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The molecular structure of the title compound, (C
21H
17N
8)
2[Ni(CN)
4], consists of two organic cations, C
21H
17N
8+ or [MTIT]
+, and a centrosymmetric inorganic dianion, [Ni(CN)
4]
2−. In the crystal structure, the ions stack along the
b axis and are connected by a number of C—H
N hydrogen bonds.
Supporting information
CCDC reference: 296672
Key indicators
- Single-crystal X-ray study
- T = 298 K
- Mean (C-C) = 0.008 Å
- R factor = 0.097
- wR factor = 0.176
- Data-to-parameter ratio = 14.9
checkCIF/PLATON results
No syntax errors found
Alert level B
PLAT432_ALERT_2_B Short Inter X...Y Contact N002 .. C19 .. 2.92 Ang.
Alert level C
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ?
PLAT164_ALERT_4_C Nr. of Refined C-H H-Atoms in Heavy-At Struct... 8
PLAT166_ALERT_4_C S.U's Given on Coordinates for calc-flagged .... H3
PLAT166_ALERT_4_C S.U's Given on Coordinates for calc-flagged .... H4
PLAT166_ALERT_4_C S.U's Given on Coordinates for calc-flagged .... H5
PLAT166_ALERT_4_C S.U's Given on Coordinates for calc-flagged .... H6
PLAT166_ALERT_4_C S.U's Given on Coordinates for calc-flagged .... H14
PLAT166_ALERT_4_C S.U's Given on Coordinates for calc-flagged .... H15
PLAT166_ALERT_4_C S.U's Given on Coordinates for calc-flagged .... H16
PLAT166_ALERT_4_C S.U's Given on Coordinates for calc-flagged .... H17
PLAT341_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ... 8
PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........ 12
0 ALERT level A = In general: serious problem
1 ALERT level B = Potentially serious problem
12 ALERT level C = Check and explain
0 ALERT level G = General alerts; check
1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
1 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
10 ALERT type 4 Improvement, methodology, query or suggestion
The starting material, MTIT perchlorate, was prepared according to a known protocol (Babichev & Romanov, 1975). The title compound, (I), was prepared from equimolar quantities of [MTIT]+·ClO4− and K2[Ni(CN)4] in an acetonitrile/propanol/water system (Yegorova et al., 2002). [MTIT]+·ClO4− (306 mg, 0.64 mmol) in acetonitrile (150 ml) was mixed with K2[Ni(CN)4] (120 mg) in a 2-propanol–water mixture (1:1, 30 ml). This mixture was heated to boiling point for 10 min and then cooled slowly to 273 K. Formation of a black–green crystalline precipitate was observed. This crystalline product was decantated, washed with water and 2-propanol, and dried at 313 K. The amount of Ni in (I) was determined by ICP atomic emission spectroscopy, and no K was found in the analyzed samples. By IR spectroscopy, the cyanine fingerprint was observed with the addition of a CN band at 2110 cm−1. The characteristic perchlorate bands at 630 and 1100 cm−1 were absent. The UV–vis spectra show the dye bands at 590 (shoulder) and 636 nm, and a new band, at 770 nm, was attributed to an NiII transition.
The methyl H atoms in the [MTIT]+ cation were included in calulated positions and refined as riding atoms [C—H = 0.96 Å and Uiso(H) = 1.5Ueq(C)]. The remainder of the H atoms were located in difference Fourier syntheses; the atomic parameters were initially refined and then held fixed (C—H = 0.88–0.98 Å), with Uiso(H) = 1.2Ueq(C). Please check changes to text.
