N2,N2′-Bis(3-nitro­benzyl­idene)pyridine-2,6-dicarbohydrazide dimethyl­formamide disolvate trihydrate

Cheng, C.; Liu, H.

doi:10.1107/S1600536807056607

organic compounds

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ISSN: 2056-9890

Volume 64| Part 1| January 2008| Page o155

https://doi.org/10.1107/S1600536807056607

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N²,N^2′-Bis(3-nitrobenzylidene)pyridine-2,6-dicarbohydrazide dimethylformamide disolvate trihydrate

Cuixia Cheng ^a and Haowen Liu ^a ^*

^aKey Laboratory of Catalysis and Materials Science of Hubei Provence, College of Chemistry and Materials Science, South Central University of Nationalities, Wuhan 430074, People's Republic of China
^*Correspondence e-mail: liuhwchem@mail.scuec.edu.cn

(Received 7 November 2007; accepted 7 November 2007; online 6 December 2007)

In the title compound, C₂₁H₁₅N₇O₆·2C₃H₇NO·3H₂O, the N²,N^2′-bis(3-nitrobenzylidene)pyridine-2,6-dicarbohydrazide and one water molecule are located on a twofold rotation axis. The molecules are connected by hydrogen bonds. One dimethylformamide molecule is disordered over two positions; the site occupancy factors are ca 0.8 and 0.2.

Related literature

Tridentate ligands with 2,6-dipicolinoyhydrazone have been intensively studied due to their interesting coordination modes (Paolucci et al., 1985 ; Chen et al., 1996 , 1997 ).

Experimental

Crystal data

C₂₁H₁₅N₇O₆·2C₃H₇NO·3H₂O
M_r = 661.64
Monoclinic, C 2/c
a = 24.704 (3) Å
b = 10.4815 (12) Å
c = 14.4792 (16) Å
β = 120.355 (2)°
V = 3235.2 (6) Å³
Z = 4
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 273 (2) K
0.22 × 0.20 × 0.20 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2001 ) T_min = 0.977, T_max = 0.979
9211 measured reflections
3170 independent reflections
2222 reflections with I > 2σ(I)
R_int = 0.018

Refinement

R[F² > 2σ(F²)] = 0.049
wR(F²) = 0.169
S = 1.08
3170 reflections
272 parameters
51 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.43 e Å⁻³
Δρ_min = −0.17 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O5—H5A⋯O6ⁱ	0.833 (16)	1.864 (17)	2.692 (2)	173 (3)
C9—H9⋯O4ⁱⁱ	0.93	2.60	3.438 (10)	150
N2—H2A⋯O5	0.90 (2)	2.03 (2)	2.9082 (19)	166.4 (19)
O6—H6A⋯O1	0.799 (18)	2.05 (2)	2.834 (2)	167 (4)
O6—H6B⋯O4	0.843 (18)	1.89 (2)	2.728 (7)	175 (4)
C5—H5⋯O5	0.93	2.48	3.2860 (18)	145
Symmetry codes: (i) $[x, -y+1, z+{\script{1\over 2}}]$ ; (ii) x, y-1, z.

Data collection: SMART (Bruker, 2001 ); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003 ); software used to prepare material for publication: SHELXTL (Bruker, 2001).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536807056607/bt2593sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536807056607/bt2593Isup2.hkl

checkCIF report

Comment top

In recent years, hydrazones, possessing different donor atoms or cavities, have been investigated due to their coordinating capability and some biological activities, especially in bis-arylhydrazones. (Paolucci et al., 1985; Chen et al., 1996, 1997) 2,6-dipicolinoylhydrazine as a multidentate ligand is very useful for the research of coordination modes. As part of our continuing studies of the structures of hydrazones, we report here the synthesis and crystal structure of a novel tridentate ligand. One water molecule is inserted in the cavity of the hydrazone, each of the remaining water molecules and dimethylformamide solvents are located at the two sides of pyridyl ring. N, N-dimethylformamide molecules are disordered over two sites with unequal occupancy (Figure 1). In the title compound (I), the two spacer units (one is from atom C1 to C6, another is from atom C1a to C6a.) adopt a nearly planar all-trans conformation. The pyridyl ring is effectively coplanar with two spacer units. The two independent aryl rings are essentially coplanar with these spacer units, while the nitro-groups are slightly twisted out of the plane of these spacer units. The independent molecular components are linked by hydrogen bonds.

