Bis(μ-N,N′-di-4-pyridylpyridine-2,6-diamine)bis[dimethacrylatocobalt(II)] dihydrate

The Co^II ion in the title complex, [Co₂(C₄H₅O₂)₄(C₁₅H₁₃N₅)₂]·2H₂O, has a distorted square-planar coordination formed by the bridging bidentate N,N′-di-4-pyridylpyrid­ine-2,6-diamine (dapmp) ligands and two monodentate carboxyl­ate groups from methacrylates. Two dapmp ligands bridge two Co atoms, forming a dinuclear complex arranged around an inversion centre. N—H...O and O—H...O hydrogen bonds involving the solvent water mol­ecule result in the formation of a three-dimensional network. The aliphatic moiety of one of the methacrylate groups is disordered over two positions with fixed occupancies of 0.67 and 0.33.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.004 Å
• Disorder in main residue
• R factor = 0.036
• wR factor = 0.113
• Data-to-parameter ratio = 13.4

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT230_ALERT_2_B Hirshfeld Test Diff for    O3     --  C20     ..      10.24 su
PLAT232_ALERT_2_B Hirshfeld Test Diff (M-X)  Co1    --  O1      ..      11.05 su
PLAT232_ALERT_2_B Hirshfeld Test Diff (M-X)  Co1    --  O3      ..      13.35 su
PLAT232_ALERT_2_B Hirshfeld Test Diff (M-X)  Co1    --  N1      ..      10.57 su

Alert level C
            Value of measurement temperature given =   298.000
            Value of melting point given =     0.000
PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density ....       2.67
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Co1    --  N5_a    ..       9.12 su
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for         O3
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        Co1
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C18
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C20
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for       C22B
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for       C22A
PLAT301_ALERT_3_C Main Residue  Disorder .........................       8.00 Perc.
PLAT380_ALERT_4_C Check Incorrectly? Oriented X(sp2)-Methyl Moiety        C19

Alert level G
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          5
PLAT779_ALERT_4_G Suspect or Irrelevant (Bond) Angle in CIF ......      31.70 Deg.
              C21B -C20  -C21A    1.555   1.555   1.555

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

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
  12 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
   2 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

Bridging bis(amidopyridine) ligands have been widely explored in coordination chemistry for building various novel structural architectures and functional solid materials. Besides their diverse coordination modes, amide groups of ligands have proved to be useful in self-assembly, since they give predictable patterns of hydrogen bonding that can add extra dimensionality and helicity to the supramolecular structures (Burchell, et al., 2006; Patra et al., 2004). The 2,4-di(2-aminopyridine)-6-methypyrimidine (dapmp) ligand is a versatile ligand like but with more diversity than terpyridine (tpy). The modified title ligand and its complexes have been reported (Thorsten et al., 2004). In this paper, we report here the synthesis and crystal structure of the title compound (I).

The Co(II) atom in the title complex, has a square coordination formed by two N atoms of two bridging dapmp ligands and two O atoms of two monodentate carboxylate groups from methacrylates. The bridging dapmp ligands bridge two Co atoms forming a dinuclear complex arranged around inversion center (Fig.1). The average Co—N bond length of 2.006 Å is close to the values observed in related complexes (Liu et al., 2008).

The occurence of N-H···O and O-H···O hydrogen bondings involving the solvent water molecule results in the formation of a three dimensionnal network (Table 1).

Related literature

For related literature, see: Liu et al. (2008); Patra et al. (2004); Thorsten et al. (2004); Burchell et al. (2006).

S2. Experimental

dapmp (0.05 g, 0.18 mmol), Co(CH3COO)2 (0.035 g, 0.16 mmol), methacrylic acid (0.032 g, 0.15 mmol) and NaOH (1M, 0.5 mL) were added distilled water(15 mL), the mixture was heated for fifty hours under reflux. during the process stirring and influx were required. The resultant was kept at room temperature, two weeks later some single crystals of the size suitable for X-Ray diffraction measurement.

