Diazido­bis(1,10-phenanthroline)cobalt(III) perchlorate

The title cobalt(III) complex, [Co(N₃)₂(C₁₂H₈N₂)₂]ClO₄, has been synthesized and structurally characterized. The complex cations have distorted octa­hedral geometry, formed by two chelating 1,10-phenanthroline ligands and two azide ligands in a cis configuration. The cations and anions lie on twofold rotation axes. The ions are linked together into a linear one-dimensional chain by hydrogen bonding.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.009 Å
• R factor = 0.047
• wR factor = 0.119
• Data-to-parameter ratio = 9.0

checkCIF/PLATON results

No syntax errors found



Alert level A
ABSTM02_ALERT_3_A  Test not performed as the _exptl_absorpt_correction_type
            has not been identified. See test ABSTY_01.
ABSTY01_ALERT_1_A  The absorption correction should be one of the following
            *  none
            *  analytical
            *  integration
            *  numerical
            *  gaussian
            *  empirical
            *  psi-scan
            *  multi-scan
            *  refdelf
            *  sphere
            *  cylinder

Alert level C
PLAT061_ALERT_3_C Tmax/Tmin Range Test RR' too Large .............       0.76
PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given .......          ?
PLAT152_ALERT_1_C Supplied and Calc Volume s.u. Inconsistent .....          ?
PLAT199_ALERT_1_C Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_C Check the Reported _diffrn_ambient_temperature .        293 K
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for         N3
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         N4
PLAT341_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ...          9
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #          1
            N3  -CO1 -N1  -C1    171.00  3.00   2.675   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #          6
            N3  -CO1 -N1  -C12   -13.00  3.00   2.675   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         13
            N2  -CO1 -N2  -C10  -133.80  0.50   2.675   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         18
            N2  -CO1 -N2  -C11    50.80  0.40   2.675   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         25
            N1  -CO1 -N3  -N4    161.00  2.00   2.675   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         26
            CO1 -N3  -N4  -N5    163.00  6.00   1.555   1.555   1.555   1.555

Alert level G
REFLT03_ALERT_4_G 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.
           From the CIF: _diffrn_reflns_theta_max           25.01
           From the CIF: _reflns_number_total               1640
           Count of symmetry unique reflns         1088
           Completeness (_total/calc)            150.74%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured       552
           Fraction of Friedel pairs measured     0.507
           Are heavy atom types Z>Si present        yes

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

   4 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   3 ALERT type 3 Indicator that the structure quality may be low
   8 ALERT type 4 Improvement, methodology, query or suggestion


checkCIF publication errors

Alert level A
PUBL010_ALERT_1_A  _publ_author_address is missing. Author(s) address(es).

   1 ALERT level A = Data missing that is essential or data in wrong format
   0 ALERT level G = General alerts. Data that may be required is missing

---

Computing details

Data collection: SMART-NT (Bruker, 1998); cell refinement: SMART-NT (Or SAINT-NT?); data reduction: SAINT-NT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL-NT (Bruker, 1998); software used to prepare material for publication: SHELXTL-NT.

Diazidobis(1,10-phenanthroline)cobalt(II) perchlorate

Crystal data

[Co(N3)2(C12H8N2)2]ClO4	Dx = 1.689 Mg m^−3
Mr = 602.85	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Iba2	Cell parameters from 933 reflections
a = 15.097 (8) Å	θ = 2.3–23.5°
b = 10.989 (6) Å	µ = 0.89 mm^−1
c = 14.291 (11) Å	T = 293 K
V = 2371 (2) Å^3	Block, red-orange
Z = 4	0.20 × 0.18 × 0.16 mm
F(000) = 1224

Data collection

Bruker SMART CCD area-detector diffractometer	1640 independent reflections
Radiation source: fine-focus sealed tube	1317 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.048
φ and ω scans	θmax = 25.0°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −16→17
Tmin = 0.638, Tmax = 0.870	k = −13→12
5746 measured reflections	l = −10→16

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)] = 0.047	H-atom parameters constrained
wR(F^2) = 0.119	w = 1/[σ^2(Fo^2) + (0.0302P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.09	(Δ/σ)max < 0.001
1640 reflections	Δρmax = 0.54 e Å^−3
182 parameters	Δρmin = −0.58 e Å^−3
1 restraint	Absolute structure: Flack (1983), with how many Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.006 (35)

