Crystal structure of bis­(benzoato-κO)[5,15-diphenyl-10,20-bis­(pyridin-4-yl)porphyrinato-κ⁴N,N′,N′′,N′′′]tin(IV)

In the crystal structure of the title compound, [Sn(C₄₂H₂₆N₆)(C₇H₅O₂)₂], the Sn^IV ion is located on a crystallographic inversion centre and is octa­hedrally coordinated with an N₄O₂ set. Four N atoms of the porphyrin ring form the equatorial plane while the axial positions are occupied by two O atoms from benzoate anions. The molecular packing of the title complex involves non-classical hydrogen bonds of the types C—H...O and C—H...N, leading to a three-dimensional network structure.

Key indicators

• Single-crystal X-ray study
• T = 173 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.030
• wR factor = 0.075
• Data-to-parameter ratio = 16.4

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT220_ALERT_2_C Non-Solvent  Resd 1  C   Ueq(max)/Ueq(min) Range        3.1 Ratio
PLAT230_ALERT_2_C Hirshfeld Test Diff for    O1       --C22      .        5.8 s.u.
PLAT230_ALERT_2_C Hirshfeld Test Diff for    N3       --C20      .        5.5 s.u.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H12A     ..N3       .       2.69 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H18A     ..O1       .       2.69 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H13A     ..O2       .       2.72 Ang.

Alert level G
PLAT794_ALERT_5_G Tentative Bond Valency for Sn1       (IV)      .       4.61 Info
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600         31 Note
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density.          9 Info

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   6 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   3 ALERT level G = General information/check it is not something unexpected

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   4 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   4 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

---

Computing details

Data collection: APEX2 (Bruker, 2014); cell refinement: SAINT (Bruker, 2014); data reduction: SAINT (Bruker, 2014); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014/7 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and Mercury (Macrae et al., 2008); software used to prepare material for publication: publCIF (Westrip, 2010).

Bis(benzoato-κO)[5,15-diphenyl-10,20-bis(pyridin-4-yl)porphyrinato-κ⁴N,N',N'',N''']tin(IV)

Crystal data

[Sn(C42H26N6)(C7H5O2)2]	F(000) = 1984
Mr = 975.60	Dx = 1.505 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 20.8021 (4) Å	Cell parameters from 8728 reflections
b = 11.4260 (2) Å	θ = 2.3–24.8°
c = 18.1164 (4) Å	µ = 0.65 mm^−1
β = 90.745 (1)°	T = 173 K
V = 4305.63 (15) Å^3	Block, violet
Z = 4	0.16 × 0.15 × 0.09 mm

Data collection

Bruker APEXII CCD diffractometer	3804 reflections with I > 2σ(I)
φ and ω scans	Rint = 0.048
Absorption correction: multi-scan (SADABS; Bruker, 2014)	θmax = 27.6°, θmin = 2.0°
Tmin = 0.705, Tmax = 0.746	h = −26→26
35578 measured reflections	k = −14→14
4972 independent reflections	l = −23→23

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.030	H-atom parameters constrained
wR(F^2) = 0.075	w = 1/[σ^2(Fo^2) + (0.0317P)^2 + 4.0687P] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max < 0.001
4972 reflections	Δρmax = 0.40 e Å^−3
304 parameters	Δρmin = −0.39 e Å^−3

