Bis(2-{[(9H-fluoren-2-yl)methyl-idene]amino}-phenolato-κ(2)N,O)zinc methanol disolvate.

In the title compound, [Zn(C(20)H(14)NO)(2)]·2CH(3)OH, the Zn(II) atom lies on a crystallographic twofold rotation axis and is coordinated by two O atoms and two N atoms from two bidentate 2-{[(9H-fluoren-2-yl)methyl-idene]amino}-phenolate ligands within a distorted tetra-hedral geometry. The dihedral angle between the two chelate rings is 82.92 (5)°. In the coordinated ligand, the phenol ring is twisted at 30.22 (9)° from the mean plane of the fluorene ring. In the crystal, O-H⋯O hydrogen bonds link the complex mol-ecules to the methanol solvent mol-ecules.

Related literature

For general background to Schiff base complexes, see: Ji et al. (2012 ▶); Niu et al. (2012 ▶); Liu et al. (2011 ▶); Roy et al. (2009 ▶). For the structures and luminescent properties of Hg(II) complexes, see: Kim et al. (2011 ▶); Kim & Kang (2010 ▶). For the physical properties of fluorene complexes, see: Scaria et al. (2010 ▶); Loy et al. (2002 ▶); Miteva et al. (2001 ▶).

Experimental

Crystal data

[Zn(C20H14NO)2]·2CH4O

M = 698.1

Monoclinic,

a = 13.7294 (3) Å

b = 13.9123 (2) Å

c = 18.8383 (3) Å

β = 110.652 (1)°

V = 3367.03 (10) Å3

Z = 4

Mo Kα radiation

μ = 0.78 mm−1

T = 296 K

0.10 × 0.05 × 0.04 mm

Data collection

Bruker SMART CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2002 ▶) T min = 0.922, T max = 0.966

10682 measured reflections

3078 independent reflections

2134 reflections with I > 2σ(I)

R int = 0.039

Refinement

R[F 2 > 2σ(F 2)] = 0.043

wR(F 2) = 0.096

S = 1.02

3078 reflections

227 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.22 e Å−3

Δρmin = −0.32 e Å−3

Data collection: SMART (Bruker, 2002 ▶); cell refinement: SAINT (Bruker, 2002 ▶); data reduction: SAINT; 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, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S160053681201272X/tk5073sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681201272X/tk5073Isup2.hkl

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

[Zn(C20H14NO)2]·2CH4O	F(000) = 1456
Mr = 698.1	Dx = 1.377 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 2869 reflections
a = 13.7294 (3) Å	θ = 2.2–25.3°
b = 13.9123 (2) Å	µ = 0.78 mm−1
c = 18.8383 (3) Å	T = 296 K
β = 110.652 (1)°	Block, orange
V = 3367.03 (10) Å3	0.1 × 0.05 × 0.04 mm
Z = 4

Bruker SMART CCD area-detector diffractometer	2134 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.039
φ and ω scans	θmax = 25.5°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2002)	h = −9→16
Tmin = 0.922, Tmax = 0.966	k = −13→16
10682 measured reflections	l = −22→16
3078 independent reflections

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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.096	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ2(Fo2) + (0.0431P)2 + 0.3461P] where P = (Fo2 + 2Fc2)/3
3078 reflections	(Δ/σ)max < 0.001
227 parameters	Δρmax = 0.22 e Å−3
0 restraints	Δρmin = −0.32 e Å−3

