Bis(6-nitro-1,10-phenanthrolin-1-ium) 2,5-di-carb-oxy-terephthalate.

In the structure of the title 2:1 proton-transfer compound, 2C12H8N3O2 (+)·C10H4O8 (2-), the 6-nitro-1,10-phenanthroline mol-ecules act as proton sponges, accepting protons from pyromellitic acid. The -NO2 group of one of the 6-nitro-1,10-phenanthrolin-1-ium cations is disordered and was refined with a site-occupancy ratio of 0.624 (15):0.376 (15). Two -COOH(-COO(-)) groups of the 2,5-di-carb-oxy-terephthalate dianion are disordered and were refined with site-occupancy ratios of 0.769 (4):0.231 (4) and 0.766 (5):0.234 (5). The -NO2 group of the second cation is also disordered about a pseudo-twofold rotation axis and was refined with a site-occupancy ratio of 0.903 (3):0.097 (3). There is an intra-molecular O-H⋯O hydrogen bond in the anion. The phenanthroline rings of the two cations are inclined to one another by 31.3 (1)°. In the anions, considering the major components only, the carb-oxy-lic acid groups (-COOH) are inclined to the benzene ring by 17.3 (2) and 22.3 (3)°. The carboxyl-ate groups (-COO(-)) are twisted by 9.3 (2) and 13.6 (6)° with respect to the benzene ring. In the crystal, adjacent 2,5-di-carb-oxy-terephthalate anions are linked via O-H⋯O hydrogen bonds, forming chains propagating along [010]. The cations are attached to the chain of anions by N-H⋯O hydrogen bonds.

Related literature

For related structures involving pyromellitic acid, see: Li et al. (2003 ▶); Guo et al. (2007 ▶); Fabelo et al. (2008 ▶); Zhong (2013 ▶).

Experimental

Crystal data

2C12H8N3O2 +·C10H4O8 2−

M = 704.56

Triclinic,

a = 8.5937 (6) Å

b = 9.8302 (7) Å

c = 18.8700 (14) Å

α = 77.810 (2)°

β = 83.622 (2)°

γ = 68.025 (2)°

V = 1444.05 (18) Å3

Z = 2

Mo Kα radiation

μ = 0.13 mm−1

T = 223 K

0.25 × 0.20 × 0.15 mm

Data collection

Rigaku Mercury CCD diffractometer

Absorption correction: multi-scan (REQAB; Jacobson, 1998 ▶) T min = 0.969, T max = 0.981

30563 measured reflections

5237 independent reflections

3942 reflections with I > 2σ(I)

R int = 0.036

Refinement

R[F 2 > 2σ(F 2)] = 0.068

wR(F 2) = 0.191

S = 1.05

5237 reflections

518 parameters

24 restraints

H-atom parameters constrained

Δρmax = 0.72 e Å−3

Δρmin = −0.73 e Å−3

Data collection: CrystalClear (Rigaku, 2007 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: XP in SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536814002414/su2687sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814002414/su2687Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S1600536814002414/su2687Isup3.cml

CCDC reference:

Additional supporting information: crystallographic information; 3D view; checkCIF report

2C12H8N3O2+·C10H4O82−	Z = 2
Mr = 704.56	F(000) = 724
Triclinic, P1	Dx = 1.620 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.5937 (6) Å	Cell parameters from 9974 reflections
b = 9.8302 (7) Å	θ = 2.3–27.2°
c = 18.8700 (14) Å	µ = 0.13 mm−1
α = 77.810 (2)°	T = 223 K
β = 83.622 (2)°	Block, pink
γ = 68.025 (2)°	0.25 × 0.20 × 0.15 mm
V = 1444.05 (18) Å3

Rigaku Mercury CCD diffractometer	5237 independent reflections
Radiation source: fine-focus sealed tube	3942 reflections with I > 2σ(I)
Graphite Monochromator monochromator	Rint = 0.036
Detector resolution: 28.5714 pixels mm-1	θmax = 25.3°, θmin = 2.3°
ω scans	h = −10→10
Absorption correction: multi-scan (REQAB; Jacobson, 1998)	k = −11→11
Tmin = 0.969, Tmax = 0.981	l = −22→22
30563 measured 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)] = 0.068	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.191	H-atom parameters constrained
S = 1.05	w = 1/[σ2(Fo2) + (0.0939P)2 + 1.9537P] where P = (Fo2 + 2Fc2)/3
5237 reflections	(Δ/σ)max = 0.001
518 parameters	Δρmax = 0.72 e Å−3
24 restraints	Δρmin = −0.73 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 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.

