C18	1.394 (2)
N1—C6	1.367 (2)	C17—HC17	0.93 (2)
N1—C10	1.371 (1)	C18—C19	1.396 (2)
C6—N2	1.356 (2)	C18—HC18	0.97 (2)
C6—C9	1.391 (2)	C19—C20	1.386 (2)
N2—C7	1.317 (2)	C19—C21	1.505 (2)
C7—N3	1.361 (2)	C21—O14	1.243 (2)
C7—HC7	0.88 (2)	C21—N7	1.335 (2)
N3—C8	1.367 (2)	N7—HN7A	0.92 (2)
N3—HN3	0.91 (2)	N7—HN7B	0.91 (2)
C8—N5	1.320 (2)	C20—HC20	0.92 (2)
C8—C9	1.412 (2)	OW1—HW1B	0.937 (9)
N5—HN5A	0.86 (2)	OW1—HW1A	0.94 (1)
N5—HN5B	0.89 (2)	OW2—HW2A	0.95 (1)
C9—N4	1.378 (2)	OW2—HW2B	0.926 (9)
N4—C10	1.322 (2)	OW3—HW3A	0.94 (1)
C10—HC10	0.96 (2)	OW3—HW3B	0.941 (9)
P2—O9	1.484 (2)	OW4—HW4A	0.95 (1)
P2—O8	1.487 (1)	OW4—HW4B	0.97 (1)
P2—O10	1.599 (2)
P1—O1—P2	132.45 (7)	O9—P2—O10	107.15 (8)
O3—P1—O2	115.86 (7)	O8—P2—O10	110.97 (7)
O3—P1—O1	107.14 (7)	O9—P2—O1	108.60 (9)
O2—P1—O1	112.13 (8)	O8—P2—O1	108.98 (7)
O3—P1—O4	109.93 (8)	O10—P2—O1	98.58 (7)
O2—P1—O4	110.20 (7)	C11—O10—P2	116.34 (8)
O1—P1—O4	100.45 (8)	O10—C11—C12	108.51 (9)
C1—O4—P1	115.82 (8)	O10—C11—H11A	111.3 (12)
O4—C1—C2	109.59 (7)	C12—C11—H11A	108.8 (12)
O4—C1—HC1A	110.3 (12)	O10—C11—H11B	109.9 (13)
C2—C1—HC1A	108.7 (12)	C12—C11—H11B	109.0 (13)
O4—C1—HC1B	109.4 (14)	H11A—C11—H11B	109.3 (17)
C2—C1—HC1B	109.5 (14)	O11—C12—C11	108.96 (8)
HC1A—C1—HC1B	109 (2)	O11—C12—C13	106.98 (7)
O5—C2—C1	109.62 (10)	C11—C12—C13	114.01 (8)
O5—C2—C3	106.11 (9)	O11—C12—HC12	108.2 (10)
C1—C2—C3	115.44 (9)	C11—C12—HC12	105.9 (10)
O5—C2—HC2	107.9 (12)	C13—C12—HC12	112.7 (10)
C1—C2—HC2	106.3 (12)	O12—C13—C12	112.06 (9)
C3—C2—HC2	111.3 (12)	O12—C13—C14	107.29 (9)
O6—C3—C2	106.99 (10)	C12—C13—C14	103.17 (8)
O6—C3—C4	111.17 (9)	O12—C13—HC13	110.6 (11)
C2—C3—C4	102.48 (10)	C12—C13—HC13	112.3 (10)
O6—C3—HC3	111.7 (12)	C14—C13—HC13	111.1 (11)
C2—C3—HC3	112.8 (12)	C13—O12—HO12	102.7 (16)
C4—C3—HC3	111.3 (12)	O13—C14—C13	113.55 (8)
C3—O6—HO6	109.8 (12)	O13—C14—C15	112.79 (10)
O7—C4—C3	113.11 (9)	C13—C14—C15	102.22 (9)
O7—C4—C5	112.96 (9)	O13—C14—HC14	108.8 (12)
C3—C4—C5	101.54 (11)	C13—C14—HC14	110.4 (11)
O7—C4—HC4	109.3 (11)	C15—C14—HC14	108.9 (12)
C3—C4—HC4	108.4 (11)	C14—O13—HO13	104.6 (14)
C5—C4—HC4	111.3 (11)	O11—C15—N6	108.26 (9)
C4—O7—HO7	113.0 (16)	O11—C15—C14	107.50 (10)
O5—C5—N1	107.33 (8)	N6—C15—C14	111.30 (9)
O5—C5—C4	106.98 (9)	O11—C15—HC15	106.4 (10)
N1—C5—C4	113.55 (10)	N6—C15—HC15	107.1 (10)
O5—C5—HC5	112.1 (12)	C14—C15—HC15	116.0 (10)
N1—C5—HC5	106.5 (12)	C15—O11—C12	110.42 (9)
