Low-dimensional compounds containing cyanide groups. XXV. Synthesis, spectroscopic properties and crystal structures of two ionic iron(II) complexes with tri­cyano­methanide: tris­(1,10-phenanthroline-κ²N,N′)iron(II) bis­(tri­cyano­methanide) and tris­(2,2′-bi­pyridine-κ²N,N′)iron(II) bis­(tri­cyano­methanide) sesquihydrate

Two new diamagnetic coordination compounds, [Fe(phen)₃][C(CN)₃]₂, (I), and [Fe(bpy)₃][C(CN)₃]₂·1.5H₂O, (II), have been synthesized and characterized by single-crystal X-ray diffraction analysis, and IR and UV–Vis spectroscopy (phen is 1,10-phenanthroline, C₁₂H₈N₂, and bpy is 2,2′-bi­pyridine, C₁₀H₈N₂). Both com­pounds are ionic with distorted octa­hedral [Fe(phen)₃]²⁺ or [Fe(bpy)₃]²⁺ complex cations, with average Fe—N distances of 1.977 (2) and 1.971 (3) Å, respectively, and two uncoordinated planar tri­cyano­methanide, or [C(CN)₃]⁻, counter-anions bal­ancing the positive charges of the cations. Solvent water mol­ecules and tcm anions in (II) are linked via O—H...N hydrogen bonds into negatively charged layers and the inter­layer space is filled by [Fe(bpy)₃]²⁺ cations. The structures of (I) and (II) are stabilized by π–π inter­actions between the stacked aromatic rings of the phen ligands of two adjacent cations and by O—H...N hydrogen bonds, respectively, and also by π–π stacking inter­actions between phen and tcm units in (I).

Computing details

For both structures, data collection: WinExpose in X-AREA (Stoe & Cie, 2002); cell refinement: WinCell in X-AREA (Stoe & Cie, 2002); data reduction: WinIntegrate in X-AREA (Stoe & Cie, 2002); program(s) used to solve structure: SHELXS2013 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2001); software used to prepare material for publication: SHELXL2013 (Sheldrick, 2008).

Tris(1,10-phenanthroline-κ²N,N')iron(II) bis(tricyanomethanide) (I)

Crystal data

[Fe(C12H8N2)3](C4N3)2	F(000) = 1592
Mr = 776.60	Dx = 1.427 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71069 Å
a = 9.3618 (5) Å	Cell parameters from 20688 reflections
b = 30.6516 (14) Å	θ = 1.8–29.5°
c = 12.5952 (8) Å	µ = 0.47 mm^−1
β = 90.683 (5)°	T = 193 K
V = 3614.0 (3) Å^3	Prism, dark red
Z = 4	0.11 × 0.11 × 0.10 mm

Data collection

Stoe IPDSII diffractometer	5624 reflections with I > 2σ(I)
ω scans	Rint = 0.039
Absorption correction: numerical (XPREP in SHELXTL; Sheldrick, 2008)	θmax = 26.5°, θmin = 1.8°
Tmin = 0.843, Tmax = 0.926	h = −11→11
27223 measured reflections	k = −38→38
7492 independent reflections	l = −15→15

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)] = 0.031	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.065	H-atom parameters constrained
S = 0.98	w = 1/[σ^2(Fo^2) + (0.0328P)^2] where P = (Fo^2 + 2Fc^2)/3
7492 reflections	(Δ/σ)max = 0.001
520 parameters	Δρmax = 0.23 e Å^−3
0 restraints	Δρmin = −0.32 e Å^−3

