Oxymatrinium tetra-chloridoferrate(III).

The asymmetric unit of the title compound, (C(15)H(25)N(2)O(2))[FeCl(4)], contains a tetra-chloridoferrate(III) anion and a oxymatrinium cation [oxymatrine is (4R,7aS,13aR,13bR,13cS)-dodeca-hydro-1H,5H,10H-dipyrido[2,1-f:3',2',1'-ij][1,6]naphthyridin-10-one 4-oxide]. The conformation of oxymatrine is similar to that of matrine with one ring having a half-chair conformation, while the others have chair conformations. Chiral chains of cations along the c axis are formed by O-H⋯O hydrogen bonds.

Related literature

For related structures, see: Chen et al. (2011 ▶); Jin et al. (2005 ▶, 2009 ▶); Zhang et al. (2003 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For the biological activity of oxymatrine, see: Song et al. (2006 ▶); Wang et al. (2005 ▶); Xiang et al. (2002 ▶); Zhang et al. (2001 ▶, 2009 ▶); Sun et al. (2008 ▶). Oxymatrine is an alkaloid extracted from the Chinese herb Sophora alopecuraides L, see: Lai et al. (2003 ▶). For the preparation and studies of related salts, see: Mao et al. (2008 ▶); Li (2006 ▶).

Experimental

Crystal data

(C15H25N2O2)[FeCl4]

M = 463.02

Orthorhombic,

a = 7.7919 (4) Å

b = 11.9518 (6) Å

c = 21.1315 (10) Å

V = 1967.92 (17) Å3

Z = 4

Mo Kα radiation

μ = 1.32 mm−1

T = 173 K

0.45 × 0.26 × 0.25 mm

Data collection

Bruker SMART 1000 CCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 2004 ▶) T min = 0.588, T max = 0.734

9963 measured reflections

4267 independent reflections

3812 reflections with I > 2σ(I)

R int = 0.020

Refinement

R[F 2 > 2σ(F 2)] = 0.026

wR(F 2) = 0.061

S = 1.03

4267 reflections

218 parameters

H-atom parameters constrained

Δρmax = 0.31 e Å−3

Δρmin = −0.28 e Å−3

Absolute structure: Flack (1983 ▶), 1787 Friedel pairs

Flack parameter: 0.006 (14)

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT-Plus (Bruker, 2003 ▶); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXTL (Sheldrick, 2008) ▶; program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812000281/mw2043sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812000281/mw2043Isup2.hkl

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

(C15H25N2O2)[FeCl4]	F(000) = 956
Mr = 463.02	Dx = 1.563 Mg m−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 6437 reflections
a = 7.7919 (4) Å	θ = 2.6–27.1°
b = 11.9518 (6) Å	µ = 1.32 mm−1
c = 21.1315 (10) Å	T = 173 K
V = 1967.92 (17) Å3	Prism, yellow
Z = 4	0.45 × 0.26 × 0.25 mm

Bruker SMART 1000 CCD diffractometer	4267 independent reflections
Radiation source: fine-focus sealed tube	3812 reflections with I > 2σ(I)
graphite	Rint = 0.020
ω scans	θmax = 27.1°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	h = −9→9
Tmin = 0.588, Tmax = 0.734	k = −7→15
9963 measured reflections	l = −23→27

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.026	H-atom parameters constrained
wR(F2) = 0.061	w = 1/[σ2(Fo2) + (0.0334P)2] where P = (Fo2 + 2Fc2)/3
S = 1.03	(Δ/σ)max = 0.001
4267 reflections	Δρmax = 0.31 e Å−3
218 parameters	Δρmin = −0.28 e Å−3
0 restraints	Absolute structure: Flack (1983), 1787 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.006 (14)

