

Supporting information
![]() | Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807061673/tk2214sup1.cif |
![]() | Structure factor file (CIF format) https://doi.org/10.1107/S1600536807061673/tk2214Isup2.hkl |
CCDC reference: 630724
Key indicators
- Single-crystal X-ray study
- T = 173 K
- Mean
(C-C) = 0.003 Å
- R factor = 0.041
- wR factor = 0.108
- Data-to-parameter ratio = 19.1
checkCIF/PLATON results
No syntax errors found
Alert level B PLAT417_ALERT_2_B Short Inter D-H..H-D H1W1 .. H3BB .. 1.94 Ang. PLAT420_ALERT_2_B D-H Without Acceptor O1W - H1W1 ... ? PLAT432_ALERT_2_B Short Inter X...Y Contact O23 .. C3A .. 2.86 Ang. PLAT432_ALERT_2_B Short Inter X...Y Contact O33 .. C3B .. 2.89 Ang.
Alert level C PLAT244_ALERT_4_C Low 'Solvent' Ueq as Compared to Neighbors for Cl1 PLAT244_ALERT_4_C Low 'Solvent' Ueq as Compared to Neighbors for Cl2 PLAT244_ALERT_4_C Low 'Solvent' Ueq as Compared to Neighbors for Cl3 PLAT432_ALERT_2_C Short Inter X...Y Contact O23 .. C .. 3.01 Ang. PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........ 31 PLAT731_ALERT_1_C Bond Calc 0.87(4), Rep 0.866(19) ...... 2.11 su-Ra O1W -H1W1 1.555 1.555 PLAT731_ALERT_1_C Bond Calc 0.80(5), Rep 0.807(19) ...... 2.63 su-Ra O1W -H1W2 1.555 1.555 PLAT735_ALERT_1_C D-H Calc 0.80(5), Rep 0.807(19) ...... 2.63 su-Ra O1W -H2# 1.555 1.555
Alert level G PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 6
0 ALERT level A = In general: serious problem 4 ALERT level B = Potentially serious problem 8 ALERT level C = Check and explain 1 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 4 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
Complex (I) was synthesized as previously described (Brewer et al., 2005) and was recrystallized from methanol solution in the presence of equimolal potassium perchlorate. The resulting crystals were analyzed by X-ray diffraction.
The positional parameters of the water-bound H atoms were refined with Uiso(H) = 1.17–1.49Ueq(C,N); see Table 1 for distances. The remaining H atoms were included in the riding model approximation with N—H = 0.88Å and C—H = 0.95 to 0.99 Å, and with Uiso(H) = 1.17–1.49Ueq(C,N).
Iron(II) and iron(III) Schiff base complexes of tris(2-aminoethyl)amine (tren) with imidazole carboxaldehyde have displayed spin crossover behavior (Brewer et al., 2006). Further, it has been demonstrated that the distance between the Fe atom and the central tren-N atom, Nap, is an indicator of spin-state (Brewer et al., 2006). Shorter distances correlate with high spin and longer distances with low spin. Quarternization of Nap, as observed in the title complex, (I), results in an elongated Fe—Nap distance due to both the conformation of the Nap atom (inverted away from the Fe atom) and the repulsive forces between the positively charged atoms (Brewer et al., 2005). Recently, it was shown that (I), without the methyl group on Nap, could serve as a bidentate hydrogen bond donor to the perchlorate anion of potassium perchlorate using the adjacent imidazole-NH and imine-CH H atoms to give supramolecular complexes (Brewer et al., 2007). Since the present molecule possesses this same structural feature, the reaction of it with potassium perchlorate was investigated. The reaction did not yield the desired product but gave (I) as a polymorph (Brewer et al., 2007). The structure of the iron cation differs from the original report in that the three arms of the ligand are not identical. In addition, the hydrogen bonding interactions with coordinated water and perchlorate are significantly different. Investigation of these effects on the spin crossover process and reactivity of the complex will be aided by the structural characterization of this new polymorph. In view of the importance of the spin crossover phenomenom and supramolecular systems, the present paper reports the crystal structure of (I) (Fig. 1).
The octahedral iron(II) atom is bound to three facial imidazole-N atoms whose average Fe–N bond distances for the imidazole- and imine-N atoms are 1.963 (5)Å and 1.951 (5) Å, respectively. The central N atom of the tripodal ligand is outside the bonding distance at 3.92 Å. Crystal packing is stabilized by the hydrogen bonding interactions between the two water molecules (acceptor) and two of the three imidazole NH groups (donor). The third imidazole NH group (donor) hydrogen bonds to one of the three perchlorate counterions (acceptor) (Table 1 & Fig. 2).
For the synthesis, see: Brewer et al. (2005). For related structures, see: Brewer et al. (2006, 2007).
Data collection: SMART (Bruker, 2000); cell refinement: SMART (Bruker, 2000); data reduction: SAINT (Bruker, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2000); software used to prepare material for publication: SHELXTL (Bruker, 2000).
