Bis(ethano-lato-κO)(5,10,15,20-tetra-phenyl-calix[4]pyrrole)manganese(III) hexa-fluoro-phosphate.

The title compound, [Mn(C(2)H(5)O)(2)(C(44)H(28)N(4))]PF(6), was synthesized from manganese(III) 2,4-penta-nedionate and 5,10,15,20-tetra-phenyl-calix[4]pyrrole by a hydro-thermal reaction. The Mn(III) atom is located on an inversion centre and the asymmetric unit comprises one half-formula unit. The Mn(III) ion is hexa-coordinated by four N atoms from one 5,10,15,20-tetra-phenyl-calix[4]pyrrole ligand and two O atoms from two deprotonated ethanol mol-ecules. The equatorially located atoms (the Mn and four N atoms) are planar. The dihedral angles between the planes of the phenyl rings and the equatorial plane are 53.3 (2) and 81.8 (2)°. One hexa-fluoro-phosphate anion balances the charge.

Related literature

For related literature, see: Church & Halvorson (1959 ▶); Chung et al. (1971 ▶); Okabe & Oya (2000 ▶); Serre et al. (2005 ▶); Pocker & Fong (1980 ▶); Scapin et al. (1997 ▶).

Experimental

Crystal data

[Mn(C2H5O)2(C44H28N4)]PF6

M = 902.73

Monoclinic,

a = 10.7487 (8) Å

b = 16.8682 (14) Å

c = 11.9913 (19) Å

β = 109.412 (9)°

V = 2050.6 (4) Å3

Z = 2

Mo Kα radiation

μ = 0.43 mm−1

T = 293 (2) K

0.43 × 0.28 × 0.22 mm

Data collection

Bruker APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2001 ▶) T min = 0.835, T max = 0.910

4407 measured reflections

3535 independent reflections

2142 reflections with I > 2σ(I)

R int = 0.040

Refinement

R[F 2 > 2σ(F 2)] = 0.063

wR(F 2) = 0.214

S = 1.00

3535 reflections

284 parameters

H-atom parameters constrained

Δρmax = 0.33 e Å−3

Δρmin = −0.42 e Å−3

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT-Plus (Bruker, 2001 ▶); data reduction: SAINT-Plus; 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.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808021879/kp2179sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808021879/kp2179Isup2.hkl

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

[Mn(C2H5O)2(C44H28N4)]PF6	F(000) = 928
Mr = 902.73	Dx = 1.462 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 3535 reflections
a = 10.7487 (8) Å	θ = 2.2–25.0°
b = 16.8682 (14) Å	µ = 0.44 mm−1
c = 11.9913 (19) Å	T = 293 K
β = 109.412 (9)°	Block, yellow
V = 2050.6 (4) Å3	0.43 × 0.28 × 0.22 mm
Z = 2

Bruker APEXII CCD area-detector diffractometer	3535 independent reflections
Radiation source: fine-focus sealed tube	2142 reflections with I > 2σ(I)
graphite	Rint = 0.040
φ and ω scans	θmax = 25.0°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −1→12
Tmin = 0.835, Tmax = 0.910	k = −1→20
4407 measured reflections	l = −14→13