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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
Zn1	0.5	0.57842 (3)	0.75	0.04130 (18)
O1	0.40411 (14)	0.65210 (12)	0.66885 (10)	0.0454 (5)
C2	0.3082 (2)	0.61436 (18)	0.64660 (16)	0.0400 (7)
C3	0.2277 (2)	0.6498 (2)	0.58475 (17)	0.0515 (8)
H3	0.2406	0.7007	0.5573	0.062*
C4	0.1294 (3)	0.6119 (2)	0.56296 (17)	0.0558 (8)
H4	0.0765	0.6381	0.5217	0.067*
C5	0.1082 (2)	0.5351 (2)	0.60185 (17)	0.0558 (8)
H5	0.0419	0.5083	0.586	0.067*
C6	0.1861 (2)	0.4984 (2)	0.66416 (16)	0.0499 (8)
H6	0.1721	0.4467	0.6903	0.06*
C7	0.2851 (2)	0.53798 (18)	0.68829 (15)	0.0380 (7)
N8	0.37074 (17)	0.50751 (14)	0.75354 (12)	0.0372 (5)
C9	0.3537 (2)	0.45901 (18)	0.80656 (16)	0.0433 (7)
H9	0.2846	0.4457	0.7997	0.052*
C10	0.4315 (2)	0.42353 (17)	0.87534 (15)	0.0410 (7)
C11	0.3957 (2)	0.38990 (19)	0.93208 (16)	0.0468 (7)
H11	0.3245	0.3882	0.9225	0.056*
C12	0.4632 (2)	0.35952 (18)	1.00140 (16)	0.0456 (7)
H12	0.4382	0.3384	1.0386	0.055*
C13	0.5689 (2)	0.36100 (17)	1.01473 (15)	0.0404 (7)
C14	0.6578 (2)	0.33320 (18)	1.08148 (15)	0.0414 (7)
C15	0.6623 (3)	0.29326 (19)	1.15031 (17)	0.0507 (8)
H15	0.6014	0.2809	1.1597	0.061*
C16	0.7570 (3)	0.2723 (2)	1.20397 (18)	0.0619 (9)
H16	0.7606	0.2456	1.2501	0.074*
C17	0.8467 (3)	0.2908 (2)	1.1897 (2)	0.0730 (10)
H17	0.9106	0.2766	1.2269	0.088*
C18	0.8446 (3)	0.3300 (2)	1.1216 (2)	0.0697 (10)
H18	0.906	0.342	1.1129	0.084*
C19	0.7496 (2)	0.35077 (19)	1.06721 (17)	0.0510 (8)
C20	0.7238 (2)	0.3916 (2)	0.98824 (17)	0.0548 (8)
H20A	0.7525	0.4556	0.9899	0.066*
H20B	0.75	0.3506	0.9574	0.066*
C21	0.6071 (2)	0.39376 (18)	0.95847 (16)	0.0411 (7)
C22	0.5384 (2)	0.42345 (18)	0.88995 (16)	0.0456 (7)
H22	0.5633	0.4439	0.8525	0.055*
C23	0.4138 (3)	0.9024 (3)	0.6538 (2)	0.0906 (12)
H23A	0.3826	0.8908	0.6003	0.136*
H23B	0.4867	0.8876	0.6704	0.136*
H23C	0.4049	0.9688	0.6641	0.136*
O24	0.36624 (18)	0.84464 (18)	0.69240 (13)	0.0716 (7)
H24	0.385 (3)	0.778 (3)	0.687 (2)	0.141 (17)*