[Fe(C19H27N10)](ClO4)3·2H2O | F(000) = 3232 |
Mr = 785.74 | Dx = 1.707 Mg m−3 |
Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ac 2ab | Cell parameters from 9963 reflections |
a = 13.9630 (18) Å | θ = 2.2–28.9° |
b = 11.7810 (15) Å | µ = 0.84 mm−1 |
c = 37.182 (5) Å | T = 173 K |
V = 6116.4 (14) Å3 | Chunk, dark-red |
Z = 8 | 0.54 × 0.45 × 0.12 mm |
Bruker SMART CCD area-detector diffractometer | 8324 independent reflections |
Radiation source: fine-focus sealed tube | 6601 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.054 |
φ and ω scans | θmax = 29.3°, θmin = 1.8° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −19→19 |
Tmin = 0.682, Tmax = 0.904 | k = −16→13 |
65065 measured reflections | l = −51→51 |
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)] = 0.041 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.108 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0471P)2 + 5.7069P] where P = (Fo2 + 2Fc2)/3 |
8324 reflections | (Δ/σ)max = 0.001 |
436 parameters | Δρmax = 0.76 e Å−3 |
6 restraints | Δρmin = −0.62 e Å−3 |
[Fe(C19H27N10)](ClO4)3·2H2O | V = 6116.4 (14) Å3 |
Mr = 785.74 | Z = 8 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 13.9630 (18) Å | µ = 0.84 mm−1 |
b = 11.7810 (15) Å | T = 173 K |
c = 37.182 (5) Å | 0.54 × 0.45 × 0.12 mm |
Bruker SMART CCD area-detector diffractometer | 8324 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 6601 reflections with I > 2σ(I) |
Tmin = 0.682, Tmax = 0.904 | Rint = 0.054 |
65065 measured reflections |
R[F2 > 2σ(F2)] = 0.041 | 6 restraints |
wR(F2) = 0.108 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | Δρmax = 0.76 e Å−3 |
8324 reflections | Δρmin = −0.62 e Å−3 |
436 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Fe | 0.542493 (19) | 0.51159 (2) | 0.110991 (7) | 0.01627 (7) | |
Cl1 | 0.32256 (4) | 0.00301 (5) | 0.015096 (15) | 0.02982 (12) | |
Cl2 | 0.24581 (4) | 0.63667 (5) | 0.208500 (15) | 0.02861 (12) | |
Cl3 | 0.57715 (4) | 0.00513 (5) | 0.181644 (16) | 0.03151 (13) | |
O11 | 0.3162 (2) | 0.0909 (2) | −0.01088 (7) | 0.0756 (8) | |
O12 | 0.23275 (13) | −0.05400 (18) | 0.01888 (6) | 0.0489 (5) | |
O13 | 0.39474 (14) | −0.07620 (18) | 0.00529 (6) | 0.0526 (5) | |
O14 | 0.34756 (14) | 0.05377 (19) | 0.04951 (5) | 0.0494 (5) | |
O21 | 0.23376 (18) | 0.51820 (17) | 0.21519 (7) | 0.0598 (6) | |
O22 | 0.19608 (18) | 0.6630 (2) | 0.17533 (6) | 0.0610 (6) | |
O23 | 0.34507 (13) | 0.66157 (19) | 0.20374 (6) | 0.0505 (5) | |
O24 | 0.20629 (13) | 0.70357 (17) | 0.23716 (5) | 0.0437 (5) | |
O31 | 0.50024 (19) | −0.0216 (2) | 0.15709 (7) | 0.0687 (7) | |
O32 | 0.61507 (15) | −0.10022 (17) | 0.19422 (8) | 0.0617 (6) | |
O33 | 0.65127 (16) | 0.06867 (16) | 0.16416 (7) | 0.0570 (6) | |
O34 | 0.53883 (17) | 0.06912 (18) | 0.21060 (6) | 0.0576 (6) | |
O1W | 0.96601 (19) | 0.4969 (3) | 0.08139 (9) | 0.1023 (13) | |
H1W1 | 0.983 (4) | 0.562 (3) | 0.0904 (16) | 0.153* | |
H1W2 | 1.003 (4) | 0.489 (5) | 0.0650 (12) | 0.153* | |
O2W | 0.28606 (16) | 0.98531 (17) | 0.12333 (6) | 0.0461 (5) | |
H2W1 | 0.287 (3) | 1.024 (3) | 0.1051 (6) | 0.069* | |
H2W2 | 0.304 (3) | 1.029 (3) | 0.1392 (7) | 0.069* | |
N | 0.56728 (13) | 0.38916 (15) | 0.20854 (4) | 0.0215 (3) | |
N1A | 0.54566 (12) | 0.61049 (14) | 0.15322 (4) | 0.0190 (3) | |
