N (2)-(4-Meth-oxy-salicyl-idene)arginine hemihydrate.

The title compound, C14H20N4O4·0.5H2O [systematic name: (2S)-5-{[amino-(iminium-yl)meth-yl]amino}-2-{[(1Z)-4-meth-oxy-2-oxido-benzyl-idene]aza-nium-yl}penta-noate hemihydrate], has been synthesized by the reaction of l-arginine and 4-meth-oxy-salicyl-aldehyde and crystallizes with two independent substituted l-arginine mol-ecules and one water mol-ecule of solvation in the asymmetric unit. Each mol-ecule exists as a zwitterion and adopts a Z configuration about the central C=N. The mol-ecular conformation is stabilized by strong intra-molecular N-H⋯O hydrogen bonds that generate S(6) and S(10) ring motifs. Inter-molecular N-H⋯O and O-H⋯O hydrogen bonds involving also the water mol-ecule and weak inter-molecular C-H⋯Owater inter-actions link the mol-ecules into an infinite one-dimensional ribbon structure extending along the b axis. The known (2S) absolute configuration for l-arginine was invoked. Weak intermolecular C-H⋯π interactions are also present.

Related literature

For the synthesis of similar compounds, see: Srinivasan et al. (1986 ▶); Moutet & Ourari (1997 ▶). For general background on Schiff bases, see: von Konig et al. (1982 ▶); Lewis et al. (2009 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For related structures, see: Oueslati et al. (2007 ▶).

Experimental

Crystal data

C14H20N4O4·0.5H2O

M = 317.35

Monoclinic,

a = 10.1828 (11) Å

b = 10.3414 (11) Å

c = 15.5542 (16) Å

β = 102.688 (2)°

V = 1597.9 (3) Å3

Z = 4

Mo Kα radiation

μ = 0.10 mm−1

T = 293 K

0.30 × 0.30 × 0.25 mm

Data collection

Bruker Kappa APEXII CCD-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2004 ▶) T min = 0.971, T max = 0.976

18648 measured reflections

7483 independent reflections

5859 reflections with I > 2σ(I)

R int = 0.036

Refinement

R[F 2 > 2σ(F 2)] = 0.072

wR(F 2) = 0.167

S = 1.10

7483 reflections

452 parameters

14 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.25 e Å−3

Δρmin = −0.21 e Å−3

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: APEX2 and SAINT (Bruker, 2004 ▶); data reduction: SAINT and XPREP (Bruker, 2004 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▶) and Mercury (Macrae et al., 2008 ▶); software used to prepare material for publication: WinGX (Farrugia, 2012 ▶) and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536813019727/zs2267sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813019727/zs2267Isup2.hkl

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

C14H20N4O4·0.5H2O	F(000) = 676
Mr = 317.35	Dx = 1.319 Mg m−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 3158 reflections
a = 10.1828 (11) Å	θ = 2.5–31.2°
b = 10.3414 (11) Å	µ = 0.10 mm−1
c = 15.5542 (16) Å	T = 293 K
β = 102.688 (2)°	Block, yellow
V = 1597.9 (3) Å3	0.30 × 0.30 × 0.25 mm
Z = 4

Bruker Kappa APEXII CCD-detector diffractometer	7483 independent reflections
Radiation source: fine-focus sealed tube	5859 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.036
ω and φ scans	θmax = 28.4°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −13→13
Tmin = 0.971, Tmax = 0.976	k = −13→13
18648 measured reflections	l = −20→20

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.072	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.167	w = 1/[σ2(Fo2) + (0.0716P)2 + 0.2262P] where P = (Fo2 + 2Fc2)/3
S = 1.10	(Δ/σ)max < 0.001
7483 reflections	Δρmax = 0.25 e Å−3
452 parameters	Δρmin = −0.21 e Å−3
14 restraints	Absolute structure: Flack (1983), 3448 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.1 (14)

