cyclo-Tetra-μ-fluorido-1:2κF;2:3κF;3:4κF;1:4κF-octa-nitrato-1κO,O';3κO,O'-tetra-kis-(1,10-phenanthroline)-2κN,N';4κN,N'-2,4-dichromium(III)-1,3-dineodymium(III) methanol tetra-solvate monohydrate.

In the title compound, [Cr(2)Nd(2)F(4)(NO(2))(8)(C(12)H(8)N(2))(4)]·4CH(3)OH·H(2)O, two cis-difluoridobis(1,10-phenanthroline)chromium(III) fragments containing octa-hedrally coordinated chromium(III) bridge via fluoride ions to two tetra-nitratoneodymate(III) fragments, forming an uncharged tetra-nuclear square-like core. The fluoride bridges are fairly linear, with Cr-F-Nd angles of 168.74 (8)°. Cr-F bond lengths are 1.8815 (15) Å, slightly elongated compared to those of the parent chromium(III) complex, which has bond lengths ranging from 1.8444 (10) to 1.8621 (10) Å. The tetra-nuclear complex is centered at a fourfold rotoinversion axis, with the Cr and Nd atoms situated on two perpendicular twofold rotation axes. The uncoordinated water mol-ecule resides on a fourfold rotation axis. The four methanol solvent mol-ecules are located around this axis, forming a cyclic hydrogen-bonded arrangement. The title compound is the first structurally characterized example of unsupported fluoride bridges between lanthanide and transition metal ions.

Related literature

For related structures of second sphere inter­actions with robust chromium(III) fluoride complexes, see: Birk et al. (2010 ▶); Terasaki et al. (1999 ▶); Kaizaki & Takemoto (1990 ▶). For other examples of n class="Chemical">fluoride bridges between 3d and 4f metal atoms, see: Pevec et al. (2003 ▶); McRobbie et al. (2011 ▶). For the structure of the cationic chromium precursor complex, see: Birk et al. (2008 ▶). For the synthesis of the precursor, see: Glerup et al. (1970 ▶). For importance of the title compound in the context of magnetic materials, see: Kahn (1985 ▶, 1987 ▶); Sessoli & Powell (2009 ▶). For crystallographic background, see: Coppens (1970 ▶).

Experimental

Crystal data

[Cr2n class="Chemical">Nd2F4(NO2)8(C12H8N2)4]·4CH4O·H2O

M = 1831.56

Tetragonal,

a = 17.632 (4) Å

c = 20.955 (3) Å

V = 6515 (2) Å3

Z = 4

Mo Kα radiation

μ = 2.01 mm−1

T = 122 K

0.35 × 0.29 × 0.24 mm

Data collection

Nonius KappaCCD area-detector diffractometer

Absorption correction: integration (Gaussian; Coppens, 1970 ▶) T min = 0.601, T max = 0.718

339826 measured reflections

10126 independent reflections

6979 reflections with I > 2σ(I)

R int = 0.047

Refinement

R[F 2 > 2σ(F 2)] = 0.036

wR(F 2) = 0.102

S = 1.27

10126 reflections

239 parameters

H-atom parameters constrained

Δρmax = 2.41 e Å−3

Δρmin = −1.78 e Å−3

Data collection: COLLECT (Nonius, 1999 ▶); cell refinement: COLLECT; data reduction: EVALCCD (Duisenberg et al., 2003 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶) and Mercury (Man class="Chemical">crae et al., 2006 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811042383/wm2538sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811042383/wm2538Isup2.hkl

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

[Cr2Nd2F4(NO2)8(C12H8N2)4]·4CH4O·H2O	Dx = 1.867 Mg m−3
Mr = 1831.56	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, P4/ncc	Cell parameters from 120466 reflections
Hall symbol: -P 4a 2ac	θ = 2.3–40.1°
a = 17.632 (4) Å	µ = 2.01 mm−1
c = 20.955 (3) Å	T = 122 K
V = 6515 (2) Å3	Prism, pink
Z = 4	0.35 × 0.29 × 0.24 mm
F(000) = 3640

