Tris(1,10-phenanthroline-κ2N,N′)iron(II) bis­(1,1-dicyano-2-eth­oxy-2-oxoethanide)

Cai, Z.-M.; Zhan, S.-Z.

doi:10.1107/S1600536812026967

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 7| July 2012| Page m956

https://doi.org/10.1107/S1600536812026967

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Tris(1,10-phenanthroline-κ²N,N′)iron(II) bis(1,1-dicyano-2-ethoxy-2-oxoethanide)

Zhan-Mao Cai ^a and Shu-Zhong Zhan ^a ^*

^aCollege of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou 510640, People's Republic of China
^*Correspondence e-mail: shzhzhan@scut.edu.cn

(Received 23 May 2012; accepted 14 June 2012; online 20 June 2012)

The title compound, [Fe(C₁₂H₈N₂)₃](C₆H₅N₂O₂)₂, consists of one [Fe(phen)₃]²⁺ cation (phen = 1,10-phenanthroline) and two 1,1-dicyano-2-ethoxy-2-oxoethanide anions. Five atoms of the anion are disordered over two positions [site occupancy = 0.521 (13) for the major component]. In the complex cation, the Fe^II atom is coordinated by six N atoms from three phen ligands in a distorted octahedral geometry. Two intramolecular C—H⋯N hydrogen bonds occur in the complex cation. The crystal structure is mainly stabilized by Coulombic interactions. Weak intermolecular C—H⋯N interactions are also observed.

Related literature

For tetracyanoethylene (TCNE) molecular reactions, see: Kaim & Moscherosch (1994 ). For geometrical parameters of TCNE, see: Miller (2006 ). For the synthesis of the dicyanoethylacetate anion, see: Lv et al. (2008 ). For the structure of free TCNE, see: Drück & Güth (1982 ). For a related structure, see: Uçar et al. (2005 ).

Experimental

Crystal data

[Fe(C₁₂H₈N₂)₃](C₆H₅N₂O₂)₂
M_r = 870.70
Monoclinic, P 2₁ /n
a = 15.5855 (5) Å
b = 13.0261 (4) Å
c = 21.4979 (6) Å
β = 109.068 (1)°
V = 4125.0 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.43 mm⁻¹
T = 296 K
0.20 × 0.10 × 0.10 mm

Data collection

Bruker APEXII diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.920, T_max = 0.959
36630 measured reflections
8551 independent reflections
4862 reflections with I > 2σ(I)
R_int = 0.081

Refinement

R[F² > 2σ(F²)] = 0.055
wR(F²) = 0.156
S = 1.02
8551 reflections
614 parameters
71 restraints
H-atom parameters constrained
Δρ_max = 0.40 e Å⁻³
Δρ_min = −0.44 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C25—H25⋯N2	0.93	2.62	3.089 (4)	112
C34—H34⋯N3	0.93	2.60	3.078 (4)	113
C3—H3⋯N8ⁱ	0.93	2.47	3.206 (6)	136
Symmetry code: (i) -x+1, -y+1, -z+1.

Data collection: APEX2 (Bruker, 2005 ); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536812026967/bx2413sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812026967/bx2413Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536812026967/bx2413Isup3.cdx

checkCIF report

Comment top

Tetracyanoethylene(TCNE) molecule is one of the most versatile organic compounds as it is used in a many different of reactions (Kaim & Moscherosch, 1994), due to its very low-lying p* orbital. Our interest focus on the reactivity of TCNE and transitionmetal complexes to form discrete as well as polymeric charge-transfer compoundsin which the donors and acceptors are coordinated through nitrile positions. With this mind, we have tried the reaction of FeCl₃×6H₂O, 1,10-phenanthroline and TCNE, surprisingly, the title complex {[Fe^II(phen)₃][(NC)₂C—CO₂C₂H₅]} is obtained. In the presence of H₂O, TCNE can react with ethanol to give dicyanoethylacetate anion-radical (Lv, et al., 2008). The title complex consists of one [Fe^II(phen)₃]²⁺ cation, and two dicyanoethylacetate anion-radical. The CN distances are normal range from 1.139 (5) to 1.154 (5) Å. The average C—CN distance of 1.400 (6) Å is 0.035 Å shorter than that observed for the free TCNE (1.435 Å) (Drück & Güth, 1982). The NC—C—CN bond angle are 118.5 (3) and 122.5 (4)^o, which are longer than observed in free TCNE (116.5 (12)^o) in accord with its sp² central carbon atom (Miller, 2006; Lv, et al., 2008). In the cation, the Fe^II atom is coordinated by six N atoms from three phen ligands in a distorted octahedral geometry.The average bond length of Fe—N is 1.973 (3) Å and similar to tris(1,10-phenanthroline-²N,N')iron(II) squarate octahydrate (Uçar, et al., 2005) as representative example.The crystal structure is mainly stabilized by coulombic interactions. Weak C—H ···N and C—H ···F interactions are also observed, See Table 1.