Data collection: Please provide; cell refinement: Please provide; data reduction: Please provide; program(s) used to solve structure: SHELXS86 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: WinGX (Farrugia, 1999).
Bis(1-methyl-5-[3-(1-methyl-1
H-tetrazolo[5,1-
a]isoindol-5-yl)allylidene]-5
H- tetrazolo[5,1-
a]isoindol-1-ium) tetracyanonickel(II)
top
Crystal data top
(C21H17N8)2[Ni(CN)4] | F(000) = 956 |
Mr = 925.61 | Dx = 1.488 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 4688 reflections |
a = 16.296 (2) Å | θ = 0–29.2° |
b = 7.5708 (7) Å | µ = 0.53 mm−1 |
c = 18.537 (3) Å | T = 298 K |
β = 115.42 (2)° | Prism, black-green |
V = 2065.6 (6) Å3 | 0.2 × 0.2 × 0.1 mm |
Z = 2 | |
Data collection top
Nonius KappaCCD diffractometer | 3172 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.069 |
ϕ or ω?, thick slices scans | θmax = 27.5°, θmin = 6.1° |
Absorption correction: multi-scan SORTAV (Blessing, 1995) | h = −21→21 |
Tmin = 0.901, Tmax = 0.949 | k = −9→9 |
18746 measured reflections | l = −24→21 |
4672 independent reflections | |
Refinement top
Refinement on F2 | 0 restraints |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.097 | w = 1/[σ2(Fo2) + (0.0001P)2 + 6.0123P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.176 | (Δ/σ)max < 0.001 |
S = 1.33 | Δρmax = 0.45 e Å−3 |
4672 reflections | Δρmin = −0.73 e Å−3 |
314 parameters | |
Crystal data top
(C21H17N8)2[Ni(CN)4] | V = 2065.6 (6) Å3 |
Mr = 925.61 | Z = 2 |
Monoclinic, P21/n | Mo Kα radiation |
a = 16.296 (2) Å | µ = 0.53 mm−1 |
b = 7.5708 (7) Å | T = 298 K |
c = 18.537 (3) Å | 0.2 × 0.2 × 0.1 mm |
β = 115.42 (2)° | |
Data collection top
Nonius KappaCCD diffractometer | 4672 independent reflections |
Absorption correction: multi-scan SORTAV (Blessing, 1995) | 3172 reflections with I > 2σ(I) |
Tmin = 0.901, Tmax = 0.949 | Rint = 0.069 |
18746 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.097 | 0 restraints |
wR(F2) = 0.176 | H-atom parameters constrained |
S = 1.33 | Δρmax = 0.45 e Å−3 |
4672 reflections | Δρmin = −0.73 e Å−3 |
314 parameters | |
Special details top
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 |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
N1 | 1.0824 (3) | 0.0890 (6) | 0.4102 (2) | 0.0358 (14) | |
N2 | 1.1162 (3) | 0.0955 (6) | 0.4918 (2) | 0.0412 (16) | |
N3 | 1.0580 (3) | 0.1757 (6) | 0.5109 (2) | 0.0406 (16) | |
N4 | 0.9862 (3) | 0.2196 (5) | 0.4409 (2) | 0.0336 (12) | |
N5 | 0.9922 (3) | 0.4016 (6) | 0.7336 (2) | 0.0342 (12) | |
N6 | 1.0603 (3) | 0.3012 (6) | 0.7299 (3) | 0.0465 (17) | |
N7 | 1.1195 (3) | 0.2787 (6) | 0.8027 (3) | 0.0476 (17) | |
N8 | 1.0914 (3) | 0.3619 (6) | 0.8527 (2) | 0.0379 (14) | |
C1 | 1.0003 (3) | 0.1665 (7) | 0.3775 (3) | 0.0332 (17) | |
C2 | 0.9240 (3) | 0.2161 (6) | 0.3054 (3) | 0.0311 (17) | |
C3 | 0.9035 (3) | 0.1923 (7) | 0.2239 (3) | 0.0338 (17) | |
C003 | 1.1444 (4) | 0.3566 (9) | 0.9394 (3) | 0.0525 (19) | |
C4 | 0.8219 (3) | 0.2625 (7) | 0.1686 (3) | 0.0372 (17) | |
C004 | 1.1370 (3) | 0.0158 (7) | 0.3721 (3) | 0.0408 (17) | |
C5 | 0.7639 (4) | 0.3553 (7) | 0.1938 (3) | 0.0384 (17) | |
C6 | 0.7847 (4) | 0.3788 (7) | 0.2735 (3) | 0.0383 (17) | |
C7 | 0.8655 (3) | 0.3088 (6) | 0.3305 (3) | 0.0322 (17) | |
C8 | 0.9039 (3) | 0.3122 (7) | 0.4174 (3) | 0.0341 (17) | |
