Crystal structure of 5,10,15-triphenyl-20-(4,4,5,5-tetra­methyl-1,3,2-dioxaborolan-2-yl)porphyrin

Senge, M.O.; Eckhardt, H.-G.

doi:10.1107/S1600536814019680

organic compounds

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ISSN: 2056-9890

Volume 70| Part 10| October 2014| Pages o1085-o1086

doi:10.1107/S1600536814019680

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Crystal structure of 5,10,15-triphenyl-20-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)porphyrin

Mathias O. Senge ^a ^* and Hans-Georg Eckhardt ^a

^aSFI Tetrapyrrole Laboratory, School of Chemistry, Trinity College Dublin, Dublin 2, Ireland
^*Correspondence e-mail: sengem@tcd.ie

Edited by U. Lee, Pukyong National University, South Korea (Received 2 June 2014; accepted 1 September 2014; online 6 September 2014)

In the title compound, C₄₄H₃₇BN₄O₂, the dihedral angle between the plane of the porphyrin macrocycle ring system [r.m.s. deviation = 0.159 (1) Å] and those of three phenyl rings are 66.11 (4), 74.75 (4) and 57.00 (4)°. The conformational distortion is characterized by a mixture of ruffled, saddle and in-plane distortion modes. In the crystal, the porphyrin molecules are linked by C—H⋯π interactions into supramolecular chains running along the a-axis direction. A pair of bifurcated N—H⋯(N,N) hydrogen bonds occur across the central region of the macrocycle.

Keywords: crystal structure; porphyrinoid; tetrapyrroles; porphyrins.

CCDC reference: 1022040

1. Related literature

For the structure and conformation of porphyrins, see: Scheidt & Lee (1987 ); Jentzen et al. (1997 ); Senge (2000 , 2006 ). For the synthesis, see: Finnigan et al. (2011 ). For the handling of crystals, see Hope (1994 ). For related boronyl porphyrin structures, see: Hyslop et al. (1998 ); Schwalbe et al. (2012 ). For other recent free base porphyrin structures, see: Miranda et al. (2012 ); Leonarska et al. (2012 ); Senge (2013 ).

2. Experimental

2.1. Crystal data

C₄₄H₃₇BN₄O₂
M_r = 664.59
Monoclinic, P 2₁ /c
a = 13.0758 (5) Å
b = 10.5245 (4) Å
c = 27.1358 (10) Å
β = 110.353 (2)°
V = 3501.2 (2) Å³
Z = 4
Cu Kα radiation
μ = 0.61 mm⁻¹
T = 100 K
0.50 × 0.50 × 0.35 mm

2.2. Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.751, T_max = 0.815
25108 measured reflections
5993 independent reflections
5788 reflections with I > 2σ(I)
R_int = 0.029

2.3. Refinement

R[F² > 2σ(F²)] = 0.041
wR(F²) = 0.103
S = 1.03
5993 reflections
464 parameters
H-atom parameters constrained
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.27 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C100–C105 phenyl ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N21—H21⋯N24	0.88	2.35	2.9084 (16)	122
N21—H21⋯N22	0.88	2.38	2.9266 (16)	121
N23—H23⋯N24	0.88	2.34	2.8978 (16)	121
N23—H23⋯N22	0.88	2.35	2.8986 (16)	120
C153—H153⋯Cg1ⁱ	0.95	2.58	3.488 (2)	160
Symmetry code: (i) x-1, y, z.

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 1998 ); software used to prepare material for publication: SHELXTL-Plus (Sheldrick, 2008).

Supporting information

CCDC reference: 1022040

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: 10.1107/S1600536814019680/lx2293sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814019680/lx2293Isup2.hkl

checkCIF report

Comment top

The compound was prepared via borylation of 5-bromo-10,15,20-triphenylporphyrin with 4,4,5,5-tetramethyl-1,3,2-dioxaborolane under dichlorobis(triphenylphosphine)palladium(II) catalysis (Finnigan et al., 2011). Crystallization from CH₂Cl₂/CH₃OH yielded monoclinic crystals without solvent inclusion.

The compound was investigated with regard to its macrocycle conformation. The porphyrin macrocycle ring system, with a mean deviation of 0.159 (1) Å from the least-squares plane defined by the 24 constituent atoms. Three phenyl rings are essentially planar, with a mean deviation of 0.001 (1) (C100–C105), 0.003 (1) (C150–C155) and 0.007 (1) (C200–C205) Å from the least-squares plane defined by the six constituent atoms. The dihedral angle formed by the porphyrin macrocycle ring system and three phenyl rings are 66.11 (4)(C100–C105), 74.75 (4) (C150–C155) and 57.00 (4) (C200–C205) °, respectively. A conformational analysis was performed using the NSD (normal structural decomposition) method developed by Shelnutt and coworkers (Jentzen et al., 1997). The compound exhibits a moderate degree of conformational distortion. The main contributing out-of-plane distortion modes are ruf, sad and wav. Likewise moderate contributions from macrocycle breathing and N-str are observed for the in-plane distortions. Related Zn(II) complexes, e.g. {5,15-diphenyl-10-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)porphyrinato}zinc(II) (Hyslop et al., 1998; Schwalbe et al., 2012) exhibit more planar conformations. Other recent porphyrin free base structures have been reported by Miranda et al. (2012), Leonarska et al. (2012), and Senge (2013).

