2-(4-tert-Butyl­phen­yl)-1H-imidazo[4,5-f][1,10]phenanthroline sesquihydrate

Zheng, C.-Y.; Sun, T.-Q.

doi:10.1107/S1600536809020261

organic compounds

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ISSN: 2056-9890

Volume 65| Part 7| July 2009| Page o1471

doi:10.1107/S1600536809020261

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2-(4-tert-Butylphenyl)-1H-imidazo[4,5-f][1,10]phenanthroline sesquihydrate

Chun-Yang Zheng ^a ^* and Ting-Quan Sun ^a

^aHubei Key Laboratory of Pollutant Analysis and Reuse Technology, Hubei Normal University, Huangshi 435002, People's Republic of China
^*Correspondence e-mail: chunyangzheng@yahoo.com.cn

(Received 16 May 2009; accepted 27 May 2009; online 6 June 2009)

In the title compound, C₂₃H₂₀N₄·1.5H₂O, the mean planes of the imidazo[4,5-f][1,10]phenanthroline system and the benzene ring make a dihedral angle of 21.76 (2)°. One water O atom lies on a twofold rotation axis. The organic molecules and water molecules are linked via N—H⋯O, O—H⋯N and O—H⋯O hydrogen bonds. Weak intermolecular C—H⋯N hydrogen bonds and π–π stacking interactions between inversion-related phenanthroline rings complete the three-dimensional hydrogen-bonding network in the crystal structure. The stacking distance is short at 3.513 (2) Å and the perpendicular distance between the rings is 3.355 Å. The three methyl groups are disordered over two positions, with a site-occupancy ratio of 0.875 (14):0.125 (14).

Related literature

For 1,10-phenanthroline derivatives as ligands, see: Cardinaels et al. (2005 ); Liu et al. (2005 ). For the crystal structures of 1,10-phenanthroline derivatives, see: Bian et al. (2002 ); Wu et al. (1998 ). For aromatic π–π stacking interactions, see: Janiak (2000 ).

Experimental

Crystal data

C₂₃H₂₀N₄·1.5H₂O
M_r = 379.46
Tetragonal, P 4₃ 2₁ 2
a = 14.809 (4) Å
c = 18.281 (6) Å
V = 4009.1 (19) Å³
Z = 8
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 298 K
0.16 × 0.13 × 0.10 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: none
46858 measured reflections
2670 independent reflections
2508 reflections with I > 2σ(I)
R_int = 0.054

Refinement

R[F² > 2σ(F²)] = 0.068
wR(F²) = 0.167
S = 1.28
2670 reflections
304 parameters
53 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.30 e Å⁻³
Δρ_min = −0.15 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯N1ⁱ	0.83 (3)	2.45 (3)	3.193 (5)	151 (5)
O1—H1A⋯N2ⁱ	0.83 (3)	2.19 (4)	2.853 (4)	137 (5)
O1—H1B⋯O2ⁱⁱ	0.83 (3)	2.065 (16)	2.878 (3)	168 (5)
O2—H2A⋯N4	0.82 (3)	2.15 (2)	2.914 (4)	156 (5)
N3—H3⋯O1	0.86 (3)	1.90 (3)	2.754 (4)	176 (4)
C12—H12⋯N4ⁱⁱⁱ	0.93	2.53	3.346 (4)	147
Symmetry codes: (i) $[-y+{\script{3\over 2}}, x-{\script{1\over 2}}, z-{\script{1\over 4}}]$ ; (ii) $[y+{\script{1\over 2}}, -x+{\script{1\over 2}}, z+{\script{1\over 4}}]$ ; (iii) y, x, -z+2.

