Di-chlorido-(5,10,15,20-tetra-phenyl-porphyrinato-κ(4) N)anti-mony(V) hexa-chlorido-anti-monate(V).

The asymmetric unit of the title compound, [Sb(C44H28N4)Cl2][SbCl6], consists of one half of an anti-mony(V) tetra-phenyl-porphyrin complex cation and one half of an hexa-chlorido-anti-monate(V) anion. In the complex cation, the Sb(V) atom lies on an inversion center and is octa-hedrally coordinated by four N atoms from a macrocyclic tetra-phenyl-porphyrinate ligand and two chloride ions. The complex cation has approximately a planar core with a maximum deviation of 0.018 (5) Å from the porphyrin mean plane. The average Sb-N distance is 2.062 (11) Å, while the Sb-Cl distance is 2.355 (1) Å. The Sb(V) atom of the anion is also located on an inversion center. The [SbCl6](-) octa-hedron exhibits rhombic distortion characterized by the Sb-Cl bond lengths [2.311 (3), 2.374 (2) and 2.393 (4) Å]. In the crystal, the cations and anions are linked C-H⋯ Cl hydrogen bonds, forming a layer parallel to (211).

Related literature

For general background and the synthesis, see: Liu et al. (1996 ▶). For related structures, see: Tsunami et al. (2008 ▶); Soury et al. (2012 ▶).

Experimental

Crystal data

[Sb(C44H28N4)Cl2][SbCl6]

M = 1139.80

Triclinic,

a = 10.2044 (4) Å

b = 11.1242 (4) Å

c = 11.3901 (4) Å

α = 70.685 (2)°

β = 83.398 (2)°

γ = 63.050 (3)°

V = 1086.73 (7) Å3

Z = 1

Mo Kα radiation

μ = 1.77 mm−1

T = 223 K

0.2 × 0.16 × 0.12 mm

Data collection

Bruker–Nonius KappaCCD diffractometer

Absorption correction: multi-scan (SORTAV; Blessing, 1995 ▶) T min = 0.723, T max = 0.773

19871 measured reflections

4749 independent reflections

4433 reflections with I > 2σ(I)

R int = 0.124

Refinement

R[F 2 > 2σ(F 2)] = 0.065

wR(F 2) = 0.173

S = 1.13

4749 reflections

266 parameters

H-atom parameters constrained

Δρmax = 2.55 e Å−3

Δρmin = −1.45 e Å−3

Data collection: COLLECT (Nonius, 2002 ▶); cell refinement: DENZO/SCALEPACK (Otwinowski & Minor, 1997 ▶); data reduction: DENZO/SCALEPACK; program(s) used to solve structure: SIR2004 (Burla et al., 2005 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S1600536814012653/is5356sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814012653/is5356Isup2.hkl

CCDC reference: 1006075

Additional supporting information: crystallographic information; 3D view; checkCIF report

[Sb(C44H28N4)Cl2][SbCl6]	Z = 1
Mr = 1139.80	F(000) = 558
Triclinic, P1	Dx = 1.742 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 10.2044 (4) Å	Cell parameters from 22201 reflections
b = 11.1242 (4) Å	θ = 1.9–30.1°
c = 11.3901 (4) Å	µ = 1.77 mm−1
α = 70.685 (2)°	T = 223 K
β = 83.398 (2)°	Prism, red
γ = 63.050 (3)°	0.2 × 0.16 × 0.12 mm
V = 1086.73 (7) Å3

Bruker–Nonius KappaCCD diffractometer	4749 independent reflections
Radiation source: fine-focus sealed tube	4433 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.124
φ & ω scans	θmax = 27.1°, θmin = 1.9°
Absorption correction: multi-scan (SORTAV; Blessing, 1995)	h = −13→13
Tmin = 0.723, Tmax = 0.773	k = −14→14
19871 measured reflections	l = −14→14

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)] = 0.065	H-atom parameters constrained
wR(F2) = 0.173	w = 1/[σ2(Fo2) + (0.0507P)2 + 7.0167P] where P = (Fo2 + 2Fc2)/3
S = 1.13	(Δ/σ)max < 0.001
4749 reflections	Δρmax = 2.55 e Å−3
266 parameters	Δρmin = −1.45 e Å−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.042 (4)

