catena-Poly[diethyl­enetriaminium [ferrate(III)-tri-μ-sulfato-κ⁶O:O′] monohydrate]

Ferric sulfate reacts with diethyl­enetriamine in the presence of acid under hydro­thermal conditions to form the title compound, (C₄H₁₆N₃)[Fe(SO₄)₃]·H₂O. The six-coordinate ferrate trianion entity exists as a tri-μ₂-sulfate-bridged chain that propagates along the c axis of the monoclinic unit cell. The trication and uncoordinated water mol­ecule connect the polyanionic chain into a three-dimensional network structure.

Key indicators

• Single-crystal X-ray study
• T = 295 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.044
• wR factor = 0.109
• Data-to-parameter ratio = 15.0

checkCIF/PLATON results

No syntax errors found



Alert level B
ABSTM02_ALERT_3_B  The ratio of expected to reported Tmax/Tmin(RR') is < 0.75
            Tmin and Tmax reported:      0.367     0.889
            Tmin' and Tmax expected:      0.662     0.886
            RR' =      0.552
            Please check that your absorption correction is appropriate.
PLAT061_ALERT_3_B Tmax/Tmin Range Test RR' too Large .............       0.55

Alert level C
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT432_ALERT_2_C Short Inter X...Y Contact  O10    ..  C4      ..       3.01 Ang.
PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........         10
PLAT731_ALERT_1_C Bond    Calc     0.85(4), Rep   0.850(10) ......       4.00 su-Rat
              O1W  -H1W1    1.555   1.555
PLAT731_ALERT_1_C Bond    Calc     0.85(4), Rep   0.850(10) ......       4.00 su-Rat
              O1W  -H1W2    1.555   1.555
PLAT735_ALERT_1_C D-H     Calc     0.85(4), Rep   0.850(10) ......       4.00 su-Rat
              O1W  -H1#     1.555   1.555
PLAT735_ALERT_1_C D-H     Calc     0.85(4), Rep   0.850(10) ......       4.00 su-Rat
              O1W  -H2#     1.555   1.555
PLAT736_ALERT_1_C H...A   Calc     2.05(4), Rep   2.060(10) ......       4.00 su-Rat
              H1#  -O3      1.555   1.555

   0 ALERT level A = In general: serious problem
   2 ALERT level B = Potentially serious problem
   8 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   6 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
   2 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion

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Computing details

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97.

catena-Poly[diethylenetriaminium [ferrate(III)-tri-µ-sulfato-κ⁶O:O'] monohydrate]

Crystal data

(C4H16N3)[Fe(SO4)3]·H2O	F(000) = 964
Mr = 468.24	Dx = 2.085 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2096 reflections
a = 9.1329 (8) Å	θ = 2.3–27.3°
b = 18.882 (2) Å	µ = 1.51 mm^−1
c = 8.8856 (7) Å	T = 295 K
β = 103.264 (1)°	Rod, yellow
V = 1491.4 (2) Å^3	0.27 × 0.10 × 0.08 mm
Z = 4

Data collection

Bruker APEX area-detector diffractometer	3369 independent reflections
Radiation source: fine-focus sealed tube	2680 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.037
φ and ω scans	θmax = 27.5°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2002)	h = −11→11
Tmin = 0.367, Tmax = 0.889	k = −13→24
8930 measured reflections	l = −11→11

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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.109	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0532P)^2 + 0.8094P] where P = (Fo^2 + 2Fc^2)/3
3369 reflections	(Δ/σ)max = 0.001
225 parameters	Δρmax = 0.58 e Å^−3
3 restraints	Δρmin = −0.44 e Å^−3

