meso-[5,10,15,20-Tetra-kis(4-cyano-phen-yl)porphyrinato]zinc.

In the title compound, [Zn(C(48)H(24)N(8))], the coordination environment of the Zn(2+) ion (site symmetry [Formula: see text]) is octa-hedral, with four indole N atoms forming the equatorial plane and the axial positions being occupied by N atoms from the cyanide groups of neighbouring molecules. In the crystal, adjacent mol-ecules are assembled into a two-dimensional supra-molecular framework parallel to ([Formula: see text]01) via the coodination bonding. Topology analysis reveals this compound to be a (4,4)-connected network.

Related literature

For background to the use of porphyrins and derivatives, see: Jiang & Ng (2009 ▶). For the use of their metal complexes as catalysts, see: Chen et al. (2004 ▶). For Zn—N bond lengths in other Zn(II) porphyrin species, see: Muniappan et al. (2006 ▶). For the synthesis of the ligand, see: Kumar et al. (1998 ▶).

Experimental

Crystal data

[Zn(C48H24N8)]

M = 778.12

Monoclinic,

a = 9.7373 (10) Å

b = 9.4468 (10) Å

c = 21.280 (2) Å

β = 101.229 (2)°

V = 1920.0 (3) Å3

Z = 2

Mo Kα radiation

μ = 0.69 mm−1

T = 295 K

0.30 × 0.05 × 0.05 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1995 ▶) T min = 0.726, T max = 0.967

9272 measured reflections

3376 independent reflections

2610 reflections with I > 2σ(I)

R int = 0.028

Refinement

R[F 2 > 2σ(F 2)] = 0.039

wR(F 2) = 0.109

S = 1.05

3376 reflections

259 parameters

H-atom parameters constrained

Δρmax = 0.34 e Å−3

Δρmin = −0.24 e Å−3

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT-Plus (Bruker, 2001 ▶); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: XP (Sheldrick, 1998 ▶); software used to prepare material for publication: XP.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053681100849X/jh2269sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053681100849X/jh2269Isup2.hkl

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

[Zn(C48H24N8)]	F(000) = 796
Mr = 778.12	Dx = 1.346 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2737 reflections
a = 9.7373 (10) Å	θ = 2.4–25.3°
b = 9.4468 (10) Å	µ = 0.69 mm−1
c = 21.280 (2) Å	T = 295 K
β = 101.229 (2)°	Needle, purple
V = 1920.0 (3) Å3	0.30 × 0.05 × 0.05 mm
Z = 2

Bruker SMART APEX CCD area-detector diffractometer	3376 independent reflections
Radiation source: fine-focus sealed tube	2610 reflections with I > 2σ(I)
graphite	Rint = 0.028
Detector resolution: 0 pixels mm-1	θmax = 25.0°, θmin = 2.0°
ω scans	h = −10→11
Absorption correction: multi-scan (SADABS; Sheldrick, 1995)	k = −11→11
Tmin = 0.726, Tmax = 0.967	l = −22→25
9272 measured reflections

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) = 0.109	H-atom parameters constrained
S = 1.05	w = 1/[σ2(Fo2) + (0.0599P)2 + 0.3654P] where P = (Fo2 + 2Fc2)/3
3376 reflections	(Δ/σ)max = 0.001
259 parameters	Δρmax = 0.34 e Å−3
0 restraints	Δρmin = −0.24 e Å−3