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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
Sb1	0.5000	0.0000	0.5000	0.0226 (2)
N1	0.4725 (5)	0.1913 (5)	0.3693 (4)	0.0259 (9)
N2	0.3841 (5)	0.1056 (5)	0.6238 (4)	0.0261 (9)
Cl1	0.28107 (16)	0.02557 (17)	0.42325 (15)	0.0368 (4)
C1	0.5256 (6)	0.2093 (6)	0.2499 (5)	0.0278 (11)
C2	0.4834 (7)	0.3574 (7)	0.1912 (6)	0.0358 (13)
H2	0.5047	0.3994	0.1098	0.043*
C3	0.4073 (7)	0.4267 (6)	0.2732 (5)	0.0317 (12)
H3	0.3669	0.5251	0.2589	0.038*
C4	0.3993 (6)	0.3234 (6)	0.3857 (5)	0.0270 (11)
C5	0.3287 (6)	0.3531 (5)	0.4932 (5)	0.0265 (11)
C6	0.3224 (6)	0.2509 (6)	0.6023 (5)	0.0273 (11)
C7	0.2497 (6)	0.2797 (6)	0.7118 (6)	0.0312 (12)
H7	0.1987	0.3696	0.7229	0.037*
C8	0.2678 (7)	0.1537 (7)	0.7969 (6)	0.0341 (13)
H8	0.2310	0.1416	0.8774	0.041*
C9	0.3518 (7)	0.0429 (6)	0.7440 (5)	0.0292 (11)
C10	0.3941 (6)	−0.1013 (6)	0.8037 (5)	0.0286 (11)
C11	0.2526 (6)	0.5050 (6)	0.4938 (5)	0.0287 (11)
C12	0.1165 (7)	0.5944 (6)	0.4362 (6)	0.0322 (12)
H12	0.0745	0.5636	0.3899	0.039*
C13	0.0393 (7)	0.7315 (7)	0.4458 (7)	0.0396 (14)
H13	−0.0549	0.7946	0.4082	0.047*
C14	0.1080 (8)	0.7667 (9)	0.5117 (6)	0.0467 (17)
H14	0.0566	0.8583	0.5192	0.056*
C15	0.2426 (8)	0.6865 (7)	0.5688 (8)	0.0437 (16)
H15	0.2841	0.7212	0.6114	0.052*
C16	0.3165 (8)	0.5489 (7)	0.5611 (7)	0.0427 (15)
H16	0.4093	0.4865	0.6015	0.051*
C17	0.3501 (6)	−0.1422 (6)	0.9394 (6)	0.0314 (12)
C18	0.2256 (10)	−0.1633 (11)	0.9654 (7)	0.059 (2)
H18	0.1746	−0.1651	0.9028	0.070*
C19	0.1769 (11)	−0.1821 (12)	1.0868 (8)	0.070 (3)
H19	0.0911	−0.1949	1.1067	0.084*
C20	0.2564 (10)	−0.1816 (8)	1.1781 (7)	0.054 (2)
H20	0.2231	−0.1922	1.2596	0.064*
C21	0.3802 (12)	−0.1662 (12)	1.1503 (7)	0.068 (3)
H21	0.4348	−0.1698	1.2136	0.081*
C22	0.4296 (10)	−0.1447 (11)	1.0289 (7)	0.054 (2)
H22	0.5156	−0.1323	1.0096	0.065*
Sb2	0.0000	0.5000	1.0000	0.0698 (4)
Cl2	−0.2299 (3)	0.5140 (4)	1.0805 (3)	0.0961 (11)
Cl3	0.0724 (3)	0.4837 (5)	1.1918 (3)	0.1218 (17)
Cl4	0.0999 (5)	0.2463 (5)	1.0692 (4)	0.1156 (13)