In the crystal packing (Fig. 2), the porphyrin molecules are linked by C—H···π interactions (Table 1, Cg1 is the centroid of the C100–C105 phenyl ring) into supramolecular chains running along the a axis. Also intramolecular N—H···N hydrogen bonds occur (Table 1).

Related literature top

For the structure and conformation of porphyrins, see: Scheidt & Lee (1987); Jentzen et al. (1997); Senge (2000, 2006). For the synthesis, see: Finnigan et al. (2011). For the handling of crystals, see Hope (1994). For related boronyl porphyrin structures, see: Hyslop et al. (1998); Schwalbe et al. (2012). For other recent free base porphyrin structures, see: Miranda et al. (2012); Leonarska et al. (2012); Senge (2013).

Experimental top

The title compound was prepared as described by Finnigan et al. (2011).

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 1998); software used to prepare material for publication: SHELXTL-Plus (Sheldrick, 2008).

Figures top

	Fig. 1. Molecular structure of the title compound. Thermal ellipsoids are drawn at 50% probability level.
	Fig. 2. A view of the N—H···N and C—H···π interactions (dotted lines) in the crystal structure of the title compound. H atoms non-participating in hydrogen-bonding were omitted for clarity. [Symmetry code: (i) x -1, y, z; (ii) x + 1, y, z.]

5,10,15-Triphenyl-20-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)porphyrin top

Crystal data top

C₄₄H₃₇BN₄O₂	F(000) = 1400
M_r = 664.59	D_x = 1.261 Mg m⁻³
Monoclinic, P2₁/c	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: -P 2ybc	Cell parameters from 9566 reflections
a = 13.0758 (5) Å	θ = 4.1–66.8°
b = 10.5245 (4) Å	µ = 0.61 mm⁻¹
c = 27.1358 (10) Å	T = 100 K
β = 110.353 (2)°	Triangle, purple
V = 3501.2 (2) Å³	0.50 × 0.50 × 0.35 mm
Z = 4

Data collection top

Bruker APEXII CCD diffractometer	5993 independent reflections
Radiation source: sealed tube	5788 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.029
Detector resolution: 8.33 pixels mm^-1	θ_max = 66.8°, θ_min = 4.0°
ϕ and ω scans	h = −15→15
Absorption correction: multi-scan (SADABS; Bruker, 2005)	k = −8→12
T_min = 0.751, T_max = 0.815	l = −31→32
25108 measured reflections

Refinement top

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: difference Fourier map
wR(F²) = 0.103	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0402P)² + 2.0737P] where P = (F_o² + 2F_c²)/3
5993 reflections	(Δ/σ)_max < 0.001
464 parameters	Δρ_max = 0.27 e Å⁻³
0 restraints	Δρ_min = −0.27 e Å⁻³

Crystal data top

C₄₄H₃₇BN₄O₂	V = 3501.2 (2) Å³
M_r = 664.59	Z = 4
Monoclinic, P2₁/c	Cu Kα radiation
a = 13.0758 (5) Å	µ = 0.61 mm⁻¹
b = 10.5245 (4) Å	T = 100 K
c = 27.1358 (10) Å	0.50 × 0.50 × 0.35 mm
β = 110.353 (2)°

Data collection top

Bruker APEXII CCD diffractometer	5993 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	5788 reflections with I > 2σ(I)
T_min = 0.751, T_max = 0.815	R_int = 0.029
25108 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	0 restraints
wR(F²) = 0.103	H-atom parameters constrained
S = 1.03	Δρ_max = 0.27 e Å⁻³
5993 reflections	Δρ_min = −0.27 e Å⁻³
464 parameters