Related literature top

Tridentate ligands with 2,6-dipicolinoyhydrazone have been intensively studied due to their interesting coordination modes (Paolucci et al., 1985; Chen et al., 1996, 1997).

Experimental top

To a solution of 3-nitrobenzaldehyde (1.66 g, 11 mmol) in absolute ethanol (40 ml) a suspension of 2,6-dipicolinoyhydrazine in the same solvent (50 ml) was added at 353 K. The mixture was left to react at reflux for 10 h, then the pale yellow product was filtered, washed with hot ethanol (20 ml portion) three times and dried in vacuo. Crystals suitable for X-ray diffraction were obtained from dimethylformamide-methanol (3:1 v/v) over a period of about three weeks. Melting point: 601 K.

Structure description top

Tridentate ligands with 2,6-dipicolinoyhydrazone have been intensively studied due to their interesting coordination modes (Paolucci et al., 1985; Chen et al., 1996, 1997).

Computing details top

Data collection: SMART (Bruker 2001); cell refinement: SAINT-Plus (Bruker 2001); data reduction: SAINT-Plus (Bruker 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXTL (Bruker 2001).

Figures top

Fig. 1. The molecular structure of the title compound with displacement ellipsoids drawn at the 50% probability level. Dashed lines indicate hydrogen bonds.

N²,N^2'—Bis(3-nitrobenzylidene)pyridine-2,6-dicarbohydrazide dimethylformamide disolvate trihydrate top

Crystal data top

C₂₁H₁₅N₇O₆·2C₃H₇NO·3H₂O	F(000) = 1392
M_r = 661.64	D_x = 1.358 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 2433 reflections
a = 24.704 (3) Å	θ = 2.4–24.1°
b = 10.4815 (12) Å	µ = 0.11 mm⁻¹
c = 14.4792 (16) Å	T = 273 K
β = 120.355 (2)°	Block, pale yellow
V = 3235.2 (6) Å³	0.22 × 0.20 × 0.20 mm
Z = 4

Data collection top

Bruker SMART CCD area-detector diffractometer	3170 independent reflections
Radiation source: fine-focus sealed tube	2222 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.018
phi and ω scans	θ_max = 26.0°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 2001)	h = −30→30
T_min = 0.977, T_max = 0.979	k = −12→12
9211 measured reflections	l = −17→17

Refinement top

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)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.169	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ²(F_o²) + (0.1056P)² + 0.1192P] where P = (F_o² + 2F_c²)/3
3170 reflections	(Δ/σ)_max < 0.001
272 parameters	Δρ_max = 0.43 e Å⁻³
51 restraints	Δρ_min = −0.17 e Å⁻³

Crystal data top

C₂₁H₁₅N₇O₆·2C₃H₇NO·3H₂O	V = 3235.2 (6) Å³
M_r = 661.64	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 24.704 (3) Å	µ = 0.11 mm⁻¹
b = 10.4815 (12) Å	T = 273 K
c = 14.4792 (16) Å	0.22 × 0.20 × 0.20 mm
β = 120.355 (2)°