N2A | 0.44316 (12) | 0.61938 (14) | 0.09684 (5) | 0.0199 (3) | |
N3A | 0.36892 (13) | 0.78081 (16) | 0.10830 (5) | 0.0269 (4) | |
H3AB | 0.3517 | 0.8440 | 0.1192 | 0.032* | |
N1B | 0.65376 (12) | 0.42147 (14) | 0.12542 (4) | 0.0193 (3) | |
N2B | 0.64328 (12) | 0.60169 (14) | 0.08733 (4) | 0.0198 (3) | |
N3B | 0.79608 (13) | 0.61176 (17) | 0.07239 (5) | 0.0288 (4) | |
H3BB | 0.8573 | 0.5947 | 0.0707 | 0.035* | |
N1C | 0.45107 (12) | 0.40472 (14) | 0.13101 (4) | 0.0192 (3) | |
N2C | 0.52259 (12) | 0.41612 (14) | 0.06825 (4) | 0.0198 (3) | |
N3C | 0.44957 (15) | 0.26827 (17) | 0.04444 (5) | 0.0304 (4) | |
H3CB | 0.4121 | 0.2086 | 0.0422 | 0.036* | |
C | 0.57789 (18) | 0.3404 (2) | 0.24639 (6) | 0.0301 (5) | |
H0A | 0.5769 | 0.2573 | 0.2452 | 0.045* | |
H0B | 0.5248 | 0.3669 | 0.2615 | 0.045* | |
H0C | 0.6388 | 0.3656 | 0.2568 | 0.045* | |
C1A | 0.56992 (16) | 0.51802 (17) | 0.21406 (5) | 0.0236 (4) | |
H1AA | 0.5037 | 0.5427 | 0.2195 | 0.028* | |
H1AB | 0.6084 | 0.5327 | 0.2359 | 0.028* | |
C2A | 0.60808 (15) | 0.59560 (17) | 0.18461 (5) | 0.0220 (4) | |
H2AA | 0.6205 | 0.6712 | 0.1952 | 0.026* | |
H2AB | 0.6702 | 0.5650 | 0.1762 | 0.026* | |
C3A | 0.49249 (15) | 0.69994 (17) | 0.15189 (5) | 0.0214 (4) | |
H3AA | 0.4921 | 0.7567 | 0.1701 | 0.026* | |
C4A | 0.43400 (14) | 0.70505 (17) | 0.12017 (5) | 0.0209 (4) | |
C5A | 0.33456 (16) | 0.7412 (2) | 0.07621 (6) | 0.0301 (5) | |
H5AA | 0.2875 | 0.7764 | 0.0615 | 0.036* | |
C6A | 0.38088 (15) | 0.64128 (19) | 0.06928 (6) | 0.0258 (4) | |
H6AA | 0.3714 | 0.5947 | 0.0487 | 0.031* | |
C1B | 0.65416 (15) | 0.34079 (18) | 0.18863 (6) | 0.0238 (4) | |
H1BA | 0.7086 | 0.3924 | 0.1934 | 0.029* | |
H1BB | 0.6700 | 0.2674 | 0.2001 | 0.029* | |
C2B | 0.65151 (15) | 0.32028 (17) | 0.14818 (5) | 0.0221 (4) | |
H2BA | 0.7068 | 0.2718 | 0.1417 | 0.026* | |
H2BB | 0.5926 | 0.2771 | 0.1425 | 0.026* | |
C3B | 0.73460 (15) | 0.45056 (18) | 0.11120 (5) | 0.0221 (4) | |
H3BA | 0.7922 | 0.4088 | 0.1144 | 0.027* | |
C4B | 0.72866 (14) | 0.55230 (18) | 0.09009 (5) | 0.0219 (4) | |
C5B | 0.65706 (16) | 0.69750 (18) | 0.06694 (6) | 0.0243 (4) | |
H5BA | 0.6089 | 0.7507 | 0.0605 | 0.029* | |
C6B | 0.75165 (17) | 0.7035 (2) | 0.05749 (6) | 0.0300 (5) | |
H6BA | 0.7809 | 0.7609 | 0.0433 | 0.036* | |
C1C | 0.47042 (15) | 0.34435 (18) | 0.19572 (6) | 0.0233 (4) | |
H1CA | 0.4811 | 0.2670 | 0.1861 | 0.028* | |
H1CB | 0.4291 | 0.3363 | 0.2172 | 0.028* | |
C2C | 0.41328 (14) | 0.40958 (18) | 0.16763 (5) | 0.0217 (4) | |
H2CA | 0.3470 | 0.3797 | 0.1674 | 0.026* | |
H2CB | 0.4100 | 0.4901 | 0.1751 | 0.026* | |
C3C | 0.41876 (15) | 0.32709 (18) | 0.10959 (6) | 0.0243 (4) | |
H3CA | 0.3723 | 0.2723 | 0.1165 | 0.029* | |
C4C | 0.46053 (15) | 0.33235 (18) | 0.07423 (6) | 0.0244 (4) | |
C5C | 0.55206 (15) | 0.40500 (19) | 0.03331 (6) | 0.0245 (4) | |
H5CA | 0.5964 | 0.4533 | 0.0214 | 0.029* | |
C6C | 0.50736 (18) | 0.3132 (2) | 0.01838 (6) | 0.0310 (5) | |
H6CA | 0.5150 | 0.2858 | −0.0055 | 0.037* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Fe | 0.01808 (13) | 0.01279 (13) | 0.01794 (13) | −0.00035 (10) | 0.00077 (10) | −0.00083 (10) |
Cl1 | 0.0326 (3) | 0.0217 (3) | 0.0352 (3) | 0.0011 (2) | −0.0064 (2) | −0.0012 (2) |
Cl2 | 0.0264 (2) | 0.0239 (3) | 0.0356 (3) | 0.00118 (19) | 0.0062 (2) | −0.0030 (2) |
