catena-Poly[bis-(4-amino-pyridinium) [[diaqua-manganese(II)]-di-μ-chlorido] dichloride].

Single crystals of the title organic-inorganic hybrid, {(C(5)H(7)N(2))(2)[MnCl(2)(H(2)O)(2)]Cl(2)}(n), were synthesized from an ethanol solution containing manganese(II) chloride tetra-hydrate and 4-amino-pyridine under acidic conditions. The asymmetric unit contains a disordered organic cation (occupancies in the ratio 0.72:0.28), a chloride anion and an MnCl(H(2)O) moiety with the Mn(II) atom located on an inversion center. The structure is built up of infinite chains of edge-sharing [MnCl(4)(H(2)O)(2)] octa-hedra developing parallel to the a axis which are separated by the 4-amino-pyridinium ions and discrete chloride ions. The organic cations occupy the empty space around each inorganic chain. Structural cohesion is organized through N-H⋯Cl and O-H⋯Cl hydrogen bonds, which build up a three-dimensional network.

Related literature

For general background to organic–inorganic hybride materials, see: Lacroix et al. (1994 ▶); Mitzi (2001 ▶); Calabrese et al. (1991 ▶); Hong et al. (1992 ▶). For related structures, see: Caputo et al. (1976 ▶); Hachuła et al. (2009 ▶); Zeng et al. (2008 ▶).

Experimental

Crystal data

(C5H7N2)2[MnCl2(H2O)2]Cl2

M = 421.01

Monoclinic,

a = 3.946 (1) Å

b = 17.586 (6) Å

c = 12.845 (4) Å

β = 93.48 (3)°

V = 889.7 (5) Å3

Z = 2

Mo Kα radiation

μ = 1.35 mm−1

T = 298 K

0.05 × 0.04 × 0.02 mm

Data collection

Enraf–Nonius CAD-4 diffractometer

Absorption correction: ψ scan (North et al., 1968 ▶) T min = 0.916, T max = 0.999

2516 measured reflections

1892 independent reflections

1473 reflections with I > 2σ(I)

R int = 0.017

2 standard reflections frequency: 120 min intensity decay: 1%

Refinement

R[F 2 > 2σ(F 2)] = 0.036

wR(F 2) = 0.095

S = 1.04

1892 reflections

112 parameters

43 restraints

H-atom parameters constrained

Δρmax = 0.38 e Å−3

Δρmin = −0.45 e Å−3

Data collection: CAD-4 EXPRESS (Duisenberg, 1992 ▶; Macíček & Yordanov, 1992 ▶); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2009 ▶) and DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809026804/dn2460sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809026804/dn2460Isup2.hkl

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

(C5H7N2)2[MnCl2(H2O)2]Cl2	F(000) = 426
Mr = 421.01	Dx = 1.572 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 25 reflections
a = 3.946 (1) Å	θ = 10–15°
b = 17.586 (6) Å	µ = 1.35 mm−1
c = 12.845 (4) Å	T = 298 K
β = 93.48 (3)°	Prism, colourless
V = 889.7 (5) Å3	0.05 × 0.04 × 0.02 mm
Z = 2

Enraf–Nonius CAD-4 diffractometer	1473 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.017
graphite	θmax = 27.0°, θmin = 2.3°
non–profiled ω/2θ scans	h = −5→1
Absorption correction: ψ scan (North et al., 1968)	k = 0→22
Tmin = 0.916, Tmax = 0.999	l = −16→16
2516 measured reflections	2 standard reflections every 120 min
1892 independent reflections	intensity decay: 1%

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) = 0.095	H-atom parameters constrained
S = 1.04	w = 1/[σ2(Fo2) + (0.0506P)2 + 0.1303P] where P = (Fo2 + 2Fc2)/3
1892 reflections	(Δ/σ)max = 0.001
112 parameters	Δρmax = 0.38 e Å−3
43 restraints	Δρmin = −0.45 e Å−3

Experimental. Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R– factors based on ALL data will be even larger.