Related literature top

For tetracyanoethylene (TCNE) molecular reactions, see: Kaim & Moscherosch (1994); For geometrical parameters of TCNE, see: Miller (2006). For the synthesis of the dicyanoethylacetate anion, see: Lv et al. (2008). For the structure of free TCNE, see: Drück & Güth (1982). For a related structure, see: Uçar et al. (2005).

Experimental top

After addition of tetracyanoethylene (0.261 g, 2 mmol) in ethanol (10 ml) to the solution containing FeCl₃×6H₂O(0.270 g, 1 mmol) and 1,10-phenanthroline (phen)(0.400 g, 2 mmol) in ethanol (10 ml), the mixture was stirred at room temperature for 1 h. The solution color turned from red to brown. Single crystals were obtained from the filtrate which was allowed to stand at room temperature for several days, collected by filtration, and dried in vacuo (0.26 g, 29.5%). Calcd for C₄₈H₃₄Fe₂N₁₀O₄:C 66.15, H 3.91, N 16.08. Found: C 65.95, H 3.93, N 16.10.

Structure description top

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

Fig. 1. ORTEP view of the title compound, at the 30% probability level.

Tris(1,10-phenanthroline-κ²N,N')iron(II) bis(1,1-dicyano-2-ethoxy-2-oxoethanide) top

Crystal data top

[Fe(C₁₂H₈N₂)₃](C₆H₅N₂O₂)₂	F(000) = 1800
M_r = 870.70	D_x = 1.402 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 15.5855 (5) Å	Cell parameters from 36630 reflections
b = 13.0261 (4) Å	θ = 1.9–26.5°
c = 21.4979 (6) Å	µ = 0.43 mm⁻¹
β = 109.068 (1)°	T = 296 K
V = 4125.0 (2) Å³	Block, brown
Z = 4	0.20 × 0.10 × 0.10 mm

Data collection top

Bruker APEXII diffractometer	4862 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.081
Graphite monochromator	θ_max = 26.5°, θ_min = 1.9°
ω scans	h = −17→19
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −15→16
T_min = 0.920, T_max = 0.959	l = −26→26
36630 measured reflections	2 standard reflections every 0 reflections
8551 independent reflections	intensity decay: none

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.055	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.156	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.072P)²] where P = (F_o² + 2F_c²)/3
8551 reflections	(Δ/σ)_max = 0.001
614 parameters	Δρ_max = 0.40 e Å⁻³
71 restraints	Δρ_min = −0.44 e Å⁻³

Crystal data top

[Fe(C₁₂H₈N₂)₃](C₆H₅N₂O₂)₂	V = 4125.0 (2) Å³
M_r = 870.70	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 15.5855 (5) Å	µ = 0.43 mm⁻¹
b = 13.0261 (4) Å	T = 296 K
c = 21.4979 (6) Å	0.20 × 0.10 × 0.10 mm
β = 109.068 (1)°

