Bis(dipyrido[3,2-a:2′,3′-c]phenazine)sulfatoiron(II) monohydrate

In the title compound, [Fe(SO₄)(C₁₈H₁₀N₄)₂]·H₂O, the Fe^II atom (site symmetry 2) is six-coodinated by four N atoms from two dipyrido[3,2-a:2′,3′-c]phenazine ligands and two O atoms from the SO₄²⁻ dianion in a distorted cis-FeO₂N₄ octa­hedral geometry. Numerous aromatic π–π stacking inter­actions [centroid separation = 3.671 (2)–4.090 (2) Å] and O—H...O hydrogen bonds help to stabilize the structure. The water molecule is disordered with a site-occupancy factor of 0.5.

Key indicators

• Single-crystal X-ray study
• T = 292 K
• Mean [sigma](C-C) = 0.005 Å
• Disorder in solvent or counterion
• R factor = 0.049
• wR factor = 0.139
• Data-to-parameter ratio = 12.0

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT152_ALERT_1_C Supplied and Calc Volume s.u. Inconsistent .....          ?
PLAT302_ALERT_4_C Anion/Solvent Disorder .........................      50.00 Perc.
PLAT333_ALERT_2_C Large Average Benzene C-C Dist.  C4     -C18           1.43 Ang.
PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........          2

Alert level G
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          3

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

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

Heteroaromatic N-donor chelating ligands such as 1,10-phenanthroline (phen) and its derivatives have been widely used in the construction of metal-organic complexes (Che, Liu et al.,2006; Li et al., 2006). As a continuation of our studies, we have prepared the title compound, FeSO₄(L)₂·H₂O, using the phen derivative dipyrido[3,2 - a:2',3'-c]phenazine (L) ligand.

In compound (I), (Fig. 1, Table 1), the Fe²⁺ atom (site symmetry 2) is six coordinated by four N atoms from two L ligands and two O atoms from the same SO₄^2- dianion in a distorted octahedral geometry. Neighbouring complexes are connected through π-π interactions between L ligands with a stacking distance of 3.671 (2) Å, leading to layers propagating in [101] (Fig. 2).

Related literature

For related complexes containing phenanthroline-derived lgands, see: Che, Liu et al. (2006); Che (2006); Li et al. (2006). For the ligand synthesis, see: Che, Li et al. (2006).

S2. Experimental

Ligand L was synthesized according to the literature method of Che, Li et al. (2006). An ethanol solution (12 ml) of L (0.5 mmol) was added slowly to an aqueous solution (10 ml) of FeSO₄ (0.5 mmol). The mixture was sealed in a Teflon-lined autoclave and heated to 433 K for 4 d. Brown blocks and slabs of (I) were obtained upon cooling and opening the autoclave (65% yield based on Fe).

S3. Refinement

The water O atom showed a large displacement parameter. Its site occupancy refined to close to 0.5 and the fit improved. Its occupancy was then fixed at 0.5. The water H atoms were located in a difference map and their positions were freely refined.

All C-bound H atoms were generated geometrically (C—H = 0.93 Å) and refined as riding with U_iso(H) = 1.2U_eq(carrier).

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: SHELXTL (Bruker, 2002); software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. View of the asymmetric unit of (I), together with further atoms to complete the Fe^II coordination sphere. Displacement ellipsoids are drawn at the 30% probability level (arbitrary spheres for the H atoms). [Symmetry code: 1 - x, y, 1/2 - z.]
	Fig. 2. View of the π-π stacking in the structure of (I) leading to chains of molecules.

Bis(dipyrido[3,2 - a:2',3'-c]phenazine)sulfatoiron(II) monohydrate

Crystal data

[Fe(SO4)(C18H10N4)2]·H2O	F(000) = 1504
Mr = 734.53	Dx = 1.657 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 1263 reflections
a = 17.527 (2) Å	θ = 2.3–26.0°
b = 7.2674 (10) Å	µ = 0.65 mm^−1
c = 23.203 (3) Å	T = 292 K
β = 94.826 (2)°	Slab, brown
V = 2944.9 (7) Å^3	0.32 × 0.14 × 0.09 mm
Z = 4

Data collection

Bruker SMART CCD diffractometer	2908 independent reflections
Radiation source: fine-focus sealed tube	2041 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.061
ω scans	θmax = 26.1°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2002)	h = −21→21
Tmin = 0.895, Tmax = 0.939	k = −8→8
12199 measured reflections	l = −28→28

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)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.139	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0651P)^2 + 4.1225P] where P = (Fo^2 + 2Fc^2)/3
2908 reflections	(Δ/σ)max < 0.001
242 parameters	Δρmax = 0.55 e Å^−3
3 restraints	Δρmin = −0.39 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.