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
Zn1	1.0000	0.0000	1.0000	0.03997 (16)
N2	0.9529 (2)	0.0662 (2)	1.08533 (8)	0.0377 (5)
C5	1.0664 (3)	−0.1265 (3)	1.15417 (10)	0.0382 (6)
C10	0.8349 (2)	0.2917 (3)	1.04962 (11)	0.0379 (6)
N1	1.0918 (2)	−0.1781 (2)	1.04326 (8)	0.0370 (5)
C4	1.1139 (3)	−0.2084 (3)	1.10731 (11)	0.0388 (6)
C16	1.0114 (3)	−0.2648 (3)	1.24674 (12)	0.0565 (7)
H16	0.9250	−0.2874	1.2216	0.068*
C13	1.2649 (3)	−0.1964 (3)	1.32212 (13)	0.0590 (8)
H13	1.3505	−0.1722	1.3475	0.071*
C9	0.8856 (3)	0.1885 (3)	1.09594 (11)	0.0399 (6)
C14	1.1741 (3)	−0.2811 (3)	1.34609 (11)	0.0487 (7)
C18	0.6411 (3)	0.3997 (3)	1.09533 (13)	0.0508 (7)
H18	0.6022	0.3099	1.0958	0.061*
C11	1.1027 (3)	−0.1798 (3)	1.22180 (10)	0.0390 (6)
N3	1.2522 (4)	−0.3731 (3)	1.46169 (12)	0.0859 (9)
C20	0.6318 (3)	0.6457 (3)	1.11635 (13)	0.0542 (7)
C8	0.8808 (3)	0.1975 (3)	1.16333 (12)	0.0516 (7)
H8	0.8407	0.2701	1.1832	0.062*
C12	1.2296 (3)	−0.1464 (3)	1.26005 (12)	0.0535 (7)
H12	1.2924	−0.0895	1.2439	0.064*
C23	0.7632 (3)	0.4171 (3)	1.07089 (11)	0.0397 (6)
C21	0.7496 (3)	0.6674 (3)	1.09048 (12)	0.0539 (7)
H21	0.7846	0.7584	1.0880	0.065*
C6	0.9912 (3)	−0.0002 (2)	1.14336 (11)	0.0386 (6)
C17	1.2141 (4)	−0.3342 (3)	1.41096 (13)	0.0638 (8)
C22	0.8154 (3)	0.5528 (3)	1.06823 (12)	0.0474 (6)
H22	0.8955	0.5673	1.0514	0.057*
C24	0.5695 (4)	0.7637 (4)	1.14423 (19)	0.0853 (11)
C19	0.5774 (3)	0.5122 (3)	1.11873 (15)	0.0558 (7)
H19	0.4980	0.4981	1.1361	0.067*
C7	0.9447 (3)	0.0823 (3)	1.19189 (11)	0.0503 (7)
H7	0.9568	0.0599	1.2352	0.060*
C15	1.0462 (3)	−0.3172 (3)	1.30882 (13)	0.0585 (8)
H15	0.9844	−0.3756	1.3250	0.070*
C1	1.1545 (3)	−0.2842 (3)	1.01528 (11)	0.0390 (6)
C2	1.2155 (3)	−0.3853 (3)	1.06340 (12)	0.0498 (7)
H2	1.2628	−0.4678	1.0567	0.060*
C3	1.1911 (3)	−0.3379 (3)	1.11993 (12)	0.0500 (7)
H3	1.2191	−0.3810	1.1597	0.060*
N4	0.5198 (5)	0.8532 (4)	1.1673 (2)	0.1405 (17)