Nonius KappaCCD area-detector diffractometer	10126 independent reflections
Radiation source: fine-focus sealed tube	6979 reflections with I > 2σ(I)
graphite	Rint = 0.047
ω and φ scans	θmax = 40.1°, θmin = 2.3°
Absorption correction: integration (Gaussian; Coppens, 1970)	h = −31→31
Tmin = 0.601, Tmax = 0.718	k = −29→31
339826 measured reflections	l = −37→37

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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.102	H-atom parameters constrained
S = 1.27	w = 1/[σ2(Fo2) + (0.0144P)2 + 22.4316P] where P = (Fo2 + 2Fc2)/3
10126 reflections	(Δ/σ)max = 0.002
239 parameters	Δρmax = 2.41 e Å−3
0 restraints	Δρmin = −1.78 e Å−3

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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
Nd1	0.120550 (5)	0.879450 (5)	0.2500	0.01191 (3)
Cr1	0.142468 (17)	0.642468 (17)	0.2500	0.01199 (6)
F1	0.14142 (8)	0.74891 (8)	0.24362 (7)	0.0179 (2)
N1	0.14262 (10)	0.52607 (10)	0.24070 (8)	0.0148 (3)
N2	0.13452 (11)	0.63381 (11)	0.15243 (8)	0.0154 (3)
N3	0.05724 (12)	0.80814 (11)	0.36783 (10)	0.0194 (3)
N4	−0.00247 (12)	0.89135 (13)	0.15390 (10)	0.0200 (3)
O1	0.12382 (11)	0.83605 (11)	0.36641 (9)	0.0224 (3)
O2	0.01948 (10)	0.81071 (10)	0.31637 (8)	0.0194 (3)
O3	0.03125 (13)	0.77993 (12)	0.41658 (9)	0.0280 (4)
O4	0.02408 (11)	0.94903 (11)	0.18224 (10)	0.0237 (3)
O5	0.01769 (11)	0.82711 (11)	0.17550 (9)	0.0227 (3)
O6	−0.04596 (12)	0.89763 (14)	0.10853 (9)	0.0297 (4)
C1	0.15642 (14)	0.47330 (13)	0.28428 (11)	0.0186 (3)
H1	0.1678	0.4886	0.3267	0.022*
C2	0.15473 (15)	0.39539 (14)	0.26990 (12)	0.0222 (4)
H2	0.1663	0.3590	0.3019	0.027*
C3	0.13624 (15)	0.37223 (13)	0.20931 (12)	0.0217 (4)
H3	0.1327	0.3197	0.1996	0.026*
C4	0.12255 (14)	0.42689 (13)	0.16182 (11)	0.0193 (4)
C5	0.10393 (16)	0.40922 (15)	0.09673 (12)	0.0248 (4)
H5	0.0975	0.3577	0.0845	0.030*
C6	0.09540 (17)	0.46455 (16)	0.05244 (12)	0.0258 (5)
H6	0.0818	0.4514	0.0100	0.031*
C7	0.10658 (14)	0.54258 (14)	0.06875 (11)	0.0203 (4)
C8	0.10612 (16)	0.60257 (16)	0.02423 (11)	0.0235 (4)
H8	0.0953	0.5929	−0.0194	0.028*
C9	0.12147 (16)	0.67492 (16)	0.04442 (12)	0.0250 (4)
H9	0.1227	0.7154	0.0145	0.030*
C10	0.13538 (15)	0.68919 (14)	0.10924 (11)	0.0206 (4)
H10	0.1457	0.7396	0.1226	0.025*
C11	0.12150 (12)	0.56114 (12)	0.13254 (10)	0.0159 (3)
C12	0.12809 (12)	0.50311 (12)	0.17959 (10)	0.0150 (3)
O20	0.14380 (18)	0.22887 (17)	0.41608 (17)	0.0543 (8)
H20	0.1608	0.2733	0.4185	0.081*
C20	0.07522 (19)	0.22365 (18)	0.45093 (15)	0.0315 (6)
H20A	0.0838	0.2404	0.4949	0.047*
H20B	0.0576	0.1709	0.4510	0.047*
H20C	0.0367	0.2560	0.4310	0.047*
O30	0.2500	0.2500	0.0863 (5)	0.225 (9)