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 (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
O1W	0.4209 (3)	0.1304 (8)	0.3969 (3)	0.0561 (17)	0.50
C1	0.4474 (2)	0.5284 (5)	0.35121 (16)	0.0351 (9)
H1	0.3998	0.5299	0.3303	0.042*
C2	0.4539 (2)	0.6080 (5)	0.40550 (16)	0.0374 (9)
H2	0.4117	0.6633	0.4201	0.045*
C3	0.52355 (19)	0.6044 (5)	0.43763 (15)	0.0335 (8)
H3	0.5292	0.6546	0.4746	0.040*
C4	0.58578 (19)	0.5231 (4)	0.41324 (15)	0.0291 (8)
C5	0.66145 (19)	0.5085 (5)	0.44494 (14)	0.0296 (8)
C6	0.7382 (2)	0.5424 (5)	0.52866 (15)	0.0335 (8)
C7	0.7487 (2)	0.5916 (5)	0.58783 (16)	0.0432 (10)
H7	0.7077	0.6361	0.6067	0.052*
C8	0.8191 (3)	0.5735 (6)	0.61717 (18)	0.0490 (11)
H8	0.8259	0.6076	0.6559	0.059*
C9	0.8811 (2)	0.5045 (5)	0.58975 (17)	0.0467 (10)
H9	0.9284	0.4921	0.6108	0.056*
C10	0.8739 (2)	0.4551 (5)	0.53300 (17)	0.0436 (10)
H10	0.9159	0.4105	0.5154	0.052*
C11	0.8013 (2)	0.4723 (5)	0.50083 (16)	0.0343 (8)
C12	0.72472 (19)	0.4395 (4)	0.41675 (15)	0.0292 (8)
C13	0.71308 (19)	0.3818 (4)	0.35639 (14)	0.0284 (8)
C14	0.77242 (19)	0.3215 (5)	0.32452 (15)	0.0341 (8)
H14	0.8228	0.3274	0.3405	0.041*
C15	0.7563 (2)	0.2534 (5)	0.26961 (15)	0.0353 (8)
H15	0.7953	0.2125	0.2479	0.042*
C16	0.6803 (2)	0.2471 (5)	0.24735 (16)	0.0362 (9)
H16	0.6692	0.1956	0.2109	0.043*
C17	0.63881 (18)	0.3793 (4)	0.32890 (14)	0.0281 (7)
C18	0.57456 (18)	0.4516 (4)	0.35795 (14)	0.0266 (7)
N1	0.50531 (15)	0.4501 (4)	0.32740 (12)	0.0297 (7)
N2	0.62257 (15)	0.3105 (4)	0.27515 (12)	0.0307 (7)
N3	0.66826 (17)	0.5592 (4)	0.50016 (12)	0.0339 (7)
N4	0.79357 (16)	0.4221 (4)	0.44431 (13)	0.0329 (7)
O1	0.48704 (15)	0.0364 (3)	0.29847 (10)	0.0432 (7)
O2	0.43230 (14)	−0.2049 (4)	0.23570 (12)	0.0496 (7)
S	0.5000	−0.09498 (18)	0.2500	0.0333 (3)
Fe	0.5000	0.28602 (10)	0.2500	0.0322 (2)
HW11	0.431 (4)	0.077 (10)	0.3686 (18)	0.048*	0.50
HW12	0.453 (3)	0.123 (12)	0.423 (2)	0.048*	0.50