	x	y	z	Uiso*/Ueq	Occ. (<1)
O1	0.3137 (4)	0.3400 (3)	0.5554 (2)	0.0744 (12)	0.903 (3)
O1'	0.491 (4)	−0.164 (2)	0.6658 (19)	0.0744 (12)	0.097 (3)
O2	0.3275 (5)	0.1593 (4)	0.64151 (19)	0.0756 (12)	0.903 (3)
O2'	0.381 (4)	0.069 (3)	0.6705 (19)	0.0756 (12)	0.097 (3)
O3	−0.1801 (12)	0.5821 (17)	0.2706 (6)	0.068 (3)	0.624 (15)
O3'	−0.123 (3)	0.582 (3)	0.2876 (10)	0.094 (7)	0.376 (15)
O4	0.0292 (11)	0.4192 (7)	0.2234 (3)	0.065 (3)	0.624 (15)
O4'	−0.0960 (19)	0.4854 (14)	0.1923 (7)	0.082 (5)	0.376 (15)
O5	0.5115 (3)	0.4118 (3)	0.20188 (16)	0.0523 (7)
O6	0.2903 (4)	0.4939 (3)	0.27486 (15)	0.0641 (9)
H6O	0.2334	0.5721	0.2898	0.096*
O7'	0.1076 (4)	0.8482 (3)	0.33626 (16)	0.0324 (8)	0.769 (4)
O7	0.1737 (14)	0.8568 (10)	0.3577 (6)	0.0324 (8)	0.231 (4)
O8'	0.3302 (4)	0.6580 (3)	0.38628 (16)	0.0420 (8)	0.769 (4)
O8	0.2274 (13)	0.6234 (9)	0.3520 (5)	0.0420 (8)	0.231 (4)
O9	0.5320 (5)	1.1519 (3)	0.11200 (17)	0.0479 (11)	0.766 (5)
O9'	0.3760 (13)	1.1813 (10)	0.1143 (5)	0.045 (3)	0.234 (5)
O10	0.4440 (6)	1.1561 (4)	0.22447 (18)	0.0537 (11)	0.766 (5)
H10O	0.4491	1.2406	0.2125	0.081*	0.766 (5)
O10'	0.5481 (17)	1.1344 (13)	0.2056 (6)	0.0537 (11)	0.234 (5)
H10'	0.5945	1.0636	0.2383	0.081*	0.234 (5)
O11	0.6743 (3)	0.9654 (3)	0.04547 (15)	0.0536 (7)
O12	0.7415 (5)	0.7292 (3)	0.04701 (17)	0.0751 (11)
N1	0.3874 (4)	0.2155 (4)	0.58681 (16)	0.0355 (8)	0.903 (3)
N1'	0.475 (2)	−0.0347 (19)	0.6420 (9)	0.0355 (8)	0.097 (3)
H12A	0.5463	−0.0502	0.6377	0.043*	0.903 (3)
N2	0.8495 (3)	0.1032 (3)	0.39818 (13)	0.0283 (6)
H2N'	0.9372	0.0357	0.3824	0.034*	0.097 (3)
N3	0.9666 (3)	−0.1817 (3)	0.47071 (13)	0.0245 (6)
H3N	1.0141	−0.1538	0.4300	0.029*	0.903 (3)
N4	−0.0665 (5)	0.5579 (4)	0.2275 (2)	0.0570 (9)
N5	0.2343 (4)	0.7762 (3)	0.02188 (14)	0.0364 (7)
N6	0.1136 (3)	1.0338 (3)	0.07212 (14)	0.0336 (6)
H6N	0.1811	1.0217	0.0341	0.040*
C1	0.5424 (4)	0.1202 (4)	0.55391 (17)	0.0293 (7)
H1A	0.4448	0.1871	0.5728	0.035*	0.097 (3)
C2	0.6201 (4)	0.1748 (3)	0.48754 (16)	0.0258 (7)
C3	0.7642 (4)	0.0698 (3)	0.45973 (15)	0.0231 (6)
C4	0.7944 (4)	0.2422 (3)	0.36302 (17)	0.0334 (7)
H4	0.8522	0.2669	0.3199	0.040*
C5	0.6551 (4)	0.3547 (3)	0.38622 (18)	0.0355 (8)
H5	0.6222	0.4526	0.3596	0.043*
C6	0.5674 (4)	0.3217 (3)	0.44759 (18)	0.0330 (7)
H6	0.4723	0.3964	0.4633	0.040*
C7	0.8291 (3)	−0.0827 (3)	0.49830 (15)	0.0222 (6)
C8	1.0286 (4)	−0.3212 (3)	0.50596 (17)	0.0299 (7)
H8	1.1248	−0.3884	0.4863	0.036*
C9	0.9570 (4)	−0.3723 (4)	0.57085 (18)	0.0346 (8)
H9	1.0041	−0.4721	0.5944	0.042*
C10	0.8179 (4)	−0.2759 (4)	0.59978 (17)	0.0327 (7)
H10	0.7677	−0.3083	0.6436	0.039*
C11	0.7504 (4)	−0.1275 (3)	0.56345 (16)	0.0261 (7)
C12	0.6032 (4)	−0.0210 (4)	0.58953 (17)	0.0307 (7)
C13	−0.0143 (5)	0.6806 (4)	0.18440 (19)	0.0414 (9)
C14	0.0943 (4)	0.6569 (4)	0.12056 (18)	0.0389 (8)
C15	0.1353 (4)	0.7798 (4)	0.08272 (17)	0.0315 (7)
C16	0.2957 (5)	0.6494 (4)	−0.0025 (2)	0.0450 (9)
H16	0.3643	0.6450	−0.0451	0.054*
C17	0.2641 (6)	0.5225 (4)	0.0315 (2)	0.0543 (10)
H17	0.3117	0.4345	0.0122	0.065*
C18	0.1644 (5)	0.5253 (4)	0.0926 (2)	0.0512 (10)
H18	0.1428	0.4393	0.1160	0.061*
C19	0.0706 (4)	0.9189 (4)	0.10846 (16)	0.0308 (7)
C20	0.0556 (5)	1.1644 (4)	0.0928 (2)	0.0434 (9)
H20	0.0873	1.2428	0.0661	0.052*
C21	−0.0522 (5)	1.1882 (5)	0.1538 (2)	0.0524 (10)
H21	−0.0954	1.2823	0.1675	0.063*
C22	−0.0935 (5)	1.0725 (5)	0.1930 (2)	0.0469 (9)
H22	−0.1623	1.0857	0.2352	0.056*
C23	−0.0344 (4)	0.9347 (4)	0.17093 (17)	0.0360 (8)
C24	−0.0752 (4)	0.8099 (4)	0.20862 (18)	0.0411 (9)
H24	−0.1452	0.8184	0.2507	0.049*
C25	0.4054 (5)	0.5133 (4)	0.23522 (19)	0.0401 (9)
C26	0.4305 (4)	0.6590 (3)	0.21941 (16)	0.0254 (6)
C27	0.3503 (4)	0.7690 (3)	0.26201 (16)	0.0251 (6)
C28	0.2554 (4)	0.7475 (3)	0.33295 (16)	0.0299 (7)
C29	0.3697 (4)	0.9063 (3)	0.24121 (16)	0.0283 (7)
H29	0.3145	0.9802	0.2693	0.034*
C30	0.4667 (4)	0.9397 (3)	0.18090 (16)	0.0274 (7)
C31	0.4709 (5)	1.0956 (4)	0.16873 (18)	0.0449 (10)
C32	0.5472 (4)	0.8295 (3)	0.13834 (16)	0.0273 (7)
C33	0.6613 (4)	0.8400 (4)	0.07175 (17)	0.0340 (8)
C34	0.5260 (4)	0.6923 (3)	0.15919 (16)	0.0268 (7)
H34	0.5796	0.6187	0.1307	0.032*