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
C1	0.1564 (4)	1.2584 (4)	0.5422 (3)	0.0774 (13)
H1A	0.1669	1.3231	0.5874	0.116*
H1B	0.0660	1.2607	0.5074	0.116*
H1C	0.2185	1.2750	0.5051	0.116*
C2	0.1744 (3)	1.0292 (4)	0.5285 (2)	0.0536 (8)
C3	0.2238 (4)	0.9149 (4)	0.5704 (2)	0.0566 (9)
H3	0.2572	0.9129	0.6310	0.068*
C4	0.2224 (3)	0.8064 (4)	0.5214 (2)	0.0515 (8)
H4	0.2571	0.7303	0.5492	0.062*
C5	0.1703 (3)	0.8047 (3)	0.4296 (2)	0.0444 (7)
C6	0.1152 (4)	0.9209 (3)	0.3871 (2)	0.0487 (8)
C7	0.1196 (4)	1.0328 (4)	0.4389 (2)	0.0559 (9)
H7	0.0853	1.1101	0.4127	0.067*
C8	0.1721 (3)	0.6905 (3)	0.3831 (2)	0.0471 (7)
H8	0.2109	0.6185	0.4146	0.057*
C9	0.1152 (3)	0.5543 (3)	0.2513 (2)	0.0462 (7)
H9	0.2055	0.5167	0.2598	0.055*
C10	0.0613 (4)	0.5805 (3)	0.1526 (2)	0.0499 (8)
C11	0.0248 (4)	0.4611 (3)	0.2890 (2)	0.0521 (8)
H11A	0.0645	0.4484	0.3510	0.063*
H11B	−0.0618	0.5025	0.2849	0.063*
C12	0.0006 (4)	0.3291 (3)	0.2457 (2)	0.0496 (8)
H12A	−0.0534	0.2779	0.2773	0.059*
H12B	−0.0510	0.3401	0.1859	0.059*
C13	0.1279 (4)	0.2552 (3)	0.2433 (2)	0.0524 (8)
H13A	0.1827	0.3057	0.2120	0.063*
H13B	0.1792	0.2420	0.3030	0.063*
C14	0.0664 (3)	0.1157 (3)	0.1148 (2)	0.0474 (7)
C15	0.6713 (5)	−0.0130 (4)	0.0132 (3)	0.0757 (12)
H15A	0.6971	−0.0757	−0.0255	0.114*
H15B	0.5757	−0.0169	0.0082	0.114*
H15C	0.7165	−0.0313	0.0728	0.114*
C16	0.6801 (4)	0.2145 (4)	0.0364 (2)	0.0574 (9)
C17	0.7369 (4)	0.3301 (4)	0.0165 (2)	0.0575 (9)
H17	0.7866	0.3324	−0.0270	0.069*
C18	0.7196 (4)	0.4378 (4)	0.0602 (2)	0.0551 (8)
H18	0.7587	0.5146	0.0472	0.066*
C19	0.6423 (3)	0.4371 (3)	0.1264 (2)	0.0494 (8)
C20	0.5796 (4)	0.3217 (3)	0.1448 (2)	0.0573 (9)
C21	0.6024 (4)	0.2094 (4)	0.0976 (2)	0.0631 (10)
H21	0.5639	0.1313	0.1086	0.076*
C22	0.6243 (3)	0.5520 (3)	0.1693 (2)	0.0480 (7)
H22	0.6677	0.6254	0.1550	0.058*
C23	0.5306 (4)	0.6853 (3)	0.2695 (2)	0.0463 (7)
H23	0.6141	0.7357	0.2800	0.056*