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1W	0.071 (4)	0.044 (3)	0.060 (4)	−0.009 (3)	0.051 (3)	−0.010 (3)
C1	0.0228 (18)	0.042 (2)	0.040 (2)	0.0028 (16)	0.0006 (16)	0.0013 (17)
C2	0.029 (2)	0.040 (2)	0.044 (2)	0.0051 (16)	0.0048 (16)	−0.0009 (17)
C3	0.032 (2)	0.037 (2)	0.0314 (19)	0.0018 (16)	0.0037 (15)	−0.0036 (16)
C4	0.0275 (18)	0.0286 (18)	0.0309 (19)	−0.0020 (14)	0.0014 (15)	0.0025 (15)
C5	0.0313 (19)	0.0279 (18)	0.0291 (19)	−0.0007 (15)	0.0001 (15)	0.0025 (15)
C6	0.039 (2)	0.0312 (19)	0.029 (2)	−0.0063 (16)	−0.0053 (16)	0.0051 (15)
C7	0.053 (3)	0.043 (2)	0.033 (2)	−0.0086 (19)	−0.0005 (18)	0.0003 (17)
C8	0.064 (3)	0.046 (2)	0.035 (2)	−0.012 (2)	−0.010 (2)	0.0043 (18)
C9	0.051 (3)	0.043 (2)	0.043 (2)	−0.008 (2)	−0.018 (2)	0.0045 (19)
C10	0.040 (2)	0.040 (2)	0.048 (3)	−0.0026 (18)	−0.0105 (19)	0.0044 (18)
C11	0.034 (2)	0.0282 (18)	0.038 (2)	−0.0047 (15)	−0.0089 (17)	0.0030 (15)
C12	0.0266 (18)	0.0287 (19)	0.0316 (19)	0.0002 (14)	−0.0027 (14)	0.0033 (14)
C13	0.0253 (18)	0.0291 (18)	0.0303 (18)	0.0019 (14)	−0.0004 (14)	0.0025 (14)
C14	0.0212 (18)	0.040 (2)	0.039 (2)	0.0000 (15)	−0.0042 (15)	0.0029 (17)
C15	0.0297 (19)	0.042 (2)	0.034 (2)	0.0035 (16)	0.0033 (15)	−0.0022 (16)
C16	0.033 (2)	0.046 (2)	0.030 (2)	0.0032 (17)	0.0012 (15)	−0.0040 (16)
C17	0.0257 (17)	0.0286 (18)	0.0300 (18)	0.0018 (14)	0.0012 (14)	0.0032 (14)
C18	0.0246 (17)	0.0288 (18)	0.0256 (18)	0.0003 (14)	−0.0018 (14)	0.0041 (14)
N1	0.0219 (15)	0.0324 (16)	0.0343 (16)	0.0004 (12)	−0.0008 (12)	0.0039 (12)
N2	0.0269 (15)	0.0392 (17)	0.0256 (15)	0.0010 (13)	0.0006 (12)	−0.0016 (13)
N3	0.0358 (17)	0.0357 (17)	0.0297 (16)	−0.0034 (13)	−0.0005 (13)	−0.0005 (13)
N4	0.0270 (16)	0.0347 (17)	0.0359 (17)	−0.0026 (13)	−0.0043 (13)	−0.0007 (13)
O1	0.0521 (17)	0.0475 (16)	0.0298 (14)	0.0019 (13)	0.0023 (12)	−0.0019 (12)
O2	0.0301 (15)	0.0503 (17)	0.0663 (19)	−0.0089 (13)	−0.0086 (13)	−0.0017 (14)
S	0.0253 (6)	0.0395 (7)	0.0341 (7)	0.000	−0.0036 (5)	0.000
Fe	0.0237 (4)	0.0425 (5)	0.0294 (4)	0.000	−0.0037 (3)	0.000

Geometric parameters (Å, º)