Data collection top

Bruker APEXII diffractometer	4862 reflections with I > 2σ(I)
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	R_int = 0.081
T_min = 0.920, T_max = 0.959	2 standard reflections every 0 reflections
36630 measured reflections	intensity decay: none
8551 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.055	71 restraints
wR(F²) = 0.156	H-atom parameters constrained
S = 1.02	Δρ_max = 0.40 e Å⁻³
8551 reflections	Δρ_min = −0.44 e Å⁻³
614 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
C1	0.6345 (3)	0.3762 (3)	0.44089 (16)	0.0541 (9)
H1	0.6799	0.3873	0.4224	0.065*
C2	0.5468 (3)	0.4080 (3)	0.40622 (19)	0.0655 (11)
H2	0.5348	0.4405	0.3657	0.079*
C3	0.4785 (3)	0.3919 (3)	0.43135 (19)	0.0651 (11)
H3	0.4194	0.4111	0.4076	0.078*
C4	0.4982 (3)	0.3459 (3)	0.49352 (18)	0.0544 (9)
C5	0.4325 (3)	0.3255 (3)	0.5255 (2)	0.0691 (11)
H5	0.3719	0.3421	0.5044	0.083*
C6	0.4576 (3)	0.2826 (3)	0.5858 (2)	0.0656 (11)
H6	0.4138	0.2710	0.6057	0.079*
C7	0.5496 (3)	0.2542 (3)	0.62009 (17)	0.0508 (9)
C8	0.5801 (3)	0.2082 (3)	0.6821 (2)	0.0650 (11)
H8	0.5395	0.1943	0.7046	0.078*
C9	0.6692 (3)	0.1840 (3)	0.70946 (18)	0.0635 (11)
H9	0.6899	0.1540	0.7510	0.076*
C10	0.7298 (3)	0.2040 (3)	0.67522 (16)	0.0521 (9)
H10	0.7907	0.1871	0.6949	0.063*
C11	0.6143 (2)	0.2716 (2)	0.58900 (15)	0.0425 (8)
C12	0.5876 (2)	0.3171 (2)	0.52548 (15)	0.0429 (8)
C13	0.7824 (3)	0.4959 (3)	0.58974 (17)	0.0511 (9)
H13	0.7223	0.5022	0.5629	0.061*
C14	0.8288 (3)	0.5838 (3)	0.61999 (18)	0.0593 (10)
H14	0.7997	0.6472	0.6130	0.071*
C15	0.9162 (3)	0.5766 (3)	0.65943 (18)	0.0564 (10)
H15	0.9473	0.6353	0.6791	0.068*
C16	0.9600 (2)	0.4812 (3)	0.67077 (16)	0.0473 (9)
C17	1.0508 (3)	0.4632 (3)	0.71111 (18)	0.0644 (11)
H17	1.0865	0.5184	0.7320	0.077*
C18	1.0870 (3)	0.3674 (3)	0.72003 (18)	0.0644 (11)
H18	1.1469	0.3585	0.7469	0.077*
C19	1.0352 (2)	0.2796 (3)	0.68906 (17)	0.0517 (9)
C20	1.0665 (3)	0.1785 (3)	0.69839 (19)	0.0648 (11)
H20	1.1253	0.1641	0.7255	0.078*
C21	1.0102 (3)	0.1015 (3)	0.6674 (2)	0.0645 (11)
H21	1.0298	0.0338	0.6739	0.077*
C22	0.9227 (3)	0.1240 (3)	0.62577 (18)	0.0539 (9)
H22	0.8857	0.0700	0.6045	0.065*
C23	0.9460 (2)	0.2961 (2)	0.64793 (15)	0.0405 (8)
C24	0.9083 (2)	0.3960 (2)	0.63876 (15)	0.0396 (8)
C25	0.6919 (2)	0.0594 (3)	0.52483 (17)	0.0526 (9)
H25	0.6742	0.0639	0.5621	0.063*
C26	0.6700 (3)	−0.0289 (3)	0.4865 (2)	0.0639 (11)
H26	0.6390	−0.0822	0.4986	0.077*
C27	0.6940 (3)	−0.0369 (3)	0.43108 (18)	0.0591 (10)
H27	0.6781	−0.0950	0.4046	0.071*
C28	0.7426 (2)	0.0423 (2)	0.41425 (15)	0.0452 (8)
C29	0.7748 (3)	0.0411 (3)	0.35912 (16)	0.0541 (9)
H29	0.7628	−0.0156	0.3313	0.065*
C30	0.8218 (2)	0.1198 (3)	0.34666 (16)	0.0519 (9)
H30	0.8417	0.1163	0.3104	0.062*
C31	0.8423 (2)	0.2094 (2)	0.38756 (14)	0.0420 (8)
C32	0.8902 (2)	0.2946 (3)	0.37698 (16)	0.0529 (9)
H32	0.9109	0.2965	0.3411	0.063*
C33	0.9061 (3)	0.3750 (3)	0.41977 (17)	0.0536 (9)
H33	0.9377	0.4322	0.4131	0.064*
C34	0.8749 (2)	0.3714 (2)	0.47350 (16)	0.0471 (8)
H34	0.8868	0.4272	0.5021	0.056*
C35	0.8125 (2)	0.2118 (2)	0.44221 (14)	0.0372 (7)
C36	0.7623 (2)	0.1283 (2)	0.45555 (14)	0.0385 (7)
C37	0.6703 (3)	0.4689 (4)	0.7487 (2)	0.0763 (12)
C38	0.6090 (3)	0.3700 (3)	0.8186 (2)	0.0660 (11)
C39	0.6846 (3)	0.4054 (3)	0.80393 (18)	0.0583 (10)
C40	0.7696 (3)	0.3642 (3)	0.8385 (2)	0.0757 (13)
C41	0.9236 (5)	0.3382 (6)	0.8253 (4)	0.165 (3)
H41A	0.9184	0.2670	0.8368	0.197*
H41B	0.9462	0.3427	0.7883	0.197*