Special details top

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 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 > 2sigma(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. The carbon atoms of one phenyl unit show some degree of thermal librational movement.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
C1	0.55291 (11)	0.54316 (12)	0.72969 (5)	0.0213 (3)
C2	0.63876 (11)	0.60493 (13)	0.77064 (5)	0.0229 (3)
H2	0.6384	0.6249	0.8047	0.027*
C3	0.72077 (11)	0.62999 (13)	0.75218 (5)	0.0233 (3)
H3	0.7872	0.6721	0.7709	0.028*
C4	0.68981 (11)	0.58188 (12)	0.69939 (5)	0.0209 (3)
C5	0.75153 (11)	0.58579 (13)	0.66621 (5)	0.0221 (3)
C6	0.72497 (11)	0.51900 (13)	0.61822 (5)	0.0225 (3)
C7	0.80206 (12)	0.50156 (14)	0.59095 (6)	0.0281 (3)
H7	0.8718	0.5401	0.5997	0.034*
C8	0.75622 (12)	0.42099 (14)	0.55110 (6)	0.0280 (3)
H8	0.7883	0.3894	0.5270	0.034*
C9	0.64820 (11)	0.39125 (13)	0.55173 (5)	0.0223 (3)
C10	0.57290 (11)	0.31342 (13)	0.51484 (5)	0.0219 (3)
C11	0.46626 (11)	0.28910 (13)	0.51343 (5)	0.0221 (3)
C12	0.38183 (12)	0.22656 (15)	0.47235 (6)	0.0278 (3)
H12	0.3891	0.1897	0.4418	0.033*
C13	0.28955 (12)	0.22871 (14)	0.48442 (6)	0.0280 (3)
H13	0.2207	0.1947	0.4637	0.034*
C14	0.31440 (11)	0.29137 (13)	0.53390 (5)	0.0222 (3)
C15	0.24417 (11)	0.31216 (13)	0.56185 (5)	0.0226 (3)
C16	0.27360 (11)	0.36879 (13)	0.61174 (5)	0.0222 (3)
C17	0.19703 (11)	0.39354 (15)	0.63825 (6)	0.0269 (3)
H17	0.1209	0.3767	0.6252	0.032*
C18	0.25478 (11)	0.44510 (15)	0.68516 (6)	0.0265 (3)
H18	0.2272	0.4709	0.7117	0.032*
C19	0.36661 (11)	0.45374 (13)	0.68739 (5)	0.0213 (3)
C20	0.45034 (11)	0.50854 (13)	0.73035 (5)	0.0212 (3)
N21	0.58829 (9)	0.52924 (11)	0.68782 (4)	0.0211 (2)
H21	0.5511	0.4919	0.6579	0.025*
N22	0.63209 (9)	0.45164 (11)	0.59351 (4)	0.0214 (2)
N23	0.42208 (9)	0.32698 (11)	0.54992 (4)	0.0213 (2)
H23	0.4573	0.3679	0.5792	0.026*
N24	0.37618 (9)	0.40825 (11)	0.64213 (4)	0.0209 (2)
B1	0.85661 (13)	0.67155 (15)	0.68378 (6)	0.0242 (3)
C50	0.99982 (12)	0.78798 (15)	0.73694 (6)	0.0314 (3)
C51	0.99019 (14)	0.80462 (17)	0.67871 (7)	0.0377 (4)
C52	0.94995 (14)	0.89499 (17)	0.75792 (7)	0.0405 (4)
H52A	0.8746	0.9086	0.7345	0.061*
H52B	0.9922	0.9729	0.7598	0.061*
H52C	0.9507	0.8731	0.7931	0.061*
C53	1.11315 (13)	0.75979 (18)	0.77465 (8)	0.0426 (4)
H53A	1.1116	0.7523	0.8104	0.064*
H53B	1.1624	0.8289	0.7734	0.064*
H53C	1.1390	0.6799	0.7646	0.064*
C54	0.9911 (2)	0.9413 (2)	0.66153 (9)	0.0655 (7)
H54A	0.9874	0.9436	0.6248	0.098*
H54B	1.0585	0.9826	0.6838	0.098*
H54C	0.9281	0.9862	0.6648	0.098*
C55	1.07129 (17)	0.7236 (3)	0.66391 (9)	0.0624 (6)
H55A	1.0661	0.6352	0.6742	0.094*
H55B	1.1453	0.7553	0.6821	0.094*
H55C	1.0547	0.7280	0.6258	0.094*
C100	0.60355 (11)	0.25149 (13)	0.47213 (5)	0.0227 (3)
C101	0.60723 (11)	0.11908 (14)	0.46904 (6)	0.0260 (3)
H101	0.5935	0.0686	0.4951	0.031*
C102	0.63066 (12)	0.06045 (14)	0.42833 (6)	0.0291 (3)
H102	0.6330	−0.0296	0.4267	0.035*
C103	0.65068 (12)	0.13354 (15)	0.39013 (6)	0.0300 (3)
H103	0.6664	0.0936	0.3622	0.036*
C104	0.64771 (12)	0.26504 (15)	0.39283 (6)	0.0293 (3)
H104	0.6617	0.3152	0.3668	0.035*
C105	0.62430 (12)	0.32356 (14)	0.43358 (6)	0.0269 (3)
H105	0.6224	0.4137	0.4352	0.032*
C150	0.12827 (11)	0.27037 (14)	0.53697 (5)	0.0254 (3)
C151	0.09046 (14)	0.16336 (18)	0.55491 (8)	0.0473 (5)
H151	0.1392	0.1135	0.5822	0.057*
C152	−0.01833 (16)	0.1288 (2)	0.53314 (9)	0.0565 (6)
H152	−0.0434	0.0548	0.5455	0.068*
C153	−0.09030 (13)	0.20004 (18)	0.49394 (7)	0.0399 (4)
H153	−0.1648	0.1759	0.4794	0.048*
C154	−0.05394 (12)	0.30615 (18)	0.47587 (6)	0.0374 (4)
H154	−0.1034	0.3560	0.4488	0.045*
C155	0.05526 (12)	0.34111 (17)	0.49711 (6)	0.0326 (4)
H155	0.0800	0.4143	0.4841	0.039*
C200	0.42271 (11)	0.53497 (14)	0.77821 (5)	0.0227 (3)
C201	0.42174 (12)	0.65766 (15)	0.79739 (6)	0.0284 (3)
H201	0.4450	0.7270	0.7815	0.034*
C202	0.38703 (12)	0.67918 (17)	0.83956 (6)	0.0350 (4)
H202	0.3871	0.7631	0.8525	0.042*
C203	0.35234 (12)	0.57919 (18)	0.86278 (6)	0.0371 (4)
H203	0.3275	0.5945	0.8912	0.044*