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)] = 0.063	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.214	H-atom parameters constrained
S = 1.00	w = 1/[σ2(Fo2) + (0.135P)2] where P = (Fo2 + 2Fc2)/3
3535 reflections	(Δ/σ)max < 0.001
284 parameters	Δρmax = 0.33 e Å−3
0 restraints	Δρmin = −0.42 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
Mn1	1.0000	0.0000	1.0000	0.0507 (3)
C1	0.8291 (4)	0.0451 (2)	0.7085 (3)	0.0579 (10)
C2	0.8243 (4)	0.0985 (2)	0.7966 (4)	0.0572 (10)
C3	0.7590 (4)	0.1738 (3)	0.7732 (4)	0.0670 (12)
H3A	0.7183	0.1961	0.6991	0.080*
C4	0.7671 (5)	0.2059 (3)	0.8768 (4)	0.0680 (12)
H4A	0.7311	0.2541	0.8881	0.082*
C5	0.8417 (4)	0.1524 (2)	0.9685 (4)	0.0572 (10)
C6	0.8735 (4)	0.1665 (2)	1.0892 (4)	0.0570 (10)
C7	0.9596 (4)	0.1198 (2)	1.1763 (4)	0.0551 (9)
C8	1.0066 (4)	0.1385 (3)	1.2992 (4)	0.0617 (10)
H8A	0.9820	0.1821	1.3345	0.074*
C9	1.0931 (4)	0.0817 (3)	1.3555 (4)	0.0598 (10)
H9A	1.1410	0.0798	1.4358	0.072*
C10	1.0973 (4)	0.0248 (2)	1.2677 (3)	0.0542 (9)
C11	0.7496 (4)	0.0648 (2)	0.5827 (4)	0.0594 (10)
C12	0.8044 (5)	0.0722 (3)	0.4937 (4)	0.0697 (12)
H12A	0.8948	0.0654	0.5115	0.084*
C13	0.7273 (6)	0.0893 (3)	0.3793 (5)	0.0814 (14)
H13A	0.7655	0.0920	0.3202	0.098*
C14	0.5958 (6)	0.1024 (3)	0.3521 (5)	0.0864 (16)
H14A	0.5448	0.1156	0.2752	0.104*
C15	0.5383 (5)	0.0959 (3)	0.4383 (5)	0.0862 (15)
H15A	0.4481	0.1041	0.4193	0.103*
C16	0.6152 (5)	0.0771 (3)	0.5547 (4)	0.0701 (12)
H16A	0.5761	0.0728	0.6129	0.084*
C17	0.8100 (4)	0.2373 (2)	1.1233 (4)	0.0560 (10)
C18	0.6787 (5)	0.2366 (3)	1.1115 (4)	0.0735 (12)
H18A	0.6285	0.1915	1.0830	0.088*
C19	0.6202 (5)	0.3030 (3)	1.1418 (5)	0.0822 (14)
H19A	0.5314	0.3019	1.1346	0.099*
C20	0.6936 (6)	0.3702 (3)	1.1824 (4)	0.0824 (15)
H20A	0.6543	0.4145	1.2027	0.099*
C21	0.8222 (6)	0.3720 (3)	1.1929 (5)	0.0829 (14)
H21A	0.8712	0.4178	1.2197	0.099*
C22	0.8817 (5)	0.3065 (3)	1.1642 (5)	0.0742 (13)
H22A	0.9707	0.3084	1.1723	0.089*
C23	1.2032 (10)	0.1503 (5)	1.0298 (13)	0.204 (6)
H23A	1.1197	0.1743	1.0256	0.245*
H23B	1.2537	0.1461	1.1133	0.245*
C24	1.2665 (15)	0.2060 (6)	0.9868 (11)	0.227 (6)
H24A	1.2841	0.2517	1.0374	0.341*
H24B	1.2119	0.2210	0.9086	0.341*
H24C	1.3481	0.1846	0.9839	0.341*
P1	0.5000	0.0000	0.0000	0.1018 (9)
N1	0.8781 (3)	0.0872 (2)	0.9162 (3)	0.0541 (8)
N2	1.0169 (3)	0.05011 (19)	1.1572 (3)	0.0552 (8)
F1	0.6259 (11)	0.0076 (5)	0.0792 (8)	0.217 (3)
F2	0.4786 (14)	0.0803 (9)	−0.0209 (16)	0.350 (8)
F3	0.460 (2)	0.0081 (15)	0.0848 (14)	0.387 (10)
O1	1.1729 (3)	0.07288 (19)	0.9912 (3)	0.0787 (10)