C24	0.4951 (3)	0.6572 (3)	0.3579 (2)	0.0470 (8)
C25	0.4207 (4)	0.7613 (3)	0.2061 (2)	0.0532 (8)
H25A	0.4490	0.7738	0.1510	0.064*
H25B	0.3392	0.7097	0.1935	0.064*
C26	0.3882 (4)	0.8927 (3)	0.2403 (2)	0.0550 (9)
H26A	0.3201	0.9348	0.1956	0.066*
H26B	0.3509	0.8803	0.2920	0.066*
C27	0.5096 (4)	0.9796 (3)	0.2639 (2)	0.0582 (9)
H27A	0.5780	0.9366	0.3078	0.070*
H27B	0.5460	0.9925	0.2119	0.070*
C28	0.4773 (3)	1.1249 (3)	0.3797 (2)	0.0456 (7)
N1	0.1241 (3)	0.6759 (3)	0.29926 (18)	0.0476 (6)
N2	0.0979 (3)	0.1312 (3)	0.20033 (17)	0.0545 (7)
H2	0.1009	0.0637	0.2330	0.065*
N3	0.0323 (4)	−0.0009 (3)	0.0810 (2)	0.0585 (8)
N4	0.0709 (3)	0.2127 (3)	0.06010 (18)	0.0525 (7)
N5	0.5525 (3)	0.5643 (3)	0.22704 (17)	0.0482 (6)
N6	0.4817 (4)	1.1051 (3)	0.29785 (19)	0.0597 (8)
H6	0.4674	1.1695	0.2620	0.072*
N7	0.4545 (3)	1.2428 (3)	0.40673 (19)	0.0524 (7)
N8	0.4954 (4)	1.0294 (3)	0.43757 (19)	0.0575 (8)
O1	0.1831 (3)	1.1333 (3)	0.58193 (18)	0.0720 (8)
O2	0.0628 (3)	0.9232 (2)	0.30397 (14)	0.0621 (7)
O3	0.0088 (3)	0.6877 (3)	0.13073 (16)	0.0692 (8)
O4	0.0710 (3)	0.4893 (2)	0.10247 (15)	0.0584 (6)
O5	0.7073 (3)	0.1124 (3)	−0.01041 (17)	0.0733 (8)
O6	0.5054 (3)	0.3186 (3)	0.20185 (19)	0.0779 (9)
O7	0.5093 (3)	0.7516 (3)	0.40963 (15)	0.0587 (6)
O8	0.4554 (3)	0.5477 (2)	0.37124 (16)	0.0586 (6)
O1W	0.8113 (4)	0.8224 (5)	0.2043 (3)	0.1180 (13)
H1W	0.834 (6)	0.892 (5)	0.244 (4)	0.177*
H2W	0.889 (4)	0.783 (6)	0.194 (5)	0.177*
H4A	0.081 (3)	0.2932 (15)	0.082 (2)	0.044 (9)*
H7A	0.459 (4)	1.306 (3)	0.3681 (19)	0.058 (11)*
H4B	0.056 (4)	0.205 (4)	0.0015 (7)	0.060 (11)*
H7B	0.461 (3)	1.251 (3)	0.4649 (8)	0.047 (9)*
H8A	0.492 (4)	0.9466 (15)	0.420 (2)	0.055 (10)*
H8B	0.492 (4)	1.045 (4)	0.4935 (10)	0.056 (10)*
H3A	0.021 (4)	−0.064 (3)	0.118 (2)	0.065 (12)*
H3B	0.003 (3)	−0.009 (4)	0.0228 (8)	0.054 (10)*
H5	0.513 (3)	0.493 (2)	0.241 (2)	0.053 (10)*
H1	0.083 (3)	0.744 (2)	0.271 (2)	0.049 (9)*