	U11	U22	U33	U12	U13	U23
O1	0.064 (2)	0.0355 (18)	0.093 (3)	0.0035 (16)	0.0379 (19)	−0.0064 (17)
O1'	0.064 (2)	0.0355 (18)	0.093 (3)	0.0035 (16)	0.0379 (19)	−0.0064 (17)
O2	0.065 (2)	0.070 (3)	0.057 (2)	0.0023 (19)	0.0344 (18)	−0.0056 (18)
O2'	0.065 (2)	0.070 (3)	0.057 (2)	0.0023 (19)	0.0344 (18)	−0.0056 (18)
O3	0.059 (5)	0.075 (4)	0.063 (5)	−0.036 (5)	0.018 (4)	0.015 (4)
O3'	0.090 (14)	0.104 (10)	0.071 (11)	−0.043 (12)	0.026 (9)	0.020 (9)
O4	0.102 (6)	0.051 (4)	0.058 (3)	−0.048 (4)	0.003 (3)	−0.006 (3)
O4'	0.096 (11)	0.066 (7)	0.106 (9)	−0.056 (8)	0.017 (8)	−0.020 (7)
O5	0.0588 (17)	0.0277 (13)	0.0744 (19)	−0.0193 (12)	0.0006 (14)	−0.0126 (13)
O6	0.093 (2)	0.070 (2)	0.0496 (17)	−0.0616 (19)	0.0145 (16)	−0.0015 (14)
O7'	0.0319 (19)	0.0326 (14)	0.0226 (17)	−0.0022 (14)	0.0039 (13)	−0.0037 (12)
O7	0.0319 (19)	0.0326 (14)	0.0226 (17)	−0.0022 (14)	0.0039 (13)	−0.0037 (12)
O8'	0.0454 (19)	0.0321 (16)	0.0299 (16)	0.0002 (13)	0.0076 (13)	0.0028 (13)
O8	0.0454 (19)	0.0321 (16)	0.0299 (16)	0.0002 (13)	0.0076 (13)	0.0028 (13)
O9	0.075 (3)	0.0351 (18)	0.0397 (19)	−0.0317 (18)	0.0217 (17)	−0.0100 (14)
O9'	0.053 (8)	0.029 (5)	0.057 (7)	−0.024 (5)	−0.009 (5)	0.005 (5)
O10	0.094 (4)	0.0337 (17)	0.045 (2)	−0.040 (2)	0.0231 (19)	−0.0130 (15)
O10'	0.094 (4)	0.0337 (17)	0.045 (2)	−0.040 (2)	0.0231 (19)	−0.0130 (15)
O11	0.0618 (18)	0.0396 (15)	0.0605 (17)	−0.0292 (13)	0.0254 (14)	−0.0053 (13)
O12	0.109 (3)	0.064 (2)	0.073 (2)	−0.0548 (19)	0.0611 (19)	−0.0440 (17)
N1	0.0292 (17)	0.0409 (19)	0.0323 (17)	−0.0057 (14)	0.0047 (13)	−0.0140 (14)
N1'	0.0292 (17)	0.0409 (19)	0.0323 (17)	−0.0057 (14)	0.0047 (13)	−0.0140 (14)
N2	0.0332 (15)	0.0240 (13)	0.0267 (13)	−0.0109 (11)	0.0042 (11)	−0.0044 (11)
N3	0.0264 (13)	0.0217 (13)	0.0247 (13)	−0.0092 (10)	0.0057 (10)	−0.0049 (10)
N4	0.066 (3)	0.071 (3)	0.046 (2)	−0.044 (2)	0.0018 (18)	0.0004 (18)
N5	0.0405 (17)	0.0386 (16)	0.0285 (14)	−0.0132 (13)	0.0065 (12)	−0.0088 (12)
N6	0.0363 (15)	0.0400 (16)	0.0277 (14)	−0.0168 (13)	0.0070 (11)	−0.0116 (12)
C1	0.0217 (16)	0.0374 (18)	0.0308 (17)	−0.0081 (14)	0.0014 (13)	−0.0164 (14)
C2	0.0225 (15)	0.0272 (16)	0.0289 (16)	−0.0068 (12)	−0.0027 (12)	−0.0110 (13)
C3	0.0227 (15)	0.0238 (15)	0.0241 (15)	−0.0098 (12)	−0.0003 (12)	−0.0052 (12)
C4	0.044 (2)	0.0289 (17)	0.0267 (16)	−0.0151 (15)	0.0006 (14)	−0.0007 (13)
