Di­azido­bis(1,10-phenathroline)­cobalt(III) nitrate

The Co atom and nitrate anion in the title compound, [Co(C₁₂H₈N₂)₂(N₃)₂]NO₃, are each disposed about a twofold axis of symmetry. The Co atom exists in a distorted octahedral geometry, with the azide ligands cis to each other.

Key indicators

• Single-crystal X-ray study
• T = 223 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.033
• wR factor = 0.082
• Data-to-parameter ratio = 18.0

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


 Alert Level C:



ABSTM_02  Alert C The ratio of expected to reported Tmax/Tmin(RR') is < 0.90
          Tmin and Tmax reported:      0.739     0.960
          Tmin' and Tmax expected:      0.822     0.959
          RR' =      0.898
          Please check that your absorption correction is appropriate.

General Notes



REFLT_03
         From the CIF: _diffrn_reflns_theta_max           30.00
         From the CIF: _reflns_number_total               3200
         Count of symmetry unique reflns         1689
         Completeness (_total/calc)            189.46%
         TEST3: Check Friedels for noncentro structure
         Estimate of Friedel pairs measured      1511
         Fraction of Friedel pairs measured     0.895
         Are heavy atom types Z>Si present          yes
          Please check that the estimate of the number of Friedel pairs is
          correct. If it is not, please give the correct count in the
          _publ_section_exptl_refinement section of the submitted CIF.


 0 Alert Level A = Potentially serious problem

 0 Alert Level B = Potential problem

 1 Alert Level C = Please check

---

Computing details

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SHELXTL (Bruker, 2000); program(s) used to solve structure: PATTY in DIRDIF92 (Beurskens et al., 1992); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97.

(I)

Crystal data

[Co(C12H8N2)2(N3)2]NO3	F(000) = 1152
Mr = 565.41	Dx = 1.686 Mg m^−3
Orthorhombic, Iba2	Mo Kα radiation, λ = 0.71069 Å
Hall symbol: I 2 -2c	Cell parameters from 3743 reflections
a = 15.4858 (6) Å	θ = 2.5–29.0°
b = 9.7359 (4) Å	µ = 0.83 mm^−1
c = 14.7769 (8) Å	T = 223 K
V = 2227.89 (17) Å^3	Block, brown
Z = 4	0.23 × 0.23 × 0.05 mm

Data collection

Bruker AXS SMART CCD diffractometer	3200 independent reflections
Radiation source: fine-focus sealed tube	2868 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.037
ω scans	θmax = 30.0°, θmin = 2.5°
Absorption correction: multi-scan (SADABS, Bruker, 2000; Blessing, 1995)	h = −16→21
Tmin = 0.739, Tmax = 0.960	k = −13→11
8877 measured reflections	l = −20→20

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.033	H-atom parameters constrained
wR(F^2) = 0.082	w = 1/[σ^2(Fo^2) + (0.0514P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.00	(Δ/σ)max < 0.001
3200 reflections	Δρmax = 0.56 e Å^−3
178 parameters	Δρmin = −0.25 e Å^−3
1 restraint	Absolute structure: Flack (1983), 0000 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.033 (14)

Special details

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.

