A second monoclinic polymorph of 2-(3,5-dimethyl-1H-pyrazol-1-yl)-2-hy­droxy­imino-N′-[1-(pyridin-2-yl)ethyl­idene]acetohydrazide

The title compound, C₁₄H₁₆N₆O₂, is a second monoclinic polymorph of 2-[1-(3,5-dimeth­yl)pyrazol­yl]-2-hy­droxy­imino-N′-[1-(2-pyrid­yl)ethyl­idene] acetohydrazide, with two crystallographically independent mol­ecules per asymmetric unit. The non-planar mol­ecules are chemically equal having similar geometric parameters. The previously reported polymorph [Plutenko et al. (2012). Acta Cryst. E68, o3281] was described in space group Cc (Z = 4). The oxime group and the O atom of the amide group are anti with respect to the C—C bond. In the crystal, mol­ecules are connected by N—H...N hydrogen bonds into zigzag chains extending along the b axis.

Key indicators

• Single-crystal X-ray study
• T = 100 K
• Mean [sigma](C-C) = 0.001 Å
• R factor = 0.038
• wR factor = 0.106
• Data-to-parameter ratio = 23.8

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT910_ALERT_3_C Missing # of FCF Reflections Below Th(Min) .....          1

Alert level G
PLAT005_ALERT_5_G No _iucr_refine_instructions_details  in the CIF          ?
PLAT128_ALERT_4_G Alternate Setting of Space-group P21/c   .......      P21/n
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600         61

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

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

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S1. Comment

Oximes are one of the most efficient bridging ligands class. Polydentate ligands containing both oxime and other donor functions are of special interest due to their potential for the bridging coordination modes and mediation of strong magnetic superexchange between metal ions (Penkova et al., 2009; Kanderal et al., 2005; Moroz et al., 2010). Oxime ligands having the pyridyl groups in the molecule have been used in the preparation of complexes with a variety of transition metals, binding to metals in different modes most commonly as chelates or serving as bridge to metals, and the resulting species have been employed in molecular magnetism and supramolecular chemistry (Moroz et al., 2010, 2012). Herein we report a second polymorph of 2-[1-(3,5-dimethyl)pyrazolyl]-2-hydroxyimino-N'-[1-(2-pyridyl)ethylidene] acetohydrazide (II) (Fig. 1). In comparison, the first polymorph I described previously (Plutenko et al., 2012), crystallized in monoclinic space group Cc, Z = 4, while the title compound II crystallized in space group P21/n with Z = 8 (Fig. 1).

Bond lengths N-N', N-C and C-O of the amide group are 1.3693 (10), 1.3589 (11) and 1.2162 (11) respectively for molecule A and 1.3705 (11), 1.3603 (11) and 1.2156 (11) respectively for molecule B. Such bond lengths are typical for the protonated amide groups (Kanderal et al., 2005). The oxime group is situated in anti- position to the amide group which was shown earlier in the structures of the amide derivatives of 2-hydroxyiminopropanoic acid (Onindo et al., 1995; Sliva et al., 1997; Fritsky et al., 2006). The NC(=NOH)C(O)NH fragment deviates from planarity because of a twist between the oxime and the amide groups about the C(8)-C9 and C(22)-C(23) bonds; the O(1)-C(8)-C(9)-N(3) and O(22)-C(23)-C(9)-N(8) torsion angles are -175.953 (2)° and 164.073 (2)°. The bond lengths N-O and C-N of the oxime group are 1.3615 (9) and 1.2836 (11) Å respectively for A and 1.3645 (10) and 1.2819 (11) Å respectively for B. The bond lengths and angles within the oxime groups are normal and comparable to those in the related structures (Świątek-Kozłowska et al., 2000; Mokhir et al., 2002; Fritsky et al., 1998). The C=N and N—O bond lengths in the oxime moiety of the molecule clearly indicates that the oxime group exists in the nitroso rather than in the isonitroso form (Duda et al., 1997; Kanderal et al., 2005; Fritsky et al., 2004).

The C-C, C-N and N-N' (1,331 (0) – 1,409 (0) Å) bond lengths in the pyrazole ring exhibit normal values (Penkova et al., 2010). The angles C-C'-C'', C-N-C', N-C-C' and N-N'-C are near 108°. The pyrazole ring deviates from the plane formed by other atoms of ligand molecule. The N(4)-C(9)-N(5)-N(6) and torsion angles are -103.589 (2) and 105.359 (2)° respectively. The C-N and C-C bond lengths in the pyridine rings are normal for 2-substituted pyridine derivatives (Fritsky et al., 2000; Krämer et al., 2000; Strotmeyer et al., 2003).