	U11	U22	U33	U12	U13	U23
C1	0.063 (2)	0.064 (3)	0.102 (3)	0.002 (2)	0.011 (2)	−0.035 (3)
C2	0.0496 (19)	0.061 (2)	0.0531 (19)	−0.0094 (17)	0.0164 (15)	−0.0168 (17)
C3	0.055 (2)	0.069 (2)	0.0425 (17)	−0.0028 (18)	0.0048 (15)	−0.0087 (18)
C4	0.0464 (18)	0.055 (2)	0.0472 (18)	−0.0038 (15)	−0.0021 (14)	−0.0025 (16)
C5	0.0464 (17)	0.0452 (17)	0.0428 (16)	−0.0023 (14)	0.0126 (14)	−0.0029 (14)
C6	0.0536 (19)	0.0472 (19)	0.0475 (18)	−0.0096 (15)	0.0158 (15)	−0.0057 (15)
C7	0.065 (2)	0.0477 (19)	0.056 (2)	−0.0052 (17)	0.0158 (17)	−0.0047 (16)
C8	0.0481 (18)	0.0470 (17)	0.0459 (17)	−0.0023 (15)	0.0097 (14)	0.0040 (15)
C9	0.0590 (19)	0.0395 (17)	0.0390 (16)	−0.0023 (15)	0.0085 (14)	−0.0018 (13)
C10	0.062 (2)	0.048 (2)	0.0410 (17)	−0.0091 (16)	0.0149 (15)	−0.0017 (15)
C11	0.075 (2)	0.0420 (18)	0.0416 (17)	−0.0030 (16)	0.0188 (16)	0.0003 (14)
C12	0.067 (2)	0.0421 (17)	0.0416 (16)	−0.0115 (16)	0.0158 (15)	−0.0018 (14)
C13	0.072 (2)	0.0427 (17)	0.0383 (16)	−0.0027 (17)	0.0039 (15)	−0.0006 (14)
C14	0.0542 (19)	0.0400 (17)	0.0479 (18)	0.0086 (15)	0.0110 (15)	−0.0007 (15)
C15	0.092 (3)	0.056 (2)	0.077 (3)	0.007 (2)	0.016 (2)	−0.017 (2)
C16	0.074 (2)	0.057 (2)	0.0395 (17)	0.0196 (18)	0.0091 (16)	0.0011 (15)
C17	0.062 (2)	0.070 (2)	0.0436 (18)	0.0046 (19)	0.0186 (16)	−0.0002 (17)
C18	0.058 (2)	0.058 (2)	0.0509 (19)	−0.0003 (17)	0.0150 (16)	0.0013 (17)
C19	0.0538 (19)	0.0484 (19)	0.0457 (17)	0.0080 (15)	0.0103 (14)	0.0053 (15)
C20	0.085 (3)	0.0418 (18)	0.0497 (19)	0.0124 (18)	0.0257 (18)	0.0095 (16)
C21	0.098 (3)	0.0403 (18)	0.057 (2)	0.0063 (19)	0.030 (2)	0.0084 (16)
C22	0.0561 (19)	0.0436 (17)	0.0435 (16)	0.0008 (15)	0.0090 (14)	0.0040 (14)
C23	0.062 (2)	0.0387 (16)	0.0384 (16)	0.0033 (15)	0.0125 (14)	0.0014 (13)
C24	0.0542 (19)	0.0458 (19)	0.0395 (17)	0.0143 (15)	0.0068 (14)	0.0091 (14)
C25	0.071 (2)	0.0432 (17)	0.0397 (17)	0.0071 (17)	0.0006 (15)	0.0000 (14)
C26	0.077 (2)	0.0447 (18)	0.0380 (17)	0.0116 (17)	0.0017 (16)	0.0011 (14)
C27	0.091 (3)	0.0456 (18)	0.0443 (18)	0.0001 (19)	0.0285 (18)	0.0043 (15)
C28	0.0564 (19)	0.0407 (17)	0.0414 (17)	−0.0062 (15)	0.0144 (14)	0.0009 (14)
N1	0.0623 (18)	0.0359 (14)	0.0433 (15)	0.0001 (13)	0.0085 (13)	0.0033 (12)
N2	0.086 (2)	0.0386 (14)	0.0359 (14)	0.0072 (14)	0.0062 (14)	0.0056 (12)
N3	0.090 (2)	0.0406 (16)	0.0440 (17)	−0.0011 (15)	0.0131 (16)	−0.0001 (14)
N4	0.082 (2)	0.0396 (15)	0.0363 (14)	−0.0004 (14)	0.0131 (14)	0.0004 (12)
N5	0.0685 (18)	0.0377 (14)	0.0424 (14)	0.0028 (13)	0.0205 (13)	0.0037 (11)
N6	0.104 (2)	0.0340 (14)	0.0457 (16)	0.0022 (15)	0.0258 (16)	0.0065 (12)
N7	0.0753 (19)	0.0424 (16)	0.0406 (15)	−0.0044 (14)	0.0153 (14)	−0.0013 (13)
N8	0.093 (2)	0.0435 (17)	0.0388 (15)	−0.0007 (16)	0.0215 (15)	0.0025 (13)
O1	0.083 (2)	0.0680 (18)	0.0646 (16)	−0.0093 (15)	0.0160 (14)	−0.0276 (14)
O2	0.0966 (19)	0.0432 (13)	0.0405 (13)	−0.0050 (13)	0.0020 (12)	0.0025 (11)
O3	0.108 (2)	0.0544 (16)	0.0412 (13)	0.0161 (15)	0.0071 (13)	0.0039 (12)
O4	0.0903 (19)	0.0466 (13)	0.0413 (12)	−0.0059 (13)	0.0210 (12)	−0.0030 (11)
O5	0.107 (2)	0.0646 (17)	0.0525 (15)	0.0202 (16)	0.0257 (15)	−0.0042 (13)
O6	0.133 (3)	0.0394 (13)	0.0811 (19)	0.0060 (16)	0.0668 (19)	0.0087 (14)
O7	0.0839 (18)	0.0523 (14)	0.0415 (12)	0.0089 (13)	0.0170 (12)	0.0003 (11)
O8	0.0798 (17)	0.0455 (14)	0.0527 (14)	0.0036 (13)	0.0189 (12)	0.0084 (11)
O1W	0.097 (3)	0.116 (3)	0.136 (4)	0.000 (2)	0.015 (2)	0.010 (3)