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Sn1	0.5000	0.5000	0.5000	0.02250 (7)
O1	0.44403 (8)	0.41626 (14)	0.42008 (9)	0.0324 (4)
O2	0.35962 (9)	0.35219 (16)	0.48265 (11)	0.0495 (5)
N1	0.49675 (8)	0.65244 (15)	0.43588 (10)	0.0245 (4)
N2	0.42420 (8)	0.56314 (15)	0.56302 (10)	0.0253 (4)
N3	0.30373 (11)	0.2884 (2)	0.83538 (13)	0.0492 (6)
C1	0.53422 (10)	0.67472 (19)	0.37562 (12)	0.0256 (5)
C2	0.51565 (11)	0.78669 (19)	0.34642 (13)	0.0298 (5)
H2A	0.5336	0.8240	0.3046	0.036*
C3	0.46794 (11)	0.82998 (19)	0.38894 (13)	0.0299 (5)
H3A	0.4464	0.9026	0.3822	0.036*
C4	0.45597 (10)	0.74582 (18)	0.44611 (12)	0.0256 (5)
C5	0.40974 (10)	0.75569 (19)	0.50169 (12)	0.0263 (5)
C6	0.39522 (10)	0.67094 (19)	0.55466 (12)	0.0268 (5)
C7	0.34847 (11)	0.6824 (2)	0.61206 (13)	0.0328 (5)
H7A	0.3210	0.7477	0.6197	0.039*
C8	0.35058 (11)	0.5841 (2)	0.65310 (13)	0.0338 (5)
H8A	0.3245	0.5678	0.6945	0.041*
C9	0.39888 (10)	0.50826 (19)	0.62359 (12)	0.0274 (5)
C10	0.41763 (10)	0.39927 (19)	0.65170 (12)	0.0260 (5)
C11	0.37336 (11)	0.86845 (19)	0.50731 (13)	0.0292 (5)
C12	0.30815 (11)	0.8741 (2)	0.48994 (13)	0.0336 (5)
H12A	0.2871	0.8075	0.4696	0.040*
C13	0.27340 (13)	0.9755 (2)	0.50184 (15)	0.0410 (6)
H13A	0.2285	0.9776	0.4915	0.049*
C14	0.30417 (15)	1.0727 (3)	0.52860 (18)	0.0572 (8)
H14A	0.2804	1.1421	0.5379	0.069*
C15	0.36917 (16)	1.0706 (3)	0.54213 (19)	0.0637 (9)
H15A	0.3906	1.1397	0.5581	0.076*
C16	0.40391 (14)	0.9680 (2)	0.53259 (17)	0.0466 (7)
H16A	0.4487	0.9665	0.5435	0.056*
C17	0.38046 (11)	0.3568 (2)	0.71710 (13)	0.0296 (5)
C18	0.38393 (11)	0.4140 (2)	0.78459 (13)	0.0338 (5)
H18A	0.4131	0.4770	0.7920	0.041*
C19	0.34427 (12)	0.3779 (2)	0.84088 (14)	0.0394 (6)
H19A	0.3461	0.4196	0.8862	0.047*
C20	0.30314 (15)	0.2318 (3)	0.77159 (18)	0.0586 (8)
H20A	0.2760	0.1653	0.7670	0.070*
C21	0.33945 (13)	0.2629 (2)	0.71119 (16)	0.0492 (7)
H21A	0.3361	0.2201	0.6664	0.059*
C22	0.39476 (12)	0.3487 (2)	0.42894 (14)	0.0340 (5)
C23	0.38259 (12)	0.2618 (2)	0.36792 (14)	0.0374 (6)
C24	0.42668 (16)	0.2422 (3)	0.31373 (17)	0.0598 (8)
H24A	0.4654	0.2863	0.3130	0.072*
C25	0.4149 (2)	0.1576 (3)	0.25950 (19)	0.0778 (11)
H25A	0.4454	0.1462	0.2216	0.093*
C26	0.36105 (18)	0.0917 (3)	0.25978 (19)	0.0694 (10)
H26A	0.3542	0.0324	0.2238	0.083*
C27	0.31690 (19)	0.1125 (3)	0.3128 (2)	0.0793 (11)
H27A	0.2783	0.0681	0.3131	0.095*
C28	0.32706 (15)	0.1974 (3)	0.3663 (2)	0.0645 (9)
H28A	0.2951	0.2110	0.4024	0.077*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Sn1	0.02343 (11)	0.02357 (11)	0.02071 (12)	0.00149 (9)	0.00881 (8)	0.00118 (9)