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

	x	y	z	Uiso*/Ueq
Fe1	0.21786 (5)	0.25291 (2)	0.21846 (5)	0.0115 (1)
S1	0.44676 (9)	0.18027 (4)	0.51862 (9)	0.0132 (2)
S3	−0.01914 (9)	0.30920 (4)	−0.09294 (9)	0.0131 (2)
S2	0.21261 (9)	0.37685 (4)	0.47439 (9)	0.0138 (2)
O1	0.3986 (2)	0.2320 (1)	0.3896 (2)	0.0156 (5)
O2	0.5946 (3)	0.2002 (1)	0.6052 (3)	0.0310 (6)
O3	0.4441 (3)	0.1084 (1)	0.4567 (3)	0.0247 (6)
O4	0.3380 (3)	0.1816 (1)	0.6212 (3)	0.0192 (5)
O5	0.1545 (3)	0.3343 (1)	0.3329 (2)	0.0183 (5)
O6	0.0837 (3)	0.4118 (1)	0.5136 (3)	0.0250 (6)
O7	0.3259 (3)	0.4265 (1)	0.4506 (3)	0.0282 (6)
O8	0.2858 (3)	0.3294 (1)	0.6053 (2)	0.0165 (5)
O9	0.0373 (3)	0.2660 (1)	0.0487 (3)	0.0184 (5)
O10	−0.0504 (3)	0.3813 (1)	−0.0540 (3)	0.0263 (6)
O11	−0.1519 (3)	0.2741 (1)	−0.1847 (3)	0.0214 (5)
O12	0.1009 (2)	0.3135 (1)	−0.1827 (2)	0.0151 (5)
O1w	0.3600 (4)	0.0102 (2)	0.6739 (4)	0.0459 (9)
N1	0.3903 (3)	−0.1339 (2)	0.7928 (3)	0.0230 (7)
N2	0.2150 (3)	−0.1308 (1)	1.1382 (3)	0.0215 (7)
N3	0.1613 (4)	0.0392 (2)	1.3315 (4)	0.0348 (8)
C1	0.3147 (4)	−0.1027 (2)	0.9079 (4)	0.0223 (8)
C2	0.3114 (4)	−0.1561 (2)	1.0324 (4)	0.0249 (8)
C3	0.2499 (4)	−0.0584 (2)	1.1980 (5)	0.0271 (8)
C4	0.1582 (5)	−0.0375 (2)	1.3091 (5)	0.033 (1)
H1w1	0.385 (6)	0.041 (2)	0.614 (4)	0.07 (2)*
H1w2	0.330 (6)	0.032 (2)	0.745 (4)	0.08 (2)*
H1n1	0.3924	−0.1033	0.7216	0.028*
H1n2	0.3416	−0.1708	0.7522	0.028*
H1n3	0.4807	−0.1457	0.8376	0.028*
H2n1	0.1223	−0.1323	1.0889	0.026*
H2n2	0.2258	−0.1594	1.2151	0.026*
H3n1	0.1079	0.0502	1.3963	0.042*
H3n2	0.1252	0.0598	1.2445	0.042*
H3n3	0.2525	0.0528	1.3669	0.042*
H1a	0.2128	−0.0890	0.8577	0.027*
H1b	0.3684	−0.0607	0.9529	0.027*
H2a	0.4130	−0.1643	1.0921	0.030*
H2b	0.2722	−0.2006	0.9854	0.030*
H3a	0.2313	−0.0253	1.1121	0.033*
H3b	0.3557	−0.0555	1.2489	0.033*
H4a	0.0551	−0.0529	1.2703	0.040*
H4b	0.1972	−0.0607	1.4075	0.040*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Fe1	0.0135 (2)	0.0129 (3)	0.0084 (2)	0.00009 (17)	0.00334 (17)	0.00037 (17)
S1	0.0134 (4)	0.0152 (4)	0.0110 (4)	0.0010 (3)	0.0031 (3)	0.0014 (3)
S3	0.0134 (4)	0.0157 (4)	0.0106 (4)	0.0015 (3)	0.0035 (3)	0.0006 (3)
S2	0.0180 (4)	0.0126 (4)	0.0109 (4)	0.0009 (3)	0.0034 (3)	−0.0004 (3)
O1	0.015 (1)	0.020 (1)	0.010 (1)	−0.001 (1)	0.000 (1)	0.003 (1)
O2	0.022 (1)	0.039 (2)	0.026 (1)	−0.009 (1)	−0.008 (1)	0.015 (1)
O3	0.037 (2)	0.018 (1)	0.024 (1)	0.004 (1)	0.017 (1)	−0.002 (1)
O4	0.027 (1)	0.018 (1)	0.016 (1)	0.003 (1)	0.013 (1)	0.001 (1)
O5	0.023 (1)	0.020 (1)	0.011 (1)	0.003 (1)	0.001 (1)	−0.002 (1)
O6	0.027 (1)	0.026 (1)	0.022 (1)	0.011 (1)	0.004 (1)	−0.007 (1)
O7	0.034 (2)	0.025 (2)	0.024 (1)	−0.010 (1)	0.003 (1)	0.007 (1)
O8	0.021 (1)	0.016 (1)	0.012 (1)	0.000 (1)	0.002 (1)	0.004 (1)
O9	0.019 (1)	0.026 (1)	0.010 (1)	0.000 (1)	0.001 (1)	0.006 (1)
O10	0.034 (2)	0.020 (1)	0.031 (2)	0.004 (1)	0.021 (1)	−0.004 (1)
O11	0.017 (1)	0.025 (1)	0.020 (1)	−0.004 (1)	−0.001 (1)	0.005 (1)
O12	0.020 (1)	0.015 (1)	0.012 (1)	0.001 (1)	0.007 (1)	−0.001 (1)
O1w	0.084 (3)	0.025 (2)	0.036 (2)	0.000 (2)	0.026 (2)	0.003 (1)
N1	0.023 (2)	0.025 (2)	0.022 (2)	−0.003 (1)	0.008 (1)	−0.001 (1)
N2	0.029 (2)	0.017 (2)	0.020 (2)	0.000 (1)	0.009 (1)	0.001 (1)
N3	0.034 (2)	0.028 (2)	0.042 (2)	0.003 (2)	0.009 (2)	−0.007 (2)
C1	0.026 (2)	0.021 (2)	0.022 (2)	0.001 (1)	0.009 (2)	−0.002 (1)
C2	0.033 (2)	0.020 (2)	0.024 (2)	0.004 (2)	0.010 (2)	0.000 (2)
C3	0.028 (2)	0.015 (2)	0.038 (2)	−0.004 (2)	0.006 (2)	−0.007 (2)
C4	0.058 (3)	0.020 (2)	0.030 (2)	−0.011 (2)	0.026 (2)	−0.006 (2)

