catena-Poly[[[(dipyrido[3,2-a:2′,3′-c]phenazine)cobalt(II)]-μ-benzene-1,3-dicarboxyl­ato] hemihydrate]

In the title compound, {[Co(C₈H₄O₄)(C₁₈H₁₀N₄)]·0.5H₂O}_n or {[Co(1,3-BDC)(L)]·0.5H₂O}_n, where 1,3-BDC is the benzene-l,3-dicarboxyl­ate dianion and L is dipyrido[3,2-a:2′,3′-c]phenazine, each Co^II atom is five-coordinated by two N atoms from one L ligand, and three O atoms from three different 1,3-BDC anions in a distorted tetra­gonal–pyramidal geometry. Adjacent Co^II atoms are bridged by the 1,3-BDC ligands to form a two-dimensional network. The 1,3-BDC ligands lie on twofold rotation axes.

Key indicators

• Single-crystal X-ray study
• T = 292 K
• Mean [sigma](C-C) = 0.008 Å
• H-atom completeness 94%
• Disorder in solvent or counterion
• R factor = 0.068
• wR factor = 0.139
• Data-to-parameter ratio = 14.6

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT220_ALERT_2_B Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       3.71 Ratio

Alert level C
RINTA01_ALERT_3_C  The value of Rint is greater than 0.10
            Rint given   0.111
STRVA01_ALERT_4_C           Flack test results are ambiguous.
           From the CIF: _refine_ls_abs_structure_Flack    0.450
           From the CIF: _refine_ls_abs_structure_Flack_su    0.030
PLAT020_ALERT_3_C The value of Rint is greater than 0.10 .........       0.11
PLAT033_ALERT_2_C Flack Parameter Value Deviates from Zero .......       0.45
PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings    Differ ....          ?
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT045_ALERT_1_C Calculated and Reported Z Differ by ............       0.25 Ratio
PLAT068_ALERT_1_C Reported F000 Differs from Calcd (or Missing)...          ?
PLAT222_ALERT_3_C Large Non-Solvent    H     Ueq(max)/Ueq(min) ...       3.34 Ratio
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for         O4
PLAT302_ALERT_4_C Anion/Solvent Disorder .........................      50.00 Perc.
PLAT341_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ...          8

Alert level G
FORMU01_ALERT_2_G  There is a discrepancy between the atom counts in the
            _chemical_formula_sum and the formula from the _atom_site* data.
            Atom count from _chemical_formula_sum:C26 H15 Co1 N4 O4.5
            Atom count from the _atom_site data:  C26 H14 Co1 N4 O4.5
CELLZ01_ALERT_1_G Difference between formula and atom_site contents detected.
CELLZ01_ALERT_1_G WARNING: H atoms missing from atom site list. Is this intentional?
           From the CIF: _cell_formula_units_Z    8
           From the CIF: _chemical_formula_sum  C26 H15 Co N4 O4.50
           TEST: Compare cell contents of formula and atom_site data

           atom    Z*formula  cif sites diff
           C        208.00    208.00    0.00
           H        120.00    112.00    8.00
           Co         8.00      8.00    0.00
           N         32.00     32.00    0.00
           O         36.00     36.00    0.00
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           27.48
           From the CIF: _reflns_number_total               4802
           Count of symmetry unique reflns         2714
           Completeness (_total/calc)            176.93%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured      2088
           Fraction of Friedel pairs measured     0.769
           Are heavy atom types Z>Si present        yes

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

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

---

Computing details

Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO; data reduction: PROCESS-AUTO; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL-Plus (Sheldrick, 1990); software used to prepare material for publication: SHELXL97.

catena-Poly[[[(dipyrido[3,2 - a:2',3'-c]phenazine)cobalt(II)]-µ-benzene- 1,3-dicarboxylato] hemihydrate}

Crystal data

[Co(C8H4O4)(C18H10N4)]·0.5H2O	F(000) = 2096
Mr = 514.35	Dx = 1.618 Mg m^−3
Orthorhombic, I212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: I 2b 2c	Cell parameters from 13068 reflections
a = 9.802 (2) Å	θ = 3.0–27.5°
b = 13.696 (3) Å	µ = 0.86 mm^−1
c = 31.459 (6) Å	T = 292 K
V = 4223.3 (15) Å^3	Block, yellow
Z = 8	0.33 × 0.31 × 0.24 mm

