Synthesis, crystal structure solution and characterization of two organic–inorganic hybrid layered materials based on metal sulfates and 1,4-phenyl­enedi­amine

Two organic–inorganic hybrid layered materials, namely poly[(μ-1,4-di­amino­benzene-κ²N:N′)[μ₃-sulfato­(VI)-κ⁴O:O′:O′′,O′′′]manganese], [Mn(SO₄)(C₆H₈N₂)]_n, 1, and poly[(μ-1,4-di­amino­benzene-κ²N:N′)[μ₃-sulfato­(VI)-κ⁴O:O′:O′′,O′′′]copper], [Cu(SO₄)(C₆H₈N₂)]_n, 2, have been synthesized using 1,4-phenyl­enedi­amine (PPD) as an organic template and component (linker). Both materials form three-dimensional frameworks. The crystal structures were determined using data from powder X-ray diffraction measurements. The purity and morphology of the compounds were studied by elemental analyses and SEM investigations, and their thermal stabilities were determined by thermogravimetric and nona­mbient powder X-ray diffraction measurements, which indicated that 1 is stable up to 537 K and 2 is stable up to 437 K.

Computing details

For both structures, data collection: X'Pert Data Collector (PANalytical, 2011); cell refinement: X'Pert Data Collector (PANalytical, 2011); data reduction: X'Pert Data Collector (PANalytical, 2011); program(s) used to solve structure: FOX (Favre-Nicolin & Cerný, 2002) and EXPO2014 (Altomare et al., 2009); program(s) used to refine structure: JANA2006 (Petříček et al., 2014); molecular graphics: DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: PLATON (Spek, 2009) and Mercury (Macrae et al., 2008).

Poly[(µ-1,4-diaminobenzene-κ²N:N')[µ₃-sulfato(VI)-κ⁴O:O':O'',O''']manganese] (MnSO4-PPD)

Crystal data

[Mn(SO4)(C6H8N2)]	F(000) = 524
Mr = 259.1	Dx = 2.075 Mg m^−3
Orthorhombic, Cmcm	Cu Kα radiation, λ = 1.5418 Å
Hall symbol: -C 2c 2	µ = 15.27 mm^−1
a = 6.6108 (3) Å	T = 293 K
b = 7.3958 (4) Å	Particle morphology: plate-like prisms
c = 16.9678 (11) Å	black
V = 829.58 (8) Å^3	cylinder, 15 × 0.7 mm
Z = 4

Data collection

Panalytical X'Pert Pro MPD diffractometer	Data collection mode: transmission
Radiation source: sealed X-ray tube	Scan method: continuous
Specimen mounting: borosilicate glass capillary	2θmin = 7.02°, 2θmax = 89.98°, 2θstep = 0.02°

Refinement

Rp = 0.011	16 restraints
Rwp = 0.016	0 constraints
Rexp = 0.008	H-atom parameters constrained
R(F) = 0.041	Weighting scheme based on measured s.u.'s
4149 data points	(Δ/σ)max = 0.027
Profile function: Pseudo-Voigt	Background function: 16 Legendre polynoms
43 parameters	Preferred orientation correction: none

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

	x	y	z	Uiso*/Ueq
Mn	0.5	0.9945 (12)	0.25	0.047 (3)*
S1	1	0.8787 (11)	0.25	0.053 (6)*
O1	1	0.7660 (12)	0.1806 (3)	0.058 (8)*
N1	0.5	0.812 (2)	0.3541 (5)	0.034 (8)*
O2	0.8220 (6)	0.9914 (12)	0.25	0.044 (6)*
C1	0.5	0.9051 (19)	0.4294 (5)	0.065 (13)*
C2	0.6818 (5)	0.9514 (14)	0.4649 (4)	0.039 (7)*
H1	0.396067	0.739795	0.351681	0.0409*
H2	0.807572	0.916331	0.441133	0.0469*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
?	?	?	?	?	?	?

