(2,3,7,8,12,13,17,18-Octa-ethyl-porphyrinato-κ(4)N)cobalt(II)-2-nitro-benzaldehyde (1/2).

The asymmetric unit of the title compound, [Co(C(36)H(44)N(4))]·2C(7)H(5)NO(3), is composed of one half of the complex, arranged about an inversion center, and a complete 2-nitro-benzaldehyde (NBA) mol-ecule. The structure consists of columns that contain inter-leaved mol-ecules of NBA and [Co(II)(OEP)] (OEP is 2,3,7,8,12,13,17,18-octa-ethyl-porphyrin), which are stacked along the a axis. The Co(II) atom is involved in a π inter-action with the ring of the NBA mol-ecule with a centroid-metal distance of 3.508 (6) Å. There is an intra-molecular C-H⋯O hydrogen bond in the NBA mol-ecule.

Related literature

For the synthesis, see: Scheidt & Tyrk (1994 ▶). For related structures, see: Olmstead et al. (2003 ▶); Smirnov et al. (1998 ▶); Ben Moussa et al. (2011 ▶); Dhifet et al. (2010 ▶); Ellison et al. (2000 ▶).

Experimental

Crystal data

[Co(C36H44N4)]·2C7H5NO3

M = 893.92

Monoclinic,

a = 10.1952 (11) Å

b = 21.2230 (17) Å

c = 10.1601 (10) Å

β = 100.771 (9)°

V = 2159.6 (4) Å3

Z = 2

Mo Kα radiation

μ = 0.46 mm−1

T = 180 K

0.52 × 0.26 × 0.14 mm

Data collection

Agilent Xcalibur diffractometer

Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012 ▶) T min = 0.797, T max = 0.939

11654 measured reflections

3782 independent reflections

2969 reflections with I > 2σ(I)

R int = 0.038

Refinement

R[F 2 > 2σ(F 2)] = 0.079

wR(F 2) = 0.197

S = 1.13

3782 reflections

272 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.99 e Å−3

Δρmin = −0.45 e Å−3

Data collection: CrysAlis PRO (Agilent, 2012 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; 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: WinGX (Farrugia, 1999 ▶) and SHELXL97.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812036112/gw2124sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812036112/gw2124Isup2.hkl

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

[Co(C36H44N4)]·2C7H5NO3	F(000) = 942
Mr = 893.92	Dx = 1.375 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4505 reflections
a = 10.1952 (11) Å	θ = 3.1–28.3°
b = 21.2230 (17) Å	µ = 0.46 mm−1
c = 10.1601 (10) Å	T = 180 K
β = 100.771 (9)°	Prism, purple
V = 2159.6 (4) Å3	0.52 × 0.26 × 0.14 mm
Z = 2

Agilent Xcalibur Sapphire1 long-nozzle diffractometer	3782 independent reflections
Radiation source: fine-focus sealed tube	2969 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.038
Detector resolution: 8.2632 pixels mm-1	θmax = 25.0°, θmin = 3.2°
ω scans	h = −12→12
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012)	k = −25→22
Tmin = 0.797, Tmax = 0.939	l = −12→11
11654 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)] = 0.079	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.197	H atoms treated by a mixture of independent and constrained refinement
S = 1.13	w = 1/[σ2(Fo2) + (0.0484P)2 + 9.9571P] where P = (Fo2 + 2Fc2)/3
3782 reflections	(Δ/σ)max < 0.001
272 parameters	Δρmax = 0.99 e Å−3
0 restraints	Δρmin = −0.45 e Å−3

Experimental. Absorption correction: empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm. CrysAlisPro (Agilent Technologies,2012)