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

	x	y	z	Uiso*/Ueq
Co	0.0000	0.0000	−0.00392 (3)	0.01734 (8)
O1	−0.5000	0.0000	−0.5083 (3)	0.0612 (8)
O2	−0.56843 (13)	−0.0141 (2)	−0.38222 (17)	0.0564 (6)
N1	−0.03337 (12)	−0.13482 (19)	0.08542 (13)	0.0275 (4)
N2	−0.08184 (10)	−0.10418 (18)	0.14527 (10)	0.0254 (3)
N3	−0.12953 (15)	−0.0837 (2)	0.20354 (14)	0.0444 (5)
N4	0.11657 (8)	−0.07178 (13)	−0.00368 (13)	0.0200 (3)
N5	0.04371 (10)	0.12165 (17)	−0.09839 (10)	0.0203 (3)
N6	−0.5000	0.0000	−0.4248 (2)	0.0349 (6)
C1	0.14995 (12)	−0.1709 (2)	0.04744 (13)	0.0258 (4)
H1	0.1131	−0.2253	0.0831	0.031*
C2	0.23908 (13)	−0.1956 (2)	0.04898 (14)	0.0292 (4)
H2	0.2614	−0.2648	0.0866	0.035*
C3	0.29422 (10)	−0.11938 (19)	−0.00410 (16)	0.0275 (3)
H3	0.3541	−0.1348	−0.0022	0.033*
C4	0.25943 (12)	−0.01814 (19)	−0.06115 (16)	0.0245 (4)
C5	0.17009 (12)	0.00255 (17)	−0.05818 (14)	0.0205 (3)
C6	0.13025 (11)	0.10457 (18)	−0.11180 (12)	0.0207 (3)
C7	0.17810 (12)	0.1817 (2)	−0.17410 (13)	0.0244 (4)
C8	0.13255 (13)	0.2782 (2)	−0.22603 (13)	0.0278 (4)
H8	0.1616	0.3322	−0.2691	0.033*
C9	0.04523 (14)	0.2931 (2)	−0.21343 (14)	0.0288 (4)
H9	0.0140	0.3563	−0.2486	0.035*
C10	0.00285 (11)	0.2142 (2)	−0.14820 (15)	0.0246 (4)
H10	−0.0567	0.2271	−0.1394	0.030*
C11	0.30841 (12)	0.0648 (2)	−0.12395 (16)	0.0309 (4)
H11	0.3687	0.0541	−0.1270	0.037*
C12	0.26935 (14)	0.1572 (2)	−0.17825 (15)	0.0317 (4)
H12	0.3029	0.2070	−0.2200	0.038*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co	0.01613 (13)	0.01956 (14)	0.01633 (13)	0.00045 (10)	0.000	0.000
O1	0.0437 (13)	0.103 (2)	0.0365 (14)	0.0159 (12)	0.000	0.000
O2	0.0390 (10)	0.0718 (15)	0.0584 (14)	0.0093 (9)	0.0117 (10)	0.0319 (10)
N1	0.0288 (8)	0.0280 (9)	0.0258 (9)	0.0019 (7)	0.0050 (7)	0.0059 (7)
N2	0.0276 (8)	0.0249 (8)	0.0238 (8)	−0.0028 (6)	0.0015 (6)	0.0037 (6)
N3	0.0540 (12)	0.0436 (11)	0.0355 (11)	0.0025 (10)	0.0213 (9)	0.0042 (9)
N4	0.0185 (6)	0.0224 (7)	0.0191 (6)	0.0001 (5)	−0.0008 (7)	0.0007 (7)
N5	0.0218 (8)	0.0210 (8)	0.0182 (8)	−0.0014 (6)	−0.0005 (6)	−0.0009 (6)
N6	0.0341 (14)	0.0342 (15)	0.0364 (15)	0.0090 (10)	0.000	0.000
C1	0.0269 (9)	0.0275 (10)	0.0230 (9)	0.0035 (7)	−0.0019 (7)	0.0024 (7)
C2	0.0290 (9)	0.0321 (10)	0.0266 (9)	0.0072 (8)	−0.0067 (8)	−0.0013 (8)
C3	0.0195 (7)	0.0304 (9)	0.0325 (9)	0.0043 (6)	−0.0047 (9)	−0.0095 (10)
C4	0.0176 (8)	0.0256 (10)	0.0304 (10)	−0.0024 (6)	0.0004 (7)	−0.0087 (7)
C5	0.0190 (8)	0.0207 (8)	0.0219 (8)	−0.0012 (6)	0.0002 (6)	−0.0044 (6)
C6	0.0210 (7)	0.0211 (8)	0.0198 (8)	−0.0036 (7)	0.0008 (6)	−0.0030 (7)
C7	0.0266 (9)	0.0230 (9)	0.0235 (9)	−0.0068 (7)	0.0022 (7)	−0.0033 (7)
C8	0.0374 (10)	0.0252 (9)	0.0207 (8)	−0.0086 (7)	0.0020 (7)	0.0007 (7)
C9	0.0358 (10)	0.0273 (10)	0.0232 (9)	−0.0030 (8)	−0.0027 (8)	0.0037 (8)
C10	0.0248 (9)	0.0253 (10)	0.0237 (9)	0.0012 (7)	−0.0032 (6)	0.0014 (7)
C11	0.0187 (8)	0.0309 (11)	0.0431 (11)	−0.0048 (7)	0.0071 (8)	−0.0079 (9)
C12	0.0294 (10)	0.0313 (11)	0.0345 (10)	−0.0098 (8)	0.0103 (8)	−0.0049 (9)