	U11	U22	U33	U12	U13	U23
Mn1	0.0513 (5)	0.0471 (5)	0.0521 (5)	0.0032 (3)	0.0152 (4)	−0.0035 (3)
C1	0.062 (2)	0.057 (2)	0.052 (2)	0.0003 (19)	0.0165 (19)	−0.0015 (18)
C2	0.056 (2)	0.058 (2)	0.055 (2)	0.0046 (19)	0.0136 (18)	0.0003 (18)
C3	0.077 (3)	0.055 (2)	0.059 (2)	0.014 (2)	0.010 (2)	0.0028 (19)
C4	0.076 (3)	0.056 (2)	0.069 (3)	0.017 (2)	0.021 (2)	0.000 (2)
C5	0.057 (2)	0.054 (2)	0.060 (2)	0.0050 (18)	0.0173 (19)	−0.0075 (18)
C6	0.058 (2)	0.049 (2)	0.064 (2)	−0.0013 (18)	0.0195 (19)	−0.0075 (18)
C7	0.057 (2)	0.052 (2)	0.059 (2)	0.0011 (18)	0.0225 (19)	−0.0026 (18)
C8	0.073 (3)	0.054 (2)	0.060 (2)	0.003 (2)	0.024 (2)	−0.0111 (19)
C9	0.066 (3)	0.057 (2)	0.053 (2)	0.004 (2)	0.0163 (19)	−0.0026 (19)
C10	0.058 (2)	0.051 (2)	0.053 (2)	−0.0007 (19)	0.0185 (19)	−0.0005 (17)
C11	0.068 (3)	0.050 (2)	0.057 (2)	−0.0011 (19)	0.016 (2)	−0.0018 (18)
C12	0.071 (3)	0.071 (3)	0.065 (3)	−0.001 (2)	0.019 (2)	0.005 (2)
C13	0.098 (4)	0.078 (3)	0.066 (3)	0.001 (3)	0.026 (3)	0.010 (2)
C14	0.095 (4)	0.089 (4)	0.060 (3)	−0.005 (3)	0.005 (3)	0.008 (3)
C15	0.071 (3)	0.086 (4)	0.083 (3)	0.008 (3)	0.002 (3)	0.004 (3)
C16	0.062 (3)	0.078 (3)	0.065 (3)	0.003 (2)	0.014 (2)	0.002 (2)
C17	0.056 (2)	0.054 (2)	0.057 (2)	0.0087 (19)	0.0183 (18)	−0.0007 (18)
C18	0.067 (3)	0.061 (3)	0.092 (3)	0.004 (2)	0.026 (2)	−0.009 (2)
C19	0.073 (3)	0.083 (3)	0.098 (4)	0.019 (3)	0.038 (3)	0.000 (3)
C20	0.115 (5)	0.065 (3)	0.070 (3)	0.031 (3)	0.035 (3)	−0.004 (2)
C21	0.095 (4)	0.062 (3)	0.093 (4)	0.006 (3)	0.031 (3)	−0.015 (3)
C22	0.074 (3)	0.057 (3)	0.093 (3)	−0.004 (2)	0.030 (3)	−0.015 (2)
C23	0.187 (9)	0.105 (6)	0.404 (18)	−0.072 (6)	0.210 (11)	−0.095 (9)
C24	0.39 (2)	0.111 (7)	0.234 (13)	−0.052 (10)	0.170 (13)	−0.041 (7)
P1	0.0807 (16)	0.1047 (19)	0.1054 (19)	0.0316 (13)	0.0113 (14)	−0.0304 (15)
N1	0.0532 (18)	0.0542 (18)	0.0538 (18)	0.0027 (15)	0.0164 (15)	−0.0062 (14)
N2	0.0538 (19)	0.0549 (19)	0.0559 (18)	0.0009 (15)	0.0171 (15)	−0.0046 (15)
F1	0.216 (9)	0.238 (8)	0.206 (8)	−0.015 (6)	0.080 (7)	−0.014 (5)
F2	0.338 (16)	0.247 (13)	0.40 (2)	0.005 (12)	0.030 (15)	−0.013 (13)
F3	0.346 (19)	0.47 (2)	0.288 (18)	0.205 (16)	0.030 (14)	0.022 (15)
O1	0.0648 (19)	0.0609 (19)	0.116 (3)	−0.0143 (15)	0.0377 (19)	−0.0146 (18)