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
Co1	0.5000	1.0000	0.09972 (7)	0.0306 (3)
N1	0.4543 (3)	0.8892 (4)	0.0029 (3)	0.0312 (11)
N2	0.3811 (2)	1.0670 (3)	0.0966 (4)	0.0327 (9)
N3	0.4669 (4)	0.8825 (5)	0.1932 (4)	0.0538 (15)
N4	0.4101 (3)	0.8997 (4)	0.2490 (4)	0.0395 (11)
N5	0.3547 (4)	0.9064 (5)	0.3047 (5)	0.0693 (17)
C1	0.4943 (4)	0.8007 (5)	−0.0437 (4)	0.0401 (13)
H1	0.5543	0.7866	−0.0336	0.048*
C2	0.4486 (4)	0.7280 (5)	−0.1075 (4)	0.0455 (15)
H2	0.4790	0.6679	−0.1402	0.055*
C3	0.3615 (4)	0.7433 (5)	−0.1225 (4)	0.0474 (16)
H3	0.3317	0.6930	−0.1642	0.057*
C4	0.3155 (4)	0.8365 (5)	−0.0744 (4)	0.0405 (13)
C5	0.2244 (4)	0.8657 (6)	−0.0829 (5)	0.0518 (16)
H5	0.1903	0.8225	−0.1257	0.062*
C6	0.1854 (4)	0.9528 (6)	−0.0321 (5)	0.0510 (16)
H6	0.1248	0.9657	−0.0384	0.061*
C7	0.2359 (3)	1.0280 (5)	0.0330 (5)	0.0416 (15)
C8	0.2016 (4)	1.1229 (5)	0.0868 (5)	0.0480 (15)
H8	0.1414	1.1406	0.0861	0.058*
C9	0.2582 (4)	1.1888 (6)	0.1400 (5)	0.0510 (16)
H9	0.2368	1.2550	0.1736	0.061*
C10	0.3483 (4)	1.1595 (5)	0.1456 (4)	0.0427 (13)
H10	0.3854	1.2051	0.1839	0.051*
C11	0.3264 (3)	1.0010 (5)	0.0396 (4)	0.0358 (12)
C12	0.3662 (3)	0.9071 (5)	−0.0117 (4)	0.0325 (12)
Cl1	0.5000	0.5000	0.69044 (16)	0.0473 (5)
O1	0.4827 (5)	0.5956 (6)	0.6305 (7)	0.134 (4)
O2	0.5724 (4)	0.5312 (8)	0.7472 (5)	0.120 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.0351 (5)	0.0375 (5)	0.0192 (5)	0.0016 (4)	0.000	0.000
N1	0.037 (3)	0.034 (3)	0.023 (3)	−0.006 (2)	0.002 (2)	0.006 (2)
N2	0.038 (2)	0.039 (2)	0.021 (2)	0.0036 (17)	0.000 (3)	0.003 (2)
N3	0.071 (3)	0.058 (4)	0.033 (3)	0.020 (3)	0.020 (3)	0.015 (3)
N4	0.052 (3)	0.040 (3)	0.027 (3)	−0.001 (2)	−0.005 (3)	0.001 (2)
N5	0.079 (4)	0.073 (4)	0.056 (4)	0.010 (3)	0.033 (4)	0.012 (3)
C1	0.048 (3)	0.040 (3)	0.032 (3)	−0.002 (3)	0.006 (3)	−0.004 (2)
C2	0.070 (4)	0.037 (3)	0.029 (3)	−0.005 (3)	0.005 (3)	−0.007 (3)
C3	0.071 (4)	0.050 (3)	0.020 (3)	−0.017 (3)	−0.007 (3)	0.000 (3)
C4	0.055 (3)	0.034 (3)	0.032 (3)	−0.017 (3)	−0.007 (3)	0.009 (3)
C5	0.054 (4)	0.051 (4)	0.051 (4)	−0.016 (3)	−0.019 (3)	0.011 (3)
C6	0.039 (3)	0.049 (3)	0.065 (5)	−0.010 (3)	−0.013 (3)	0.016 (4)
C7	0.030 (3)	0.053 (4)	0.042 (4)	−0.005 (2)	0.001 (3)	0.021 (3)
C8	0.040 (3)	0.061 (3)	0.043 (4)	0.008 (3)	0.011 (3)	0.015 (3)
C9	0.059 (4)	0.063 (4)	0.030 (3)	0.028 (3)	0.009 (3)	0.005 (3)
C10	0.046 (3)	0.057 (3)	0.025 (3)	0.004 (3)	−0.002 (3)	−0.003 (3)
C11	0.036 (3)	0.042 (3)	0.029 (3)	−0.007 (2)	0.002 (2)	0.018 (3)
C12	0.039 (3)	0.036 (3)	0.022 (3)	−0.005 (2)	0.002 (2)	0.008 (2)
Cl1	0.0553 (12)	0.0477 (11)	0.0389 (13)	−0.0014 (10)	0.000	0.000
O1	0.133 (6)	0.098 (4)	0.170 (12)	0.002 (4)	−0.041 (6)	0.059 (6)
O2	0.072 (4)	0.229 (7)	0.060 (4)	−0.054 (4)	−0.015 (3)	0.024 (5)