S3. Refinement

All H atoms attached to C atoms and N atom were fixed geometrically and treated as riding with C—H = 0.98 Å (methyl) or 0.97 Å (methylene) and N—H = 0.86 Å with U_iso(H) = 1.2U_eq(C or N). H atoms of water molecule were located in difference Fourier maps and included in the subsequent refinement using restraints (O-H= 0.82 (1)Å and H···H= 1.38 (2)Å) with U_iso(H) = 1.5U_eq(O). In the last stage of refinement, they were treated as riding on their parent O atom.

The C atoms of one of the methacrylate group are disordered. The ratio of the occupancy factors of each component was determined to be 0.33/0.67. The two components were refined using the tools available in SHELXL-97 (PART and SAME instructions). Each corresponding C atoms were anisotropically refined using EADP restraints.

Computing details

Data collection: APEX2 (Bruker, 2004); cell refinement: APEX2 (Bruker, 2004); data reduction: APEX2 (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996); ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures

Fig. 1. The structure of the dinuclear complex showing the atom-labeling scheme.Displacement ellipsoids are shown at the 30% probability level. H atoms and solvent water molecule have been omitted for clarity. Only one component of the disordered methacrylate is represented. [Symmetric codes: (i) 1/2-x, 1/2-y, 2-z].

Bis(µ-N,N'-di-4-pyridylpyridine-2,6-diamine)bis[dimethacrylatocobalt(II)] dihydrate

Crystal data

[Co2(C4H5O2)4(C15H13N5)2]·2H2O	F(000) = 2120
Mr = 1020.82	Dx = 1.425 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 4289 reflections
a = 16.852 (3) Å	θ = 1.7–25.2°
b = 17.425 (3) Å	µ = 0.77 mm^−1
c = 16.206 (2) Å	T = 298 K
β = 91.848 (2)°	Block, pink
V = 4756.6 (12) Å^3	0.28 × 0.20 × 0.16 mm
Z = 4

Data collection

Bruker APEXII area-detector diffractometer	4289 independent reflections
Radiation source: fine-focus sealed tube	3333 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.021
ϕ and ω scan	θmax = 25.2°, θmin = 1.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −20→19
Tmin = 0.814, Tmax = 0.887	k = −20→13
11993 measured reflections	l = −19→19