	U11	U22	U33	U12	U13	U23
Zn1	0.0383 (3)	0.0397 (3)	0.0464 (3)	0	0.0155 (2)	0
O1	0.0421 (13)	0.0433 (11)	0.0542 (12)	−0.0024 (9)	0.0210 (10)	0.0088 (9)
C2	0.0394 (19)	0.0400 (15)	0.0429 (18)	0.0036 (14)	0.0176 (16)	0.0002 (14)
C3	0.052 (2)	0.0487 (17)	0.053 (2)	0.0051 (16)	0.0180 (18)	0.0143 (15)
C4	0.046 (2)	0.064 (2)	0.0497 (19)	0.0113 (17)	0.0070 (17)	0.0078 (16)
C5	0.044 (2)	0.066 (2)	0.054 (2)	−0.0049 (17)	0.0124 (18)	0.0040 (17)
C6	0.046 (2)	0.0517 (17)	0.0512 (19)	−0.0036 (16)	0.0163 (17)	0.0059 (15)
C7	0.0383 (18)	0.0370 (14)	0.0400 (16)	0.0024 (13)	0.0155 (15)	−0.0011 (13)
N8	0.0392 (14)	0.0354 (12)	0.0392 (13)	0.0002 (11)	0.0165 (12)	0.0007 (11)
C9	0.0421 (19)	0.0404 (15)	0.0502 (19)	−0.0046 (14)	0.0197 (16)	−0.0011 (14)
C10	0.0484 (19)	0.0363 (14)	0.0405 (17)	−0.0011 (14)	0.0184 (15)	0.0020 (14)
C11	0.0410 (19)	0.0538 (17)	0.0475 (19)	−0.0024 (14)	0.0178 (16)	0.0054 (15)
C12	0.047 (2)	0.0503 (17)	0.0452 (18)	0.0003 (15)	0.0232 (16)	0.0069 (14)
C13	0.045 (2)	0.0310 (14)	0.0466 (18)	−0.0013 (14)	0.0177 (16)	−0.0020 (13)
C14	0.046 (2)	0.0336 (15)	0.0435 (17)	0.0020 (13)	0.0141 (16)	0.0006 (13)
C15	0.054 (2)	0.0461 (17)	0.051 (2)	0.0051 (15)	0.0167 (18)	0.0000 (15)
C16	0.070 (3)	0.058 (2)	0.053 (2)	0.0075 (19)	0.015 (2)	0.0081 (16)
C17	0.052 (2)	0.078 (2)	0.070 (2)	0.0054 (19)	−0.002 (2)	0.016 (2)
C18	0.047 (2)	0.078 (2)	0.076 (3)	−0.0037 (18)	0.013 (2)	0.017 (2)
C19	0.046 (2)	0.0468 (17)	0.057 (2)	−0.0035 (15)	0.0131 (18)	0.0079 (15)
C20	0.045 (2)	0.0551 (18)	0.067 (2)	−0.0028 (15)	0.0223 (17)	0.0119 (16)
C21	0.0400 (18)	0.0382 (15)	0.0450 (18)	−0.0013 (13)	0.0151 (16)	0.0045 (13)
C22	0.050 (2)	0.0434 (16)	0.0505 (19)	−0.0010 (15)	0.0262 (17)	0.0063 (15)
C23	0.076 (3)	0.095 (3)	0.102 (3)	−0.004 (2)	0.032 (3)	0.034 (2)
O24	0.0702 (17)	0.0578 (14)	0.0988 (18)	−0.0035 (12)	0.0448 (15)	0.0010 (13)