Geometric parameters (Å, º)

Mn—S1^i	2.842 (12)	S1—O2	1.442 (8)
Mn—O1^i	2.328 (11)	S1—O2^iv	1.442 (8)
Mn—O1^ii	2.328 (11)	N1—C1	1.451 (15)
Mn—N1	2.225 (13)	N1—H1	0.87
Mn—N1^iii	2.225 (13)	N1—H1^v	0.87
Mn—O2	2.129 (4)	C1—C2	1.388 (7)
Mn—O2^iii	2.129 (4)	C1—C2^v	1.388 (7)
S1—O1	1.443 (8)	C2—C2^vi	1.390 (10)
S1—O1^iv	1.443 (8)	C2—H2	0.96
S1^i—Mn—O1^i	30.38 (18)	Mn^vii—S1—O2	125.3 (4)
S1^i—Mn—O1^ii	30.38 (18)	Mn^vii—S1—O2^iv	125.3 (4)
S1^i—Mn—N1	127.4 (4)	O1—S1—O1^iv	109.4 (7)
S1^i—Mn—N1^iii	127.4 (4)	O1—S1—O2	109.5 (2)
S1^i—Mn—O2	90.6 (3)	O1—S1—O2^iv	109.5 (2)
S1^i—Mn—O2^iii	90.6 (3)	O1^iv—S1—O2	109.5 (2)
O1^i—Mn—O1^ii	60.8 (3)	O1^iv—S1—O2^iv	109.5 (2)
O1^i—Mn—N1	157.8 (5)	O2—S1—O2^iv	109.4 (7)
O1^i—Mn—N1^iii	97.0 (4)	Mn^vii—O1—S1	94.9 (4)
O1^i—Mn—O2	90.5 (3)	Mn—N1—C1	114.2 (10)
O1^i—Mn—O2^iii	90.5 (3)	Mn—N1—H1	109.47
O1^ii—Mn—N1	97.0 (4)	Mn—N1—H1^v	109.47
O1^ii—Mn—N1^iii	157.8 (5)	C1—N1—H1	109.47
O1^ii—Mn—O2	90.5 (3)	C1—N1—H1^v	109.47
O1^ii—Mn—O2^iii	90.5 (3)	H1—N1—H1^v	104.32
N1—Mn—N1^iii	105.2 (6)	Mn—O2—S1	145.3 (6)
N1—Mn—O2	89.6 (2)	N1—C1—C2	120.0 (4)
N1—Mn—O2^iii	89.6 (2)	N1—C1—C2^v	120.0 (4)
N1^iii—Mn—O2	89.6 (2)	C2—C1—C2^v	120.0 (8)
N1^iii—Mn—O2^iii	89.6 (2)	C1—C2—C2^vi	120.0 (5)
O2—Mn—O2^iii	178.8 (6)	C1—C2—H2	120
Mn^vii—S1—O1	54.7 (4)	C2^vi—C2—H2	120
Mn^vii—S1—O1^iv	54.7 (4)

Symmetry codes: (i) x−1/2, y+1/2, z; (ii) −x+3/2, y+1/2, −z+1/2; (iii) −x+1, y, −z+1/2; (iv) −x+2, y, −z+1/2; (v) −x+1, y, z; (vi) x, −y+2, −z+1; (vii) x+1/2, y−1/2, z.

Poly[(µ-1,4-diaminobenzene-κ²N:N')[µ₃-sulfato(VI)-κ⁴O:O':O'',O''']manganese] (CuSO4-PPD)

Crystal data

[Cu(SO4)(C6H8N2)]	F(000) = 540
Mr = 267.7	Dx = 2.120 Mg m^−3
Orthorhombic, Pbcn	Cu Kα radiation, λ = 1.5418 Å
Hall symbol: -P 2n 2ab	µ = 5.98 mm^−1
a = 7.0852 (7) Å	T = 293 K
b = 7.2052 (7) Å	Particle morphology: plate-like prisms
c = 16.431 (2) Å	black
V = 838.80 (17) Å^3	cylinder, 15 × 0.7 mm
Z = 4

Data collection

Panalytical X'Pert Pro MPD diffractometer	Data collection mode: transmission
Radiation source: sealed X-ray tube	Scan method: continuous
Specimen mounting: borosilicate glass capillary	2θmin = 7.007°, 2θmax = 89.986°, 2θstep = 0.013°

Refinement

Rp = 0.031	19 restraints
Rwp = 0.040	0 constraints
Rexp = 0.012	H-atom parameters constrained
R(F) = 0.038	Weighting scheme based on measured s.u.'s
6384 data points	(Δ/σ)max = 0.043
Profile function: Pseudo-Voigt	Background function: 15 Legendre polynoms
47 parameters	Preferred orientation correction: none