Geometric parameters (Å, º)

Co—N1^i	1.9320 (18)	C2—H2	0.9400
Co—N1	1.9320 (18)	C3—C4	1.404 (3)
Co—N4^i	1.9358 (12)	C3—H3	0.9400
Co—N4	1.9358 (12)	C4—C5	1.399 (3)
Co—N5^i	1.9518 (16)	C4—C11	1.445 (3)
Co—N5	1.9518 (16)	C5—C6	1.412 (3)
O1—N6	1.233 (6)	C6—C7	1.400 (3)
O2—N6	1.240 (3)	C7—C8	1.403 (3)
N1—N2	1.198 (2)	C7—C12	1.434 (3)
N2—N3	1.152 (2)	C8—C9	1.373 (3)
N4—C1	1.330 (2)	C8—H8	0.9400
N4—C5	1.364 (2)	C9—C10	1.397 (3)
N5—C10	1.324 (3)	C9—H9	0.9400
N5—C6	1.365 (2)	C10—H10	0.9400
N6—O2^ii	1.240 (3)	C11—C12	1.349 (3)
C1—C2	1.401 (3)	C11—H11	0.9400
C1—H1	0.9400	C12—H12	0.9400
C2—C3	1.376 (3)
N1—Co—N4	90.16 (7)	C1—C2—H2	119.7
N1—Co—N5	173.57 (8)	C2—C3—C4	118.83 (16)
N1—Co—N1^i	93.80 (12)	C2—C3—H3	120.6
N1—Co—N4^i	89.69 (7)	C4—C3—H3	120.6
N1—Co—N5^i	89.06 (6)	C5—C4—C3	117.49 (18)
N4—Co—N5	84.09 (7)	C5—C4—C11	117.30 (19)
N4—Co—N4^i	179.79 (12)	C3—C4—C11	125.19 (18)
N4—Co—N5^i	96.06 (7)	N4—C5—C4	122.90 (18)
N5—Co—N5^i	88.68 (9)	N4—C5—C6	116.05 (16)
N1^i—Co—N4	89.69 (7)	C4—C5—C6	121.05 (18)
N1^i—Co—N4^i	90.16 (7)	N5—C6—C7	123.36 (17)
N1^i—Co—N5^i	173.57 (8)	N5—C6—C5	115.67 (16)
N4^i—Co—N5^i	84.09 (7)	C7—C6—C5	120.98 (16)
N1^i—Co—N5	89.06 (6)	C6—C7—C8	116.90 (17)
N4^i—Co—N5	96.06 (7)	C6—C7—C12	117.42 (18)
Co—N1—N2	120.19 (15)	C8—C7—C12	125.67 (18)
N1—N2—N3	175.6 (2)	C9—C8—C7	119.47 (18)
C1—N4—C5	118.97 (15)	C9—C8—H8	120.3
C1—N4—Co	128.71 (13)	C7—C8—H8	120.3
C5—N4—Co	111.97 (12)	C8—C9—C10	119.89 (18)
C10—N5—C6	118.12 (16)	C8—C9—H9	120.1
C10—N5—Co	130.13 (13)	C10—C9—H9	120.1
C6—N5—Co	111.74 (12)	N5—C10—C9	122.23 (17)
O1—N6—O2^ii	120.48 (18)	N5—C10—H10	118.9
O1—N6—O2	120.48 (18)	C9—C10—H10	118.9
O2^ii—N6—O2	119.0 (4)	C12—C11—C4	121.30 (17)
N4—C1—C2	121.08 (18)	C12—C11—H11	119.4
N4—C1—H1	119.5	C4—C11—H11	119.4
C2—C1—H1	119.5	C11—C12—C7	121.81 (18)
C3—C2—C1	120.64 (19)	C11—C12—H12	119.1
C3—C2—H2	119.7	C7—C12—H12	119.1

Symmetry codes: (i) −x, −y, z; (ii) −x−1, −y, z.