Substitutional disorder in bis-[(cyanato-κO)/hydroxido(0.5/0.5)](5,10,15,20-tetra-phenyl-porphyrinato-κN)tin(IV).

The title complex, [Sn(IV)(C(44)H(28)N(4))(CNO)(OH)], exhibits substitutional disorder of the OH(-) and OCN(-) axial ligands. Thus, the cyanato-O ligand and the hydroxyl group bonded to the central Sn(IV) atom share statistically the axial position. The Sn(IV) ion is hexa-coordinated by the four N atoms of the pyrrole rings of the tetra-phenyl-porphyrin (TPP) and the O atoms of the two disordered OCN(-) and OH(-) axial ligands. The equatorial tin-pyrrole N atom distance (Sn-N(p)) is 2.100 (2) Å and the axial Sn-O(OCN) or Sn-O(OH) bond length is 2.074 (2) Å.

Related literature

For a review of porphyrin complexes, see: Scheidt (2000 ▶). For the synthesis of tin(IV) porphyrin species, see: Fallon et al. (2002 ▶); Martelli et al. (2009 ▶). For comparative bond lengths, see: Allen et al. (1987 ▶); Smith et al. (1991 ▶). For a description of the Cambridge Structural Database, see: Allen (2002 ▶).

Experimental

Crystal data

[Sn(C44H28N4)(CNO)(OH)]

M = 790.42

Monoclinic,

a = 11.2943 (6) Å

b = 12.6972 (7) Å

c = 13.0711 (7) Å

β = 114.251 (2)°

V = 1709.06 (16) Å3

Z = 2

Mo Kα radiation

μ = 0.80 mm−1

T = 293 K

0.20 × 0.18 × 0.12 mm

Data collection

Bruker APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2007 ▶) T min = 0.870, T max = 0.954

27811 measured reflections

5968 independent reflections

5241 reflections with I > 2σ(I)

R int = 0.028

Refinement

R[F 2 > 2σ(F 2)] = 0.039

wR(F 2) = 0.097

S = 1.13

5968 reflections

250 parameters

H-atom parameters constrained

Δρmax = 0.73 e Å−3

Δρmin = −1.34 e Å−3

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SIR2004 (Burla et al., 2005 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEPIII (Burnett & Johnson, 1996 ▶) and ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: publCIF (Westrip 2010 ▶).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811021544/dn2696sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811021544/dn2696Isup2.hkl

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

[Sn(C44H28N4)(CNO)(OH)]	F(000) = 800
Mr = 790.42	Dx = 1.536 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 27811 reflections
a = 11.2943 (6) Å	θ = 2.6–32.2°
b = 12.6972 (7) Å	µ = 0.80 mm−1
c = 13.0711 (7) Å	T = 293 K
β = 114.251 (2)°	Prism, purple
V = 1709.06 (16) Å3	0.20 × 0.18 × 0.12 mm
Z = 2

Bruker APEXII CCD area-detector diffractometer	5968 independent reflections
Radiation source: fine-focus sealed tube	5241 reflections with I > 2σ(I)
graphite	Rint = 0.028
φ and ω scans	θmax = 32.2°, θmin = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 2007)	h = −16→15
Tmin = 0.870, Tmax = 0.954	k = 0→18
27811 measured reflections	l = 0→19

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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.097	H-atom parameters constrained
S = 1.13	w = 1/[σ2(Fo2) + (0.0357P)2 + 1.5751P] where P = (Fo2 + 2Fc2)/3
5968 reflections	(Δ/σ)max < 0.001
250 parameters	Δρmax = 0.73 e Å−3
0 restraints	Δρmin = −1.34 e Å−3

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. 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^ > σ(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.

