Di­aqua­bis(4,5-di­aza­fluoren-9-one-κ²N,N′)­zinc(II) dinitrate

The Zn atom in the crystal structure of [Zn(C₁₁H₆N₂O)₂(H₂O)₂](NO₃)₂ lies on an inversion center; it is chelated by the 4,5-diazo­fluoren-9-one entity in a nearly isobidentate manner. The coordinated water mol­ecules link the nitrate anions to produce a linear hydrogen-bonded chain that runs along the a axis.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.047
• wR factor = 0.106
• Data-to-parameter ratio = 14.1

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


 Alert Level C:



GOODF_01  Alert C The least squares goodness of fit parameter lies
          outside the range 0.80 <> 2.00
          Goodness of fit given =      0.780

REFLT_03
         From the CIF: _diffrn_reflns_theta_max           28.30
         From the CIF: _reflns_number_total               2623
         TEST2: Reflns within _diffrn_reflns_theta_max
         Count of symmetry unique reflns         2897
         Completeness (_total/calc)             90.54%
          Alert C: < 95% complete


 0 Alert Level A = Potentially serious problem

 0 Alert Level B = Potential problem

 2 Alert Level C = Please check

---

S1. Comment

4,5-Diazafluoren-9-one also chelates to the Cu atom of a copper dinitrate adduct that crystallizes as a dihydrate in which the two water molecules coordinate to the metal atom. Unfortunately, [Cu(C₁₁H₆N₂O)₂(H₂O)₂](NO₃)₂ was refined in the P1 space group (Hu et al., 2001) rather than the correct P1 space group, so that the reported bond dimensions may not be reliable. Nevertheless, one Cu—N distance (ca 2.0 Å) is distinctly shorter than the other (ca 2.6 Å).

The present Zn analog, (I) (Fig. 1), is not isomorphous to the Cu compound. In this case, the ligand chelates to the Zn atom, which lies on an inversion center (1/2, 1/2, 1/2) in a nearly isobidentate manner [Zn—N = 2.201 (3) and 2.290 (3) Å]. The two other coordination sites of the octahedron around it are occupied by the water molecules [Zn—O = 2.061 (3) Å]. Hydrogen bonds link the the cations to the nitrate anions [O···O = 2.702 (4) and 2.744 (4) Å] leading to the formation of a chain motif running along the a axis of the crystal (Fig. 2). Nearly isobidentate chelation by the ligand is also noted in the dihydrated copper perchlorate complex (Gu et al., 2002; Zhang et al., 2003).

S2. Experimental

4,5-Diazafluoren-9-one (Henderson et al., 1984) (0.18 g, 1 mmol) was reacted with lithium hydride (0.01 g, 0.5 mmol) in tetrahydrofuran solvent (10 ml) in a Schlenk apparatus. The yellow solution was refluxed for 1 h, after which zinc nitrate (0.09 g, 0.5 mmol) dissolved in tetrahydrofuran (10 ml) was added. Reflux was continued for another hour. Yellow crystals separated from the solution after several days, m.p. 552 K. CH&N analysis: calculated for C₂₂H₁₆N₆O₁₀Zn: C 44.76, H 2.71, N 14.24%; found C 44.60, H 2.72, N 13.78%.

S3. Refinement

The water H atoms were located and refined. The aromatic H atoms were generated geometrically (C—H = 0.93 Å) in the riding-model approximation; their displacement parameters were set to 1.2 times those of their parent C atoms. The crystal used for data collection was a weak scatterer such that high-angle reflections, particularly those beyond θ of 25°, were not included in any calculations.

Computing details

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); 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.

Figures

	Fig. 1. ORTEPII (Johnson, 1976) plot of (I), with ellipsoids drawn at the 50% probability level. H atoms are drawn as spheres of arbitrary radii.
	Fig. 2. ORTEPII (Johnson, 1976) plot of hydrogen-bonded chain structure of (I), with ellipsoids drawn at the 50% probability level. H atoms are drawn as spheres of arbitrary radii.