In the crystal packing both molecules A and B are each connected by N-H···N hydrogen bonds, where the oxime nitrogen acts as donor and the pyrazole nitrogen atom acts as acceptor (Table 1). Thus, zig-zag supramolecular chains along b-axis are formed.

Related literature

For uses of oxime ligands, see: Penkova et al. (2009); Kanderal et al. (2005). For uses of oximes having additional donor functions as versatile ligands, see: Fritsky et al. (1998, 2004, 2006), Kanderal et al. (2005), Onindo et al. (1995); Sliva et al. (1997). For related structures, see: Duda et al. (1997); Kanderal et al. (2005); Krämer & Fritsky (2000); Moroz et al. (2010, 2012); Sliva et al. (1997); Świątek-Kozłowska et al. (2000); Mokhir et al. (2002); Penkova et al. (2010); Strotmeyer et al. (2003); Fritsky et al. (2000). For structure of the first polymorph, see Plutenko et al. (2012). For the synthesis, see: Kozikowski & Adamczyk (1983).

S2. Experimental

The present compound was synthesized according to Plutenko et al. (2012):

Synthesis of ethyl 2-[1-(3,5-dimethyl)pyrazolyl]-2-hydroxyiminoacetate: A mixture of ethyl 2-chloro-2-hydroxyiminoacetate synthesized according to Kozikowski et al. (1983) (0.906g, 6 mmol) and 3,5-dimethylpyrazol (1.152g, 12 mmol) in 10 ml of chloroform was left for evaporation in the air overnight. The resulting precipitate was crystallized from water. Yield: 1.12g (88 %).

Synthesis of 2-[1-(3,5-dimethyl)pyrazolyl]-2-hydroxyiminoacetohydrazide: A solution of hydrazine hydrate (0.57 ml, 60%, 10.6 mmol) in water was added to a solution of ethyl 2-[1-(3,5-dimethyl)pyrazolyl]-2-hydroxyiminoacetate (1.12g, 5.3 mmol) in methanol (30 ml). The resulting mixture was heating under reflux for 1.5 hours. After that solvent was evaporated and product was crystallized from methanol. Yield 0.5g (48 %).

Synthesis of 2-[1-(3,5-dimethyl)pyrazolyl]-2-hydroxyimino-N'-[1-(2-pyridyl)ethylidene]acetohydrazide: A solution of 2-[1-(3,5-dimethyl)pyrazolyl]-2-hydroxyiminoacetohydrazide (0.5g, 2.54 mmol) in methanol (30 ml) was treated with 2-acetylpyridine (0.307g, 2.54 mmol) and the mixture was heated under reflux for 3 hours. After that the solvent was evaporated in vacuum and the product was crystallized from methanol. Yield 0.65g (85 %).

S3. Refinement

OH, NH and CH₃ hydrogen atoms were located from difference Fourier maps, other hydrogen atoms were positioned geometrically and all but H(N) and H(O) were refined at idealized positions riding on the parent atoms, with C—H = 0.95–0.98 Å, and U_iso = 1.2–1.5 U_eq(parent atom). H(N) and H(O) atoms were refined freely with Uiso(H) = 1.2U_eq(N) or 1.5U_eq(O). All CH₃ hydrogen atoms were allowed to rotate but not to tip. The highest peak is located 0.74 Å from atom C9 and the deepest hole is located 1.03 Å from atom N4.

Computing details

Data collection: APEX2 (Bruker, 2010); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures

	Fig. 1. Molecular structure of molecules A and B of the title compound, with displacement ellipsoids shown at the 50% probability level. H atoms are drawn as spheres of arbitrary radii.
	Fig. 2. Crystal packing viewed along b-axis. Hydrogen bonds are indicated by dashed lines. H atoms not involved in H-bonds are omitted for clarity.