Mn1—N1	2.004 (3)	C13—C14	1.358 (8)
Mn1—N1i	2.004 (3)	C13—H13A	0.9300
Mn1—N2	2.018 (3)	C14—C15	1.373 (8)
Mn1—N2i	2.018 (3)	C14—H14A	0.9300
Mn1—O1i	2.260 (3)	C15—C16	1.402 (7)
Mn1—O1	2.260 (3)	C15—H15A	0.9300
C1—C10i	1.395 (6)	C16—H16A	0.9300
C1—C2	1.403 (6)	C17—C18	1.371 (6)
C1—C11	1.504 (6)	C17—C22	1.394 (6)
C2—N1	1.369 (5)	C18—C19	1.390 (7)
C2—C3	1.432 (6)	C18—H18A	0.9300
C3—C4	1.331 (6)	C19—C20	1.375 (8)
C3—H3A	0.9300	C19—H19A	0.9300
C4—C5	1.442 (6)	C20—C21	1.346 (8)
C4—H4A	0.9300	C20—H20A	0.9300
C5—N1	1.386 (5)	C21—C22	1.377 (7)
C5—C6	1.393 (6)	C21—H21A	0.9300
C6—C7	1.388 (6)	C22—H22A	0.9300
C6—C17	1.497 (5)	C23—C24	1.358 (11)
C7—N2	1.381 (5)	C23—O1	1.388 (8)
C7—C8	1.425 (6)	C23—H23A	0.9700
C8—C9	1.348 (6)	C23—H23B	0.9700
C8—H8A	0.9300	C24—H24A	0.9600
C9—C10	1.436 (6)	C24—H24B	0.9600
C9—H9A	0.9300	C24—H24C	0.9600
C10—N2	1.387 (5)	P1—F3	1.23 (2)
C10—C1i	1.395 (6)	P1—F3ii	1.23 (2)
C11—C12	1.385 (6)	P1—F1ii	1.376 (11)
C11—C16	1.385 (6)	P1—F1	1.376 (11)
C12—C13	1.378 (7)	P1—F2	1.382 (15)
C12—H12A	0.9300	P1—F2ii	1.382 (15)
N1—Mn1—N1i	180.000 (1)	C14—C15—H15A	119.9
N1—Mn1—N2	90.13 (13)	C16—C15—H15A	119.9
N1i—Mn1—N2	89.87 (13)	C11—C16—C15	119.8 (5)
N1—Mn1—N2i	89.87 (13)	C11—C16—H16A	120.1
N1i—Mn1—N2i	90.13 (13)	C15—C16—H16A	120.1
N2—Mn1—N2i	180.000 (1)	C18—C17—C22	118.2 (4)
N1—Mn1—O1i	90.70 (13)	C18—C17—C6	120.8 (4)
N1i—Mn1—O1i	89.30 (13)	C22—C17—C6	121.0 (4)
N2—Mn1—O1i	90.25 (13)	C17—C18—C19	120.4 (5)
N2i—Mn1—O1i	89.75 (13)	C17—C18—H18A	119.8
N1—Mn1—O1	89.30 (13)	C19—C18—H18A	119.8
N1i—Mn1—O1	90.70 (13)	C20—C19—C18	120.0 (5)
N2—Mn1—O1	89.75 (13)	C20—C19—H19A	120.0
N2i—Mn1—O1	90.25 (13)	C18—C19—H19A	120.0
O1i—Mn1—O1	180.0	C21—C20—C19	120.2 (5)
C10i—C1—C2	123.3 (4)	C21—C20—H20A	119.9
C10i—C1—C11	119.2 (4)	C19—C20—H20A	119.9