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.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Fe1	0.55637 (2)	0.11933 (2)	0.73383 (2)	0.02313 (6)
N10	0.65910 (13)	0.10485 (4)	0.86705 (9)	0.0247 (3)
N20	0.51520 (13)	0.05610 (4)	0.73296 (9)	0.0252 (3)
N30	0.38084 (14)	0.13332 (4)	0.81261 (10)	0.0264 (3)
N40	0.58829 (14)	0.18291 (4)	0.74655 (10)	0.0277 (3)
N50	0.46751 (14)	0.13060 (4)	0.59297 (10)	0.0270 (3)
N60	0.72861 (14)	0.10868 (4)	0.64813 (10)	0.0265 (3)
C11	0.65446 (16)	0.06141 (5)	0.89074 (11)	0.0255 (3)
C12	0.73437 (17)	0.13043 (5)	0.93300 (12)	0.0294 (3)
H12	0.7396	0.1608	0.9180	0.035*
C13	0.80581 (18)	0.11444 (6)	1.02315 (12)	0.0346 (4)
H13	0.8577	0.1338	1.0681	0.041*
C14	0.80077 (18)	0.07083 (6)	1.04642 (13)	0.0352 (4)
H14	0.8487	0.0598	1.1076	0.042*
C15	0.72384 (17)	0.04255 (5)	0.97869 (12)	0.0303 (3)
C16	0.71353 (19)	−0.00371 (5)	0.99315 (13)	0.0360 (4)
H16	0.7609	−0.0169	1.0520	0.043*
C21	0.57622 (16)	0.03478 (5)	0.81770 (11)	0.0251 (3)
C22	0.44028 (18)	0.03219 (5)	0.66375 (13)	0.0328 (4)
H22	0.3983	0.0462	0.6038	0.039*
C23	0.4211 (2)	−0.01279 (5)	0.67599 (14)	0.0402 (4)
H23	0.3652	−0.0286	0.6257	0.048*
C24	0.4829 (2)	−0.03398 (5)	0.76043 (13)	0.0386 (4)
H24	0.4706	−0.0645	0.7689	0.046*
C25	0.56477 (18)	−0.01018 (5)	0.83453 (12)	0.0304 (3)
C26	0.63755 (19)	−0.02896 (5)	0.92453 (13)	0.0360 (4)
H26	0.6324	−0.0595	0.9361	0.043*
C31	0.36801 (17)	0.17667 (5)	0.83462 (12)	0.0283 (3)
C32	0.27761 (18)	0.10704 (5)	0.84723 (13)	0.0331 (4)
H32	0.2837	0.0768	0.8318	0.040*
C33	0.16158 (19)	0.12196 (6)	0.90484 (15)	0.0429 (4)
H33	0.0919	0.1019	0.9293	0.051*
C34	0.1479 (2)	0.16542 (6)	0.92629 (15)	0.0464 (5)
H34	0.0686	0.1758	0.9653	0.056*
C35	0.25242 (19)	0.19461 (6)	0.88988 (14)	0.0374 (4)
C36	0.2493 (2)	0.24074 (6)	0.90564 (17)	0.0510 (5)
H36	0.1722	0.2535	0.9429	0.061*
C41	0.47959 (17)	0.20372 (5)	0.79708 (12)	0.0284 (3)
C42	0.69335 (19)	0.20759 (5)	0.70878 (14)	0.0369 (4)
H42	0.7708	0.1938	0.6740	0.044*
C43	0.6936 (2)	0.25311 (6)	0.71848 (15)	0.0453 (5)
H43	0.7699	0.2696	0.6897	0.054*
C44	0.5852 (2)	0.27385 (6)	0.76900 (15)	0.0453 (5)
H44	0.5852	0.3047	0.7753	0.054*
C45	0.4737 (2)	0.24909 (5)	0.81167 (14)	0.0377 (4)
C46	0.3545 (2)	0.26650 (6)	0.86829 (17)	0.0507 (5)
H46	0.3494	0.2971	0.8799	0.061*
C51	0.56352 (17)	0.12778 (5)	0.51211 (11)	0.0267 (3)
C52	0.33459 (18)	0.14250 (5)	0.56701 (13)	0.0343 (4)
H52	0.2660	0.1448	0.6217	0.041*
C53	0.2918 (2)	0.15172 (6)	0.46238 (14)	0.0412 (4)
H53	0.1958	0.1600	0.4475	0.049*
C54	0.3876 (2)	0.14890 (6)	0.38159 (13)	0.0390 (4)
H54	0.3590	0.1551	0.3106	0.047*
C55	0.52884 (18)	0.13677 (5)	0.40527 (12)	0.0313 (4)
C56	0.6394 (2)	0.13198 (5)	0.32783 (13)	0.0353 (4)
H56	0.6190	0.1387	0.2556	0.042*
C61	0.70413 (16)	0.11476 (5)	0.54171 (11)	0.0264 (3)