2-(3,5-Dimethyl-1H-pyrazol-1-yl)-2-hydroxyimino-N'-[1-(pyridin-2-yl)ethylidene]acetohydrazide

Crystal data

C14H16N6O2	F(000) = 1264
Mr = 300.33	Dx = 1.343 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 9866 reflections
a = 19.4734 (4) Å	θ = 2.8–31.6°
b = 7.7679 (2) Å	µ = 0.10 mm^−1
c = 19.8042 (4) Å	T = 100 K
β = 97.552 (1)°	Block, colourless
V = 2969.74 (11) Å^3	0.39 × 0.33 × 0.28 mm
Z = 8

Data collection

Bruker Kappa APEXII DUO CCD diffractometer	9973 independent reflections
Radiation source: fine-focus sealed tube	8213 reflections with I > 2σ(I)
Curved graphite crystal monochromator	Rint = 0.027
Detector resolution: 16 pixels mm^-1	θmax = 31.7°, θmin = 1.6°
φ scans and ω scans with κ offset	h = −28→28
Absorption correction: multi-scan (SADABS; Sheldrick, 2008)	k = −11→11
Tmin = 0.964, Tmax = 0.974	l = −29→29
64574 measured reflections

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)] = 0.038	Hydrogen site location: difference Fourier map
wR(F^2) = 0.106	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0555P)^2 + 0.8835P] where P = (Fo^2 + 2Fc^2)/3
9973 reflections	(Δ/σ)max = 0.001
419 parameters	Δρmax = 0.49 e Å^−3
0 restraints	Δρmin = −0.25 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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	0.23337 (4)	0.28795 (10)	0.54568 (4)	0.02361 (15)
O2	0.24501 (3)	0.03509 (9)	0.75693 (3)	0.01915 (13)
H2O	0.2117 (9)	−0.025 (2)	0.7803 (8)	0.046 (4)*
O3	0.45992 (4)	0.18904 (10)	0.25984 (4)	0.02138 (14)
O4	0.24039 (3)	−0.02793 (9)	0.25464 (3)	0.01929 (13)
H4O	0.2170 (9)	−0.087 (2)	0.2888 (9)	0.052 (5)*
N1	0.09028 (4)	0.25022 (10)	0.52885 (4)	0.01688 (14)
H2N	0.1179 (7)	0.1554 (19)	0.6202 (7)	0.030 (4)*
N2	0.13341 (4)	0.20263 (11)	0.58605 (4)	0.01772 (15)
N3	0.20653 (4)	0.08553 (10)	0.69785 (4)	0.01612 (14)
N4	0.31385 (4)	0.18287 (9)	0.66691 (4)	0.01408 (13)
N5	0.34090 (4)	0.34130 (10)	0.68560 (4)	0.01503 (14)
N6	0.47175 (4)	0.22400 (11)	0.40050 (4)	0.01828 (15)
H7N	0.3769 (8)	0.131 (2)	0.3781 (7)	0.033 (4)*
N7	0.41368 (4)	0.16597 (11)	0.36033 (4)	0.01910 (15)
N8	0.30122 (4)	0.02189 (10)	0.29165 (4)	0.01648 (14)
N9	0.33140 (4)	0.11492 (9)	0.18502 (4)	0.01428 (13)
N10	0.31523 (4)	0.27505 (9)	0.15885 (4)	0.01431 (13)
N11	−0.08655 (4)	0.22180 (11)	0.46263 (4)	0.01968 (15)
N16	0.53482 (4)	0.25441 (12)	0.57576 (4)	0.02314 (17)
C1	0.00368 (5)	0.38205 (12)	0.41941 (4)	0.01765 (16)
H1	0.0500	0.4235	0.4260	0.021*
C2	−0.04025 (5)	0.42371 (13)	0.36098 (5)	0.02003 (17)
H2	−0.0242	0.4911	0.3262	0.024*
C3	−0.10829 (5)	0.36503 (14)	0.35412 (5)	0.02119 (18)
H3	−0.1399	0.3915	0.3147	0.025*
C4	−0.12863 (5)	0.26698 (14)	0.40633 (5)	0.02197 (18)