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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.113	H-atom parameters constrained
S = 1.00	w = 1/[σ^2(Fo^2) + (0.073P)^2 + 1.1663P] where P = (Fo^2 + 2Fc^2)/3
4289 reflections	(Δ/σ)max = 0.003
319 parameters	Δρmax = 0.67 e Å^−3
5 restraints	Δρmin = −0.25 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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)
Co1	0.235159 (18)	0.431425 (16)	0.937768 (18)	0.05265 (14)
N1	0.20029 (13)	0.45034 (12)	1.05235 (13)	0.0639 (5)
N2	0.10374 (13)	0.46526 (12)	1.28525 (13)	0.0653 (5)
H2	0.0961	0.5113	1.3023	0.078*
N3	0.08770 (11)	0.33476 (11)	1.31525 (12)	0.0558 (5)
N4	0.07043 (12)	0.20360 (11)	1.34321 (13)	0.0643 (5)
H4	0.0504	0.1709	1.3764	0.077*
N5	0.19558 (12)	0.10578 (11)	1.15108 (12)	0.0605 (5)
O1	0.25618 (10)	0.53794 (9)	0.91709 (11)	0.0603 (4)
O2	0.37530 (12)	0.52113 (10)	0.97624 (14)	0.0822 (6)
O3	0.18484 (15)	0.32931 (12)	0.93913 (15)	0.0935 (7)
O4	0.1035 (2)	0.38372 (17)	0.8496 (2)	0.1382 (11)
O5	0.50106 (12)	0.59087 (12)	1.05678 (14)	0.0931 (7)
H5B	0.4648	0.5637	1.0324	0.140*
H5C	0.5423	0.5617	1.0600	0.140*
C1	0.16847 (16)	0.51510 (13)	1.08051 (16)	0.0622 (6)
H1	0.1669	0.5578	1.0460	0.075*
C2	0.13828 (16)	0.52194 (14)	1.15691 (16)	0.0637 (6)
H2A	0.1165	0.5684	1.1732	0.076*
C3	0.13977 (14)	0.45961 (14)	1.21099 (15)	0.0565 (6)
C4	0.17974 (16)	0.39479 (15)	1.18482 (17)	0.0673 (7)
H4A	0.1881	0.3536	1.2205	0.081*
C5	0.20654 (17)	0.39206 (15)	1.10674 (18)	0.0745 (8)
H5	0.2308	0.3471	1.0897	0.089*
C6	0.07752 (14)	0.40755 (14)	1.33749 (15)	0.0545 (5)
C7	0.03970 (16)	0.42917 (15)	1.40823 (16)	0.0649 (7)
H7	0.0346	0.4806	1.4223	0.078*
C8	0.00997 (16)	0.37248 (16)	1.45714 (16)	0.0690 (7)
H8	−0.0163	0.3852	1.5049	0.083*
C9	0.01910 (15)	0.29651 (15)	1.43540 (16)	0.0643 (6)
H9	−0.0008	0.2573	1.4677	0.077*
C10	0.05876 (13)	0.28040 (14)	1.36400 (15)	0.0554 (6)
C11	0.10900 (13)	0.17245 (13)	1.27789 (15)	0.0550 (6)
C12	0.13584 (16)	0.09731 (14)	1.28272 (17)	0.0652 (7)
H12	0.1252	0.0675	1.3286	0.078*
C13	0.17805 (16)	0.06716 (13)	1.21981 (17)	0.0650 (7)
H13	0.1957	0.0168	1.2249	0.078*
C14	0.16509 (16)	0.17700 (14)	1.14514 (15)	0.0643 (6)
H14	0.1737	0.2046	1.0971	0.077*
C15	0.12263 (15)	0.21124 (14)	1.20446 (15)	0.0613 (6)
H15	0.1026	0.2605	1.1962	0.074*
C16	0.32418 (15)	0.56277 (13)	0.94107 (16)	0.0592 (6)
C17	0.34147 (17)	0.64439 (15)	0.92618 (19)	0.0729 (7)
H17	0.3916	0.6623	0.9425	0.087*
C18	0.29301 (18)	0.69284 (16)	0.8925 (2)	0.0808 (8)
H18	0.2430	0.6747	0.8763	0.097*
C19	0.3099 (3)	0.77605 (18)	0.8772 (3)	0.1243 (15)
H19A	0.3629	0.7879	0.8966	0.186*
H19B	0.2728	0.8071	0.9060	0.186*
H19C	0.3049	0.7864	0.8190	0.186*
C20	0.1275 (2)	0.32774 (18)	0.8840 (2)	0.0810 (9)
C21A	0.1154 (8)	0.2382 (5)	0.8948 (7)	0.0857 (13)	0.33
H21A	0.1329	0.2140	0.9432	0.103*	0.33
C22A	0.0812 (6)	0.1992 (5)	0.8364 (7)	0.0802 (12)	0.33
H22A	0.0648	0.2209	0.7862	0.096*	0.33
C23A	0.070 (6)	0.1110 (16)	0.857 (5)	0.134 (4)	0.33
H23A	0.1120	0.0940	0.8936	0.201*	0.33
H23B	0.0701	0.0816	0.8068	0.201*	0.33
H23C	0.0197	0.1038	0.8829	0.201*	0.33
C21B	0.0859 (3)	0.2565 (2)	0.8567 (3)	0.0857 (13)	0.67
H21B	0.0453	0.2601	0.8166	0.103*	0.67
C22B	0.1039 (3)	0.1905 (2)	0.8862 (3)	0.0802 (12)	0.67
H22B	0.1384	0.1870	0.9321	0.096*	0.67
C23B	0.069 (3)	0.1154 (8)	0.846 (2)	0.134 (4)	0.67
H23D	0.0147	0.1243	0.8282	0.201*	0.67
H23E	0.0705	0.0748	0.8863	0.201*	0.67
H23F	0.0995	0.1012	0.7998	0.201*	0.67