	U11	U22	U33	U12	U13	U23
Sb1	0.0246 (3)	0.0192 (3)	0.0262 (3)	−0.0102 (2)	0.00596 (18)	−0.01060 (19)
N1	0.031 (2)	0.020 (2)	0.029 (2)	−0.0120 (19)	0.0057 (18)	−0.0106 (17)
N2	0.030 (2)	0.021 (2)	0.028 (2)	−0.0111 (19)	0.0079 (18)	−0.0115 (17)
Cl1	0.0294 (7)	0.0389 (8)	0.0467 (8)	−0.0157 (6)	0.0003 (6)	−0.0178 (6)
C1	0.030 (3)	0.026 (3)	0.027 (2)	−0.012 (2)	0.007 (2)	−0.009 (2)
C2	0.044 (3)	0.031 (3)	0.032 (3)	−0.020 (3)	0.007 (2)	−0.007 (2)
C3	0.035 (3)	0.021 (3)	0.036 (3)	−0.011 (2)	0.001 (2)	−0.007 (2)
C4	0.027 (3)	0.023 (2)	0.031 (3)	−0.010 (2)	0.005 (2)	−0.010 (2)
C5	0.027 (3)	0.018 (2)	0.036 (3)	−0.008 (2)	0.003 (2)	−0.013 (2)
C6	0.029 (3)	0.023 (2)	0.033 (3)	−0.011 (2)	0.004 (2)	−0.013 (2)
C7	0.032 (3)	0.027 (3)	0.036 (3)	−0.010 (2)	0.011 (2)	−0.020 (2)
C8	0.039 (3)	0.034 (3)	0.033 (3)	−0.016 (3)	0.014 (2)	−0.020 (2)
C9	0.031 (3)	0.031 (3)	0.029 (3)	−0.014 (2)	0.011 (2)	−0.016 (2)
C10	0.031 (3)	0.026 (3)	0.031 (3)	−0.014 (2)	0.007 (2)	−0.012 (2)
C11	0.030 (3)	0.027 (3)	0.032 (3)	−0.014 (2)	0.008 (2)	−0.013 (2)
C12	0.028 (3)	0.025 (3)	0.042 (3)	−0.007 (2)	0.001 (2)	−0.014 (2)
C13	0.027 (3)	0.029 (3)	0.060 (4)	−0.005 (2)	0.002 (3)	−0.021 (3)
C14	0.034 (3)	0.064 (5)	0.043 (3)	−0.032 (3)	0.002 (3)	−0.003 (3)
C15	0.037 (3)	0.032 (3)	0.070 (5)	−0.012 (3)	−0.003 (3)	−0.030 (3)
C16	0.039 (3)	0.030 (3)	0.062 (4)	−0.010 (3)	−0.008 (3)	−0.021 (3)
C17	0.026 (3)	0.022 (2)	0.046 (3)	−0.008 (2)	0.003 (2)	−0.016 (2)
C18	0.061 (5)	0.096 (7)	0.046 (4)	−0.056 (5)	0.021 (4)	−0.029 (4)
C19	0.056 (5)	0.093 (7)	0.054 (5)	−0.040 (5)	0.025 (4)	−0.013 (5)
C20	0.072 (5)	0.045 (4)	0.035 (3)	−0.025 (4)	0.023 (3)	−0.012 (3)
C21	0.090 (7)	0.098 (8)	0.034 (4)	−0.055 (6)	0.015 (4)	−0.028 (4)
C22	0.055 (5)	0.088 (6)	0.038 (3)	−0.048 (5)	0.013 (3)	−0.023 (4)
Sb2	0.0346 (4)	0.1176 (8)	0.0807 (6)	−0.0245 (4)	0.0141 (4)	−0.0767 (6)
Cl2	0.0491 (13)	0.171 (3)	0.110 (2)	−0.0501 (17)	0.0332 (13)	−0.103 (2)
Cl3	0.0586 (15)	0.222 (5)	0.119 (2)	−0.039 (2)	0.0162 (15)	−0.133 (3)
Cl4	0.116 (3)	0.121 (3)	0.112 (3)	−0.034 (2)	0.039 (2)	−0.075 (2)