Data collection top

Bruker SMART CCD area-detector diffractometer	3170 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2001)	2222 reflections with I > 2σ(I)
T_min = 0.977, T_max = 0.979	R_int = 0.018
9211 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.049	51 restraints
wR(F²) = 0.169	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	Δρ_max = 0.43 e Å⁻³
3170 reflections	Δρ_min = −0.17 e Å⁻³
272 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
C1	0.02389 (8)	0.81428 (16)	0.20004 (15)	0.0577 (5)
C2	0.02453 (11)	0.94590 (19)	0.1985 (2)	0.0813 (7)
H2	0.0415	0.9888	0.1627	0.098*
C3	0.0000	1.0127 (3)	0.2500	0.0923 (11)
H3	0.0000	1.1015	0.2500	0.111*
C4	0.05053 (9)	0.74204 (17)	0.14262 (16)	0.0583 (5)
C5	0.07425 (8)	0.42180 (18)	0.11595 (15)	0.0603 (5)
H5	0.0574	0.3909	0.1562	0.072*
C6	0.09827 (8)	0.33080 (17)	0.06894 (15)	0.0563 (5)
C7	0.09512 (10)	0.20133 (19)	0.08487 (19)	0.0724 (6)
H7	0.0777	0.1746	0.1255	0.087*
C8	0.11679 (11)	0.11154 (19)	0.0428 (2)	0.0797 (7)
H8	0.1135	0.0253	0.0543	0.096*
C9	0.14336 (10)	0.1483 (2)	−0.01612 (18)	0.0739 (6)
H9	0.1585	0.0882	−0.0447	0.089*
C10	0.14703 (8)	0.27662 (19)	−0.03173 (15)	0.0601 (5)
C11	0.12441 (8)	0.36987 (18)	0.00764 (15)	0.0562 (5)
H11	0.1265	0.4558	−0.0062	0.067*
N1	0.0000	0.74859 (17)	0.2500	0.0504 (5)
N2	0.05128 (7)	0.61435 (14)	0.15307 (13)	0.0569 (4)
H2A	0.0369 (9)	0.573 (2)	0.1909 (17)	0.068*
N3	0.07557 (7)	0.54085 (15)	0.10391 (12)	0.0569 (4)
N4	0.17601 (8)	0.3184 (2)	−0.09403 (15)	0.0781 (5)
O1	0.06961 (7)	0.79807 (14)	0.09078 (13)	0.0815 (5)
O2	0.18130 (10)	0.4303 (2)	−0.10546 (17)	0.1116 (7)
O3	0.19383 (10)	0.2370 (2)	−0.13148 (17)	0.1126 (7)
O5	0.0000	0.44674 (18)	0.2500	0.0710 (6)
H5A	0.0265 (11)	0.402 (2)	0.3000 (19)	0.107*
O6	0.07737 (13)	0.7056 (2)	−0.08613 (17)	0.1214 (8)
H6A	0.070 (2)	0.726 (4)	−0.040 (3)	0.182*
H6B	0.1015 (18)	0.756 (3)	−0.094 (4)	0.182*
C12	0.18750 (15)	0.7702 (3)	−0.1301 (2)	0.0744 (9)	0.781 (4)
H12A	0.1756	0.6860	−0.1300	0.089*	0.781 (4)
C13	0.2617 (2)	0.6854 (4)	−0.1750 (4)	0.1137 (14)	0.781 (4)
H13A	0.2487	0.6065	−0.1586	0.171*	0.781 (4)
H13B	0.3065	0.6928	−0.1325	0.171*	0.781 (4)
H13C	0.2491	0.6871	−0.2495	0.171*	0.781 (4)
C14	0.2445 (2)	0.9163 (4)	−0.1734 (4)	0.1282 (17)	0.781 (4)
H14A	0.2229	0.9772	−0.1541	0.192*	0.781 (4)
H14B	0.2301	0.9235	−0.2484	0.192*	0.781 (4)
H14C	0.2888	0.9327	−0.1330	0.192*	0.781 (4)
O4	0.1592 (3)	0.8575 (10)	−0.1098 (8)	0.096 (2)	0.781 (4)
N5	0.2325 (5)	0.7922 (5)	−0.1510 (10)	0.073 (2)	0.781 (4)
C12'	0.1999 (5)	0.8886 (10)	−0.1353 (9)	0.082 (3)	0.219 (4)
H12B	0.2177	0.9686	−0.1109	0.099*	0.219 (4)
C13'	0.2179 (6)	0.6684 (10)	−0.1392 (10)	0.095 (4)	0.219 (4)