	x	y	z	Uiso*/Ueq	Occ. (<1)
Sn1	0.5000	0.0000	0.5000	0.02969 (7)
N2	0.50052 (16)	0.15106 (14)	0.43522 (13)	0.0276 (3)
N1	0.63300 (16)	0.04991 (14)	0.65913 (13)	0.0269 (3)
O1	0.65060 (16)	−0.03859 (15)	0.45502 (15)	0.0389 (4)	0.50
N3	0.8546 (4)	0.0655 (5)	0.5244 (4)	0.0513 (12)	0.50
C23	0.7509 (6)	0.0155 (5)	0.4921 (5)	0.0479 (13)	0.50
O2	0.65060 (16)	−0.03859 (15)	0.45502 (15)	0.0389 (4)	0.50
H2A	0.6917	−0.0883	0.4933	0.058*	0.50
C1	0.68716 (18)	−0.01306 (15)	0.75191 (15)	0.0245 (3)
C2	0.78155 (19)	0.04888 (16)	0.84031 (15)	0.0259 (4)
H2	0.8319	0.0262	0.9130	0.031*
C3	0.78367 (19)	0.14687 (17)	0.79813 (16)	0.0274 (4)
H3	0.8360	0.2030	0.8365	0.033*
C4	0.68969 (18)	0.14729 (16)	0.68298 (16)	0.0262 (4)
C5	0.66400 (19)	0.23239 (16)	0.60800 (16)	0.0266 (4)
C6	0.57669 (19)	0.23375 (16)	0.49389 (16)	0.0268 (4)
C7	0.55237 (19)	0.32147 (16)	0.41809 (17)	0.0284 (4)
H7	0.5903	0.3878	0.4360	0.034*
C8	0.46382 (19)	0.29004 (16)	0.31546 (16)	0.0279 (4)
H8	0.4310	0.3306	0.2505	0.033*
C9	0.43046 (18)	0.18217 (16)	0.32611 (15)	0.0253 (4)
C10	0.65856 (18)	−0.11936 (16)	0.75997 (15)	0.0247 (3)
C11	0.73248 (19)	−0.17185 (16)	0.87048 (15)	0.0251 (3)
C12	0.8373 (2)	−0.23659 (18)	0.88507 (17)	0.0314 (4)
H12	0.8602	−0.2483	0.8253	0.038*
C13	0.9080 (2)	−0.2840 (2)	0.98771 (19)	0.0376 (5)
H13	0.9778	−0.3274	0.9964	0.045*
C14	0.8756 (2)	−0.2673 (2)	1.07638 (18)	0.0387 (5)
H14	0.9238	−0.2986	1.1454	0.046*
C15	0.7702 (3)	−0.2033 (2)	1.06295 (18)	0.0393 (5)
H15	0.7475	−0.1924	1.1229	0.047*
C16	0.6988 (2)	−0.15561 (19)	0.96030 (17)	0.0334 (4)
H16	0.6285	−0.1128	0.9516	0.040*
C17	0.74361 (19)	0.32920 (16)	0.65294 (17)	0.0280 (4)
C18	0.8459 (2)	0.35026 (19)	0.62357 (18)	0.0341 (4)
H18	0.8621	0.3061	0.5740	0.041*
C19	0.9245 (2)	0.4378 (2)	0.6684 (2)	0.0448 (6)
H19	0.9926	0.4522	0.6481	0.054*
C20	0.9024 (3)	0.5030 (2)	0.7422 (3)	0.0563 (8)
H20	0.9560	0.5608	0.7725	0.068*
C21	0.8015 (4)	0.4829 (2)	0.7712 (3)	0.0622 (9)
H21	0.7861	0.5275	0.8208	0.075*
C22	0.7216 (3)	0.3962 (2)	0.7270 (3)	0.0490 (6)
H22	0.6530	0.3831	0.7472	0.059*