Cl3 | 0.0313 (3) | 0.0234 (3) | 0.0399 (3) | 0.0000 (2) | 0.0070 (2) | −0.0013 (2) |
O11 | 0.118 (2) | 0.0463 (14) | 0.0629 (15) | 0.0105 (14) | −0.0153 (15) | 0.0256 (12) |
O12 | 0.0305 (9) | 0.0428 (11) | 0.0734 (14) | −0.0057 (8) | −0.0084 (9) | −0.0190 (10) |
O13 | 0.0387 (11) | 0.0425 (12) | 0.0765 (15) | 0.0111 (9) | 0.0060 (10) | −0.0037 (10) |
O14 | 0.0471 (11) | 0.0592 (13) | 0.0418 (11) | −0.0193 (10) | −0.0031 (9) | −0.0152 (10) |
O21 | 0.0761 (16) | 0.0259 (10) | 0.0775 (16) | −0.0005 (10) | 0.0343 (13) | 0.0033 (10) |
O22 | 0.0761 (16) | 0.0557 (14) | 0.0512 (12) | 0.0259 (12) | −0.0215 (11) | −0.0124 (10) |
O23 | 0.0311 (9) | 0.0589 (13) | 0.0615 (13) | −0.0122 (9) | 0.0157 (9) | −0.0303 (10) |
O24 | 0.0441 (10) | 0.0425 (11) | 0.0447 (10) | 0.0049 (9) | 0.0181 (8) | −0.0097 (8) |
O31 | 0.0615 (15) | 0.0787 (18) | 0.0660 (16) | −0.0064 (13) | −0.0182 (12) | 0.0026 (13) |
O32 | 0.0452 (12) | 0.0272 (10) | 0.113 (2) | 0.0029 (9) | −0.0029 (12) | 0.0131 (11) |
O33 | 0.0592 (13) | 0.0294 (10) | 0.0824 (16) | −0.0085 (9) | 0.0369 (12) | −0.0004 (10) |
O34 | 0.0787 (16) | 0.0403 (12) | 0.0538 (13) | −0.0004 (11) | 0.0307 (11) | −0.0083 (10) |
O1W | 0.0430 (14) | 0.185 (4) | 0.079 (2) | 0.0426 (19) | 0.0211 (13) | 0.056 (2) |
O2W | 0.0545 (12) | 0.0397 (11) | 0.0442 (11) | 0.0104 (10) | −0.0002 (10) | −0.0089 (9) |
N | 0.0263 (8) | 0.0185 (8) | 0.0196 (8) | −0.0007 (7) | 0.0005 (7) | 0.0020 (6) |
N1A | 0.0221 (8) | 0.0159 (8) | 0.0190 (8) | −0.0029 (6) | 0.0008 (6) | 0.0002 (6) |
N2A | 0.0207 (8) | 0.0163 (8) | 0.0227 (8) | 0.0005 (6) | 0.0009 (6) | 0.0007 (6) |
N3A | 0.0275 (9) | 0.0192 (9) | 0.0340 (10) | 0.0054 (7) | 0.0034 (8) | 0.0025 (7) |
N1B | 0.0221 (8) | 0.0155 (8) | 0.0203 (8) | 0.0013 (6) | 0.0020 (6) | −0.0021 (6) |
N2B | 0.0230 (8) | 0.0168 (8) | 0.0195 (8) | −0.0023 (6) | 0.0008 (6) | −0.0013 (6) |
N3B | 0.0237 (9) | 0.0324 (10) | 0.0304 (9) | −0.0048 (8) | 0.0048 (7) | 0.0049 (8) |
N1C | 0.0198 (8) | 0.0161 (8) | 0.0218 (8) | −0.0002 (6) | 0.0013 (6) | 0.0000 (6) |
N2C | 0.0227 (8) | 0.0158 (8) | 0.0209 (8) | 0.0024 (6) | 0.0001 (6) | −0.0013 (6) |
N3C | 0.0373 (10) | 0.0250 (10) | 0.0288 (9) | −0.0055 (8) | −0.0040 (8) | −0.0109 (8) |
C | 0.0424 (13) | 0.0268 (11) | 0.0212 (10) | −0.0012 (10) | −0.0011 (9) | 0.0066 (8) |
C1A | 0.0323 (10) | 0.0193 (10) | 0.0193 (9) | −0.0004 (8) | −0.0019 (8) | −0.0014 (7) |
C2A | 0.0267 (10) | 0.0177 (9) | 0.0217 (9) | −0.0037 (8) | −0.0044 (8) | −0.0026 (7) |
C3A | 0.0268 (10) | 0.0150 (9) | 0.0224 (9) | −0.0010 (7) | 0.0047 (8) | −0.0023 (7) |
C4A | 0.0212 (9) | 0.0170 (9) | 0.0243 (10) | 0.0005 (7) | 0.0040 (7) | 0.0015 (7) |
C5A | 0.0277 (11) | 0.0297 (12) | 0.0329 (12) | 0.0038 (9) | −0.0022 (9) | 0.0069 (9) |
C6A | 0.0246 (10) | 0.0276 (11) | 0.0251 (10) | −0.0010 (8) | −0.0022 (8) | 0.0025 (8) |
C1B | 0.0246 (10) | 0.0214 (10) | 0.0254 (10) | 0.0031 (8) | −0.0014 (8) | 0.0038 (8) |
C2B | 0.0254 (10) | 0.0163 (9) | 0.0245 (10) | 0.0025 (8) | 0.0021 (8) | 0.0021 (7) |
C3B | 0.0213 (9) | 0.0220 (10) | 0.0231 (9) | 0.0014 (8) | 0.0009 (8) | −0.0022 (8) |
C4B | 0.0218 (9) | 0.0231 (10) | 0.0209 (9) | −0.0026 (8) | 0.0033 (7) | −0.0012 (8) |
C5B | 0.0301 (10) | 0.0191 (10) | 0.0236 (10) | −0.0033 (8) | −0.0012 (8) | 0.0022 (8) |
C6B | 0.0344 (12) | 0.0275 (12) | 0.0279 (10) | −0.0087 (9) | 0.0032 (9) | 0.0049 (9) |