Data collection: SMART (Bruker, 1997 ); cell refinement: SAINT (Bruker, 1999 ); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809020261/si2177sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809020261/si2177Isup2.hkl

checkCIF report

Comment top

1,10-Phenanthroline and its derivatives are commonly used as ligands in metal complexes (Bian et al. 2002; Cardinaels et al. 2005; Liu et al. 2005; Wu et al. 1998). We report here the structure of the title compound (I) (Fig. 1), which was synthesized from [4,5-f]1,10-phenanthroline. The mean plane of the [4,5-f]1,10-phenanthroline moiety and the benzene ring (C14 - C19) make a dihedral angle of 21.76 (2) °. The water oxygen atom O2 occupies a twofold rotation axis, generating a symmetric four-centre hydrogen bond system that link two imidazo groups and two water molecules O1 via O—H···N and O—H···O bonds (Fig. 2). The other water molecules O1 link the two phenanthroline N-atoms through bifurcated O—H···N hydrogen bonds (Table 1). Intermolecular C—H···N hydrogen bonds and π—π stacking interactions (Janiak, 2000) between inversion related phenanthroline rings complete the hydrogen bonding network in the crystal structure. The short stacking distance Cg_i—Cg_j is 3.513 (2) Å, the perpendicular distance between the rings is 3.355 Å, and the dihedral angle between the rings is 2.48 °. Cg is the centroid of ring (N2, C5, C4, C12, C11, C10), a symmetry code for Cg_j was given as (1 - y, 1 - x, 5/2 - z. The three methyl groups are disordered over two positions, with a site occupancy ratio of ca 7:1.

Related literature top

For 1,10-phenanthroline derivatives as ligands, see: Cardinaels et al. (2005); Liu et al. (2005). For the crystal structures of 1,10-phenanthroline derivatives, see: Bian et al. (2002); Wu et al. (1998). For aromatic π—π stacking interactions, see: Janiak (2000).

Experimental top

1,10-Phenanthroline-5,6-dione (0.84 g, 0.004 mol) and ammonium acetate (3.1 g, 0.04 mmol) were dissolved in 40 ml of hot glacial acetic acid. While the mixture was stirred, a solution of 4-tert-butylbenzaldehyde (0.65 g, 0.004 mmol) in 10 ml of glacial acetic acid was added dropwise to the mixture. The mixture was heated at 363 K for 3 h and was then poured in 200 ml of water. The solution was neutralized with ammonia to pH=8 and was then cooled to room temperature. The precipitate was filtered off and recrystallized from dillute ethanol solution to give the title compound (I). Crystals suitable for X-ray diffraction were grown by slow evaporation of the EtOH solutions at room temperature.

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. View of the molecular structure of (I), showing the atomic numbering. Displacement ellipsoids are drawn at the 50% probability level. Hydrogen bonds are indicated by dashed lines. The three disordered methyl groups were omitted for clarity.
	Fig. 2. A section of the structure of (I) with intermolecular hydrogen bonds indicated as dashed lines.

2-(4-tert-Butylphenyl)-1H-imidazo[4,5-f][1,10] phenanthroline sesquihydrate top

Crystal data top

C₂₃H₂₀N₄·1.5H₂O	D_x = 1.257 Mg m⁻³
M_r = 379.46	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, P4₃2₁2	Cell parameters from 5405 reflections
Hall symbol: P4nw 2abw	θ = 2.2–22.5°
a = 14.809 (4) Å	µ = 0.08 mm⁻¹
c = 18.281 (6) Å	T = 298 K
V = 4009.1 (19) Å³	Block, yellow
Z = 8	0.16 × 0.13 × 0.10 mm
F(000) = 1608

Data collection top

Bruker SMART CCD area-detector diffractometer	2508 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.054
Graphite monochromator	θ_max = 27.5°, θ_min = 1.9°
ϕ and ω scans	h = −19→19
46858 measured reflections	k = −19→19
2670 independent reflections	l = −23→23

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)] = 0.068	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.167	H atoms treated by a mixture of independent and constrained refinement
S = 1.28	w = 1/[σ²(F_o²) + (0.0765P)² + 0.9688P] where P = (F_o² + 2F_c²)/3
2670 reflections	(Δ/σ)_max < 0.001
304 parameters	Δρ_max = 0.30 e Å⁻³
53 restraints	Δρ_min = −0.15 e Å⁻³

