Bis(isocyanato-κN)bis­(1,10-phenanthroline-κ²N,N′)cobalt(II)

In the title complex, [Co(NCO)₂(C₁₂H₈N₂)₂], the Co^II atom, lying on a twofold rotation axis, is coordinated in a distorted octa­hedral environment by four N atoms from two chelating phenanthroline ligands and two N atoms from two isocyanate ligands in cis positions.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.044
• wR factor = 0.144
• Data-to-parameter ratio = 11.9

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT230_ALERT_2_C Hirshfeld Test Diff for    C3     --  C4      ..       5.82 su
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C13
PLAT927_ALERT_1_C Reported and Calculated  wR2 * 100.0 Differ by .      -0.11

Alert level G
PLAT333_ALERT_2_G Check Large Av C6-Ring C-C Dist. C4     -C12           1.41 Ang.
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported   _diffrn_ambient_temperature        293 K

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   3 ALERT level C = Check and explain
   3 ALERT level G = General alerts; check

   3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   3 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
   0 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

As has been known for a very long time, 1,10-phenanthroline (phen) is a good bidentate chelating ligand, and has been widely introduced into the transition metal complexes. Here, we present a new six-coordinated cobalt(II) complex based on phen.

The molecular structure of the title compound is shown in Fig. 1. The coordination geometry of the Co^II ion is distorted octahedral, in which four positions are occupied by four N atoms of two chelating phen ligands and the other two occupied by two N atoms of two isocyanate ligands at a cis position. The Co—N_phen and Co—N_isocyanate bond lengths are 2.168 (2), 2.223 (3) and 2.058 (3) Å (Table 1), respectively, which are all comparable to those found in other bis(phen)cobalt(II) complexes (Cheng & Hu, 2003; He et al., 2004; Yin, 2007).

Related literature

For related structures, see: Cheng & Hu (2003); He et al. (2004); Yin (2007).

S2. Experimental

To a solution of 1,10-phenanthroline monohydrate (39.6 mg, 0.2 mmol) dissolved in methanol (15 ml) was added Co(ClO₄)₂.6H₂O (36.6 mg, 0.1 mmol). The mixture was stirred for 5 min before NaNCO (13 mg, 0.2 mmol) was added. After the stirring process was continued for an additional 5 min, the mixture was filtered, and the filtrate was allowed to slow evaporate to afford orange-yellow crystals suitable for X-ray diffraction with a yield about 55%.

S3. Refinement

H atoms were positioned geometrically and refined as riding atoms, with C—H = 0.93 Å and with U_iso(H) = 1.2U_eq(C).

Computing details

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT-Plus (Bruker, 2007); data reduction: SAINT-Plus (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures

Fig. 1. The molecular structure of the title compound. Displacement ellipsoids are drawn at the 30% probability level. H atoms are omitted for clarity. [Symmetry code: (i) 1-x, y, 3/2-z.]

Bis(isocyanato-κN)bis(1,10-phenanthroline- κ²N,N')cobalt(II)

Crystal data

[Co(CNO)2(C12H8N2)2]	F(000) = 1028
Mr = 503.38	Dx = 1.556 Mg m^−3
Orthorhombic, Pbcn	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2n 2ab	Cell parameters from 1231 reflections
a = 13.2317 (8) Å	θ = 2.6–27.0°
b = 9.7095 (6) Å	µ = 0.84 mm^−1
c = 16.7265 (10) Å	T = 293 K
V = 2148.9 (2) Å^3	Block, orange-yellow
Z = 4	0.27 × 0.25 × 0.18 mm

Data collection

Bruker APEXII CCD diffractometer	1890 independent reflections
Radiation source: fine-focus sealed tube	1553 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.023
φ and ω scans	θmax = 25.0°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −15→15
Tmin = 0.805, Tmax = 0.864	k = −7→11
9949 measured reflections	l = −19→19

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.144	H-atom parameters constrained
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0851P)^2 + 1.8714P] where P = (Fo^2 + 2Fc^2)/3
1890 reflections	(Δ/σ)max = 0.001
159 parameters	Δρmax = 0.70 e Å^−3
0 restraints	Δρmin = −0.62 e Å^−3

