Poly[[diaqua-tetra-kis-(μ(2)-benzene-1,4-di-carbonitrile-κN:N')iron(II)] bis-[tetra-chlorido-ferrate(III)] nitro-methane tetra-solvate].

In the title compound, {[Fe(II)(C(8)H(4)N(2))(2)(H(2)O)(2)][Fe(III)Cl(4)](2)·4CH(3)NO(2)}(n), the Fe(II) and Fe(III) ions are hexa- and tetra-coordinated, respectively. Each unique benzene-1,4-dicarbonitrile mol-ecule lies across a crystallographic inversion centre and bridges two Fe(II) ions (each situated on an inversion centre), generating two-dimensional (4,4) square grid layers. The tetra-chloridoferrate(III) anions and nitro-methane solvent mol-ecules lie between the square grid layers and are further link to the adjacent layers into a three-dimensional supra-molecular structure through O-H⋯Cl and O-H⋯O hydrogen bonds.

Related literature

For background to FeII spin-crossover complexes, see: Kahn & Martinez (1998 ▶); Neville et al. (2007 ▶, 2008 ▶); Murray (2008 ▶). For the use of two connecting organodinitrile ligands for the development of magnetism, see: Chainok et al. (2010 ▶, 2012 ▶). For the synthesis, see: Chainok et al. (2012 ▶).

Experimental

Crystal data

[Fe(C8H4N2)2(H2O)2][FeCl4]2·4CH3NO2

M = 987.62

Monoclinic,

a = 12.1307 (9) Å

b = 12.1554 (9) Å

c = 13.8209 (10) Å

β = 102.466 (1)°

V = 1989.9 (3) Å3

Z = 2

Mo Kα radiation

μ = 1.67 mm−1

T = 100 K

0.27 × 0.27 × 0.24 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.661, T max = 0.690

11573 measured reflections

4397 independent reflections

3541 reflections with I > 2σ(I)

R int = 0.030

Refinement

R[F 2 > 2σ(F 2)] = 0.032

wR(F 2) = 0.073

S = 1.03

4397 reflections

233 parameters

3 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.76 e Å−3

Δρmin = −0.50 e Å−3

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT (Bruker, 2002 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶) and DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812002486/tk5052sup1.cif

Supplementary material file. DOI: 10.1107/S1600536812002486/tk5052Isup2.cdx

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812002486/tk5052Isup3.hkl

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

[Fe(C8H4N2)2(H2O)2][FeCl4]2·4CH3NO2	F(000) = 988
Mr = 987.62	Dx = 1.648 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 3583 reflections
a = 12.1307 (9) Å	θ = 2.4–27.4°
b = 12.1554 (9) Å	µ = 1.67 mm−1
c = 13.8209 (10) Å	T = 100 K
β = 102.466 (1)°	Block, yellow
V = 1989.9 (3) Å3	0.27 × 0.27 × 0.24 mm
Z = 2

Bruker SMART APEX CCD area-detector diffractometer	4397 independent reflections
Radiation source: fine-focus sealed tube	3541 reflections with I > 2σ(I)
graphite	Rint = 0.030
Detector resolution: 8 pixels mm-1	θmax = 28.1°, θmin = 2.0°
ω and φ scans	h = −15→16
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −12→15
Tmin = 0.661, Tmax = 0.690	l = −17→17
11573 measured reflections