C9 | 0.8729 (4) | 0.3863 (7) | 0.4694 (3) | 0.0380 (17) | |
C10 | 0.9139 (4) | 0.3844 (7) | 0.5522 (3) | 0.0375 (17) | |
C11 | 0.8734 (3) | 0.4627 (7) | 0.5970 (3) | 0.0360 (17) | |
C12 | 0.9074 (3) | 0.4702 (7) | 0.6790 (3) | 0.0334 (17) | |
C13 | 0.8719 (3) | 0.5500 (7) | 0.7309 (3) | 0.0349 (17) | |
C14 | 0.7885 (4) | 0.6303 (7) | 0.7130 (3) | 0.0377 (17) | |
C15 | 0.7699 (4) | 0.6896 (7) | 0.7742 (3) | 0.0404 (17) | |
C16 | 0.8344 (4) | 0.6727 (8) | 0.8543 (3) | 0.046 (2) | |
C17 | 0.9170 (4) | 0.5938 (7) | 0.8744 (3) | 0.0408 (17) | |
C18 | 0.9357 (3) | 0.5319 (7) | 0.8120 (3) | 0.0348 (16) | |
C19 | 1.0098 (3) | 0.4363 (7) | 0.8104 (3) | 0.0342 (17) | |
Ni1 | 0.00000 | 0.00000 | 0.00000 | 0.0340 (3) | |
N001 | −0.1639 (3) | 0.2038 (7) | −0.0087 (3) | 0.0562 (18) | |
N002 | −0.0465 (3) | 0.0775 (6) | −0.1739 (3) | 0.0426 (16) | |
C001 | −0.1010 (4) | 0.1264 (7) | −0.0055 (3) | 0.0380 (16) | |
C002 | −0.0309 (3) | 0.0487 (7) | −0.1085 (3) | 0.0382 (17) | |
H00D | 1.11960 | 0.26870 | 0.96170 | 0.0790* | |
H00E | 1.14210 | 0.47000 | 0.96160 | 0.0790* | |
H3 | 0.945 (2) | 0.129 (3) | 0.2070 (9) | 0.0410* | |
H00F | 1.20640 | 0.32750 | 0.95170 | 0.0790* | |
H4 | 0.8046 (10) | 0.2473 (11) | 0.112 (3) | 0.0450* | |
H00A | 1.10350 | 0.02280 | 0.31520 | 0.0610* | |
H5 | 0.713 (3) | 0.400 (3) | 0.157 (2) | 0.0460* | |
H00B | 1.15100 | −0.10550 | 0.38770 | 0.0610* | |
H6 | 0.744 (2) | 0.442 (4) | 0.2894 (9) | 0.0460* | |
H00C | 1.19240 | 0.08200 | 0.38860 | 0.0610* | |
H9 | 0.81740 | 0.44470 | 0.44570 | 0.0460* | |
H10 | 0.97000 | 0.32940 | 0.57860 | 0.0450* | |
H11 | 0.81720 | 0.51570 | 0.56830 | 0.0430* | |
H14 | 0.747 (2) | 0.6432 (10) | 0.662 (3) | 0.0450* | |
H15 | 0.713 (3) | 0.742 (3) | 0.7627 (8) | 0.0490* | |
H16 | 0.8206 (10) | 0.716 (3) | 0.894 (3) | 0.0560* | |
H17 | 0.961 (3) | 0.5815 (10) | 0.929 (3) | 0.0490* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
N1 | 0.041 (3) | 0.036 (2) | 0.036 (2) | 0.002 (2) | 0.022 (2) | 0.003 (2) |
N2 | 0.046 (3) | 0.041 (3) | 0.035 (2) | 0.001 (2) | 0.016 (2) | 0.006 (2) |
N3 | 0.041 (3) | 0.048 (3) | 0.032 (2) | 0.003 (2) | 0.015 (2) | 0.003 (2) |
N4 | 0.040 (2) | 0.037 (2) | 0.027 (2) | −0.002 (2) | 0.0174 (19) | 0.0024 (19) |
N5 | 0.037 (2) | 0.036 (2) | 0.038 (2) | 0.002 (2) | 0.024 (2) | 0.004 (2) |
N6 | 0.047 (3) | 0.054 (3) | 0.045 (3) | 0.003 (2) | 0.026 (2) | 0.003 (2) |
N7 | 0.049 (3) | 0.054 (3) | 0.050 (3) | 0.000 (2) | 0.031 (3) | −0.005 (2) |
N8 | 0.035 (2) | 0.041 (3) | 0.039 (2) | −0.002 (2) | 0.017 (2) | 0.000 (2) |
C1 | 0.038 (3) | 0.036 (3) | 0.032 (3) | −0.006 (2) | 0.021 (2) | 0.000 (2) |
C2 | 0.038 (3) | 0.029 (3) | 0.030 (3) | −0.001 (2) | 0.018 (2) | 0.000 (2) |
C3 | 0.038 (3) | 0.040 (3) | 0.031 (3) | −0.003 (2) | 0.022 (2) | 0.001 (2) |
C003 | 0.049 (3) | 0.064 (4) | 0.035 (3) | 0.001 (3) | 0.009 (3) | 0.000 (3) |
C4 | 0.044 (3) | 0.041 (3) | 0.030 (3) | −0.008 (3) | 0.019 (2) | −0.006 (2) |
C004 | 0.040 (3) | 0.044 (3) | 0.042 (3) | 0.000 (3) | 0.021 (2) | 0.002 (3) |
C5 | 0.044 (3) | 0.037 (3) | 0.031 (3) | 0.000 (3) | 0.013 (2) | 0.002 (2) |
C6 | 0.040 (3) | 0.045 (3) | 0.036 (3) | 0.000 (3) | 0.022 (2) | 0.002 (2) |
C7 | 0.040 (3) | 0.030 (3) | 0.035 (3) | −0.003 (2) | 0.024 (2) | −0.001 (2) |
C8 | 0.040 (3) | 0.037 (3) | 0.027 (3) | 0.002 (2) | 0.016 (2) | 0.000 (2) |