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.0661 (2)	0.03338 (19)	0.0593 (2)	−0.00546 (13)	0.01459 (15)	−0.00101 (13)
N1	0.0783 (14)	0.0434 (11)	0.0706 (13)	0.0006 (10)	0.0128 (11)	0.0045 (10)
N2	0.0872 (15)	0.0476 (11)	0.0614 (13)	0.0011 (11)	0.0100 (11)	−0.0024 (10)
N3	0.0622 (11)	0.0488 (11)	0.0566 (11)	−0.0004 (9)	0.0051 (9)	−0.0009 (9)
N4	0.0753 (13)	0.0483 (11)	0.0704 (13)	−0.0017 (10)	0.0186 (11)	0.0029 (10)
N5	0.0723 (13)	0.0426 (11)	0.0673 (13)	−0.0016 (10)	0.0106 (10)	0.0014 (9)
O1	0.0619 (9)	0.0440 (9)	0.0750 (11)	−0.0025 (8)	0.0048 (8)	0.0018 (8)
O2	0.0795 (12)	0.0498 (10)	0.1157 (16)	0.0080 (9)	−0.0190 (11)	0.0010 (10)
O3	0.1185 (18)	0.0611 (12)	0.1031 (16)	−0.0207 (12)	0.0382 (14)	−0.0023 (11)
O4	0.167 (3)	0.101 (2)	0.147 (3)	−0.010 (2)	0.012 (2)	0.0440 (19)
O5	0.0819 (13)	0.0755 (13)	0.1209 (18)	0.0158 (11)	−0.0102 (12)	−0.0395 (12)
C1	0.0803 (16)	0.0408 (12)	0.0657 (15)	−0.0017 (12)	0.0067 (13)	0.0037 (11)
C2	0.0817 (17)	0.0406 (13)	0.0691 (16)	0.0003 (12)	0.0066 (13)	−0.0038 (11)
C3	0.0655 (14)	0.0438 (12)	0.0603 (14)	−0.0024 (11)	0.0003 (11)	−0.0003 (11)
C4	0.0770 (16)	0.0540 (14)	0.0719 (17)	0.0105 (13)	0.0158 (13)	0.0161 (13)
C5	0.0934 (19)	0.0492 (15)	0.0823 (19)	0.0154 (14)	0.0272 (15)	0.0130 (13)
C6	0.0586 (13)	0.0484 (13)	0.0563 (13)	0.0010 (11)	0.0003 (11)	−0.0022 (11)
C7	0.0734 (16)	0.0564 (15)	0.0652 (16)	0.0010 (12)	0.0090 (13)	−0.0109 (12)
C8	0.0767 (16)	0.0668 (17)	0.0643 (15)	0.0012 (14)	0.0155 (13)	−0.0107 (13)
C9	0.0698 (15)	0.0609 (15)	0.0630 (15)	−0.0033 (12)	0.0121 (12)	−0.0024 (12)
C10	0.0543 (13)	0.0509 (13)	0.0609 (14)	−0.0012 (11)	0.0034 (11)	−0.0013 (11)
C11	0.0554 (13)	0.0474 (13)	0.0623 (14)	−0.0022 (10)	0.0048 (11)	−0.0044 (11)
C12	0.0809 (17)	0.0457 (13)	0.0701 (16)	0.0002 (12)	0.0180 (13)	0.0065 (12)
C13	0.0754 (16)	0.0425 (13)	0.0778 (17)	0.0025 (12)	0.0124 (14)	0.0043 (12)
C14	0.0870 (18)	0.0494 (13)	0.0566 (14)	0.0046 (13)	0.0055 (13)	0.0022 (11)
C15	0.0759 (16)	0.0484 (13)	0.0594 (14)	0.0088 (12)	−0.0011 (12)	−0.0004 (11)
C16	0.0629 (15)	0.0444 (13)	0.0707 (16)	0.0016 (12)	0.0080 (12)	−0.0010 (11)
C17	0.0677 (16)	0.0481 (14)	0.102 (2)	−0.0056 (13)	−0.0045 (15)	0.0045 (14)
C18	0.0806 (18)	0.0525 (16)	0.108 (2)	−0.0039 (14)	−0.0137 (16)	0.0082 (15)
C19	0.140 (3)	0.0547 (18)	0.176 (4)	−0.008 (2)	−0.038 (3)	0.029 (2)
C20	0.103 (2)	0.0555 (17)	0.086 (2)	−0.0206 (17)	0.0293 (19)	−0.0119 (16)
C21A	0.115 (4)	0.055 (3)	0.085 (4)	−0.020 (3)	−0.010 (3)	0.008 (2)
C22A	0.101 (3)	0.054 (2)	0.086 (3)	−0.003 (2)	0.001 (3)	0.009 (3)
C23A	0.163 (4)	0.066 (3)	0.173 (12)	−0.041 (3)	0.025 (5)	−0.019 (4)
C21B	0.115 (4)	0.055 (3)	0.085 (4)	−0.020 (3)	−0.010 (3)	0.008 (2)
C22B	0.101 (3)	0.054 (2)	0.086 (3)	−0.003 (2)	0.001 (3)	0.009 (3)
C23B	0.163 (4)	0.066 (3)	0.173 (12)	−0.041 (3)	0.025 (5)	−0.019 (4)

