2-(4-tert-Butyl-phen-yl)-1H-imidazo[4,5-f][1,10]phenanthroline sesquihydrate.

In the title compound, C(23)H(20)N(4)·1.5H(2)O, 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 mol-ecules and water mol-ecules are linked via N-H⋯O, O-H⋯N and O-H⋯O hydrogen bonds. Weak inter-molecular C-H⋯N hydrogen bonds and π-π stacking inter-actions 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 = 379.46

Tetragonal,

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[F 2 > 2σ(F 2)] = 0.068

wR(F 2) = 0.167

S = 1.28

2670 reflections

304 parameters

53 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.30 e Å−3

Δρmin = −0.15 e Å−3

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 ▶).

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

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

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

C23H20N4·1.5H2O	Dx = 1.257 Mg m−3
Mr = 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

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

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(Fo2) + (0.0765P)2 + 0.9688P] where P = (Fo2 + 2Fc2)/3
2670 reflections	(Δ/σ)max < 0.001
304 parameters	Δρmax = 0.30 e Å−3
53 restraints	Δρmin = −0.15 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)
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*

	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)

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)

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

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) ; (ii) ; (iii) .