H4	−0.1754	0.2292	0.4020	0.026*
C5	−0.02103 (4)	0.27821 (12)	0.46846 (4)	0.01566 (15)
C6	0.02508 (4)	0.22338 (12)	0.53059 (4)	0.01642 (16)
C7	−0.00595 (5)	0.14381 (14)	0.58873 (5)	0.02139 (18)
H7A	0.0014	0.2204	0.6284	0.032*
H7B	0.0163	0.0326	0.6004	0.032*
H7C	−0.0557	0.1266	0.5754	0.032*
C8	0.20300 (4)	0.22472 (11)	0.58951 (4)	0.01588 (15)
C9	0.24134 (4)	0.16000 (11)	0.65548 (4)	0.01431 (15)
C10	0.40910 (4)	0.31716 (12)	0.69744 (4)	0.01572 (15)
C11	0.45625 (5)	0.46298 (13)	0.72087 (5)	0.02263 (18)
H11A	0.4290	0.5586	0.7357	0.034*
H11B	0.4807	0.5012	0.6833	0.034*
H11C	0.4900	0.4249	0.7590	0.034*
C12	0.42576 (4)	0.14436 (12)	0.68606 (4)	0.01676 (16)
H12	0.4708	0.0952	0.6904	0.020*
C13	0.36410 (5)	0.06078 (11)	0.66743 (4)	0.01532 (15)
C14	0.34846 (6)	−0.12230 (12)	0.64969 (5)	0.02392 (19)
H14A	0.3254	−0.1296	0.6027	0.036*
H14B	0.3180	−0.1697	0.6807	0.036*
H14C	0.3917	−0.1884	0.6540	0.036*
C15	0.58299 (5)	0.37652 (12)	0.48087 (5)	0.01906 (17)
H15	0.5786	0.3991	0.4334	0.023*
C16	0.64057 (5)	0.43270 (14)	0.52371 (5)	0.02242 (18)
H16	0.6768	0.4924	0.5059	0.027*
C17	0.64462 (5)	0.40039 (15)	0.59324 (5)	0.0246 (2)
H17	0.6834	0.4378	0.6239	0.030*
C18	0.59051 (5)	0.31215 (15)	0.61631 (5)	0.0256 (2)
H18	0.5930	0.2913	0.6638	0.031*
C19	0.53144 (5)	0.28602 (12)	0.50876 (5)	0.01802 (16)
C20	0.46937 (5)	0.21770 (12)	0.46535 (5)	0.01815 (16)
C21	0.41019 (5)	0.14593 (15)	0.49801 (5)	0.02440 (19)
H21A	0.3683	0.2132	0.4836	0.037*
H21B	0.4213	0.1520	0.5477	0.037*
H21C	0.4023	0.0257	0.4841	0.037*
C22	0.41232 (5)	0.15523 (11)	0.29161 (4)	0.01576 (15)
C23	0.34393 (4)	0.09303 (11)	0.25621 (4)	0.01461 (15)
C24	0.30610 (4)	0.25375 (12)	0.09149 (4)	0.01495 (15)
C25	0.28426 (5)	0.40217 (13)	0.04578 (5)	0.02124 (18)
H25A	0.2684	0.4966	0.0727	0.032*
H25B	0.2464	0.3662	0.0111	0.032*
H25C	0.3236	0.4411	0.0236	0.032*
C26	0.31770 (5)	0.08076 (12)	0.07453 (4)	0.01728 (16)
H26	0.3155	0.0333	0.0301	0.021*
C27	0.33293 (5)	−0.00536 (11)	0.13529 (4)	0.01654 (16)
C28	0.34777 (6)	−0.18986 (13)	0.15142 (6)	0.0263 (2)
H28A	0.3918	−0.1995	0.1815	0.039*
H28B	0.3509	−0.2533	0.1092	0.039*
H28C	0.3104	−0.2383	0.1742	0.039*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0180 (3)	0.0324 (4)	0.0200 (3)	−0.0017 (3)	0.0009 (2)	0.0084 (3)
O2	0.0143 (3)	0.0255 (3)	0.0163 (3)	−0.0025 (2)	−0.0030 (2)	0.0069 (2)
O3	0.0169 (3)	0.0272 (3)	0.0204 (3)	−0.0039 (3)	0.0040 (2)	−0.0007 (3)
O4	0.0160 (3)	0.0253 (3)	0.0161 (3)	−0.0069 (2)	0.0004 (2)	0.0022 (2)
N1	0.0141 (3)	0.0204 (3)	0.0149 (3)	0.0017 (3)	−0.0026 (2)	0.0008 (3)
N2	0.0129 (3)	0.0239 (4)	0.0154 (3)	0.0002 (3)	−0.0019 (3)	0.0040 (3)
N3	0.0140 (3)	0.0177 (3)	0.0155 (3)	−0.0008 (3)	−0.0022 (2)	0.0023 (3)