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 > 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
Co	0.5000	0.0000	1.0000	0.0223 (3)
N1	0.3667 (4)	0.06811 (18)	0.9652 (4)	0.0219 (8)
N2	0.6428 (4)	0.06272 (18)	1.0557 (4)	0.0241 (9)
C1	0.5113 (5)	0.1592 (2)	1.0282 (4)	0.0284 (11)
H1	0.5142	0.2029	1.0362	0.034*
C2	0.8358 (5)	−0.0066 (2)	1.1098 (4)	0.0278 (11)
H2	0.9279	−0.0084	1.1384	0.033*
C11	0.2321 (5)	0.0628 (2)	0.9185 (4)	0.0249 (10)
C12	0.1692 (5)	0.1241 (2)	0.9020 (5)	0.0294 (11)
C13	0.2667 (5)	0.1669 (2)	0.9403 (5)	0.0298 (11)
C14	0.3887 (5)	0.1319 (2)	0.9805 (4)	0.0235 (10)
C21	0.6293 (5)	0.1270 (2)	1.0647 (4)	0.0237 (10)
C22	0.7556 (5)	0.1565 (2)	1.1157 (5)	0.0289 (11)
C23	0.8479 (5)	0.1099 (2)	1.1354 (5)	0.0294 (11)
C24	0.7768 (4)	0.0520 (2)	1.0987 (4)	0.0220 (10)
C121	0.0251 (5)	0.1352 (3)	0.8455 (5)	0.0366 (13)
H12A	−0.0004	0.1764	0.8734	0.044*
H12B	−0.0282	0.1039	0.8813	0.044*
C122	−0.0048 (6)	0.1315 (3)	0.6913 (5)	0.0425 (14)
H12C	0.0467	0.1628	0.6554	0.064*
H12D	−0.0981	0.1390	0.6591	0.064*
H12E	0.0185	0.0905	0.6633	0.064*
C131	0.2557 (5)	0.2373 (2)	0.9361 (5)	0.0356 (12)
H13A	0.3161	0.2549	1.0124	0.043*
H13B	0.1655	0.2494	0.9432	0.043*
C132	0.2888 (7)	0.2648 (3)	0.8080 (7)	0.0515 (16)
H13C	0.3767	0.2516	0.7987	0.077*
H13D	0.2857	0.3099	0.8118	0.077*
H13E	0.2250	0.2501	0.7325	0.077*
C221	0.7747 (5)	0.2255 (2)	1.1470 (5)	0.0346 (12)
H22A	0.7175	0.2497	1.0780	0.041*
H22B	0.8665	0.2369	1.1451	0.041*
C222	0.7430 (6)	0.2430 (3)	1.2831 (6)	0.0454 (15)
H22C	0.6508	0.2341	1.2838	0.068*
H22D	0.7597	0.2871	1.2994	0.068*
H22E	0.7984	0.2189	1.3517	0.068*
C231	0.9941 (5)	0.1149 (3)	1.1924 (5)	0.0351 (12)
H23A	1.0250	0.1567	1.1744	0.042*
H23B	1.0422	0.0847	1.1478	0.042*
C232	1.0261 (3)	0.10290 (19)	1.3431 (2)	0.0475 (15)
H23C	0.9777	0.1323	1.3878	0.071*
H23D	1.1201	0.1082	1.3752	0.071*
H23E	1.0005	0.0607	1.3612	0.071*
N3	0.4262 (3)	0.10463 (13)	0.6484 (2)	0.0731 (19)
O1	0.7932 (3)	0.01832 (13)	0.7585 (2)	0.0880 (18)
O31	0.3191 (3)	0.12778 (13)	0.6159 (2)	0.109 (2)
O32	0.5322 (3)	0.13821 (13)	0.6534 (2)	0.112 (2)
C100	0.4442 (2)	0.03814 (12)	0.6568 (2)	0.0412 (14)
C101	0.5620 (3)	0.00702 (11)	0.7012 (2)	0.0372 (12)
C102	0.5715 (3)	−0.05699 (11)	0.7001 (2)	0.0581 (19)
H102	0.6525	−0.0767	0.7326	0.070*
C103	0.4612 (7)	−0.0916 (3)	0.6509 (6)	0.0528 (16)
H103	0.4679	−0.1352	0.6466	0.063*
C104	0.3390 (6)	−0.0629 (3)	0.6070 (5)	0.0442 (15)
H104	0.2643	−0.0877	0.5766	0.053*
C105	0.3263 (7)	0.0006 (4)	0.6076 (6)	0.0558 (17)
H105	0.2441	0.0197	0.5772	0.067*
C106	0.6934 (6)	0.0416 (4)	0.7524 (6)	0.0517 (17)
H106	0.683 (7)	0.097 (3)	0.732 (6)	0.062*