O1	0.0359 (9)	0.0332 (9)	0.0281 (9)	−0.0071 (7)	0.0024 (7)	0.0017 (7)
O2	0.0420 (11)	0.0505 (11)	0.0563 (13)	−0.0084 (9)	0.0170 (10)	−0.0137 (10)
N1	0.0241 (9)	0.0268 (9)	0.0227 (10)	0.0013 (7)	0.0087 (8)	0.0014 (8)
N2	0.0250 (10)	0.0272 (10)	0.0241 (10)	0.0004 (8)	0.0098 (8)	0.0006 (8)
N3	0.0519 (14)	0.0578 (15)	0.0384 (14)	−0.0046 (12)	0.0197 (11)	0.0095 (12)
C1	0.0253 (11)	0.0301 (12)	0.0214 (11)	−0.0026 (9)	0.0043 (9)	0.0005 (9)
C2	0.0335 (13)	0.0307 (12)	0.0251 (12)	−0.0036 (10)	0.0051 (10)	0.0048 (10)
C3	0.0331 (13)	0.0263 (11)	0.0304 (13)	0.0010 (10)	0.0022 (10)	0.0021 (10)
C4	0.0259 (11)	0.0237 (11)	0.0274 (12)	0.0014 (9)	0.0032 (9)	−0.0001 (9)
C5	0.0259 (11)	0.0279 (11)	0.0252 (12)	0.0021 (9)	0.0022 (9)	−0.0034 (9)
C6	0.0262 (11)	0.0300 (12)	0.0244 (12)	0.0023 (9)	0.0068 (9)	−0.0025 (9)
C7	0.0312 (13)	0.0393 (13)	0.0281 (13)	0.0102 (10)	0.0098 (10)	−0.0014 (10)
C8	0.0294 (12)	0.0440 (14)	0.0283 (13)	0.0061 (11)	0.0136 (10)	0.0029 (11)
C9	0.0247 (11)	0.0346 (12)	0.0231 (11)	−0.0009 (10)	0.0086 (9)	−0.0005 (10)
C10	0.0262 (11)	0.0302 (12)	0.0216 (11)	−0.0039 (9)	0.0066 (9)	0.0002 (9)
C11	0.0341 (13)	0.0276 (12)	0.0260 (12)	0.0052 (10)	0.0056 (10)	−0.0022 (9)
C12	0.0342 (13)	0.0321 (12)	0.0346 (14)	0.0018 (10)	0.0056 (11)	−0.0016 (10)
C13	0.0384 (14)	0.0433 (16)	0.0414 (16)	0.0135 (11)	0.0024 (12)	−0.0026 (11)
C14	0.065 (2)	0.0432 (17)	0.064 (2)	0.0247 (15)	−0.0122 (16)	−0.0192 (15)
C15	0.068 (2)	0.0367 (16)	0.086 (3)	0.0102 (15)	−0.0248 (18)	−0.0261 (16)
C16	0.0427 (16)	0.0372 (14)	0.0597 (19)	0.0074 (12)	−0.0135 (14)	−0.0143 (13)
C17	0.0279 (12)	0.0351 (13)	0.0262 (12)	−0.0002 (10)	0.0109 (10)	0.0019 (10)
C18	0.0335 (13)	0.0387 (13)	0.0294 (13)	−0.0002 (11)	0.0084 (10)	0.0023 (11)
C19	0.0436 (15)	0.0493 (16)	0.0255 (13)	0.0026 (12)	0.0099 (11)	0.0046 (11)
C20	0.0584 (19)	0.0545 (18)	0.064 (2)	−0.0252 (15)	0.0254 (16)	0.0005 (16)
C21	0.0535 (17)	0.0533 (17)	0.0414 (16)	−0.0213 (14)	0.0208 (14)	−0.0102 (13)
C22	0.0335 (13)	0.0330 (13)	0.0357 (14)	0.0046 (11)	0.0025 (11)	0.0034 (11)
C23	0.0444 (15)	0.0317 (13)	0.0362 (14)	−0.0012 (11)	0.0030 (12)	0.0021 (11)
C24	0.070 (2)	0.0571 (19)	0.0525 (19)	−0.0200 (16)	0.0203 (17)	−0.0149 (15)
C25	0.105 (3)	0.073 (2)	0.057 (2)	−0.023 (2)	0.027 (2)	−0.0246 (18)
C26	0.095 (3)	0.0534 (19)	0.060 (2)	−0.0219 (19)	0.002 (2)	−0.0125 (17)
C27	0.079 (3)	0.071 (2)	0.089 (3)	−0.032 (2)	0.007 (2)	−0.030 (2)
C28	0.0524 (19)	0.064 (2)	0.078 (2)	−0.0141 (16)	0.0102 (17)	−0.0252 (18)