Crystal data top

C₂₃H₂₀N₄·1.5H₂O	Z = 8
M_r = 379.46	Mo Kα radiation
Tetragonal, P4₃2₁2	µ = 0.08 mm⁻¹
a = 14.809 (4) Å	T = 298 K
c = 18.281 (6) Å	0.16 × 0.13 × 0.10 mm
V = 4009.1 (19) Å³

Data collection top

Bruker SMART CCD area-detector diffractometer	2508 reflections with I > 2σ(I)
46858 measured reflections	R_int = 0.054
2670 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.068	53 restraints
wR(F²) = 0.167	H atoms treated by a mixture of independent and constrained refinement
S = 1.28	Δρ_max = 0.30 e Å⁻³
2670 reflections	Δρ_min = −0.15 e Å⁻³
304 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	0.7310 (2)	0.4019 (2)	1.19064 (17)	0.0436 (7)
C2	0.6832 (2)	0.3733 (2)	1.12626 (16)	0.0412 (7)
C3	0.6074 (2)	0.4156 (2)	1.10102 (16)	0.0392 (7)
C4	0.5709 (2)	0.4934 (2)	1.13671 (16)	0.0399 (7)
C5	0.6151 (2)	0.5242 (2)	1.20079 (17)	0.0424 (7)
C6	0.6959 (2)	0.4778 (2)	1.22760 (17)	0.0453 (8)
N1	0.7345 (2)	0.5111 (2)	1.28912 (17)	0.0593 (9)
C7	0.8061 (3)	0.4692 (3)	1.3142 (2)	0.0723 (13)
H7	0.8325	0.4915	1.3567	0.087*
C8	0.8453 (3)	0.3944 (4)	1.2822 (3)	0.0760 (14)
H8	0.8961	0.3676	1.3027	0.091*
C9	0.8074 (3)	0.3605 (3)	1.2194 (2)	0.0623 (10)
H9	0.8325	0.3104	1.1965	0.075*
N2	0.5840 (2)	0.5952 (2)	1.23928 (16)	0.0505 (7)
C10	0.5114 (3)	0.6373 (3)	1.2156 (2)	0.0538 (9)
H10	0.4901	0.6860	1.2428	0.065*
C11	0.4647 (3)	0.6138 (3)	1.1531 (2)	0.0569 (9)
H11	0.4139	0.6460	1.1385	0.068*
C12	0.4950 (2)	0.5420 (2)	1.11298 (19)	0.0504 (8)
H12	0.4654	0.5254	1.0702	0.060*
C13	0.6348 (2)	0.3069 (2)	1.02710 (16)	0.0416 (7)
C14	0.6341 (2)	0.2461 (2)	0.96339 (16)	0.0426 (7)
C15	0.5563 (2)	0.2359 (2)	0.92178 (18)	0.0480 (8)
H15	0.5038	0.2657	0.9359	0.058*
C16	0.5553 (3)	0.1825 (2)	0.85987 (18)	0.0500 (8)
H16	0.5020	0.1764	0.8335	0.060*
C17	0.6319 (3)	0.1377 (2)	0.83626 (18)	0.0510 (9)
C18	0.7096 (3)	0.1491 (3)	0.8774 (2)	0.0616 (11)
H18	0.7623	0.1202	0.8627	0.074*
C19	0.7112 (3)	0.2021 (3)	0.93992 (19)	0.0566 (10)
H19	0.7646	0.2082	0.9663	0.068*
C20	0.6326 (3)	0.0806 (3)	0.76548 (19)	0.0646 (11)
C21	0.5375 (4)	0.0646 (6)	0.7367 (4)	0.110 (3)	0.875 (14)
H21A	0.5404	0.0291	0.6928	0.165*	0.875 (14)
H21B	0.5094	0.1216	0.7262	0.165*	0.875 (14)
H21C	0.5028	0.0331	0.7729	0.165*	0.875 (14)
C22	0.6769 (8)	−0.0099 (5)	0.7785 (4)	0.122 (4)	0.875 (14)
H22A	0.6722	−0.0460	0.7351	0.183*	0.875 (14)
H22B	0.6472	−0.0401	0.8182	0.183*	0.875 (14)
H22C	0.7394	−0.0010	0.7904	0.183*	0.875 (14)
C23	0.6840 (7)	0.1327 (6)	0.7075 (3)	0.125 (4)	0.875 (14)
H23A	0.7410	0.1519	0.7269	0.188*	0.875 (14)
H23B	0.6495	0.1846	0.6929	0.188*	0.875 (14)
H23C	0.6940	0.0945	0.6658	0.188*	0.875 (14)
C21'	0.565 (3)	0.003 (3)	0.765 (3)	0.13 (2)	0.125 (14)
H21D	0.5711	−0.0303	0.7199	0.188*	0.125 (14)
H21E	0.5047	0.0268	0.7680	0.188*	0.125 (14)
H21F	0.5762	−0.0362	0.8054	0.188*	0.125 (14)
C22'	0.7261 (17)	0.040 (4)	0.752 (3)	0.099 (17)	0.125 (14)
H22D	0.7216	−0.0080	0.7169	0.149*	0.125 (14)
H22E	0.7490	0.0154	0.7976	0.149*	0.125 (14)
H22F	0.7664	0.0853	0.7347	0.149*	0.125 (14)