Data collection

Rigaku R-AXIS RAPID diffractometer	4802 independent reflections
Radiation source: rotorating anode	3142 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.111
Detector resolution: 10.0 pixels mm^-1	θmax = 27.5°, θmin = 3.2°
ω scans	h = −11→12
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −17→17
Tmin = 0.744, Tmax = 0.811	l = −37→40
20249 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.068	H-atom parameters constrained
wR(F^2) = 0.139	w = 1/[σ^2(Fo^2) + (0.0515P)^2 + 5.9091P] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max = 0.001
4802 reflections	Δρmax = 0.73 e Å^−3
328 parameters	Δρmin = −0.55 e Å^−3
18 restraints	Absolute structure: Flack (1983), 2111 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.45 (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)
C1	0.9184 (5)	0.1187 (4)	0.38150 (16)	0.0447 (12)
H1	0.9141	0.1163	0.4110	0.054*
C2	1.0462 (6)	0.1222 (6)	0.36220 (18)	0.0525 (17)
H2	1.1252	0.1232	0.3786	0.063*
C3	1.0537 (5)	0.1242 (5)	0.31911 (18)	0.0465 (15)
H3	1.1384	0.1251	0.3058	0.056*
C4	0.9351 (5)	0.1249 (5)	0.29480 (16)	0.0348 (13)
C5	0.8119 (5)	0.1220 (5)	0.31663 (15)	0.0333 (12)
C6	0.6827 (5)	0.1254 (4)	0.29418 (15)	0.0305 (12)
C7	0.4486 (5)	0.1266 (5)	0.29899 (16)	0.0407 (15)
H7	0.3698	0.1271	0.3154	0.049*
C8	0.4355 (5)	0.1253 (6)	0.25513 (15)	0.0446 (16)
H8	0.3495	0.1256	0.2427	0.053*
C9	0.5500 (5)	0.1237 (5)	0.23035 (16)	0.0366 (13)
H9	0.5423	0.1213	0.2009	0.044*
C10	0.6783 (5)	0.1255 (5)	0.24946 (15)	0.0324 (12)
C11	0.8074 (5)	0.1252 (5)	0.22614 (16)	0.0360 (12)
C12	0.9329 (5)	0.1250 (5)	0.24817 (16)	0.0382 (13)
C13	1.0489 (5)	0.1262 (5)	0.18470 (17)	0.0397 (14)
C14	1.1723 (6)	0.1260 (6)	0.16121 (19)	0.0533 (18)
H14	1.2560	0.1281	0.1751	0.064*
C15	1.1662 (6)	0.1227 (6)	0.1181 (2)	0.0597 (17)
H15	1.2469	0.1237	0.1025	0.072*
C16	1.0414 (6)	0.1177 (6)	0.09638 (18)	0.0582 (17)
H16	1.0407	0.1128	0.0669	0.070*
C17	0.9217 (6)	0.1201 (5)	0.11797 (18)	0.0490 (13)
H17	0.8394	0.1187	0.1033	0.059*
C18	0.9225 (6)	0.1246 (5)	0.16290 (16)	0.0447 (15)
C19	0.6515 (5)	0.2970 (5)	0.42716 (15)	0.0332 (13)
C20	0.7027 (5)	0.3540 (4)	0.46467 (17)	0.0325 (12)
C21	0.7014 (6)	0.4548 (5)	0.4653 (2)	0.0532 (17)
H21	0.6675	0.4893	0.4421	0.064*
C22	0.7500	0.5041 (7)	0.5000	0.064 (3)
H22	0.7500	0.5720	0.5000	0.077*
C23	0.7500	0.3032 (6)	0.5000	0.0345 (18)
H23	0.7500	0.2353	0.5000	0.041*
C24	0.5546 (6)	−0.0716 (5)	0.4023 (2)	0.0433 (16)
C25	0.5310 (6)	−0.1653 (5)	0.42481 (19)	0.0427 (15)
C26	0.5365 (9)	−0.1666 (5)	0.4684 (2)	0.082 (3)
H26	0.5649	−0.1112	0.4830	0.099*
C27	0.5000	−0.2500	0.4909 (4)	0.114 (5)
H27	0.5000	−0.2500	0.5205	0.137*
C28	0.5000	−0.2500	0.4033 (3)	0.041 (2)
H28	0.5000	−0.2500	0.3738	0.049*
N1	0.5680 (4)	0.1273 (4)	0.31853 (12)	0.0326 (10)
N2	0.8025 (4)	0.1185 (4)	0.35973 (13)	0.0395 (11)
N3	1.0522 (4)	0.1274 (4)	0.22815 (14)	0.0409 (12)
N4	0.8012 (4)	0.1247 (4)	0.18385 (13)	0.0374 (11)
O1	0.6069 (4)	0.3457 (3)	0.39526 (10)	0.0430 (10)
O2	0.6588 (4)	0.2072 (3)	0.42816 (12)	0.0451 (10)
O3	0.4994 (5)	−0.0574 (4)	0.36758 (15)	0.0601 (13)
O4	0.6257 (4)	−0.0046 (3)	0.42080 (16)	0.0574 (13)
Co1	0.59293 (7)	0.11406 (6)	0.38385 (2)	0.0354 (2)
O5	0.6468 (12)	0.0350 (11)	0.5197 (3)	0.099 (4)	0.50