C1C | 0.0250 (10) | 0.0211 (10) | 0.0238 (10) | −0.0045 (8) | 0.0026 (8) | 0.0025 (8) |
C2C | 0.0199 (9) | 0.0213 (10) | 0.0241 (10) | −0.0008 (8) | 0.0039 (8) | −0.0003 (8) |
C3C | 0.0240 (10) | 0.0195 (10) | 0.0293 (10) | −0.0046 (8) | 0.0004 (8) | −0.0019 (8) |
C4C | 0.0273 (10) | 0.0197 (10) | 0.0261 (10) | −0.0011 (8) | −0.0039 (8) | −0.0056 (8) |
C5C | 0.0292 (10) | 0.0229 (10) | 0.0213 (9) | 0.0046 (8) | −0.0007 (8) | −0.0019 (8) |
C6C | 0.0384 (12) | 0.0309 (12) | 0.0236 (10) | 0.0044 (10) | −0.0027 (9) | −0.0080 (9) |
Fe—N1C | 1.9414 (17) | N1C—C3C | 1.294 (3) |
Fe—N2A | 1.9528 (17) | N1C—C2C | 1.461 (3) |
Fe—N1A | 1.9559 (17) | N2C—C4C | 1.332 (3) |
Fe—N1B | 1.9567 (17) | N2C—C5C | 1.369 (3) |
Fe—N2C | 1.9665 (17) | N3C—C4C | 1.349 (3) |
Fe—N2B | 1.9701 (17) | N3C—C6C | 1.368 (3) |
Cl1—O11 | 1.418 (2) | N3C—H3CB | 0.8800 |
Cl1—O13 | 1.421 (2) | C—H0A | 0.9800 |
Cl1—O12 | 1.4295 (19) | C—H0B | 0.9800 |
Cl1—O14 | 1.4548 (19) | C—H0C | 0.9800 |
Cl2—O23 | 1.4277 (18) | C1A—C2A | 1.523 (3) |
Cl2—O21 | 1.428 (2) | C1A—H1AA | 0.9900 |
Cl2—O24 | 1.4357 (18) | C1A—H1AB | 0.9900 |
Cl2—O22 | 1.449 (2) | C2A—H2AA | 0.9900 |
Cl3—O34 | 1.419 (2) | C2A—H2AB | 0.9900 |
Cl3—O32 | 1.428 (2) | C3A—C4A | 1.436 (3) |
Cl3—O33 | 1.4330 (19) | C3A—H3AA | 0.9500 |
Cl3—O31 | 1.444 (2) | C5A—C6A | 1.368 (3) |
O1W—H1W1 | 0.866 (19) | C5A—H5AA | 0.9500 |
O1W—H1W2 | 0.807 (19) | C6A—H6AA | 0.9500 |
O2W—H2W1 | 0.820 (17) | C1B—C2B | 1.524 (3) |
O2W—H2W2 | 0.821 (18) | C1B—H1BA | 0.9900 |
N—C | 1.527 (3) | C1B—H1BB | 0.9900 |
N—C1C | 1.528 (3) | C2B—H2BA | 0.9900 |
N—C1B | 1.531 (3) | C2B—H2BB | 0.9900 |
N—C1A | 1.532 (3) | C3B—C4B | 1.435 (3) |
N1A—C3A | 1.290 (3) | C3B—H3BA | 0.9500 |
N1A—C2A | 1.467 (2) | C5B—C6B | 1.369 (3) |
N2A—C4A | 1.337 (3) | C5B—H5BA | 0.9500 |
N2A—C6A | 1.368 (3) | C6B—H6BA | 0.9500 |
N3A—C4A | 1.348 (3) | C1C—C2C | 1.523 (3) |
N3A—C5A | 1.368 (3) | C1C—H1CA | 0.9900 |
N3A—H3AB | 0.8800 | C1C—H1CB | 0.9900 |
N1B—C3B | 1.293 (3) | C2C—H2CA | 0.9900 |
N1B—C2B | 1.462 (3) | C2C—H2CB | 0.9900 |
N2B—C4B | 1.330 (3) | C3C—C4C | 1.440 (3) |
N2B—C5B | 1.373 (3) | C3C—H3CA | 0.9500 |
N3B—C4B | 1.345 (3) | C5C—C6C | 1.367 (3) |
N3B—C6B | 1.364 (3) | C5C—H5CA | 0.9500 |
N3B—H3BB | 0.8800 | C6C—H6CA | 0.9500 |
N1C—Fe—N2A | 93.33 (7) | H0B—C—H0C | 109.5 |
N1C—Fe—N1A | 95.36 (7) | C2A—C1A—N | 120.44 (17) |
N2A—Fe—N1A | 81.09 (7) | C2A—C1A—H1AA | 107.2 |
N1C—Fe—N1B | 93.73 (7) | N—C1A—H1AA | 107.2 |
N2A—Fe—N1B | 172.17 (7) | C2A—C1A—H1AB | 107.2 |
N1A—Fe—N1B | 94.88 (7) | N—C1A—H1AB | 107.2 |
N1C—Fe—N2C | 81.14 (7) | H1AA—C1A—H1AB | 106.8 |
N2A—Fe—N2C | 93.08 (7) | N1A—C2A—C1A | 115.85 (17) |
N1A—Fe—N2C | 173.05 (7) | N1A—C2A—H2AA | 108.3 |
N1B—Fe—N2C | 91.34 (7) | C1A—C2A—H2AA | 108.3 |
N1C—Fe—N2B | 172.05 (7) | N1A—C2A—H2AB | 108.3 |
N2A—Fe—N2B | 92.10 (7) | C1A—C2A—H2AB | 108.3 |
N1A—Fe—N2B | 91.22 (7) | H2AA—C2A—H2AB | 107.4 |
N1B—Fe—N2B | 81.23 (7) | N1A—C3A—C4A | 113.15 (18) |
N2C—Fe—N2B | 92.77 (7) | N1A—C3A—H3AA | 123.4 |
O11—Cl1—O13 | 110.43 (16) | C4A—C3A—H3AA | 123.4 |
O11—Cl1—O12 | 110.79 (16) | N2A—C4A—N3A | 110.61 (18) |
O13—Cl1—O12 | 109.80 (12) | N2A—C4A—C3A | 116.54 (18) |
O11—Cl1—O14 | 108.29 (15) | N3A—C4A—C3A | 132.85 (19) |
O13—Cl1—O14 | 108.99 (13) | C6A—C5A—N3A | 106.98 (19) |