Geometric parameters (Å, º)

Co1—N3^i	1.924 (6)	C4—C12	1.411 (7)
Co1—N3	1.924 (6)	C4—C5	1.417 (8)
Co1—N2^i	1.940 (4)	C5—C6	1.338 (10)
Co1—N2	1.940 (4)	C5—H5	0.9300
Co1—N1	1.967 (5)	C6—C7	1.459 (9)
Co1—N1^i	1.967 (5)	C6—H6	0.9300
N1—C1	1.325 (7)	C7—C8	1.395 (8)
N1—C12	1.361 (7)	C7—C11	1.402 (7)
N2—C10	1.331 (7)	C8—C9	1.354 (9)
N2—C11	1.368 (7)	C8—H8	0.9300
N3—N4	1.187 (7)	C9—C10	1.399 (8)
N4—N5	1.156 (7)	C9—H9	0.9300
C1—C2	1.394 (8)	C10—H10	0.9300
C1—H1	0.9300	C11—C12	1.401 (8)
C2—C3	1.343 (9)	Cl1—O1^ii	1.380 (7)
C2—H2	0.9300	Cl1—O1	1.380 (7)
C3—C4	1.417 (8)	Cl1—O2	1.404 (6)
C3—H3	0.9300	Cl1—O2^ii	1.404 (6)
N3^i—Co1—N3	92.1 (4)	C12—C4—C5	117.2 (6)
N3^i—Co1—N2^i	91.8 (2)	C3—C4—C5	126.7 (5)
N3—Co1—N2^i	90.1 (2)	C6—C5—C4	122.8 (6)
N3^i—Co1—N2	90.1 (2)	C6—C5—H5	118.6
N3—Co1—N2	91.8 (2)	C4—C5—H5	118.6
N2^i—Co1—N2	177.3 (3)	C5—C6—C7	121.4 (5)
N3^i—Co1—N1	174.0 (2)	C5—C6—H6	119.3
N3—Co1—N1	89.0 (2)	C7—C6—H6	119.3
N2^i—Co1—N1	94.19 (19)	C8—C7—C11	118.9 (6)
N2—Co1—N1	83.92 (19)	C8—C7—C6	125.5 (5)
N3^i—Co1—N1^i	89.0 (2)	C11—C7—C6	115.6 (6)
N3—Co1—N1^i	174.0 (2)	C9—C8—C7	118.4 (5)
N2^i—Co1—N1^i	83.92 (19)	C9—C8—H8	120.8
N2—Co1—N1^i	94.19 (19)	C7—C8—H8	120.8
N1—Co1—N1^i	90.6 (3)	C8—C9—C10	121.5 (6)
C1—N1—C12	118.3 (5)	C8—C9—H9	119.2
C1—N1—Co1	130.4 (4)	C10—C9—H9	119.2
C12—N1—Co1	111.2 (4)	N2—C10—C9	120.5 (5)
C10—N2—C11	119.6 (4)	N2—C10—H10	119.8
C10—N2—Co1	128.5 (4)	C9—C10—H10	119.8
C11—N2—Co1	111.8 (3)	N2—C11—C12	116.3 (4)
N4—N3—Co1	123.1 (4)	N2—C11—C7	121.1 (5)
N5—N4—N3	174.4 (6)	C12—C11—C7	122.6 (5)
N1—C1—C2	121.7 (5)	N1—C12—C11	116.4 (5)
N1—C1—H1	119.2	N1—C12—C4	123.3 (5)
C2—C1—H1	119.2	C11—C12—C4	120.2 (5)
C3—C2—C1	121.1 (5)	O1^ii—Cl1—O1	103.3 (8)
C3—C2—H2	119.4	O1^ii—Cl1—O2	113.4 (5)
