1,1',2,2',3,3',4,4'-Octa-methyl-ferro-cenium 2,5-dibromo-4-hy-droxy-3,6-dioxocyclo-hexa-1,4-dien-1-olate.

In the title salt, octa-methyl-ferrocenium bromanilate, [Fe(C(9)H(13))(2)](C(6)HBr(2)O(4)), the Fe atom and the bromanilate anion lie on a mirror plane. The octa-methyl-ferrocenium cation adopts an eclipsed conformation. An intra-molecular O-H⋯O hydrogen bond is present in the bromanilate anion. In the crystal, the cations and anions are stacked alternately, forming a one-dimensional columnar structure along [010].

Related literature

For general background to ferrocene-based charge-transfer complexes, see: Miller et al. (1994 ▶); Mochida et al. (2007 ▶). For organometallic supra­molecular compounds, see: Braga et al. (2001 ▶); Horikoshi et al. (2004 ▶). For phase transitions in octa- and deca­methyl­ferrocene complexes, see: Mochida et al. (2011 ▶); Mochida & Yoza (2010 ▶). For related structures containing bromanilic acid, see: Mochida (2010 ▶); Thomas et al. (2009 ▶); Tomura & Yamashita (2000 ▶); Zaman et al. (2001a ▶,b ▶, 2004 ▶). For the structure of the octa­methyl­ferrocenium cation, see: Miller et al. (1989 ▶).

Experimental

Crystal data

[Fe(C9H13)2](C6HBr2O4)

M = 595.13

Orthorhombic,

a = 14.7106 (15) Å

b = 10.4938 (11) Å

c = 14.9461 (15) Å

V = 2307.2 (4) Å3

Z = 4

Mo Kα radiation

μ = 4.15 mm−1

T = 173 K

0.38 × 0.08 × 0.08 mm

Data collection

Bruker APEX CCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.306, T max = 0.746

14287 measured reflections

2804 independent reflections

1699 reflections with I > 2σ(I)

R int = 0.087

Refinement

R[F 2 > 2σ(F 2)] = 0.041

wR(F 2) = 0.084

S = 1.00

2804 reflections

167 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.56 e Å−3

Δρmin = −0.39 e Å−3

Data collection: SMART (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811025499/hy2444sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811025499/hy2444Isup2.hkl

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

[Fe(C9H13)2](C6HBr2O4)	F(000) = 1196
Mr = 595.13	Dx = 1.713 Mg m−3
Orthorhombic, Pnma	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2n	Cell parameters from 1436 reflections
a = 14.7106 (15) Å	θ = 2.7–24.0°
b = 10.4938 (11) Å	µ = 4.15 mm−1
c = 14.9461 (15) Å	T = 173 K
V = 2307.2 (4) Å3	Needle, violet
Z = 4	0.38 × 0.08 × 0.08 mm

Bruker APEX CCD diffractometer	2804 independent reflections
Radiation source: fine-focus sealed tube	1699 reflections with I > 2σ(I)
graphite	Rint = 0.087
φ and ω scans	θmax = 27.5°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −19→18
Tmin = 0.306, Tmax = 0.746	k = −13→13
14287 measured reflections	l = −19→15

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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.084	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ2(Fo2) + (0.032P)2] where P = (Fo2 + 2Fc2)/3
2804 reflections	(Δ/σ)max = 0.001
167 parameters	Δρmax = 0.56 e Å−3
0 restraints	Δρmin = −0.39 e Å−3