Geometric parameters (Å, º)

Fe1—O1	2.010 (2)	N3—C4	1.461 (4)
Fe1—O4^i	1.978 (2)	C1—C2	1.502 (5)
Fe1—O5	2.001 (2)	C3—C4	1.487 (5)
Fe1—O8^i	2.024 (2)	O1W—H1w1	0.85 (1)
Fe1—O9	1.978 (2)	O1W—H1w2	0.85 (1)
Fe1—O12^ii	1.978 (2)	N1—H1n1	0.86
S1—O2	1.442 (3)	N1—H1n2	0.86
S1—O3	1.462 (2)	N1—H1n3	0.86
S1—O1	1.494 (2)	N2—H2n1	0.86
S1—O4	1.494 (2)	N2—H2n2	0.86
S3—O10	1.449 (2)	N3—H3n1	0.86
S3—O11	1.456 (2)	N3—H3n2	0.86
S3—O9	1.489 (2)	N3—H3n3	0.86
S3—O12	1.499 (2)	C1—H1a	0.97
S2—O7	1.447 (3)	C1—H1b	0.97
S2—O6	1.460 (2)	C2—H2a	0.97
S2—O5	1.483 (2)	C2—H2b	0.97
S2—O8	1.499 (2)	C3—H3a	0.97
N1—C1	1.481 (4)	C3—H3b	0.97
N2—C3	1.475 (4)	C4—H4a	0.97
N2—C2	1.505 (4)	C4—H4b	0.97
O1—Fe1—O4^i	90.7 (1)	N2—C3—C4	112.2 (3)
O1—Fe1—O5	92.8 (1)	N3—C4—C3	110.9 (3)
O1—Fe1—O8^i	86.2 (1)	H1W1—O1W—H1W2	109 (2)
O1—Fe1—O9	175.9 (1)	C1—N1—H1n1	109.5
O1—Fe1—O12^ii	88.5 (1)	C1—N1—H1n2	109.5
O4^i—Fe1—O5	89.8 (1)	H1n1—N1—H1n2	109.5
O4^i—Fe1—O8^i	89.9 (1)	C1—N1—H1n3	109.5
O4^i—Fe1—O9	92.2 (1)	H1n1—N1—H1n3	109.5
O4^i—Fe1—O12^ii	179.0 (1)	H1n2—N1—H1n3	109.5
O5—Fe1—O8^i	178.9 (1)	C3—N2—H2n1	108.7
O5—Fe1—O9	90.2 (1)	C2—N2—H2n1	108.7
O5—Fe1—O12^ii	90.7 (1)	C3—N2—H2n2	108.7
O8^i—Fe1—O9	90.8 (1)	C2—N2—H2n2	108.7
O8^i—Fe1—O12^ii	89.6 (1)	H2n1—N2—H2n2	107.6
O9—Fe1—O12^ii	88.7 (1)	C4—N3—H3n1	109.5
O2—S1—O3	112.0 (2)	C4—N3—H3n2	109.5
O2—S1—O1	108.3 (1)	H3n1—N3—H3n2	109.5
O3—S1—O1	110.0 (1)	C4—N3—H3n3	109.5
O2—S1—O4	110.0 (2)	H3n1—N3—H3n3	109.5
O3—S1—O4	106.8 (1)	H3n2—N3—H3n3	109.5
O1—S1—O4	109.7 (1)	N1—C1—H1a	109.8
O10—S3—O11	112.2 (2)	C2—C1—H1a	109.8
O10—S3—O9	111.2 (1)	N1—C1—H1b	109.8
O11—S3—O9	107.8 (1)	C2—C1—H1b	109.8
O10—S3—O12	106.6 (1)	H1a—C1—H1b	108.2
O11—S3—O12	110.1 (1)	C1—C2—H2a	109.4
O9—S3—O12	109.0 (1)	N2—C2—H2a	109.4
O7—S2—O6	112.6 (2)	C1—C2—H2b	109.4
O7—S2—O5	110.9 (1)	N2—C2—H2b	109.4
O6—S2—O5	107.2 (1)	H2a—C2—H2b	108.0
O7—S2—O8	107.1 (1)	N2—C3—C4	112.2 (3)