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)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.073	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ2(Fo2) + (0.042P)2] where P = (Fo2 + 2Fc2)/3
4397 reflections	(Δ/σ)max = 0.001
233 parameters	Δρmax = 0.76 e Å−3
3 restraints	Δρmin = −0.50 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
Fe1	0.5000	0.5000	0.5000	0.01056 (10)
Cl1	0.31456 (5)	0.45491 (4)	0.76369 (4)	0.02217 (13)
O1	0.52584 (13)	0.46637 (12)	0.65141 (11)	0.0173 (3)
N1	0.74782 (15)	0.26095 (15)	0.71549 (13)	0.0200 (4)
C1	0.7964 (2)	0.15057 (19)	0.74355 (17)	0.0270 (5)
H1A	0.7828	0.1301	0.8086	0.040*
H1B	0.8778	0.1522	0.7465	0.040*
H1C	0.7606	0.0965	0.6941	0.040*
H1	0.576 (2)	0.417 (2)	0.676 (2)	0.052 (9)*
Fe2	0.29049 (3)	0.29511 (2)	0.83208 (2)	0.01702 (9)
Cl2	0.42489 (5)	0.18565 (5)	0.80885 (4)	0.02811 (14)
O2	0.64553 (13)	0.26786 (12)	0.68614 (12)	0.0259 (4)
N2	0.67018 (18)	0.34984 (17)	0.93557 (15)	0.0297 (5)
C2	0.6206 (3)	0.3774 (2)	1.0194 (2)	0.0437 (7)
H2A	0.6721	0.3550	1.0810	0.066*
H2B	0.5485	0.3388	1.0131	0.066*
H2C	0.6080	0.4570	1.0205	0.066*
H2	0.4716 (18)	0.466 (2)	0.6803 (19)	0.043 (9)*
Cl3	0.12062 (5)	0.23479 (4)	0.76444 (4)	0.02225 (13)
O3	0.81115 (14)	0.33973 (14)	0.72375 (13)	0.0318 (4)
Cl4	0.30172 (5)	0.31921 (5)	0.99164 (4)	0.02609 (14)
O4	0.6489 (2)	0.41206 (17)	0.86466 (15)	0.0661 (7)
O5	0.72545 (17)	0.26586 (17)	0.93885 (17)	0.0515 (6)
N11	0.49078 (14)	0.32436 (14)	0.47352 (13)	0.0159 (4)
C11	0.49325 (17)	0.23044 (17)	0.47862 (15)	0.0151 (4)
C12	0.49595 (17)	0.11201 (16)	0.48873 (15)	0.0164 (4)
C13	0.48332 (19)	0.06644 (17)	0.57797 (16)	0.0203 (5)
H13	0.4724	0.1125	0.6306	0.024*
C14	0.51318 (19)	0.04656 (17)	0.41060 (16)	0.0200 (5)
H14	0.5224	0.0791	0.3503	0.024*
N21	0.32197 (14)	0.50641 (13)	0.48775 (13)	0.0166 (4)
C21	0.22841 (17)	0.50554 (16)	0.48975 (15)	0.0148 (4)
C22	0.11031 (17)	0.50257 (16)	0.49328 (15)	0.0146 (4)
C23	0.07732 (17)	0.42932 (16)	0.55939 (15)	0.0160 (4)
H23	0.1310	0.3821	0.5994	0.019*
C24	0.03464 (17)	0.57343 (17)	0.43427 (15)	0.0164 (4)
H24	0.0595	0.6230	0.3903	0.020*