O12—Cl1—O14 | 108.48 (12) | C6A—C5A—H5AA | 126.5 |
O23—Cl2—O21 | 109.69 (14) | N3A—C5A—H5AA | 126.5 |
O23—Cl2—O24 | 110.63 (11) | C5A—C6A—N2A | 108.8 (2) |
O21—Cl2—O24 | 111.22 (13) | C5A—C6A—H6AA | 125.6 |
O23—Cl2—O22 | 108.41 (15) | N2A—C6A—H6AA | 125.6 |
O21—Cl2—O22 | 107.53 (15) | C2B—C1B—N | 121.13 (17) |
O24—Cl2—O22 | 109.27 (13) | C2B—C1B—H1BA | 107.0 |
O34—Cl3—O32 | 110.68 (15) | N—C1B—H1BA | 107.0 |
O34—Cl3—O33 | 109.81 (13) | C2B—C1B—H1BB | 107.0 |
O32—Cl3—O33 | 109.56 (13) | N—C1B—H1BB | 107.0 |
O34—Cl3—O31 | 108.37 (16) | H1BA—C1B—H1BB | 106.8 |
O32—Cl3—O31 | 107.02 (15) | N1B—C2B—C1B | 116.20 (17) |
O33—Cl3—O31 | 111.37 (16) | N1B—C2B—H2BA | 108.2 |
H1W1—O1W—H1W2 | 103 (3) | C1B—C2B—H2BA | 108.2 |
H2W1—O2W—H2W2 | 104 (2) | N1B—C2B—H2BB | 108.2 |
C—N—C1C | 104.07 (16) | C1B—C2B—H2BB | 108.2 |
C—N—C1B | 103.21 (16) | H2BA—C2B—H2BB | 107.4 |
C1C—N—C1B | 114.95 (16) | N1B—C3B—C4B | 113.24 (18) |
C—N—C1A | 104.30 (16) | N1B—C3B—H3BA | 123.4 |
C1C—N—C1A | 113.92 (16) | C4B—C3B—H3BA | 123.4 |
C1B—N—C1A | 114.49 (16) | N2B—C4B—N3B | 111.19 (19) |
C3A—N1A—C2A | 118.04 (17) | N2B—C4B—C3B | 117.34 (18) |
C3A—N1A—Fe | 116.28 (14) | N3B—C4B—C3B | 131.4 (2) |
C2A—N1A—Fe | 125.51 (13) | C6B—C5B—N2B | 108.64 (19) |
C4A—N2A—C6A | 106.42 (17) | C6B—C5B—H5BA | 125.7 |
C4A—N2A—Fe | 112.58 (14) | N2B—C5B—H5BA | 125.7 |
C6A—N2A—Fe | 140.88 (15) | N3B—C6B—C5B | 107.06 (19) |
C4A—N3A—C5A | 107.23 (18) | N3B—C6B—H6BA | 126.5 |
C4A—N3A—H3AB | 126.4 | C5B—C6B—H6BA | 126.5 |
C5A—N3A—H3AB | 126.4 | C2C—C1C—N | 120.22 (17) |
C3B—N1B—C2B | 118.14 (17) | C2C—C1C—H1CA | 107.3 |
C3B—N1B—Fe | 115.93 (14) | N—C1C—H1CA | 107.3 |
C2B—N1B—Fe | 125.72 (13) | C2C—C1C—H1CB | 107.3 |
C4B—N2B—C5B | 106.05 (17) | N—C1C—H1CB | 107.3 |
C4B—N2B—Fe | 111.71 (13) | H1CA—C1C—H1CB | 106.9 |
C5B—N2B—Fe | 142.13 (15) | N1C—C2C—C1C | 115.48 (17) |
C4B—N3B—C6B | 107.04 (19) | N1C—C2C—H2CA | 108.4 |
C4B—N3B—H3BB | 126.5 | C1C—C2C—H2CA | 108.4 |
C6B—N3B—H3BB | 126.5 | N1C—C2C—H2CB | 108.4 |
C3C—N1C—C2C | 118.37 (17) | C1C—C2C—H2CB | 108.4 |
C3C—N1C—Fe | 116.85 (14) | H2CA—C2C—H2CB | 107.5 |
C2C—N1C—Fe | 124.70 (13) | N1C—C3C—C4C | 112.98 (18) |
C4C—N2C—C5C | 106.43 (17) | N1C—C3C—H3CA | 123.5 |
C4C—N2C—Fe | 112.39 (14) | C4C—C3C—H3CA | 123.5 |
C5C—N2C—Fe | 141.17 (15) | N2C—C4C—N3C | 110.58 (19) |
C4C—N3C—C6C | 107.37 (19) | N2C—C4C—C3C | 116.60 (18) |
C4C—N3C—H3CB | 126.3 | N3C—C4C—C3C | 132.8 (2) |
C6C—N3C—H3CB | 126.3 | C6C—C5C—N2C | 108.9 (2) |
N—C—H0A | 109.5 | C6C—C5C—H5CA | 125.5 |
N—C—H0B | 109.5 | N2C—C5C—H5CA | 125.5 |
H0A—C—H0B | 109.5 | C5C—C6C—N3C | 106.71 (19) |
N—C—H0C | 109.5 | C5C—C6C—H6CA | 126.6 |
H0A—C—H0C | 109.5 | N3C—C6C—H6CA | 126.6 |
N1C—Fe—N1A—C3A | −98.03 (15) | Fe—N1A—C3A—C4A | 4.9 (2) |
N2A—Fe—N1A—C3A | −5.49 (15) | C6A—N2A—C4A—N3A | −0.5 (2) |
N1B—Fe—N1A—C3A | 167.75 (15) | Fe—N2A—C4A—N3A | 176.30 (13) |
N2B—Fe—N1A—C3A | 86.44 (15) | C6A—N2A—C4A—C3A | 179.43 (18) |
N2A—Fe—N1A—C2A | 179.28 (16) | Fe—N2A—C4A—C3A | −3.7 (2) |
N1B—Fe—N1A—C2A | −7.49 (16) | C5A—N3A—C4A—N2A | 0.6 (2) |
N2B—Fe—N1A—C2A | −88.79 (16) | C5A—N3A—C4A—C3A | −179.4 (2) |
N1C—Fe—N2A—C4A | 99.71 (14) | N1A—C3A—C4A—N2A | −0.7 (3) |
N1A—Fe—N2A—C4A | 4.80 (14) | N1A—C3A—C4A—N3A | 179.3 (2) |
N2C—Fe—N2A—C4A | −178.99 (14) | C4A—N3A—C5A—C6A | −0.4 (2) |
N2B—Fe—N2A—C4A | −86.10 (14) | N3A—C5A—C6A—N2A | 0.0 (2) |