C62	0.85816 (17)	0.09536 (5)	0.67781 (13)	0.0319 (4)
H62	0.8774	0.0911	0.7513	0.038*
C63	0.96753 (19)	0.08726 (6)	0.60545 (14)	0.0376 (4)
H63	1.0578	0.0770	0.6300	0.045*
C64	0.94392 (19)	0.09415 (5)	0.49967 (14)	0.0368 (4)
H64	1.0180	0.0892	0.4502	0.044*
C65	0.80927 (18)	0.10867 (5)	0.46456 (12)	0.0307 (4)
C66	0.77202 (19)	0.11813 (5)	0.35566 (12)	0.0363 (4)
H66	0.8419	0.1146	0.3023	0.044*
C1	0.89240 (19)	−0.03417 (6)	0.71828 (14)	0.0388 (4)
C2	0.9753 (2)	−0.00248 (6)	0.77134 (15)	0.0464 (5)
N2	1.0423 (2)	0.02325 (6)	0.81577 (16)	0.0692 (6)
C3	0.8157 (2)	−0.02292 (7)	0.62522 (16)	0.0491 (5)
N3	0.7544 (2)	−0.01431 (7)	0.54861 (16)	0.0752 (6)
C4	0.8888 (2)	−0.07696 (7)	0.75797 (14)	0.0408 (4)
N4	0.8900 (2)	−0.11228 (6)	0.78832 (14)	0.0580 (5)
C5	0.6279 (2)	0.23478 (7)	1.08715 (16)	0.0480 (5)
C6	0.560 (2)	0.2752 (7)	1.0993 (10)	0.049 (2)	0.5
C6A	0.578 (2)	0.2748 (7)	1.1324 (10)	0.049 (2)	0.5
N6	0.5113 (14)	0.3091 (5)	1.1153 (7)	0.074 (2)	0.5
N6A	0.5349 (14)	0.3074 (5)	1.1630 (7)	0.074 (2)	0.5
C7	0.7709 (2)	0.23323 (7)	1.05501 (18)	0.0541 (5)
N7	0.8877 (2)	0.23200 (7)	1.0286 (2)	0.0838 (7)
C8	0.5449 (2)	0.19672 (7)	1.09071 (14)	0.0451 (5)
N8	0.4783 (2)	0.16503 (7)	1.09364 (14)	0.0603 (5)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Fe1	0.02155 (11)	0.02257 (10)	0.02527 (10)	0.00107 (9)	0.00007 (7)	0.00098 (9)
N10	0.0233 (7)	0.0254 (6)	0.0255 (6)	0.0007 (5)	0.0024 (5)	−0.0005 (5)
N20	0.0248 (7)	0.0257 (6)	0.0253 (6)	0.0011 (5)	−0.0007 (5)	−0.0014 (5)
N30	0.0249 (7)	0.0263 (6)	0.0281 (6)	0.0021 (5)	0.0004 (5)	0.0030 (5)
N40	0.0272 (7)	0.0263 (7)	0.0297 (7)	−0.0009 (5)	−0.0015 (5)	0.0019 (5)
N50	0.0252 (7)	0.0240 (6)	0.0317 (7)	0.0006 (5)	−0.0009 (5)	0.0036 (5)
N60	0.0262 (7)	0.0252 (6)	0.0281 (6)	0.0014 (5)	−0.0003 (5)	−0.0005 (5)
C11	0.0232 (8)	0.0273 (8)	0.0260 (7)	0.0016 (6)	0.0019 (6)	0.0010 (6)
C12	0.0301 (9)	0.0271 (8)	0.0311 (8)	−0.0012 (7)	−0.0007 (6)	−0.0033 (6)
C13	0.0324 (9)	0.0394 (9)	0.0317 (8)	−0.0034 (8)	−0.0051 (7)	−0.0037 (7)
C14	0.0325 (10)	0.0435 (9)	0.0295 (8)	0.0016 (8)	−0.0081 (7)	0.0025 (7)
C15	0.0282 (9)	0.0339 (8)	0.0287 (8)	0.0010 (7)	−0.0011 (6)	0.0030 (6)
C16	0.0389 (10)	0.0353 (9)	0.0336 (9)	0.0044 (8)	−0.0057 (7)	0.0089 (7)
C21	0.0234 (8)	0.0254 (7)	0.0266 (7)	0.0022 (6)	0.0007 (6)	0.0005 (6)
C22	0.0357 (10)	0.0317 (8)	0.0307 (8)	−0.0006 (7)	−0.0064 (7)	−0.0006 (6)
C23	0.0488 (11)	0.0315 (9)	0.0400 (9)	−0.0079 (8)	−0.0092 (8)	−0.0061 (7)
C24	0.0495 (12)	0.0248 (8)	0.0413 (10)	−0.0029 (8)	−0.0034 (8)	−0.0012 (7)
C25	0.0332 (9)	0.0262 (8)	0.0318 (8)	0.0021 (7)	0.0006 (7)	0.0006 (6)
C26	0.0408 (10)	0.0275 (8)	0.0396 (9)	0.0026 (8)	−0.0012 (7)	0.0075 (7)
C31	0.0288 (9)	0.0277 (8)	0.0284 (8)	0.0052 (7)	−0.0016 (6)	0.0011 (6)
C32	0.0298 (9)	0.0307 (8)	0.0387 (9)	0.0008 (7)	0.0040 (7)	0.0039 (7)