	U11	U22	U33	U12	U13	U23
Fe1	0.0092 (2)	0.00766 (19)	0.0156 (2)	0.00009 (14)	0.00442 (15)	0.00041 (15)
Cl1	0.0274 (3)	0.0176 (3)	0.0228 (3)	−0.0022 (2)	0.0083 (2)	0.0030 (2)
O1	0.0169 (8)	0.0178 (8)	0.0186 (8)	0.0021 (6)	0.0067 (6)	0.0021 (6)
N1	0.0243 (11)	0.0234 (10)	0.0130 (9)	0.0027 (8)	0.0053 (8)	0.0015 (7)
C1	0.0316 (14)	0.0252 (13)	0.0236 (12)	0.0121 (10)	0.0046 (10)	0.0056 (10)
Fe2	0.02082 (17)	0.01520 (16)	0.01655 (17)	0.00175 (12)	0.00737 (13)	0.00109 (12)
Cl2	0.0319 (3)	0.0281 (3)	0.0275 (3)	0.0120 (2)	0.0134 (3)	0.0028 (2)
O2	0.0192 (8)	0.0229 (8)	0.0328 (9)	0.0043 (6)	−0.0009 (7)	−0.0019 (7)
N2	0.0383 (13)	0.0251 (11)	0.0270 (11)	−0.0068 (9)	0.0104 (9)	−0.0065 (9)
C2	0.072 (2)	0.0264 (14)	0.0435 (17)	0.0025 (13)	0.0369 (16)	−0.0013 (12)
Cl3	0.0246 (3)	0.0183 (3)	0.0254 (3)	−0.0026 (2)	0.0088 (2)	−0.0022 (2)
O3	0.0274 (10)	0.0317 (10)	0.0394 (10)	−0.0080 (7)	0.0139 (8)	−0.0008 (8)
Cl4	0.0343 (3)	0.0283 (3)	0.0175 (3)	0.0041 (2)	0.0098 (2)	0.0008 (2)
O4	0.132 (2)	0.0412 (13)	0.0303 (11)	−0.0064 (13)	0.0280 (13)	0.0054 (10)
O5	0.0399 (12)	0.0445 (12)	0.0723 (15)	0.0128 (9)	0.0172 (11)	−0.0088 (11)
N11	0.0160 (9)	0.0117 (9)	0.0203 (9)	−0.0003 (6)	0.0046 (7)	−0.0003 (7)
C11	0.0140 (10)	0.0146 (11)	0.0176 (10)	−0.0011 (8)	0.0055 (8)	−0.0002 (8)
C12	0.0167 (10)	0.0095 (9)	0.0228 (11)	−0.0021 (8)	0.0041 (9)	−0.0010 (8)
C13	0.0283 (12)	0.0125 (10)	0.0219 (11)	−0.0007 (8)	0.0097 (9)	−0.0039 (9)
C14	0.0285 (12)	0.0131 (10)	0.0197 (11)	−0.0022 (9)	0.0081 (9)	0.0017 (9)
N21	0.0145 (9)	0.0137 (9)	0.0223 (9)	−0.0001 (7)	0.0058 (7)	−0.0005 (7)
C21	0.0165 (11)	0.0118 (10)	0.0169 (10)	0.0000 (8)	0.0053 (8)	−0.0001 (8)
C22	0.0109 (9)	0.0154 (10)	0.0186 (10)	−0.0018 (7)	0.0054 (8)	−0.0041 (8)
C23	0.0147 (10)	0.0149 (10)	0.0178 (10)	0.0018 (8)	0.0018 (8)	−0.0010 (8)
C24	0.0157 (10)	0.0151 (10)	0.0198 (11)	−0.0022 (8)	0.0071 (9)	−0.0003 (8)