	U11	U22	U33	U12	U13	U23
Sn1	0.03022 (10)	0.02873 (10)	0.02008 (9)	−0.01209 (8)	0.00016 (7)	0.00446 (7)
N2	0.0283 (8)	0.0275 (8)	0.0206 (7)	−0.0088 (6)	0.0037 (6)	0.0030 (6)
N1	0.0266 (7)	0.0268 (8)	0.0208 (7)	−0.0068 (6)	0.0031 (6)	0.0026 (6)
O1	0.0350 (8)	0.0416 (9)	0.0396 (9)	0.0014 (7)	0.0149 (7)	0.0072 (7)
N3	0.037 (2)	0.076 (4)	0.044 (2)	−0.013 (2)	0.0184 (19)	−0.005 (2)
C23	0.048 (3)	0.055 (3)	0.040 (3)	0.001 (2)	0.017 (2)	0.005 (2)
O2	0.0350 (8)	0.0416 (9)	0.0396 (9)	0.0014 (7)	0.0149 (7)	0.0072 (7)
C1	0.0231 (8)	0.0279 (9)	0.0195 (7)	−0.0017 (7)	0.0057 (6)	0.0009 (6)
C2	0.0249 (8)	0.0288 (9)	0.0202 (7)	−0.0008 (7)	0.0055 (6)	−0.0021 (7)
C3	0.0247 (8)	0.0305 (10)	0.0224 (8)	−0.0054 (7)	0.0049 (7)	−0.0033 (7)
C4	0.0240 (8)	0.0283 (9)	0.0221 (8)	−0.0063 (7)	0.0054 (6)	−0.0011 (7)
C5	0.0257 (8)	0.0256 (9)	0.0248 (8)	−0.0073 (7)	0.0066 (7)	−0.0009 (7)
C6	0.0257 (8)	0.0264 (9)	0.0241 (8)	−0.0074 (7)	0.0060 (7)	0.0018 (7)
C7	0.0287 (9)	0.0254 (9)	0.0280 (9)	−0.0068 (7)	0.0085 (7)	0.0032 (7)
C8	0.0283 (9)	0.0278 (9)	0.0254 (8)	−0.0035 (7)	0.0088 (7)	0.0053 (7)
C9	0.0247 (8)	0.0268 (9)	0.0217 (7)	−0.0038 (7)	0.0068 (6)	0.0031 (6)
C10	0.0237 (8)	0.0288 (9)	0.0196 (7)	−0.0027 (7)	0.0070 (6)	0.0020 (6)
C11	0.0268 (8)	0.0247 (8)	0.0199 (7)	−0.0035 (7)	0.0056 (6)	0.0005 (6)
C12	0.0309 (9)	0.0356 (11)	0.0238 (8)	0.0024 (8)	0.0072 (7)	−0.0005 (7)
C13	0.0311 (10)	0.0377 (12)	0.0327 (10)	0.0004 (9)	0.0017 (8)	0.0033 (9)
C14	0.0376 (11)	0.0405 (12)	0.0259 (9)	−0.0074 (10)	0.0008 (8)	0.0086 (8)
C15	0.0485 (13)	0.0441 (13)	0.0249 (9)	−0.0062 (11)	0.0148 (9)	0.0042 (9)
C16	0.0388 (11)	0.0375 (11)	0.0264 (9)	0.0011 (9)	0.0159 (8)	0.0033 (8)
C17	0.0271 (8)	0.0241 (9)	0.0266 (8)	−0.0052 (7)	0.0049 (7)	0.0009 (7)
C18	0.0323 (10)	0.0344 (11)	0.0311 (10)	−0.0076 (8)	0.0084 (8)	0.0010 (8)
C19	0.0340 (11)	0.0420 (13)	0.0462 (13)	−0.0153 (10)	0.0042 (10)	0.0105 (11)
C20	0.0528 (16)	0.0293 (12)	0.0615 (18)	−0.0169 (11)	−0.0019 (13)	−0.0039 (12)
C21	0.067 (2)	0.0404 (16)	0.075 (2)	−0.0133 (14)	0.0255 (18)	−0.0291 (15)
C22	0.0483 (14)	0.0454 (15)	0.0580 (16)	−0.0131 (12)	0.0265 (13)	−0.0187 (12)

