





Supporting information
![]() | Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807063131/hb2664sup1.cif |
![]() | Structure factor file (CIF format) https://doi.org/10.1107/S1600536807063131/hb2664Isup2.hkl |
CCDC reference: 676063
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean
(C-C) = 0.006 Å
- R factor = 0.029
- wR factor = 0.078
- Data-to-parameter ratio = 11.6
checkCIF/PLATON results
No syntax errors found
Alert level B PLAT417_ALERT_2_B Short Inter D-H..H-D H1A .. H2A .. 2.08 Ang. PLAT417_ALERT_2_B Short Inter D-H..H-D H1A .. H33 .. 1.98 Ang. PLAT420_ALERT_2_B D-H Without Acceptor O1 - H1A ... ?
Alert level C PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ? PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for Co1 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for Co2
Alert level G REFLT03_ALERT_4_G WARNING: Large fraction of Friedel related reflns may be needed to determine absolute structure From the CIF: _diffrn_reflns_theta_max 27.50 From the CIF: _reflns_number_total 4846 Count of symmetry unique reflns 3926 Completeness (_total/calc) 123.43% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 920 Fraction of Friedel pairs measured 0.234 Are heavy atom types Z>Si present yes PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature 293 K PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature . 293 K PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 3
0 ALERT level A = In general: serious problem 3 ALERT level B = Potentially serious problem 3 ALERT level C = Check and explain 4 ALERT level G = General alerts; check 3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 5 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
Due to the unsuccesful attempts at the synthesis of (I), the deposited structure factors and other data have been taken from the original paper of Zhang et al. (2004).
All H atoms were located in difference Fourier syntheses but were repositioned with ideal geometry (C–H = 0.93, N–H = 0.86 and O–H = 0.82 Å) and refined as riding with Uiso(H) = 1.2Ueq(C, N) or 1.5Ueq(O).
The crystal structure of the salt-like title compound, (I), C6H6N3+.[CoCl3(C6H5N3)]-.H2O, was originally modelled as a [CoCl3(C6H5N3)].C6H5N3.H2O complex (Zhang et al., 2004). A few facts point that the structure was incorrectly described as CoIII instead of CoII complex. The blue colour of the crystal and a tetrahedral coordination geometry around the central metal atom is typical for the CoIICl3N chromophore, e.g. in pyridinium trichloro-pyridine-cobalt(II) (Hahn et al., 1997), quinolinium trichloro-quinoline-cobalt(II) (Pan & Xu, 2004) and 2-aminopyridinium (2-aminopyridine)-trichloro-cobalt(II) (Zhang et al., 2006).
A decrease of the metal oxidation number in (I) from III to II requires the presence of an additional proton for charge balance. In fact, an analysis of difference Fourier maps has shown two peaks in the positions expected for missing benzotriazole H atoms (N–Q = 0.85 and 0.89 Å). Both of these are involved in short, strong N–H···Owater hydrogen bonds which confirms the supposition (Fig. 1). The N–N bond lengths in the benzimidazolium cations are practically equalized and range from 1.309 (4) to 1.316 (5) Å, indicating full delocalization of their π electrons, which is not observed in neutral benzotriazole molecules (Krawczyk & Gdaniec, 2005). The metal bond distances and hydrogen bonds are listed in Tables 1 and 2, respectively.
For the previous stucture, see: Zhang et al. (2006). For related Co(II)-containing structures, see: Hahn et al. (1997); Krawczyk & Gdaniec (2005); Pan & Xu (2004); Zhang et al. (2004)
Data collection: XSCANS (Bruker, 1997); cell refinement: XSCANS (Bruker, 1997); data reduction: XSCANS (Bruker, 1997); program(s) used to solve structure: SHELXTL (Bruker, 2003); program(s) used to refine structure: SHELXTL (Bruker, 2003); molecular graphics: SHELXTL (Bruker, 2003); software used to prepare material for publication: PLATON (Spek, 2003).