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	0.48378 (4)	0.01347 (2)	0.169548 (12)	0.02484 (8)
Cl1	0.48652 (8)	−0.12257 (4)	0.23956 (2)	0.03028 (12)
Cl2	0.72310 (9)	0.10944 (6)	0.17647 (3)	0.04546 (17)
Cl3	0.25496 (9)	0.11672 (6)	0.18583 (3)	0.04688 (18)
Cl4	0.46744 (8)	−0.05810 (5)	0.07447 (2)	0.03739 (14)
N1	1.1039 (2)	0.60782 (15)	0.13234 (8)	0.0221 (4)
C2	1.1716 (3)	0.72196 (19)	0.14985 (10)	0.0276 (5)
H2A	1.2898	0.7305	0.1334	0.033*
H2B	1.1759	0.7290	0.1965	0.033*
C3	1.0591 (3)	0.81319 (19)	0.12295 (11)	0.0298 (5)
H3A	1.0615	0.8094	0.0762	0.036*
H3B	1.1048	0.8870	0.1358	0.036*
C4	0.8751 (3)	0.8018 (2)	0.14585 (11)	0.0325 (5)
H4A	0.8030	0.8576	0.1237	0.039*
H4B	0.8708	0.8189	0.1917	0.039*
C5	0.8001 (3)	0.68571 (19)	0.13492 (10)	0.0259 (5)
H5	0.6964	0.6806	0.1627	0.031*
C6	0.9204 (3)	0.59318 (19)	0.15665 (9)	0.0248 (5)
H6	0.9271	0.5996	0.2038	0.030*
C7	0.8473 (3)	0.47659 (19)	0.14298 (10)	0.0272 (5)
H7	0.7408	0.4703	0.1692	0.033*
C8	0.9697 (3)	0.38652 (19)	0.16806 (11)	0.0381 (5)
H8A	0.9718	0.3896	0.2149	0.046*
H8B	0.9267	0.3118	0.1555	0.046*
C9	1.1505 (3)	0.40203 (19)	0.14288 (12)	0.0366 (6)
H9A	1.2269	0.3446	0.1615	0.044*
H9B	1.1506	0.3921	0.0964	0.044*
C10	1.2176 (3)	0.51723 (19)	0.15907 (10)	0.0298 (5)
H10A	1.2239	0.5253	0.2056	0.036*
H10B	1.3351	0.5258	0.1419	0.036*
C11	0.7893 (3)	0.46034 (17)	0.07363 (9)	0.0235 (4)
H11	0.8923	0.4642	0.0455	0.028*
C12	0.7037 (3)	0.34673 (18)	0.06509 (11)	0.0328 (5)
H12A	0.7916	0.2870	0.0663	0.039*
H12B	0.6216	0.3335	0.1000	0.039*
C13	0.6095 (3)	0.3433 (2)	0.00198 (12)	0.0369 (6)
H13A	0.6897	0.3611	−0.0329	0.044*
H13B	0.5620	0.2675	−0.0054	0.044*
C14	0.4664 (3)	0.4280 (2)	0.00382 (12)	0.0402 (6)
H14A	0.4237	0.4395	−0.0398	0.048*
H14B	0.3706	0.3968	0.0291	0.048*
C15	0.5150 (3)	0.53988 (18)	0.03113 (9)	0.0267 (4)
N16	0.6714 (2)	0.55307 (14)	0.05703 (8)	0.0213 (4)
C17	0.7358 (3)	0.66798 (17)	0.06706 (10)	0.0232 (4)
H17A	0.6427	0.7220	0.0580	0.028*
H17B	0.8308	0.6829	0.0371	0.028*
O1	0.41292 (18)	0.62004 (14)	0.02719 (7)	0.0319 (4)
O2	1.09826 (17)	0.59837 (13)	0.06528 (6)	0.0218 (3)
H2	1.1963	0.6109	0.0503	0.033*