C2—C1—C11	117.5 (4)	C20—C21—C22	120.4 (5)
N1—C2—C1	126.2 (4)	C20—C21—H21A	119.8
N1—C2—C3	109.7 (4)	C22—C21—H21A	119.8
C1—C2—C3	124.1 (4)	C21—C22—C17	120.8 (5)
C4—C3—C2	107.6 (4)	C21—C22—H22A	119.6
C4—C3—H3A	126.2	C17—C22—H22A	119.6
C2—C3—H3A	126.2	C24—C23—O1	128.0 (9)
C3—C4—C5	107.7 (4)	C24—C23—H23A	105.3
C3—C4—H4A	126.1	O1—C23—H23A	105.3
C5—C4—H4A	126.1	C24—C23—H23B	105.3
N1—C5—C6	126.7 (4)	O1—C23—H23B	105.3
N1—C5—C4	108.7 (3)	H23A—C23—H23B	106.0
C6—C5—C4	124.6 (4)	C23—C24—H24A	109.5
C7—C6—C5	123.8 (4)	C23—C24—H24B	109.5
C7—C6—C17	119.9 (4)	H24A—C24—H24B	109.5
C5—C6—C17	116.3 (4)	C23—C24—H24C	109.5
N2—C7—C6	125.6 (4)	H24A—C24—H24C	109.5
N2—C7—C8	109.6 (3)	H24B—C24—H24C	109.5
C6—C7—C8	124.8 (4)	F3—P1—F3ii	180 (2)
C9—C8—C7	108.0 (4)	F3—P1—F1ii	92.8 (9)
C9—C8—H8A	126.0	F3ii—P1—F1ii	87.2 (9)
C7—C8—H8A	126.0	F3—P1—F1	87.2 (9)
C8—C9—C10	107.0 (4)	F3ii—P1—F1	92.8 (9)
C8—C9—H9A	126.5	F1ii—P1—F1	180.0 (13)
C10—C9—H9A	126.5	F3—P1—F2	87.6 (9)
N2—C10—C1i	125.9 (4)	F3ii—P1—F2	92.4 (9)
N2—C10—C9	109.4 (4)	F1ii—P1—F2	84.2 (6)
C1i—C10—C9	124.7 (4)	F1—P1—F2	95.8 (6)
C12—C11—C16	118.4 (4)	F3—P1—F2ii	92.4 (9)
C12—C11—C1	123.1 (4)	F3ii—P1—F2ii	87.6 (9)
C16—C11—C1	118.4 (4)	F1ii—P1—F2ii	95.8 (6)
C13—C12—C11	121.1 (5)	F1—P1—F2ii	84.2 (6)
C13—C12—H12A	119.4	F2—P1—F2ii	180.0 (3)
C11—C12—H12A	119.4	C2—N1—C5	106.2 (3)
C14—C13—C12	120.4 (5)	C2—N1—Mn1	127.3 (3)
C14—C13—H13A	119.8	C5—N1—Mn1	126.3 (3)
C12—C13—H13A	119.8	C7—N2—C10	105.9 (3)
C13—C14—C15	120.0 (5)	C7—N2—Mn1	127.2 (3)
C13—C14—H14A	120.0	C10—N2—Mn1	126.7 (3)
C15—C14—H14A	120.0	C23—O1—Mn1	127.0 (4)
C14—C15—C16	120.2 (5)

Mn1—N1	2.004 (3)
Mn1—N2	2.018 (3)
Mn1—O1	2.260 (3)

N1—Mn1—N2	90.13 (13)
N1—Mn1—O1i	90.70 (13)
N2—Mn1—O1i	90.25 (13)
N2—Mn1—O1	89.75 (13)

Symmetry code: (i) .