C42	0.9732 (6)	0.3985 (6)	0.8793 (4)	0.200 (4)
H42A	1.0345	0.3738	0.8960	0.300*
H42B	0.9457	0.3942	0.9132	0.300*
H42C	0.9732	0.4686	0.8655	0.300*
C43	0.2814 (3)	0.4440 (3)	0.66824 (19)	0.0667 (11)
C44	0.3051 (3)	0.2615 (3)	0.68039 (17)	0.0541 (9)
C45	0.2585 (3)	0.3446 (3)	0.64328 (17)	0.0560 (10)
Fe1	0.77305 (3)	0.27189 (3)	0.55530 (2)	0.03744 (16)
N1	0.65628 (18)	0.33070 (19)	0.49930 (12)	0.0418 (6)
N2	0.70377 (19)	0.24633 (19)	0.61563 (12)	0.0413 (7)
N3	0.82099 (19)	0.40325 (18)	0.59777 (12)	0.0393 (6)
N4	0.88960 (18)	0.21919 (18)	0.61503 (12)	0.0397 (6)
N5	0.73710 (18)	0.13796 (19)	0.51064 (12)	0.0409 (6)
N6	0.82885 (17)	0.29195 (18)	0.48604 (12)	0.0372 (6)
N7	0.5459 (3)	0.3409 (3)	0.8287 (2)	0.0994 (14)
N8	0.6593 (3)	0.5196 (4)	0.7032 (2)	0.1231 (18)
N9	0.3453 (3)	0.1940 (3)	0.70941 (16)	0.0832 (12)
N10	0.3005 (3)	0.5257 (3)	0.68888 (19)	0.1009 (14)
O1	0.7877 (2)	0.3023 (2)	0.88383 (16)	0.0938 (10)
O2	0.8340 (3)	0.4014 (4)	0.8148 (2)	0.157 (2)
C46	0.2022 (7)	0.3307 (8)	0.5764 (4)	0.053 (4)	0.479 (13)
C47	0.0833 (11)	0.2138 (9)	0.5114 (7)	0.105 (5)	0.479 (13)
H47A	0.0920	0.2512	0.4749	0.126*	0.479 (13)
H47B	0.0288	0.2400	0.5183	0.126*	0.479 (13)
C48	0.0702 (12)	0.1014 (9)	0.4937 (8)	0.097 (5)	0.479 (13)
H48A	0.0112	0.0911	0.4619	0.146*	0.479 (13)
H48B	0.0754	0.0620	0.5326	0.146*	0.479 (13)
H48C	0.1159	0.0795	0.4756	0.146*	0.479 (13)
O3	0.1259 (6)	0.3932 (8)	0.5550 (5)	0.079 (3)	0.479 (13)
O4	0.1607 (7)	0.2316 (9)	0.5704 (5)	0.061 (3)	0.479 (13)
C46'	0.1785 (7)	0.3322 (10)	0.5883 (4)	0.069 (4)	0.521 (13)
C47'	0.1297 (7)	0.2109 (7)	0.4935 (4)	0.064 (3)	0.521 (13)
H47C	0.1612	0.1765	0.4673	0.076*	0.521 (13)
H47D	0.1020	0.2731	0.4710	0.076*	0.521 (13)
C48'	0.0582 (9)	0.1405 (12)	0.5053 (8)	0.095 (4)	0.521 (13)
H48D	0.0184	0.1158	0.4639	0.142*	0.521 (13)
H48E	0.0237	0.1781	0.5274	0.142*	0.521 (13)
H48F	0.0876	0.0834	0.5320	0.142*	0.521 (13)
O3'	0.1696 (10)	0.4051 (7)	0.5404 (4)	0.099 (3)	0.521 (13)
O4'	0.1919 (8)	0.2343 (9)	0.5587 (5)	0.074 (3)	0.521 (13)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.053 (3)	0.060 (2)	0.048 (2)	0.0086 (19)	0.0151 (18)	0.0114 (17)
C2	0.063 (3)	0.070 (3)	0.057 (2)	0.010 (2)	0.011 (2)	0.0147 (19)
C3	0.048 (3)	0.069 (3)	0.068 (3)	0.015 (2)	0.004 (2)	0.008 (2)
C4	0.041 (2)	0.054 (2)	0.065 (2)	0.0016 (18)	0.0134 (19)	−0.0042 (17)
C5	0.038 (3)	0.074 (3)	0.094 (3)	0.006 (2)	0.020 (2)	0.000 (2)
C6	0.053 (3)	0.068 (3)	0.087 (3)	−0.001 (2)	0.039 (2)	−0.001 (2)
C7	0.052 (3)	0.052 (2)	0.056 (2)	−0.0057 (18)	0.0281 (19)	−0.0062 (16)
C8	0.072 (3)	0.073 (3)	0.067 (3)	−0.007 (2)	0.046 (2)	−0.002 (2)
C9	0.079 (3)	0.073 (3)	0.042 (2)	−0.002 (2)	0.027 (2)	0.0065 (18)
C10	0.058 (3)	0.057 (2)	0.0433 (19)	−0.0047 (18)	0.0190 (18)	0.0011 (15)
C11	0.044 (2)	0.0387 (18)	0.0463 (19)	−0.0010 (16)	0.0173 (16)	−0.0053 (14)
C12	0.039 (2)	0.0422 (18)	0.0475 (19)	−0.0017 (16)	0.0137 (16)	−0.0046 (14)
C13	0.058 (3)	0.042 (2)	0.055 (2)	0.0050 (18)	0.0198 (18)	−0.0033 (16)
C14	0.079 (3)	0.042 (2)	0.064 (2)	0.004 (2)	0.033 (2)	−0.0053 (17)
C15	0.078 (3)	0.041 (2)	0.060 (2)	−0.015 (2)	0.036 (2)	−0.0143 (16)
C16	0.053 (3)	0.050 (2)	0.0442 (19)	−0.0133 (18)	0.0227 (18)	−0.0078 (15)
C17	0.054 (3)	0.070 (3)	0.065 (3)	−0.023 (2)	0.014 (2)	−0.014 (2)
C18	0.043 (3)	0.078 (3)	0.063 (2)	−0.011 (2)	0.0060 (19)	−0.004 (2)
C19	0.039 (2)	0.060 (2)	0.051 (2)	−0.0027 (19)	0.0091 (17)	0.0015 (17)