C204	0.35386 (13)	0.45689 (17)	0.84452 (6)	0.0350 (4)
H204	0.3302	0.3880	0.8605	0.042*
C205	0.38975 (12)	0.43456 (15)	0.80300 (5)	0.0278 (3)
H205	0.3920	0.3500	0.7912	0.033*
O1	0.92954 (8)	0.67730 (10)	0.73411 (4)	0.0297 (2)
O2	0.88183 (9)	0.75138 (11)	0.65026 (4)	0.0355 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0237 (7)	0.0168 (6)	0.0236 (7)	0.0005 (5)	0.0084 (5)	0.0006 (5)
C2	0.0250 (7)	0.0209 (7)	0.0227 (7)	−0.0002 (6)	0.0082 (5)	−0.0009 (5)
C3	0.0218 (7)	0.0200 (7)	0.0265 (7)	−0.0019 (5)	0.0064 (5)	−0.0013 (6)
C4	0.0203 (6)	0.0155 (6)	0.0255 (7)	0.0011 (5)	0.0063 (5)	0.0010 (5)
C5	0.0220 (7)	0.0174 (7)	0.0267 (7)	0.0012 (5)	0.0083 (5)	0.0015 (5)
C6	0.0249 (7)	0.0176 (7)	0.0263 (7)	−0.0008 (5)	0.0106 (6)	0.0014 (5)
C7	0.0260 (7)	0.0281 (8)	0.0341 (8)	−0.0076 (6)	0.0155 (6)	−0.0038 (6)
C8	0.0297 (8)	0.0282 (8)	0.0322 (8)	−0.0045 (6)	0.0186 (6)	−0.0043 (6)
C9	0.0262 (7)	0.0178 (7)	0.0256 (7)	−0.0004 (5)	0.0122 (6)	0.0021 (5)
C10	0.0263 (7)	0.0177 (7)	0.0230 (7)	0.0018 (5)	0.0101 (6)	0.0020 (5)
C11	0.0252 (7)	0.0186 (7)	0.0229 (7)	0.0027 (5)	0.0087 (5)	0.0002 (5)
C12	0.0268 (7)	0.0308 (8)	0.0252 (7)	0.0019 (6)	0.0080 (6)	−0.0069 (6)
C13	0.0232 (7)	0.0301 (8)	0.0273 (7)	−0.0004 (6)	0.0047 (6)	−0.0075 (6)
C14	0.0208 (7)	0.0205 (7)	0.0233 (7)	0.0013 (5)	0.0050 (5)	−0.0006 (5)
C15	0.0213 (7)	0.0206 (7)	0.0243 (7)	0.0006 (5)	0.0058 (5)	0.0011 (5)
C16	0.0207 (6)	0.0225 (7)	0.0235 (7)	0.0000 (5)	0.0077 (5)	0.0015 (5)
C17	0.0198 (7)	0.0363 (8)	0.0252 (7)	−0.0029 (6)	0.0084 (6)	0.0001 (6)
C18	0.0238 (7)	0.0339 (8)	0.0240 (7)	−0.0008 (6)	0.0111 (6)	−0.0008 (6)
C19	0.0231 (7)	0.0194 (7)	0.0224 (7)	−0.0007 (5)	0.0091 (5)	0.0013 (5)
C20	0.0235 (7)	0.0168 (6)	0.0233 (7)	−0.0002 (5)	0.0083 (5)	0.0007 (5)
N21	0.0205 (6)	0.0200 (6)	0.0228 (6)	−0.0023 (5)	0.0074 (4)	−0.0024 (5)
N22	0.0237 (6)	0.0178 (6)	0.0234 (6)	−0.0011 (5)	0.0091 (5)	−0.0005 (5)
N23	0.0216 (6)	0.0212 (6)	0.0208 (5)	−0.0002 (5)	0.0070 (4)	−0.0022 (4)
N24	0.0216 (6)	0.0201 (6)	0.0208 (5)	−0.0004 (5)	0.0072 (4)	−0.0007 (4)
B1	0.0240 (8)	0.0198 (8)	0.0309 (8)	0.0013 (6)	0.0121 (7)	−0.0018 (6)
C50	0.0267 (7)	0.0292 (8)	0.0394 (9)	−0.0090 (6)	0.0130 (7)	−0.0062 (7)
C51	0.0372 (9)	0.0385 (9)	0.0403 (9)	−0.0189 (7)	0.0172 (7)	−0.0085 (7)
C52	0.0371 (9)	0.0374 (9)	0.0480 (10)	−0.0056 (7)	0.0161 (8)	−0.0108 (8)
C53	0.0287 (8)	0.0416 (10)	0.0528 (10)	−0.0074 (7)	0.0082 (8)	−0.0063 (8)
C54	0.0834 (16)	0.0572 (13)	0.0492 (11)	−0.0405 (12)	0.0147 (11)	0.0048 (10)
C55	0.0476 (11)	0.0894 (17)	0.0638 (13)	−0.0248 (11)	0.0364 (10)	−0.0324 (12)
C100	0.0206 (6)	0.0224 (7)	0.0245 (7)	0.0006 (5)	0.0071 (5)	−0.0021 (6)
C101	0.0238 (7)	0.0224 (7)	0.0331 (8)	−0.0011 (6)	0.0115 (6)	−0.0013 (6)
C102	0.0248 (7)	0.0221 (7)	0.0407 (8)	−0.0009 (6)	0.0116 (6)	−0.0074 (6)
C103	0.0252 (7)	0.0353 (9)	0.0295 (7)	0.0034 (6)	0.0096 (6)	−0.0091 (6)
C104	0.0313 (8)	0.0327 (8)	0.0253 (7)	0.0048 (6)	0.0116 (6)	0.0020 (6)
C105	0.0320 (8)	0.0226 (7)	0.0274 (7)	0.0047 (6)	0.0118 (6)	0.0003 (6)
C150	0.0218 (7)	0.0286 (8)	0.0251 (7)	−0.0006 (6)	0.0073 (6)	−0.0054 (6)
C151	0.0320 (9)	0.0420 (10)	0.0543 (11)	−0.0088 (8)	−0.0021 (8)	0.0141 (9)
C152	0.0385 (10)	0.0521 (12)	0.0673 (13)	−0.0192 (9)	0.0037 (9)	0.0144 (10)
C153	0.0233 (8)	0.0526 (11)	0.0400 (9)	−0.0075 (7)	0.0063 (7)	−0.0086 (8)
C154	0.0235 (8)	0.0570 (11)	0.0298 (8)	0.0043 (7)	0.0068 (6)	0.0027 (7)
C155	0.0244 (7)	0.0438 (9)	0.0302 (8)	0.0010 (7)	0.0102 (6)	0.0054 (7)
C200	0.0191 (6)	0.0251 (7)	0.0229 (7)	−0.0027 (5)	0.0059 (5)	−0.0027 (6)
C201	0.0253 (7)	0.0268 (8)	0.0345 (8)	−0.0044 (6)	0.0120 (6)	−0.0058 (6)
C202	0.0266 (8)	0.0413 (9)	0.0362 (8)	−0.0023 (7)	0.0099 (6)	−0.0164 (7)
C203	0.0267 (8)	0.0623 (11)	0.0223 (7)	−0.0055 (7)	0.0087 (6)	−0.0093 (7)
C204	0.0322 (8)	0.0495 (10)	0.0218 (7)	−0.0082 (7)	0.0075 (6)	0.0026 (7)
C205	0.0291 (7)	0.0294 (8)	0.0221 (7)	−0.0046 (6)	0.0055 (6)	0.0006 (6)
O1	0.0250 (5)	0.0272 (5)	0.0351 (6)	−0.0047 (4)	0.0080 (4)	0.0000 (4)
O2	0.0385 (6)	0.0351 (6)	0.0325 (6)	−0.0149 (5)	0.0119 (5)	−0.0018 (5)