	U11	U22	U33	U12	U13	U23
Nd1	0.01150 (4)	0.01150 (4)	0.01274 (5)	0.00073 (4)	−0.00057 (3)	−0.00057 (3)
Cr1	0.01221 (9)	0.01221 (9)	0.01155 (14)	−0.00036 (12)	0.00017 (10)	−0.00017 (10)
F1	0.0179 (5)	0.0122 (5)	0.0237 (6)	0.0010 (4)	0.0006 (5)	−0.0002 (5)
N1	0.0151 (7)	0.0146 (6)	0.0147 (7)	−0.0010 (5)	0.0001 (5)	0.0003 (5)
N2	0.0189 (8)	0.0152 (7)	0.0120 (5)	−0.0002 (5)	0.0008 (6)	0.0010 (5)
N3	0.0232 (9)	0.0175 (8)	0.0176 (7)	0.0015 (6)	0.0030 (6)	−0.0008 (6)
N4	0.0179 (8)	0.0260 (9)	0.0160 (7)	0.0005 (7)	−0.0011 (6)	−0.0001 (6)
O1	0.0222 (8)	0.0268 (8)	0.0181 (7)	−0.0014 (6)	−0.0026 (6)	0.0010 (6)
O2	0.0188 (7)	0.0216 (7)	0.0178 (7)	−0.0028 (6)	0.0004 (5)	0.0008 (6)
O3	0.0395 (11)	0.0260 (9)	0.0183 (7)	−0.0027 (8)	0.0073 (7)	0.0043 (6)
O4	0.0230 (8)	0.0207 (7)	0.0274 (8)	0.0029 (6)	−0.0073 (7)	−0.0023 (6)
O5	0.0242 (8)	0.0210 (8)	0.0229 (8)	−0.0026 (6)	−0.0054 (6)	0.0011 (6)
O6	0.0282 (9)	0.0411 (12)	0.0198 (8)	0.0035 (8)	−0.0104 (7)	0.0011 (8)
C1	0.0219 (9)	0.0178 (8)	0.0161 (8)	0.0003 (7)	0.0010 (7)	0.0025 (7)
C2	0.0267 (11)	0.0171 (9)	0.0229 (9)	0.0001 (8)	0.0008 (8)	0.0056 (8)
C3	0.0255 (10)	0.0157 (8)	0.0238 (9)	−0.0012 (7)	0.0013 (8)	0.0002 (7)
C4	0.0208 (9)	0.0171 (8)	0.0201 (9)	−0.0022 (7)	−0.0002 (7)	−0.0029 (7)
C5	0.0307 (12)	0.0221 (10)	0.0214 (9)	−0.0049 (9)	0.0002 (9)	−0.0072 (8)
C6	0.0333 (13)	0.0273 (11)	0.0167 (9)	−0.0052 (10)	−0.0022 (8)	−0.0059 (8)
C7	0.0228 (10)	0.0236 (10)	0.0144 (8)	−0.0009 (8)	−0.0010 (7)	−0.0028 (7)
C8	0.0281 (11)	0.0293 (12)	0.0131 (7)	0.0006 (8)	−0.0008 (8)	0.0000 (8)
C9	0.0319 (12)	0.0269 (11)	0.0161 (8)	0.0014 (9)	−0.0001 (8)	0.0049 (8)
C10	0.0253 (10)	0.0197 (9)	0.0168 (8)	0.0007 (8)	0.0014 (7)	0.0029 (7)
C11	0.0165 (8)	0.0179 (8)	0.0134 (7)	−0.0003 (6)	0.0013 (6)	−0.0006 (6)
C12	0.0147 (7)	0.0156 (8)	0.0149 (7)	−0.0006 (6)	0.0012 (6)	−0.0008 (6)
O20	0.0445 (16)	0.0375 (14)	0.081 (2)	−0.0003 (12)	0.0101 (16)	−0.0038 (15)
C20	0.0370 (15)	0.0287 (13)	0.0288 (12)	0.0012 (11)	0.0023 (11)	0.0038 (10)
O30	0.317 (15)	0.317 (15)	0.040 (5)	0.000	0.000	0.000