C1—C2—H2	119.4	O1—Cl1—O2	108.6 (4)
C2—C3—C4	119.6 (5)	O1^ii—Cl1—O2^ii	108.6 (4)
C2—C3—H3	120.2	O1—Cl1—O2^ii	113.4 (5)
C4—C3—H3	120.2	O2—Cl1—O2^ii	109.4 (6)
C12—C4—C3	116.0 (5)
N3^i—Co1—N1—C1	171 (3)	C12—C4—C5—C6	−2.6 (9)
N3—Co1—N1—C1	−88.9 (5)	C3—C4—C5—C6	177.5 (6)
N2^i—Co1—N1—C1	1.1 (5)	C4—C5—C6—C7	3.0 (9)
N2—Co1—N1—C1	179.2 (5)	C5—C6—C7—C8	178.0 (6)
N1^i—Co1—N1—C1	85.1 (5)	C5—C6—C7—C11	−1.2 (8)
N3^i—Co1—N1—C12	−13 (3)	C11—C7—C8—C9	2.9 (8)
N3—Co1—N1—C12	87.3 (4)	C6—C7—C8—C9	−176.2 (6)
N2^i—Co1—N1—C12	177.3 (3)	C7—C8—C9—C10	−3.4 (9)
N2—Co1—N1—C12	−4.6 (4)	C11—N2—C10—C9	0.6 (8)
N1^i—Co1—N1—C12	−98.7 (4)	Co1—N2—C10—C9	−174.5 (4)
N3^i—Co1—N2—C10	0.2 (5)	C8—C9—C10—N2	1.6 (10)
N3—Co1—N2—C10	92.3 (5)	C10—N2—C11—C12	178.3 (5)
N2^i—Co1—N2—C10	−133.8 (5)	Co1—N2—C11—C12	−5.8 (6)
N1—Co1—N2—C10	−178.9 (5)	C10—N2—C11—C7	−1.0 (8)
N1^i—Co1—N2—C10	−88.8 (5)	Co1—N2—C11—C7	174.9 (4)
N3^i—Co1—N2—C11	−175.2 (4)	C8—C7—C11—N2	−0.8 (8)
N3—Co1—N2—C11	−83.1 (4)	C6—C7—C11—N2	178.4 (5)
N2^i—Co1—N2—C11	50.8 (4)	C8—C7—C11—C12	179.9 (5)
N1—Co1—N2—C11	5.7 (4)	C6—C7—C11—C12	−0.9 (7)
N1^i—Co1—N2—C11	95.8 (4)	C1—N1—C12—C11	179.4 (5)
N3^i—Co1—N3—N4	61.0 (6)	Co1—N1—C12—C11	2.7 (5)
N2^i—Co1—N3—N4	152.7 (6)	C1—N1—C12—C4	−0.4 (8)
N2—Co1—N3—N4	−29.2 (6)	Co1—N1—C12—C4	−177.1 (4)
N1—Co1—N3—N4	−113.1 (6)	N2—C11—C12—N1	2.0 (7)
N1^i—Co1—N3—N4	161 (2)	C7—C11—C12—N1	−178.7 (5)
Co1—N3—N4—N5	163 (6)	N2—C11—C12—C4	−178.1 (5)
C12—N1—C1—C2	1.1 (8)	C7—C11—C12—C4	1.2 (8)
Co1—N1—C1—C2	177.1 (4)	C3—C4—C12—N1	0.2 (7)
N1—C1—C2—C3	−1.6 (9)	C5—C4—C12—N1	−179.7 (5)
C1—C2—C3—C4	1.4 (8)	C3—C4—C12—C11	−179.6 (5)
C2—C3—C4—C12	−0.8 (8)	C5—C4—C12—C11	0.5 (7)
C2—C3—C4—C5	179.1 (6)

Symmetry codes: (i) −x+1, −y+2, z; (ii) −x+1, −y+1, z.