C9 | 0.045 (3) | 0.035 (3) | 0.041 (3) | 0.004 (2) | 0.025 (3) | 0.007 (2) |
C10 | 0.046 (3) | 0.038 (3) | 0.037 (3) | −0.007 (3) | 0.026 (2) | −0.003 (2) |
C11 | 0.040 (3) | 0.038 (3) | 0.035 (3) | 0.000 (2) | 0.021 (2) | 0.004 (2) |
C12 | 0.037 (3) | 0.035 (3) | 0.035 (3) | −0.002 (2) | 0.022 (2) | 0.005 (2) |
C13 | 0.037 (3) | 0.037 (3) | 0.031 (3) | −0.006 (2) | 0.015 (2) | 0.003 (2) |
C14 | 0.044 (3) | 0.040 (3) | 0.031 (3) | −0.002 (3) | 0.018 (2) | −0.002 (2) |
C15 | 0.040 (3) | 0.040 (3) | 0.045 (3) | 0.003 (3) | 0.022 (3) | −0.003 (3) |
C16 | 0.066 (4) | 0.049 (4) | 0.041 (3) | −0.006 (3) | 0.039 (3) | −0.008 (3) |
C17 | 0.041 (3) | 0.050 (3) | 0.031 (3) | −0.008 (3) | 0.015 (2) | −0.010 (3) |
C18 | 0.042 (3) | 0.037 (3) | 0.031 (2) | −0.008 (2) | 0.021 (2) | −0.002 (2) |
C19 | 0.034 (3) | 0.035 (3) | 0.034 (3) | −0.005 (2) | 0.015 (2) | 0.001 (2) |
Ni1 | 0.0349 (5) | 0.0439 (6) | 0.0264 (5) | −0.0017 (5) | 0.0161 (4) | −0.0018 (4) |
N001 | 0.051 (3) | 0.085 (4) | 0.031 (2) | 0.022 (3) | 0.016 (2) | −0.008 (3) |
N002 | 0.044 (3) | 0.055 (3) | 0.035 (2) | −0.004 (2) | 0.023 (2) | −0.003 (2) |
C001 | 0.044 (3) | 0.047 (3) | 0.020 (2) | −0.004 (3) | 0.011 (2) | −0.004 (2) |
C002 | 0.036 (3) | 0.046 (3) | 0.038 (3) | −0.002 (2) | 0.021 (2) | −0.007 (2) |
Geometric parameters (Å, º) top
Ni1—C001i | 1.868 (7) | C9—C10 | 1.386 (7) |
Ni1—C002i | 1.888 (5) | C10—C11 | 1.395 (8) |
Ni1—C001 | 1.868 (7) | C11—C12 | 1.378 (7) |
Ni1—C002 | 1.888 (5) | C12—C13 | 1.450 (7) |
N1—N2 | 1.371 (5) | C13—C18 | 1.421 (7) |
N1—C004 | 1.462 (7) | C13—C14 | 1.393 (9) |
N1—C1 | 1.344 (7) | C14—C15 | 1.370 (8) |
N2—N3 | 1.297 (7) | C15—C16 | 1.409 (7) |
N3—N4 | 1.364 (5) | C16—C17 | 1.370 (9) |
N4—C1 | 1.352 (7) | C17—C18 | 1.398 (8) |
N4—C8 | 1.407 (7) | C18—C19 | 1.419 (8) |
N5—C19 | 1.352 (6) | C3—H3 | 0.9800 |
N5—N6 | 1.371 (7) | C003—H00D | 0.9600 |
N5—C12 | 1.415 (7) | C003—H00F | 0.9600 |
N6—N7 | 1.290 (7) | C003—H00E | 0.9600 |
N7—N8 | 1.353 (7) | C4—H4 | 0.9700 |
N8—C003 | 1.463 (6) | C004—H00C | 0.9600 |
N8—C19 | 1.344 (7) | C004—H00A | 0.9600 |
N001—C001 | 1.160 (9) | C004—H00B | 0.9600 |
N002—C002 | 1.148 (7) | C5—H5 | 0.8800 |
C1—C2 | 1.431 (7) | C6—H6 | 0.9600 |
C2—C3 | 1.412 (7) | C9—H9 | 0.9300 |
C2—C7 | 1.414 (7) | C10—H10 | 0.9300 |
C3—C4 | 1.390 (7) | C11—H11 | 0.9300 |
C4—C5 | 1.409 (8) | C14—H14 | 0.9000 |
C5—C6 | 1.378 (7) | C15—H15 | 0.9400 |
C6—C7 | 1.392 (8) | C16—H16 | 0.9200 |
C7—C8 | 1.457 (7) | C17—H17 | 0.9600 |
C8—C9 | 1.385 (8) | | |
| | | |
Ni1···C003ii | 4.044 (7) | C10···N3 | 3.184 (8) |
Ni1···C16iii | 3.803 (6) | C10···C004ix | 3.583 (8) |
Ni1···C17iii | 3.742 (5) | C10···N4x | 3.388 (7) |
Ni1···C16iv | 3.803 (6) | C10···N6 | 3.193 (7) |
Ni1···C17iv | 3.742 (5) | C11···C1x | 3.392 (8) |
Ni1···C003v | 4.044 (7) | C12···C1x | 3.504 (8) |
Ni1···H00Dii | 3.1000 | C12···C2x | 3.548 (7) |
Ni1···H16iii | 3.4800 | C13···C15xvi | 3.551 (8) |
Ni1···H00Dv | 3.1000 | C14···C004x | 3.576 (8) |
Ni1···H16iv | 3.4800 | C14···C15xvi | 3.505 (8) |
Ni1···H17iv | 3.3800 | C15···C13xvii | 3.551 (8) |
Ni1···H17iii | 3.3800 | C15···C14xvii | 3.505 (8) |
N1···N4 | 2.127 (7) | C15···N002xviii | 3.409 (8) |
N001···C4vi | 3.421 (7) | C16···C002xix | 3.478 (8) |
N2···N4 | 2.132 (7) | C16···Ni1iii | 3.803 (6) |
N002···N7v | 3.291 (7) | C16···Ni1xix | 3.803 (6) |