Sn1—O2i	2.0737 (18)	C8—C9	1.442 (3)
Sn1—O1i	2.0737 (18)	C8—H8	0.9300
Sn1—O1	2.0737 (18)	C9—C10i	1.408 (3)
Sn1—N2i	2.0976 (17)	C10—C9i	1.408 (3)
Sn1—N2	2.0976 (17)	C10—C11	1.496 (3)
Sn1—N1	2.1018 (16)	C11—C12	1.388 (3)
Sn1—N1i	2.1018 (16)	C11—C16	1.390 (3)
N2—C6	1.374 (2)	C12—C13	1.386 (3)
N2—C9	1.375 (2)	C12—H12	0.9300
N1—C4	1.368 (3)	C13—C14	1.368 (4)
N1—C1	1.369 (2)	C13—H13	0.9300
O1—C23	1.241 (6)	C14—C15	1.391 (4)
O1—H2A	0.8202	C14—H14	0.9300
N3—C23	1.244 (7)	C15—C16	1.389 (3)
C23—H2A	1.4810	C15—H15	0.9300
C1—C10	1.402 (3)	C16—H16	0.9300
C1—C2	1.442 (3)	C17—C18	1.385 (3)
C2—C3	1.365 (3)	C17—C22	1.386 (3)
C2—H2	0.9300	C18—C19	1.393 (3)
C3—C4	1.442 (3)	C18—H18	0.9300
C3—H3	0.9300	C19—C20	1.370 (5)
C4—C5	1.407 (3)	C19—H19	0.9300
C5—C6	1.410 (3)	C20—C21	1.364 (5)
C5—C17	1.494 (3)	C20—H20	0.9300
C6—C7	1.440 (3)	C21—C22	1.390 (4)
C7—C8	1.363 (3)	C21—H21	0.9300
C7—H7	0.9300	C22—H22	0.9300
O2i—Sn1—O1i	0.00 (4)	C5—C6—C7	126.15 (18)
O2i—Sn1—O1	180.0	C8—C7—C6	107.83 (17)
O1i—Sn1—O1	180.0	C8—C7—H7	126.1
O2i—Sn1—N2i	87.88 (7)	C6—C7—H7	126.1
O1i—Sn1—N2i	87.88 (7)	C7—C8—C9	107.36 (17)
O1—Sn1—N2i	92.12 (7)	C7—C8—H8	126.3
O2i—Sn1—N2	92.12 (7)	C9—C8—H8	126.3
O1i—Sn1—N2	92.12 (7)	N2—C9—C10i	125.74 (18)
O1—Sn1—N2	87.88 (7)	N2—C9—C8	108.13 (16)
N2i—Sn1—N2	180.0	C10i—C9—C8	126.13 (17)
O2i—Sn1—N1	89.10 (7)	C1—C10—C9i	126.59 (17)
O1i—Sn1—N1	89.10 (7)	C1—C10—C11	116.56 (16)
O1—Sn1—N1	90.90 (7)	C9i—C10—C11	116.83 (17)
N2i—Sn1—N1	89.75 (6)	C12—C11—C16	119.03 (18)
N2—Sn1—N1	90.25 (6)	C12—C11—C10	120.18 (18)
O2i—Sn1—N1i	90.90 (7)	C16—C11—C10	120.79 (19)
O1i—Sn1—N1i	90.90 (7)	C13—C12—C11	120.7 (2)
O1—Sn1—N1i	89.10 (7)	C13—C12—H12	119.7
N2i—Sn1—N1i	90.25 (6)	C11—C12—H12	119.7
N2—Sn1—N1i	89.75 (6)	C14—C13—C12	120.3 (2)
N1—Sn1—N1i	180.0	C14—C13—H13	119.9
C6—N2—C9	108.73 (16)	C12—C13—H13	119.9
C6—N2—Sn1	125.33 (13)	C13—C14—C15	119.8 (2)
C9—N2—Sn1	125.86 (13)	C13—C14—H14	120.1
C4—N1—C1	109.20 (15)	C15—C14—H14	120.1
C4—N1—Sn1	125.12 (13)	C16—C15—C14	120.2 (2)
C1—N1—Sn1	125.33 (13)	C16—C15—H15	119.9
C23—O1—Sn1	118.8 (3)	C14—C15—H15	119.9
C23—O1—H2A	89.5	C15—C16—C11	120.0 (2)
Sn1—O1—H2A	109.4	C15—C16—H16	120.0
O1—C23—N3	175.3 (6)	C11—C16—H16	120.0
O1—C23—H2A	33.6	C18—C17—C22	119.0 (2)
N3—C23—H2A	144.8	C18—C17—C5	119.1 (2)
N1—C1—C10	126.57 (17)	C22—C17—C5	121.9 (2)
N1—C1—C2	107.80 (17)	C17—C18—C19	119.8 (2)
C10—C1—C2	125.62 (17)	C17—C18—H18	120.1
C3—C2—C1	107.66 (16)	C19—C18—H18	120.1
C3—C2—H2	126.2	C20—C19—C18	120.7 (3)
C1—C2—H2	126.2	C20—C19—H19	119.7
C2—C3—C4	107.30 (17)	C18—C19—H19	119.7
C2—C3—H3	126.3	C21—C20—C19	119.8 (2)
C4—C3—H3	126.3	C21—C20—H20	120.1
N1—C4—C5	126.31 (17)	C19—C20—H20	120.1
N1—C4—C3	108.03 (17)	C20—C21—C22	120.5 (3)
C5—C4—C3	125.64 (18)	C20—C21—H21	119.8
C4—C5—C6	126.92 (18)	C22—C21—H21	119.8
C4—C5—C17	116.08 (16)	C17—C22—C21	120.3 (3)
C6—C5—C17	116.89 (17)	C17—C22—H22	119.9
N2—C6—C5	125.89 (18)	C21—C22—H22	119.9
N2—C6—C7	107.95 (16)