![]() | Fig. 1. A view of (I), showing displacement ellipsoids for the non-H atoms drawn at the 30% probability level. |
(C6H6N3)[CoCl3(C6H5N3)]·H2O | Z = 2 |
Mr = 422.56 | F(000) = 426 |
Triclinic, P1 | Dx = 1.640 Mg m−3 |
Hall symbol: P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 6.8760 (8) Å | Cell parameters from 28 reflections |
b = 7.8033 (12) Å | θ = 5.3–12.6° |
c = 16.657 (3) Å | µ = 1.48 mm−1 |
α = 95.450 (13)° | T = 293 K |
β = 95.962 (8)° | Prism, blue |
γ = 103.989 (9)° | 0.40 × 0.40 × 0.20 mm |
V = 855.8 (2) Å3 |
Bruker P4 diffractometer | 4526 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.078 |
Graphite monochromator | θmax = 27.5°, θmin = 2.5° |
ω scans | h = −8→1 |
Absorption correction: ψ scan (North et al., 1968) | k = −9→10 |
Tmin = 0.611, Tmax = 0.744 | l = −21→21 |
4906 measured reflections | 3 standard reflections every 100 reflections |
4846 independent reflections | intensity decay: none |
Refinement on F2 | Secondary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Hydrogen site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.029 | H-atom parameters constrained |
wR(F2) = 0.078 | w = 1/[σ2(Fo2) + (0.0331P)2 + 0.2297P] where P = (Fo2 + 2Fc2)/3 |
S = 1.08 | (Δ/σ)max < 0.001 |
4846 reflections | Δρmax = 0.34 e Å−3 |
417 parameters | Δρmin = −0.26 e Å−3 |
3 restraints | Absolute structure: Flack (1983), 920 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.008 (13) |
(C6H6N3)[CoCl3(C6H5N3)]·H2O | γ = 103.989 (9)° |
Mr = 422.56 | V = 855.8 (2) Å3 |
Triclinic, P1 | Z = 2 |
a = 6.8760 (8) Å | Mo Kα radiation |
b = 7.8033 (12) Å | µ = 1.48 mm−1 |
c = 16.657 (3) Å | T = 293 K |
α = 95.450 (13)° | 0.40 × 0.40 × 0.20 mm |
β = 95.962 (8)° |
Bruker P4 diffractometer | 4526 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.078 |
Tmin = 0.611, Tmax = 0.744 | 3 standard reflections every 100 reflections |
4906 measured reflections | intensity decay: none |
4846 independent reflections |
R[F2 > 2σ(F2)] = 0.029 | H-atom parameters constrained |
wR(F2) = 0.078 | Δρmax = 0.34 e Å−3 |
S = 1.08 | Δρmin = −0.26 e Å−3 |
4846 reflections | Absolute structure: Flack (1983), 920 Friedel pairs |
417 parameters | Absolute structure parameter: −0.008 (13) |
3 restraints |
Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles |
Refinement. Refinement on F2 for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion of F2 > σ(F2) is used only for calculating -R-factor-obs 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 | ||
Co1 | 0.44420 (6) | 0.01369 (5) | 0.90042 (3) | 0.0462 (1) | |
Cl1 | 0.1994 (2) | −0.24333 (13) | 0.89041 (6) | 0.0706 (3) | |