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.046 (3)	0.059 (4)	0.029 (2)	0.006 (3)	−0.007 (3)	−0.008 (4)
C2	0.038 (3)	0.075 (5)	0.045 (3)	−0.003 (4)	−0.008 (2)	−0.008 (4)
C3	0.036 (3)	0.059 (4)	0.044 (3)	0.002 (3)	−0.001 (2)	−0.008 (4)
C4	0.036 (3)	0.035 (3)	0.033 (3)	−0.003 (3)	0.003 (2)	−0.005 (3)
C5	0.036 (3)	0.033 (3)	0.030 (3)	0.004 (3)	−0.004 (2)	−0.007 (3)
C6	0.033 (3)	0.030 (3)	0.029 (3)	−0.004 (3)	−0.001 (2)	−0.004 (3)
C7	0.031 (3)	0.058 (4)	0.033 (3)	0.000 (3)	0.004 (2)	−0.003 (3)
C8	0.033 (3)	0.072 (5)	0.029 (3)	0.001 (3)	−0.004 (2)	−0.003 (3)
C9	0.039 (3)	0.047 (4)	0.024 (2)	0.002 (3)	−0.001 (2)	−0.002 (3)
C10	0.035 (3)	0.034 (4)	0.028 (3)	0.002 (3)	0.001 (2)	−0.003 (3)
C11	0.040 (3)	0.033 (3)	0.034 (3)	−0.001 (3)	0.008 (2)	−0.001 (3)
C12	0.040 (3)	0.035 (4)	0.039 (3)	0.000 (3)	0.005 (2)	−0.005 (3)
C13	0.036 (3)	0.045 (4)	0.038 (3)	−0.003 (3)	0.006 (2)	−0.001 (3)
C14	0.035 (3)	0.074 (5)	0.051 (4)	−0.011 (4)	0.014 (3)	−0.012 (4)
C15	0.046 (3)	0.083 (5)	0.050 (3)	−0.008 (4)	0.013 (3)	−0.007 (5)
C16	0.073 (4)	0.073 (5)	0.029 (3)	0.000 (4)	0.013 (3)	0.006 (4)
C17	0.048 (3)	0.068 (4)	0.030 (2)	−0.002 (3)	0.009 (3)	0.002 (4)
C18	0.040 (3)	0.057 (4)	0.037 (3)	−0.006 (4)	0.009 (2)	−0.001 (3)
C19	0.032 (3)	0.056 (4)	0.012 (2)	−0.001 (3)	0.001 (2)	−0.002 (3)
C20	0.035 (3)	0.035 (3)	0.028 (3)	0.000 (2)	−0.004 (2)	0.003 (2)
C21	0.074 (5)	0.038 (4)	0.047 (4)	0.000 (3)	−0.025 (3)	0.006 (3)
C22	0.086 (6)	0.039 (5)	0.067 (6)	0.000	−0.028 (5)	0.000
C23	0.043 (4)	0.031 (5)	0.030 (4)	0.000	−0.012 (3)	0.000
C24	0.043 (4)	0.033 (4)	0.054 (4)	0.004 (3)	0.007 (3)	0.002 (3)
C25	0.056 (4)	0.029 (4)	0.042 (4)	0.003 (3)	−0.001 (3)	0.002 (3)
C26	0.147 (7)	0.041 (4)	0.059 (4)	−0.012 (4)	−0.017 (4)	0.002 (4)
C27	0.187 (9)	0.079 (8)	0.076 (7)	−0.014 (7)	0.000	0.000
C28	0.037 (4)	0.044 (6)	0.041 (5)	0.004 (4)	0.000	0.000
N1	0.028 (2)	0.042 (3)	0.029 (2)	0.003 (2)	−0.0023 (17)	−0.005 (2)
N2	0.050 (3)	0.039 (3)	0.029 (2)	−0.001 (3)	−0.0073 (19)	−0.005 (3)
N3	0.031 (2)	0.050 (4)	0.042 (3)	−0.008 (2)	0.0041 (19)	−0.001 (3)
N4	0.041 (2)	0.040 (3)	0.032 (2)	−0.001 (2)	0.0041 (19)	−0.002 (3)
O1	0.039 (2)	0.062 (3)	0.029 (2)	−0.0036 (19)	−0.0045 (16)	0.0053 (17)
O2	0.052 (2)	0.047 (3)	0.037 (2)	0.005 (2)	−0.0090 (19)	−0.008 (2)
O3	0.080 (3)	0.051 (3)	0.050 (3)	0.006 (3)	0.013 (2)	0.009 (2)
O4	0.056 (3)	0.032 (3)	0.084 (3)	−0.006 (2)	0.002 (2)	0.001 (2)
Co1	0.0356 (3)	0.0459 (4)	0.0246 (3)	−0.0005 (4)	−0.0005 (3)	−0.0041 (4)
O5	0.101 (8)	0.126 (11)	0.070 (8)	−0.022 (8)	−0.011 (6)	−0.040 (7)