Geometric parameters (Å, º) top

C1—N21	1.3755 (18)	C51—O2	1.4685 (19)
C1—C20	1.3958 (19)	C51—C54	1.514 (3)
C1—C2	1.4317 (19)	C51—C55	1.520 (3)
C2—C3	1.358 (2)	C52—H52A	0.9800
C2—H2	0.9500	C52—H52B	0.9800
C3—C4	1.4382 (19)	C52—H52C	0.9800
C3—H3	0.9500	C53—H53A	0.9800
C4—N21	1.3704 (17)	C53—H53B	0.9800
C4—C5	1.4033 (19)	C53—H53C	0.9800
C5—C6	1.413 (2)	C54—H54A	0.9800
C5—B1	1.573 (2)	C54—H54B	0.9800
C6—N22	1.3641 (18)	C54—H54C	0.9800
C6—C7	1.4549 (19)	C55—H55A	0.9800
C7—C8	1.340 (2)	C55—H55B	0.9800
C7—H7	0.9500	C55—H55C	0.9800
C8—C9	1.4527 (19)	C100—C105	1.393 (2)
C8—H8	0.9500	C100—C101	1.398 (2)
C9—N22	1.3781 (18)	C101—C102	1.389 (2)
C9—C10	1.399 (2)	C101—H101	0.9500
C10—C11	1.4050 (19)	C102—C103	1.387 (2)
C10—C100	1.5007 (19)	C102—H102	0.9500
C11—N23	1.3678 (17)	C103—C104	1.387 (2)
C11—C12	1.428 (2)	C103—H103	0.9500
C12—C13	1.356 (2)	C104—C105	1.390 (2)
C12—H12	0.9500	C104—H104	0.9500
C13—C14	1.428 (2)	C105—H105	0.9500
C13—H13	0.9500	C150—C151	1.385 (2)
C14—N23	1.3734 (18)	C150—C155	1.385 (2)
C14—C15	1.3967 (19)	C151—C152	1.386 (2)
C15—C16	1.405 (2)	C151—H151	0.9500
C15—C150	1.4947 (19)	C152—C153	1.372 (3)
C16—N24	1.3719 (18)	C152—H152	0.9500
C16—C17	1.4454 (19)	C153—C154	1.370 (3)
C17—C18	1.348 (2)	C153—H153	0.9500
C17—H17	0.9500	C154—C155	1.391 (2)
C18—C19	1.4453 (19)	C154—H154	0.9500
C18—H18	0.9500	C155—H155	0.9500
C19—N24	1.3639 (18)	C200—C201	1.394 (2)
C19—C20	1.4151 (19)	C200—C205	1.399 (2)
C20—C200	1.4903 (19)	C201—C202	1.389 (2)
N21—H21	0.8800	C201—H201	0.9500
N23—H23	0.8800	C202—C203	1.382 (3)
B1—O2	1.361 (2)	C202—H202	0.9500
B1—O1	1.368 (2)	C203—C204	1.382 (3)
C50—O1	1.4690 (18)	C203—H203	0.9500
C50—C52	1.509 (2)	C204—C205	1.383 (2)
C50—C53	1.509 (2)	C204—H204	0.9500
C50—C51	1.551 (2)	C205—H205	0.9500