Fe1—O1	2.0884 (15)	N2—C2	1.455 (3)
Fe1—O1i	2.0884 (15)	C2—H2A	0.9800
Fe1—N21i	2.1309 (17)	C2—H2B	0.9800
Fe1—N21	2.1309 (17)	C2—H2C	0.9800
Fe1—N11	2.1649 (17)	N11—C11	1.144 (3)
Fe1—N11i	2.1649 (17)	C11—C12	1.446 (3)
Cl1—Fe2	2.2070 (6)	C12—C13	1.390 (3)
O1—H1	0.872 (17)	C12—C14	1.393 (3)
O1—H2	0.840 (16)	C13—C14ii	1.382 (3)
N1—O3	1.218 (2)	C13—H13	0.9500
N1—O2	1.222 (2)	C14—C13ii	1.382 (3)
N1—C1	1.483 (3)	C14—H14	0.9500
C1—H1A	0.9800	N21—C21	1.141 (3)
C1—H1B	0.9800	C21—C22	1.444 (3)
C1—H1C	0.9800	C22—C24	1.388 (3)
Fe2—Cl2	2.1811 (6)	C22—C23	1.395 (3)
Fe2—Cl3	2.1968 (6)	C23—C24iii	1.380 (3)
Fe2—Cl4	2.1996 (6)	C23—H23	0.9500
N2—O5	1.217 (3)	C24—C23iii	1.380 (3)
N2—O4	1.221 (3)	C24—H24	0.9500
O1—Fe1—O1i	180.0	Cl4—Fe2—Cl1	109.08 (2)
O1—Fe1—N21i	89.02 (6)	O5—N2—O4	124.7 (2)
O1i—Fe1—N21i	90.98 (6)	O5—N2—C2	118.9 (2)
O1—Fe1—N21	90.98 (6)	O4—N2—C2	116.4 (2)
O1i—Fe1—N21	89.02 (6)	N2—C2—H2A	109.5
N21i—Fe1—N21	180.00 (9)	N2—C2—H2B	109.5
O1—Fe1—N11	88.13 (6)	H2A—C2—H2B	109.5
O1i—Fe1—N11	91.87 (6)	N2—C2—H2C	109.5
N21i—Fe1—N11	89.53 (6)	H2A—C2—H2C	109.5
N21—Fe1—N11	90.47 (6)	H2B—C2—H2C	109.5
O1—Fe1—N11i	91.87 (6)	C11—N11—Fe1	166.95 (17)
O1i—Fe1—N11i	88.13 (6)	N11—C11—C12	177.9 (2)
N21i—Fe1—N11i	90.47 (6)	C13—C12—C14	121.59 (19)
N21—Fe1—N11i	89.53 (6)	C13—C12—C11	118.55 (19)
N11—Fe1—N11i	180.0	C14—C12—C11	119.85 (19)
Fe1—O1—H1	118.0 (19)	C14ii—C13—C12	119.4 (2)
Fe1—O1—H2	120.9 (19)	C14ii—C13—H13	120.3
H1—O1—H2	111 (2)	C12—C13—H13	120.3
O3—N1—O2	123.50 (19)	C13ii—C14—C12	119.0 (2)
O3—N1—C1	118.69 (19)	C13ii—C14—H14	120.5
O2—N1—C1	117.81 (18)	C12—C14—H14	120.5
N1—C1—H1A	109.5	C21—N21—Fe1	173.63 (17)
N1—C1—H1B	109.5	N21—C21—C22	179.0 (2)
H1A—C1—H1B	109.5	C24—C22—C23	122.29 (19)
N1—C1—H1C	109.5	C24—C22—C21	119.98 (19)
H1A—C1—H1C	109.5	C23—C22—C21	117.71 (18)
H1B—C1—H1C	109.5	C24iii—C23—C22	118.85 (19)
Cl2—Fe2—Cl3	113.33 (3)	C24iii—C23—H23	120.6
Cl2—Fe2—Cl4	110.02 (2)	C22—C23—H23	120.6
Cl3—Fe2—Cl4	108.69 (2)	C23iii—C24—C22	118.86 (19)
Cl2—Fe2—Cl1	107.56 (2)	C23iii—C24—H24	120.6
Cl3—Fe2—Cl1	108.07 (2)	C22—C24—H24	120.6
O1—Fe1—N11—C11	−10.8 (7)	O1—Fe1—N21—C21	−13.1 (15)
O1i—Fe1—N11—C11	169.2 (7)	O1i—Fe1—N21—C21	166.9 (15)
N21i—Fe1—N11—C11	78.2 (7)	N21i—Fe1—N21—C21	141 (2)
N21—Fe1—N11—C11	−101.8 (7)	N11—Fe1—N21—C21	75.1 (15)
N11i—Fe1—N11—C11	−43 (18)	N11i—Fe1—N21—C21	−104.9 (15)
Fe1—N11—C11—C12	25 (7)	Fe1—N21—C21—C22	−35 (15)
N11—C11—C12—C13	2(6)	N21—C21—C22—C24	−168 (13)
N11—C11—C12—C14	−177 (100)	N21—C21—C22—C23	14 (14)
C14—C12—C13—C14ii	−0.6 (4)	C24—C22—C23—C24iii	0.6 (3)
C11—C12—C13—C14ii	−179.35 (19)	C21—C22—C23—C24iii	178.61 (18)
C13—C12—C14—C13ii	0.6 (4)	C23—C22—C24—C23iii	−0.6 (3)
C11—C12—C14—C13ii	179.33 (19)	C21—C22—C24—C23iii	−178.57 (18)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2	0.87 (2)	1.99 (2)	2.804 (2)	155 (3)
O1—H1···O4	0.87 (2)	2.57 (3)	3.074 (3)	118 (2)
O1—H2···Cl1	0.84 (2)	2.43 (2)	3.2731 (16)	177 (3)

Table 1

Selected bond lengths (Å)

Fe1—O1	2.0884 (15)
Fe1—N21	2.1309 (17)
Fe1—N11	2.1649 (17)
Cl1—Fe2	2.2070 (6)
Fe2—Cl2	2.1811 (6)
Fe2—Cl3	2.1968 (6)
Fe2—Cl4	2.1996 (6)

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O2	0.87 (2)	1.99 (2)	2.804 (2)	155 (3)
O1—H1⋯O4	0.87 (2)	2.57 (3)	3.074 (3)	118 (2)
O1—H2⋯Cl1	0.84 (2)	2.43 (2)	3.2731 (16)	177 (3)