C33	0.0316 (10)	0.0474 (10)	0.0499 (10)	−0.0012 (9)	0.0119 (8)	0.0047 (9)
C34	0.0328 (10)	0.0527 (12)	0.0539 (11)	0.0088 (9)	0.0142 (8)	−0.0029 (9)
C35	0.0321 (10)	0.0388 (9)	0.0413 (9)	0.0085 (8)	0.0028 (7)	−0.0040 (7)
C36	0.0470 (12)	0.0412 (11)	0.0649 (13)	0.0162 (9)	0.0068 (10)	−0.0120 (9)
C41	0.0305 (9)	0.0249 (7)	0.0298 (8)	0.0042 (7)	−0.0041 (6)	0.0004 (6)
C42	0.0352 (10)	0.0339 (9)	0.0417 (10)	−0.0076 (8)	0.0028 (7)	0.0015 (7)
C43	0.0469 (12)	0.0341 (9)	0.0548 (11)	−0.0148 (9)	−0.0014 (9)	0.0041 (8)
C44	0.0552 (13)	0.0251 (8)	0.0554 (11)	−0.0053 (8)	−0.0102 (9)	0.0012 (8)
C45	0.0434 (11)	0.0255 (8)	0.0439 (10)	0.0038 (8)	−0.0089 (8)	0.0002 (7)
C46	0.0549 (13)	0.0275 (9)	0.0695 (13)	0.0123 (9)	−0.0025 (10)	−0.0096 (9)
C51	0.0311 (9)	0.0220 (8)	0.0271 (7)	−0.0032 (6)	−0.0002 (6)	0.0000 (6)
C52	0.0284 (9)	0.0368 (9)	0.0377 (9)	0.0032 (7)	−0.0024 (7)	0.0069 (7)
C53	0.0320 (10)	0.0471 (10)	0.0444 (10)	0.0021 (8)	−0.0106 (8)	0.0108 (8)
C54	0.0442 (11)	0.0404 (10)	0.0323 (9)	−0.0048 (8)	−0.0103 (8)	0.0086 (7)
C55	0.0388 (10)	0.0249 (7)	0.0299 (8)	−0.0058 (7)	−0.0051 (7)	0.0020 (6)
C56	0.0499 (11)	0.0308 (8)	0.0250 (8)	−0.0091 (8)	−0.0002 (7)	0.0007 (6)
C61	0.0292 (8)	0.0223 (7)	0.0276 (7)	−0.0017 (6)	0.0014 (6)	−0.0009 (6)
C62	0.0271 (9)	0.0336 (9)	0.0348 (9)	0.0038 (7)	0.0004 (7)	0.0008 (7)
C63	0.0265 (9)	0.0400 (9)	0.0463 (10)	0.0065 (8)	0.0040 (7)	0.0001 (8)
C64	0.0319 (10)	0.0379 (9)	0.0409 (9)	0.0013 (8)	0.0114 (7)	−0.0052 (7)
C65	0.0346 (9)	0.0257 (8)	0.0320 (8)	−0.0041 (7)	0.0056 (7)	−0.0047 (6)
C66	0.0455 (10)	0.0329 (8)	0.0306 (8)	−0.0080 (8)	0.0084 (7)	−0.0034 (7)
C1	0.0345 (10)	0.0443 (10)	0.0375 (9)	0.0072 (8)	−0.0071 (7)	−0.0084 (8)
C2	0.0503 (13)	0.0395 (10)	0.0490 (11)	0.0095 (9)	−0.0195 (9)	0.0037 (8)
N2	0.0880 (15)	0.0439 (10)	0.0747 (13)	−0.0050 (10)	−0.0487 (11)	0.0082 (9)
C3	0.0419 (11)	0.0579 (12)	0.0473 (11)	0.0067 (10)	−0.0097 (9)	−0.0117 (9)
N3	0.0734 (14)	0.0923 (15)	0.0592 (12)	0.0065 (12)	−0.0312 (11)	−0.0060 (11)
C4	0.0330 (10)	0.0493 (11)	0.0402 (10)	−0.0014 (8)	0.0009 (8)	−0.0126 (8)
N4	0.0614 (12)	0.0485 (11)	0.0642 (11)	−0.0063 (9)	0.0021 (9)	−0.0048 (9)
C5	0.0374 (11)	0.0539 (12)	0.0529 (12)	0.0118 (9)	0.0040 (9)	−0.0030 (9)
C6	0.031 (4)	0.0544 (14)	0.062 (7)	0.006 (3)	0.003 (5)	0.002 (6)
C6A	0.031 (4)	0.0544 (14)	0.062 (7)	0.006 (3)	0.003 (5)	0.002 (6)
N6	0.048 (4)	0.0540 (16)	0.122 (7)	0.008 (2)	0.026 (5)	0.000 (5)
N6A	0.048 (4)	0.0540 (16)	0.122 (7)	0.008 (2)	0.026 (5)	0.000 (5)
C7	0.0438 (13)	0.0524 (12)	0.0660 (14)	0.0096 (10)	−0.0005 (10)	−0.0162 (10)
N7	0.0464 (12)	0.0772 (14)	0.128 (2)	0.0102 (11)	0.0171 (12)	−0.0346 (13)
C8	0.0438 (12)	0.0561 (12)	0.0353 (10)	0.0131 (10)	−0.0001 (8)	0.0033 (8)
N8	0.0586 (12)	0.0691 (13)	0.0532 (11)	0.0035 (10)	−0.0015 (9)	0.0075 (9)