C20	0.044 (3)	0.067 (3)	0.074 (3)	0.007 (2)	0.008 (2)	0.013 (2)
C21	0.054 (3)	0.049 (2)	0.086 (3)	0.014 (2)	0.016 (2)	0.013 (2)
C22	0.055 (3)	0.0355 (19)	0.068 (2)	0.0039 (17)	0.016 (2)	0.0051 (16)
C23	0.036 (2)	0.047 (2)	0.0389 (17)	−0.0058 (15)	0.0121 (15)	−0.0028 (14)
C24	0.044 (2)	0.0392 (18)	0.0383 (17)	−0.0023 (16)	0.0171 (16)	−0.0032 (13)
C25	0.064 (3)	0.044 (2)	0.053 (2)	−0.0112 (18)	0.0235 (19)	−0.0044 (16)
C26	0.076 (3)	0.042 (2)	0.078 (3)	−0.017 (2)	0.030 (2)	−0.0052 (18)
C27	0.065 (3)	0.044 (2)	0.065 (2)	−0.0106 (19)	0.018 (2)	−0.0161 (17)
C28	0.043 (2)	0.0416 (19)	0.048 (2)	0.0016 (16)	0.0105 (16)	−0.0062 (15)
C29	0.058 (3)	0.054 (2)	0.046 (2)	0.0073 (19)	0.0103 (18)	−0.0144 (16)
C30	0.049 (2)	0.065 (2)	0.0411 (19)	0.0140 (19)	0.0142 (17)	−0.0026 (16)
C31	0.038 (2)	0.049 (2)	0.0363 (17)	0.0077 (16)	0.0093 (15)	0.0003 (14)
C32	0.054 (3)	0.064 (2)	0.047 (2)	0.0060 (19)	0.0236 (18)	0.0102 (17)
C33	0.060 (3)	0.052 (2)	0.058 (2)	−0.0038 (19)	0.0319 (19)	0.0051 (17)
C34	0.054 (2)	0.0381 (18)	0.052 (2)	−0.0023 (17)	0.0224 (18)	0.0015 (15)
C35	0.036 (2)	0.0394 (18)	0.0348 (16)	0.0074 (14)	0.0092 (14)	0.0008 (13)
C36	0.037 (2)	0.0387 (17)	0.0372 (17)	0.0044 (15)	0.0082 (14)	−0.0001 (13)
C37	0.060 (3)	0.078 (3)	0.080 (3)	−0.007 (2)	0.008 (2)	0.013 (2)
C38	0.071 (3)	0.047 (2)	0.084 (3)	0.002 (2)	0.031 (3)	−0.0013 (19)
C39	0.059 (3)	0.051 (2)	0.061 (2)	−0.004 (2)	0.015 (2)	0.0043 (18)
C40	0.066 (3)	0.065 (3)	0.091 (3)	−0.010 (2)	0.019 (3)	0.018 (2)
C41	0.185 (9)	0.158 (7)	0.139 (6)	−0.006 (7)	0.037 (6)	0.052 (6)
C42	0.229 (10)	0.144 (7)	0.173 (8)	−0.026 (7)	−0.007 (7)	0.016 (6)
C43	0.083 (3)	0.058 (3)	0.057 (2)	−0.003 (2)	0.019 (2)	0.0041 (19)
C44	0.065 (3)	0.056 (2)	0.0398 (19)	−0.005 (2)	0.0150 (18)	−0.0088 (18)
C45	0.067 (3)	0.049 (2)	0.050 (2)	0.0041 (19)	0.016 (2)	−0.0046 (17)
Fe1	0.0397 (3)	0.0350 (3)	0.0381 (3)	−0.0002 (2)	0.0134 (2)	−0.00014 (19)
N1	0.0431 (18)	0.0413 (15)	0.0392 (14)	−0.0023 (13)	0.0112 (13)	−0.0004 (11)
N2	0.0422 (19)	0.0451 (16)	0.0369 (14)	−0.0004 (13)	0.0132 (13)	−0.0015 (11)
N3	0.0465 (18)	0.0328 (14)	0.0419 (15)	0.0044 (12)	0.0191 (13)	−0.0003 (11)
N4	0.0405 (17)	0.0355 (15)	0.0430 (15)	−0.0027 (13)	0.0136 (12)	0.0007 (11)
N5	0.0419 (18)	0.0404 (15)	0.0396 (14)	−0.0020 (13)	0.0123 (13)	−0.0026 (11)
N6	0.0349 (16)	0.0364 (15)	0.0408 (14)	0.0012 (12)	0.0129 (12)	0.0001 (11)
N7	0.096 (4)	0.070 (3)	0.151 (4)	0.008 (2)	0.065 (3)	0.017 (2)
N8	0.092 (3)	0.151 (4)	0.103 (3)	−0.014 (3)	0.000 (3)	0.065 (3)
N9	0.117 (3)	0.060 (2)	0.054 (2)	0.011 (2)	0.003 (2)	−0.0038 (17)
N10	0.135 (4)	0.059 (2)	0.089 (3)	−0.020 (2)	0.011 (3)	−0.007 (2)
O1	0.090 (2)	0.078 (2)	0.099 (2)	−0.0072 (17)	0.0109 (19)	0.0327 (18)
O2	0.060 (3)	0.169 (4)	0.237 (5)	0.023 (3)	0.039 (3)	0.130 (4)
C46	0.070 (7)	0.052 (6)	0.042 (5)	0.027 (5)	0.025 (5)	0.003 (4)
C47	0.101 (9)	0.081 (7)	0.103 (8)	0.014 (7)	−0.008 (6)	−0.028 (6)
C48	0.092 (9)	0.089 (8)	0.095 (8)	0.008 (7)	0.010 (6)	−0.017 (6)
O3	0.082 (6)	0.057 (4)	0.079 (5)	0.017 (4)	−0.003 (4)	0.000 (4)
O4	0.052 (5)	0.058 (4)	0.059 (5)	0.014 (4)	−0.002 (3)	−0.020 (3)
C46'	0.083 (8)	0.060 (6)	0.066 (6)	0.023 (5)	0.026 (6)	−0.010 (5)
C47'	0.070 (6)	0.066 (5)	0.049 (4)	0.015 (4)	0.013 (4)	0.002 (3)
C48'	0.074 (7)	0.087 (8)	0.096 (8)	0.021 (7)	−0.009 (5)	0.001 (7)
O3'	0.136 (8)	0.066 (4)	0.074 (4)	0.019 (5)	0.006 (5)	0.012 (3)
O4'	0.087 (7)	0.064 (4)	0.055 (4)	0.026 (5)	0.004 (4)	−0.010 (3)