C23'	0.612 (4)	0.140 (3)	0.6995 (18)	0.12 (2)	0.125 (14)
H23D	0.6390	0.1146	0.6565	0.174*	0.125 (14)
H23E	0.6365	0.1996	0.7076	0.174*	0.125 (14)
H23F	0.5479	0.1446	0.6929	0.174*	0.125 (14)
N3	0.70020 (19)	0.30431 (19)	1.07917 (14)	0.0433 (6)
H3	0.734 (2)	0.2580 (17)	1.086 (2)	0.052*
N4	0.57632 (19)	0.37297 (18)	1.03858 (13)	0.0417 (6)
O1	0.8076 (2)	0.1575 (2)	1.11023 (13)	0.0661 (9)
H1A	0.852 (2)	0.159 (4)	1.0831 (19)	0.099*
H1B	0.824 (3)	0.140 (4)	1.1511 (13)	0.099*
O2	0.38586 (17)	0.38586 (17)	1.0000	0.0487 (8)
H2A	0.4347 (17)	0.366 (3)	1.014 (3)	0.073*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0486 (18)	0.0470 (18)	0.0354 (14)	−0.0038 (15)	−0.0049 (13)	0.0075 (13)
C2	0.0490 (18)	0.0405 (16)	0.0341 (14)	−0.0017 (14)	−0.0012 (13)	0.0037 (12)
C3	0.0475 (17)	0.0393 (15)	0.0307 (13)	−0.0020 (13)	−0.0058 (12)	0.0041 (12)
C4	0.0453 (17)	0.0405 (16)	0.0340 (14)	−0.0022 (13)	−0.0008 (13)	0.0001 (12)
C5	0.0510 (18)	0.0420 (17)	0.0342 (14)	−0.0069 (14)	0.0002 (13)	0.0027 (12)
C6	0.0514 (18)	0.0490 (18)	0.0355 (15)	−0.0111 (15)	−0.0054 (14)	0.0018 (13)
N1	0.064 (2)	0.069 (2)	0.0451 (15)	−0.0063 (17)	−0.0158 (15)	−0.0029 (15)
C7	0.079 (3)	0.081 (3)	0.057 (2)	−0.006 (3)	−0.031 (2)	−0.004 (2)
C8	0.069 (3)	0.086 (3)	0.072 (3)	0.010 (3)	−0.031 (2)	0.002 (3)
C9	0.062 (2)	0.064 (2)	0.061 (2)	0.005 (2)	−0.0200 (19)	−0.0030 (19)
N2	0.0604 (18)	0.0486 (16)	0.0425 (14)	−0.0071 (13)	−0.0021 (14)	−0.0057 (13)
C10	0.061 (2)	0.0452 (18)	0.0552 (19)	−0.0009 (16)	0.0023 (18)	−0.0122 (17)
C11	0.060 (2)	0.048 (2)	0.062 (2)	0.0087 (17)	−0.0095 (18)	−0.0069 (17)
C12	0.058 (2)	0.0471 (18)	0.0459 (17)	0.0003 (16)	−0.0133 (16)	−0.0037 (15)
C13	0.0492 (17)	0.0409 (16)	0.0347 (14)	0.0019 (14)	−0.0003 (13)	0.0050 (13)
C14	0.0523 (18)	0.0408 (16)	0.0349 (14)	0.0042 (14)	−0.0006 (14)	0.0033 (13)
C15	0.0472 (19)	0.0515 (19)	0.0452 (16)	0.0083 (15)	0.0009 (15)	−0.0064 (15)
C16	0.058 (2)	0.051 (2)	0.0408 (16)	0.0000 (17)	−0.0041 (16)	−0.0042 (15)
C17	0.073 (2)	0.0489 (19)	0.0317 (14)	0.0097 (17)	0.0009 (16)	−0.0007 (14)
C18	0.066 (2)	0.074 (3)	0.0446 (18)	0.029 (2)	−0.0004 (18)	−0.0092 (18)
C19	0.056 (2)	0.069 (2)	0.0449 (18)	0.0161 (19)	−0.0064 (16)	−0.0076 (17)
C20	0.090 (3)	0.069 (3)	0.0340 (17)	0.016 (2)	−0.0018 (19)	−0.0102 (18)
C21	0.111 (5)	0.131 (7)	0.088 (5)	−0.003 (5)	−0.016 (4)	−0.068 (5)
C22	0.194 (10)	0.100 (6)	0.072 (4)	0.064 (6)	−0.030 (5)	−0.038 (4)
C23	0.169 (9)	0.162 (8)	0.044 (3)	−0.053 (7)	0.024 (4)	−0.020 (4)
C21'	0.13 (3)	0.12 (3)	0.13 (3)	−0.006 (19)	−0.007 (19)	−0.019 (19)
C22'	0.11 (2)	0.10 (2)	0.09 (2)	0.019 (17)	−0.012 (17)	−0.026 (18)
C23'	0.13 (3)	0.11 (3)	0.11 (2)	0.003 (19)	−0.011 (19)	−0.014 (18)
N3	0.0484 (16)	0.0451 (15)	0.0363 (13)	0.0073 (12)	−0.0044 (12)	0.0032 (12)
N4	0.0514 (15)	0.0418 (14)	0.0319 (11)	0.0064 (12)	−0.0039 (12)	−0.0008 (11)
O1	0.0715 (19)	0.086 (2)	0.0412 (12)	0.0343 (17)	0.0099 (13)	0.0085 (14)
O2	0.0519 (12)	0.0519 (12)	0.0422 (17)	−0.0066 (17)	0.0024 (11)	−0.0024 (11)