	U11	U22	U33	U12	U13	U23
Co	0.0218 (5)	0.0259 (5)	0.0186 (4)	−0.0027 (4)	0.0019 (3)	−0.0006 (4)
N1	0.020 (2)	0.029 (2)	0.0165 (18)	−0.0002 (16)	0.0020 (15)	−0.0001 (15)
N2	0.031 (2)	0.030 (2)	0.0122 (18)	−0.0023 (17)	0.0055 (16)	0.0010 (15)
C1	0.036 (3)	0.026 (2)	0.022 (2)	−0.004 (2)	0.002 (2)	0.0014 (19)
C2	0.024 (2)	0.040 (3)	0.019 (2)	−0.004 (2)	0.0026 (18)	0.000 (2)
C11	0.031 (3)	0.030 (3)	0.014 (2)	0.002 (2)	0.0063 (19)	0.0008 (18)
C12	0.031 (3)	0.036 (3)	0.023 (2)	0.008 (2)	0.009 (2)	0.002 (2)
C13	0.033 (3)	0.037 (3)	0.019 (2)	0.005 (2)	0.005 (2)	0.000 (2)
C14	0.022 (3)	0.030 (3)	0.019 (2)	0.0018 (19)	0.0042 (18)	−0.0004 (19)
C21	0.025 (3)	0.029 (3)	0.016 (2)	−0.004 (2)	0.0028 (19)	−0.0007 (18)
C22	0.031 (3)	0.035 (3)	0.021 (2)	−0.012 (2)	0.005 (2)	−0.001 (2)
C23	0.032 (3)	0.039 (3)	0.018 (2)	−0.012 (2)	0.007 (2)	−0.002 (2)
C24	0.018 (2)	0.032 (3)	0.015 (2)	−0.0056 (19)	0.0013 (18)	−0.0001 (18)
C121	0.031 (3)	0.044 (3)	0.035 (3)	0.012 (2)	0.006 (2)	−0.002 (2)
C122	0.039 (3)	0.053 (4)	0.032 (3)	0.007 (3)	−0.003 (2)	0.001 (3)
C131	0.031 (3)	0.036 (3)	0.039 (3)	0.010 (2)	0.005 (2)	−0.003 (2)
C132	0.057 (4)	0.038 (3)	0.061 (4)	0.005 (3)	0.013 (3)	0.011 (3)
C221	0.033 (3)	0.035 (3)	0.035 (3)	−0.017 (2)	0.003 (2)	−0.001 (2)
C222	0.050 (4)	0.042 (3)	0.044 (3)	−0.012 (3)	0.007 (3)	−0.012 (3)
C231	0.026 (3)	0.050 (3)	0.028 (3)	−0.017 (2)	0.002 (2)	−0.003 (2)
C232	0.031 (3)	0.078 (4)	0.029 (3)	−0.008 (3)	−0.005 (2)	−0.001 (3)
N3	0.088 (5)	0.068 (4)	0.067 (4)	0.020 (4)	0.023 (4)	0.003 (3)
O1	0.058 (4)	0.108 (5)	0.094 (4)	−0.016 (3)	0.005 (3)	−0.016 (4)
O31	0.099 (5)	0.085 (4)	0.138 (6)	0.051 (4)	0.005 (4)	0.016 (4)
O32	0.109 (6)	0.104 (5)	0.126 (6)	−0.037 (4)	0.033 (5)	−0.041 (4)
C100	0.052 (4)	0.050 (4)	0.025 (3)	0.008 (3)	0.017 (3)	0.008 (2)
C101	0.047 (3)	0.044 (3)	0.025 (3)	0.008 (3)	0.017 (2)	0.008 (2)
C102	0.088 (6)	0.049 (4)	0.045 (4)	−0.003 (4)	0.033 (4)	0.003 (3)
C103	0.052 (4)	0.069 (4)	0.043 (3)	−0.005 (3)	0.023 (3)	0.005 (3)
C104	0.043 (4)	0.062 (4)	0.029 (3)	−0.023 (3)	0.010 (3)	0.000 (3)
C105	0.060 (4)	0.080 (5)	0.031 (3)	0.001 (4)	0.017 (3)	0.005 (3)
C106	0.028 (3)	0.085 (5)	0.041 (3)	0.006 (3)	0.005 (3)	0.015 (3)