H13D	0.1813	0.6642	−0.1324	0.142*	0.219 (4)
H13E	0.2544	0.6488	−0.0716	0.142*	0.219 (4)
H13F	0.2141	0.6078	−0.1919	0.142*	0.219 (4)
C14'	0.2747 (6)	0.8196 (17)	−0.1897 (12)	0.121 (6)	0.219 (4)
H14D	0.2748	0.9089	−0.2045	0.181*	0.219 (4)
H14E	0.2695	0.7707	−0.2497	0.181*	0.219 (4)
H14F	0.3137	0.7973	−0.1272	0.181*	0.219 (4)
O4'	0.1497 (12)	0.849 (4)	−0.142 (3)	0.099 (8)	0.219 (4)
N5'	0.2237 (16)	0.7926 (15)	−0.171 (3)	0.062 (6)	0.219 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0639 (10)	0.0489 (10)	0.0711 (12)	−0.0025 (8)	0.0420 (10)	0.0030 (8)
C2	0.1114 (17)	0.0489 (11)	0.1180 (19)	−0.0064 (10)	0.0832 (16)	0.0050 (10)
C3	0.136 (3)	0.0412 (15)	0.138 (3)	0.000	0.097 (3)	0.000
C4	0.0662 (11)	0.0531 (11)	0.0706 (12)	−0.0024 (8)	0.0455 (10)	0.0034 (8)
C5	0.0680 (11)	0.0576 (11)	0.0738 (13)	0.0000 (8)	0.0493 (10)	0.0025 (9)
C6	0.0582 (10)	0.0519 (10)	0.0657 (11)	0.0016 (8)	0.0363 (9)	0.0012 (8)
C7	0.0847 (13)	0.0597 (12)	0.0920 (15)	0.0015 (10)	0.0589 (13)	0.0080 (10)
C8	0.0949 (15)	0.0510 (11)	0.1070 (18)	0.0048 (10)	0.0612 (15)	0.0002 (10)
C9	0.0766 (13)	0.0655 (13)	0.0842 (15)	0.0101 (10)	0.0441 (12)	−0.0066 (10)
C10	0.0562 (10)	0.0695 (12)	0.0600 (11)	0.0031 (8)	0.0334 (9)	−0.0026 (9)
C11	0.0557 (10)	0.0547 (10)	0.0615 (11)	0.0002 (7)	0.0319 (9)	−0.0001 (8)
N1	0.0563 (11)	0.0434 (10)	0.0603 (12)	0.000	0.0359 (10)	0.000
N2	0.0685 (9)	0.0526 (9)	0.0702 (10)	0.0018 (7)	0.0503 (9)	0.0019 (7)
N3	0.0634 (9)	0.0556 (9)	0.0663 (9)	0.0017 (7)	0.0434 (8)	−0.0011 (7)
N4	0.0780 (11)	0.0949 (14)	0.0733 (12)	0.0066 (10)	0.0469 (10)	−0.0077 (10)
O1	0.1125 (12)	0.0662 (9)	0.1074 (12)	−0.0021 (8)	0.0861 (11)	0.0069 (7)
O2	0.1550 (18)	0.0978 (14)	0.1371 (17)	−0.0115 (12)	0.1145 (15)	0.0072 (11)
O3	0.1362 (16)	0.1242 (15)	0.1246 (16)	0.0128 (12)	0.1007 (15)	−0.0147 (12)
O5	0.0975 (16)	0.0544 (12)	0.0868 (15)	0.000	0.0654 (13)	0.000
O6	0.1643 (19)	0.1363 (18)	0.1002 (14)	−0.0651 (14)	0.0939 (14)	−0.0337 (12)
C12	0.090 (2)	0.0651 (18)	0.080 (2)	−0.0044 (15)	0.0518 (17)	−0.0003 (14)
C13	0.114 (3)	0.124 (3)	0.128 (3)	0.012 (2)	0.080 (3)	−0.008 (2)
C14	0.152 (4)	0.118 (3)	0.138 (3)	−0.064 (3)	0.091 (3)	−0.016 (3)
O4	0.119 (3)	0.088 (2)	0.120 (6)	0.003 (3)	0.090 (4)	−0.002 (3)
N5	0.073 (3)	0.085 (3)	0.071 (6)	−0.0111 (18)	0.044 (4)	−0.0078 (18)
C12'	0.094 (6)	0.074 (6)	0.098 (7)	−0.016 (5)	0.063 (5)	−0.008 (5)
C13'	0.092 (7)	0.077 (7)	0.105 (8)	0.010 (6)	0.043 (6)	−0.016 (6)
C14'	0.104 (8)	0.175 (14)	0.133 (10)	−0.008 (8)	0.096 (8)	−0.035 (9)
O4'	0.103 (9)	0.126 (13)	0.088 (13)	0.006 (8)	0.063 (8)	0.002 (9)
N5'	0.064 (9)	0.083 (9)	0.043 (8)	−0.004 (6)	0.030 (7)	−0.001 (5)