Geometric parameters (Å, º)

Fe1—N10	1.9745 (12)	C35—C36	1.428 (3)
Fe1—N20	1.9761 (12)	C36—C46	1.351 (3)
Fe1—N30	1.9767 (13)	C36—H36	0.9500
Fe1—N40	1.9779 (13)	C41—C45	1.404 (2)
Fe1—N60	1.9782 (13)	C42—C43	1.401 (2)
Fe1—N50	1.9810 (13)	C42—H42	0.9500
N10—C12	1.3369 (19)	C43—C44	1.362 (3)
N10—C11	1.3654 (19)	C43—H43	0.9500
N20—C22	1.332 (2)	C44—C45	1.403 (3)
N20—C21	1.3704 (19)	C44—H44	0.9500
N30—C32	1.336 (2)	C45—C46	1.434 (3)
N30—C31	1.3628 (19)	C46—H46	0.9500
N40—C42	1.333 (2)	C51—C55	1.408 (2)
N40—C41	1.365 (2)	C51—C61	1.421 (2)
N50—C52	1.334 (2)	C52—C53	1.402 (2)
N50—C51	1.3691 (19)	C52—H52	0.9500
N60—C62	1.329 (2)	C53—C54	1.367 (3)
N60—C61	1.3700 (19)	C53—H53	0.9500
C11—C15	1.402 (2)	C54—C55	1.402 (2)
C11—C21	1.426 (2)	C54—H54	0.9500
C12—C13	1.400 (2)	C55—C56	1.438 (2)
C12—H12	0.9500	C56—C66	1.354 (3)
C13—C14	1.370 (2)	C56—H56	0.9500
C13—H13	0.9500	C61—C65	1.404 (2)
C14—C15	1.408 (2)	C62—C63	1.401 (2)
C14—H14	0.9500	C62—H62	0.9500
C15—C16	1.433 (2)	C63—C64	1.364 (2)
C16—C26	1.356 (2)	C63—H63	0.9500
C16—H16	0.9500	C64—C65	1.403 (2)
C21—C25	1.399 (2)	C64—H64	0.9500
C22—C23	1.399 (2)	C65—C66	1.441 (2)
C22—H22	0.9500	C66—H66	0.9500
C23—C24	1.368 (2)	C1—C4	1.404 (3)
C23—H23	0.9500	C1—C2	1.407 (3)
C24—C25	1.405 (2)	C1—C3	1.410 (3)
C24—H24	0.9500	C2—N2	1.149 (2)
C25—C26	1.436 (2)	C3—N3	1.148 (3)
C26—H26	0.9500	C4—N4	1.148 (2)
C31—C35	1.406 (2)	C5—C6	1.40 (2)
C31—C41	1.419 (2)	C5—C8	1.403 (3)
C32—C33	1.391 (2)	C5—C7	1.404 (3)
C32—H32	0.9500	C5—C6A	1.43 (2)
C33—C34	1.366 (3)	C6—N6	1.15 (2)
C33—H33	0.9500	C6A—N6A	1.15 (2)
C34—C35	1.407 (3)	C7—N7	1.147 (3)
C34—H34	0.9500	C8—N8	1.155 (3)
N10—Fe1—N20	82.96 (5)	C33—C34—C35	119.23 (16)
N10—Fe1—N30	91.24 (5)	C33—C34—H34	120.4
N20—Fe1—N30	93.00 (5)	C35—C34—H34	120.4
N10—Fe1—N40	94.65 (5)	C31—C35—C34	117.08 (16)
N20—Fe1—N40	174.97 (5)	C31—C35—C36	118.26 (17)
N30—Fe1—N40	82.60 (5)	C34—C35—C36	124.66 (17)
N10—Fe1—N60	91.98 (5)	C46—C36—C35	120.91 (18)
N20—Fe1—N60	89.73 (5)	C46—C36—H36	119.5
N30—Fe1—N60	176.01 (5)	C35—C36—H36	119.5
N40—Fe1—N60	94.79 (5)	N40—C41—C45	123.68 (15)
N10—Fe1—N50	174.50 (5)	N40—C41—C31	116.00 (13)
N20—Fe1—N50	94.95 (5)	C45—C41—C31	120.32 (15)
N30—Fe1—N50	93.95 (5)	N40—C42—C43	122.33 (17)
N40—Fe1—N50	87.83 (5)	N40—C42—H42	118.8
N60—Fe1—N50	82.90 (5)	C43—C42—H42	118.8
C12—N10—C11	117.01 (13)	C44—C43—C42	120.34 (17)
C12—N10—Fe1	130.09 (10)	C44—C43—H43	119.8
C11—N10—Fe1	112.86 (10)	C42—C43—H43	119.8
C22—N20—C21	117.31 (13)	C43—C44—C45	119.26 (16)
C22—N20—Fe1	130.12 (11)	C43—C44—H44	120.4
C21—N20—Fe1	112.57 (9)	C45—C44—H44	120.4
C32—N30—C31	117.12 (14)	C44—C45—C41	117.06 (16)
C32—N30—Fe1	129.95 (11)	C44—C45—C46	125.19 (16)
C31—N30—Fe1	112.92 (10)	C41—C45—C46	117.75 (16)
C42—N40—C41	117.31 (14)	C36—C46—C45	122.04 (17)
C42—N40—Fe1	129.91 (11)	C36—C46—H46	119.0
C41—N40—Fe1	112.67 (10)	C45—C46—H46	119.0
C52—N50—C51	116.99 (13)	N50—C51—C55	123.56 (15)
C52—N50—Fe1	130.39 (11)	N50—C51—C61	115.91 (13)
C51—N50—Fe1	112.51 (10)	C55—C51—C61	120.53 (14)
C62—N60—C61	117.29 (13)	N50—C52—C53	122.74 (16)
C62—N60—Fe1	130.11 (11)	N50—C52—H52	118.6
C61—N60—Fe1	112.55 (10)	C53—C52—H52	118.6
N10—C11—C15	124.00 (14)	C54—C53—C52	120.30 (16)
N10—C11—C21	115.77 (13)	C54—C53—H53	119.8
C15—C11—C21	120.21 (14)	C52—C53—H53	119.8
N10—C12—C13	122.81 (14)	C53—C54—C55	118.93 (15)
N10—C12—H12	118.6	C53—C54—H54	120.5
C13—C12—H12	118.6	C55—C54—H54	120.5
C14—C13—C12	119.88 (15)	C54—C55—C51	117.47 (15)
C14—C13—H13	120.1	C54—C55—C56	124.57 (15)
C12—C13—H13	120.1	C51—C55—C56	117.94 (15)
C13—C14—C15	119.33 (15)	C66—C56—C55	121.44 (15)
C13—C14—H14	120.3	C66—C56—H56	119.3
C15—C14—H14	120.3	C55—C56—H56	119.3
C11—C15—C14	116.97 (14)	N60—C61—C65	123.27 (14)
C11—C15—C16	118.50 (15)	N60—C61—C51	116.01 (13)
C14—C15—C16	124.53 (15)	C65—C61—C51	120.71 (14)
C26—C16—C15	121.30 (15)	N60—C62—C63	122.88 (15)
C26—C16—H16	119.3	N60—C62—H62	118.6
C15—C16—H16	119.3	C63—C62—H62	118.6
N20—C21—C25	123.77 (14)	C64—C63—C62	119.78 (16)
N20—C21—C11	115.83 (13)	C64—C63—H63	120.1
C25—C21—C11	120.40 (14)	C62—C63—H63	120.1
N20—C22—C23	122.50 (15)	C63—C64—C65	119.43 (15)
N20—C22—H22	118.8	C63—C64—H64	120.3
C23—C22—H22	118.8	C65—C64—H64	120.3
C24—C23—C22	119.98 (16)	C64—C65—C61	117.30 (15)
C24—C23—H23	120.0	C64—C65—C66	124.76 (15)
C22—C23—H23	120.0	C61—C65—C66	117.93 (15)
C23—C24—C25	119.49 (15)	C56—C66—C65	121.35 (15)
C23—C24—H24	120.3	C56—C66—H66	119.3
C25—C24—H24	120.3	C65—C66—H66	119.3
C21—C25—C24	116.93 (14)	C4—C1—C2	119.42 (16)
C21—C25—C26	118.57 (15)	C4—C1—C3	120.67 (17)
C24—C25—C26	124.50 (15)	C2—C1—C3	119.90 (17)
C16—C26—C25	120.99 (15)	N2—C2—C1	179.2 (2)
C16—C26—H26	119.5	N3—C3—C1	178.9 (2)
C25—C26—H26	119.5	N4—C4—C1	177.6 (2)
N30—C31—C35	123.54 (15)	C6—C5—C8	118.8 (9)
N30—C31—C41	115.77 (14)	C6—C5—C7	119.6 (9)
C35—C31—C41	120.69 (14)	C8—C5—C7	120.77 (18)
N30—C32—C33	123.00 (16)	C8—C5—C6A	121.1 (9)
N30—C32—H32	118.5	C7—C5—C6A	117.3 (9)
C33—C32—H32	118.5	N6—C6—C5	175.1 (12)
C34—C33—C32	119.99 (17)	N6A—C6A—C5	176.0 (10)
C34—C33—H33	120.0	N7—C7—C5	179.9 (3)
C32—C33—H33	120.0	N8—C8—C5	179.1 (2)