C1—O1	1.434 (5)	C17—C18	1.336 (5)
C1—H1A	0.9600	C17—H17	0.9300
C1—H1B	0.9600	C18—C19	1.428 (5)
C1—H1C	0.9600	C18—H18	0.9300
C2—O1	1.351 (4)	C19—C22	1.394 (5)
C2—C7	1.383 (5)	C19—C20	1.412 (5)
C2—C3	1.390 (5)	C20—O6	1.286 (4)
C3—C4	1.355 (5)	C20—C21	1.420 (5)
C3—H3	0.9300	C21—H21	0.9300
C4—C5	1.409 (4)	C22—N5	1.282 (4)
C4—H4	0.9300	C22—H22	0.9300
C5—C8	1.388 (5)	C23—N5	1.454 (4)
C5—C6	1.426 (5)	C23—C24	1.525 (4)
C6—O2	1.286 (4)	C23—C25	1.535 (5)
C6—C7	1.405 (5)	C23—H23	0.9800
C7—H7	0.9300	C24—O8	1.235 (4)
C8—N1	1.297 (4)	C24—O7	1.253 (4)
C8—H8	0.9300	C25—C26	1.523 (5)
C9—N1	1.455 (4)	C25—H25A	0.9700
C9—C11	1.535 (5)	C25—H25B	0.9700
C9—C10	1.537 (4)	C26—C27	1.507 (6)
C9—H9	0.9800	C26—H26A	0.9700
C10—O4	1.241 (4)	C26—H26B	0.9700
C10—O3	1.245 (4)	C27—N6	1.452 (4)
C11—C12	1.518 (5)	C27—H27A	0.9700
C11—H11A	0.9700	C27—H27B	0.9700
C11—H11B	0.9700	C28—N6	1.300 (4)
C12—C13	1.512 (5)	C28—N8	1.321 (4)
C12—H12A	0.9700	C28—N7	1.326 (4)
C12—H12B	0.9700	N1—H1	0.891 (10)
C13—N2	1.448 (4)	N2—H2	0.8600
C13—H13A	0.9700	N3—H3A	0.894 (10)
C13—H13B	0.9700	N3—H3B	0.892 (10)
C14—N2	1.309 (4)	N4—H4A	0.898 (10)
C14—N4	1.323 (4)	N4—H4B	0.894 (10)
C14—N3	1.330 (4)	N5—H5	0.896 (10)
C15—O5	1.418 (5)	N6—H6	0.8600
C15—H15A	0.9600	N7—H7A	0.893 (10)
C15—H15B	0.9600	N7—H7B	0.896 (10)
C15—H15C	0.9600	N8—H8A	0.898 (10)
C16—O5	1.346 (4)	N8—H8B	0.893 (10)
C16—C21	1.366 (5)	O1W—H1W	0.940 (10)
C16—C17	1.393 (6)	O1W—H2W	0.937 (10)
O1—C1—H1A	109.5	C19—C18—H18	119.4
O1—C1—H1B	109.5	C22—C19—C20	120.7 (3)
H1A—C1—H1B	109.5	C22—C19—C18	119.5 (3)
O1—C1—H1C	109.5	C20—C19—C18	119.7 (3)
H1A—C1—H1C	109.5	O6—C20—C19	121.4 (3)
H1B—C1—H1C	109.5	O6—C20—C21	121.5 (3)
O1—C2—C7	123.8 (4)	C19—C20—C21	117.1 (3)
O1—C2—C3	114.9 (3)	C16—C21—C20	120.9 (4)
C7—C2—C3	121.3 (3)	C16—C21—H21	119.5
C4—C3—C2	118.8 (3)	C20—C21—H21	119.5
C4—C3—H3	120.6	N5—C22—C19	125.1 (3)
C2—C3—H3	120.6	N5—C22—H22	117.5
C3—C4—C5	122.4 (3)	C19—C22—H22	117.5
C3—C4—H4	118.8	N5—C23—C24	109.6 (3)
C5—C4—H4	118.8	N5—C23—C25	108.2 (3)
C8—C5—C4	119.6 (3)	C24—C23—C25	113.1 (3)
C8—C5—C6	121.6 (3)	N5—C23—H23	108.6
C4—C5—C6	118.8 (3)	C24—C23—H23	108.6
O2—C6—C7	121.0 (3)	C25—C23—H23	108.6
O2—C6—C5	121.1 (3)	O8—C24—O7	127.0 (3)