Co—N1	1.970 (4)	C131—H13B	0.9700
Co—N1i	1.970 (4)	C132—H13C	0.9600
Co—N2	1.976 (4)	C132—H13D	0.9600
Co—N2i	1.976 (4)	C132—H13E	0.9600
N1—C11	1.370 (6)	C221—C222	1.524 (8)
N1—C14	1.376 (6)	C221—H22A	0.9700
N2—C24	1.373 (6)	C221—H22B	0.9700
N2—C21	1.376 (6)	C222—H22C	0.9600
C1—C21	1.373 (7)	C222—H22D	0.9600
C1—C14	1.381 (7)	C222—H22E	0.9600
C1—H1	0.9300	C231—C232	1.526 (5)
C2—C24	1.376 (7)	C231—H23A	0.9700
C2—C11i	1.383 (7)	C231—H23B	0.9700
C2—H2	0.9300	C232—H23C	0.9600
C11—C2i	1.383 (7)	C232—H23D	0.9600
C11—C12	1.445 (7)	C232—H23E	0.9600
C12—C13	1.350 (7)	N3—O31	1.1858
C12—C121	1.492 (7)	N3—O32	1.2882
C13—C14	1.441 (7)	N3—C100	1.4235
C13—C131	1.499 (7)	O1—C106	1.123 (7)
C21—C22	1.438 (7)	C100—C101	1.3708
C22—C23	1.353 (7)	C100—C105	1.451 (7)
C22—C221	1.503 (7)	C101—C102	1.3620
C23—C24	1.442 (7)	C101—C106	1.531 (7)
C23—C231	1.499 (7)	C102—C103	1.357 (7)
C121—C122	1.542 (7)	C102—H102	0.9300
C121—H12A	0.9700	C103—C104	1.383 (9)
C121—H12B	0.9700	C103—H103	0.9300
C122—H12C	0.9600	C104—C105	1.354 (9)
C122—H12D	0.9600	C104—H104	0.9300
C122—H12E	0.9600	C105—H105	0.9300
C131—C132	1.520 (8)	C106—H106	1.19 (7)
C131—H13A	0.9700
N1—Co—N1i	180.000 (1)	C13—C131—H13B	109.1
N1—Co—N2	90.21 (16)	C132—C131—H13B	109.1
N1i—Co—N2	89.79 (16)	H13A—C131—H13B	107.9
N1—Co—N2i	89.79 (16)	C131—C132—H13C	109.5
N1i—Co—N2i	90.21 (16)	C131—C132—H13D	109.5
N2—Co—N2i	180.00 (16)	H13C—C132—H13D	109.5
C11—N1—C14	104.5 (4)	C131—C132—H13E	109.5
C11—N1—Co	127.9 (3)	H13C—C132—H13E	109.5
C14—N1—Co	127.5 (3)	H13D—C132—H13E	109.5
C24—N2—C21	104.4 (4)	C22—C221—C222	112.9 (4)
C24—N2—Co	127.9 (3)	C22—C221—H22A	109.0
C21—N2—Co	127.6 (3)	C222—C221—H22A	109.0
C21—C1—C14	125.2 (5)	C22—C221—H22B	109.0
C21—C1—H1	117.4	C222—C221—H22B	109.0
C14—C1—H1	117.4	H22A—C221—H22B	107.8
C24—C2—C11i	124.6 (4)	C221—C222—H22C	109.5
C24—C2—H2	117.7	C221—C222—H22D	109.5
C11i—C2—H2	117.7	H22C—C222—H22D	109.5
N1—C11—C2i	124.9 (4)	C221—C222—H22E	109.5