Nd1—F1i	2.3348 (15)	C1—C2	1.407 (3)
Nd1—F1	2.3348 (15)	C1—H1	0.9500
Nd1—O4	2.5328 (19)	C2—C3	1.373 (4)
Nd1—O4i	2.5328 (19)	C2—H2	0.9500
Nd1—O1	2.5574 (18)	C3—C4	1.406 (3)
Nd1—O1i	2.5574 (18)	C3—H3	0.9500
Nd1—O5	2.5648 (19)	C4—C12	1.398 (3)
Nd1—O5i	2.5648 (19)	C4—C5	1.437 (3)
Nd1—O2	2.5650 (18)	C5—C6	1.355 (4)
Nd1—O2i	2.5650 (18)	C5—H5	0.9500
Cr1—F1ii	1.8815 (15)	C6—C7	1.431 (4)
Cr1—F1	1.8815 (15)	C6—H6	0.9500
Cr1—N2	2.0551 (17)	C7—C11	1.401 (3)
Cr1—N2ii	2.0551 (17)	C7—C8	1.410 (4)
Cr1—N1	2.0616 (19)	C8—C9	1.371 (4)
Cr1—N1ii	2.0616 (19)	C8—H8	0.9500
N1—C1	1.326 (3)	C9—C10	1.403 (3)
N1—C12	1.367 (3)	C9—H9	0.9500
N2—C10	1.332 (3)	C10—H10	0.9500
N2—C11	1.367 (3)	C11—C12	1.425 (3)
N3—O3	1.225 (3)	O20—C20	1.416 (4)
N3—O2	1.268 (3)	O20—H20	0.8400
N3—O1	1.273 (3)	C20—H20A	0.9800
N4—O6	1.226 (3)	C20—H20B	0.9800
N4—O4	1.267 (3)	C20—H20C	0.9800
N4—O5	1.271 (3)
F1i—Nd1—F1	72.09 (7)	Cr1—F1—Nd1	168.74 (8)
F1i—Nd1—O4	140.40 (6)	C1—N1—C12	118.15 (19)
F1—Nd1—O4	123.46 (5)	C1—N1—Cr1	129.31 (15)
F1i—Nd1—O4i	123.46 (5)	C12—N1—Cr1	112.52 (14)
F1—Nd1—O4i	140.40 (6)	C10—N2—C11	118.83 (19)
O4—Nd1—O4i	70.35 (9)	C10—N2—Cr1	128.39 (16)
F1i—Nd1—O1	82.88 (5)	C11—N2—Cr1	112.61 (13)
F1—Nd1—O1	75.88 (6)	O3—N3—O2	121.8 (2)
O4—Nd1—O1	134.02 (6)	O3—N3—O1	121.4 (2)
O4i—Nd1—O1	71.16 (7)	O2—N3—O1	116.77 (19)
F1i—Nd1—O1i	75.88 (6)	O6—N4—O4	121.5 (2)
F1—Nd1—O1i	82.87 (5)	O6—N4—O5	122.1 (2)
O4—Nd1—O1i	71.16 (7)	O4—N4—O5	116.4 (2)
O4i—Nd1—O1i	134.02 (6)	N3—O1—Nd1	96.72 (13)
O1—Nd1—O1i	153.69 (9)	N3—O2—Nd1	96.50 (13)
F1i—Nd1—O5	132.47 (6)	N4—O4—Nd1	97.01 (14)
F1—Nd1—O5	73.85 (5)	N4—O5—Nd1	95.39 (13)
O4—Nd1—O5	50.07 (6)	N1—C1—C2	122.3 (2)
O4i—Nd1—O5	103.91 (6)	N1—C1—H1	118.9
O1—Nd1—O5	119.27 (6)	C2—C1—H1	118.9
O1i—Nd1—O5	67.84 (6)	C3—C2—C1	119.6 (2)