Tris(2,2'-bipyridine-κ²N,N')iron(II) bis(tricyanomethanide) sesquihydrate (II)

Crystal data

[Fe(C10H8N2)3](C4N3)2·1.5H2O	Dx = 1.299 Mg m^−3
Mr = 731.56	Mo Kα radiation, λ = 0.71069 Å
Trigonal, R32:H	Cell parameters from 19620 reflections
a = 15.4137 (6) Å	θ = 1.7–29.5°
c = 27.2718 (14) Å	µ = 0.45 mm^−1
V = 5611.2 (5) Å^3	T = 193 K
Z = 6	Prism, dark red
F(000) = 2262	0.20 × 0.11 × 0.11 mm

Data collection

Stoe IPDSII diffractometer	2420 reflections with I > 2σ(I)
ω scans	Rint = 0.029
Absorption correction: numerical (XPREP in SHELXTL; Sheldrick, 2008)	θmax = 26.5°, θmin = 1.7°
Tmin = 0.854, Tmax = 0.914	h = −19→19
14192 measured reflections	k = −19→19
2592 independent reflections	l = −34→34

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.027	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.061	w = 1/[σ^2(Fo^2) + (0.0418P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.01	(Δ/σ)max = 0.001
2592 reflections	Δρmax = 0.26 e Å^−3
166 parameters	Δρmin = −0.32 e Å^−3
0 restraints	Absolute structure: Refined as an inversion twin; Flack (1983), with HOW MANY Friedel pairs?
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.48 (2)

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. Refined as a 2-component inversion twin.