Geometric parameters (Å, º)

Sn1—O1^i	2.0794 (15)	C11—C16	1.378 (3)
Sn1—O1	2.0794 (15)	C11—C12	1.390 (3)
Sn1—N2	2.0874 (17)	C12—C13	1.384 (3)
Sn1—N2^i	2.0874 (17)	C12—H12A	0.9500
Sn1—N1^i	2.0941 (17)	C13—C14	1.368 (4)
Sn1—N1	2.0942 (17)	C13—H13A	0.9500
O1—C22	1.294 (3)	C14—C15	1.371 (4)
O2—C22	1.225 (3)	C14—H14A	0.9500
N1—C1	1.373 (3)	C15—C16	1.389 (4)
N1—C4	1.377 (3)	C15—H15A	0.9500
N2—C9	1.375 (3)	C16—H16A	0.9500
N2—C6	1.379 (3)	C17—C21	1.374 (3)
N3—C20	1.325 (4)	C17—C18	1.387 (3)
N3—C19	1.328 (3)	C18—C19	1.383 (3)
C1—C10^i	1.406 (3)	C18—H18A	0.9500
C1—C2	1.435 (3)	C19—H19A	0.9500
C2—C3	1.358 (3)	C20—C21	1.384 (4)
C2—H2A	0.9500	C20—H20A	0.9500
C3—C4	1.437 (3)	C21—H21A	0.9500
C3—H3A	0.9500	C22—C23	1.505 (3)
C4—C5	1.406 (3)	C23—C28	1.370 (4)
C5—C6	1.399 (3)	C23—C24	1.370 (4)
C5—C11	1.498 (3)	C24—C25	1.398 (4)
C6—C7	1.439 (3)	C24—H24A	0.9500
C7—C8	1.348 (3)	C25—C26	1.349 (5)
C7—H7A	0.9500	C25—H25A	0.9500
C8—C9	1.435 (3)	C26—C27	1.358 (5)
C8—H8A	0.9500	C26—H26A	0.9500
C9—C10	1.399 (3)	C27—C28	1.386 (4)
C10—C1^i	1.406 (3)	C27—H27A	0.9500
C10—C17	1.504 (3)	C28—H28A	0.9500
O1^i—Sn1—O1	180.0	C16—C11—C5	120.1 (2)
O1^i—Sn1—N2	83.12 (7)	C12—C11—C5	121.1 (2)
O1—Sn1—N2	96.88 (7)	C13—C12—C11	120.9 (2)
O1^i—Sn1—N2^i	96.88 (7)	C13—C12—H12A	119.5
O1—Sn1—N2^i	83.12 (7)	C11—C12—H12A	119.5
N2—Sn1—N2^i	180.00 (8)	C14—C13—C12	119.5 (3)
O1^i—Sn1—N1^i	89.01 (6)	C14—C13—H13A	120.3
O1—Sn1—N1^i	90.99 (6)	C12—C13—H13A	120.3
N2—Sn1—N1^i	90.19 (7)	C13—C14—C15	120.3 (3)
N2^i—Sn1—N1^i	89.81 (7)	C13—C14—H14A	119.8
O1^i—Sn1—N1	90.99 (6)	C15—C14—H14A	119.8
O1—Sn1—N1	89.01 (6)	C14—C15—C16	120.4 (3)
N2—Sn1—N1	89.81 (7)	C14—C15—H15A	119.8
N2^i—Sn1—N1	90.19 (7)	C16—C15—H15A	119.8
N1^i—Sn1—N1	180.0	C11—C16—C15	120.0 (3)
C22—O1—Sn1	128.68 (15)	C11—C16—H16A	120.0