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

	x	y	z	Uiso*/Ueq
Cu1	0.5	0.9549 (9)	0.25	0.028 (3)*
S1	0.5	0.5939 (12)	0.25	0.016 (4)*
O1	0.453 (2)	0.7107 (17)	0.1804 (7)	0.016 (4)*
O2	0.3372 (17)	0.4761 (16)	0.2704 (10)	0.016 (4)*
C1	0.659 (4)	1.064 (4)	0.0400 (16)	0.020 (7)*
N1	0.470 (4)	1.143 (2)	0.1608 (5)	0.020 (7)*
C2	0.325 (5)	1.005 (4)	0.0386 (16)	0.020 (7)*
C3	0.485 (3)	1.071 (3)	0.0784 (6)	0.020 (7)*
H1	0.769418	1.108144	0.067991	0.0236*
H2	0.204634	1.007385	0.065311	0.0236*
H3	0.361941	1.199817	0.166458	0.0236*
H4	0.551095	1.232002	0.167491	0.0236*

Geometric parameters (Å, º)

Cu1—S1	2.601 (11)	S1—O2^i	1.471 (13)
Cu1—O1	2.124 (13)	C1—C2^iv	1.39 (4)
Cu1—O1^i	2.124 (13)	C1—C3	1.39 (4)
Cu1—O2^ii	2.417 (12)	C1—H1	0.96
Cu1—O2^iii	2.417 (12)	N1—C3	1.455 (16)
Cu1—N1	2.008 (14)	N1—H3	0.87
Cu1—N1^i	2.008 (14)	N1—H4	0.87
S1—O1	1.458 (13)	C2—C3	1.39 (4)
S1—O1^i	1.458 (13)	C2—H2	0.96
S1—O2	1.471 (13)
S1—Cu1—O1	34.1 (3)	Cu1—S1—O2^i	125.3 (5)
S1—Cu1—O1^i	34.1 (3)	O1—S1—O1^i	109.5 (9)
S1—Cu1—O2^ii	93.6 (3)	O1—S1—O2	109.5 (9)
S1—Cu1—O2^iii	93.6 (3)	O1—S1—O2^i	109.5 (9)
S1—Cu1—N1	132.5 (4)	O1^i—S1—O2	109.5 (9)
S1—Cu1—N1^i	132.5 (4)	O1^i—S1—O2^i	109.5 (9)
O1—Cu1—O1^i	68.1 (5)	O2—S1—O2^i	109.5 (8)
O1—Cu1—O2^ii	97.6 (6)	Cu1—O1—S1	91.2 (7)
O1—Cu1—O2^iii	88.4 (6)	Cu1^v—O2—S1	141.3 (8)
O1—Cu1—N1	98.6 (5)	C2^iv—C1—C3	120 (3)
O1—Cu1—N1^i	165.6 (6)	C2^iv—C1—H1	119.82
O1^i—Cu1—O2^ii	88.4 (6)	C3—C1—H1	119.82
O1^i—Cu1—O2^iii	97.6 (6)	Cu1—N1—C3	115.4 (13)
O1^i—Cu1—N1	165.6 (6)	Cu1—N1—H3	109.47
O1^i—Cu1—N1^i	98.6 (5)	Cu1—N1—H4	109.47
O2^ii—Cu1—O2^iii	172.8 (5)	C3—N1—H3	109.47
O2^ii—Cu1—N1	87.9 (10)	C3—N1—H4	109.47
O2^ii—Cu1—N1^i	87.3 (9)	H3—N1—H4	102.84
O2^iii—Cu1—N1	87.3 (9)	C1^iv—C2—C3	120 (3)
O2^iii—Cu1—N1^i	87.9 (10)	C1^iv—C2—H2	120.18
N1—Cu1—N1^i	95.1 (6)	C3—C2—H2	120.18
Cu1—S1—O1	54.7 (5)	C1—C3—N1	120 (2)
Cu1—S1—O1^i	54.7 (5)	C1—C3—C2	120.0 (19)
Cu1—S1—O2	125.3 (5)	N1—C3—C2	120 (2)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H3···O1^iii	0.87	2.25	3.05 (3)	153.95
N1—H4···O2^vi	0.87	2.18	2.99 (2)	153.36

Symmetry codes: (iii) −x+1/2, y+1/2, z; (vi) −x+1, y+1, −z+1/2.