	x	y	z	Uiso*/Ueq
Br1	0.62817 (4)	0.2500	0.60939 (4)	0.04543 (19)
Br2	0.89861 (5)	0.2500	0.25105 (4)	0.0542 (2)
Fe1	0.24413 (4)	0.2500	0.60312 (4)	0.02121 (17)
C2	0.2127 (2)	0.0859 (3)	0.5266 (2)	0.0264 (8)
C1	0.1616 (2)	0.0870 (3)	0.6081 (2)	0.0266 (8)
C5	0.2252 (2)	0.0881 (3)	0.6802 (2)	0.0298 (8)
H5	0.2094	0.0869	0.7453	0.036*
C3	0.3072 (2)	0.0853 (3)	0.5494 (2)	0.0256 (8)
C4	0.3147 (2)	0.0867 (3)	0.6443 (2)	0.0285 (8)
C8	0.3846 (2)	0.0811 (4)	0.4848 (2)	0.0410 (10)
H8A	0.4334	0.1372	0.5058	0.062*
H8B	0.3637	0.1097	0.4259	0.062*
H8C	0.4074	−0.0064	0.4803	0.062*
C7	0.1734 (3)	0.0829 (3)	0.4341 (2)	0.0389 (10)
H7A	0.1633	−0.0057	0.4160	0.058*
H7B	0.2157	0.1236	0.3923	0.058*
H7C	0.1154	0.1288	0.4335	0.058*
C9	0.4003 (2)	0.0809 (4)	0.6978 (3)	0.0420 (10)
H9A	0.4187	−0.0083	0.7052	0.063*
H9B	0.3899	0.1192	0.7567	0.063*
H9C	0.4484	0.1278	0.6666	0.063*
C6	0.0605 (2)	0.0820 (3)	0.6176 (2)	0.0415 (10)
H6A	0.0323	0.1336	0.5705	0.062*
H6B	0.0430	0.1155	0.6763	0.062*
H6C	0.0399	−0.0065	0.6121	0.062*
C12	0.7307 (4)	0.2500	0.3449 (3)	0.0328 (13)
C10	0.7062 (4)	0.2500	0.5083 (3)	0.0324 (13)
C11	0.6678 (4)	0.2500	0.4242 (3)	0.0357 (13)
C15	0.8004 (4)	0.2500	0.5240 (4)	0.0332 (13)
C14	0.8635 (4)	0.2500	0.4391 (4)	0.0365 (13)
C13	0.8211 (4)	0.2500	0.3525 (3)	0.0366 (13)
O1	0.5845 (3)	0.2500	0.4037 (2)	0.0482 (10)
O4	0.8385 (3)	0.2500	0.5975 (2)	0.0473 (11)
O3	0.9454 (3)	0.2500	0.4508 (3)	0.0532 (11)
O2	0.6862 (3)	0.2500	0.2669 (2)	0.0457 (11)
H1	0.625 (5)	0.2500	0.297 (6)	0.13 (3)*

	U11	U22	U33	U12	U13	U23
Br1	0.0608 (5)	0.0432 (4)	0.0323 (3)	0.000	0.0033 (3)	0.000
Br2	0.0666 (5)	0.0589 (4)	0.0373 (4)	0.000	0.0083 (3)	0.000
Fe1	0.0223 (4)	0.0178 (3)	0.0235 (4)	0.000	−0.0008 (3)	0.000
C2	0.032 (2)	0.0177 (17)	0.030 (2)	−0.0013 (16)	−0.0022 (16)	−0.0020 (15)
C1	0.0208 (18)	0.0214 (18)	0.038 (2)	−0.0037 (14)	0.0036 (16)	0.0001 (17)
C5	0.040 (2)	0.0222 (19)	0.027 (2)	−0.0008 (16)	0.0022 (17)	0.0046 (15)
C3	0.027 (2)	0.0155 (17)	0.034 (2)	0.0029 (15)	0.0043 (15)	−0.0034 (16)
C4	0.031 (2)	0.0206 (19)	0.034 (2)	0.0040 (16)	−0.0047 (16)	−0.0004 (16)
C8	0.038 (3)	0.035 (2)	0.050 (3)	0.0073 (18)	0.0156 (19)	−0.003 (2)
C7	0.055 (3)	0.029 (2)	0.032 (2)	−0.0029 (19)	−0.0125 (18)	−0.0037 (18)
C9	0.040 (2)	0.035 (2)	0.051 (3)	−0.0002 (19)	−0.0165 (19)	0.005 (2)
C6	0.028 (2)	0.036 (2)	0.060 (3)	−0.0081 (18)	0.0086 (19)	0.003 (2)
C12	0.049 (4)	0.026 (3)	0.024 (3)	0.000	−0.010 (3)	0.000
C10	0.049 (4)	0.028 (3)	0.020 (3)	0.000	−0.001 (2)	0.000
C11	0.050 (4)	0.027 (3)	0.030 (3)	0.000	−0.006 (3)	0.000
C15	0.055 (4)	0.014 (3)	0.031 (3)	0.000	−0.006 (3)	0.000
C14	0.041 (4)	0.029 (3)	0.040 (3)	0.000	−0.004 (3)	0.000
C13	0.051 (4)	0.027 (3)	0.032 (3)	0.000	0.001 (3)	0.000
O1	0.046 (3)	0.055 (3)	0.043 (2)	0.000	−0.011 (2)	0.000
O4	0.064 (3)	0.045 (3)	0.033 (2)	0.000	−0.016 (2)	0.000
O3	0.048 (3)	0.060 (3)	0.051 (3)	0.000	−0.006 (2)	0.000
O2	0.060 (3)	0.053 (3)	0.024 (2)	0.000	−0.014 (2)	0.000