Geometric parameters (Å, º)

C1—N2	1.327 (6)	C16—H16	0.93
C1—C2	1.393 (7)	C17—C18	1.415 (7)
C1—H1	0.93	C17—H17	0.93
C2—C3	1.358 (8)	C18—N4	1.359 (7)
C2—H2	0.93	C19—O2	1.232 (7)
C3—C4	1.391 (7)	C19—O1	1.282 (6)
C3—H3	0.93	C19—C20	1.501 (7)
C4—C5	1.390 (7)	C20—C21	1.381 (8)
C4—C12	1.467 (7)	C20—C23	1.391 (6)
C5—N2	1.360 (6)	C21—C22	1.370 (8)
C5—C6	1.451 (6)	C21—H21	0.93
C6—N1	1.360 (6)	C22—C21^i	1.370 (8)
C6—C10	1.407 (6)	C22—H22	0.93
C7—N1	1.322 (6)	C23—C20^i	1.391 (6)
C7—C8	1.386 (7)	C23—H23	0.9300
C7—H7	0.93	C24—O3	1.235 (7)
C8—C9	1.366 (6)	C24—O4	1.290 (7)
C8—H8	0.93	C24—C25	1.484 (8)
C9—C10	1.395 (7)	C25—C26	1.372 (9)
C9—H9	0.93	C25—C28	1.376 (7)
C10—C11	1.463 (7)	C26—C27	1.391 (9)
C11—N4	1.332 (6)	C26—H26	0.93
C11—C12	1.412 (7)	C27—C26^ii	1.391 (9)
C12—N3	1.328 (6)	C27—H27	0.93
C13—N3	1.367 (7)	C28—C25^ii	1.376 (7)
C13—C18	1.417 (8)	C28—H28	0.93
C13—C14	1.417 (7)	Co1—N1	2.077 (4)
C14—C15	1.359 (9)	Co1—N2	2.191 (5)
C14—H14	0.93	Co1—O1^iii	2.067 (4)
C15—C16	1.403 (8)	Co1—O2	1.997 (4)
C15—H15	0.93	Co1—O4	2.024 (5)
C16—C17	1.356 (8)
N2—C1—C2	123.0 (5)	C17—C18—C13	119.3 (5)
N2—C1—H1	118.5	O2—C19—O1	124.0 (5)
C2—C1—H1	118.5	O2—C19—C20	118.7 (5)
C3—C2—C1	119.0 (5)	O1—C19—C20	117.3 (6)
C3—C2—H2	120.5	C21—C20—C23	119.5 (6)
C1—C2—H2	120.5	C21—C20—C19	121.9 (5)
C2—C3—C4	120.3 (5)	C23—C20—C19	118.6 (5)
C2—C3—H3	119.9	C22—C21—C20	120.1 (7)
C4—C3—H3	119.9	C22—C21—H21	120.0
C5—C4—C3	117.0 (5)	C20—C21—H21	120.0
C5—C4—C12	118.7 (4)	C21—C22—C21^i	120.9 (9)
C3—C4—C12	124.2 (5)	C21—C22—H22	119.5
N2—C5—C4	123.5 (5)	C21^i—C22—H22	119.5
N2—C5—C6	115.3 (4)	C20^i—C23—C20	120.0 (7)
C4—C5—C6	121.1 (4)	C20^i—C23—H23	120.0