C5	0.043 (2)	0.0213 (16)	0.0372 (18)	−0.0068 (14)	−0.0065 (15)	−0.0010 (13)
C6	0.0302 (17)	0.0253 (16)	0.0383 (18)	−0.0014 (13)	−0.0043 (14)	−0.0097 (14)
C7	0.0208 (15)	0.0248 (15)	0.0225 (14)	−0.0093 (12)	−0.0005 (11)	−0.0060 (12)
C8	0.0297 (17)	0.0232 (15)	0.0335 (17)	−0.0054 (13)	−0.0009 (13)	−0.0061 (13)
C9	0.0413 (19)	0.0237 (16)	0.0364 (18)	−0.0120 (14)	−0.0037 (15)	0.0016 (13)
C10	0.0381 (19)	0.0339 (18)	0.0265 (16)	−0.0182 (15)	0.0023 (13)	0.0018 (14)
C11	0.0259 (16)	0.0313 (16)	0.0246 (15)	−0.0145 (13)	0.0013 (12)	−0.0062 (12)
C12	0.0281 (17)	0.0405 (19)	0.0277 (16)	−0.0164 (14)	0.0066 (13)	−0.0113 (14)
C13	0.043 (2)	0.055 (2)	0.0313 (18)	−0.0286 (18)	−0.0008 (15)	0.0009 (16)
C14	0.041 (2)	0.045 (2)	0.0332 (18)	−0.0209 (17)	−0.0028 (15)	−0.0015 (15)
C15	0.0331 (18)	0.0369 (18)	0.0263 (16)	−0.0156 (14)	0.0014 (13)	−0.0055 (13)
C16	0.052 (2)	0.039 (2)	0.043 (2)	−0.0147 (17)	0.0113 (17)	−0.0165 (17)
C17	0.066 (3)	0.038 (2)	0.061 (3)	−0.0191 (19)	0.011 (2)	−0.0184 (19)
C18	0.064 (3)	0.038 (2)	0.056 (2)	−0.0261 (19)	0.007 (2)	−0.0073 (18)
C19	0.0302 (17)	0.0432 (19)	0.0221 (15)	−0.0161 (15)	−0.0002 (13)	−0.0075 (14)
C20	0.047 (2)	0.044 (2)	0.045 (2)	−0.0211 (17)	0.0122 (17)	−0.0201 (17)
C21	0.057 (3)	0.055 (2)	0.054 (2)	−0.023 (2)	0.0160 (19)	−0.031 (2)
C22	0.044 (2)	0.066 (3)	0.038 (2)	−0.0224 (19)	0.0148 (16)	−0.0285 (19)
C23	0.0324 (18)	0.055 (2)	0.0256 (16)	−0.0192 (16)	0.0024 (13)	−0.0133 (15)
C24	0.0369 (19)	0.066 (3)	0.0248 (17)	−0.0262 (18)	0.0030 (14)	−0.0050 (16)
C25	0.055 (2)	0.0309 (18)	0.0377 (19)	−0.0223 (17)	−0.0136 (17)	0.0062 (15)
C26	0.0263 (16)	0.0225 (15)	0.0263 (15)	−0.0094 (12)	−0.0037 (12)	0.0004 (12)
C27	0.0249 (15)	0.0244 (15)	0.0251 (15)	−0.0087 (12)	−0.0012 (12)	−0.0026 (12)
C28	0.0340 (18)	0.0208 (15)	0.0310 (17)	−0.0074 (14)	0.0059 (14)	−0.0047 (13)
C29	0.0324 (17)	0.0255 (16)	0.0253 (16)	−0.0086 (13)	0.0032 (13)	−0.0066 (12)
C30	0.0292 (16)	0.0250 (16)	0.0271 (16)	−0.0101 (13)	0.0007 (12)	−0.0030 (12)
C31	0.054 (2)	0.0260 (17)	0.049 (2)	−0.0144 (17)	0.0295 (19)	−0.0101 (16)
C32	0.0310 (17)	0.0283 (16)	0.0240 (15)	−0.0129 (13)	0.0012 (12)	−0.0050 (12)
C33	0.042 (2)	0.0395 (19)	0.0274 (17)	−0.0221 (16)	0.0069 (14)	−0.0117 (15)
C34	0.0313 (17)	0.0247 (15)	0.0253 (15)	−0.0101 (13)	0.0004 (13)	−0.0069 (12)