C4—C5—HC5	110.5 (12)	C20—N6—C16	122.02 (9)
C5—O5—C2	110.28 (8)	C20—N6—C15	116.82 (9)
C6—N1—C10	106.23 (10)	C16—N6—C15	121.16 (7)
C6—N1—C5	126.99 (8)	N6—C16—C17	119.53 (8)
C10—N1—C5	126.78 (8)	N6—C16—HC16	112.9 (13)
N2—C6—N1	127.35 (9)	C17—C16—HC16	127.5 (13)
N2—C6—C9	126.83 (8)	C16—C17—C18	119.78 (10)
N1—C6—C9	105.80 (9)	C16—C17—HC17	115.8 (13)
C7—N2—C6	112.19 (10)	C18—C17—HC17	124.3 (13)
N2—C7—N3	125.41 (9)	C17—C18—C19	119.31 (9)
N2—C7—HC7	121.8 (13)	C17—C18—HC18	122.4 (12)
N3—C7—HC7	112.6 (13)	C19—C18—HC18	118.3 (12)
C7—N3—C8	123.37 (8)	C20—C19—C18	118.86 (8)
C7—N3—HN3	113.8 (12)	C20—C19—C21	121.80 (9)
C8—N3—HN3	122.8 (12)	C18—C19—C21	119.29 (9)
N5—C8—N3	119.80 (8)	O14—C21—N7	123.24 (9)
N5—C8—C9	126.39 (9)	O14—C21—C19	118.32 (10)
N3—C8—C9	113.81 (9)	N7—C21—C19	118.44 (10)
C8—N5—HN5A	119.0 (14)	C21—N7—HN7A	119.3 (15)
C8—N5—HN5B	121.3 (14)	C21—N7—HN7B	123.5 (13)
HN5A—N5—HN5B	118.6 (19)	HN7A—N7—HN7B	116 (2)
N4—C9—C6	110.62 (8)	N6—C20—C19	120.48 (9)
N4—C9—C8	131.16 (8)	N6—C20—HC20	112.8 (11)
C6—C9—C8	118.22 (9)	C19—C20—HC20	126.7 (11)
C10—N4—C9	104.11 (8)	HW1B—OW1—HW1A	109.0 (19)
N4—C10—N1	113.24 (9)	HW2A—OW2—HW2B	104 (2)
N4—C10—HC10	124.1 (11)	HW3A—OW3—HW3B	107.1 (18)
N1—C10—HC10	122.6 (11)	HW4A—OW4—HW4B	103 (3)
O9—P2—O8	120.34 (8)
P2—O1—P1—O3	160.9 (1)	C8—C9—N4—C10	−179.33 (8)
P2—O1—P1—O2	32.7 (1)	C9—N4—C10—N1	−0.23 (9)
P2—O1—P1—O4	−84.3 (1)	C6—N1—C10—N4	−0.43 (9)
O3—P1—O4—C1	−64.8 (1)	C5—N1—C10—N4	−179.77 (7)
O2—P1—O4—C1	64.1 (1)	P1—O1—P2—O9	−87.7 (1)
O1—P1—O4—C1	−177.5 (1)	P1—O1—P2—O8	45.2 (1)
P1—O4—C1—C2	−147.2 (1)	P1—O1—P2—O10	160.9 (1)
O4—C1—C2—O5	−64.9 (1)	O9—P2—O10—C11	177.5 (1)
O4—C1—C2—C3	54.81 (11)	O8—P2—O10—C11	44.3 (1)
O5—C2—C3—O6	−88.45 (10)	O1—P2—O10—C11	−69.9 (1)
C1—C2—C3—O6	149.92 (7)	P2—O10—C11—C12	170.2 (1)
O5—C2—C3—C4	28.58 (8)	O10—C11—C12—O11	−71.3 (1)
C1—C2—C3—C4	−93.06 (10)	O10—C11—C12—C13	48.1 (1)
O6—C3—C4—O7	−41.97 (10)	O11—C12—C13—O12	−94.00 (11)
C2—C3—C4—O7	−155.96 (7)	C11—C12—C13—O12	145.48 (8)
O6—C3—C4—C5	79.36 (10)	O11—C12—C13—C14	21.10 (8)
C2—C3—C4—C5	−34.63 (8)	C11—C12—C13—C14	−99.42 (9)
O7—C4—C5—O5	151.39 (7)	O12—C13—C14—O13	−32.88 (9)
C3—C4—C5—O5	29.95 (7)	C12—C13—C14—O13	−151.36 (7)
O7—C4—C5—N1	−90.40 (9)	O12—C13—C14—C15	88.89 (10)
C3—C4—C5—N1	148.17 (7)	C12—C13—C14—C15	−29.58 (8)
N1—C5—O5—C2	−134.87 (9)	O13—C14—C15—O11	151.64 (7)
C4—C5—O5—C2	−12.67 (7)	C13—C14—C15—O11	29.34 (8)