	U11	U22	U33	U12	U13	U23
Zn1	0.0588 (3)	0.0366 (3)	0.0254 (2)	0.01046 (19)	0.01037 (17)	0.00220 (16)
N2	0.0477 (12)	0.0378 (11)	0.0285 (10)	0.0083 (10)	0.0098 (9)	0.0020 (9)
C5	0.0476 (14)	0.0389 (14)	0.0275 (12)	0.0001 (11)	0.0061 (10)	0.0028 (10)
C10	0.0418 (13)	0.0395 (14)	0.0324 (12)	0.0046 (11)	0.0075 (10)	−0.0015 (10)
N1	0.0479 (12)	0.0367 (11)	0.0263 (9)	0.0073 (9)	0.0070 (8)	−0.0001 (8)
C4	0.0497 (14)	0.0358 (13)	0.0297 (12)	0.0037 (11)	0.0048 (10)	0.0021 (10)
C16	0.0678 (19)	0.0610 (18)	0.0364 (14)	−0.0128 (15)	−0.0002 (13)	0.0056 (13)
C13	0.0562 (17)	0.076 (2)	0.0393 (15)	0.0041 (16)	−0.0047 (13)	0.0030 (14)
C9	0.0471 (14)	0.0415 (14)	0.0319 (12)	0.0050 (11)	0.0097 (10)	−0.0008 (10)
C14	0.0720 (19)	0.0447 (15)	0.0280 (12)	0.0195 (14)	0.0063 (13)	0.0003 (11)
C18	0.0547 (16)	0.0402 (15)	0.0610 (17)	0.0013 (13)	0.0195 (13)	−0.0009 (13)
C11	0.0523 (15)	0.0365 (13)	0.0277 (12)	0.0063 (11)	0.0068 (11)	0.0001 (10)
N3	0.129 (3)	0.088 (2)	0.0374 (14)	0.0310 (19)	0.0062 (15)	0.0121 (14)
C20	0.0636 (18)	0.0475 (17)	0.0531 (17)	0.0133 (14)	0.0152 (14)	−0.0054 (13)
C8	0.0727 (18)	0.0519 (17)	0.0327 (13)	0.0172 (14)	0.0168 (13)	−0.0011 (12)
C12	0.0564 (17)	0.0639 (19)	0.0394 (14)	−0.0039 (14)	0.0075 (13)	0.0074 (13)
C23	0.0472 (14)	0.0391 (15)	0.0315 (12)	0.0068 (11)	0.0049 (10)	−0.0009 (11)
C21	0.075 (2)	0.0362 (15)	0.0485 (16)	−0.0011 (14)	0.0061 (14)	−0.0061 (12)
C6	0.0490 (14)	0.0399 (14)	0.0270 (11)	0.0027 (11)	0.0076 (10)	0.0011 (10)
C17	0.092 (2)	0.0591 (19)	0.0392 (16)	0.0252 (17)	0.0088 (15)	0.0042 (14)
C22	0.0531 (16)	0.0479 (15)	0.0417 (14)	0.0013 (13)	0.0102 (12)	−0.0025 (12)
C24	0.105 (3)	0.050 (2)	0.111 (3)	0.0098 (19)	0.047 (2)	−0.013 (2)
C19	0.0550 (17)	0.0512 (18)	0.0669 (19)	0.0081 (14)	0.0254 (14)	−0.0049 (14)
C7	0.0736 (19)	0.0507 (17)	0.0288 (13)	0.0152 (14)	0.0149 (12)	0.0045 (12)
C15	0.085 (2)	0.0498 (17)	0.0425 (15)	−0.0079 (16)	0.0159 (15)	0.0093 (13)
C1	0.0441 (14)	0.0393 (14)	0.0330 (12)	0.0067 (11)	0.0061 (11)	0.0006 (10)
C2	0.0650 (18)	0.0457 (15)	0.0378 (14)	0.0208 (13)	0.0077 (12)	0.0026 (12)
C3	0.0685 (18)	0.0485 (16)	0.0310 (13)	0.0172 (14)	0.0049 (12)	0.0081 (11)
N4	0.181 (4)	0.070 (2)	0.197 (4)	0.024 (3)	0.101 (3)	−0.036 (3)