O1—N1	1.203 (4)	C4—C5	1.395 (5)
O1'—N1'	1.219 (18)	C4—H4	0.9400
O1'—H12A	1.3632	C5—C6	1.358 (5)
O2—N1	1.220 (4)	C5—H5	0.9400
O2'—N1'	1.223 (19)	C6—H6	0.9400
O3—N4	1.184 (10)	C7—C11	1.405 (4)
O3'—N4	1.218 (17)	C8—C9	1.391 (5)
O4—N4	1.316 (7)	C8—H8	0.9400
O4'—N4	1.177 (10)	C9—C10	1.360 (5)
O5—C25	1.296 (4)	C9—H9	0.9400
O6—C25	1.221 (5)	C10—C11	1.402 (4)
O6—H6O	0.8300	C10—H10	0.9400
O7'—C28	1.290 (4)	C11—C12	1.424 (4)
O7—C28	1.200 (8)	C12—H12A	1.0218
O8'—C28	1.243 (4)	C13—C24	1.339 (5)
O8—C28	1.300 (8)	C13—C14	1.443 (5)
O9—C31	1.253 (4)	C14—C18	1.396 (5)
O9'—C31	1.317 (7)	C14—C15	1.412 (5)
O10—C31	1.273 (4)	C15—C19	1.437 (5)
O10—H10O	0.8300	C16—C17	1.385 (5)
O10'—C31	1.214 (7)	C16—H16	0.9400
O10'—H10'	0.8300	C17—C18	1.358 (6)
O11—C33	1.269 (4)	C17—H17	0.9400
O12—C33	1.209 (4)	C18—H18	0.9400
N1—C1	1.472 (4)	C19—C23	1.402 (4)
N1'—C12	1.423 (16)	C20—C21	1.397 (5)
N1'—H12A	0.5737	C20—H20	0.9400
N2—C4	1.316 (4)	C21—C22	1.362 (6)
N2—C3	1.350 (4)	C21—H21	0.9400
N2—H2N'	0.8700	C22—C23	1.394 (5)
N3—C8	1.324 (4)	C22—H22	0.9400
N3—C7	1.353 (4)	C23—C24	1.425 (5)
N3—H3N	0.8700	C24—H24	0.9400
N4—C13	1.492 (5)	C25—C26	1.491 (4)
N5—C16	1.319 (4)	C26—C34	1.382 (4)
N5—C15	1.349 (4)	C26—C27	1.406 (4)
N6—C20	1.319 (4)	C27—C29	1.390 (4)
N6—C19	1.346 (4)	C27—C28	1.506 (4)
N6—H6N	0.8700	C29—C30	1.391 (4)
C1—C12	1.339 (5)	C29—H29	0.9400
C1—C2	1.449 (4)	C30—C32	1.407 (4)
C1—H1A	0.9400	C30—C31	1.514 (4)
C2—C6	1.409 (4)	C32—C34	1.397 (4)
C2—C3	1.415 (4)	C32—C33	1.516 (4)
C3—C7	1.446 (4)	C34—H34	0.9400
C25—O6—H6O	109.5	C18—C14—C13	127.1 (3)
C31—O10—H10O	109.5	C15—C14—C13	116.4 (3)
C31—O10'—H10'	109.5	N5—C15—C14	123.7 (3)
O1—N1—O2	121.6 (3)	N5—C15—C19	116.1 (3)
O1—N1—C1	119.7 (3)	C14—C15—C19	120.2 (3)
O2—N1—C1	118.1 (3)	N5—C16—C17	123.2 (3)
O2'—N1'—O1'	123 (3)	N5—C16—H16	118.4
O2'—N1'—C12	123 (2)	C17—C16—H16	118.4
O1'—N1'—C12	112.6 (19)	C18—C17—C16	120.0 (4)
O2'—N1'—H12A	125.2	C18—C17—H17	120.0
O1'—N1'—H12A	91.8	C16—C17—H17	120.0
C4—N2—C3	117.3 (3)	C17—C18—C14	119.4 (4)
C4—N2—H2N'	121.3	C17—C18—H18	120.3
C3—N2—H2N'	121.3	C14—C18—H18	120.3
C8—N3—C7	119.7 (3)	N6—C19—C23	120.2 (3)
C8—N3—H3N	120.2	N6—C19—C15	119.1 (3)
C7—N3—H3N	120.2	C23—C19—C15	120.7 (3)
O4'—N4—O3	103.7 (8)	N6—C20—C21	121.0 (4)
O4'—N4—O3'	128.7 (14)	N6—C20—H20	119.5
O4'—N4—O4	55.9 (7)	C21—C20—H20	119.5
O3—N4—O4	119.8 (8)	C22—C21—C20	118.8 (4)
O3'—N4—O4	116.5 (14)	C22—C21—H21	120.6
O4'—N4—C13	114.4 (6)	C20—C21—H21	120.6
O3—N4—C13	121.3 (8)	C21—C22—C23	120.5 (3)
O3'—N4—C13	112.0 (14)	C21—C22—H22	119.8
O4—N4—C13	118.4 (4)	C23—C22—H22	119.8