N1C—Fe—N2A—C6A | −85.1 (2) | C4A—N2A—C6A—C5A | 0.3 (2) |
N1A—Fe—N2A—C6A | 180.0 (2) | Fe—N2A—C6A—C5A | −175.06 (17) |
N2C—Fe—N2A—C6A | −3.8 (2) | C—N—C1B—C2B | 151.74 (19) |
N2B—Fe—N2A—C6A | 89.1 (2) | C1C—N—C1B—C2B | 39.1 (3) |
N1C—Fe—N1B—C3B | 167.02 (15) | C1A—N—C1B—C2B | −95.6 (2) |
N1A—Fe—N1B—C3B | −97.27 (15) | C3B—N1B—C2B—C1B | 99.6 (2) |
N2C—Fe—N1B—C3B | 85.81 (15) | Fe—N1B—C2B—C1B | −85.8 (2) |
N2B—Fe—N1B—C3B | −6.79 (15) | N—C1B—C2B—N1B | 72.2 (2) |
N1C—Fe—N1B—C2B | −7.71 (16) | C2B—N1B—C3B—C4B | −178.72 (17) |
N1A—Fe—N1B—C2B | 88.00 (16) | Fe—N1B—C3B—C4B | 6.1 (2) |
N2C—Fe—N1B—C2B | −88.92 (16) | C5B—N2B—C4B—N3B | −0.2 (2) |
N2B—Fe—N1B—C2B | 178.48 (16) | Fe—N2B—C4B—N3B | 177.05 (14) |
N2A—Fe—N2B—C4B | −178.30 (14) | C5B—N2B—C4B—C3B | 178.36 (18) |
N1A—Fe—N2B—C4B | 100.57 (14) | Fe—N2B—C4B—C3B | −4.4 (2) |
N1B—Fe—N2B—C4B | 5.82 (14) | C6B—N3B—C4B—N2B | −0.1 (2) |
N2C—Fe—N2B—C4B | −85.11 (14) | C6B—N3B—C4B—C3B | −178.4 (2) |
N2A—Fe—N2B—C5B | −2.7 (2) | N1B—C3B—C4B—N2B | −1.0 (3) |
N1A—Fe—N2B—C5B | −83.8 (2) | N1B—C3B—C4B—N3B | 177.2 (2) |
N1B—Fe—N2B—C5B | −178.5 (2) | C4B—N2B—C5B—C6B | 0.4 (2) |
N2C—Fe—N2B—C5B | 90.5 (2) | Fe—N2B—C5B—C6B | −175.37 (17) |
N2A—Fe—N1C—C3C | 91.28 (16) | C4B—N3B—C6B—C5B | 0.4 (3) |
N1A—Fe—N1C—C3C | 172.62 (16) | N2B—C5B—C6B—N3B | −0.5 (3) |
N1B—Fe—N1C—C3C | −92.11 (16) | C—N—C1C—C2C | 153.57 (18) |
N2C—Fe—N1C—C3C | −1.33 (15) | C1B—N—C1C—C2C | −94.3 (2) |
N2A—Fe—N1C—C2C | −85.53 (16) | C1A—N—C1C—C2C | 40.6 (2) |
N1A—Fe—N1C—C2C | −4.18 (16) | C3C—N1C—C2C—C1C | 93.2 (2) |
N1B—Fe—N1C—C2C | 91.09 (16) | Fe—N1C—C2C—C1C | −90.1 (2) |
N2C—Fe—N1C—C2C | −178.13 (16) | N—C1C—C2C—N1C | 72.7 (2) |
N1C—Fe—N2C—C4C | 0.15 (14) | C2C—N1C—C3C—C4C | 179.14 (18) |
N2A—Fe—N2C—C4C | −92.75 (15) | Fe—N1C—C3C—C4C | 2.1 (2) |
N1B—Fe—N2C—C4C | 93.72 (15) | C5C—N2C—C4C—N3C | 0.1 (2) |
N2B—Fe—N2C—C4C | 175.00 (15) | Fe—N2C—C4C—N3C | −179.40 (14) |
N2A—Fe—N2C—C5C | 88.0 (2) | C5C—N2C—C4C—C3C | −179.55 (18) |
N1B—Fe—N2C—C5C | −85.6 (2) | Fe—N2C—C4C—C3C | 0.9 (2) |
N2B—Fe—N2C—C5C | −4.3 (2) | C6C—N3C—C4C—N2C | 0.1 (3) |
C—N—C1A—C2A | 150.83 (19) | C6C—N3C—C4C—C3C | 179.7 (2) |
C1C—N—C1A—C2A | −96.4 (2) | N1C—C3C—C4C—N2C | −2.0 (3) |
C1B—N—C1A—C2A | 38.8 (3) | N1C—C3C—C4C—N3C | 178.4 (2) |
C3A—N1A—C2A—C1A | 98.1 (2) | C4C—N2C—C5C—C6C | −0.3 (2) |
Fe—N1A—C2A—C1A | −86.8 (2) | Fe—N2C—C5C—C6C | 178.98 (18) |
N—C1A—C2A—N1A | 73.3 (2) | N2C—C5C—C6C—N3C | 0.4 (3) |
C2A—N1A—C3A—C4A | −179.54 (17) | C4C—N3C—C6C—C5C | −0.3 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1W2···O14i | 0.81 (2) | 2.29 (4) | 2.938 (3) | 138 (5) |
O2W—H2W1···O14ii | 0.82 (2) | 2.26 (2) | 2.987 (3) | 148 (4) |
O2W—H2W2···O22iii | 0.82 (2) | 2.07 (2) | 2.861 (3) | 160 (4) |
N3A—H3AB···O2W | 0.88 | 1.91 | 2.730 (3) | 155 |
N3B—H3BB···O1W | 0.88 | 1.95 | 2.752 (3) | 152 |
N3C—H3CB···O14 | 0.88 | 2.05 | 2.907 (3) | 163 |
Symmetry codes: (i) −x+3/2, y+1/2, z; (ii) x, y+1, z; (iii) −x+1/2, y+1/2, z. |
Experimental details
Crystal data | |
Chemical formula | [Fe(C19H27N10)](ClO4)3·2H2O |
Mr | 785.74 |
Crystal system, space group | Orthorhombic, Pbca |
Temperature (K) | 173 |
a, b, c (Å) | 13.9630 (18), 11.7810 (15), 37.182 (5) |
V (Å3) | 6116.4 (14) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.84 |