N1—C11—C12	111.2 (4)	H22C—C222—H22E	109.5
C2i—C11—C12	123.9 (5)	H22D—C222—H22E	109.5
C13—C12—C11	106.6 (5)	C23—C231—C232	112.7 (4)
C13—C12—C121	128.6 (5)	C23—C231—H23A	109.0
C11—C12—C121	124.8 (5)	C232—C231—H23A	109.0
C12—C13—C14	106.5 (4)	C23—C231—H23B	109.0
C12—C13—C131	128.1 (5)	C232—C231—H23B	109.0
C14—C13—C131	125.3 (5)	H23A—C231—H23B	107.8
N1—C14—C1	124.8 (4)	C231—C232—H23C	109.5
N1—C14—C13	111.2 (4)	C231—C232—H23D	109.5
C1—C14—C13	124.0 (4)	H23C—C232—H23D	109.5
C1—C21—N2	124.6 (4)	C231—C232—H23E	109.5
C1—C21—C22	124.1 (4)	H23C—C232—H23E	109.5
N2—C21—C22	111.2 (4)	H23D—C232—H23E	109.5
C23—C22—C21	106.6 (4)	O31—N3—O32	120.2
C23—C22—C221	128.4 (5)	O31—N3—C100	122.0
C21—C22—C221	124.9 (5)	O32—N3—C100	116.6
C22—C23—C24	106.4 (4)	C101—C100—N3	126.4
C22—C23—C231	128.3 (5)	C101—C100—C105	117.9 (3)
C24—C23—C231	125.2 (5)	N3—C100—C105	115.7 (3)
N2—C24—C2	124.8 (4)	C102—C101—C100	122.5
N2—C24—C23	111.3 (4)	C102—C101—C106	115.0 (3)
C2—C24—C23	123.9 (4)	C100—C101—C106	122.5 (3)
C12—C121—C122	112.1 (4)	C103—C102—C101	119.2 (3)
C12—C121—H12A	109.2	C103—C102—H102	120.4
C122—C121—H12A	109.2	C101—C102—H102	120.4
C12—C121—H12B	109.2	C102—C103—C104	121.0 (6)
C122—C121—H12B	109.2	C102—C103—H103	119.5
H12A—C121—H12B	107.9	C104—C103—H103	119.5
C121—C122—H12C	109.5	C105—C104—C103	121.2 (6)
C121—C122—H12D	109.5	C105—C104—H104	119.4
H12C—C122—H12D	109.5	C103—C104—H104	119.4
C121—C122—H12E	109.5	C104—C105—C100	118.3 (6)
H12C—C122—H12E	109.5	C104—C105—H105	120.9
H12D—C122—H12E	109.5	C100—C105—H105	120.9
C13—C131—C132	112.3 (4)	O1—C106—C101	122.3 (7)
C13—C131—H13A	109.1	O1—C106—H106	120 (3)
C132—C131—H13A	109.1	C101—C106—H106	112 (3)

D—H···A	D—H	H···A	D···A	D—H···A
C106—H106···O32	1.19 (7)	1.82 (7)	2.701 (7)	126 (5)

	Cg···Co (Å)	Co-Perp (Å)	Beta (°)
Co···Cg1i	3.508	-3.219	23.39
Co···Cg1ii	3.508	-3.219	23.39

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C106—H106⋯O32	1.19 (7)	1.82 (7)	2.701 (7)	126 (5)