N002···N8v | 2.996 (7) | C17···Ni1iii | 3.742 (5) |
N002···C15vii | 3.409 (8) | C17···Ni1xix | 3.742 (5) |
N002···C19v | 2.921 (7) | C17···C002xix | 3.529 (8) |
N002···N5v | 3.207 (7) | C19···C3x | 3.328 (8) |
N002···C004viii | 3.394 (7) | C19···C002xi | 3.488 (7) |
N3···N4ix | 3.290 (6) | C19···N002xi | 2.921 (7) |
N3···N3ix | 3.187 (7) | C19···C4x | 3.458 (8) |
N3···C10 | 3.184 (8) | C001···H17iii | 3.0500 |
N4···C10x | 3.388 (7) | C001···H14vii | 2.8600 |
N4···N3ix | 3.290 (6) | C002···H3viii | 3.0500 |
N4···N1 | 2.127 (7) | C002···H00Dv | 2.7800 |
N5···C2x | 3.408 (7) | C3···H6xx | 2.9900 |
N5···C3x | 3.437 (7) | C003···H16xxi | 2.9400 |
N5···N8 | 2.125 (5) | C4···H6xx | 2.8900 |
N5···N002xi | 3.207 (7) | C6···H9 | 3.0400 |
N6···N8 | 2.159 (6) | C9···H00Fxv | 3.0500 |
N6···C10 | 3.193 (7) | C10···H00Bix | 2.8000 |
N7···C5x | 3.345 (8) | C11···H00Bix | 2.7700 |
N7···C6xii | 3.196 (9) | C12···H00Bix | 3.0100 |
N7···N002xi | 3.291 (7) | C13···H15xvi | 2.7400 |
N8···N002xi | 2.996 (7) | C14···H00Cx | 2.9800 |
N8···C002xi | 3.368 (7) | C14···H11 | 3.0400 |
N8···C4x | 3.274 (7) | C14···H15xvi | 2.9800 |
N8···N5 | 2.125 (5) | H00D···Ni1xi | 3.1000 |
N001···H00Cxiii | 2.8100 | H00D···Ni1ii | 3.1000 |
N001···H14vii | 2.6100 | H00D···H16xxi | 2.4200 |
N001···H11vii | 2.6700 | H00D···C002xi | 2.7800 |
N001···H4vi | 2.5200 | H00E···N001iii | 2.5900 |
N001···H00Eiii | 2.5900 | H3···N002viii | 2.5400 |
N2···H5xii | 2.7800 | H3···C002viii | 3.0500 |
N002···H15vii | 2.7900 | H00F···C9xii | 3.0500 |
N002···H00Aviii | 2.4900 | H4···N001xiv | 2.5200 |
N002···H3viii | 2.5400 | H00A···N002viii | 2.4900 |
N3···H5xii | 2.8600 | H5···N3xv | 2.8600 |
N3···H10 | 2.5600 | H5···N2xv | 2.7800 |
N4···H10 | 2.8000 | H00B···C12ix | 3.0100 |
N5···H10 | 2.7900 | H00B···C10ix | 2.8000 |
N6···H10 | 2.5600 | H00B···C11ix | 2.7700 |
N7···H6xii | 2.7200 | H6···N7xv | 2.7200 |
C1···C12x | 3.504 (8) | H6···C3xxii | 2.9900 |
C1···C11x | 3.392 (8) | H6···C4xxii | 2.8900 |
C001···C002 | 2.678 (8) | H00C···C14x | 2.9800 |
C001···C002i | 2.635 (8) | H00C···N001xxiii | 2.8100 |
C2···C12x | 3.548 (7) | H9···H11 | 2.3400 |
C2···N5x | 3.408 (7) | H9···C6 | 3.0400 |
C002···C19v | 3.488 (7) | H10···N3 | 2.5600 |
C002···C003v | 3.494 (9) | H10···N6 | 2.5600 |
C002···C001i | 2.635 (8) | H10···N4 | 2.8000 |
C002···C17iv | 3.529 (8) | H10···N5 | 2.7900 |
C002···C001 | 2.678 (8) | H11···H9 | 2.3400 |
C002···N8v | 3.368 (7) | H11···N001xviii | 2.6700 |
C002···C16iv | 3.478 (8) | H11···C14 | 3.0400 |
C3···N5x | 3.437 (7) | H14···N001xviii | 2.6100 |
C3···C19x | 3.328 (8) | H14···C001xviii | 2.8600 |
C003···Ni1xi | 4.044 (7) | H15···N002xviii | 2.7900 |
C003···C002xi | 3.494 (9) | H15···C13xvii | 2.7400 |
C003···Ni1ii | 4.044 (7) | H15···C14xvii | 2.9800 |
C4···C19x | 3.458 (8) | H16···C003xxi | 2.9400 |
C4···N8x | 3.274 (7) | H16···H00Dxxi | 2.4200 |
C4···N001xiv | 3.421 (7) | H16···Ni1iii | 3.4800 |
C004···C10ix | 3.583 (8) | H16···Ni1xix | 3.4800 |
C004···C14x | 3.576 (8) | H17···C001iii | 3.0500 |
C004···N002viii | 3.394 (7) | H17···Ni1xix | 3.3800 |
C5···N7x | 3.345 (8) | H17···Ni1iii | 3.3800 |
C6···N7xv | 3.196 (9) | | |
| | | |
C001—Ni1—C002 | 90.9 (2) | C13—C14—C15 | 119.1 (5) |
C001—Ni1—C001i | 180 | C14—C15—C16 | 120.9 (6) |
C001—Ni1—C002i | 89.1 (2) | C15—C16—C17 | 121.8 (5) |
C001i—Ni1—C002 | 89.1 (2) | C16—C17—C18 | 117.3 (5) |