Cl2 | 0.3415 (2) | 0.22168 (14) | 0.97717 (6) | 0.0707 (4) | |
Cl3 | 0.7529 (2) | −0.0156 (3) | 0.93735 (8) | 0.0969 (6) | |
N1 | 0.4450 (5) | 0.0908 (4) | 0.78758 (16) | 0.0436 (8) | |
N2 | 0.3859 (5) | −0.0327 (4) | 0.72406 (17) | 0.0491 (9) | |
N3 | 0.3929 (5) | 0.0501 (4) | 0.65771 (17) | 0.0487 (9) | |
C4 | 0.4831 (7) | 0.3714 (6) | 0.6303 (3) | 0.0585 (12) | |
C5 | 0.5466 (8) | 0.5379 (6) | 0.6726 (3) | 0.0669 (16) | |
C6 | 0.5824 (8) | 0.5658 (5) | 0.7580 (3) | 0.0674 (15) | |
C7 | 0.5560 (6) | 0.4277 (5) | 0.8042 (2) | 0.0560 (11) | |
C8 | 0.4911 (5) | 0.2557 (4) | 0.7616 (2) | 0.0441 (9) | |
C9 | 0.4567 (5) | 0.2298 (5) | 0.6770 (2) | 0.0446 (9) | |
Co2 | 0.55479 (7) | 0.48473 (5) | 0.39999 (3) | 0.0484 (1) | |
Cl4 | 0.6620 (2) | 0.24123 (14) | 0.42163 (7) | 0.0745 (4) | |
Cl5 | 0.7823 (3) | 0.72314 (15) | 0.46890 (8) | 0.0979 (6) | |
Cl6 | 0.2402 (2) | 0.4745 (2) | 0.43067 (8) | 0.0891 (5) | |
N11 | 0.5282 (5) | 0.5107 (4) | 0.27999 (16) | 0.0445 (8) | |
N12 | 0.4780 (6) | 0.3689 (4) | 0.22487 (17) | 0.0514 (9) | |
N13 | 0.4662 (6) | 0.4279 (4) | 0.15251 (17) | 0.0542 (9) | |
C14 | 0.5165 (7) | 0.7309 (6) | 0.1018 (2) | 0.0570 (11) | |
C15 | 0.5618 (8) | 0.9044 (6) | 0.1336 (3) | 0.0630 (16) | |
C16 | 0.5992 (7) | 0.9600 (5) | 0.2186 (3) | 0.0606 (13) | |
C17 | 0.5933 (6) | 0.8414 (5) | 0.2737 (2) | 0.0512 (10) | |
C18 | 0.5479 (5) | 0.6616 (4) | 0.24206 (18) | 0.0409 (9) | |
C19 | 0.5082 (6) | 0.6077 (5) | 0.1583 (2) | 0.0453 (10) | |
N21 | 0.9897 (6) | 0.4698 (4) | 0.59051 (19) | 0.0554 (10) | |
N22 | 1.0593 (6) | 0.6201 (4) | 0.6387 (2) | 0.0608 (11) | |
N23 | 1.0793 (5) | 0.5710 (4) | 0.71148 (18) | 0.0531 (9) | |
C24 | 1.0184 (7) | 0.2821 (6) | 0.7735 (2) | 0.0581 (11) | |
C25 | 0.9546 (7) | 0.1017 (6) | 0.7485 (3) | 0.0670 (16) | |
C26 | 0.8995 (7) | 0.0348 (6) | 0.6655 (3) | 0.0695 (16) | |
C27 | 0.9026 (7) | 0.1394 (5) | 0.6052 (3) | 0.0605 (14) | |
C28 | 0.9658 (6) | 0.3237 (5) | 0.6305 (2) | 0.0462 (10) | |
C29 | 1.0242 (5) | 0.3911 (5) | 0.7118 (2) | 0.0439 (10) | |
N31 | 0.0523 (6) | 0.8803 (5) | 0.0749 (2) | 0.0609 (13) | |
N32 | 0.0951 (7) | 1.0044 (5) | 0.1374 (2) | 0.0673 (14) | |
N33 | 0.0884 (6) | 0.9186 (5) | 0.2018 (2) | 0.0581 (11) | |
C34 | 0.0247 (7) | 0.5974 (7) | 0.2283 (3) | 0.0671 (16) | |
C35 | −0.0210 (9) | 0.4337 (7) | 0.1856 (4) | 0.0788 (19) | |
C36 | −0.0493 (8) | 0.4068 (6) | 0.1003 (4) | 0.0805 (18) | |
C37 | −0.0293 (8) | 0.5435 (6) | 0.0545 (3) | 0.0688 (14) | |
C38 | 0.0182 (7) | 0.7128 (5) | 0.0974 (2) | 0.0531 (11) | |
C39 | 0.0438 (6) | 0.7406 (5) | 0.1818 (2) | 0.0514 (11) | |
O1 | 0.1150 (10) | 0.0529 (7) | 0.3557 (2) | 0.127 (2) | |