Geometric parameters (Å, º)

Co1—O1	1.9210 (17)	C8—H8	0.9300
Co1—O3	1.972 (2)	C9—C10	1.383 (3)
Co1—N5^i	1.991 (2)	C9—H9	0.9300
Co1—N1	1.993 (2)	C11—C12	1.387 (3)
N1—C1	1.336 (3)	C11—C15	1.394 (3)
N1—C5	1.347 (3)	C12—C13	1.367 (4)
N2—C3	1.369 (3)	C12—H12	0.9300
N2—C6	1.395 (3)	C13—H13	0.9300
N2—H2	0.8600	C14—C15	1.355 (3)
N3—C6	1.331 (3)	C14—H14	0.9300
N3—C10	1.336 (3)	C15—H15	0.9300
N4—C11	1.372 (3)	C16—C17	1.473 (3)
N4—C10	1.395 (3)	C17—C18	1.284 (4)
N4—H4	0.8600	C17—H17	0.9300
N5—C13	1.342 (3)	C18—C19	1.500 (4)
N5—C14	1.346 (3)	C18—H18	0.9300
N5—Co1^i	1.991 (2)	C19—H19A	0.9600
O1—C16	1.274 (3)	C19—H19B	0.9600
O2—C16	1.250 (3)	C19—H19C	0.9600
O3—C20	1.295 (4)	C20—C21B	1.485 (5)
O4—C20	1.188 (4)	C20—C21A	1.583 (10)
O5—H5B	0.8591	C21A—C22A	1.287 (12)
O5—H5C	0.8618	C21A—H21A	0.9300
C1—C2	1.359 (4)	C22A—C23A	1.59 (2)
C1—H1	0.9300	C22A—H22A	0.9300
C2—C3	1.395 (3)	C23A—H23A	0.9600
C2—H2A	0.9300	C23A—H23B	0.9600
C3—C4	1.388 (3)	C23A—H23C	0.9600
C4—C5	1.358 (4)	C21B—C22B	1.279 (6)
C4—H4A	0.9300	C21B—H21B	0.9300
C5—H5	0.9300	C22B—C23B	1.568 (18)
C6—C7	1.382 (4)	C22B—H22B	0.9300
C7—C8	1.371 (4)	C23B—H23D	0.9600
C7—H7	0.9300	C23B—H23E	0.9600
C8—C9	1.380 (4)	C23B—H23F	0.9600
O1—Co1—O3	162.90 (10)	N4—C11—C15	124.2 (2)
O1—Co1—N5^i	94.17 (8)	C12—C11—C15	116.3 (2)
O3—Co1—N5^i	88.66 (8)	C13—C12—C11	119.8 (2)
O1—Co1—N1	93.69 (8)	C13—C12—H12	120.1
O3—Co1—N1	89.94 (9)	C11—C12—H12	120.1
N5^i—Co1—N1	157.66 (9)	N5—C13—C12	124.1 (2)
C1—N1—C5	115.9 (2)	N5—C13—H13	118.0
C1—N1—Co1	126.27 (18)	C12—C13—H13	118.0
C5—N1—Co1	117.78 (18)	N5—C14—C15	124.4 (2)
C3—N2—C6	129.8 (2)	N5—C14—H14	117.8
C3—N2—H2	115.1	C15—C14—H14	117.8
C6—N2—H2	115.1	C14—C15—C11	119.8 (2)
C6—N3—C10	117.6 (2)	C14—C15—H15	120.1
C11—N4—C10	129.8 (2)	C11—C15—H15	120.1
C11—N4—H4	115.1	O2—C16—O1	122.8 (2)
C10—N4—H4	115.1	O2—C16—C17	119.9 (2)