C002—Ni1—C002i | 180 | C13—C18—C19 | 105.7 (4) |
C001i—Ni1—C002i | 90.9 (2) | C13—C18—C17 | 121.5 (5) |
C1—N1—C004 | 130.0 (4) | C17—C18—C19 | 132.7 (5) |
N2—N1—C1 | 109.4 (4) | N5—C19—C18 | 108.9 (5) |
N2—N1—C004 | 120.5 (4) | N5—C19—N8 | 104.0 (4) |
N1—N2—N3 | 108.9 (4) | N8—C19—C18 | 147.1 (5) |
N2—N3—N4 | 106.5 (3) | C4—C3—H3 | 122.00 |
N3—N4—C8 | 137.0 (4) | C2—C3—H3 | 122.00 |
N3—N4—C1 | 111.0 (4) | N8—C003—H00D | 109.00 |
C1—N4—C8 | 112.0 (4) | H00E—C003—H00F | 110.00 |
N6—N5—C12 | 136.9 (4) | N8—C003—H00F | 109.00 |
N6—N5—C19 | 110.5 (4) | H00D—C003—H00E | 110.00 |
C12—N5—C19 | 112.5 (5) | N8—C003—H00E | 109.00 |
N5—N6—N7 | 106.2 (4) | H00D—C003—H00F | 109.00 |
N6—N7—N8 | 109.5 (5) | C3—C4—H4 | 120.00 |
N7—N8—C19 | 109.7 (4) | C5—C4—H4 | 120.00 |
N7—N8—C003 | 121.8 (5) | N1—C004—H00B | 109.00 |
C003—N8—C19 | 128.5 (5) | N1—C004—H00A | 109.00 |
N1—C1—C2 | 146.5 (5) | H00A—C004—H00C | 110.00 |
N1—C1—N4 | 104.2 (4) | N1—C004—H00C | 109.00 |
N4—C1—C2 | 109.3 (5) | H00A—C004—H00B | 109.00 |
C3—C2—C7 | 122.2 (5) | H00B—C004—H00C | 109.00 |
C1—C2—C3 | 132.7 (5) | C6—C5—H5 | 120.00 |
C1—C2—C7 | 105.2 (4) | C4—C5—H5 | 118.00 |
C2—C3—C4 | 116.9 (5) | C5—C6—H6 | 121.00 |
C3—C4—C5 | 120.8 (5) | C7—C6—H6 | 121.00 |
C4—C5—C6 | 121.9 (5) | C8—C9—H9 | 116.00 |
C5—C6—C7 | 118.8 (6) | C10—C9—H9 | 116.00 |
C2—C7—C8 | 110.0 (4) | C11—C10—H10 | 119.00 |
C2—C7—C6 | 119.4 (5) | C9—C10—H10 | 119.00 |
C6—C7—C8 | 130.6 (5) | C10—C11—H11 | 116.00 |
C7—C8—C9 | 131.7 (5) | C12—C11—H11 | 116.00 |
N4—C8—C9 | 124.8 (5) | C13—C14—H14 | 121.00 |
N4—C8—C7 | 103.5 (4) | C15—C14—H14 | 120.00 |
C8—C9—C10 | 128.3 (6) | C16—C15—H15 | 119.00 |
C9—C10—C11 | 121.9 (6) | C14—C15—H15 | 120.00 |
C10—C11—C12 | 127.3 (5) | C15—C16—H16 | 119.00 |
C11—C12—C13 | 131.5 (5) | C17—C16—H16 | 119.00 |
N5—C12—C11 | 125.5 (5) | C18—C17—H17 | 121.00 |
N5—C12—C13 | 102.9 (4) | C16—C17—H17 | 122.00 |
C12—C13—C14 | 130.6 (5) | Ni1—C001—N001 | 179.5 (5) |
C14—C13—C18 | 119.4 (5) | Ni1—C002—N002 | 177.6 (5) |
C12—C13—C18 | 110.0 (5) | | |
| | | |
C1—N1—N2—N3 | −0.4 (6) | C1—C2—C3—C4 | −178.7 (5) |
C004—N1—N2—N3 | 175.9 (5) | C1—C2—C7—C6 | 178.7 (5) |
N2—N1—C1—C2 | 179.5 (8) | C3—C2—C7—C6 | 0.3 (8) |
N2—N1—C1—N4 | 0.3 (6) | C7—C2—C3—C4 | −0.8 (7) |
C004—N1—C1—N4 | −175.6 (5) | C3—C2—C7—C8 | 180.0 (5) |
C004—N1—C1—C2 | 3.6 (12) | C2—C3—C4—C5 | 1.0 (8) |
N1—N2—N3—N4 | 0.4 (6) | C3—C4—C5—C6 | −0.7 (9) |
N2—N3—N4—C1 | −0.3 (6) | C4—C5—C6—C7 | 0.1 (9) |
N2—N3—N4—C8 | −176.5 (6) | C5—C6—C7—C8 | −179.5 (5) |
C1—N4—C8—C9 | −178.2 (5) | C5—C6—C7—C2 | 0.1 (8) |
C1—N4—C8—C7 | 1.2 (6) | C2—C7—C8—C9 | 179.7 (6) |
N3—N4—C8—C9 | −2.0 (10) | C6—C7—C8—N4 | 180.0 (5) |
C8—N4—C1—N1 | 177.2 (4) | C2—C7—C8—N4 | 0.3 (5) |
N3—N4—C8—C7 | 177.4 (5) | C6—C7—C8—C9 | −0.7 (10) |
N3—N4—C1—N1 | 0.0 (6) | N4—C8—C9—C10 | −0.5 (10) |
N3—N4—C1—C2 | −179.5 (4) | C7—C8—C9—C10 | −179.8 (6) |
C8—N4—C1—C2 | −2.3 (6) | C8—C9—C10—C11 | −178.8 (6) |
C12—N5—N6—N7 | −177.8 (6) | C9—C10—C11—C12 | −179.7 (6) |
N6—N5—C12—C13 | 174.9 (6) | C10—C11—C12—N5 | 1.5 (9) |
C19—N5—C12—C13 | −1.3 (6) | C10—C11—C12—C13 | 178.8 (6) |
C12—N5—C19—C18 | 0.3 (6) | C11—C12—C13—C14 | 6.3 (10) |
C12—N5—C19—N8 | 179.8 (4) | N5—C12—C13—C14 | −175.9 (6) |
C19—N5—N6—N7 | −1.6 (6) | N5—C12—C13—C18 | 1.7 (6) |
N6—N5—C19—N8 | 2.6 (6) | C11—C12—C13—C18 | −176.1 (6) |