O2 | 0.3201 (10) | 0.8988 (6) | 0.4999 (2) | 0.124 (2) | |
H3 | 0.36100 | −0.00330 | 0.60880 | 0.0580* | |
H4 | 0.45880 | 0.35330 | 0.57380 | 0.0710* | |
H5 | 0.56690 | 0.63600 | 0.64400 | 0.0810* | |
H6 | 0.62540 | 0.68190 | 0.78410 | 0.0810* | |
H7 | 0.57990 | 0.44690 | 0.86070 | 0.0670* | |
H13 | 0.43520 | 0.35920 | 0.10710 | 0.0650* | |
H14 | 0.49230 | 0.69560 | 0.04600 | 0.0680* | |
H15 | 0.56870 | 0.99050 | 0.09830 | 0.0760* | |
H16 | 0.62860 | 1.08080 | 0.23720 | 0.0730* | |
H17 | 0.61810 | 0.87790 | 0.32940 | 0.0620* | |
H21 | 0.96190 | 0.46410 | 0.53860 | 0.074 (15)* | |
H23 | 1.12300 | 0.64520 | 0.75490 | 0.0640* | |
H24 | 1.05520 | 0.32800 | 0.82800 | 0.0700* | |
H25 | 0.94790 | 0.02270 | 0.78710 | 0.0800* | |
H26 | 0.85880 | −0.08790 | 0.65150 | 0.0840* | |
H27 | 0.86550 | 0.09280 | 0.55080 | 0.0730* | |
H31 | 0.04630 | 0.90190 | 0.02520 | 0.0730* | |
H33 | 0.11010 | 0.97010 | 0.25110 | 0.10 (2)* | |
H34 | 0.04250 | 0.61440 | 0.28480 | 0.0810* | |
H35 | −0.03420 | 0.33520 | 0.21380 | 0.0940* | |
H36 | −0.08290 | 0.29080 | 0.07420 | 0.0970* | |
H37 | −0.04650 | 0.52480 | −0.00210 | 0.0820* | |
H1A | 0.23890 | 0.07600 | 0.36260 | 0.1910* | |
H1B | 0.04880 | 0.12670 | 0.36090 | 0.1910* | |
H2A | 0.30780 | 0.97330 | 0.46940 | 0.1850* | |
H2B | 0.27160 | 0.79140 | 0.48810 | 0.1850* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Co1 | 0.0523 (3) | 0.0539 (2) | 0.0332 (2) | 0.0160 (2) | 0.0026 (2) | 0.0071 (2) |
Cl1 | 0.0959 (8) | 0.0581 (5) | 0.0467 (4) | −0.0033 (5) | 0.0175 (5) | 0.0019 (4) |
Cl2 | 0.1015 (9) | 0.0690 (6) | 0.0423 (4) | 0.0284 (6) | 0.0096 (5) | −0.0074 (4) |
Cl3 | 0.0682 (7) | 0.1819 (15) | 0.0594 (6) | 0.0585 (9) | 0.0058 (5) | 0.0423 (7) |
N1 | 0.0503 (16) | 0.0458 (13) | 0.0372 (12) | 0.0171 (13) | 0.0039 (12) | 0.0076 (10) |
N2 | 0.0596 (18) | 0.0496 (14) | 0.0389 (13) | 0.0173 (14) | 0.0029 (13) | 0.0050 (11) |
N3 | 0.0563 (18) | 0.0541 (15) | 0.0365 (12) | 0.0166 (15) | 0.0054 (13) | 0.0034 (11) |
C4 | 0.060 (2) | 0.072 (2) | 0.055 (2) | 0.026 (2) | 0.0196 (19) | 0.0287 (19) |
C5 | 0.066 (3) | 0.061 (2) | 0.088 (3) | 0.024 (2) | 0.030 (2) | 0.038 (2) |
C6 | 0.065 (3) | 0.0468 (19) | 0.093 (3) | 0.0146 (19) | 0.019 (2) | 0.0109 (19) |
C7 | 0.057 (2) | 0.0533 (18) | 0.0544 (19) | 0.0098 (18) | 0.0087 (18) | −0.0001 (15) |
C8 | 0.0424 (17) | 0.0504 (16) | 0.0423 (15) | 0.0161 (14) | 0.0055 (14) | 0.0084 (13) |
C9 | 0.0431 (18) | 0.0526 (16) | 0.0426 (15) | 0.0169 (15) | 0.0089 (14) | 0.0118 (13) |
Co2 | 0.0625 (3) | 0.0495 (2) | 0.0336 (2) | 0.0159 (2) | 0.0033 (2) | 0.0060 (2) |
Cl4 | 0.1100 (10) | 0.0605 (5) | 0.0572 (5) | 0.0355 (6) | −0.0038 (6) | 0.0083 (4) |