O6—S2—O8	109.0 (1)	N2—C3—H3a	109.2
O5—S2—O8	110.1 (1)	C4—C3—H3a	109.2
S1—O1—Fe1	139.0 (1)	N2—C3—H3b	109.2
S1—O4—Fe1^ii	142.2 (2)	C4—C3—H3b	109.2
S2—O5—Fe1	139.3 (2)	H3a—C3—H3b	107.9
S2—O8—Fe1^ii	135.4 (1)	N3—C4—C3	110.9 (3)
S3—O9—Fe1	141.2 (2)	N3—C4—H4a	109.5
S3—O12—Fe1^i	137.5 (1)	C3—C4—H4a	109.5
C3—N2—C2	114.2 (3)	N3—C4—H4b	109.5
N1—C1—C2	109.5 (3)	C3—C4—H4b	109.5
C1—C2—N2	111.1 (3)	H4a—C4—H4b	108.0
O2—S1—O1—Fe1	−176.4 (2)	O7—S2—O8—Fe1^ii	179.4 (2)
O3—S1—O1—Fe1	60.9 (2)	O6—S2—O8—Fe1^ii	57.3 (2)
O4—S1—O1—Fe1	−56.4 (2)	O5—S2—O8—Fe1^ii	−60.0 (2)
O12^ii—Fe1—O1—S1	12.0 (2)	O10—S3—O9—Fe1	−72.9 (3)
O4^i—Fe1—O1—S1	−167.5 (2)	O11—S3—O9—Fe1	163.7 (2)
O5—Fe1—O1—S1	102.7 (2)	O12—S3—O9—Fe1	44.2 (3)
O8^i—Fe1—O1—S1	−77.6 (2)	O12^ii—Fe1—O9—S3	173.5 (2)
O2—S1—O4—Fe1^ii	77.9 (3)	O4^i—Fe1—O9—S3	−7.0 (2)
O3—S1—O4—Fe1^ii	−160.3 (2)	O5—Fe1—O9—S3	82.8 (2)
O1—S1—O4—Fe1^ii	−41.1 (3)	O8^i—Fe1—O9—S3	−97.0 (2)
O7—S2—O5—Fe1	76.1 (3)	O10—S3—O12—Fe1^i	179.0 (2)
O6—S2—O5—Fe1	−160.6 (2)	O11—S3—O12—Fe1^i	−59.1 (2)
O8—S2—O5—Fe1	−42.2 (3)	O9—S3—O12—Fe1^i	58.9 (2)
O12^ii—Fe1—O5—S2	97.2 (2)	N1—C1—C2—N2	−171.2 (3)
O9—Fe1—O5—S2	−174.1 (2)	C3—N2—C2—C1	−50.3 (4)
O4^i—Fe1—O5—S2	−81.9 (2)	C2—N2—C3—C4	−176.5 (3)
O1—Fe1—O5—S2	8.7 (2)	N2—C3—C4—N3	−163.4 (3)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1w—H1w1···O3	0.85 (1)	2.06 (1)	2.904 (4)	176 (4)
O1w—H1w2···O7^ii	0.85 (1)	2.00 (2)	2.815 (4)	161 (6)
N1—H1n1···O1w	0.86	2.19	2.909 (4)	141
N1—H1n2···O11^iii	0.86	1.99	2.779 (4)	152
N1—H1n3···O8^iv	0.86	2.13	2.971 (4)	166
N2—H2n2···O2^v	0.86	2.15	2.850 (4)	138
N2—H2n1···O6^vi	0.86	2.07	2.867 (4)	154
N3—H3n3···O3^vii	0.86	2.04	2.881 (4)	166
N3—H3n2···O6^ii	0.86	2.07	2.902 (4)	162
N3—H3n1···O10^viii	0.86	2.06	2.816 (4)	146

Symmetry codes: (ii) x, −y+1/2, z+1/2; (iii) −x, y−1/2, −z+1/2; (iv) −x+1, y−1/2, −z+3/2; (v) −x+1, −y, −z+2; (vi) −x, y−1/2, −z+3/2; (vii) x, y, z+1; (viii) x, −y+1/2, z+3/2.