Br1—C10	1.898 (5)	C8—H8B	0.9800
Br2—C13	1.897 (5)	C8—H8C	0.9800
Fe1—C5i	2.072 (3)	C7—H7A	0.9800
Fe1—C5	2.072 (3)	C7—H7B	0.9800
Fe1—C4i	2.096 (3)	C7—H7C	0.9800
Fe1—C4	2.096 (3)	C9—H9A	0.9800
Fe1—C1i	2.099 (3)	C9—H9B	0.9800
Fe1—C1	2.099 (3)	C9—H9C	0.9800
Fe1—C2i	2.119 (3)	C6—H6A	0.9800
Fe1—C2	2.119 (3)	C6—H6B	0.9800
Fe1—C3i	2.120 (3)	C6—H6C	0.9800
Fe1—C3	2.120 (3)	C12—C13	1.334 (7)
C2—C1	1.432 (4)	C12—O2	1.337 (6)
C2—C3	1.433 (5)	C12—C11	1.505 (7)
C2—C7	1.499 (4)	C10—C11	1.378 (7)
C1—C5	1.427 (5)	C10—C15	1.405 (7)
C1—C6	1.495 (4)	C11—O1	1.262 (6)
C5—C4	1.422 (5)	C15—O4	1.234 (6)
C5—H5	1.0000	C15—C14	1.571 (7)
C3—C4	1.421 (5)	C14—O3	1.218 (6)
C3—C8	1.493 (4)	C14—C13	1.437 (7)
C4—C9	1.493 (4)	O2—H1	1.01 (8)
C8—H8A	0.9800
C5i—Fe1—C5	110.2 (2)	C1—C5—Fe1	71.03 (19)
C5i—Fe1—C4i	39.90 (13)	C4—C5—H5	125.6
C5—Fe1—C4i	125.03 (14)	C1—C5—H5	125.6
C5i—Fe1—C4	125.03 (14)	Fe1—C5—H5	125.6
C5—Fe1—C4	39.90 (13)	C4—C3—C2	108.2 (3)
C4i—Fe1—C4	109.68 (19)	C4—C3—C8	125.9 (3)
C5i—Fe1—C1i	40.01 (13)	C2—C3—C8	125.9 (3)
C5—Fe1—C1i	124.82 (13)	C4—C3—Fe1	69.39 (19)
C4i—Fe1—C1i	67.03 (14)	C2—C3—Fe1	70.21 (18)
C4—Fe1—C1i	160.47 (14)	C8—C3—Fe1	127.1 (2)
C5i—Fe1—C1	124.82 (13)	C3—C4—C5	107.8 (3)
C5—Fe1—C1	40.00 (13)	C3—C4—C9	126.8 (3)
C4i—Fe1—C1	160.47 (14)	C5—C4—C9	125.4 (3)
C4—Fe1—C1	67.03 (14)	C3—C4—Fe1	71.20 (19)
C1i—Fe1—C1	109.18 (18)	C5—C4—Fe1	69.14 (19)
C5i—Fe1—C2i	66.68 (13)	C9—C4—Fe1	127.5 (2)
C5—Fe1—C2i	159.65 (14)	C3—C8—H8A	109.5
C4i—Fe1—C2i	66.55 (13)	C3—C8—H8B	109.5
C4—Fe1—C2i	158.63 (14)	H8A—C8—H8B	109.5
C1i—Fe1—C2i	39.67 (12)	C3—C8—H8C	109.5
C1—Fe1—C2i	123.73 (13)	H8A—C8—H8C	109.5
C5i—Fe1—C2	159.65 (14)	H8B—C8—H8C	109.5
C5—Fe1—C2	66.68 (13)	C2—C7—H7A	109.5