Diaquabis(4,5-diazafluoren-9-one-κ²N,N')zinc(II) dinitrate

Crystal data

[Zn(C11H6N2O)2(H2O)2](NO3)2	Z = 1
Mr = 589.78	F(000) = 300
Triclinic, P1	Dx = 1.69 Mg m^−3
a = 6.989 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.283 (3) Å	Cell parameters from 583 reflections
c = 10.222 (3) Å	θ = 3.0–23.3°
α = 94.909 (4)°	µ = 1.13 mm^−1
β = 91.394 (4)°	T = 298 K
γ = 99.860 (4)°	Block, yellow
V = 580.4 (3) Å^3	0.28 × 0.22 × 0.15 mm

Data collection

Bruker AXS 1K CCD diffractometer	2623 independent reflections
Radiation source: fine-focus sealed tube	1462 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.034
ϕ and ω scans	θmax = 28.3°, θmin = 2.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→9
Tmin = 0.724, Tmax = 0.844	k = −5→10
3777 measured reflections	l = −13→13

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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.106	H atoms treated by a mixture of independent and constrained refinement
S = 0.78	w = 1/[σ^2(Fo^2) + (0.0431P)^2] where P = (Fo^2 + 2Fc^2)/3
2623 reflections	(Δ/σ)max = 0.001
186 parameters	Δρmax = 0.69 e Å^−3
0 restraints	Δρmin = −0.68 e Å^−3

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

	x	y	z	Uiso*/Ueq
Zn1	0.5000	0.5000	0.5000	0.0457 (2)
O1	0.3247 (4)	0.7199 (3)	−0.0513 (2)	0.063 (1)
O2	0.0408 (4)	0.3804 (3)	0.7268 (3)	0.066 (1)
O3	−0.0632 (4)	0.1360 (4)	0.7704 (3)	0.088 (1)
O4	−0.0975 (4)	0.2023 (4)	0.5738 (3)	0.084 (1)
O1w	0.2504 (4)	0.5767 (4)	0.5646 (3)	0.054 (1)
N1	0.3430 (4)	0.3900 (3)	0.3051 (2)	0.042 (1)
N2	0.5607 (4)	0.7182 (3)	0.3891 (2)	0.038 (1)
N3	−0.0409 (4)	0.2381 (4)	0.6893 (3)	0.050 (1)
C1	0.2327 (5)	0.2530 (5)	0.2529 (4)	0.059 (1)
C2	0.1519 (5)	0.2336 (5)	0.1239 (4)	0.059 (1)
C3	0.1838 (5)	0.3646 (5)	0.0461 (3)	0.051 (1)
C4	0.2976 (5)	0.5080 (4)	0.1002 (3)	0.039 (1)
C5	0.3703 (4)	0.5115 (4)	0.2281 (3)	0.037 (1)
C6	0.3604 (5)	0.6745 (4)	0.0542 (3)	0.044 (1)
C7	0.4790 (4)	0.6760 (4)	0.2698 (3)	0.036 (1)
C8	0.4755 (5)	0.7760 (4)	0.1684 (3)	0.040 (1)
C9	0.5667 (5)	0.9356 (5)	0.1903 (3)	0.054 (1)
C10	0.6543 (5)	0.9853 (5)	0.3144 (4)	0.054 (1)
C11	0.6497 (5)	0.8769 (4)	0.4093 (3)	0.046 (1)
H1w1	0.187 (6)	0.516 (5)	0.613 (4)	0.07 (2)*
H1w2	0.194 (5)	0.628 (4)	0.520 (3)	0.05 (1)*
H1	0.2071	0.1647	0.3041	0.070*
H2	0.0775	0.1337	0.0909	0.071*
H3	0.1303	0.3556	−0.0390	0.061*
H9	0.5703	1.0079	0.1253	0.065*
H10	0.7169	1.0936	0.3334	0.065*
H11	0.7105	0.9143	0.4909	0.056*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.0509 (4)	0.0449 (4)	0.0414 (4)	0.0049 (3)	−0.0058 (3)	0.0127 (3)
O1	0.083 (2)	0.063 (2)	0.042 (1)	0.006 (2)	−0.011 (1)	0.019 (1)
O2	0.081 (2)	0.053 (2)	0.059 (2)	−0.002 (2)	0.010 (1)	0.002 (2)
O3	0.086 (2)	0.070 (2)	0.111 (2)	0.006 (2)	0.009 (2)	0.044 (2)
O4	0.097 (2)	0.081 (2)	0.072 (2)	0.028 (2)	−0.039 (2)	−0.015 (2)
O1w	0.053 (2)	0.056 (2)	0.057 (2)	0.011 (2)	0.005 (1)	0.022 (2)
N1	0.048 (2)	0.040 (2)	0.038 (2)	0.003 (2)	−0.007 (1)	0.009 (1)
N2	0.036 (2)	0.039 (2)	0.039 (2)	0.005 (1)	−0.002 (2)	0.002 (1)
N3	0.043 (2)	0.048 (2)	0.061 (2)	0.012 (2)	0.002 (2)	0.006 (2)
C1	0.063 (3)	0.042 (2)	0.066 (3)	−0.007 (2)	−0.006 (2)	0.016 (2)
C2	0.061 (2)	0.052 (3)	0.058 (2)	−0.007 (2)	−0.015 (2)	0.007 (2)
C3	0.049 (2)	0.059 (3)	0.042 (2)	0.007 (2)	−0.008 (2)	0.003 (2)
C4	0.038 (2)	0.042 (2)	0.035 (2)	0.007 (2)	−0.004 (1)	0.004 (2)
C5	0.036 (2)	0.036 (2)	0.037 (2)	0.006 (2)	−0.003 (1)	0.003 (2)
C6	0.049 (2)	0.047 (2)	0.038 (2)	0.013 (2)	0.001 (2)	0.007 (2)
C7	0.034 (2)	0.036 (2)	0.040 (2)	0.009 (2)	0.002 (1)	0.006 (2)
C8	0.043 (2)	0.037 (2)	0.039 (2)	0.007 (2)	0.001 (2)	0.008 (2)
C9	0.072 (3)	0.041 (2)	0.052 (2)	0.008 (2)	0.002 (2)	0.018 (2)
C10	0.065 (2)	0.036 (2)	0.058 (2)	−0.001 (2)	−0.001 (2)	0.005 (2)
C11	0.047 (2)	0.042 (2)	0.048 (2)	0.004 (2)	−0.003 (2)	0.000 (2)