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	Occ. (<1)
Mn1	0.5000	0.5000	1.0000	0.03113 (15)
Cl1	0.05805 (18)	0.09651 (5)	0.82588 (5)	0.0535 (2)
Cl2	−0.01007 (15)	0.40847 (3)	0.95374 (5)	0.03833 (17)
O1	0.4739 (4)	0.54280 (11)	0.84390 (13)	0.0451 (5)
HW1	0.6426	0.5601	0.8110	0.068*
HW2	0.3186	0.5559	0.8160	0.068*
N1	0.2765 (11)	0.2731 (2)	0.7899 (3)	0.0640 (10)	0.72
H1A	0.2411	0.2253	0.7984	0.077*	0.72
H1B	0.2264	0.3050	0.8374	0.077*	0.72
N2	0.6831 (9)	0.3534 (2)	0.5246 (3)	0.0569 (9)	0.72
C1	0.4091 (13)	0.2978 (3)	0.7031 (3)	0.0501 (6)	0.72
C2	0.4949 (15)	0.2487 (3)	0.6239 (4)	0.0501 (6)	0.72
H2	0.4608	0.1966	0.6298	0.060*	0.72
C3	0.6292 (14)	0.2782 (3)	0.5378 (4)	0.0501 (6)	0.72
H3	0.6869	0.2451	0.4853	0.060*	0.72
C4	0.6020 (12)	0.4012 (3)	0.6012 (3)	0.0501 (6)	0.72
H4	0.6453	0.4528	0.5937	0.060*	0.72
C5	0.4562 (16)	0.3764 (4)	0.6909 (5)	0.0501 (6)	0.72
H5	0.3920	0.4107	0.7412	0.060*	0.72
N1'	0.704 (3)	0.4342 (5)	0.5481 (7)	0.060 (3)	0.28
H1'1	0.7695	0.4343	0.4855	0.072*	0.28
H1'2	0.6962	0.4761	0.5824	0.072*	0.28
N2'	0.400 (2)	0.2381 (5)	0.6940 (6)	0.049 (2)	0.28
C1'	0.614 (3)	0.3697 (5)	0.5917 (8)	0.0483 (15)	0.28
C2'	0.619 (4)	0.3023 (5)	0.5432 (10)	0.0483 (15)	0.28
H2'	0.6893	0.2985	0.4756	0.058*	0.28
C3'	0.517 (4)	0.2379 (6)	0.5971 (8)	0.0483 (15)	0.28
H3'	0.5299	0.1912	0.5635	0.058*	0.28
C4'	0.377 (3)	0.3078 (5)	0.7366 (9)	0.0483 (15)	0.28
H4'	0.2683	0.3122	0.7986	0.058*	0.28
C5'	0.507 (4)	0.3743 (10)	0.6929 (12)	0.0483 (15)	0.28
H5'	0.5207	0.4197	0.7301	0.058*	0.28

	U11	U22	U33	U12	U13	U23
Mn1	0.0294 (3)	0.0381 (3)	0.0263 (2)	0.0004 (2)	0.00499 (18)	0.00265 (19)
Cl1	0.0426 (4)	0.0783 (5)	0.0402 (3)	−0.0008 (3)	0.0075 (3)	−0.0189 (3)
Cl2	0.0326 (3)	0.0375 (3)	0.0455 (3)	0.0002 (2)	0.0071 (2)	−0.0063 (2)
O1	0.0335 (9)	0.0706 (13)	0.0317 (9)	0.0022 (9)	0.0050 (7)	0.0172 (8)
N1	0.086 (3)	0.061 (2)	0.0471 (19)	−0.003 (2)	0.0207 (19)	0.0011 (17)
N2	0.051 (2)	0.078 (3)	0.0413 (19)	0.0024 (19)	0.0022 (16)	0.0057 (18)
C1	0.0557 (14)	0.0510 (11)	0.0435 (11)	0.0032 (12)	0.0032 (10)	−0.0060 (10)
C2	0.0557 (14)	0.0510 (11)	0.0435 (11)	0.0032 (12)	0.0032 (10)	−0.0060 (10)
C3	0.0557 (14)	0.0510 (11)	0.0435 (11)	0.0032 (12)	0.0032 (10)	−0.0060 (10)
C4	0.0557 (14)	0.0510 (11)	0.0435 (11)	0.0032 (12)	0.0032 (10)	−0.0060 (10)
C5	0.0557 (14)	0.0510 (11)	0.0435 (11)	0.0032 (12)	0.0032 (10)	−0.0060 (10)
N1'	0.094 (8)	0.049 (5)	0.038 (4)	−0.017 (5)	0.002 (5)	−0.003 (4)
N2'	0.052 (5)	0.050 (5)	0.045 (5)	0.000 (4)	0.005 (4)	−0.004 (4)
C1'	0.052 (3)	0.040 (3)	0.052 (3)	0.008 (2)	−0.002 (3)	−0.018 (3)
C2'	0.052 (3)	0.040 (3)	0.052 (3)	0.008 (2)	−0.002 (3)	−0.018 (3)
C3'	0.052 (3)	0.040 (3)	0.052 (3)	0.008 (2)	−0.002 (3)	−0.018 (3)
C4'	0.052 (3)	0.040 (3)	0.052 (3)	0.008 (2)	−0.002 (3)	−0.018 (3)
C5'	0.052 (3)	0.040 (3)	0.052 (3)	0.008 (2)	−0.002 (3)	−0.018 (3)