Crystal size (mm) | 0.54 × 0.45 × 0.12 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.682, 0.904 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 65065, 8324, 6601 |
Rint | 0.054 |
(sin θ/λ)max (Å−1) | 0.689 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.041, 0.108, 1.04 |
No. of reflections | 8324 |
No. of parameters | 436 |
No. of restraints | 6 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.76, −0.62 |
Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2006), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2000).
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1W2···O14i | 0.807 (19) | 2.29 (4) | 2.938 (3) | 138 (5) |
O2W—H2W1···O14ii | 0.820 (17) | 2.26 (2) | 2.987 (3) | 148 (4) |
O2W—H2W2···O22iii | 0.821 (18) | 2.07 (2) | 2.861 (3) | 160 (4) |
N3A—H3AB···O2W | 0.88 | 1.91 | 2.730 (3) | 155 |
N3B—H3BB···O1W | 0.88 | 1.95 | 2.752 (3) | 152 |
N3C—H3CB···O14 | 0.88 | 2.05 | 2.907 (3) | 163 |
Symmetry codes: (i) −x+3/2, y+1/2, z; (ii) x, y+1, z; (iii) −x+1/2, y+1/2, z. |
Iron(II) and iron(III) Schiff base complexes of tris(2-aminoethyl)amine (tren) with imidazole carboxaldehyde have displayed spin crossover behavior (Brewer et al., 2006). Further, it has been demonstrated that the distance between the Fe atom and the central tren-N atom, Nap, is an indicator of spin-state (Brewer et al., 2006). Shorter distances correlate with high spin and longer distances with low spin. Quarternization of Nap, as observed in the title complex, (I), results in an elongated Fe—Nap distance due to both the conformation of the Nap atom (inverted away from the Fe atom) and the repulsive forces between the positively charged atoms (Brewer et al., 2005). Recently, it was shown that (I), without the methyl group on Nap, could serve as a bidentate hydrogen bond donor to the perchlorate anion of potassium perchlorate using the adjacent imidazole-NH and imine-CH H atoms to give supramolecular complexes (Brewer et al., 2007). Since the present molecule possesses this same structural feature, the reaction of it with potassium perchlorate was investigated. The reaction did not yield the desired product but gave (I) as a polymorph (Brewer et al., 2007). The structure of the iron cation differs from the original report in that the three arms of the ligand are not identical. In addition, the hydrogen bonding interactions with coordinated water and perchlorate are significantly different. Investigation of these effects on the spin crossover process and reactivity of the complex will be aided by the structural characterization of this new polymorph. In view of the importance of the spin crossover phenomenom and supramolecular systems, the present paper reports the crystal structure of (I) (Fig. 1).
The octahedral iron(II) atom is bound to three facial imidazole-N atoms whose average Fe–N bond distances for the imidazole- and imine-N atoms are 1.963 (5)Å and 1.951 (5) Å, respectively. The central N atom of the tripodal ligand is outside the bonding distance at 3.92 Å. Crystal packing is stabilized by the hydrogen bonding interactions between the two water molecules (acceptor) and two of the three imidazole NH groups (donor). The third imidazole NH group (donor) hydrogen bonds to one of the three perchlorate counterions (acceptor) (Table 1 & Fig. 2).