Geometric parameters (Å, º)

Zn1—O1w	2.061 (3)	C4—C5	1.387 (4)
Zn1—O1w^i	2.061 (3)	C4—C6	1.493 (5)
Zn1—N1	2.290 (3)	C5—C7	1.465 (4)
Zn1—N1^i	2.290 (3)	C6—C8	1.508 (5)
Zn1—N2	2.201 (3)	C7—C8	1.383 (4)
Zn1—N2^i	2.201 (3)	C8—C9	1.363 (4)
O1—C6	1.206 (3)	C9—C10	1.393 (5)
O2—N3	1.242 (4)	C10—C11	1.375 (4)
O3—N3	1.228 (4)	O1w—H1w1	0.82 (4)
O4—N3	1.231 (4)	O1w—H1w2	0.79 (3)
N1—C1	1.320 (4)	C1—H1	0.93
N1—C5	1.321 (4)	C2—H2	0.93
N2—C7	1.327 (4)	C3—H3	0.93
N2—C11	1.351 (4)	C9—H9	0.93
C1—C2	1.407 (5)	C10—H10	0.93
C2—C3	1.390 (5)	C11—H11	0.93
C3—C4	1.376 (4)
O1w—Zn1—O1w^i	180.0 (1)	N1—C5—C4	126.8 (3)
O1w—Zn1—N1	90.5 (1)	N1—C5—C7	123.7 (3)
O1w—Zn1—N1^i	89.5 (1)	C4—C5—C7	109.4 (3)
O1w—Zn1—N2	89.3 (1)	O1—C6—C4	127.6 (3)
O1w—Zn1—N2^i	90.8 (1)	O1—C6—C8	126.9 (3)
O1w^i—Zn1—N1	89.5 (1)	C4—C6—C8	105.5 (3)
O1w^i—Zn1—N1^i	90.5 (1)	N2—C7—C8	127.2 (3)
O1w^i—Zn1—N2	90.8 (1)	N2—C7—C5	123.3 (3)
O1w^i—Zn1—N2^i	89.3 (1)	C8—C7—C5	109.5 (3)
N1—Zn1—N1^i	180.0	C9—C8—C7	117.8 (3)
N1—Zn1—N2	81.3 (1)	C9—C8—C6	134.5 (3)
N1—Zn1—N2^i	98.7 (1)	C7—C8—C6	107.6 (3)
N1^i—Zn1—N2	98.7 (1)	C8—C9—C10	117.0 (3)
N1^i—Zn1—N2^i	81.3 (1)	C11—C10—C9	121.0 (3)
N2—Zn1—N2^i	180.0 (1)	N2—C11—C10	122.8 (3)
C1—N1—C5	115.2 (3)	Zn1—O1w—H1w1	115 (3)
C1—N1—Zn1	140.2 (2)	Zn1—O1w—H1w2	120 (3)
C5—N1—Zn1	104.5 (2)	H1w1—O1w—H1w2	118 (4)
C7—N2—C11	114.2 (3)	N1—C1—H1	118.3
C7—N2—Zn1	107.2 (2)	C2—C1—H1	118.3
C11—N2—Zn1	138.5 (2)	C3—C2—H2	120.2
O3—N3—O4	121.6 (4)	C1—C2—H2	120.2
O3—N3—O2	118.2 (3)	C4—C3—H3	121.4
O4—N3—O2	120.2 (3)	C2—C3—H3	121.4
N1—C1—C2	123.4 (3)	C8—C9—H9	121.5
C3—C2—C1	119.6 (3)	C10—C9—H9	121.5