Mn1—O1i	2.1383 (17)	C3—H3	0.9300
Mn1—O1	2.1383 (17)	C4—C5	1.389 (7)
Mn1—Cl2ii	2.6117 (8)	C4—H4	0.9300
Mn1—Cl2iii	2.6117 (8)	C5—H5	0.9300
Mn1—Cl2	2.6173 (8)	N1'—C1'	1.323 (11)
Mn1—Cl2i	2.6173 (8)	N1'—H1'1	0.8600
Cl2—Mn1iv	2.6117 (8)	N1'—H1'2	0.8600
O1—HW1	0.8654	N2'—C4'	1.348 (10)
O1—HW2	0.7285	N2'—C3'	1.353 (10)
N1—C1	1.332 (5)	C1'—C2'	1.339 (11)
N1—H1A	0.8600	C1'—C5'	1.393 (13)
N1—H1B	0.8600	C2'—C3'	1.400 (12)
N2—C4	1.348 (5)	C2'—H2'	0.9300
N2—C3	1.351 (6)	C3'—H3'	0.9300
C1—C2	1.392 (6)	C4'—C5'	1.408 (13)
C1—C5	1.405 (8)	C4'—H4'	0.9300
C2—C3	1.359 (6)	C5'—H5'	0.9300
C2—H2	0.9300
O1i—Mn1—O1	180.000 (1)	N2—C3—C2	123.2 (4)
O1i—Mn1—Cl2ii	90.13 (6)	N2—C3—H3	118.4
O1—Mn1—Cl2ii	89.87 (6)	C2—C3—H3	118.4
O1i—Mn1—Cl2iii	89.87 (6)	N2—C4—C5	122.6 (5)
O1—Mn1—Cl2iii	90.13 (6)	N2—C4—H4	118.7
Cl2ii—Mn1—Cl2iii	180.0	C5—C4—H4	118.7
O1i—Mn1—Cl2	89.37 (6)	C4—C5—C1	117.8 (6)
O1—Mn1—Cl2	90.63 (6)	C4—C5—H5	121.1
Cl2ii—Mn1—Cl2	97.99 (3)	C1—C5—H5	121.1
Cl2iii—Mn1—Cl2	82.01 (3)	C1'—N1'—H1'1	120.0
O1i—Mn1—Cl2i	90.63 (6)	C1'—N1'—H1'2	120.0
O1—Mn1—Cl2i	89.37 (6)	H1'1—N1'—H1'2	120.0
Cl2ii—Mn1—Cl2i	82.01 (3)	C4'—N2'—C3'	114.4 (10)
Cl2iii—Mn1—Cl2i	97.99 (3)	N1'—C1'—C2'	123.4 (12)
Cl2—Mn1—Cl2i	180.00 (2)	N1'—C1'—C5'	116.6 (10)
Mn1iv—Cl2—Mn1	97.99 (3)	C2'—C1'—C5'	120.0 (13)
Mn1—O1—HW1	126.0	C1'—C2'—C3'	118.3 (12)
Mn1—O1—HW2	124.3	C1'—C2'—H2'	120.9
HW1—O1—HW2	107.3	C3'—C2'—H2'	120.9
C1—N1—H1A	120.0	N2'—C3'—C2'	125.2 (10)
C1—N1—H1B	120.0	N2'—C3'—H3'	117.4
H1A—N1—H1B	120.0	C2'—C3'—H3'	117.4
C4—N2—C3	118.2 (4)	N2'—C4'—C5'	123.9 (13)
N1—C1—C2	122.3 (5)	N2'—C4'—H4'	118.0
N1—C1—C5	118.4 (5)	C5'—C4'—H4'	118.0
C2—C1—C5	119.3 (5)	C1'—C5'—C4'	117.5 (14)
C3—C2—C1	118.8 (5)	C1'—C5'—H5'	121.3
C3—C2—H2	120.6	C4'—C5'—H5'	121.3
C1—C2—H2	120.6

D—H···A	D—H	H···A	D···A	D—H···A
O1—HW1···Cl1v	0.87	2.27	3.090 (2)	158
O1—HW2···Cl1vi	0.73	2.39	3.082 (2)	159
N1—H1A···Cl1	0.86	2.41	3.264 (4)	172
N1—H1B···Cl2	0.86	2.57	3.415 (4)	169
N1'—H1'1···Cl1vii	0.86	2.47	3.299 (10)	163
N1'—H1'2···Cl1v	0.86	2.58	3.386 (9)	156

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—HW1⋯Cl1i	0.87	2.27	3.090 (2)	158
O1—HW2⋯Cl1ii	0.73	2.39	3.082 (2)	159
N1—H1A⋯Cl1	0.86	2.41	3.264 (4)	172
N1—H1B⋯Cl2	0.86	2.57	3.415 (4)	169
N1′—H1′1⋯Cl1iii	0.86	2.47	3.299 (10)	163
N1′—H1′2⋯Cl1i	0.86	2.58	3.386 (9)	156

Symmetry codes: (i) ; (ii) ; (iii) .