	U11	U22	U33	U12	U13	U23
Fe1	0.03331 (16)	0.02190 (14)	0.01931 (13)	−0.00039 (14)	0.00051 (12)	−0.00073 (11)
Cl1	0.0359 (3)	0.0272 (2)	0.0277 (2)	−0.0024 (3)	−0.0005 (2)	0.00547 (19)
Cl2	0.0571 (4)	0.0398 (4)	0.0395 (3)	−0.0238 (3)	−0.0061 (3)	0.0081 (3)
Cl3	0.0607 (4)	0.0372 (4)	0.0427 (4)	0.0213 (3)	0.0135 (3)	0.0028 (3)
Cl4	0.0444 (3)	0.0461 (3)	0.0216 (2)	0.0090 (3)	−0.0043 (2)	−0.0082 (2)
N1	0.0239 (8)	0.0255 (9)	0.0169 (8)	−0.0008 (8)	−0.0052 (7)	−0.0010 (8)
C2	0.0260 (11)	0.0290 (12)	0.0277 (11)	−0.0047 (9)	−0.0072 (9)	−0.0038 (10)
C3	0.0318 (12)	0.0205 (10)	0.0372 (12)	−0.0016 (9)	−0.0087 (9)	−0.0025 (9)
C4	0.0284 (11)	0.0307 (13)	0.0383 (13)	0.0028 (10)	−0.0043 (10)	−0.0100 (11)
C5	0.0211 (10)	0.0325 (13)	0.0240 (11)	0.0007 (9)	0.0035 (8)	−0.0054 (9)
C6	0.0249 (10)	0.0335 (12)	0.0160 (10)	−0.0037 (9)	0.0030 (8)	−0.0001 (9)
C7	0.0281 (10)	0.0297 (12)	0.0237 (10)	−0.0040 (10)	0.0018 (8)	0.0046 (10)
C8	0.0486 (14)	0.0297 (11)	0.0359 (12)	−0.0076 (11)	−0.0129 (12)	0.0132 (10)
C9	0.0415 (13)	0.0247 (12)	0.0436 (14)	0.0044 (10)	−0.0142 (11)	0.0045 (11)
C10	0.0322 (11)	0.0299 (12)	0.0272 (11)	0.0048 (10)	−0.0105 (9)	0.0030 (10)
C11	0.0203 (9)	0.0239 (11)	0.0265 (11)	−0.0011 (8)	0.0002 (8)	0.0028 (9)
C12	0.0337 (12)	0.0228 (11)	0.0419 (13)	−0.0032 (10)	−0.0013 (10)	0.0007 (10)
C13	0.0362 (13)	0.0304 (13)	0.0441 (14)	−0.0097 (11)	0.0005 (11)	−0.0084 (11)
C14	0.0318 (13)	0.0401 (13)	0.0487 (14)	−0.0093 (12)	−0.0080 (11)	−0.0059 (11)
C15	0.0210 (10)	0.0336 (11)	0.0257 (10)	−0.0028 (10)	0.0029 (9)	0.0030 (8)
N16	0.0190 (8)	0.0225 (9)	0.0226 (9)	−0.0022 (7)	0.0014 (6)	0.0005 (7)
C17	0.0204 (10)	0.0214 (10)	0.0278 (10)	0.0004 (8)	−0.0010 (9)	−0.0013 (9)
O1	0.0194 (7)	0.0359 (9)	0.0404 (9)	−0.0004 (7)	−0.0015 (6)	0.0040 (8)
O2	0.0190 (7)	0.0307 (8)	0.0157 (6)	−0.0011 (6)	0.0001 (5)	−0.0008 (6)