Geometric parameters (Å, º) top

C1—N1	1.333 (2)	N4—O2	1.202 (3)
C1—C2	1.380 (3)	O5—O6	6.641 (2)
C1—C4	1.500 (3)	O5—H5A	0.833 (16)
C2—C3	1.368 (3)	O6—H6A	0.799 (18)
C2—H2	0.9300	O6—H6B	0.843 (18)
C3—C2ⁱ	1.368 (3)	C12—O4	1.272 (10)
C3—H3	0.9300	C12—N5	1.312 (5)
C4—O1	1.220 (2)	C12—H12A	0.9300
C4—N2	1.346 (2)	C13—N5	1.466 (6)
C5—N3	1.263 (2)	C13—H13A	0.9600
C5—C6	1.461 (3)	C13—H13B	0.9600
C5—H5	0.9300	C13—H13C	0.9600
C6—C11	1.397 (3)	C14—N5	1.408 (6)
C6—C7	1.385 (3)	C14—H14A	0.9600
C7—C8	1.369 (3)	C14—H14B	0.9600
C7—H7	0.9300	C14—H14C	0.9600
C8—C9	1.368 (3)	C12'—O4'	1.27 (2)
C8—H8	0.9300	C12'—N5'	1.394 (14)
C9—C10	1.375 (3)	C12'—H12B	0.9300
C9—H9	0.9300	C13'—N5'	1.414 (14)
C10—C11	1.384 (3)	C13'—H13D	0.9600
C10—N4	1.473 (3)	C13'—H13E	0.9600
C11—H11	0.9300	C13'—H13F	0.9600
N1—C1ⁱ	1.333 (2)	C14'—N5'	1.440 (14)
N2—N3	1.376 (2)	C14'—H14D	0.9600
N2—O5	2.9082 (19)	C14'—H14E	0.9600
N2—H2A	0.90 (2)	C14'—H14F	0.9600
N4—O3	1.207 (2)

N1—C1—C2	122.48 (18)	O2—N4—C10	119.66 (18)
N1—C1—C4	118.58 (15)	N2—O5—H5A	115 (2)
C2—C1—C4	118.93 (17)	O6—O5—H5A	118 (2)
C3—C2—C1	119.4 (2)	O5—O6—H6B	146 (3)
C3—C2—H2	120.3	H6A—O6—H6B	114 (3)
C1—C2—H2	120.3	O4—C12—N5	123.7 (5)
C2ⁱ—C3—C2	118.4 (3)	O4—C12—H12A	118.2
C2ⁱ—C3—H3	120.8	N5—C12—H12A	118.2
C2—C3—H3	120.8	N5—C13—H13A	109.5
O1—C4—N2	124.07 (17)	N5—C13—H13B	109.5
O1—C4—C1	120.80 (16)	H13A—C13—H13B	109.5
N2—C4—C1	115.13 (15)	N5—C13—H13C	109.5
N3—C5—C6	122.41 (17)	H13A—C13—H13C	109.5
N3—C5—H5	118.8	H13B—C13—H13C	109.5
C6—C5—H5	118.8	N5—C14—H14A	109.5
C11—C6—C7	118.41 (17)	N5—C14—H14B	109.5
C11—C6—C5	122.13 (16)	H14A—C14—H14B	109.5
C7—C6—C5	119.46 (17)	N5—C14—H14C	109.5
C8—C7—C6	122.1 (2)	H14A—C14—H14C	109.5
C8—C7—H7	118.9	H14B—C14—H14C	109.5
C6—C7—H7	118.9	C12—N5—C14	121.2 (5)
C7—C8—C9	120.19 (19)	C12—N5—C13	119.8 (4)
C7—C8—H8	119.9	C14—N5—C13	117.6 (4)
C9—C8—H8	119.9	O4'—C12'—N5'	109 (2)
C10—C9—C8	118.04 (19)	O4'—C12'—H12B	125.7
C10—C9—H9	121.0	N5'—C12'—H12B	125.7
C8—C9—H9	121.0	N5'—C13'—H13D	109.5
C9—C10—C11	123.34 (19)	N5'—C13'—H13E	109.5
C9—C10—N4	118.96 (18)	H13D—C13'—H13E	109.5
C11—C10—N4	117.70 (18)	N5'—C13'—H13F	109.5
C6—C11—C10	117.86 (17)	H13D—C13'—H13F	109.5
C6—C11—H11	121.1	H13E—C13'—H13F	109.5
C10—C11—H11	121.1	N5'—C14'—H14D	109.5
C1ⁱ—N1—C1	117.8 (2)	N5'—C14'—H14E	109.5
C4—N2—N3	118.92 (15)	H14D—C14'—H14E	109.5
C4—N2—O5	132.09 (12)	N5'—C14'—H14F	109.5
N3—N2—O5	108.77 (11)	H14D—C14'—H14F	109.5
C4—N2—H2A	124.1 (13)	H14E—C14'—H14F	109.5
N3—N2—H2A	117.0 (13)	C14'—N5'—C13'	119.0 (15)
C5—N3—N2	115.69 (15)	C14'—N5'—C12'	120.1 (16)
O3—N4—O2	122.6 (2)	C13'—N5'—C12'	114.2 (14)
O3—N4—C10	117.8 (2)