C7—C6—C5	117.9 (3)	O8—C24—C23	118.6 (3)
C2—C7—C6	120.8 (4)	O7—C24—C23	114.5 (3)
C2—C7—H7	119.6	C26—C25—C23	114.6 (3)
C6—C7—H7	119.6	C26—C25—H25A	108.6
N1—C8—C5	125.3 (3)	C23—C25—H25A	108.6
N1—C8—H8	117.3	C26—C25—H25B	108.6
C5—C8—H8	117.3	C23—C25—H25B	108.6
N1—C9—C11	108.8 (3)	H25A—C25—H25B	107.6
N1—C9—C10	109.1 (3)	C27—C26—C25	112.8 (3)
C11—C9—C10	112.3 (3)	C27—C26—H26A	109.0
N1—C9—H9	108.8	C25—C26—H26A	109.0
C11—C9—H9	108.8	C27—C26—H26B	109.0
C10—C9—H9	108.8	C25—C26—H26B	109.0
O4—C10—O3	126.4 (3)	H26A—C26—H26B	107.8
O4—C10—C9	115.6 (3)	N6—C27—C26	114.0 (3)
O3—C10—C9	117.9 (3)	N6—C27—H27A	108.8
C12—C11—C9	116.7 (3)	C26—C27—H27A	108.8
C12—C11—H11A	108.1	N6—C27—H27B	108.8
C9—C11—H11A	108.1	C26—C27—H27B	108.8
C12—C11—H11B	108.1	H27A—C27—H27B	107.7
C9—C11—H11B	108.1	N6—C28—N8	121.3 (3)
H11A—C11—H11B	107.3	N6—C28—N7	120.1 (3)
C13—C12—C11	114.1 (3)	N8—C28—N7	118.6 (3)
C13—C12—H12A	108.7	C8—N1—C9	125.7 (3)
C11—C12—H12A	108.7	C8—N1—H1	116 (2)
C13—C12—H12B	108.7	C9—N1—H1	118 (2)
C11—C12—H12B	108.7	C14—N2—C13	123.9 (3)
H12A—C12—H12B	107.6	C14—N2—H2	118.0
N2—C13—C12	111.3 (3)	C13—N2—H2	118.0
N2—C13—H13A	109.4	C14—N3—H3A	118 (3)
C12—C13—H13A	109.4	C14—N3—H3B	119 (2)
N2—C13—H13B	109.4	H3A—N3—H3B	122 (4)
C12—C13—H13B	109.4	C14—N4—H4A	118 (2)
H13A—C13—H13B	108.0	C14—N4—H4B	125 (3)
N2—C14—N4	121.7 (3)	H4A—N4—H4B	117 (3)
N2—C14—N3	119.8 (3)	C22—N5—C23	124.8 (3)
N4—C14—N3	118.4 (3)	C22—N5—H5	117 (2)
O5—C15—H15A	109.5	C23—N5—H5	118 (2)
O5—C15—H15B	109.5	C28—N6—C27	123.2 (3)
H15A—C15—H15B	109.5	C28—N6—H6	118.4
O5—C15—H15C	109.5	C27—N6—H6	118.4
H15A—C15—H15C	109.5	C28—N7—H7A	115 (2)
H15B—C15—H15C	109.5	C28—N7—H7B	115 (2)
O5—C16—C21	124.5 (4)	H7A—N7—H7B	127 (3)
O5—C16—C17	114.1 (3)	C28—N8—H8A	121 (2)
C21—C16—C17	121.4 (3)	C28—N8—H8B	120 (2)
C18—C17—C16	119.6 (3)	H8A—N8—H8B	118 (3)
C18—C17—H17	120.2	C2—O1—C1	118.2 (3)
C16—C17—H17	120.2	C16—O5—C15	118.8 (3)
C17—C18—C19	121.2 (3)	H1W—O1W—H2W	110.4 (17)
C17—C18—H18	119.4
O1—C2—C3—C4	−178.2 (3)	C18—C19—C20—C21	2.6 (5)
C7—C2—C3—C4	2.5 (5)	O5—C16—C21—C20	179.4 (4)
C2—C3—C4—C5	−1.2 (5)	C17—C16—C21—C20	−1.6 (6)
C3—C4—C5—C8	179.9 (3)	O6—C20—C21—C16	179.2 (4)
