(2-Amino-7-methyl-4-oxido­pteridine-6-carboxyl­ato-κ3O4,N5,O6)aqua(1,10-phen­an­thro­line-κ2N,N′)cobalt(II) trihydrate

Baisya, S.S.; Sen, S.; Roy, P.S.

doi:10.1107/S1600536812051185

(2-Amino-7-methyl-4-oxidopteridine-6-carboxylato-κ³O⁴,N⁵,O⁶)aqua(1,10-phenanthroline-κ²N,N′)cobalt(II) trihydrate

In the title compound, [Co(C₈H₅N₅O₃)(C₁₂H₈N₂)(H₂O)]·3H₂O, a tridentate 2-amino-7-methyl-4-oxidopteridine-6-carboxylate ligand, a bidentate ancillary 1,10-phenanthroline (phen) ligand and a water molecule complete a distorted octahedral geometry around the Co^II atom. The pterin ligand forms two chelate rings. The phen and pterin ring systems are nearly perpendicular [dihedral angle = 85.15 (8)°]. N—H

O, O—H

N and O—H

O hydrogen bonds link the complex molecules and lattice water molecules into a layer parallel to (001). π–π stacking contacts (involving phen–phen and pteridine–pteridine) are also observed [centroid–centroid distances = 3.670 (2), 3.547 (2), 3.698 (2) and 3.349 (2) Å].

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536812051185/hy2609sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536812051185/hy2609Isup2.hkl Contains datablock I

CCDC reference: 920202

checkCIF report

Key indicators

Single-crystal X-ray study
T = 110 K
Mean (C-C) = 0.005 Å
R factor = 0.057
wR factor = 0.129
Data-to-parameter ratio = 15.0

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT417_ALERT_2_C Short Inter D-H..H-D       H341   ..  H351    ..       2.11 Ang.
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600         44

Alert level G
PLAT005_ALERT_5_G No _iucr_refine_instructions_details  in the CIF          ?
PLAT007_ALERT_5_G Note: Number of Unrefined D-H Atoms ............         10
PLAT154_ALERT_1_G The su's on the Cell Angles are Equal ..........    0.00400 Deg.
PLAT790_ALERT_4_G Centre of Gravity not Within Unit Cell: Resd.  #          2
              H2 O
PLAT790_ALERT_4_G Centre of Gravity not Within Unit Cell: Resd.  #          3
              H2 O
PLAT809_ALERT_1_G Can not Parse the SHELXL Weighting Scheme String          !
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600        431
PLAT929_ALERT_5_G No Weight Pars,Obs and Calc R1,wR2,S not checked          !
PLAT960_ALERT_3_G Number of Intensities with I .LT. - 2*sig(I) ...          1

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   2 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   9 ALERT level G = General information/check it is not something unexpected

   2 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
   3 ALERT type 4 Improvement, methodology, query or suggestion
   3 ALERT type 5 Informative message, check

Comment top

The primary motivation for pursuing coordination chemistry of pterins is the ubiquitous presence of this heterocyclic system in nature including a substantial number of metalloenzymes (Basu & Burgmayer, 2011; Burgmayer, 1998; Fitzpatrick, 2003; Fukuzumi & Kojima, 2008). Literature survey reveals the existence of only a few X-ray structurally characterized cobalt-pterin/pteridine/lumazine complexes as well as one containing an organocobalt moiety (Acuña-Cueva et al., 2003; Beddoes et al., 1997; Burgmayer & Stiefel, 1988; Funahashi et al., 1997). The concerned ligands usually act as bidentate O,N-donors and none of the above complexes possesses a typical π-acceptor ancillary ligand like 1,10-phenanthroline (phen). In this crystallographic study on the title cobalt(II) complex, possessing both a tridentate pterin ligand and a π-acidic ligand like phen, different aspects are considered, e.g. crystal, molecular and electronic structures.