N21—C1—C20	125.69 (12)	C55—C51—C50	112.90 (17)
N21—C1—C2	106.93 (11)	C50—C52—H52A	109.5
C20—C1—C2	127.31 (13)	C50—C52—H52B	109.5
C3—C2—C1	107.97 (12)	H52A—C52—H52B	109.5
C3—C2—H2	126.0	C50—C52—H52C	109.5
C1—C2—H2	126.0	H52A—C52—H52C	109.5
C2—C3—C4	108.31 (12)	H52B—C52—H52C	109.5
C2—C3—H3	125.8	C50—C53—H53A	109.5
C4—C3—H3	125.8	C50—C53—H53B	109.5
N21—C4—C5	126.32 (12)	H53A—C53—H53B	109.5
N21—C4—C3	106.57 (11)	C50—C53—H53C	109.5
C5—C4—C3	127.10 (12)	H53A—C53—H53C	109.5
C4—C5—C6	124.40 (13)	H53B—C53—H53C	109.5
C4—C5—B1	117.32 (12)	C51—C54—H54A	109.5
C6—C5—B1	118.28 (12)	C51—C54—H54B	109.5
N22—C6—C5	127.11 (12)	H54A—C54—H54B	109.5
N22—C6—C7	109.88 (12)	C51—C54—H54C	109.5
C5—C6—C7	122.68 (13)	H54A—C54—H54C	109.5
C8—C7—C6	107.20 (12)	H54B—C54—H54C	109.5
C8—C7—H7	126.4	C51—C55—H55A	109.5
C6—C7—H7	126.4	C51—C55—H55B	109.5
C7—C8—C9	106.89 (12)	H55A—C55—H55B	109.5
C7—C8—H8	126.6	C51—C55—H55C	109.5
C9—C8—H8	126.6	H55A—C55—H55C	109.5
N22—C9—C10	126.00 (12)	H55B—C55—H55C	109.5
N22—C9—C8	109.74 (12)	C105—C100—C101	118.56 (13)
C10—C9—C8	124.26 (12)	C105—C100—C10	121.17 (13)
C9—C10—C11	124.82 (12)	C101—C100—C10	120.22 (13)
C9—C10—C100	119.77 (12)	C102—C101—C100	120.81 (14)
C11—C10—C100	115.40 (12)	C102—C101—H101	119.6
N23—C11—C10	126.31 (13)	C100—C101—H101	119.6
N23—C11—C12	107.04 (12)	C103—C102—C101	119.94 (14)
C10—C11—C12	126.57 (13)	C103—C102—H102	120.0
C13—C12—C11	108.37 (13)	C101—C102—H102	120.0
C13—C12—H12	125.8	C102—C103—C104	119.86 (14)
C11—C12—H12	125.8	C102—C103—H103	120.1
C12—C13—C14	107.71 (13)	C104—C103—H103	120.1
C12—C13—H13	126.1	C103—C104—C105	120.14 (14)
C14—C13—H13	126.1	C103—C104—H104	119.9
N23—C14—C15	125.50 (12)	C105—C104—H104	119.9
N23—C14—C13	107.25 (12)	C104—C105—C100	120.69 (14)
C15—C14—C13	127.24 (13)	C104—C105—H105	119.7
C14—C15—C16	125.32 (13)	C100—C105—H105	119.7
C14—C15—C150	117.61 (12)	C151—C150—C155	118.59 (14)
C16—C15—C150	117.06 (12)	C151—C150—C15	120.70 (13)
N24—C16—C15	126.20 (12)	C155—C150—C15	120.65 (13)
N24—C16—C17	110.36 (12)	C150—C151—C152	120.19 (17)
C15—C16—C17	123.44 (12)	C150—C151—H151	119.9
C18—C17—C16	106.57 (12)	C152—C151—H151	119.9
C18—C17—H17	126.7	C153—C152—C151	120.83 (18)
C16—C17—H17	126.7	C153—C152—H152	119.6
C17—C18—C19	106.92 (12)	C151—C152—H152	119.6
C17—C18—H18	126.5	C154—C153—C152	119.55 (15)
C19—C18—H18	126.5	C154—C153—H153	120.2
N24—C19—C20	126.72 (12)	C152—C153—H153	120.2
N24—C19—C18	110.41 (12)	C153—C154—C155	120.11 (15)
C20—C19—C18	122.80 (12)	C153—C154—H154	119.9
C1—C20—C19	124.57 (12)	C155—C154—H154	119.9
C1—C20—C200	119.18 (12)	C150—C155—C154	120.73 (15)
C19—C20—C200	116.19 (12)	C150—C155—H155	119.6
C4—N21—C1	110.18 (11)	C154—C155—H155	119.6
C4—N21—H21	124.9	C201—C200—C205	118.42 (13)
C1—N21—H21	124.9	C201—C200—C20	122.32 (13)
C6—N22—C9	106.23 (11)	C205—C200—C20	119.13 (13)
C11—N23—C14	109.64 (11)	C202—C201—C200	120.45 (14)
C11—N23—H23	125.2	C202—C201—H201	119.8
C14—N23—H23	125.2	C200—C201—H201	119.8
C19—N24—C16	105.71 (11)	C203—C202—C201	120.33 (15)
O2—B1—O1	113.15 (13)	C203—C202—H202	119.8
O2—B1—C5	122.75 (13)	C201—C202—H202	119.8
O1—B1—C5	124.06 (13)	C202—C203—C204	119.86 (14)
O1—C50—C52	105.50 (12)	C202—C203—H203	120.1
O1—C50—C53	109.19 (13)	C204—C203—H203	120.1
C52—C50—C53	110.02 (14)	C203—C204—C205	120.11 (15)
O1—C50—C51	102.03 (11)	C203—C204—H204	119.9
C52—C50—C51	114.05 (15)	C205—C204—H204	119.9
C53—C50—C51	115.20 (14)	C204—C205—C200	120.80 (15)
O2—C51—C54	108.07 (16)	C204—C205—H205	119.6
O2—C51—C55	106.34 (14)	C200—C205—H205	119.6
C54—C51—C55	111.76 (18)	B1—O1—C50	107.07 (12)
O2—C51—C50	102.37 (11)	B1—O2—C51	107.33 (12)
C54—C51—C50	114.50 (15)