N1—C6—C10	122.6 (4)	C20—C23—H23	120.0
N1—C6—C5	116.6 (4)	O3—C24—O4	121.6 (6)
C10—C6—C5	120.8 (4)	O3—C24—C25	119.3 (6)
N1—C7—C8	123.0 (5)	O4—C24—C25	119.0 (6)
N1—C7—H7	118.5	C26—C25—C28	119.3 (6)
C8—C7—H7	118.5	C26—C25—C24	118.7 (6)
C9—C8—C7	119.5 (5)	C28—C25—C24	122.0 (6)
C9—C8—H8	120.3	C25—C26—C27	120.6 (8)
C7—C8—H8	120.3	C25—C26—H26	119.7
C8—C9—C10	119.6 (5)	C27—C26—H26	119.7
C8—C9—H9	120.2	C26^ii—C27—C26	118.7 (12)
C10—C9—H9	120.2	C26^ii—C27—H27	120.6
C9—C10—C6	117.2 (4)	C26—C27—H27	120.6
C9—C10—C11	124.4 (4)	C25—C28—C25^ii	121.2 (8)
C6—C10—C11	118.4 (4)	C25—C28—H28	119.4
N4—C11—C12	122.0 (5)	C25^ii—C28—H28	119.4
N4—C11—C10	117.5 (4)	C7—N1—C6	118.0 (4)
C12—C11—C10	120.5 (4)	C7—N1—Co1	124.3 (3)
N3—C12—C11	122.3 (5)	C6—N1—Co1	117.3 (3)
N3—C12—C4	117.4 (5)	C1—N2—C5	117.2 (4)
C11—C12—C4	120.3 (4)	C1—N2—Co1	128.6 (3)
N3—C13—C18	120.3 (5)	C5—N2—Co1	114.2 (3)
N3—C13—C14	120.1 (5)	C12—N3—C13	117.0 (4)
C18—C13—C14	119.6 (5)	C11—N4—C18	116.4 (4)
C15—C14—C13	118.9 (5)	C19—O1—Co1^iii	126.7 (3)
C15—C14—H14	120.5	C19—O2—Co1	126.9 (4)
C13—C14—H14	120.5	C24—O4—Co1	103.1 (4)
C14—C15—C16	121.7 (5)	O2—Co1—O4	93.47 (19)
C14—C15—H15	119.1	O2—Co1—O1^iii	90.87 (15)
C16—C15—H15	119.1	O4—Co1—O1^iii	105.36 (16)
C17—C16—C15	120.6 (5)	O2—Co1—N1	132.31 (19)
C17—C16—H16	119.7	O4—Co1—N1	131.1 (2)
C15—C16—H16	119.7	O1^iii—Co1—N1	92.14 (14)
C16—C17—C18	119.8 (6)	O2—Co1—N2	85.45 (17)
C16—C17—H17	120.1	O4—Co1—N2	94.14 (19)
C18—C17—H17	120.1	O1^iii—Co1—N2	160.35 (19)
N4—C18—C17	118.7 (5)	N1—Co1—N2	76.42 (15)
N4—C18—C13	122.0 (4)

Symmetry codes: (i) −x+3/2, y, −z+1; (ii) −x+1, −y−1/2, z; (iii) −x+1, −y+1/2, z.