In the title compound (Fig. 1), the stereochemistry around the Co^II atom is essentially distorted octahedral with two N atoms of phen, a pyrazine ring N atom (N3) of the pterin ligand and an aqua O atom forming the equatorial plane; two pterin O atoms (O1 and O3) define the longer axial positions, with the phenolate O3 forming the longest axial bond [2.270 (2) Å]. Extent of distortion of this coordination octahedron is much more pronounced as compared to that of the Co(II)-pteridine complexes reported earlier (Acuña-Cueva et al., 2003; Burgmayer & Stiefel, 1988; Funahashi et al., 1997). A major cause of this departure from regular geometry is that the pterin ligand forms two five-membered chelate rings having small bite angles [75.10 (10) and 76.26 (9)°], instead of only one per pteridine ligand for the earlier cases. Location of the short Co1—N3 bond [2.016 (3) Å] in the equatorial plane is consistent with the literature, which suggests a strong cobalt-pterin interaction (Odani et al., 1992). The pterin ligand is coordinated here as a binegative tridentate ONO donor, as evident from the charge balance of this complex. The phen and pterin rings are nearly perpendicular to each other for minimizing the steric repulsion. The Co1—N1 [2.079 (3) Å] and Co1—N2 [2.123 (3) Å] bond lengths are at par with that of the Co1—N3 bond [2.016 (3) Å] and indicate receipt of π-back donation to both phen and pterin rings from the Co(II) centre (d⁷) through dπ–pπ interactions. This process is further strengthened by the presence of π-donating phenolate and carboxylate O atoms around the metal centre (Kohzuma et al., 1988).

For rationalizing the near double bond nature of the O3—C18 [1.265 (4) Å] bond, a hypothesis of Joule (Beddoes et al., 1993; Russell et al., 1992) may be invoked, which suggests withdrawl of electron density from the pyrazine ring N6 by the pyrimidine ring C18-carbonyl group through mesomeric interaction. Formation of the O3—Co1 bond accentuates this electron withdrawal towards O3. The electron-rich N7—C17 [1.337 (4) Å] bond may also participate in this electron transfer. The pyrimidine ring is fairly planer and deviations of the C16/N5/C17 and C17/N4/C18 segments with respect to the N7—C17 multiple bonds are 2.6 and 0.7°, respectively.

In the crystal, intermolecular N—H···O, O—H···N and O—H···O hydrogen bonds (Table 1) link the complex molecules and lattice water molecules into a layer parallel to (001) (Fig. 2). The lattice water molecules are decisive for the crystal packing. Fig. 3 reveals π–π stacking interactions involving two parallel, inversion-related pterin rings within the same unit cell and showing face-to-face distance of 3.283 (4) and 3.366 (4) Å. Again the phen rings display two types of π–π stacking on either side of the unit cell. In one case, the adjacent phen rings are essentially parallel to each other with an average interplanar distance of 3.496 (4) Å; on the other side of the unit cell, the face-to-face seperations between parallel phen rings are 3.578 (4) and 3.629 (5) Å.

Related literature top

For background to the chemistry of pterins in metalloenzymes, see: Basu & Burgmayer (2011); Burgmayer (1998); Fitzpatrick (2003); Fukuzumi & Kojima (2008). For structures of related cobalt complexes, see: Acuña-Cueva et al. (2003); Beddoes et al. (1997); Burgmayer & Stiefel (1988); Funahashi et al. (1997). For structures of related copper complexes, see: Odani et al. (1992). For the electron-shuffling ability of the pterin unit as well as its donor groups and the affect on the geometric parameters of related complexes, see: Beddoes et al. (1993); Kohzuma et al. (1988); Russell et al. (1992). For the synthesis and nomenclature of the pterin ligand, see: Wittle et al. (1947).

Experimental top

2-Amino-4-hydroxy-7-methylpteridine-6-carboxylic acid sesquihydrate (C₈H₇N₅O₃.1.5H₂O) was obtained by published procedure (Wittle et al., 1947). The title complex was prepared by the dropwise addition of an aqueous alkaline solution (NaOH: 11 mg, 0.275 mmol) of the pterin ligand (31 mg, 0.125 mmol) to a warm (311 K) aqueous reaction medium containing CoSO₄.7H₂O (35 mg, 0.125 mmol) and 1,10-phenanthroline monohydrate (25 mg, 0.125 mmol) in a total volume of 60 ml. The pH value was adjusted to 10.8 using aqueous NaOH solution and dioxygen was bubbled in for 48 h; final pH was 10.3. Initially a small amount of yellow-white precipitate came out and the reaction mixture ultimately assumed a reddish-pink tinge. It was transferred to a 100 ml beaker, requisite quantity of water was added to make up for the evaporation loss and allowed to stand at room temperature. Pink crystals suitable for single-crystal X-ray diffraction appeared after 15 days (yield: 30%).