N4	0.0114 (3)	0.0138 (3)	0.0166 (3)	−0.0002 (2)	0.0003 (2)	0.0001 (3)
N5	0.0129 (3)	0.0145 (3)	0.0173 (3)	−0.0012 (2)	0.0005 (2)	−0.0010 (3)
N6	0.0155 (3)	0.0217 (4)	0.0167 (3)	−0.0014 (3)	−0.0011 (3)	−0.0006 (3)
N7	0.0158 (3)	0.0260 (4)	0.0152 (3)	−0.0046 (3)	0.0007 (3)	−0.0001 (3)
N8	0.0152 (3)	0.0177 (3)	0.0161 (3)	−0.0020 (3)	0.0005 (3)	0.0012 (3)
N9	0.0167 (3)	0.0135 (3)	0.0129 (3)	−0.0001 (2)	0.0025 (2)	0.0001 (2)
N10	0.0146 (3)	0.0148 (3)	0.0135 (3)	0.0014 (2)	0.0016 (2)	0.0007 (2)
N11	0.0137 (3)	0.0266 (4)	0.0181 (3)	−0.0003 (3)	−0.0002 (3)	−0.0005 (3)
N16	0.0203 (4)	0.0316 (4)	0.0172 (3)	0.0015 (3)	0.0009 (3)	−0.0005 (3)
C1	0.0149 (4)	0.0220 (4)	0.0155 (4)	0.0001 (3)	0.0001 (3)	−0.0009 (3)
C2	0.0201 (4)	0.0246 (4)	0.0148 (4)	0.0016 (3)	0.0001 (3)	−0.0002 (3)
C3	0.0176 (4)	0.0294 (5)	0.0152 (4)	0.0043 (3)	−0.0031 (3)	−0.0027 (3)
C4	0.0132 (4)	0.0321 (5)	0.0195 (4)	0.0000 (3)	−0.0020 (3)	−0.0028 (4)
C5	0.0132 (4)	0.0186 (4)	0.0146 (3)	0.0022 (3)	−0.0002 (3)	−0.0022 (3)
C6	0.0146 (4)	0.0194 (4)	0.0147 (4)	0.0015 (3)	−0.0001 (3)	−0.0006 (3)
C7	0.0169 (4)	0.0288 (5)	0.0184 (4)	0.0009 (3)	0.0021 (3)	0.0037 (3)
C8	0.0141 (4)	0.0171 (4)	0.0155 (3)	0.0003 (3)	−0.0014 (3)	0.0007 (3)
C9	0.0118 (3)	0.0148 (3)	0.0155 (3)	−0.0005 (3)	−0.0010 (3)	0.0002 (3)
C10	0.0126 (4)	0.0201 (4)	0.0142 (3)	−0.0009 (3)	0.0009 (3)	0.0011 (3)
C11	0.0165 (4)	0.0241 (4)	0.0263 (4)	−0.0054 (3)	−0.0005 (3)	−0.0009 (4)
C12	0.0130 (4)	0.0218 (4)	0.0155 (4)	0.0033 (3)	0.0019 (3)	0.0017 (3)
C13	0.0161 (4)	0.0164 (4)	0.0135 (3)	0.0030 (3)	0.0021 (3)	0.0006 (3)
C14	0.0264 (5)	0.0166 (4)	0.0287 (5)	0.0028 (3)	0.0034 (4)	−0.0036 (3)
C15	0.0176 (4)	0.0210 (4)	0.0185 (4)	0.0024 (3)	0.0019 (3)	−0.0019 (3)
C16	0.0162 (4)	0.0257 (4)	0.0249 (4)	0.0021 (3)	0.0010 (3)	−0.0042 (4)
C17	0.0165 (4)	0.0332 (5)	0.0229 (4)	0.0050 (4)	−0.0021 (3)	−0.0070 (4)
C18	0.0216 (4)	0.0367 (5)	0.0175 (4)	0.0052 (4)	−0.0005 (3)	−0.0023 (4)
C19	0.0167 (4)	0.0204 (4)	0.0164 (4)	0.0030 (3)	0.0004 (3)	−0.0018 (3)
C20	0.0165 (4)	0.0205 (4)	0.0172 (4)	0.0007 (3)	0.0015 (3)	−0.0002 (3)
C21	0.0223 (4)	0.0314 (5)	0.0197 (4)	−0.0058 (4)	0.0034 (3)	0.0005 (4)
C22	0.0156 (4)	0.0151 (4)	0.0161 (4)	0.0001 (3)	0.0004 (3)	0.0005 (3)
C23	0.0154 (4)	0.0145 (3)	0.0138 (3)	0.0001 (3)	0.0012 (3)	0.0008 (3)
C24	0.0116 (3)	0.0198 (4)	0.0134 (3)	0.0001 (3)	0.0015 (3)	−0.0001 (3)
C25	0.0212 (4)	0.0259 (4)	0.0162 (4)	0.0049 (3)	0.0012 (3)	0.0030 (3)
C26	0.0159 (4)	0.0212 (4)	0.0149 (4)	−0.0013 (3)	0.0027 (3)	−0.0037 (3)
C27	0.0158 (4)	0.0162 (4)	0.0183 (4)	−0.0019 (3)	0.0048 (3)	−0.0031 (3)
C28	0.0349 (5)	0.0151 (4)	0.0311 (5)	−0.0007 (4)	0.0126 (4)	−0.0015 (4)