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

	x	y	z	Uiso*/Ueq
Fe1	1.0000	1.0000	0.80752 (2)	0.03149 (13)
N10	0.98006 (13)	0.88285 (13)	0.84557 (6)	0.0366 (4)
N20	0.88653 (13)	0.89542 (13)	0.76990 (6)	0.0355 (4)
C11	0.9064 (2)	0.79337 (15)	0.82873 (8)	0.0442 (5)
C12	1.03318 (19)	0.8830 (2)	0.88472 (8)	0.0458 (5)
H12	1.0857	0.9452	0.8965	0.055*
C13	1.0142 (2)	0.7958 (2)	0.90847 (11)	0.0601 (7)
H13	1.0518	0.7985	0.9366	0.072*
C14	0.9406 (3)	0.7057 (2)	0.89086 (14)	0.0765 (10)
H14	0.9273	0.6450	0.9062	0.092*
C15	0.8858 (2)	0.7040 (2)	0.85052 (12)	0.0690 (9)
H15	0.8344	0.6421	0.8378	0.083*
C21	0.85033 (17)	0.80076 (17)	0.78679 (9)	0.0416 (5)
C22	0.83910 (16)	0.90937 (19)	0.73183 (7)	0.0417 (5)
H22	0.8640	0.9753	0.7196	0.050*
C23	0.75557 (19)	0.8314 (2)	0.70987 (9)	0.0495 (6)
H23	0.7242	0.8437	0.6829	0.059*
C24	0.7185 (2)	0.7358 (2)	0.72764 (10)	0.0574 (7)
H24	0.6606	0.6814	0.7134	0.069*
C25	0.7665 (2)	0.7197 (2)	0.76646 (10)	0.0554 (7)
H25	0.7424	0.6541	0.7790	0.066*
C1	0.6667	0.3333	0.95444 (14)	0.0506 (9)
C2	0.7673 (2)	0.4078 (2)	0.95174 (10)	0.0568 (7)
N2	0.8505 (2)	0.4692 (2)	0.94954 (13)	0.0829 (8)
C3	0.6667	0.3333	0.8333	0.0385 (9)
C4	0.6667	0.4242 (2)	0.8333	0.0456 (7)
N4	0.6667	0.4985 (2)	0.8333	0.0698 (10)
C5	1.0000	1.0000	1.0000	0.0444 (11)
C6	0.9082 (3)	0.9082 (3)	1.0000	0.0485 (8)
N6	0.8337 (2)	0.8337 (2)	1.0000	0.0687 (10)
O1	1.0000	0.6426 (3)	1.0000	0.1135 (17)
H1	0.950 (4)	0.575 (4)	0.9843 (18)	0.136*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Fe1	0.03306 (16)	0.03306 (16)	0.0284 (2)	0.01653 (8)	0.000	0.000
N10	0.0371 (9)	0.0393 (10)	0.0345 (9)	0.0199 (8)	−0.0032 (8)	0.0009 (8)
N20	0.0378 (9)	0.0392 (10)	0.0310 (9)	0.0204 (8)	−0.0013 (7)	−0.0001 (8)
C11	0.0444 (14)	0.0372 (10)	0.0473 (11)	0.0176 (11)	−0.0067 (11)	0.0043 (8)
C12	0.0481 (13)	0.0501 (13)	0.0420 (12)	0.0267 (11)	−0.0093 (10)	0.0011 (10)
C13	0.0646 (17)	0.0634 (17)	0.0560 (15)	0.0347 (14)	−0.0138 (13)	0.0128 (13)
C14	0.081 (2)	0.0515 (17)	0.087 (2)	0.0260 (16)	−0.0208 (19)	0.0221 (16)
C15	0.0714 (19)	0.0392 (13)	0.081 (2)	0.0164 (12)	−0.0248 (16)	0.0110 (13)
C21	0.0400 (12)	0.0385 (11)	0.0428 (11)	0.0168 (10)	−0.0052 (10)	0.0014 (9)
C22	0.0435 (11)	0.0456 (14)	0.0347 (9)	0.0214 (11)	−0.0041 (8)	0.0017 (10)
C23	0.0488 (13)	0.0612 (16)	0.0375 (12)	0.0266 (12)	−0.0108 (10)	−0.0032 (11)
C24	0.0498 (14)	0.0532 (15)	0.0549 (15)	0.0150 (12)	−0.0183 (12)	−0.0093 (12)
C25	0.0545 (15)	0.0407 (13)	0.0565 (15)	0.0130 (11)	−0.0130 (13)	0.0007 (11)
C1	0.0579 (14)	0.0579 (14)	0.0361 (17)	0.0289 (7)	0.000	0.000
C2	0.0639 (18)	0.0589 (17)	0.0489 (14)	0.0317 (14)	−0.0049 (12)	−0.0053 (11)
N2	0.0629 (17)	0.0726 (18)	0.102 (2)	0.0258 (16)	−0.0078 (15)	−0.0082 (16)
C3	0.0392 (14)	0.0392 (14)	0.037 (2)	0.0196 (7)	0.000	0.000
C4	0.0376 (17)	0.0439 (14)	0.0531 (19)	0.0188 (9)	0.0054 (15)	0.0027 (7)
N4	0.0541 (19)	0.0455 (13)	0.113 (3)	0.0271 (10)	0.012 (2)	0.0061 (10)
C5	0.0459 (16)	0.0459 (16)	0.041 (2)	0.0230 (8)	0.000	0.000
C6	0.0515 (16)	0.0515 (16)	0.0414 (18)	0.0250 (19)	−0.0060 (8)	0.0060 (8)
N6	0.0595 (15)	0.0595 (15)	0.070 (2)	0.0172 (18)	−0.0113 (10)	0.0113 (10)
O1	0.147 (4)	0.0912 (18)	0.121 (4)	0.073 (2)	−0.072 (3)	−0.0362 (17)