Structure description top

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: CRYSTALS (Betteridge et al., 2003); molecular graphics: CAMERON (Watkin et al., 1996); software used to prepare material for publication: CRYSTALS (Betteridge et al., 2003).

Figures top

	Fig. 1. The molecular structure of the title compound. Displacement ellipsoids are drawn at the 50% probability level. Lattice water molecules are omitted for clarity.
	Fig. 2. The crystal packing diagram of the title compound, viewed along the b axis. Dotted lines indicate hydrogen bonds, assisting the formation of a layer structure parallel to (001).
	Fig. 3. A molecular packing diagram highlighting π–π stacking interactions between two neighbouring phen–phen and pterin–pterin rings, respectively.

(2-Amino-7-methyl-4-oxidopteridine-6-carboxylato- κ³O⁴,N⁵,O⁶)aqua(1,10-phenanthroline- κ²N,N')cobalt(II) trihydrate top

Crystal data top

[Co(C₈H₅N₅O₃)(C₁₂H₈N₂)(H₂O)]·3H₂O	Z = 2
M_r = 530.36	F(000) = 546
Triclinic, P1	D_x = 1.659 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.454 (2) Å	Cell parameters from 8945 reflections
b = 9.934 (3) Å	θ = 2–28°
c = 13.778 (4) Å	µ = 0.87 mm⁻¹
α = 97.534 (4)°	T = 110 K
β = 95.281 (4)°	Block, pink
γ = 110.603 (4)°	0.23 × 0.11 × 0.04 mm
V = 1061.8 (5) Å³

Data collection top

Bruker Kappa APEXII CCD diffractometer	4360 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.030
φ and ω scans	θ_max = 28.2°, θ_min = 1.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −11→11
T_min = 0.82, T_max = 0.97	k = −12→13
8945 measured reflections	l = −18→18
4726 independent reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F² > 2σ(F²)] = 0.057	H-atom parameters constrained
wR(F²) = 0.129	Method = Modified Sheldrick w = 1/[σ²(F²) + ( 0.04P)² + 3.34P], where P = (max(F_o²,0) + 2F_c²)/3
S = 1.03	(Δ/σ)_max = 0.0001859
4726 reflections	Δρ_max = 0.99 e Å⁻³
316 parameters	Δρ_min = −0.88 e Å⁻³
0 restraints

Crystal data top

[Co(C₈H₅N₅O₃)(C₁₂H₈N₂)(H₂O)]·3H₂O	γ = 110.603 (4)°
M_r = 530.36	V = 1061.8 (5) Å³
Triclinic, P1	Z = 2
a = 8.454 (2) Å	Mo Kα radiation
b = 9.934 (3) Å	µ = 0.87 mm⁻¹
c = 13.778 (4) Å	T = 110 K
α = 97.534 (4)°	0.23 × 0.11 × 0.04 mm
β = 95.281 (4)°