Geometric parameters (Å, º)

O1—C8	1.2162 (11)	C7—H7B	0.9800
O2—N3	1.3615 (9)	C7—H7C	0.9800
O2—H2O	0.964 (17)	C8—C9	1.5035 (12)
O3—C22	1.2156 (11)	C10—C12	1.4061 (13)
O4—N8	1.3645 (10)	C10—C11	1.4931 (13)
O4—H4O	0.978 (18)	C11—H11A	0.9800
N1—C6	1.2915 (11)	C11—H11B	0.9800
N1—N2	1.3693 (10)	C11—H11C	0.9800
N2—C8	1.3589 (11)	C12—C13	1.3721 (12)
N2—H2N	0.859 (15)	C12—H12	0.9500
N3—C9	1.2836 (11)	C13—C14	1.4868 (13)
N4—C13	1.3619 (11)	C14—H14A	0.9800
N4—N5	1.3703 (10)	C14—H14B	0.9800
N4—C9	1.4115 (11)	C14—H14C	0.9800
N5—C10	1.3313 (11)	C15—C16	1.3846 (13)
N6—C20	1.2921 (12)	C15—C19	1.3974 (13)
N6—N7	1.3705 (11)	C15—H15	0.9500
N7—C22	1.3603 (11)	C16—C17	1.3916 (14)
N7—H7N	0.882 (15)	C16—H16	0.9500
N8—C23	1.2819 (11)	C17—C18	1.3840 (15)
N9—C27	1.3607 (11)	C17—H17	0.9500
N9—N10	1.3683 (10)	C18—H18	0.9500
N9—C23	1.4090 (11)	C19—C20	1.4862 (13)
N10—C24	1.3327 (11)	C20—C21	1.5010 (13)
N11—C5	1.3396 (11)	C21—H21A	0.9800
N11—C4	1.3408 (12)	C21—H21B	0.9800
N16—C18	1.3391 (13)	C21—H21C	0.9800
N16—C19	1.3425 (12)	C22—C23	1.5010 (12)
C1—C2	1.3841 (12)	C24—C26	1.4105 (13)
C1—C5	1.3959 (12)	C24—C25	1.4927 (13)
C1—H1	0.9500	C25—H25A	0.9800
C2—C3	1.3909 (14)	C25—H25B	0.9800
C2—H2	0.9500	C25—H25C	0.9800
C3—C4	1.3834 (14)	C26—C27	1.3747 (13)
C3—H3	0.9500	C26—H26	0.9500
C4—H4	0.9500	C27—C28	1.4884 (13)
C5—C6	1.4872 (12)	C28—H28A	0.9800
C6—C7	1.5019 (13)	C28—H28B	0.9800
C7—H7A	0.9800	C28—H28C	0.9800
N3—O2—H2O	102.8 (10)	C13—C12—H12	126.8
N8—O4—H4O	102.3 (10)	C10—C12—H12	126.8
C6—N1—N2	115.63 (8)	N4—C13—C12	105.97 (8)
C8—N2—N1	120.46 (8)	N4—C13—C14	122.66 (8)
C8—N2—H2N	117.7 (10)	C12—C13—C14	131.37 (8)
N1—N2—H2N	121.8 (10)	C13—C14—H14A	109.5
C9—N3—O2	114.41 (7)	C13—C14—H14B	109.5
C13—N4—N5	111.90 (7)	H14A—C14—H14B	109.5
C13—N4—C9	128.04 (8)	C13—C14—H14C	109.5
N5—N4—C9	119.83 (7)	H14A—C14—H14C	109.5
C10—N5—N4	105.09 (7)	H14B—C14—H14C	109.5
C20—N6—N7	115.45 (8)	C16—C15—C19	118.83 (9)
C22—N7—N6	120.46 (8)	C16—C15—H15	120.6
C22—N7—H7N	118.1 (10)	C19—C15—H15	120.6
N6—N7—H7N	121.4 (10)	C15—C16—C17	119.05 (9)
C23—N8—O4	114.08 (7)	C15—C16—H16	120.5