Geometric parameters (Å, º) top

C1—N1	1.329 (4)	C29—H29	0.9300
C1—C2	1.389 (5)	C30—C31	1.433 (5)
C1—H1	0.9300	C30—H30	0.9300
C2—C3	1.357 (5)	C31—C32	1.396 (5)
C2—H2	0.9300	C31—C35	1.398 (4)
C3—C4	1.404 (5)	C32—C33	1.362 (5)
C3—H3	0.9300	C32—H32	0.9300
C4—C12	1.389 (5)	C33—C34	1.392 (4)
C4—C5	1.432 (5)	C33—H33	0.9300
C5—C6	1.347 (5)	C34—N6	1.337 (4)
C5—H5	0.9300	C34—H34	0.9300
C6—C7	1.429 (5)	C35—N6	1.373 (4)
C6—H6	0.9300	C35—C36	1.423 (4)
C7—C8	1.396 (5)	C36—N5	1.370 (4)
C7—C11	1.399 (4)	C37—N8	1.147 (5)
C8—C9	1.356 (5)	C37—C39	1.403 (6)
C8—H8	0.9300	C38—N7	1.139 (5)
C9—C10	1.400 (5)	C38—C39	1.394 (6)
C9—H9	0.9300	C39—C40	1.398 (6)
C10—N2	1.330 (4)	C40—O1	1.224 (5)
C10—H10	0.9300	C40—O2	1.356 (5)
C11—N2	1.363 (4)	C41—C42	1.405 (7)
C11—C12	1.421 (4)	C41—O2	1.573 (7)
C12—N1	1.374 (4)	C41—H41A	0.9700
C13—N3	1.334 (4)	C41—H41B	0.9700
C13—C14	1.397 (5)	C42—H42A	0.9600
C13—H13	0.9300	C42—H42B	0.9600
C14—C15	1.352 (5)	C42—H42C	0.9600
C14—H14	0.9300	C43—N10	1.154 (5)
C15—C16	1.401 (5)	C43—C45	1.403 (5)
C15—H15	0.9300	C44—N9	1.139 (5)
C16—C24	1.411 (4)	C44—C45	1.399 (5)
C16—C17	1.417 (5)	C45—C46'	1.420 (8)
C17—C18	1.357 (5)	C45—C46	1.431 (8)
C17—H17	0.9300	Fe1—N2	1.968 (2)
C18—C19	1.432 (5)	Fe1—N3	1.968 (3)
C18—H18	0.9300	Fe1—N6	1.972 (2)
C19—C20	1.396 (5)	Fe1—N4	1.974 (3)
C19—C23	1.399 (5)	Fe1—N1	1.979 (3)
C20—C21	1.355 (5)	Fe1—N5	1.982 (2)
C20—H20	0.9300	C46—O3	1.390 (9)
C21—C22	1.396 (5)	C46—O4	1.431 (16)
C21—H21	0.9300	C47—O4	1.456 (9)
C22—N4	1.334 (4)	C47—C48	1.509 (9)
C22—H22	0.9300	C47—H47A	0.9700
C23—N4	1.368 (4)	C47—H47B	0.9700
C23—C24	1.414 (4)	C48—H48A	0.9600
C24—N3	1.362 (4)	C48—H48B	0.9600
C25—N5	1.332 (4)	C48—H48C	0.9600
C25—C26	1.391 (5)	C46'—O3'	1.375 (9)
C25—H25	0.9300	C46'—O4'	1.470 (17)
C26—C27	1.365 (5)	C47'—O4'	1.452 (8)
C26—H26	0.9300	C47'—C48'	1.526 (9)
C27—C28	1.396 (5)	C47'—H47C	0.9700
C27—H27	0.9300	C47'—H47D	0.9700
C28—C36	1.400 (4)	C48'—H48D	0.9600
C28—C29	1.430 (4)	C48'—H48E	0.9600
C29—C30	1.337 (5)	C48'—H48F	0.9600