Fe1—Cl4	2.1874 (6)	C8—H8A	0.9900
Fe1—Cl2	2.1942 (7)	C8—H8B	0.9900
Fe1—Cl3	2.1954 (7)	C9—C10	1.512 (3)
Fe1—Cl1	2.1984 (5)	C9—H9A	0.9900
N1—O2	1.422 (2)	C9—H9B	0.9900
N1—C2	1.509 (3)	C10—H10A	0.9900
N1—C10	1.509 (3)	C10—H10B	0.9900
N1—C6	1.529 (3)	C11—N16	1.482 (3)
C2—C3	1.510 (3)	C11—C12	1.523 (3)
C2—H2A	0.9900	C11—H11	1.0000
C2—H2B	0.9900	C12—C13	1.523 (3)
C3—C4	1.520 (3)	C12—H12A	0.9900
C3—H3A	0.9900	C12—H12B	0.9900
C3—H3B	0.9900	C13—C14	1.507 (3)
C4—C5	1.523 (3)	C13—H13A	0.9900
C4—H4A	0.9900	C13—H13B	0.9900
C4—H4B	0.9900	C14—C15	1.505 (3)
C5—C6	1.521 (3)	C14—H14A	0.9900
C5—C17	1.534 (3)	C14—H14B	0.9900
C5—H5	1.0000	C15—O1	1.248 (3)
C6—C7	1.533 (3)	C15—N16	1.345 (3)
C6—H6	1.0000	N16—C17	1.478 (3)
C7—C8	1.533 (3)	C17—H17A	0.9900
C7—C11	1.546 (3)	C17—H17B	0.9900
C7—H7	1.0000	O2—H2	0.8400
C8—C9	1.518 (4)
Cl4—Fe1—Cl2	108.37 (3)	C7—C8—H8B	109.3
Cl4—Fe1—Cl3	108.45 (3)	H8A—C8—H8B	107.9
Cl2—Fe1—Cl3	112.70 (3)	C10—C9—C8	110.7 (2)
Cl4—Fe1—Cl1	109.23 (2)	C10—C9—H9A	109.5
Cl2—Fe1—Cl1	109.48 (3)	C8—C9—H9A	109.5
Cl3—Fe1—Cl1	108.55 (3)	C10—C9—H9B	109.5
O2—N1—C2	109.09 (15)	C8—C9—H9B	109.5
O2—N1—C10	109.52 (15)	H9A—C9—H9B	108.1
C2—N1—C10	110.59 (15)	N1—C10—C9	111.44 (17)
O2—N1—C6	107.26 (14)	N1—C10—H10A	109.3
C2—N1—C6	110.36 (17)	C9—C10—H10A	109.3
C10—N1—C6	109.95 (16)	N1—C10—H10B	109.3
N1—C2—C3	110.95 (16)	C9—C10—H10B	109.3
N1—C2—H2A	109.4	H10A—C10—H10B	108.0
C3—C2—H2A	109.4	N16—C11—C12	111.55 (17)
N1—C2—H2B	109.4	N16—C11—C7	108.17 (16)
C3—C2—H2B	109.4	C12—C11—C7	110.63 (18)
H2A—C2—H2B	108.0	N16—C11—H11	108.8
C2—C3—C4	111.3 (2)	C12—C11—H11	108.8
C2—C3—H3A	109.4	C7—C11—H11	108.8
C4—C3—H3A	109.4	C13—C12—C11	109.82 (18)
C2—C3—H3B	109.4	C13—C12—H12A	109.7
C4—C3—H3B	109.4	C11—C12—H12A	109.7
H3A—C3—H3B	108.0	C13—C12—H12B	109.7
C3—C4—C5	113.30 (19)	C11—C12—H12B	109.7
C3—C4—H4A	108.9	H12A—C12—H12B	108.2
C5—C4—H4A	108.9	C14—C13—C12	108.42 (19)
C3—C4—H4B	108.9	C14—C13—H13A	110.0
C5—C4—H4B	108.9	C12—C13—H13A	110.0
H4A—C4—H4B	107.7	C14—C13—H13B	110.0
C6—C5—C4	112.33 (17)	C12—C13—H13B	110.0
C6—C5—C17	112.53 (17)	H13A—C13—H13B	108.4
C4—C5—C17	113.14 (19)	C15—C14—C13	114.89 (19)