Data collection top

Bruker Kappa APEXII CCD diffractometer	4726 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	4360 reflections with I > 2σ(I)
T_min = 0.82, T_max = 0.97	R_int = 0.030
8945 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.057	0 restraints
wR(F²) = 0.129	H-atom parameters constrained
S = 1.03	Δρ_max = 0.99 e Å⁻³
4726 reflections	Δρ_min = −0.88 e Å⁻³
316 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Co1	0.45982 (5)	0.22172 (4)	0.22887 (3)	0.0125
O1	0.2062 (3)	0.0747 (2)	0.23341 (17)	0.0176
C13	0.1224 (4)	0.1182 (3)	0.2948 (2)	0.0159
O2	−0.0205 (3)	0.0408 (2)	0.31159 (18)	0.0204
C14	0.2096 (4)	0.2762 (3)	0.3463 (2)	0.0150
N3	0.3618 (3)	0.3367 (3)	0.32052 (19)	0.0137
C19	0.4572 (4)	0.4746 (3)	0.3559 (2)	0.0137
C16	0.4012 (4)	0.5628 (3)	0.4205 (2)	0.0151
N5	0.4986 (3)	0.7057 (3)	0.4529 (2)	0.0154
C17	0.6493 (4)	0.7539 (3)	0.4170 (2)	0.0157
N4	0.7169 (3)	0.6739 (3)	0.3559 (2)	0.0161
C18	0.6243 (4)	0.5321 (3)	0.3254 (2)	0.0148
O3	0.6704 (3)	0.4463 (2)	0.26886 (17)	0.0174
N7	0.7460 (4)	0.8957 (3)	0.4440 (2)	0.0199
H141	0.8293	0.9343	0.4135	0.0223*
H142	0.7086	0.9522	0.4775	0.0228*
N6	0.2466 (3)	0.5028 (3)	0.4504 (2)	0.0176
C15	0.1508 (4)	0.3621 (3)	0.4146 (2)	0.0171
C20	−0.0163 (4)	0.2992 (4)	0.4506 (3)	0.0256
H172	−0.0359	0.3696	0.4963	0.0378*
H173	−0.0185	0.2188	0.4829	0.0383*
H171	−0.1061	0.2680	0.3985	0.0380*
O4	0.5538 (3)	0.1469 (2)	0.35063 (17)	0.0185
H181	0.4964	0.0663	0.3597	0.0272*
H182	0.5418	0.1894	0.4013	0.0271*
N2	0.3758 (3)	0.2801 (3)	0.0963 (2)	0.0162
C12	0.2567 (4)	0.3370 (4)	0.0798 (3)	0.0196
C11	0.2191 (4)	0.3750 (4)	−0.0116 (3)	0.0230
C10	0.3071 (4)	0.3548 (4)	−0.0867 (3)	0.0220
C8	0.4354 (4)	0.2958 (4)	−0.0719 (2)	0.0183
C9	0.4634 (4)	0.2593 (3)	0.0218 (2)	0.0138
C5	0.5897 (4)	0.1963 (3)	0.0422 (2)	0.0147
N1	0.6075 (3)	0.1592 (3)	0.1330 (2)	0.0152
C1	0.7247 (4)	0.1018 (3)	0.1537 (2)	0.0178
C2	0.8260 (4)	0.0749 (4)	0.0839 (3)	0.0225
C3	0.8069 (4)	0.1096 (4)	−0.0079 (3)	0.0221
C4	0.6854 (4)	0.1721 (3)	−0.0323 (2)	0.0179
C6	0.6545 (4)	0.2115 (4)	−0.1271 (3)	0.0227
C7	0.5346 (5)	0.2690 (4)	−0.1461 (3)	0.0241
H321	0.5124	0.2898	−0.2083	0.0280*
H311	0.7136	0.1926	−0.1771	0.0268*
H291	0.8704	0.0898	−0.0554	0.0258*
H281	0.9086	0.0377	0.1020	0.0257*
H271	0.7401	0.0814	0.2171	0.0208*
H221	0.2815	0.3779	−0.1477	0.0263*
H211	0.1346	0.4115	−0.0211	0.0270*
H201	0.1976	0.3531	0.1304	0.0229*
O7	0.9931 (4)	0.4695 (3)	0.1919 (3)	0.0445
H331	1.0355	0.5568	0.1993	0.0644*
H332	0.9309	0.4819	0.2305	0.0648*
O5	0.0341 (3)	−0.2327 (3)	0.28207 (18)	0.0224
H341	0.0418	−0.1559	0.2637	0.0322*
H342	−0.0472	−0.2571	0.3124	0.0321*
O6	0.3374 (3)	−0.0951 (2)	0.40693 (18)	0.0204
H351	0.2468	−0.1420	0.3696	0.0287*