N1—C1—C2	122.9 (3)	C33—C34—H34	118.4
N1—C1—H1	118.5	N6—C35—C31	123.8 (3)
C2—C1—H1	118.5	N6—C35—C36	115.7 (3)
C3—C2—C1	120.1 (4)	C31—C35—C36	120.5 (3)
C3—C2—H2	119.9	N5—C36—C28	123.8 (3)
C1—C2—H2	119.9	N5—C36—C35	115.9 (3)
C2—C3—C4	119.3 (4)	C28—C36—C35	120.3 (3)
C2—C3—H3	120.3	N8—C37—C39	178.8 (6)
C4—C3—H3	120.3	N7—C38—C39	178.0 (5)
C12—C4—C3	117.2 (3)	C38—C39—C40	118.5 (4)
C12—C4—C5	118.1 (3)	C38—C39—C37	118.3 (4)
C3—C4—C5	124.7 (4)	C40—C39—C37	122.5 (4)
C6—C5—C4	120.7 (4)	O1—C40—O2	121.9 (4)
C6—C5—H5	119.6	O1—C40—C39	127.4 (4)
C4—C5—H5	119.6	O2—C40—C39	110.7 (4)
C5—C6—C7	122.1 (4)	C42—C41—O2	92.8 (7)
C5—C6—H6	119.0	C42—C41—H41A	113.1
C7—C6—H6	119.0	O2—C41—H41A	113.1
C8—C7—C11	116.9 (4)	C42—C41—H41B	113.1
C8—C7—C6	125.1 (3)	O2—C41—H41B	113.1
C11—C7—C6	118.0 (3)	H41A—C41—H41B	110.5
C9—C8—C7	119.7 (3)	C41—C42—H42A	109.5
C9—C8—H8	120.2	C41—C42—H42B	109.5
C7—C8—H8	120.2	H42A—C42—H42B	109.5
C8—C9—C10	120.0 (3)	C41—C42—H42C	109.5
C8—C9—H9	120.0	H42A—C42—H42C	109.5
C10—C9—H9	120.0	H42B—C42—H42C	109.5
N2—C10—C9	122.5 (4)	N10—C43—C45	179.7 (6)
N2—C10—H10	118.7	N9—C44—C45	177.5 (4)
C9—C10—H10	118.7	C44—C45—C43	118.5 (3)
N2—C11—C7	124.0 (3)	C44—C45—C46'	122.5 (6)
N2—C11—C12	116.3 (3)	C43—C45—C46'	117.9 (6)
C7—C11—C12	119.7 (3)	C44—C45—C46	120.6 (5)
N1—C12—C4	123.5 (3)	C43—C45—C46	119.8 (5)
N1—C12—C11	115.1 (3)	C46'—C45—C46	20.8 (8)
C4—C12—C11	121.3 (3)	N2—Fe1—N3	92.77 (10)
N3—C13—C14	122.6 (4)	N2—Fe1—N6	172.88 (11)
N3—C13—H13	118.7	N3—Fe1—N6	92.34 (10)
C14—C13—H13	118.7	N2—Fe1—N4	95.68 (10)
C15—C14—C13	119.8 (4)	N3—Fe1—N4	82.61 (11)
C15—C14—H14	120.1	N6—Fe1—N4	89.89 (10)
C13—C14—H14	120.1	N2—Fe1—N1	82.70 (11)
C14—C15—C16	120.3 (3)	N3—Fe1—N1	94.58 (11)
C14—C15—H15	119.8	N6—Fe1—N1	91.95 (10)
C16—C15—H15	119.8	N4—Fe1—N1	176.71 (10)
C15—C16—C24	116.4 (3)	N2—Fe1—N5	92.36 (10)
C15—C16—C17	125.9 (3)	N3—Fe1—N5	173.92 (11)
C24—C16—C17	117.7 (3)	N6—Fe1—N5	82.84 (10)
C18—C17—C16	121.7 (4)	N4—Fe1—N5	93.64 (10)
C18—C17—H17	119.2	N1—Fe1—N5	89.30 (11)
C16—C17—H17	119.2	C1—N1—C12	116.8 (3)
C17—C18—C19	121.5 (4)	C1—N1—Fe1	130.4 (2)
C17—C18—H18	119.2	C12—N1—Fe1	112.7 (2)
C19—C18—H18	119.2	C10—N2—C11	116.9 (3)
C20—C19—C23	117.7 (3)	C10—N2—Fe1	130.1 (2)
C20—C19—C18	124.7 (4)	C11—N2—Fe1	112.9 (2)
C23—C19—C18	117.6 (3)	C13—N3—C24	117.4 (3)
C21—C20—C19	119.1 (4)	C13—N3—Fe1	129.8 (2)
C21—C20—H20	120.4	C24—N3—Fe1	112.79 (19)
C19—C20—H20	120.4	C22—N4—C23	116.4 (3)
C20—C21—C22	120.0 (4)	C22—N4—Fe1	131.1 (2)
C20—C21—H21	120.0	C23—N4—Fe1	112.4 (2)
C22—C21—H21	120.0	C25—N5—C36	116.7 (3)
N4—C22—C21	123.2 (3)	C25—N5—Fe1	130.7 (2)
N4—C22—H22	118.4	C36—N5—Fe1	112.6 (2)
C21—C22—H22	118.4	C34—N6—C35	116.2 (3)
N4—C23—C19	123.5 (3)	C34—N6—Fe1	130.8 (2)
N4—C23—C24	115.7 (3)	C35—N6—Fe1	112.9 (2)
C19—C23—C24	120.8 (3)	C40—O2—C41	119.4 (4)