N21—C1—C2—C3	1.93 (15)	C20—C19—N24—C16	−178.05 (13)
C20—C1—C2—C3	−175.19 (13)	C18—C19—N24—C16	−1.13 (15)
C1—C2—C3—C4	−1.34 (16)	C15—C16—N24—C19	−178.43 (13)
C2—C3—C4—N21	0.26 (15)	C17—C16—N24—C19	1.58 (15)
C2—C3—C4—C5	−178.83 (13)	C4—C5—B1—O2	−134.75 (15)
N21—C4—C5—C6	−9.8 (2)	C6—C5—B1—O2	44.7 (2)
C3—C4—C5—C6	169.07 (13)	C4—C5—B1—O1	42.9 (2)
N21—C4—C5—B1	169.59 (13)	C6—C5—B1—O1	−137.66 (14)
C3—C4—C5—B1	−11.5 (2)	O1—C50—C51—O2	27.64 (15)
C4—C5—C6—N22	7.2 (2)	C52—C50—C51—O2	−85.58 (15)
B1—C5—C6—N22	−172.24 (13)	C53—C50—C51—O2	145.78 (14)
C4—C5—C6—C7	−165.55 (13)	O1—C50—C51—C54	144.32 (16)
B1—C5—C6—C7	15.0 (2)	C52—C50—C51—C54	31.1 (2)
N22—C6—C7—C8	−1.82 (17)	C53—C50—C51—C54	−97.5 (2)
C5—C6—C7—C8	172.03 (13)	O1—C50—C51—C55	−86.27 (16)
C6—C7—C8—C9	2.27 (17)	C52—C50—C51—C55	160.50 (15)
C7—C8—C9—N22	−2.08 (17)	C53—C50—C51—C55	31.9 (2)
C7—C8—C9—C10	177.52 (14)	C9—C10—C100—C105	−65.26 (18)
N22—C9—C10—C11	2.9 (2)	C11—C10—C100—C105	113.43 (15)
C8—C9—C10—C11	−176.60 (13)	C9—C10—C100—C101	117.51 (15)
N22—C9—C10—C100	−178.50 (12)	C11—C10—C100—C101	−63.80 (17)
C8—C9—C10—C100	2.0 (2)	C105—C100—C101—C102	−0.2 (2)
C9—C10—C11—N23	−6.4 (2)	C10—C100—C101—C102	177.08 (13)
C100—C10—C11—N23	175.03 (12)	C100—C101—C102—C103	0.0 (2)
C9—C10—C11—C12	169.88 (14)	C101—C102—C103—C104	0.3 (2)
C100—C10—C11—C12	−8.7 (2)	C102—C103—C104—C105	−0.3 (2)
N23—C11—C12—C13	0.46 (17)	C103—C104—C105—C100	0.0 (2)
C10—C11—C12—C13	−176.36 (14)	C101—C100—C105—C104	0.3 (2)
C11—C12—C13—C14	−0.79 (17)	C10—C100—C105—C104	−177.03 (13)
C12—C13—C14—N23	0.82 (16)	C14—C15—C150—C151	105.95 (18)
C12—C13—C14—C15	−178.41 (14)	C16—C15—C150—C151	−73.76 (19)
N23—C14—C15—C16	−2.4 (2)	C14—C15—C150—C155	−77.00 (18)
C13—C14—C15—C16	176.65 (14)	C16—C15—C150—C155	103.29 (16)
N23—C14—C15—C150	177.87 (13)	C155—C150—C151—C152	0.0 (3)
C13—C14—C15—C150	−3.0 (2)	C15—C150—C151—C152	177.07 (18)
C14—C15—C16—N24	−2.8 (2)	C150—C151—C152—C153	−0.5 (3)
C150—C15—C16—N24	176.88 (13)	C151—C152—C153—C154	0.5 (3)
C14—C15—C16—C17	177.18 (14)	C152—C153—C154—C155	0.1 (3)
C150—C15—C16—C17	−3.1 (2)	C151—C150—C155—C154	0.6 (2)
N24—C16—C17—C18	−1.47 (17)	C15—C150—C155—C154	−176.50 (14)
C15—C16—C17—C18	178.55 (14)	C153—C154—C155—C150	−0.7 (3)
C16—C17—C18—C19	0.71 (17)	C1—C20—C200—C201	60.41 (19)
C17—C18—C19—N24	0.24 (17)	C19—C20—C200—C201	−117.00 (15)
C17—C18—C19—C20	177.30 (13)	C1—C20—C200—C205	−123.79 (14)
N21—C1—C20—C19	−0.2 (2)	C19—C20—C200—C205	58.80 (17)
C2—C1—C20—C19	176.38 (13)	C205—C200—C201—C202	−1.1 (2)
N21—C1—C20—C200	−177.40 (12)	C20—C200—C201—C202	174.77 (13)
C2—C1—C20—C200	−0.8 (2)	C200—C201—C202—C203	−0.4 (2)
N24—C19—C20—C1	10.7 (2)	C201—C202—C203—C204	1.1 (2)
C18—C19—C20—C1	−165.86 (13)	C202—C203—C204—C205	−0.2 (2)
N24—C19—C20—C200	−172.05 (13)	C203—C204—C205—C200	−1.4 (2)
C18—C19—C20—C200	11.4 (2)	C201—C200—C205—C204	2.0 (2)
C5—C4—N21—C1	−179.92 (13)	C20—C200—C205—C204	−174.01 (13)
C3—C4—N21—C1	0.98 (15)	O2—B1—O1—C50	11.02 (16)
C20—C1—N21—C4	175.39 (13)	C5—B1—O1—C50	−166.80 (13)
C2—C1—N21—C4	−1.79 (15)	C52—C50—O1—B1	95.52 (14)
C5—C6—N22—C9	−173.02 (13)	C53—C50—O1—B1	−146.28 (13)
C7—C6—N22—C9	0.49 (15)	C51—C50—O1—B1	−23.93 (15)
C10—C9—N22—C6	−178.67 (13)	O1—B1—O2—C51	8.13 (17)
C8—C9—N22—C6	0.92 (15)	C5—B1—O2—C51	−174.01 (13)
C10—C11—N23—C14	176.90 (13)	C54—C51—O2—B1	−143.58 (15)
C12—C11—N23—C14	0.06 (15)	C55—C51—O2—B1	96.28 (17)
C15—C14—N23—C11	178.71 (13)	C50—C51—O2—B1	−22.37 (16)
C13—C14—N23—C11	−0.54 (15)