C16—N5—C15	117.2 (3)	C22—C23—C19	117.9 (3)
C20—N6—C19	121.5 (3)	C22—C23—C24	123.4 (3)
C20—N6—H6N	119.3	C19—C23—C24	118.7 (3)
C19—N6—H6N	119.3	C13—C24—C23	120.3 (3)
C12—C1—C2	123.1 (3)	C13—C24—H24	119.8
C12—C1—N1	114.5 (3)	C23—C24—H24	119.8
C2—C1—N1	122.4 (3)	O6—C25—O5	123.2 (3)
C12—C1—H1A	118.5	O6—C25—C26	122.0 (3)
C2—C1—H1A	118.5	O5—C25—C26	114.7 (3)
C6—C2—C3	116.3 (3)	C34—C26—C27	118.3 (3)
C6—C2—C1	126.9 (3)	C34—C26—C25	120.1 (3)
C3—C2—C1	116.8 (3)	C27—C26—C25	121.5 (3)
N2—C3—C2	123.7 (3)	C29—C27—C26	118.5 (3)
N2—C3—C7	116.3 (2)	C29—C27—C28	115.8 (3)
C2—C3—C7	119.9 (3)	C26—C27—C28	125.4 (3)
N2—C4—C5	123.6 (3)	O7—C28—O8'	103.2 (6)
N2—C4—H4	118.2	O8'—C28—O7'	124.4 (3)
C5—C4—H4	118.2	O7—C28—O8	122.1 (7)
C6—C5—C4	119.6 (3)	O8'—C28—O8	62.8 (5)
C6—C5—H5	120.2	O7'—C28—O8	103.2 (5)
C4—C5—H5	120.2	O7—C28—C27	117.5 (6)
C5—C6—C2	119.5 (3)	O8'—C28—C27	120.0 (3)
C5—C6—H6	120.3	O7'—C28—C27	114.0 (3)
C2—C6—H6	120.3	O8—C28—C27	117.3 (5)
N3—C7—C11	120.4 (3)	C27—C29—C30	123.3 (3)
N3—C7—C3	119.1 (3)	C27—C29—H29	118.3
C11—C7—C3	120.5 (3)	C30—C29—H29	118.3
N3—C8—C9	122.6 (3)	C29—C30—C32	118.2 (3)
N3—C8—H8	118.7	C29—C30—C31	114.3 (3)
C9—C8—H8	118.7	C32—C30—C31	127.5 (3)
C10—C9—C8	119.2 (3)	O10'—C31—O9	90.6 (7)
C10—C9—H9	120.4	O9—C31—O10	118.9 (3)
C8—C9—H9	120.4	O10'—C31—O9'	126.0 (8)
C9—C10—C11	119.2 (3)	O9—C31—O9'	58.6 (5)
C9—C10—H10	120.4	O10—C31—O9'	113.0 (6)
C11—C10—H10	120.4	O10'—C31—C30	123.9 (6)
C10—C11—C7	118.9 (3)	O9—C31—C30	122.9 (3)
C10—C11—C12	122.4 (3)	O10—C31—C30	116.5 (3)
C7—C11—C12	118.7 (3)	O9'—C31—C30	110.1 (5)
C1—C12—C11	121.1 (3)	C34—C32—C30	118.2 (3)
C1—C12—N1'	104.9 (8)	C34—C32—C33	114.5 (3)
C11—C12—N1'	132.8 (8)	C30—C32—C33	127.2 (3)
C1—C12—H12A	118.9	O12—C33—O11	122.0 (3)
C11—C12—H12A	119.9	O12—C33—C32	119.7 (3)
C24—C13—C14	123.8 (3)	O11—C33—C32	118.2 (3)
C24—C13—N4	115.9 (3)	C26—C34—C32	123.5 (3)
C14—C13—N4	120.4 (3)	C26—C34—H34	118.3
C18—C14—C15	116.6 (3)	C32—C34—H34	118.3
O1—N1—C1—C12	−172.9 (4)	C15—N5—C16—C17	−0.5 (6)
O2—N1—C1—C12	−1.0 (5)	N5—C16—C17—C18	0.6 (7)
O1—N1—C1—C2	5.9 (5)	C16—C17—C18—C14	0.2 (7)
O2—N1—C1—C2	177.7 (3)	C15—C14—C18—C17	−0.9 (6)
C12—C1—C2—C6	−178.3 (3)	C13—C14—C18—C17	179.8 (4)
N1—C1—C2—C6	3.1 (5)	C20—N6—C19—C23	−1.7 (5)
C12—C1—C2—C3	1.6 (4)	C20—N6—C19—C15	178.9 (3)
N1—C1—C2—C3	−177.0 (3)	N5—C15—C19—N6	−1.1 (4)
C4—N2—C3—C2	0.5 (4)	C14—C15—C19—N6	179.0 (3)
C4—N2—C3—C7	−178.7 (3)	N5—C15—C19—C23	179.5 (3)
C6—C2—C3—N2	−0.6 (4)	C14—C15—C19—C23	−0.4 (5)
C1—C2—C3—N2	179.4 (3)	C19—N6—C20—C21	0.5 (5)
C6—C2—C3—C7	178.5 (3)	N6—C20—C21—C22	1.7 (6)