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

	x	y	z	Uiso*/Ueq
Co1	0.5000	0.18820 (5)	0.7500	0.0357 (2)
O1	0.3547 (3)	0.4750 (4)	0.9117 (2)	0.1113 (12)
N1	0.34514 (17)	0.1463 (3)	0.71529 (15)	0.0407 (6)
N2	0.51307 (17)	0.0223 (3)	0.65894 (15)	0.0402 (6)
N3	0.4590 (2)	0.3270 (3)	0.83709 (18)	0.0551 (7)
C1	0.2633 (3)	0.2026 (4)	0.7466 (2)	0.0519 (9)
H1	0.2713	0.2725	0.7841	0.062*
C2	0.1656 (3)	0.1624 (4)	0.7262 (3)	0.0636 (10)
H2	0.1099	0.2033	0.7503	0.076*
C3	0.1531 (3)	0.0611 (4)	0.6696 (3)	0.0694 (11)
H3	0.0886	0.0323	0.6553	0.083*
C4	0.2379 (2)	0.0016 (3)	0.6335 (2)	0.0507 (8)
C5	0.2324 (3)	−0.1020 (4)	0.5729 (3)	0.0721 (11)
H5	0.1695	−0.1280	0.5532	0.086*
C6	0.3168 (3)	−0.1634 (4)	0.5432 (2)	0.0705 (11)
H6	0.3108	−0.2326	0.5050	0.085*
C7	0.4141 (3)	−0.1225 (4)	0.5701 (2)	0.0581 (9)
C8	0.5032 (3)	−0.1852 (5)	0.5447 (3)	0.0720 (14)
H8	0.5003	−0.2574	0.5082	0.086*
C9	0.5947 (3)	−0.1417 (5)	0.5727 (2)	0.0759 (12)
H9	0.6545	−0.1807	0.5542	0.091*
C10	0.5961 (3)	−0.0358 (4)	0.6307 (2)	0.0548 (8)
H10	0.6583	−0.0057	0.6499	0.066*
C11	0.4227 (2)	−0.0189 (3)	0.62939 (17)	0.0402 (7)
C12	0.3333 (2)	0.0450 (3)	0.65996 (17)	0.0410 (7)
C13	0.4114 (3)	0.4017 (4)	0.8731 (2)	0.0548 (8)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.0293 (4)	0.0381 (4)	0.0396 (4)	0.000	−0.0021 (2)	0.000
O1	0.112 (3)	0.117 (3)	0.105 (3)	0.031 (2)	0.026 (2)	−0.026 (2)
N1	0.0337 (13)	0.0439 (13)	0.0446 (14)	−0.0007 (11)	−0.0062 (11)	0.0051 (11)
N2	0.0395 (13)	0.0402 (14)	0.0409 (13)	0.0017 (10)	−0.0029 (10)	−0.0013 (11)
N3	0.0524 (17)	0.0535 (16)	0.0593 (17)	0.0016 (13)	0.0047 (15)	−0.0093 (14)
C1	0.0381 (19)	0.055 (2)	0.062 (2)	0.0014 (15)	−0.0010 (13)	−0.0053 (15)
C2	0.0308 (17)	0.068 (2)	0.092 (3)	−0.0021 (16)	0.0034 (18)	0.002 (2)
C3	0.0423 (19)	0.071 (2)	0.095 (3)	−0.0157 (18)	−0.0190 (19)	0.004 (2)
C4	0.0464 (18)	0.0461 (17)	0.0598 (19)	−0.0053 (14)	−0.0155 (15)	0.0057 (15)
C5	0.065 (2)	0.071 (2)	0.080 (3)	−0.020 (2)	−0.032 (2)	−0.004 (2)
C6	0.080 (3)	0.064 (2)	0.067 (2)	−0.015 (2)	−0.021 (2)	−0.0126 (19)
C7	0.070 (2)	0.058 (2)	0.0467 (18)	−0.0031 (18)	−0.0113 (17)	−0.0070 (16)
C8	0.073 (3)	0.081 (3)	0.062 (3)	0.0094 (19)	−0.0093 (18)	−0.032 (2)
C9	0.073 (3)	0.095 (3)	0.060 (2)	0.021 (2)	0.000 (2)	−0.030 (2)
C10	0.0512 (19)	0.060 (2)	0.0529 (19)	0.0070 (16)	−0.0040 (15)	−0.0139 (16)
C11	0.0435 (16)	0.0374 (15)	0.0398 (15)	−0.0038 (12)	−0.0097 (13)	0.0058 (12)
C12	0.0440 (16)	0.0365 (14)	0.0426 (15)	−0.0042 (12)	−0.0106 (13)	0.0112 (12)
C13	0.055 (2)	0.0567 (19)	0.0525 (19)	0.0017 (17)	0.0092 (16)	−0.0045 (16)