Zn1—O1i	1.9239 (18)	C12—H12	0.93
Zn1—O1	1.9239 (17)	C13—C21	1.413 (3)
Zn1—N8	2.052 (2)	C13—C14	1.462 (4)
Zn1—N8i	2.052 (2)	C14—C15	1.392 (4)
O1—C2	1.341 (3)	C14—C19	1.399 (4)
C2—C3	1.383 (4)	C15—C16	1.367 (4)
C2—C7	1.422 (4)	C15—H15	0.93
C3—C4	1.370 (4)	C16—C17	1.374 (4)
C3—H3	0.93	C16—H16	0.93
C4—C5	1.384 (4)	C17—C18	1.385 (4)
C4—H4	0.93	C17—H17	0.93
C5—C6	1.376 (4)	C18—C19	1.376 (4)
C5—H5	0.93	C18—H18	0.93
C6—C7	1.387 (4)	C19—C20	1.513 (4)
C6—H6	0.93	C20—C21	1.499 (4)
C7—N8	1.433 (3)	C20—H20A	0.97
N8—C9	1.293 (3)	C20—H20B	0.97
C9—C10	1.445 (4)	C21—C22	1.367 (4)
C9—H9	0.93	C22—H22	0.93
C10—C22	1.395 (4)	C23—O24	1.392 (4)
C10—C11	1.404 (3)	C23—H23A	0.96
C11—C12	1.374 (4)	C23—H23B	0.96
C11—H11	0.93	C23—H23C	0.96
C12—C13	1.384 (4)	O24—H24	0.98 (4)
O1i—Zn1—O1	115.61 (11)	C12—C13—C21	120.8 (3)
O1i—Zn1—N8	125.99 (8)	C12—C13—C14	131.0 (3)
O1—Zn1—N8	85.68 (8)	C21—C13—C14	108.2 (3)
O1i—Zn1—N8i	85.68 (8)	C15—C14—C19	120.1 (3)
O1—Zn1—N8i	125.99 (8)	C15—C14—C13	131.0 (3)
N8—Zn1—N8i	122.53 (11)	C19—C14—C13	108.9 (2)
C2—O1—Zn1	111.18 (15)	C16—C15—C14	119.5 (3)
O1—C2—C3	121.9 (3)	C16—C15—H15	120.3
O1—C2—C7	120.4 (3)	C14—C15—H15	120.3
C3—C2—C7	117.7 (3)	C15—C16—C17	120.0 (3)
C4—C3—C2	121.7 (3)	C15—C16—H16	120
C4—C3—H3	119.2	C17—C16—H16	120
C2—C3—H3	119.2	C16—C17—C18	121.8 (3)
C3—C4—C5	120.5 (3)	C16—C17—H17	119.1
C3—C4—H4	119.8	C18—C17—H17	119.1
C5—C4—H4	119.8	C19—C18—C17	118.5 (3)
C6—C5—C4	119.5 (3)	C19—C18—H18	120.7
C6—C5—H5	120.2	C17—C18—H18	120.7
C4—C5—H5	120.2	C18—C19—C14	120.1 (3)
C5—C6—C7	120.6 (3)	C18—C19—C20	130.0 (3)
C5—C6—H6	119.7	C14—C19—C20	109.9 (3)
C7—C6—H6	119.7	C21—C20—C19	102.9 (2)
C6—C7—C2	119.9 (3)	C21—C20—H20A	111.2
C6—C7—N8	125.2 (2)	C19—C20—H20A	111.2
C2—C7—N8	114.8 (2)	C21—C20—H20B	111.2
C9—N8—C7	120.0 (2)	C19—C20—H20B	111.2
C9—N8—Zn1	132.1 (2)	H20A—C20—H20B	109.1
C7—N8—Zn1	106.68 (16)	C22—C21—C13	119.4 (3)
N8—C9—C10	126.4 (3)	C22—C21—C20	130.6 (3)
N8—C9—H9	116.8	C13—C21—C20	110.0 (3)
C10—C9—H9	116.8	C21—C22—C10	121.0 (2)
C22—C10—C11	118.4 (3)	C21—C22—H22	119.5
C22—C10—C9	124.8 (2)	C10—C22—H22	119.5
C11—C10—C9	116.7 (3)	O24—C23—H23A	109.5
C12—C11—C10	121.7 (3)	O24—C23—H23B	109.5
C12—C11—H11	119.1	H23A—C23—H23B	109.5
C10—C11—H11	119.1	O24—C23—H23C	109.5
C11—C12—C13	118.7 (3)	H23A—C23—H23C	109.5
C11—C12—H12	120.6	H23B—C23—H23C	109.5
C13—C12—H12	120.6	C23—O24—H24	108 (2)

D—H···A	D—H	H···A	D···A	D—H···A
O24—H24···O1	0.98 (4)	1.82 (5)	2.794 (3)	173 (4)

Zn1—O1	1.9239 (17)
Zn1—N8	2.052 (2)
C7—N8	1.433 (3)
N8—C9	1.293 (3)

O1i—Zn1—O1	115.61 (11)
O1i—Zn1—N8	125.99 (8)
O1—Zn1—N8	85.68 (8)
N8—Zn1—N8i	122.53 (11)

Symmetry code: (i) .

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O24—H24⋯O1	0.98 (4)	1.82 (5)	2.794 (3)	173 (4)