N3—C24—C16	123.5 (3)	O3—C46—O4	100.7 (11)
N3—C24—C23	115.8 (3)	O3—C46—C45	115.9 (8)
C16—C24—C23	120.7 (3)	O4—C46—C45	108.4 (8)
N5—C25—C26	123.0 (3)	O4—C47—C48	112.2 (11)
N5—C25—H25	118.5	O4—C47—H47A	109.2
C26—C25—H25	118.5	C48—C47—H47A	109.2
C27—C26—C25	119.7 (3)	O4—C47—H47B	109.2
C27—C26—H26	120.1	C48—C47—H47B	109.2
C25—C26—H26	120.1	H47A—C47—H47B	107.9
C26—C27—C28	119.8 (3)	C47—C48—H48A	109.5
C26—C27—H27	120.1	C47—C48—H48B	109.5
C28—C27—H27	120.1	H48A—C48—H48B	109.5
C27—C28—C36	116.9 (3)	C47—C48—H48C	109.5
C27—C28—C29	125.0 (3)	H48A—C48—H48C	109.5
C36—C28—C29	118.1 (3)	H48B—C48—H48C	109.5
C30—C29—C28	121.4 (3)	C46—O4—C47	116.4 (10)
C30—C29—H29	119.3	O3'—C46'—C45	113.0 (9)
C28—C29—H29	119.3	O3'—C46'—O4'	105.5 (12)
C29—C30—C31	121.9 (3)	C45—C46'—O4'	104.4 (9)
C29—C30—H30	119.0	O4'—C47'—C48'	105.0 (9)
C31—C30—H30	119.0	O4'—C47'—H47C	110.7
C32—C31—C35	117.4 (3)	C48'—C47'—H47C	110.7
C32—C31—C30	124.9 (3)	O4'—C47'—H47D	110.7
C35—C31—C30	117.7 (3)	C48'—C47'—H47D	110.7
C33—C32—C31	119.4 (3)	H47C—C47'—H47D	108.8
C33—C32—H32	120.3	C47'—C48'—H48D	109.5
C31—C32—H32	120.3	C47'—C48'—H48E	109.5
C32—C33—C34	119.9 (3)	H48D—C48'—H48E	109.5
C32—C33—H33	120.0	C47'—C48'—H48F	109.5
C34—C33—H33	120.0	H48D—C48'—H48F	109.5
N6—C34—C33	123.3 (3)	H48E—C48'—H48F	109.5
N6—C34—H34	118.4	C47'—O4'—C46'	117.1 (8)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C25—H25···N2	0.93	2.62	3.089 (4)	112
C34—H34···N3	0.93	2.60	3.078 (4)	113
C3—H3···N8ⁱ	0.93	2.47	3.206 (6)	136

Symmetry code: (i) −x+1, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	[Fe(C₁₂H₈N₂)₃](C₆H₅N₂O₂)₂
M_r	870.70
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	296
a, b, c (Å)	15.5855 (5), 13.0261 (4), 21.4979 (6)
β (°)	109.068 (1)
V (Å³)	4125.0 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.43
Crystal size (mm)	0.20 × 0.10 × 0.10

Data collection
Diffractometer	Bruker APEXII
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.920, 0.959
No. of measured, independent and observed [I > 2σ(I)] reflections	36630, 8551, 4862
R_int	0.081
(sin θ/λ)_max (Å⁻¹)	0.628

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.055, 0.156, 1.02
No. of reflections	8551
No. of parameters	614
No. of restraints	71
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.40, −0.44

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C25—H25···N2	0.93	2.62	3.089 (4)	112
C34—H34···N3	0.93	2.60	3.078 (4)	113
C3—H3···N8ⁱ	0.93	2.47	3.206 (6)	136

Symmetry code: (i) −x+1, −y+1, −z+1.

Acknowledgements

We thank Dr Yan-Wei Ren and Professor Zhi-Yong Fu of the College of Chemistry and Chemical Engineering, South China University of Technology, for their help with this study.

References

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