O1W—HW11	0.79 (2)	C11—N4	1.357 (4)
O1W—HW12	0.80 (2)	C12—N4	1.323 (4)
C1—N1	1.324 (4)	C12—C13	1.460 (5)
C1—C2	1.382 (5)	C13—C14	1.396 (5)
C1—H1	0.9300	C13—C17	1.401 (4)
C2—C3	1.377 (5)	C14—C15	1.374 (5)
C2—H2	0.9300	C14—H14	0.9300
C3—C4	1.401 (5)	C15—C16	1.389 (5)
C3—H3	0.9300	C15—H15	0.9300
C4—C18	1.383 (5)	C16—N2	1.327 (4)
C4—C5	1.465 (5)	C16—H16	0.9300
C5—N3	1.329 (4)	C17—N2	1.352 (4)
C5—C12	1.425 (5)	C17—C18	1.458 (4)
C6—N3	1.348 (4)	C18—N1	1.353 (4)
C6—C7	1.416 (5)	O1—S	1.507 (3)
C6—C11	1.422 (5)	O2—S	1.446 (2)
C7—C8	1.364 (5)	S—O2^i	1.446 (3)
C7—H7	0.9300	S—O1^i	1.507 (3)
C8—C9	1.399 (6)	Fe—N1	2.151 (3)
C8—H8	0.9300	Fe—N2	2.185 (3)
C9—C10	1.361 (5)	Fe—O1	2.156 (3)
C9—H9	0.9300	Fe—N1^i	2.151 (3)
C10—C11	1.425 (5)	Fe—O1^i	2.156 (3)
C10—H10	0.9300	Fe—N2^i	2.185 (3)
HW11—O1W—HW12	114 (4)	C14—C15—C16	118.2 (3)
N1—C1—C2	123.6 (3)	C14—C15—H15	120.9
N1—C1—H1	118.2	C16—C15—H15	120.9
C2—C1—H1	118.2	N2—C16—C15	123.7 (3)
C3—C2—C1	119.1 (3)	N2—C16—H16	118.2
C3—C2—H2	120.5	C15—C16—H16	118.2
C1—C2—H2	120.5	N2—C17—C13	122.7 (3)
C2—C3—C4	118.3 (3)	N2—C17—C18	116.7 (3)
C2—C3—H3	120.8	C13—C17—C18	120.6 (3)
C4—C3—H3	120.8	N1—C18—C4	122.7 (3)
C18—C4—C3	118.6 (3)	N1—C18—C17	116.6 (3)
C18—C4—C5	119.4 (3)	C4—C18—C17	120.6 (3)
C3—C4—C5	122.0 (3)	C1—N1—C18	117.6 (3)
N3—C5—C12	122.0 (3)	C1—N1—Fe	127.3 (2)
N3—C5—C4	117.9 (3)	C18—N1—Fe	114.6 (2)
C12—C5—C4	120.1 (3)	C16—N2—C17	117.8 (3)
N3—C6—C7	119.4 (4)	C16—N2—Fe	127.9 (2)
N3—C6—C11	121.3 (3)	C17—N2—Fe	113.7 (2)
C7—C6—C11	119.2 (3)	C5—N3—C6	116.9 (3)
C8—C7—C6	119.9 (4)	C12—N4—C11	117.0 (3)
C8—C7—H7	120.1	S—O1—Fe	96.58 (13)
C6—C7—H7	120.1	O2—S—O2^i	112.9 (2)
C7—C8—C9	120.8 (4)	O2—S—O1	110.43 (15)
C7—C8—H8	119.6	O2^i—S—O1	110.55 (15)
C9—C8—H8	119.6	O2—S—O1^i	110.55 (15)
C10—C9—C8	121.5 (4)	O2^i—S—O1^i	110.43 (15)
C10—C9—H9	119.3	O1—S—O1^i	101.4 (2)
C8—C9—H9	119.3	N1—Fe—N1^i	112.66 (15)
C9—C10—C11	119.4 (4)	N1—Fe—O1^i	154.52 (10)
C9—C10—H10	120.3	N1^i—Fe—O1^i	91.72 (10)
C11—C10—H10	120.3	N1—Fe—O1	91.72 (10)
N4—C11—C6	121.1 (3)	N1^i—Fe—O1	154.52 (10)
N4—C11—C10	119.7 (4)	O1^i—Fe—O1	65.47 (13)
C6—C11—C10	119.2 (3)	N1—Fe—N2^i	98.64 (10)
N4—C12—C5	121.7 (3)	N1^i—Fe—N2^i	76.08 (10)
N4—C12—C13	119.0 (3)	O1^i—Fe—N2^i	94.22 (10)
C5—C12—C13	119.3 (3)	O1—Fe—N2^i	93.64 (10)
C14—C13—C17	117.4 (3)	N1—Fe—N2	76.08 (10)
C14—C13—C12	123.2 (3)	N1^i—Fe—N2	98.64 (10)
C17—C13—C12	119.3 (3)	O1^i—Fe—N2	93.64 (10)
C15—C14—C13	120.0 (3)	O1—Fe—N2	94.22 (10)
C15—C14—H14	120.0	N2^i—Fe—N2	170.66 (15)
C13—C14—H14	120.0

Symmetry code: (i) −x+1, y, −z+1/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—HW11···O1	0.80 (5)	1.99 (5)	2.734 (7)	155 (7)