C1—C2—O5—C5	115.11 (9)	O13—C14—C15—N6	−89.96 (10)
C3—C2—O5—C5	−10.19 (7)	C13—C14—C15—N6	147.74 (7)
O5—C5—N1—C6	−144.2 (1)	N6—C15—O11—C12	−137.18 (8)
C4—C5—N1—C6	97.79 (11)	C14—C15—O11—C12	−16.83 (8)
O5—C5—N1—C10	35.01 (11)	C11—C12—O11—C15	120.80 (9)
C4—C5—N1—C10	−83.00 (11)	C13—C12—O11—C15	−2.90 (8)
C10—N1—C6—N2	−177.65 (8)	O11—C15—N6—C20	−150.33 (7)
C5—N1—C6—N2	1.68 (13)	C14—C15—N6—C20	91.73 (12)
C10—N1—C6—C9	0.89 (8)	O11—C15—N6—C16	29.43 (10)
C5—N1—C6—C9	−179.77 (7)	C14—C15—N6—C16	−88.52 (12)
N1—C6—N2—C7	−178.19 (8)	C20—N6—C16—C17	−0.65 (12)
C9—C6—N2—C7	3.6 (1)	C15—N6—C16—C17	179.61 (7)
C6—N2—C7—N3	−0.97 (13)	N6—C16—C17—C18	1.18 (13)
N2—C7—N3—C8	−2.83 (14)	C16—C17—C18—C19	−0.33 (13)
C7—N3—C8—N5	−176.85 (8)	C17—C18—C19—C20	−1.04 (12)
C7—N3—C8—C9	3.86 (11)	C17—C18—C19—C21	176.32 (8)
N2—C6—C9—N4	177.47 (8)	C20—C19—C21—O14	−170.77 (8)
N1—C6—C9—N4	−1.09 (9)	C18—C19—C21—O14	11.95 (12)
N2—C6—C9—C8	−2.4 (1)	C20—C19—C21—N7	9.6 (1)
N1—C6—C9—C8	179.04 (7)	C18—C19—C21—N7	−167.67 (8)
N5—C8—C9—N4	−0.49 (14)	C16—N6—C20—C19	−0.76 (12)
N3—C8—C9—N4	178.74 (8)	C15—N6—C20—C19	178.99 (7)
N5—C8—C9—C6	179.35 (8)	C18—C19—C20—N6	1.59 (11)
N3—C8—C9—C6	−1.42 (10)	C21—C19—C20—N6	−175.69 (7)
C6—C9—N4—C10	0.82 (8)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O6—HO6···N4^i	0.83 (2)	1.99 (2)	2.764 (3)	154 (2)
O7—HO7···OW3	0.86 (2)	1.86 (2)	2.693 (3)	161 (2)
O12—HO12···O14^ii	0.86 (2)	1.90 (2)	2.719 (2)	161 (2)
O13—HO13···O12	0.86 (2)	2.05 (2)	2.629 (3)	124 (2)
O13—HO13···O6^iii	0.86 (2)	2.20 (2)	2.905 (3)	139 (2)
N3—HN3···O2^iv	0.91 (2)	1.72 (2)	2.615 (2)	165 (2)
N5—HN5A···O3^iv	0.86 (2)	1.99 (2)	2.830 (3)	166 (2)
N5—HN5B···O7^v	0.89 (2)	1.97 (2)	2.823 (2)	159 (2)
N7—HN7A···OW2^vi	0.92 (2)	2.06 (2)	2.971 (2)	174 (2)
N7—HN7B···O9^v	0.91 (2)	1.92 (2)	2.815 (3)	171 (2)
OW1—HW1A···O3	0.94 (1)	1.87 (1)	2.790 (3)	164 (2)
OW1—HW1B···N2^vii	0.94 (1)	2.04 (1)	2.975 (3)	176 (2)
OW2—HW2A···OW1^viii	0.95 (1)	1.86 (1)	2.806 (3)	175 (3)
OW2—HW2B···O6^ix	0.93 (1)	1.95 (1)	2.877 (3)	175 (2)
OW3—HW3A···OW2	0.94 (1)	2.02 (1)	2.947 (3)	168 (2)
OW3—HW3B···O8	0.94 (1)	1.82 (1)	2.746 (3)	168 (2)
OW4—HW4A···O3	0.95 (1)	1.95 (1)	2.900 (4)	173 (2)
OW4—HW4B···O13^x	0.97 (1)	1.81 (1)	2.773 (3)	172 (4)

Symmetry codes: (i) x, y−1, z; (ii) x, y, z+1; (iii) x−1, y+1, z; (iv) x, y+1, z+1; (v) x, y+1, z; (vi) x, y+1, z−1; (vii) x, y, z−1; (viii) x−1, y, z+1; (ix) x−1, y, z; (x) x+1, y, z.