Sb1—N2i	2.054 (4)	C11—C16	1.379 (9)
Sb1—N2	2.054 (4)	C12—C13	1.400 (8)
Sb1—N1	2.070 (4)	C12—H12	0.9400
Sb1—N1i	2.070 (4)	C13—C14	1.332 (10)
Sb1—Cl1i	2.3547 (14)	C13—H13	0.9400
Sb1—Cl1	2.3547 (14)	C14—C15	1.347 (10)
N1—C4	1.380 (7)	C14—H14	0.9400
N1—C1	1.390 (7)	C15—C16	1.396 (9)
N2—C6	1.386 (7)	C15—H15	0.9400
N2—C9	1.394 (7)	C16—H16	0.9400
C1—C10i	1.402 (8)	C17—C22	1.359 (10)
C1—C2	1.429 (8)	C17—C18	1.377 (10)
C2—C3	1.356 (9)	C18—C19	1.395 (11)
C2—H2	0.9400	C18—H18	0.9400
C3—C4	1.434 (8)	C19—C20	1.394 (14)
C3—H3	0.9400	C19—H19	0.9400
C4—C5	1.406 (8)	C20—C21	1.339 (13)
C5—C6	1.398 (8)	C20—H20	0.9400
C5—C11	1.508 (7)	C21—C22	1.398 (10)
C6—C7	1.430 (8)	C21—H21	0.9400
C7—C8	1.359 (9)	C22—H22	0.9400
C7—H7	0.9400	Sb2—Cl3	2.311 (3)
C8—C9	1.426 (8)	Sb2—Cl3ii	2.311 (3)
C8—H8	0.9400	Sb2—Cl2ii	2.374 (2)
C9—C10	1.393 (8)	Sb2—Cl2	2.374 (2)
C10—C1i	1.402 (8)	Sb2—Cl4	2.393 (4)
C10—C17	1.536 (8)	Sb2—Cl4ii	2.393 (4)
C11—C12	1.369 (8)
N2i—Sb1—N2	180.00 (16)	C12—C11—C16	120.6 (6)
N2i—Sb1—N1	90.19 (18)	C12—C11—C5	120.1 (5)
N2—Sb1—N1	89.81 (18)	C16—C11—C5	119.1 (5)
N2i—Sb1—N1i	89.81 (18)	C11—C12—C13	120.5 (6)
N2—Sb1—N1i	90.19 (18)	C11—C12—H12	119.8
N1—Sb1—N1i	180.0 (2)	C13—C12—H12	119.8
N2i—Sb1—Cl1i	90.57 (14)	C14—C13—C12	115.6 (7)
N2—Sb1—Cl1i	89.43 (14)	C14—C13—H13	122.2
N1—Sb1—Cl1i	89.98 (14)	C12—C13—H13	122.2
N1i—Sb1—Cl1i	90.02 (14)	C13—C14—C15	127.7 (8)
N2i—Sb1—Cl1	89.43 (14)	C13—C14—H14	116.2
N2—Sb1—Cl1	90.57 (14)	C15—C14—H14	116.2
N1—Sb1—Cl1	90.02 (14)	C14—C15—C16	116.0 (7)
N1i—Sb1—Cl1	89.98 (14)	C14—C15—H15	122.0
Cl1i—Sb1—Cl1	180.0	C16—C15—H15	122.0
C4—N1—C1	108.0 (4)	C11—C16—C15	119.6 (6)
C4—N1—Sb1	126.0 (4)	C11—C16—H16	120.2
C1—N1—Sb1	126.0 (4)	C15—C16—H16	120.2
C6—N2—C9	108.0 (4)	C22—C17—C18	122.1 (6)
C6—N2—Sb1	126.3 (4)	C22—C17—C10	118.2 (6)
C9—N2—Sb1	125.6 (4)	C18—C17—C10	119.5 (6)
N1—C1—C10i	126.1 (5)	C17—C18—C19	118.5 (8)
N1—C1—C2	107.9 (5)	C17—C18—H18	120.7
C10i—C1—C2	126.0 (5)	C19—C18—H18	120.7
C3—C2—C1	108.1 (5)	C20—C19—C18	119.4 (8)
C3—C2—H2	125.9	C20—C19—H19	120.3
C1—C2—H2	125.9	C18—C19—H19	120.3
C2—C3—C4	107.9 (5)	C21—C20—C19	120.4 (7)
C2—C3—H3	126.0	C21—C20—H20	119.8
C4—C3—H3	126.0	C19—C20—H20	119.8
N1—C4—C5	126.6 (5)	C20—C21—C22	121.1 (8)
N1—C4—C3	108.1 (5)	C20—C21—H21	119.4
C5—C4—C3	125.4 (5)	C22—C21—H21	119.4
C6—C5—C4	124.6 (5)	C17—C22—C21	118.4 (7)
C6—C5—C11	116.2 (5)	C17—C22—H22	120.8
C4—C5—C11	119.2 (5)	C21—C22—H22	120.8
N2—C6—C5	126.6 (5)	Cl3—Sb2—Cl3ii	180.000 (1)
N2—C6—C7	108.1 (5)	Cl3—Sb2—Cl2ii	90.36 (11)
C5—C6—C7	125.3 (5)	Cl3ii—Sb2—Cl2ii	89.64 (11)
C8—C7—C6	107.7 (5)	Cl3—Sb2—Cl2	89.64 (11)
C8—C7—H7	126.2	Cl3ii—Sb2—Cl2	90.36 (11)
C6—C7—H7	126.2	Cl2ii—Sb2—Cl2	180.0
C7—C8—C9	108.7 (5)	Cl3—Sb2—Cl4	87.99 (16)
C7—C8—H8	125.7	Cl3ii—Sb2—Cl4	92.01 (16)
C9—C8—H8	125.7	Cl2ii—Sb2—Cl4	90.45 (14)
C10—C9—N2	127.0 (5)	Cl2—Sb2—Cl4	89.55 (14)
C10—C9—C8	125.5 (5)	Cl3—Sb2—Cl4ii	92.01 (16)
N2—C9—C8	107.5 (5)	Cl3ii—Sb2—Cl4ii	87.99 (16)
C9—C10—C1i	125.1 (5)	Cl2ii—Sb2—Cl4ii	89.55 (14)
C9—C10—C17	116.2 (5)	Cl2—Sb2—Cl4ii	90.45 (14)
C1i—C10—C17	118.7 (5)	Cl4—Sb2—Cl4ii	180.000 (1)

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7···Cl3ii	0.94	2.76	3.490 (8)	135
C8—H8···Cl4	0.94	2.74	3.593 (8)	151
C12—H12···Cl3iii	0.94	2.69	3.539 (8)	151

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C7—H7⋯Cl3i	0.94	2.76	3.490 (8)	135
C8—H8⋯Cl4	0.94	2.74	3.593 (8)	151
C12—H12⋯Cl3ii	0.94	2.69	3.539 (8)	151

Symmetry codes: (i) ; (ii) .