C1—C2—C3—C7	−1.4 (4)	C20—C21—C22—C23	−2.5 (6)
C3—N2—C4—C5	0.4 (5)	C21—C22—C23—C19	1.3 (6)
N2—C4—C5—C6	−1.2 (5)	C21—C22—C23—C24	−178.8 (4)
C4—C5—C6—C2	1.0 (5)	N6—C19—C23—C22	0.8 (5)
C3—C2—C6—C5	−0.2 (4)	C15—C19—C23—C22	−179.8 (3)
C1—C2—C6—C5	179.8 (3)	N6—C19—C23—C24	−179.1 (3)
C8—N3—C7—C11	−1.0 (4)	C15—C19—C23—C24	0.3 (5)
C8—N3—C7—C3	179.2 (3)	C14—C13—C24—C23	0.2 (6)
N2—C3—C7—N3	−1.1 (4)	N4—C13—C24—C23	−179.3 (3)
C2—C3—C7—N3	179.7 (3)	C22—C23—C24—C13	179.9 (3)
N2—C3—C7—C11	179.0 (3)	C19—C23—C24—C13	−0.2 (5)
C2—C3—C7—C11	−0.2 (4)	O6—C25—C26—C34	−160.3 (3)
C7—N3—C8—C9	0.6 (5)	O5—C25—C26—C34	17.6 (4)
N3—C8—C9—C10	−0.1 (5)	O6—C25—C26—C27	15.7 (5)
C8—C9—C10—C11	0.0 (5)	O5—C25—C26—C27	−166.5 (3)
C9—C10—C11—C7	−0.3 (5)	C34—C26—C27—C29	0.5 (4)
C9—C10—C11—C12	178.7 (3)	C25—C26—C27—C29	−175.5 (3)
N3—C7—C11—C10	0.8 (4)	C34—C26—C27—C28	−173.9 (3)
C3—C7—C11—C10	−179.3 (3)	C25—C26—C27—C28	10.1 (5)
N3—C7—C11—C12	−178.2 (3)	C29—C27—C28—O7	15.9 (8)
C3—C7—C11—C12	1.7 (4)	C26—C27—C28—O7	−169.5 (7)
C2—C1—C12—C11	−0.2 (5)	C29—C27—C28—O8'	−110.8 (4)
N1—C1—C12—C11	178.6 (3)	C26—C27—C28—O8'	63.8 (4)
C2—C1—C12—N1'	−169.0 (9)	C29—C27—C28—O7'	55.7 (4)
N1—C1—C12—N1'	9.8 (9)	C26—C27—C28—O7'	−129.7 (3)
C10—C11—C12—C1	179.5 (3)	C29—C27—C28—O8	176.4 (6)
C7—C11—C12—C1	−1.5 (5)	C26—C27—C28—O8	−9.0 (7)
C10—C11—C12—N1'	−15.3 (13)	C26—C27—C29—C30	−1.0 (5)
C7—C11—C12—N1'	163.6 (12)	C28—C27—C29—C30	173.9 (3)
O2'—N1'—C12—C1	−32 (3)	C27—C29—C30—C32	0.9 (5)
O1'—N1'—C12—C1	162 (3)	C27—C29—C30—C31	−179.7 (3)
O2'—N1'—C12—C11	161 (3)	C29—C30—C31—O10'	73.5 (9)
O1'—N1'—C12—C11	−5 (3)	C32—C30—C31—O10'	−107.2 (9)
O4'—N4—C13—C24	140.4 (9)	C29—C30—C31—O9	−169.8 (4)
O3—N4—C13—C24	15.0 (9)	C32—C30—C31—O9	9.6 (6)
O3'—N4—C13—C24	−16.8 (13)	C29—C30—C31—O10	25.4 (5)
O4—N4—C13—C24	−156.7 (5)	C32—C30—C31—O10	−155.2 (4)
O4'—N4—C13—C14	−39.1 (10)	C29—C30—C31—O9'	−104.9 (6)
O3—N4—C13—C14	−164.6 (7)	C32—C30—C31—O9'	74.4 (7)
O3'—N4—C13—C14	163.6 (13)	C29—C30—C32—C34	−0.4 (4)
O4—N4—C13—C14	23.7 (6)	C31—C30—C32—C34	−179.7 (3)
C24—C13—C14—C18	179.0 (4)	C29—C30—C32—C33	−178.5 (3)
N4—C13—C14—C18	−1.5 (6)	C31—C30—C32—C33	2.2 (5)
C24—C13—C14—C15	−0.3 (5)	C34—C32—C33—O12	−9.3 (5)
N4—C13—C14—C15	179.2 (3)	C30—C32—C33—O12	168.9 (4)
C16—N5—C15—C14	−0.4 (5)	C34—C32—C33—O11	173.5 (3)
C16—N5—C15—C19	179.7 (3)	C30—C32—C33—O11	−8.3 (5)
C18—C14—C15—N5	1.1 (5)	C27—C26—C34—C32	0.0 (4)
C13—C14—C15—N5	−179.5 (3)	C25—C26—C34—C32	176.1 (3)
C18—C14—C15—C19	−179.0 (3)	C30—C32—C34—C26	−0.1 (5)
C13—C14—C15—C19	0.4 (5)	C33—C32—C34—C26	178.3 (3)