H352	0.3795	−0.1552	0.4182	0.0294*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.0135 (2)	0.0131 (2)	0.0129 (2)	0.00622 (16)	0.00458 (15)	0.00324 (15)
O1	0.0164 (11)	0.0142 (11)	0.0210 (12)	0.0040 (9)	0.0048 (9)	0.0026 (9)
C13	0.0156 (15)	0.0157 (15)	0.0168 (15)	0.0064 (12)	−0.0002 (12)	0.0050 (12)
O2	0.0143 (11)	0.0173 (11)	0.0269 (13)	0.0015 (9)	0.0059 (9)	0.0056 (10)
C14	0.0134 (14)	0.0150 (15)	0.0185 (15)	0.0062 (12)	0.0048 (12)	0.0053 (12)
N3	0.0134 (12)	0.0130 (12)	0.0153 (13)	0.0049 (10)	0.0035 (10)	0.0038 (10)
C19	0.0139 (14)	0.0141 (14)	0.0156 (15)	0.0062 (12)	0.0053 (12)	0.0057 (12)
C16	0.0158 (15)	0.0172 (15)	0.0152 (15)	0.0085 (12)	0.0029 (12)	0.0050 (12)
N5	0.0149 (13)	0.0129 (12)	0.0196 (14)	0.0060 (10)	0.0040 (10)	0.0030 (10)
C17	0.0157 (15)	0.0175 (15)	0.0167 (15)	0.0083 (12)	0.0030 (12)	0.0063 (12)
N4	0.0150 (13)	0.0148 (13)	0.0202 (14)	0.0057 (10)	0.0078 (11)	0.0047 (11)
C18	0.0144 (15)	0.0169 (15)	0.0150 (15)	0.0065 (12)	0.0036 (12)	0.0063 (12)
O3	0.0173 (11)	0.0170 (11)	0.0193 (12)	0.0073 (9)	0.0065 (9)	0.0028 (9)
N7	0.0188 (14)	0.0136 (13)	0.0264 (15)	0.0044 (11)	0.0081 (12)	0.0020 (11)
N6	0.0164 (13)	0.0169 (13)	0.0224 (14)	0.0083 (11)	0.0071 (11)	0.0041 (11)
C15	0.0148 (15)	0.0171 (15)	0.0226 (16)	0.0075 (12)	0.0065 (12)	0.0079 (13)
C20	0.0163 (16)	0.0207 (17)	0.040 (2)	0.0056 (14)	0.0126 (15)	0.0024 (15)
O4	0.0198 (12)	0.0193 (11)	0.0174 (11)	0.0069 (9)	0.0052 (9)	0.0063 (9)
N2	0.0151 (13)	0.0150 (13)	0.0203 (14)	0.0061 (10)	0.0063 (11)	0.0055 (11)
C12	0.0169 (16)	0.0171 (15)	0.0263 (18)	0.0064 (13)	0.0075 (13)	0.0055 (13)
C11	0.0193 (17)	0.0195 (16)	0.0319 (19)	0.0082 (14)	0.0003 (14)	0.0098 (14)
C10	0.0202 (17)	0.0232 (17)	0.0224 (17)	0.0061 (14)	−0.0007 (13)	0.0107 (14)
C8	0.0177 (16)	0.0168 (15)	0.0178 (16)	0.0030 (12)	0.0007 (12)	0.0044 (13)
C9	0.0133 (14)	0.0114 (14)	0.0153 (15)	0.0026 (11)	0.0032 (11)	0.0022 (11)
C5	0.0129 (14)	0.0113 (14)	0.0176 (15)	0.0020 (11)	0.0022 (12)	0.0015 (12)
N1	0.0152 (13)	0.0133 (12)	0.0158 (13)	0.0040 (10)	0.0034 (10)	0.0013 (10)
C1	0.0171 (15)	0.0150 (15)	0.0199 (16)	0.0058 (12)	0.0002 (12)	0.0005 (12)
C2	0.0169 (16)	0.0214 (17)	0.0312 (19)	0.0103 (14)	0.0035 (14)	0.0025 (14)
C3	0.0162 (16)	0.0190 (16)	0.0298 (19)	0.0059 (13)	0.0079 (14)	−0.0016 (14)
C4	0.0152 (15)	0.0162 (15)	0.0200 (16)	0.0032 (12)	0.0055 (13)	0.0009 (13)
C6	0.0241 (17)	0.0251 (17)	0.0181 (17)	0.0072 (14)	0.0093 (14)	0.0026 (14)
C7	0.0299 (19)	0.0254 (18)	0.0169 (16)	0.0070 (15)	0.0085 (14)	0.0086 (14)
O7	0.0352 (16)	0.0272 (15)	0.074 (2)	0.0127 (13)	0.0292 (16)	−0.0010 (15)
O5	0.0178 (11)	0.0184 (12)	0.0318 (14)	0.0057 (9)	0.0095 (10)	0.0059 (10)
O6	0.0192 (12)	0.0166 (11)	0.0266 (13)	0.0077 (9)	0.0020 (10)	0.0060 (10)