Geometric parameters (Å, º) top

C1—C9	1.390 (5)	C17—C18	1.384 (6)
C1—C6	1.411 (5)	C17—C20	1.545 (5)
C1—C2	1.437 (4)	C18—C19	1.387 (5)
C2—N3	1.360 (4)	C18—H18	0.9300
C2—C3	1.366 (4)	C19—H19	0.9300
C3—N4	1.383 (4)	C20—C22	1.511 (6)
C3—C4	1.431 (5)	C20—C23	1.516 (6)
C4—C12	1.403 (5)	C20—C21	1.522 (6)
C4—C5	1.418 (4)	C20—C21'	1.524 (10)
C5—N2	1.346 (4)	C20—C23'	1.527 (10)
C5—C6	1.465 (5)	C20—C22'	1.532 (10)
C6—N1	1.354 (4)	C21—H21A	0.9600
N1—C7	1.312 (6)	C21—H21B	0.9600
C7—C8	1.381 (7)	C21—H21C	0.9600
C7—H7	0.9300	C22—H22A	0.9600
C8—C9	1.372 (6)	C22—H22B	0.9600
C8—H8	0.9300	C22—H22C	0.9600
C9—H9	0.9300	C23—H23A	0.9600
N2—C10	1.316 (5)	C23—H23B	0.9600
C10—C11	1.382 (5)	C23—H23C	0.9600
C10—H10	0.9300	C21'—H21D	0.9600
C11—C12	1.367 (5)	C21'—H21E	0.9600
C11—H11	0.9300	C21'—H21F	0.9600
C12—H12	0.9300	C22'—H22D	0.9600
C13—N4	1.323 (4)	C22'—H22E	0.9600
C13—N3	1.359 (4)	C22'—H22F	0.9600
C13—C14	1.472 (4)	C23'—H23D	0.9600
C14—C19	1.383 (5)	C23'—H23E	0.9600
C14—C15	1.389 (5)	C23'—H23F	0.9600
C15—C16	1.381 (5)	N3—H3	0.86 (3)
C15—H15	0.9300	O1—H1A	0.83 (3)
C16—C17	1.383 (5)	O1—H1B	0.83 (3)
C16—H16	0.9300	O2—H2A	0.82 (3)

C9—C1—C6	118.0 (3)	C19—C18—H18	119.0
C9—C1—C2	125.5 (3)	C14—C19—C18	120.5 (4)
C6—C1—C2	116.4 (3)	C14—C19—H19	119.7
N3—C2—C3	106.4 (3)	C18—C19—H19	119.7
N3—C2—C1	130.4 (3)	C22—C20—C23	110.0 (5)
C3—C2—C1	123.2 (3)	C22—C20—C21	108.5 (5)
C2—C3—N4	110.1 (3)	C23—C20—C21	107.6 (5)
C2—C3—C4	121.7 (3)	C23—C20—C21'	135 (2)
N4—C3—C4	128.2 (3)	C22—C20—C23'	136.5 (19)
C12—C4—C5	117.4 (3)	C21'—C20—C23'	107.3 (10)
C12—C4—C3	125.1 (3)	C21—C20—C22'	136.1 (18)
C5—C4—C3	117.5 (3)	C21'—C20—C22'	107.1 (9)
N2—C5—C4	121.7 (3)	C23'—C20—C22'	106.7 (9)
N2—C5—C6	118.1 (3)	C22—C20—C17	110.9 (3)
C4—C5—C6	120.2 (3)	C23—C20—C17	108.1 (4)
N1—C6—C1	122.2 (3)	C21—C20—C17	111.7 (4)
N1—C6—C5	116.9 (3)	C21'—C20—C17	115 (2)