F1i—Nd1—O5i	73.85 (5)	C3—C2—H2	120.2
F1—Nd1—O5i	132.47 (6)	C1—C2—H2	120.2
O4—Nd1—O5i	103.91 (6)	C2—C3—C4	119.4 (2)
O4i—Nd1—O5i	50.07 (6)	C2—C3—H3	120.3
O1—Nd1—O5i	67.84 (6)	C4—C3—H3	120.3
O1i—Nd1—O5i	119.27 (6)	C12—C4—C3	117.3 (2)
O5—Nd1—O5i	151.57 (9)	C12—C4—C5	118.5 (2)
F1i—Nd1—O2	125.40 (5)	C3—C4—C5	124.2 (2)
F1—Nd1—O2	71.02 (5)	C6—C5—C4	121.3 (2)
O4—Nd1—O2	93.81 (6)	C6—C5—H5	119.4
O4i—Nd1—O2	71.14 (6)	C4—C5—H5	119.4
O1—Nd1—O2	49.98 (6)	C5—C6—C7	120.9 (2)
O1i—Nd1—O2	135.60 (6)	C5—C6—H6	119.6
O5—Nd1—O2	70.66 (6)	C7—C6—H6	119.6
O5i—Nd1—O2	104.72 (6)	C11—C7—C8	117.2 (2)
F1i—Nd1—O2i	71.02 (5)	C11—C7—C6	118.6 (2)
F1—Nd1—O2i	125.40 (5)	C8—C7—C6	124.2 (2)
O4—Nd1—O2i	71.14 (6)	C9—C8—C7	119.5 (2)
O4i—Nd1—O2i	93.81 (6)	C9—C8—H8	120.2
O1—Nd1—O2i	135.60 (6)	C7—C8—H8	120.2
O1i—Nd1—O2i	49.98 (6)	C8—C9—C10	120.0 (2)
O5—Nd1—O2i	104.72 (6)	C8—C9—H9	120.0
O5i—Nd1—O2i	70.66 (6)	C10—C9—H9	120.0
O2—Nd1—O2i	161.92 (8)	N2—C10—C9	121.6 (2)
F1ii—Cr1—F1	91.41 (8)	N2—C10—H10	119.2
F1ii—Cr1—N2	97.93 (7)	C9—C10—H10	119.2
F1—Cr1—N2	90.16 (7)	N2—C11—C7	122.8 (2)
F1ii—Cr1—N2ii	90.16 (7)	N2—C11—C12	116.64 (18)
F1—Cr1—N2ii	97.93 (7)	C7—C11—C12	120.5 (2)
N2—Cr1—N2ii	168.43 (10)	N1—C12—C4	123.2 (2)
F1ii—Cr1—N1	89.75 (7)	N1—C12—C11	116.78 (19)
F1—Cr1—N1	170.49 (6)	C4—C12—C11	120.0 (2)
N2—Cr1—N1	80.33 (7)	C20—O20—H20	109.5
N2ii—Cr1—N1	91.51 (7)	O20—C20—H20A	109.5
F1ii—Cr1—N1ii	170.49 (6)	O20—C20—H20B	109.5
F1—Cr1—N1ii	89.75 (7)	H20A—C20—H20B	109.5
N2—Cr1—N1ii	91.50 (7)	O20—C20—H20C	109.5
N2ii—Cr1—N1ii	80.33 (7)	H20A—C20—H20C	109.5
N1—Cr1—N1ii	90.66 (10)	H20B—C20—H20C	109.5

D—H···A	D—H	H···A	D···A	D—H···A
O20—H20···O20iii	0.84	1.89	2.700 (4)	161.

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O20—H20⋯O20i	0.84	1.89	2.700 (4)	161

Symmetry code: (i) .