Zn1—N1i	2.0391 (19)	C18—C19	1.372 (4)
Zn1—N1	2.0391 (19)	C18—C23	1.396 (4)
Zn1—N2	2.0546 (18)	C18—H18	0.9300
Zn1—N2i	2.0546 (18)	C11—C12	1.377 (4)
Zn1—N3ii	2.675 (2)	N3—C17	1.132 (3)
Zn1—N3iii	2.675 (2)	C20—C19	1.372 (4)
N2—C9	1.369 (3)	C20—C21	1.381 (4)
N2—C6	1.370 (3)	C20—C24	1.450 (4)
C5—C6	1.396 (3)	C8—C7	1.339 (4)
C5—C4	1.409 (3)	C8—H8	0.9300
C5—C11	1.501 (3)	C12—H12	0.9300
C10—C9	1.406 (3)	C23—C22	1.384 (4)
C10—C1i	1.406 (3)	C21—C22	1.387 (4)
C10—C23	1.490 (3)	C21—H21	0.9300
N1—C4	1.368 (3)	C6—C7	1.435 (3)
N1—C1	1.368 (3)	C22—H22	0.9300
C4—C3	1.434 (3)	C24—N4	1.134 (4)
C16—C11	1.379 (4)	C19—H19	0.9300
C16—C15	1.390 (4)	C7—H7	0.9300
C16—H16	0.9300	C15—H15	0.9300
C13—C14	1.363 (4)	C1—C10i	1.406 (3)
C13—C12	1.382 (4)	C1—C2	1.441 (3)
C13—H13	0.9300	C2—C3	1.348 (3)
C9—C8	1.446 (3)	C2—H2	0.9300
C14—C15	1.383 (4)	C3—H3	0.9300
C14—C17	1.449 (4)
N1i—Zn1—N1	180.000 (1)	C19—C20—C24	119.7 (3)
N1i—Zn1—N2	89.67 (7)	C21—C20—C24	119.7 (3)
N1—Zn1—N2	90.33 (7)	C7—C8—C9	107.5 (2)
N1i—Zn1—N2i	90.33 (7)	C7—C8—H8	126.3
N1—Zn1—N2i	89.67 (7)	C9—C8—H8	126.3
N2—Zn1—N2i	180.000 (1)	C11—C12—C13	121.0 (3)
C9—N2—C6	106.99 (18)	C11—C12—H12	119.5
C9—N2—Zn1	126.80 (15)	C13—C12—H12	119.5
C6—N2—Zn1	126.09 (16)	C22—C23—C18	118.1 (2)
C6—C5—C4	125.9 (2)	C22—C23—C10	121.7 (2)
C6—C5—C11	117.6 (2)	C18—C23—C10	120.2 (2)
C4—C5—C11	116.5 (2)	C20—C21—C22	119.6 (3)
C9—C10—C1i	124.8 (2)	C20—C21—H21	120.2
C9—C10—C23	117.4 (2)	C22—C21—H21	120.2
C1i—C10—C23	117.8 (2)	N2—C6—C5	125.5 (2)
C4—N1—C1	106.49 (18)	N2—C6—C7	109.4 (2)
C4—N1—Zn1	126.31 (16)	C5—C6—C7	125.1 (2)
C1—N1—Zn1	126.96 (15)	N3—C17—C14	176.4 (4)
N1—C4—C5	125.5 (2)	C23—C22—C21	120.7 (3)
N1—C4—C3	109.9 (2)	C23—C22—H22	119.6
C5—C4—C3	124.6 (2)	C21—C22—H22	119.6
C11—C16—C15	121.2 (3)	N4—C24—C20	177.9 (4)
C11—C16—H16	119.4	C20—C19—C18	119.6 (3)
C15—C16—H16	119.4	C20—C19—H19	120.2
C14—C13—C12	120.0 (3)	C18—C19—H19	120.2
C14—C13—H13	120.0	C8—C7—C6	107.4 (2)
C12—C13—H13	120.0	C8—C7—H7	126.3
N2—C9—C10	125.7 (2)	C6—C7—H7	126.3
N2—C9—C8	108.8 (2)	C14—C15—C16	118.9 (3)
C10—C9—C8	125.4 (2)	C14—C15—H15	120.6
C13—C14—C15	120.5 (2)	C16—C15—H15	120.6
C13—C14—C17	119.1 (3)	N1—C1—C10i	126.1 (2)
C15—C14—C17	120.4 (3)	N1—C1—C2	109.5 (2)
C19—C18—C23	121.4 (3)	C10i—C1—C2	124.4 (2)
C19—C18—H18	119.3	C3—C2—C1	107.1 (2)
C23—C18—H18	119.3	C3—C2—H2	126.5
C12—C11—C16	118.5 (2)	C1—C2—H2	126.5
C12—C11—C5	120.5 (2)	C2—C3—C4	107.1 (2)
C16—C11—C5	121.0 (2)	C2—C3—H3	126.5
C19—C20—C21	120.5 (3)	C4—C3—H3	126.5