C27—N9—N10	112.07 (7)	C17—C16—H16	120.5
C27—N9—C23	128.60 (8)	C18—C17—C16	117.99 (9)
N10—N9—C23	119.32 (7)	C18—C17—H17	121.0
C24—N10—N9	105.08 (7)	C16—C17—H17	121.0
C5—N11—C4	117.20 (8)	N16—C18—C17	124.04 (9)
C18—N16—C19	117.51 (9)	N16—C18—H18	118.0
C2—C1—C5	119.02 (8)	C17—C18—H18	118.0
C2—C1—H1	120.5	N16—C19—C15	122.57 (9)
C5—C1—H1	120.5	N16—C19—C20	115.91 (8)
C1—C2—C3	118.76 (9)	C15—C19—C20	121.53 (8)
C1—C2—H2	120.6	N6—C20—C19	115.39 (8)
C3—C2—H2	120.6	N6—C20—C21	124.91 (8)
C4—C3—C2	118.04 (8)	C19—C20—C21	119.70 (8)
C4—C3—H3	121.0	C20—C21—H21A	109.5
C2—C3—H3	121.0	C20—C21—H21B	109.5
N11—C4—C3	124.19 (9)	H21A—C21—H21B	109.5
N11—C4—H4	117.9	C20—C21—H21C	109.5
C3—C4—H4	117.9	H21A—C21—H21C	109.5
N11—C5—C1	122.73 (8)	H21B—C21—H21C	109.5
N11—C5—C6	116.25 (8)	O3—C22—N7	126.06 (8)
C1—C5—C6	121.02 (8)	O3—C22—C23	121.19 (8)
N1—C6—C5	114.87 (8)	N7—C22—C23	112.74 (7)
N1—C6—C7	125.65 (8)	N8—C23—N9	124.08 (8)
C5—C6—C7	119.48 (8)	N8—C23—C22	118.86 (8)
C6—C7—H7A	109.5	N9—C23—C22	117.06 (7)
C6—C7—H7B	109.5	N10—C24—C26	110.62 (8)
H7A—C7—H7B	109.5	N10—C24—C25	120.07 (8)
C6—C7—H7C	109.5	C26—C24—C25	129.28 (8)
H7A—C7—H7C	109.5	C24—C25—H25A	109.5
H7B—C7—H7C	109.5	C24—C25—H25B	109.5
O1—C8—N2	126.18 (8)	H25A—C25—H25B	109.5
O1—C8—C9	121.51 (8)	C24—C25—H25C	109.5
N2—C8—C9	112.31 (7)	H25A—C25—H25C	109.5
N3—C9—N4	123.70 (8)	H25B—C25—H25C	109.5
N3—C9—C8	118.31 (8)	C27—C26—C24	106.14 (8)
N4—C9—C8	117.99 (7)	C27—C26—H26	126.9
N5—C10—C12	110.61 (8)	C24—C26—H26	126.9
N5—C10—C11	120.42 (8)	N9—C27—C26	106.07 (8)
C12—C10—C11	128.96 (8)	N9—C27—C28	121.87 (8)
C10—C11—H11A	109.5	C26—C27—C28	132.05 (9)
C10—C11—H11B	109.5	C27—C28—H28A	109.5
H11A—C11—H11B	109.5	C27—C28—H28B	109.5
C10—C11—H11C	109.5	H28A—C28—H28B	109.5
H11A—C11—H11C	109.5	C27—C28—H28C	109.5
H11B—C11—H11C	109.5	H28A—C28—H28C	109.5
C13—C12—C10	106.42 (8)	H28B—C28—H28C	109.5

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2O···N5^i	0.964 (17)	1.664 (17)	2.6193 (10)	170.1 (16)
O4—H4O···N10^ii	0.978 (18)	1.670 (18)	2.6341 (10)	167.8 (17)

Symmetry codes: (i) −x+1/2, y−1/2, −z+3/2; (ii) −x+1/2, y−1/2, −z+1/2.