C1—C6—C5	121.0 (3)	C23'—C20—C17	110.1 (19)
C7—N1—C6	117.4 (4)	C22'—C20—C17	110.7 (17)
N1—C7—C8	124.8 (4)	C20—C21—H21A	109.5
N1—C7—H7	117.6	C20—C21—H21B	109.5
C8—C7—H7	117.6	C20—C21—H21C	109.5
C9—C8—C7	118.5 (4)	C20—C22—H22A	109.5
C9—C8—H8	120.8	C20—C22—H22B	109.5
C7—C8—H8	120.8	C20—C22—H22C	109.5
C8—C9—C1	119.2 (4)	C20—C23—H23A	109.5
C8—C9—H9	120.4	C20—C23—H23B	109.5
C1—C9—H9	120.4	C20—C23—H23C	109.5
C10—N2—C5	118.5 (3)	C20—C21'—H21D	109.5
N2—C10—C11	124.2 (3)	C20—C21'—H21E	109.5
N2—C10—H10	117.9	H21D—C21'—H21E	109.5
C11—C10—H10	117.9	C20—C21'—H21F	109.5
C12—C11—C10	118.4 (4)	H21D—C21'—H21F	109.5
C12—C11—H11	120.8	H21E—C21'—H21F	109.5
C10—C11—H11	120.8	C20—C22'—H22D	109.5
C11—C12—C4	119.7 (3)	C20—C22'—H22E	109.5
C11—C12—H12	120.1	H22D—C22'—H22E	109.5
C4—C12—H12	120.1	C20—C22'—H22F	109.5
N4—C13—N3	112.1 (3)	H22D—C22'—H22F	109.5
N4—C13—C14	125.0 (3)	H22E—C22'—H22F	109.5
N3—C13—C14	122.8 (3)	C20—C23'—H23D	109.5
C19—C14—C15	117.7 (3)	C20—C23'—H23E	109.5
C19—C14—C13	121.8 (3)	H23D—C23'—H23E	109.5
C15—C14—C13	120.4 (3)	C20—C23'—H23F	109.5
C16—C15—C14	121.3 (3)	H23D—C23'—H23F	109.5
C16—C15—H15	119.4	H23E—C23'—H23F	109.5
C14—C15—H15	119.4	C13—N3—C2	106.9 (3)
C15—C16—C17	121.5 (3)	C13—N3—H3	123 (3)
C15—C16—H16	119.3	C2—N3—H3	128 (3)
C17—C16—H16	119.3	C13—N4—C3	104.5 (3)
C16—C17—C18	117.0 (3)	C13—N4—H2A	124.9 (13)
C16—C17—C20	121.9 (4)	C3—N4—H2A	121.2 (13)
C18—C17—C20	121.1 (3)	H3—O1—H1A	107 (4)
C17—C18—C19	122.1 (4)	H3—O1—H1B	128 (4)
C17—C18—H18	119.0	H1A—O1—H1B	109 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···N1ⁱ	0.83 (3)	2.45 (3)	3.193 (5)	151 (5)
O1—H1A···N2ⁱ	0.83 (3)	2.19 (4)	2.853 (4)	137 (5)
O1—H1B···O2ⁱⁱ	0.83 (3)	2.07 (2)	2.878 (3)	168 (5)
O2—H2A···N4	0.82 (3)	2.15 (2)	2.914 (4)	156 (5)
N3—H3···O1	0.86 (3)	1.90 (3)	2.754 (4)	176 (4)
C12—H12···N4ⁱⁱⁱ	0.93	2.53	3.346 (4)	147