Cl5 | 0.1390 (14) | 0.0598 (6) | 0.0697 (7) | 0.0027 (8) | −0.0386 (8) | −0.0015 (5) |
Cl6 | 0.0837 (9) | 0.1346 (11) | 0.0667 (6) | 0.0474 (9) | 0.0314 (6) | 0.0256 (7) |
N11 | 0.0564 (17) | 0.0426 (13) | 0.0350 (11) | 0.0145 (13) | 0.0044 (12) | 0.0038 (10) |
N12 | 0.069 (2) | 0.0467 (14) | 0.0382 (13) | 0.0191 (15) | 0.0004 (14) | 0.0000 (11) |
N13 | 0.069 (2) | 0.0590 (16) | 0.0355 (12) | 0.0233 (16) | 0.0014 (14) | −0.0013 (11) |
C14 | 0.061 (2) | 0.077 (2) | 0.0418 (17) | 0.027 (2) | 0.0099 (17) | 0.0230 (17) |
C15 | 0.067 (3) | 0.073 (3) | 0.062 (2) | 0.029 (2) | 0.017 (2) | 0.035 (2) |
C16 | 0.068 (3) | 0.0489 (18) | 0.069 (2) | 0.0182 (19) | 0.010 (2) | 0.0174 (17) |
C17 | 0.061 (2) | 0.0456 (16) | 0.0485 (18) | 0.0161 (17) | 0.0085 (17) | 0.0057 (14) |
C18 | 0.0440 (17) | 0.0461 (15) | 0.0353 (14) | 0.0155 (14) | 0.0053 (13) | 0.0083 (11) |
C19 | 0.048 (2) | 0.0568 (18) | 0.0362 (14) | 0.0211 (16) | 0.0094 (14) | 0.0070 (13) |
N21 | 0.065 (2) | 0.0601 (17) | 0.0392 (14) | 0.0147 (16) | −0.0007 (15) | 0.0087 (12) |
N22 | 0.069 (2) | 0.0514 (16) | 0.0605 (19) | 0.0148 (16) | −0.0018 (18) | 0.0115 (14) |
N23 | 0.0579 (19) | 0.0524 (15) | 0.0470 (15) | 0.0168 (15) | −0.0020 (14) | −0.0018 (12) |
C24 | 0.058 (2) | 0.078 (2) | 0.0472 (18) | 0.028 (2) | 0.0105 (18) | 0.0202 (17) |
C25 | 0.056 (2) | 0.073 (3) | 0.084 (3) | 0.024 (2) | 0.019 (2) | 0.040 (2) |
C26 | 0.055 (2) | 0.0473 (19) | 0.105 (4) | 0.0122 (19) | 0.005 (2) | 0.011 (2) |
C27 | 0.057 (2) | 0.0491 (19) | 0.071 (3) | 0.0143 (18) | −0.003 (2) | −0.0047 (17) |
C28 | 0.0429 (18) | 0.0501 (17) | 0.0452 (16) | 0.0122 (15) | 0.0032 (14) | 0.0064 (13) |
C29 | 0.0408 (18) | 0.0527 (17) | 0.0400 (15) | 0.0162 (15) | 0.0043 (14) | 0.0044 (13) |
N31 | 0.072 (3) | 0.0657 (19) | 0.0476 (16) | 0.0224 (19) | 0.0014 (17) | 0.0150 (14) |
N32 | 0.079 (3) | 0.063 (2) | 0.063 (2) | 0.0251 (19) | 0.0019 (19) | 0.0135 (16) |
N33 | 0.060 (2) | 0.0635 (19) | 0.0504 (17) | 0.0182 (17) | 0.0014 (15) | 0.0054 (14) |
C34 | 0.053 (2) | 0.088 (3) | 0.069 (3) | 0.023 (2) | 0.013 (2) | 0.034 (2) |
C35 | 0.069 (3) | 0.066 (3) | 0.109 (4) | 0.019 (2) | 0.019 (3) | 0.036 (3) |
C36 | 0.068 (3) | 0.056 (2) | 0.116 (4) | 0.013 (2) | 0.017 (3) | 0.005 (2) |
C37 | 0.069 (3) | 0.070 (2) | 0.065 (2) | 0.016 (2) | 0.011 (2) | −0.0019 (19) |
C38 | 0.052 (2) | 0.063 (2) | 0.0476 (17) | 0.0197 (18) | 0.0068 (16) | 0.0093 (15) |
C39 | 0.045 (2) | 0.0578 (18) | 0.0526 (19) | 0.0151 (17) | 0.0035 (16) | 0.0111 (15) |
O1 | 0.161 (5) | 0.126 (4) | 0.074 (2) | 0.015 (4) | 0.002 (3) | −0.019 (2) |
O2 | 0.187 (6) | 0.111 (3) | 0.065 (2) | 0.033 (4) | 0.016 (3) | −0.014 (2) |