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the C100–C105 phenyl ring.

D—H···A	D—H	H···A	D···A	D—H···A
N21—H21···N24	0.88	2.35	2.9084 (16)	122
N21—H21···N22	0.88	2.38	2.9266 (16)	121
N23—H23···N24	0.88	2.34	2.8978 (16)	121
N23—H23···N22	0.88	2.35	2.8986 (16)	120
C153—H153···Cg1ⁱ	0.95	2.58	3.488 (2)	160

Symmetry code: (i) x−1, y, z.

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the C100–C105 phenyl ring.

D—H···A	D—H	H···A	D···A	D—H···A
N21—H21···N24	0.88	2.35	2.9084 (16)	121.8
N21—H21···N22	0.88	2.38	2.9266 (16)	120.9
N23—H23···N24	0.88	2.34	2.8978 (16)	121.3
N23—H23···N22	0.88	2.35	2.8986 (16)	120.4
C153—H153···Cg1ⁱ	0.95	2.58	3.488 (2)	160.1

Symmetry code: (i) x−1, y, z.

Acknowledgements

This work was supported by a grant from Science Foundation Ireland (SFI P·I. 09/IN.1/B2650).

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Volume 70| Part 10| October 2014| Pages o1085-o1086

doi:10.1107/S1600536814019680

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Crystal structure of 5,10,15-tri­phenyl-20-(4,4,5,5-tetra­methyl-1,3,2-dioxaborolan-2-yl)porphyrin

1. Related literature

2. Experimental

2.1. Crystal data

2.2. Data collection

2.3. Refinement

Supporting information

Acknowledgements

References

organic compounds

Crystal structure of 5,10,15-triphenyl-20-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)porphyrin