N6—N5—C19—C18 | −176.8 (4) | C14—C13—C18—C17 | −0.4 (8) |
C19—N5—C12—C11 | 176.7 (5) | C12—C13—C18—C19 | −1.6 (6) |
N6—N5—C12—C11 | −7.2 (10) | C12—C13—C18—C17 | −178.3 (5) |
N5—N6—N7—N8 | −0.1 (6) | C14—C13—C18—C19 | 176.3 (5) |
N6—N7—N8—C003 | 179.0 (5) | C12—C13—C14—C15 | 177.3 (6) |
N6—N7—N8—C19 | 1.8 (6) | C18—C13—C14—C15 | −0.2 (8) |
N7—N8—C19—N5 | −2.7 (6) | C13—C14—C15—C16 | 1.0 (9) |
C003—N8—C19—C18 | −0.5 (13) | C14—C15—C16—C17 | −1.3 (9) |
C003—N8—C19—N5 | −179.6 (5) | C15—C16—C17—C18 | 0.8 (9) |
N7—N8—C19—C18 | 176.4 (8) | C16—C17—C18—C19 | −175.6 (6) |
N1—C1—C2—C3 | 1.4 (13) | C16—C17—C18—C13 | 0.1 (8) |
N1—C1—C2—C7 | −176.8 (8) | C13—C18—C19—N5 | 0.8 (6) |
N4—C1—C2—C3 | −179.4 (5) | C17—C18—C19—N8 | −2.1 (14) |
N4—C1—C2—C7 | 2.4 (6) | C13—C18—C19—N8 | −178.3 (8) |
C1—C2—C7—C8 | −1.7 (6) | C17—C18—C19—N5 | 177.0 (6) |
Symmetry codes: (i) −x, −y, −z; (ii) −x+1, −y, −z+1; (iii) −x+1, −y+1, −z+1; (iv) x−1, y−1, z−1; (v) x−1, y, z−1; (vi) x−1, y, z; (vii) −x+1/2, y−1/2, −z+1/2; (viii) −x+1, −y, −z; (ix) −x+2, −y, −z+1; (x) −x+2, −y+1, −z+1; (xi) x+1, y, z+1; (xii) x+1/2, −y+1/2, z+1/2; (xiii) x−3/2, −y+1/2, z−1/2; (xiv) x+1, y, z; (xv) x−1/2, −y+1/2, z−1/2; (xvi) −x+3/2, y−1/2, −z+3/2; (xvii) −x+3/2, y+1/2, −z+3/2; (xviii) −x+1/2, y+1/2, −z+1/2; (xix) x+1, y+1, z+1; (xx) −x+3/2, y−1/2, −z+1/2; (xxi) −x+2, −y+1, −z+2; (xxii) −x+3/2, y+1/2, −z+1/2; (xxiii) x+3/2, −y+1/2, z+1/2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C003—H00E···N001iii | 0.96 | 2.59 | 3.532 (9) | 166 |
C3—H3···N002viii | 0.98 | 2.54 | 3.509 (7) | 171 |
C4—H4···N001xiv | 0.97 | 2.52 | 3.421 (7) | 154 |
C004—H00A···N002viii | 0.96 | 2.49 | 3.394 (7) | 157 |
C10—H10···N3 | 0.93 | 2.56 | 3.184 (8) | 125 |
C10—H10···N6 | 0.93 | 2.56 | 3.193 (7) | 126 |
C14—H14···N001xviii | 0.90 | 2.61 | 3.489 (7) | 165 |
Symmetry codes: (iii) −x+1, −y+1, −z+1; (viii) −x+1, −y, −z; (xiv) x+1, y, z; (xviii) −x+1/2, y+1/2, −z+1/2. |
Experimental details
Crystal data |
Chemical formula | (C21H17N8)2[Ni(CN)4] |
Mr | 925.61 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 298 |
a, b, c (Å) | 16.296 (2), 7.5708 (7), 18.537 (3) |
β (°) | 115.42 (2) |
V (Å3) | 2065.6 (6) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.53 |
Crystal size (mm) | 0.2 × 0.2 × 0.1 |
|
Data collection |
Diffractometer | Nonius KappaCCD diffractometer |
Absorption correction | Multi-scan SORTAV (Blessing, 1995) |
Tmin, Tmax | 0.901, 0.949 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 18746, 4672, 3172 |
Rint | 0.069 |
(sin θ/λ)max (Å−1) | 0.651 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.097, 0.176, 1.33 |
No. of reflections | 4672 |
No. of parameters | 314 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.45, −0.73 |
Selected geometric parameters (Å, º) topNi1—C001 | 1.868 (7) | N5—C19 | 1.352 (6) |
Ni1—C002 | 1.888 (5) | N5—N6 | 1.371 (7) |
N1—N2 | 1.371 (5) | N5—C12 | 1.415 (7) |
N1—C004 | 1.462 (7) | N6—N7 | 1.290 (7) |
N1—C1 | 1.344 (7) | N7—N8 | 1.353 (7) |
N2—N3 | 1.297 (7) | N8—C003 | 1.463 (6) |
N3—N4 | 1.364 (5) | N8—C19 | 1.344 (7) |
N4—C1 | 1.352 (7) | N001—C001 | 1.160 (9) |
N4—C8 | 1.407 (7) | N002—C002 | 1.148 (7) |
| | | |
C001—Ni1—C002 | 90.9 (2) | N6—N7—N8 | 109.5 (5) |
C001—Ni1—C001i | 180 | N7—N8—C19 | 109.7 (4) |
C001—Ni1—C002i | 89.1 (2) | N7—N8—C003 | 121.8 (5) |
