Crystal structure and magnetic properties of the layered hybrid organic–inorganic compounds M₂(OH)₂(C₁₄H₈O₄) (M = Mn, Fe)

The structure of M₂(OH)₂(bpdc) (bpdc = bi­phenyl di­carboxyl­ate, C₁₄H₈O₄) is distinct from that of the isoreticular compounds M₂(OH)₂(bdc) (bdc = benzene di­carboxyl­ate, C₈H₄O₄) (M = Mn, Fe), in the sense that no disorder of the bpdc molecules from one layer to the other needs to be considered. The global symmetry is lower in the bpdc compounds (P1) than in the bdc compounds (C2/m). Both Mn₂(OH)₂(bpdc) and Fe₂(OH)₂(bpdc) order magnetically at 36.8 and 46.5 K, respectively, and can be considered as uncompensated antiferromagnets, whereas Mn₂(OH)₂(bdc) (Néel temperature T_N = 38.5 K) and Fe₂(OH)₂(bdc) (T_N = 66 K) are compensated antiferromagnets.

Computing details

Program(s) used to solve structure: FOX; program(s) used to refine structure: FULLPROF; molecular graphics: DIAMOND; software used to prepare material for publication: WORD.

(I)

Crystal data

C14H10Mn2O6	V = 315.35 (2) Å^3
Mr = 384.10	Z = 1
Triclinic, P1	F(000) = 382
Hall symbol: -P 1	Dx = 2.022 Mg m^−3
a = 14.2037 (4) Å	Synchrotron radiation
b = 6.47851 (8) Å	µ = 2.58 mm^−1
c = 3.4532 (2) Å	T = 293 K
α = 90.091 (9)°	light brown
β = 96.839 (13)°	cylinder, × 0.5 mm
γ = 91.7101 (16)°

Data collection

CRISTAL Beamline, SOLEIL diffractometer	Data collection mode: transmission
Radiation source: CRISTAL Beamline, SOLEIL	2θmin = 2.511°, 2θmax = 44.003°, 2θstep = 0.004°

Refinement

Rp = 0.106	Profile function: T-C-H Pseudo-Voigt function
Rwp = 0.135	23 parameters
Rexp = 0.189	0 restraints
RBragg = 0.066	H-atom parameters not refined
10374 data points

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
M_1	−0.37529	0.61064	0.95341	0.041 (2)*
M_2	−0.39876	0.73540	0.93222	0.041 (2)*
M_3	−0.28226	0.55603	0.94477	0.041 (2)*
M_4	−0.22387	0.66881	0.90837	0.041 (2)*
M_5	−0.25743	0.35254	0.98226	0.041 (2)*
M_6	−0.32925	0.20550	1.02876	0.041 (2)*
M_7	−0.31615	0.07181	1.05409	0.041 (2)*
M_8	−0.42235	0.25958	1.03754	0.041 (2)*
M_9	−0.47352	0.17741	1.06593	0.041 (2)*
M_10	−0.44861	0.46419	1.00014	0.041 (2)*
M_24	−0.15499	0.29272	0.97265	0.041 (2)*
M_25	−0.14087	0.10376	1.00938	0.041 (2)*
M_26	−0.09594	0.43893	0.92907	0.041 (2)*
AB	0.00000	0.00000	0.00000	0.019 (2)*
CD	0.00000	0.50000	0.50000	0.027 (3)*
GH	0.0499 (6)	0.1721 (14)	0.551 (10)	0.010 (4)*

Geometric parameters (Å, º)

AB—GH^i	2.09 (3)	CD—CD^i	3.4532 (2)
AB—GH^ii	2.09 (3)	CD—CD^vi	3.4532 (2)
AB—M_25^i	2.1336 (1)	M_1—M_2	0.8833 (1)
AB—M_25^ii	2.1336 (1)	M_1—M_3	1.3818 (1)
AB—GH	2.23 (3)	M_1—M_10	1.4115 (1)
AB—GH^iii	2.23 (3)	M_3—M_4	1.1074 (1)
CD—M_26	2.1586 (2)	M_3—M_5	1.3771 (1)
CD—M_26^iv	2.1586 (2)	M_5—M_6	1.3983 (1)
CD—GH	2.260 (9)	M_5—M_24	1.5210 (1)
CD—GH^iv	2.260 (9)	M_24—M_25	1.2506 (1)
CD—M_26^i	2.2860 (3)	M_24—M_26	1.2675 (1)
CD—M_26^v	2.2860 (3)	M_6—M_7	0.8935 (1)
AB—AB^i	3.4532 (2)	M_6—M_8	1.3818 (1)
AB—AB^vi	3.4532 (2)	M_8—M_9	0.9029 (1)
AB—CD^vii	3.6683 (2)	M_8—M_10	1.3898 (1)
AB—CD^viii	3.6731 (2)	M_10—M_1	1.4115 (1)
AB—CD^i	3.6731 (2)	M_10—M_10^ix	1.5449 (1)
AB—CD	3.6683 (2)
M_25—M_24—M_26	128.884 (5)	M_3—M_1—M_10	122.498 (6)
M_5—M_24—M_25	114.749 (4)	M_1—M_3—M_5	120.478 (4)
M_5—M_24—M_26	116.367 (6)	CD—M_26—CD^vi	101.925 (12)
M_6—M_5—M_24	121.860 (6)	AB—GH—AB^vi	105.9 (11)
M_5—M_6—M_8	121.934 (6)	AB—GH—CD	109.4 (8)
M_6—M_8—M_10	121.064 (4)	AB^vi—GH—CD	115.1 (8)
M_1—M_10—M_8	116.289 (5)

Symmetry codes: (i) x, y, z−1; (ii) −x, −y, −z+1; (iii) −x, −y, −z; (iv) −x, −y+1, −z+1; (v) −x, −y+1, −z+2; (vi) x, y, z+1; (vii) x, y−1, z−1; (viii) x, y−1, z; (ix) −x−1, −y+1, −z+2.