Geometric parameters (Å, º)

Co1—N1	2.168 (2)	C4—C12	1.403 (4)
Co1—N2	2.223 (3)	C4—C5	1.430 (5)
Co1—N3	2.058 (3)	C5—C6	1.360 (6)
O1—C13	1.220 (4)	C5—H5	0.9300
N1—C1	1.321 (5)	C6—C7	1.420 (5)
N1—C12	1.359 (4)	C6—H6	0.9300
N2—C10	1.322 (4)	C7—C8	1.394 (5)
N2—C11	1.354 (4)	C7—C11	1.418 (5)
N3—C13	1.133 (4)	C8—C9	1.365 (6)
C1—C2	1.393 (5)	C8—H8	0.9300
C1—H1	0.9300	C9—C10	1.414 (5)
C2—C3	1.374 (6)	C9—H9	0.9300
C2—H2	0.9300	C10—H10	0.9300
C3—C4	1.399 (5)	C11—C12	1.430 (4)
C3—H3	0.9300
N3^i—Co1—N3	98.13 (17)	C4—C3—H3	120.1
N3^i—Co1—N1	100.52 (11)	C3—C4—C12	117.5 (3)
N3—Co1—N1	93.64 (11)	C3—C4—C5	123.8 (3)
N3^i—Co1—N1^i	93.64 (11)	C12—C4—C5	118.7 (3)
N3—Co1—N1^i	100.52 (11)	C6—C5—C4	121.7 (3)
N1—Co1—N1^i	158.36 (13)	C6—C5—H5	119.2
N3^i—Co1—N2	88.23 (11)	C4—C5—H5	119.2
N3—Co1—N2	168.55 (10)	C5—C6—C7	120.4 (4)
N1—Co1—N2	75.76 (9)	C5—C6—H6	119.8
N1^i—Co1—N2	88.51 (9)	C7—C6—H6	119.8
N3^i—Co1—N2^i	168.55 (10)	C8—C7—C11	117.1 (3)
N3—Co1—N2^i	88.23 (11)	C8—C7—C6	123.3 (3)
N1—Co1—N2^i	88.51 (9)	C11—C7—C6	119.5 (4)
N1^i—Co1—N2^i	75.76 (9)	C9—C8—C7	120.7 (4)
N2—Co1—N2^i	87.17 (13)	C9—C8—H8	119.6
C1—N1—C12	118.3 (3)	C7—C8—H8	119.6
C1—N1—Co1	126.2 (2)	C8—C9—C10	118.2 (4)
C12—N1—Co1	115.26 (19)	C8—C9—H9	120.9
C10—N2—C11	118.5 (3)	C10—C9—H9	120.9
C10—N2—Co1	128.2 (2)	N2—C10—C9	123.0 (3)
C11—N2—Co1	113.28 (19)	N2—C10—H10	118.5
C13—N3—Co1	160.3 (3)	C9—C10—H10	118.5
N1—C1—C2	123.2 (3)	N2—C11—C7	122.4 (3)
N1—C1—H1	118.4	N2—C11—C12	118.1 (3)
C2—C1—H1	118.4	C7—C11—C12	119.5 (3)
C3—C2—C1	118.7 (4)	N1—C12—C4	122.4 (3)
C3—C2—H2	120.6	N1—C12—C11	117.5 (2)
C1—C2—H2	120.6	C4—C12—C11	120.1 (3)
C2—C3—C4	119.8 (3)	N3—C13—O1	175.3 (4)
C2—C3—H3	120.1

Symmetry code: (i) −x+1, y, −z+3/2.