C6—C5—H5	106.0	C15—C14—H14A	108.5
C4—C5—H5	106.0	C13—C14—H14A	108.5
C17—C5—H5	106.0	C15—C14—H14B	108.5
C5—C6—N1	113.07 (17)	C13—C14—H14B	108.5
C5—C6—C7	112.02 (17)	H14A—C14—H14B	107.5
N1—C6—C7	112.84 (18)	O1—C15—N16	120.96 (19)
C5—C6—H6	106.1	O1—C15—C14	119.75 (19)
N1—C6—H6	106.1	N16—C15—C14	119.22 (19)
C7—C6—H6	106.1	C15—N16—C17	118.37 (17)
C8—C7—C6	110.00 (17)	C15—N16—C11	124.78 (17)
C8—C7—C11	114.93 (19)	C17—N16—C11	116.77 (15)
C6—C7—C11	113.68 (17)	N16—C17—C5	111.93 (17)
C8—C7—H7	105.8	N16—C17—H17A	109.2
C6—C7—H7	105.8	C5—C17—H17A	109.2
C11—C7—H7	105.8	N16—C17—H17B	109.2
C9—C8—C7	111.76 (18)	C5—C17—H17B	109.2
C9—C8—H8A	109.3	H17A—C17—H17B	107.9
C7—C8—H8A	109.3	N1—O2—H2	109.5
C9—C8—H8B	109.3
O2—N1—C2—C3	59.1 (2)	C2—N1—C10—C9	179.15 (19)
C10—N1—C2—C3	179.66 (18)	C6—N1—C10—C9	57.0 (2)
C6—N1—C2—C3	−58.5 (2)	C8—C9—C10—N1	−58.5 (2)
N1—C2—C3—C4	57.9 (2)	C8—C7—C11—N16	179.53 (16)
C2—C3—C4—C5	−52.4 (3)	C6—C7—C11—N16	−52.5 (2)
C3—C4—C5—C6	47.8 (2)	C8—C7—C11—C12	57.1 (2)
C3—C4—C5—C17	−81.0 (2)	C6—C7—C11—C12	−174.92 (18)
C4—C5—C6—N1	−48.8 (2)	N16—C11—C12—C13	45.7 (2)
C17—C5—C6—N1	80.3 (2)	C7—C11—C12—C13	166.21 (18)
C4—C5—C6—C7	−177.63 (17)	C11—C12—C13—C14	−64.4 (2)
C17—C5—C6—C7	−48.6 (2)	C12—C13—C14—C15	44.5 (3)
O2—N1—C6—C5	−64.5 (2)	C13—C14—C15—O1	170.62 (19)
C2—N1—C6—C5	54.2 (2)	C13—C14—C15—N16	−6.5 (3)
C10—N1—C6—C5	176.50 (16)	O1—C15—N16—C17	−14.0 (3)
O2—N1—C6—C7	63.9 (2)	C14—C15—N16—C17	163.0 (2)
C2—N1—C6—C7	−177.34 (16)	O1—C15—N16—C11	169.15 (18)
C10—N1—C6—C7	−55.1 (2)	C14—C15—N16—C11	−13.8 (3)
C5—C6—C7—C8	−177.77 (18)	C12—C11—N16—C15	−6.8 (3)
N1—C6—C7—C8	53.3 (2)	C7—C11—N16—C15	−128.66 (19)
C5—C6—C7—C11	51.7 (2)	C12—C11—N16—C17	176.39 (17)
N1—C6—C7—C11	−77.2 (2)	C7—C11—N16—C17	54.5 (2)
C6—C7—C8—C9	−53.7 (2)	C15—N16—C17—C5	129.11 (19)
C11—C7—C8—C9	76.1 (2)	C11—N16—C17—C5	−53.8 (2)
C7—C8—C9—C10	56.7 (2)	C6—C5—C17—N16	48.7 (2)
O2—N1—C10—C9	−60.6 (2)	C4—C5—C17—N16	177.31 (17)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O1i	0.84	1.76	2.5935 (19)	171

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯O1i	0.84	1.76	2.5935 (19)	171

Symmetry code: (i) .