Symmetry codes: (i) −y+3/2, x−1/2, z−1/4; (ii) y+1/2, −x+1/2, z+1/4; (iii) y, x, −z+2.

Experimental details

Crystal data
Chemical formula	C₂₃H₂₀N₄·1.5H₂O
M_r	379.46
Crystal system, space group	Tetragonal, P4₃2₁2
Temperature (K)	298
a, c (Å)	14.809 (4), 18.281 (6)
V (Å³)	4009.1 (19)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.16 × 0.13 × 0.10

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	46858, 2670, 2508
R_int	0.054
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.068, 0.167, 1.28
No. of reflections	2670
No. of parameters	304
No. of restraints	53
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.30, −0.15

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1999), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···N1ⁱ	0.83 (3)	2.45 (3)	3.193 (5)	151 (5)
O1—H1A···N2ⁱ	0.83 (3)	2.19 (4)	2.853 (4)	137 (5)
O1—H1B···O2ⁱⁱ	0.83 (3)	2.065 (16)	2.878 (3)	168 (5)
O2—H2A···N4	0.82 (3)	2.15 (2)	2.914 (4)	156 (5)
N3—H3···O1	0.86 (3)	1.90 (3)	2.754 (4)	176 (4)
C12—H12···N4ⁱⁱⁱ	0.93	2.53	3.346 (4)	146.9

Symmetry codes: (i) −y+3/2, x−1/2, z−1/4; (ii) y+1/2, −x+1/2, z+1/4; (iii) y, x, −z+2.

Acknowledgements

The authors are grateful to the Postgraduate Programme of Hubei Normal University for financial support under grant No. 2008D53.

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