C1—N1—C4	108.68 (18)	C15—C16—H16A	120.0
C1—N1—Sn1	125.49 (14)	C21—C17—C18	117.5 (2)
C4—N1—Sn1	125.82 (14)	C21—C17—C10	121.0 (2)
C9—N2—C6	108.88 (17)	C18—C17—C10	121.4 (2)
C9—N2—Sn1	125.37 (14)	C19—C18—C17	119.0 (2)
C6—N2—Sn1	125.52 (14)	C19—C18—H18A	120.5
C20—N3—C19	116.1 (2)	C17—C18—H18A	120.5
N1—C1—C10^i	125.6 (2)	N3—C19—C18	123.9 (2)
N1—C1—C2	107.78 (19)	N3—C19—H19A	118.0
C10^i—C1—C2	126.6 (2)	C18—C19—H19A	118.0
C3—C2—C1	108.1 (2)	N3—C20—C21	124.4 (3)
C3—C2—H2A	125.9	N3—C20—H20A	117.8
C1—C2—H2A	125.9	C21—C20—H20A	117.8
C2—C3—C4	107.4 (2)	C17—C21—C20	118.9 (3)
C2—C3—H3A	126.3	C17—C21—H21A	120.5
C4—C3—H3A	126.3	C20—C21—H21A	120.5
N1—C4—C5	125.9 (2)	O2—C22—O1	124.1 (2)
N1—C4—C3	107.97 (19)	O2—C22—C23	120.5 (2)
C5—C4—C3	126.1 (2)	O1—C22—C23	115.3 (2)
C6—C5—C4	126.3 (2)	C28—C23—C24	118.0 (3)
C6—C5—C11	115.77 (19)	C28—C23—C22	120.2 (2)
C4—C5—C11	117.94 (19)	C24—C23—C22	121.7 (2)
N2—C6—C5	126.6 (2)	C23—C24—C25	120.2 (3)
N2—C6—C7	107.51 (19)	C23—C24—H24A	119.9
C5—C6—C7	125.9 (2)	C25—C24—H24A	119.9
C8—C7—C6	107.8 (2)	C26—C25—C24	121.4 (3)
C8—C7—H7A	126.1	C26—C25—H25A	119.3
C6—C7—H7A	126.1	C24—C25—H25A	119.3
C7—C8—C9	108.4 (2)	C25—C26—C27	118.3 (3)
C7—C8—H8A	125.8	C25—C26—H26A	120.9
C9—C8—H8A	125.8	C27—C26—H26A	120.9
N2—C9—C10	126.1 (2)	C26—C27—C28	121.3 (3)
N2—C9—C8	107.41 (19)	C26—C27—H27A	119.4
C10—C9—C8	126.5 (2)	C28—C27—H27A	119.4
C9—C10—C1^i	127.1 (2)	C23—C28—C27	120.8 (3)
C9—C10—C17	115.50 (19)	C23—C28—H28A	119.6
C1^i—C10—C17	117.33 (19)	C27—C28—H28A	119.6
C16—C11—C12	118.7 (2)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C12—H12A···N3^ii	0.95 (1)	2.69 (1)	3.360 (3)	128 (1)
C18—H18A···O1^ii	0.95 (1)	2.69 (2)	3.357 (3)	128 (1)
C13—H13A···O2^iii	0.95 (1)	2.72 (1)	3.411 (3)	130 (1)

Symmetry codes: (ii) x, −y+1, z−1/2; (iii) −x+1/2, −y+3/2, −z+1.