Co1—Cl1 | 2.2649 (13) | C6—C7 | 1.371 (6) |
Co1—Cl2 | 2.2616 (13) | C7—C8 | 1.403 (5) |
Co1—Cl3 | 2.2195 (16) | C8—C9 | 1.392 (5) |
Co1—N1 | 2.027 (3) | C4—H4 | 0.93 |
Co2—Cl4 | 2.2441 (13) | C5—H5 | 0.93 |
Co2—Cl5 | 2.2450 (15) | C6—H6 | 0.93 |
Co2—Cl6 | 2.2584 (16) | C7—H7 | 0.93 |
Co2—N11 | 2.022 (3) | C14—C15 | 1.355 (6) |
O1—H1B | 0.82 | C14—C19 | 1.404 (5) |
O1—H1A | 0.82 | C15—C16 | 1.419 (7) |
N1—C8 | 1.371 (4) | C16—C17 | 1.361 (6) |
N1—N2 | 1.320 (4) | C17—C18 | 1.399 (5) |
N2—N3 | 1.332 (4) | C18—C19 | 1.397 (4) |
N3—C9 | 1.360 (5) | C14—H14 | 0.93 |
O2—H2B | 0.82 | C15—H15 | 0.93 |
O2—H2A | 0.82 | C16—H16 | 0.93 |
N3—H3 | 0.86 | C17—H17 | 0.93 |
N11—N12 | 1.320 (4) | C24—C25 | 1.378 (6) |
N11—C18 | 1.373 (4) | C24—C29 | 1.393 (5) |
N12—N13 | 1.332 (4) | C25—C26 | 1.409 (7) |
N13—C19 | 1.354 (5) | C26—C27 | 1.352 (7) |
N13—H13 | 0.86 | C27—C28 | 1.407 (5) |
N21—C28 | 1.359 (5) | C28—C29 | 1.386 (5) |
N21—N22 | 1.311 (4) | C24—H24 | 0.93 |
N22—N23 | 1.309 (4) | C25—H25 | 0.93 |
N23—C29 | 1.363 (5) | C26—H26 | 0.93 |
N21—H21 | 0.86 | C27—H27 | 0.93 |
N23—H23 | 0.86 | C34—C39 | 1.407 (6) |
N31—C38 | 1.366 (5) | C34—C35 | 1.350 (8) |
N31—N32 | 1.310 (5) | C35—C36 | 1.403 (9) |
N32—N33 | 1.316 (5) | C36—C37 | 1.358 (7) |
N33—C39 | 1.349 (5) | C37—C38 | 1.388 (6) |
N31—H31 | 0.86 | C38—C39 | 1.388 (5) |
N33—H33 | 0.86 | C34—H34 | 0.93 |
C4—C5 | 1.365 (7) | C35—H35 | 0.93 |
C4—C9 | 1.398 (6) | C36—H36 | 0.93 |
C5—C6 | 1.405 (7) | C37—H37 | 0.93 |
Cl1—Co1—Cl2 | 106.81 (5) | C5—C6—H6 | 119 |
Cl1—Co1—Cl3 | 113.73 (7) | C8—C7—H7 | 122 |
Cl1—Co1—N1 | 106.87 (10) | C6—C7—H7 | 122 |
Cl2—Co1—Cl3 | 116.75 (6) | C15—C14—C19 | 115.9 (3) |
Cl2—Co1—N1 | 105.84 (10) | C14—C15—C16 | 122.6 (4) |
Cl3—Co1—N1 | 106.16 (11) | C15—C16—C17 | 121.8 (4) |
Cl6—Co2—N11 | 102.70 (11) | C16—C17—C18 | 116.4 (3) |
Cl4—Co2—Cl6 | 114.49 (6) | C17—C18—C19 | 121.4 (3) |
Cl4—Co2—N11 | 110.22 (10) | N11—C18—C19 | 107.4 (3) |
Cl4—Co2—Cl5 | 108.33 (6) | N11—C18—C17 | 131.2 (3) |
Cl5—Co2—N11 | 109.56 (10) | N13—C19—C14 | 134.5 (3) |
Cl5—Co2—Cl6 | 111.40 (7) | C14—C19—C18 | 121.8 (3) |
H1A—O1—H1B | 125 | N13—C19—C18 | 103.7 (3) |
N2—N1—C8 | 109.5 (3) | C15—C14—H14 | 122 |
Co1—N1—N2 | 118.5 (2) | C19—C14—H14 | 122 |
Co1—N1—C8 | 131.9 (2) | C16—C15—H15 | 119 |
N1—N2—N3 | 107.4 (3) | C14—C15—H15 | 119 |
N2—N3—C9 | 111.5 (3) | C15—C16—H16 | 119 |
H2A—O2—H2B | 124 | C17—C16—H16 | 119 |
C9—N3—H3 | 124 | C18—C17—H17 | 122 |
N2—N3—H3 | 124 | C16—C17—H17 | 122 |
N12—N11—C18 | 109.6 (3) | C25—C24—C29 | 115.7 (3) |
Co2—N11—N12 | 120.6 (2) | C24—C25—C26 | 121.3 (4) |
Co2—N11—C18 | 129.7 (2) | C25—C26—C27 | 123.6 (4) |