Geometric parameters (Å, º) top

Co1—O1	2.140 (2)	N2—C12	1.333 (4)
Co1—N3	2.016 (3)	N2—C9	1.355 (4)
Co1—O3	2.270 (2)	C12—C11	1.402 (5)
Co1—O4	2.120 (2)	C12—H201	0.923
Co1—N2	2.123 (3)	C11—C10	1.363 (5)
Co1—N1	2.079 (3)	C11—H211	0.914
O1—C13	1.279 (4)	C10—C8	1.414 (5)
C13—O2	1.244 (4)	C10—H221	0.926
C13—C14	1.519 (4)	C8—C9	1.408 (4)
C14—N3	1.319 (4)	C8—C7	1.435 (5)
C14—C15	1.426 (4)	C9—C5	1.439 (4)
N3—C19	1.319 (4)	C5—N1	1.359 (4)
C19—C16	1.397 (4)	C5—C4	1.411 (4)
C19—C18	1.450 (4)	N1—C1	1.333 (4)
C16—N5	1.354 (4)	C1—C2	1.406 (5)
C16—N6	1.360 (4)	C1—H271	0.930
N5—C17	1.360 (4)	C2—C3	1.363 (5)
C17—N4	1.378 (4)	C2—H281	0.928
C17—N7	1.337 (4)	C3—C4	1.412 (5)
N4—C18	1.335 (4)	C3—H291	0.928
C18—O3	1.265 (4)	C4—C6	1.439 (5)
N7—H141	0.852	C6—C7	1.349 (5)
N7—H142	0.843	C6—H311	0.925
N6—C15	1.342 (4)	C7—H321	0.926
C15—C20	1.491 (4)	O7—H331	0.800
C20—H172	0.947	O7—H332	0.810
C20—H173	0.960	O5—H341	0.811
C20—H171	0.930	O5—H342	0.820
O4—H181	0.810	O6—H351	0.830
O4—H182	0.801	O6—H352	0.820