C002—Ni1—C002i | 180 | C003—N8—C19 | 128.5 (5) |
C1—N1—C004 | 130.0 (4) | N1—C1—C2 | 146.5 (5) |
N2—N1—C1 | 109.4 (4) | N1—C1—N4 | 104.2 (4) |
N2—N1—C004 | 120.5 (4) | N4—C1—C2 | 109.3 (5) |
N1—N2—N3 | 108.9 (4) | N4—C8—C9 | 124.8 (5) |
N2—N3—N4 | 106.5 (3) | N4—C8—C7 | 103.5 (4) |
N3—N4—C8 | 137.0 (4) | N5—C12—C11 | 125.5 (5) |
N3—N4—C1 | 111.0 (4) | N5—C12—C13 | 102.9 (4) |
C1—N4—C8 | 112.0 (4) | N5—C19—C18 | 108.9 (5) |
N6—N5—C12 | 136.9 (4) | N5—C19—N8 | 104.0 (4) |
N6—N5—C19 | 110.5 (4) | N8—C19—C18 | 147.1 (5) |
C12—N5—C19 | 112.5 (5) | Ni1—C001—N001 | 179.5 (5) |
N5—N6—N7 | 106.2 (4) | Ni1—C002—N002 | 177.6 (5) |
Symmetry code: (i) −x, −y, −z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C003—H00E···N001ii | 0.96 | 2.59 | 3.532 (9) | 166 |
C3—H3···N002iii | 0.98 | 2.54 | 3.509 (7) | 171 |
C4—H4···N001iv | 0.97 | 2.52 | 3.421 (7) | 154 |
C004—H00A···N002iii | 0.96 | 2.49 | 3.394 (7) | 157 |
C10—H10···N3 | 0.93 | 2.56 | 3.184 (8) | 125 |
C10—H10···N6 | 0.93 | 2.56 | 3.193 (7) | 126 |
C14—H14···N001v | 0.90 | 2.61 | 3.489 (7) | 165 |
Symmetry codes: (ii) −x+1, −y+1, −z+1; (iii) −x+1, −y, −z; (iv) x+1, y, z; (v) −x+1/2, y+1/2, −z+1/2. |
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The study of the title compound, (I), was undertaken to establish its three dimensional structure. To our knowledge only one other cyanine molecular complex, [cy+·AuCl2−] has been reported to date (Falkenberg et al., 1973).
The molecular strucure of (I), consisting of two 1-methyl-5-[3-(1-methyl-1H-tetrazolo[5,1-a]isoindol-5-yl)- allylidene]-5H-tetrazolo[5,1-a]isoindol-1-ium monocations, [MTIT]+, and an [Ni(CN)4]2− dianion, is illustrated in Fig. 1. Selected bond lengths and angles are given in Table 1. The organic [MTIT]+ cation is planar and the C—C bonds lengths range from 1.370 (9) to 1.457 (7) Å, thus indicating the aromaticity of the dye molecule. Both [MTIT]+ cations possess identical geometry in the carbon–nitrogen skeleton.
The geometry of the [Ni(CN)4]2− anion is typical for a square-planar Ni atom with four CN groups (Table 1). The Ni atom lies on a twofold rotation axis. These flat anions are located parallel to one another at a distance of 6.83 (s.u.?) Å, forming stacks. The stacks are inclined to the ac plane at 60 (s.u.?) and 120 (s.u.?)°, and are staggered (Fig. 2).
The [MTIT]+ dye cations are stacked stepwise with two oppositely oriented molecules. The [Ni(CN)4]2− anion is located between these steps, and the Ni···C distances are ca 3.796 and 3.739 Å, thus indicating additional interactions of the Ni atoms with the conjugated system of the dye (Fig. 3).
The N atoms of the CN groups are bound to the [MTIT]+ dye cations via C—H···N hydrogen bonds (the N···H distances are 2.432–2.530 Å [not in accord with Table 2]). Each [Ni(CN)4]2− anion has three N···H contacts with two dye molecules that lie in one plane (Table 2). These molecules are axial to the Ni atoms. One more pair of N···H contacts is formed with two dye molecules that are almost perpendicular to the plane of the [Ni(CN)4]2− complex anion. This situtation is shown in Fig. 4 and details are given in Table 2.
In view of these stabilizating interactions, (I) can be considered not as a simple cation–anion salt but as a molecular complex with specific intermolecular interactions.