N11—N12—N13 | 106.7 (3) | C26—C27—C28 | 115.4 (4) |
N12—N13—C19 | 112.7 (3) | N21—C28—C29 | 104.7 (3) |
N12—N13—H13 | 124 | N21—C28—C27 | 133.7 (3) |
C19—N13—H13 | 124 | C27—C28—C29 | 121.6 (4) |
N22—N21—C28 | 113.5 (3) | C24—C29—C28 | 122.5 (4) |
N21—N22—N23 | 104.1 (3) | N23—C29—C24 | 133.3 (3) |
N22—N23—C29 | 113.6 (3) | N23—C29—C28 | 104.3 (3) |
C28—N21—H21 | 123 | C29—C24—H24 | 122 |
N22—N21—H21 | 123 | C25—C24—H24 | 122 |
N22—N23—H23 | 123 | C24—C25—H25 | 119 |
C29—N23—H23 | 123 | C26—C25—H25 | 119 |
N32—N31—C38 | 112.6 (3) | C25—C26—H26 | 118 |
N31—N32—N33 | 105.2 (3) | C27—C26—H26 | 118 |
N32—N33—C39 | 112.3 (3) | C28—C27—H27 | 122 |
C38—N31—H31 | 124 | C26—C27—H27 | 122 |
N32—N31—H31 | 124 | C35—C34—C39 | 115.8 (5) |
C39—N33—H33 | 124 | C34—C35—C36 | 122.5 (5) |
N32—N33—H33 | 124 | C35—C36—C37 | 122.5 (5) |
C5—C4—C9 | 116.0 (4) | C36—C37—C38 | 115.8 (5) |
C4—C5—C6 | 122.1 (4) | N31—C38—C39 | 104.2 (3) |
C5—C6—C7 | 122.2 (4) | N31—C38—C37 | 133.7 (4) |
C6—C7—C8 | 116.4 (3) | C37—C38—C39 | 122.1 (4) |
N1—C8—C9 | 107.2 (3) | C34—C39—C38 | 121.3 (4) |
N1—C8—C7 | 131.9 (3) | N33—C39—C34 | 133.0 (4) |
C7—C8—C9 | 120.9 (3) | N33—C39—C38 | 105.7 (3) |
N3—C9—C8 | 104.5 (3) | C35—C34—H34 | 122 |
N3—C9—C4 | 133.1 (3) | C39—C34—H34 | 122 |
C4—C9—C8 | 122.4 (4) | C36—C35—H35 | 119 |
C5—C4—H4 | 122 | C34—C35—H35 | 119 |
C9—C4—H4 | 122 | C35—C36—H36 | 119 |
C6—C5—H5 | 119 | C37—C36—H36 | 119 |
C4—C5—H5 | 119 | C38—C37—H37 | 122 |
C7—C6—H6 | 119 | C36—C37—H37 | 122 |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1B···Cl6 | 0.82 | 2.79 | 3.279 (5) | 120 |
O2—H2A···O1i | 0.82 | 2.41 | 3.142 (7) | 148 |
O2—H2B···Cl6 | 0.82 | 2.52 | 3.295 (5) | 159 |
N3—H3···O2ii | 0.86 | 1.87 | 2.721 (4) | 173 |
N13—H13···Cl2iii | 0.86 | 2.28 | 3.127 (3) | 169 |
N21—H21···Cl4 | 0.86 | 2.80 | 3.458 (4) | 134 |
N21—H21···Cl6iv | 0.86 | 2.75 | 3.316 (4) | 125 |
N23—H23···Cl1v | 0.86 | 2.30 | 3.123 (3) | 160 |
N31—H31···Cl3vi | 0.86 | 2.61 | 3.214 (4) | 128 |
N33—H33···O1i | 0.86 | 1.79 | 2.646 (5) | 170 |
Symmetry codes: (i) x, y+1, z; (ii) x, y−1, z; (iii) x, y, z−1; (iv) x+1, y, z; (v) x+1, y+1, z; (vi) x−1, y+1, z−1. |
Experimental details
Crystal data | |
Chemical formula | (C6H6N3)[CoCl3(C6H5N3)]·H2O |
Mr | 422.56 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 6.8760 (8), 7.8033 (12), 16.657 (3) |
α, β, γ (°) | 95.450 (13), 95.962 (8), 103.989 (9) |
V (Å3) | 855.8 (2) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.48 |
Crystal size (mm) | 0.40 × 0.40 × 0.20 |
Data collection | |
Diffractometer | Bruker P4 |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.611, 0.744 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4906, 4846, 4526 |