O1—Co1—N3	75.10 (10)	H172—C20—H171	106.6
O1—Co1—O3	151.22 (8)	H173—C20—H171	109.7
N3—Co1—O3	76.26 (9)	Co1—O4—H181	116.6
O1—Co1—O4	90.13 (9)	Co1—O4—H182	109.7
N3—Co1—O4	90.23 (10)	H181—O4—H182	95.0
O3—Co1—O4	92.74 (9)	Co1—N2—C12	128.8 (2)
O1—Co1—N2	90.99 (10)	Co1—N2—C9	112.7 (2)
N3—Co1—N2	96.45 (10)	C12—N2—C9	118.5 (3)
O3—Co1—N2	89.46 (9)	N2—C12—C11	122.3 (3)
O4—Co1—N2	173.29 (10)	N2—C12—H201	119.1
O1—Co1—N1	119.55 (10)	C11—C12—H201	118.6
N3—Co1—N1	164.48 (10)	C12—C11—C10	119.6 (3)
O3—Co1—N1	88.76 (9)	C12—C11—H211	120.2
O4—Co1—N1	94.58 (10)	C10—C11—H211	120.2
N2—Co1—N1	79.12 (10)	C11—C10—C8	119.9 (3)
Co1—O1—C13	116.8 (2)	C11—C10—H221	120.1
O1—C13—O2	124.1 (3)	C8—C10—H221	120.0
O1—C13—C14	114.6 (3)	C10—C8—C9	116.7 (3)
O2—C13—C14	121.2 (3)	C10—C8—C7	124.4 (3)
C13—C14—N3	111.4 (3)	C9—C8—C7	118.9 (3)
C13—C14—C15	129.9 (3)	C8—C9—N2	123.1 (3)
N3—C14—C15	118.8 (3)	C8—C9—C5	120.1 (3)
Co1—N3—C14	121.6 (2)	N2—C9—C5	116.8 (3)
Co1—N3—C19	117.6 (2)	C9—C5—N1	117.5 (3)
C14—N3—C19	120.8 (3)	C9—C5—C4	119.5 (3)
N3—C19—C16	121.8 (3)	N1—C5—C4	123.0 (3)
N3—C19—C18	117.4 (3)	Co1—N1—C5	113.6 (2)
C16—C19—C18	120.7 (3)	Co1—N1—C1	127.6 (2)
C19—C16—N5	120.8 (3)	C5—N1—C1	118.5 (3)
C19—C16—N6	118.7 (3)	N1—C1—C2	122.0 (3)
N5—C16—N6	120.4 (3)	N1—C1—H271	118.0
C16—N5—C17	115.1 (3)	C2—C1—H271	120.0
N5—C17—N4	127.9 (3)	C1—C2—C3	119.8 (3)
N5—C17—N7	117.0 (3)	C1—C2—H281	119.3
N4—C17—N7	115.1 (3)	C3—C2—H281	120.9
C17—N4—C18	117.6 (3)	C2—C3—C4	119.9 (3)
C19—C18—N4	117.7 (3)	C2—C3—H291	120.7
C19—C18—O3	118.1 (3)	C4—C3—H291	119.4
N4—C18—O3	124.2 (3)	C3—C4—C5	116.8 (3)
Co1—O3—C18	110.63 (19)	C3—C4—C6	124.2 (3)
C17—N7—H141	119.8	C5—C4—C6	119.0 (3)
C17—N7—H142	119.9	C4—C6—C7	121.2 (3)
H141—N7—H142	117.6	C4—C6—H311	119.5
C16—N6—C15	119.0 (3)	C7—C6—H311	119.2
C14—C15—N6	120.8 (3)	C8—C7—C6	121.3 (3)
C14—C15—C20	121.7 (3)	C8—C7—H321	118.4
N6—C15—C20	117.4 (3)	C6—C7—H321	120.3
C15—C20—H172	111.5	H331—O7—H332	86.2
C15—C20—H173	110.1	H341—O5—H342	108.7
H172—C20—H173	108.2	H351—O6—H352	105.5
C15—C20—H171	110.7

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N7—H141···O2ⁱ	0.85	2.12	2.942 (4)	163
N7—H142···O6ⁱⁱ	0.84	2.15	2.970 (4)	165
O4—H181···O6	0.81	1.93	2.717 (3)	164
O4—H182···N5ⁱⁱ	0.80	2.25	3.051 (4)	176
O5—H341···O1	0.82	2.34	3.079 (4)	151
O5—H341···O2	0.82	2.23	2.896 (4)	139
O5—H342···N4ⁱⁱⁱ	0.82	2.04	2.844 (4)	166
O6—H351···O5	0.83	1.92	2.740 (4)	174
O6—H352···N5^iv	0.82	2.05	2.871 (4)	176
O7—H331···O5ⁱ	0.80	2.25	2.941 (4)	145
O7—H332···O3	0.81	2.23	2.962 (5)	151

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

Experimental details

Crystal data
Chemical formula	[Co(C₈H₅N₅O₃)(C₁₂H₈N₂)(H₂O)]·3H₂O
M_r	530.36
Crystal system, space group	Triclinic, P1
Temperature (K)	110
a, b, c (Å)	8.454 (2), 9.934 (3), 13.778 (4)
α, β, γ (°)	97.534 (4), 95.281 (4), 110.603 (4)
V (Å³)	1061.8 (5)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.87
Crystal size (mm)	0.23 × 0.11 × 0.04

Data collection
Diffractometer	Bruker Kappa APEXII CCD
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.82, 0.97
No. of measured, independent and observed [I > 2σ(I)] reflections	8945, 4726, 4360
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.665

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.057, 0.129, 1.03
No. of reflections	4726
No. of parameters	316
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.99, −0.88

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), CRYSTALS (Betteridge et al., 2003), CAMERON (Watkin et al., 1996).