D—H···A	D—H	H···A	D···A	D—H···A
O6—H6O···O8	0.83	1.36	2.031 (10)	135
O6—H6O···O8′	0.83	2.50	3.024 (4)	123
O10—H10O···O5i	0.83	1.92	2.724 (4)	164
N2—H2N′···O7′ii	0.87	2.16	3.012 (4)	165
N3—H3N···O7′ii	0.87	1.86	2.695 (4)	160
N2—H2N′···O7ii	0.87	2.21	3.078 (9)	172
N3—H3N···O7ii	0.87	1.84	2.678 (11)	162
N6—H6N···O11iii	0.87	1.85	2.712 (4)	168

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O6—H6O⋯O8	0.83	1.36	2.031 (10)	135
O6—H6O⋯O8′	0.83	2.50	3.024 (4)	123
O10—H10O⋯O5i	0.83	1.92	2.724 (4)	164
N2—H2N′⋯O7′ii	0.87	2.16	3.012 (4)	165
N3—H3N⋯O7′ii	0.87	1.86	2.695 (4)	160
N2—H2N′⋯O7ii	0.87	2.21	3.078 (9)	172
N3—H3N⋯O7ii	0.87	1.84	2.678 (11)	162
N6—H6N⋯O11iii	0.87	1.85	2.712 (4)	168

Symmetry codes: (i) ; (ii) ; (iii) .