C3—C4—C5—C6	−1.0 (5)	C19—C20—C21—C16	−1.0 (6)
C8—C5—C6—O2	1.2 (5)	C20—C19—C22—N5	0.0 (5)
C4—C5—C6—O2	−177.9 (3)	C18—C19—C22—N5	176.9 (3)
C8—C5—C6—C7	−178.9 (3)	N5—C23—C24—O8	−18.7 (4)
C4—C5—C6—C7	2.0 (4)	C25—C23—C24—O8	102.2 (4)
O1—C2—C7—C6	179.3 (3)	N5—C23—C24—O7	161.9 (3)
C3—C2—C7—C6	−1.5 (5)	C25—C23—C24—O7	−77.3 (4)
O2—C6—C7—C2	179.1 (3)	N5—C23—C25—C26	−178.7 (3)
C5—C6—C7—C2	−0.8 (5)	C24—C23—C25—C26	59.7 (4)
C4—C5—C8—N1	178.1 (3)	C23—C25—C26—C27	57.0 (4)
C6—C5—C8—N1	−1.1 (5)	C25—C26—C27—N6	−179.2 (3)
N1—C9—C10—O4	167.8 (3)	C5—C8—N1—C9	−174.4 (3)
C11—C9—C10—O4	−71.5 (4)	C11—C9—N1—C8	60.9 (4)
N1—C9—C10—O3	−14.6 (4)	C10—C9—N1—C8	−176.2 (3)
C11—C9—C10—O3	106.2 (4)	N4—C14—N2—C13	6.0 (5)
N1—C9—C11—C12	178.7 (3)	N3—C14—N2—C13	−175.9 (3)
C10—C9—C11—C12	57.7 (4)	C12—C13—N2—C14	79.9 (4)
C9—C11—C12—C13	55.3 (4)	C19—C22—N5—C23	−177.9 (3)
C11—C12—C13—N2	−179.3 (3)	C24—C23—N5—C22	−155.8 (3)
O5—C16—C17—C18	−178.4 (3)	C25—C23—N5—C22	80.4 (4)
C21—C16—C17—C18	2.5 (6)	N8—C28—N6—C27	−1.6 (6)
C16—C17—C18—C19	−0.8 (6)	N7—C28—N6—C27	178.4 (3)
C17—C18—C19—C22	−178.7 (3)	C26—C27—N6—C28	83.0 (5)
C17—C18—C19—C20	−1.8 (5)	C7—C2—O1—C1	−11.4 (5)
C22—C19—C20—O6	−0.7 (5)	C3—C2—O1—C1	169.3 (3)
C18—C19—C20—O6	−177.6 (4)	C21—C16—O5—C15	−9.9 (6)
C22—C19—C20—C21	179.5 (3)	C17—C16—O5—C15	171.0 (4)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2	0.89 (1)	1.94 (3)	2.638 (4)	134 (3)
N4—H4A···O4	0.90 (1)	2.06 (1)	2.935 (4)	165 (3)
N5—H5···O6	0.90 (1)	1.90 (3)	2.600 (4)	134 (3)
N8—H8A···O7	0.90 (1)	2.03 (1)	2.914 (4)	166 (3)
N2—H2···O2i	0.86	1.92	2.758 (4)	166
N3—H3A···O3i	0.89 (1)	2.58 (3)	3.333 (4)	142 (3)
N3—H3B···O4ii	0.89 (1)	1.93 (1)	2.817 (4)	175 (4)
N4—H4B···O3ii	0.89 (1)	2.03 (1)	2.912 (4)	171 (3)
N6—H6···O6iii	0.86	1.89	2.705 (4)	158
N7—H7A···O8iii	0.89 (1)	2.50 (3)	3.202 (4)	135 (3)
N7—H7B···O7iv	0.90 (1)	1.91 (1)	2.800 (4)	173 (3)
N8—H8B···O8iv	0.89 (1)	2.05 (2)	2.911 (4)	161 (3)
O1W—H1W···O2v	0.94 (1)	2.33 (6)	2.882 (5)	117 (4)
O1W—H2W···O3v	0.94 (1)	1.98 (2)	2.881 (5)	159 (6)
C15—H15C···O1Wi	0.96	2.56	3.451 (7)	155
C22—H22···O1W	0.93	2.53	3.359 (6)	149
C1—H1C···Cg1vi	0.96	2.96	3.669 (4)	132
C15—H15C···Cg2vii	0.96	2.98	3.762 (5)	139