N1—C1—C2—C3	0.1 (3)	C2—C1—N1—C1ⁱ	−0.07 (15)
C4—C1—C2—C3	179.59 (17)	C4—C1—N1—C1ⁱ	−179.52 (19)
C1—C2—C3—C2ⁱ	−0.07 (14)	O1—C4—N2—N3	0.8 (3)
N1—C1—C4—O1	175.80 (17)	C1—C4—N2—N3	−179.30 (15)
C2—C1—C4—O1	−3.7 (3)	O1—C4—N2—O5	−173.09 (14)
N1—C1—C4—N2	−4.1 (2)	C1—C4—N2—O5	6.8 (3)
C2—C1—C4—N2	176.45 (18)	C6—C5—N3—N2	−179.94 (16)
N3—C5—C6—C11	0.1 (3)	C4—N2—N3—C5	−179.27 (17)
N3—C5—C6—C7	−179.70 (17)	O5—N2—N3—C5	−4.04 (19)
C11—C6—C7—C8	0.1 (3)	C9—C10—N4—O3	2.0 (3)
C5—C6—C7—C8	179.9 (2)	C11—C10—N4—O3	−177.54 (19)
C6—C7—C8—C9	0.8 (4)	C9—C10—N4—O2	−177.7 (2)
C7—C8—C9—C10	−0.4 (4)	C11—C10—N4—O2	2.7 (3)
C8—C9—C10—C11	−1.0 (3)	C4—N2—O5—O6	132.8 (3)
C8—C9—C10—N4	179.4 (2)	N3—N2—O5—O6	−41.54 (13)
C7—C6—C11—C10	−1.4 (3)	O4—C12—N5—C14	−12.8 (15)
C5—C6—C11—C10	178.74 (17)	O4—C12—N5—C13	−179.1 (8)
C9—C10—C11—C6	1.9 (3)	O4'—C12'—N5'—C14'	170 (3)
N4—C10—C11—C6	−178.49 (16)	O4'—C12'—N5'—C13'	−39 (4)

Symmetry code: (i) −x, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5A···O6ⁱⁱ	0.83 (2)	1.86 (2)	2.692 (2)	173 (3)
C9—H9···O4ⁱⁱⁱ	0.93	2.60	3.438 (10)	150
N2—H2A···O5	0.90 (2)	2.03 (2)	2.9082 (19)	166.4 (19)
O6—H6A···O1	0.80 (2)	2.05 (2)	2.834 (2)	167 (4)
O6—H6B···O4	0.84 (2)	1.89 (2)	2.728 (7)	175 (4)
C5—H5···O5	0.93	2.48	3.2860 (18)	145

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

Experimental details

Crystal data
Chemical formula	C₂₁H₁₅N₇O₆·2C₃H₇NO·3H₂O
M_r	661.64
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	273
a, b, c (Å)	24.704 (3), 10.4815 (12), 14.4792 (16)
β (°)	120.355 (2)
V (Å³)	3235.2 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.22 × 0.20 × 0.20

Data collection
Diffractometer	Bruker SMART CCD area-detector
Absorption correction	Multi-scan (SADABS; Sheldrick, 2001)
T_min, T_max	0.977, 0.979
No. of measured, independent and observed [I > 2σ(I)] reflections	9211, 3170, 2222
R_int	0.018
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.049, 0.169, 1.08
No. of reflections	3170
No. of parameters	272
No. of restraints	51
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.43, −0.17

Computer programs: SMART (Bruker 2001), SAINT-Plus (Bruker 2001), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2003), SHELXTL (Bruker 2001).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5A···O6ⁱ	0.833 (16)	1.864 (17)	2.692 (2)	173 (3)
C9—H9···O4ⁱⁱ	0.93	2.60	3.438 (10)	150.4
N2—H2A···O5	0.90 (2)	2.03 (2)	2.9082 (19)	166.4 (19)
O6—H6A···O1	0.799 (18)	2.05 (2)	2.834 (2)	167 (4)
O6—H6B···O4	0.843 (18)	1.89 (2)	2.728 (7)	175 (4)
C5—H5···O5	0.93	2.48	3.2860 (18)	145.4

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

Acknowledgements

This work was supported by the Science Foundation of the South Central National University (grant No. y2205007) and Hubei Provincial Natural Science Foundation of China (grant No. 2007ABA345)

References

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