Rint | 0.078 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.029, 0.078, 1.08 |
No. of reflections | 4846 |
No. of parameters | 417 |
No. of restraints | 3 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.34, −0.26 |
Absolute structure | Flack (1983), 920 Friedel pairs |
Absolute structure parameter | −0.008 (13) |
Computer programs: XSCANS (Bruker, 1997), SHELXTL (Bruker, 2003), PLATON (Spek, 2003).
Co1—Cl1 | 2.2649 (13) | Co2—Cl4 | 2.2441 (13) |
Co1—Cl2 | 2.2616 (13) | Co2—Cl5 | 2.2450 (15) |
Co1—Cl3 | 2.2195 (16) | Co2—Cl6 | 2.2584 (16) |
Co1—N1 | 2.027 (3) | Co2—N11 | 2.022 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1B···Cl6 | 0.82 | 2.79 | 3.279 (5) | 120 |
O2—H2A···O1i | 0.82 | 2.41 | 3.142 (7) | 148 |
O2—H2B···Cl6 | 0.82 | 2.52 | 3.295 (5) | 159 |
N3—H3···O2ii | 0.86 | 1.87 | 2.721 (4) | 173 |
N13—H13···Cl2iii | 0.86 | 2.28 | 3.127 (3) | 169 |
N21—H21···Cl4 | 0.86 | 2.80 | 3.458 (4) | 134 |
N21—H21···Cl6iv | 0.86 | 2.75 | 3.316 (4) | 125 |
N23—H23···Cl1v | 0.86 | 2.30 | 3.123 (3) | 160 |
N31—H31···Cl3vi | 0.86 | 2.61 | 3.214 (4) | 128 |
N33—H33···O1i | 0.86 | 1.79 | 2.646 (5) | 170 |
Symmetry codes: (i) x, y+1, z; (ii) x, y−1, z; (iii) x, y, z−1; (iv) x+1, y, z; (v) x+1, y+1, z; (vi) x−1, y+1, z−1. |
The crystal structure of the salt-like title compound, (I), C6H6N3+.[CoCl3(C6H5N3)]-.H2O, was originally modelled as a [CoCl3(C6H5N3)].C6H5N3.H2O complex (Zhang et al., 2004). A few facts point that the structure was incorrectly described as CoIII instead of CoII complex. The blue colour of the crystal and a tetrahedral coordination geometry around the central metal atom is typical for the CoIICl3N chromophore, e.g. in pyridinium trichloro-pyridine-cobalt(II) (Hahn et al., 1997), quinolinium trichloro-quinoline-cobalt(II) (Pan & Xu, 2004) and 2-aminopyridinium (2-aminopyridine)-trichloro-cobalt(II) (Zhang et al., 2006).
A decrease of the metal oxidation number in (I) from III to II requires the presence of an additional proton for charge balance. In fact, an analysis of difference Fourier maps has shown two peaks in the positions expected for missing benzotriazole H atoms (N–Q = 0.85 and 0.89 Å). Both of these are involved in short, strong N–H···Owater hydrogen bonds which confirms the supposition (Fig. 1). The N–N bond lengths in the benzimidazolium cations are practically equalized and range from 1.309 (4) to 1.316 (5) Å, indicating full delocalization of their π electrons, which is not observed in neutral benzotriazole molecules (Krawczyk & Gdaniec, 2005). The metal bond distances and hydrogen bonds are listed in Tables 1 and 2, respectively.