C4i—Fe1—C2	158.63 (14)	C2—C7—H7B	109.5
C4—Fe1—C2	66.55 (13)	H7A—C7—H7B	109.5
C1i—Fe1—C2	123.73 (13)	C2—C7—H7C	109.5
C1—Fe1—C2	39.68 (12)	H7A—C7—H7C	109.5
C2i—Fe1—C2	108.75 (18)	H7B—C7—H7C	109.5
C5i—Fe1—C3i	66.45 (14)	C4—C9—H9A	109.5
C5—Fe1—C3i	159.74 (13)	C4—C9—H9B	109.5
C4i—Fe1—C3i	39.41 (13)	H9A—C9—H9B	109.5
C4—Fe1—C3i	124.10 (13)	C4—C9—H9C	109.5
C1i—Fe1—C3i	66.56 (13)	H9A—C9—H9C	109.5
C1—Fe1—C3i	158.65 (14)	H9B—C9—H9C	109.5
C2i—Fe1—C3i	39.52 (12)	C1—C6—H6A	109.5
C2—Fe1—C3i	123.65 (14)	C1—C6—H6B	109.5
C5i—Fe1—C3	159.74 (13)	H6A—C6—H6B	109.5
C5—Fe1—C3	66.45 (14)	C1—C6—H6C	109.5
C4i—Fe1—C3	124.10 (13)	H6A—C6—H6C	109.5
C4—Fe1—C3	39.41 (13)	H6B—C6—H6C	109.5
C1i—Fe1—C3	158.65 (14)	C13—C12—O2	124.2 (5)
C1—Fe1—C3	66.56 (13)	C13—C12—C11	123.1 (5)
C2i—Fe1—C3	123.66 (14)	O2—C12—C11	112.7 (5)
C2—Fe1—C3	39.52 (12)	C11—C10—C15	123.9 (5)
C3i—Fe1—C3	109.26 (18)	C11—C10—Br1	118.5 (4)
C1—C2—C3	107.8 (3)	C15—C10—Br1	117.6 (4)
C1—C2—C7	125.7 (3)	O1—C11—C10	128.3 (5)
C3—C2—C7	126.5 (3)	O1—C11—C12	114.0 (5)
C1—C2—Fe1	69.42 (18)	C10—C11—C12	117.8 (5)
C3—C2—Fe1	70.27 (18)	O4—C15—C10	126.6 (5)
C7—C2—Fe1	126.8 (2)	O4—C15—C14	116.8 (5)
C5—C1—C2	107.4 (3)	C10—C15—C14	116.6 (4)
C5—C1—C6	125.5 (3)	O3—C14—C13	123.9 (5)
C2—C1—C6	127.0 (3)	O3—C14—C15	118.0 (5)
C5—C1—Fe1	68.97 (18)	C13—C14—C15	118.1 (5)
C2—C1—Fe1	70.90 (18)	C12—C13—C14	120.6 (5)
C6—C1—Fe1	127.4 (2)	C12—C13—Br2	122.1 (4)
C4—C5—C1	108.8 (3)	C14—C13—Br2	117.4 (4)
C4—C5—Fe1	70.95 (19)	C12—O2—H1	92 (5)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H1···O1	1.01 (8)	1.70 (9)	2.534 (5)	137 (7)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H1⋯O1	1.01 (8)	1.70 (9)	2.534 (5)	137 (7)