C13—N5—C14	115.4 (2)	O1—C16—C17	117.3 (2)
C13—N5—Co1^i	125.92 (17)	C18—C17—C16	125.3 (3)
C14—N5—Co1^i	118.68 (16)	C18—C17—H17	117.3
C16—O1—Co1	116.37 (15)	C16—C17—H17	117.3
C20—O3—Co1	108.8 (2)	C17—C18—C19	125.8 (3)
H5B—O5—H5C	105.3	C17—C18—H18	117.1
N1—C1—C2	123.5 (2)	C19—C18—H18	117.1
N1—C1—H1	118.3	C18—C19—H19A	109.5
C2—C1—H1	118.3	C18—C19—H19B	109.5
C1—C2—C3	120.3 (2)	H19A—C19—H19B	109.5
C1—C2—H2A	119.9	C18—C19—H19C	109.5
C3—C2—H2A	119.9	H19A—C19—H19C	109.5
N2—C3—C4	124.1 (2)	H19B—C19—H19C	109.5
N2—C3—C2	119.8 (2)	O4—C20—O3	122.8 (3)
C4—C3—C2	116.1 (2)	O4—C20—C21B	113.3 (4)
C5—C4—C3	119.5 (2)	O3—C20—C21B	123.9 (4)
C5—C4—H4A	120.3	O4—C20—C21A	144.8 (5)
C3—C4—H4A	120.3	O3—C20—C21A	92.3 (5)
N1—C5—C4	124.2 (2)	C21B—C20—C21A	31.7 (4)
N1—C5—H5	117.9	C22A—C21A—C20	119.7 (9)
C4—C5—H5	117.9	C22A—C21A—H21A	120.1
N3—C6—C7	123.5 (2)	C20—C21A—H21A	120.1
N3—C6—N2	118.4 (2)	C21A—C22A—C23A	114 (3)
C7—C6—N2	118.1 (2)	C21A—C22A—H22A	122.8
C8—C7—C6	118.0 (2)	C23A—C22A—H22A	122.8
C8—C7—H7	121.0	C22B—C21B—C20	122.4 (5)
C6—C7—H7	121.0	C22B—C21B—H21B	118.8
C7—C8—C9	119.8 (2)	C20—C21B—H21B	118.8
C7—C8—H8	120.1	C21B—C22B—C23B	121.0 (15)
C9—C8—H8	120.1	C21B—C22B—H22B	119.5
C8—C9—C10	118.0 (2)	C23B—C22B—H22B	119.5
C8—C9—H9	121.0	C22B—C23B—H23D	109.5
C10—C9—H9	121.0	C22B—C23B—H23E	109.5
N3—C10—C9	123.1 (2)	H23D—C23B—H23E	109.5
N3—C10—N4	118.7 (2)	C22B—C23B—H23F	109.5
C9—C10—N4	118.2 (2)	H23D—C23B—H23F	109.5
N4—C11—C12	119.5 (2)	H23E—C23B—H23F	109.5

Symmetry code: (i) −x+1/2, −y+1/2, −z+2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O4^ii	0.86	1.99	2.831 (4)	167
N4—H4···O5^iii	0.86	1.98	2.840 (3)	174
O5—H5B···O2	0.86	1.89	2.737 (3)	170
O5—H5C···O2^iv	0.86	2.10	2.917 (3)	158

Symmetry codes: (ii) x, −y+1, z+1/2; (iii) −x+1/2, y−1/2, −z+5/2; (iv) −x+1, −y+1, −z+2.