C4—C3—C2	117.2 (3)	C11—C10—H10	119.5
C3—C4—C5	117.7 (3)	C9—C10—H10	119.5
C3—C4—C6	134.3 (3)	N2—C11—H11	118.6
C5—C4—C6	107.9 (3)	C10—C11—H11	118.6
O1w—Zn1—N1—C1	−86.2 (4)	C3—C4—C5—C7	−177.2 (3)
O1w^i—Zn1—N1—C1	93.8 (4)	C6—C4—C5—C7	0.4 (4)
N2—Zn1—N1—C1	−175.3 (4)	C3—C4—C6—O1	−2.4 (6)
N2^i—Zn1—N1—C1	4.7 (4)	C5—C4—C6—O1	−179.5 (3)
O1w—Zn1—N1—C5	89.5 (2)	C3—C4—C6—C8	176.6 (4)
O1w^i—Zn1—N1—C5	−90.5 (2)	C5—C4—C6—C8	−0.5 (3)
N2—Zn1—N1—C5	0.3 (2)	C11—N2—C7—C8	−0.5 (5)
N2^i—Zn1—N1—C5	−179.7 (2)	Zn1—N2—C7—C8	178.0 (3)
O1w—Zn1—N2—C7	−90.9 (2)	C11—N2—C7—C5	−178.3 (3)
O1w^i—Zn1—N2—C7	89.1 (2)	Zn1—N2—C7—C5	0.2 (4)
N1^i—Zn1—N2—C7	179.7 (2)	N1—C5—C7—N2	0.2 (5)
N1—Zn1—N2—C7	−0.3 (2)	C4—C5—C7—N2	177.9 (3)
O1w—Zn1—N2—C11	87.0 (3)	N1—C5—C7—C8	−178.0 (3)
O1w^i—Zn1—N2—C11	−93.0 (3)	C4—C5—C7—C8	−0.2 (4)
N1^i—Zn1—N2—C11	−2.4 (3)	N2—C7—C8—C9	0.7 (5)
N1—Zn1—N2—C11	177.6 (3)	C5—C7—C8—C9	178.8 (3)
C5—N1—C1—C2	1.3 (5)	N2—C7—C8—C6	−178.2 (3)
Zn1—N1—C1—C2	176.7 (3)	C5—C7—C8—C6	−0.1 (4)
N1—C1—C2—C3	−1.5 (6)	O1—C6—C8—C9	0.7 (6)
C1—C2—C3—C4	1.0 (6)	C4—C6—C8—C9	−178.3 (4)
C2—C3—C4—C5	−0.5 (5)	O1—C6—C8—C7	179.4 (3)
C2—C3—C4—C6	−177.4 (4)	C4—C6—C8—C7	0.4 (3)
C1—N1—C5—C4	−0.8 (5)	C7—C8—C9—C10	−0.8 (5)
Zn1—N1—C5—C4	−177.8 (3)	C6—C8—C9—C10	177.8 (4)
C1—N1—C5—C7	176.6 (3)	C8—C9—C10—C11	0.6 (5)
Zn1—N1—C5—C7	−0.4 (4)	C7—N2—C11—C10	0.3 (5)
C3—C4—C5—N1	0.5 (5)	Zn1—N2—C11—C10	−177.5 (3)
C6—C4—C5—N1	178.1 (3)	C9—C10—C11—N2	−0.4 (6)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1w—H1w1···O2	0.82 (4)	1.89 (4)	2.702 (4)	179 (4)
O1w—H1w2···O4^ii	0.79 (3)	1.97 (4)	2.744 (4)	167 (3)

Symmetry code: (ii) −x, −y+1, −z+1.