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O2	0.89 (1)	1.94 (3)	2.638 (4)	134 (3)
N4—H4A⋯O4	0.90 (1)	2.06 (1)	2.935 (4)	165 (3)
N5—H5⋯O6	0.90 (1)	1.90 (3)	2.600 (4)	134 (3)
N8—H8A⋯O7	0.90 (1)	2.03 (1)	2.914 (4)	166 (3)
N2—H2⋯O2i	0.86	1.92	2.758 (4)	166
N3—H3A⋯O3i	0.89 (1)	2.58 (3)	3.333 (4)	142 (3)
N3—H3B⋯O4ii	0.89 (1)	1.93 (1)	2.817 (4)	175 (4)
N4—H4B⋯O3ii	0.89 (1)	2.03 (1)	2.912 (4)	171 (3)
N6—H6⋯O6iii	0.86	1.89	2.705 (4)	158
N7—H7A⋯O8iii	0.89 (1)	2.50 (3)	3.202 (4)	135 (3)
N7—H7B⋯O7iv	0.90 (1)	1.91 (1)	2.800 (4)	173 (3)
N8—H8B⋯O8iv	0.89 (1)	2.05 (2)	2.911 (4)	161 (3)
O1W—H2W⋯O3v	0.94 (1)	1.98 (2)	2.881 (5)	159 (6)
C15—H15C⋯O1W i	0.96	2.56	3.451 (7)	155
C22—H22⋯O1W	0.93	2.53	3.359 (6)	149
C1—H1C⋯Cg1vi	0.96	2.96	3.669 (4)	132
C15—H15C⋯Cg2vii	0.96	2.98	3.762 (5)	139

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) ; (vi) ; (vii) .