Geometric parameters (Å, º)

Fe1—N10	1.9689 (18)	C22—C23	1.383 (3)
Fe1—N10^i	1.9690 (18)	C22—H22	0.9500
Fe1—N10^ii	1.9690 (18)	C23—C24	1.375 (4)
Fe1—N20	1.9725 (18)	C23—H23	0.9500
Fe1—N20^ii	1.9725 (18)	C24—C25	1.383 (4)
Fe1—N20^i	1.9725 (18)	C24—H24	0.9500
N10—C12	1.345 (3)	C25—H25	0.9500
N10—C11	1.355 (3)	C1—C2^iii	1.396 (3)
N20—C22	1.348 (3)	C1—C2^iv	1.396 (3)
N20—C21	1.356 (3)	C1—C2	1.396 (3)
C11—C15	1.383 (3)	C2—N2	1.154 (4)
C11—C21	1.472 (3)	C3—C4^iii	1.400 (3)
C12—C13	1.384 (4)	C3—C4^iv	1.400 (4)
C12—H12	0.9500	C3—C4	1.400 (3)
C13—C14	1.367 (4)	C4—N4	1.146 (5)
C13—H13	0.9500	C5—C6^ii	1.415 (4)
C14—C15	1.379 (4)	C5—C6^i	1.415 (4)
C14—H14	0.9500	C5—C6	1.415 (4)
C15—H15	0.9500	C6—N6	1.149 (5)
C21—C25	1.387 (4)	O1—H1	1.02 (5)
N10—Fe1—N10^i	94.78 (7)	C15—C14—H14	120.4
N10—Fe1—N10^ii	94.78 (7)	C14—C15—C11	119.4 (3)
N10^i—Fe1—N10^ii	94.78 (7)	C14—C15—H15	120.3
N10—Fe1—N20	81.76 (7)	C11—C15—H15	120.3
N10^i—Fe1—N20	175.62 (8)	N20—C21—C25	122.0 (2)
N10^ii—Fe1—N20	88.21 (7)	N20—C21—C11	113.93 (19)
N10—Fe1—N20^ii	175.62 (8)	C25—C21—C11	124.0 (2)
N10^i—Fe1—N20^ii	88.21 (7)	N20—C22—C23	122.6 (2)
N10^ii—Fe1—N20^ii	81.76 (7)	N20—C22—H22	118.7
N20—Fe1—N20^ii	95.40 (7)	C23—C22—H22	118.7
N10—Fe1—N20^i	88.21 (7)	C24—C23—C22	119.1 (2)
N10^i—Fe1—N20^i	81.76 (7)	C24—C23—H23	120.5
N10^ii—Fe1—N20^i	175.62 (8)	C22—C23—H23	120.5
N20—Fe1—N20^i	95.40 (7)	C23—C24—C25	119.3 (2)
N20^ii—Fe1—N20^i	95.40 (7)	C23—C24—H24	120.4
C12—N10—C11	118.0 (2)	C25—C24—H24	120.4
C12—N10—Fe1	126.97 (16)	C24—C25—C21	119.0 (2)
C11—N10—Fe1	114.96 (14)	C24—C25—H25	120.5
C22—N20—C21	118.0 (2)	C21—C25—H25	120.5
C22—N20—Fe1	126.90 (16)	C2^iii—C1—C2^iv	119.72 (4)
C21—N20—Fe1	114.99 (15)	C2^iii—C1—C2	119.72 (4)
N10—C11—C15	121.8 (2)	C2^iv—C1—C2	119.72 (4)
N10—C11—C21	114.21 (19)	N2—C2—C1	179.9 (4)
C15—C11—C21	124.0 (2)	C4^iii—C3—C4^iv	120.004 (2)
N10—C12—C13	122.5 (2)	C4^iii—C3—C4	119.998 (4)
N10—C12—H12	118.8	C4^iv—C3—C4	119.997 (2)
C13—C12—H12	118.8	N4—C4—C3	180.0
C14—C13—C12	119.1 (3)	C6^ii—C5—C6^i	120.000 (7)
C14—C13—H13	120.4	C6^ii—C5—C6	120.000 (2)
C12—C13—H13	120.4	C6^i—C5—C6	120.000 (2)
C13—C14—C15	119.2 (3)	N6—C6—C5	180.0 (6)
C13—C14—H14	120.4

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N2	1.02 (5)	1.85 (5)	2.861 (4)	168 (4)