Ethyl 4-(3,4,6-trimethyl-1-phenyl-1H-pyrazolo[3,4-b]pyridin-5-yl)benzoate

In the title compound, C₂₄H₂₃N₃O₂, the dihedral angles between the pyrazolo­pyridine ring system (r.m.s. deviation = 0.001 Å) and the N-bound and C-bound benzene rings are 15.95 (2) and 83.71 (4)°, respectively. The conformation of the former is influenced by an intra­molecular C—H...N hydrogen bond, which generates an S(6) ring. In the crystal, stepped layers are generated by three sets of C—H...π inter­actions.

Key indicators

• Single-crystal X-ray study
• T = 100 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.046
• wR factor = 0.137
• Data-to-parameter ratio = 14.9

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density ....       2.56 Report
PLAT911_ALERT_3_C Missing FCF Refl Between Thmin & STh/L=    0.600          3 Report

Alert level G
PLAT066_ALERT_1_G Predicted and Reported Tmin&Tmax Range Identical          ? Check
PLAT154_ALERT_1_G The s.u.'s on the Cell Angles are Equal ..(Note)      0.002 Degree
PLAT910_ALERT_3_G Missing # of FCF Reflection(s) Below Theta(Min).          1 Note
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600        185 Note
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density.         18 Info

   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
   5 ALERT level G = General information/check it is not something unexpected

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


checkCIF publication errors

Alert level A
PUBL024_ALERT_1_A The number of authors is greater than 5.
              Please specify the role of each of the co-authors
              for your paper.

   1 ALERT level A = Data missing that is essential or data in wrong format
   0 ALERT level G = General alerts. Data that may be required is missing

---

Computing details

Data collection: APEX3 (Bruker, 2016); cell refinement: SAINT (Bruker, 2016); data reduction: SAINT (Bruker, 2016); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015b); molecular graphics: Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Ethyl 4-(3,4,6-trimethyl-1-phenyl-1H-pyrazolo[3,4-b]pyridin-5-yl)benzoate

Crystal data

C24H23N3O2	Z = 2
Mr = 385.45	F(000) = 408
Triclinic, P1	Dx = 1.320 Mg m^−3
a = 8.6962 (12) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.7349 (12) Å	Cell parameters from 8772 reflections
c = 14.559 (2) Å	θ = 2.6–29.6°
α = 106.468 (2)°	µ = 0.09 mm^−1
β = 92.949 (2)°	T = 100 K
γ = 111.771 (2)°	Block, colourless
V = 969.5 (2) Å^3	0.34 × 0.29 × 0.18 mm

Data collection

Bruker SMART APEX CCD diffractometer	5268 independent reflections
Radiation source: fine-focus sealed tube	4248 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.029
ω and φ scans	θmax = 29.6°, θmin = 2.6°
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	h = −12→12
Tmin = 0.97, Tmax = 0.98	k = −12→12
18971 measured reflections	l = −20→20

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)] = 0.046	Hydrogen site location: difference Fourier map
wR(F^2) = 0.137	All H-atom parameters refined
S = 1.12	w = 1/[σ^2(Fo^2) + (0.0918P)^2] where P = (Fo^2 + 2Fc^2)/3
5268 reflections	(Δ/σ)max < 0.001
354 parameters	Δρmax = 0.48 e Å^−3
0 restraints	Δρmin = −0.19 e Å^−3

Special details

Experimental. The diffraction data were obtained from 3 sets of 400 frames, each of width 0.5 deg. in omega, colllected at phi = 0.00, 90.00 and 180.00 deg. and 2 sets of 800 frames, each of width 0.45 deg in phi, collected at omega = -30.00 and 210.00 deg. The scan time was 20 sec/frame.

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 > 2sigma(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
O1	0.23175 (11)	0.57825 (12)	−0.07653 (6)	0.0290 (2)
O2	0.51281 (10)	0.69386 (10)	−0.02991 (5)	0.02180 (19)
N1	0.23651 (11)	0.88745 (11)	0.52975 (6)	0.01411 (19)
N2	0.16953 (11)	0.75274 (11)	0.65507 (6)	0.01468 (19)
N3	0.16485 (11)	0.60229 (11)	0.66993 (6)	0.0164 (2)
C1	0.27729 (12)	0.85912 (12)	0.44097 (7)	0.0138 (2)
C2	0.29302 (13)	0.70350 (12)	0.38726 (7)	0.0133 (2)
C3	0.27667 (13)	0.57422 (12)	0.42865 (7)	0.0136 (2)
C4	0.23587 (12)	0.60380 (12)	0.52264 (7)	0.0134 (2)
C5	0.21382 (12)	0.75768 (12)	0.56641 (7)	0.0132 (2)
C6	0.30824 (15)	1.00548 (14)	0.40044 (8)	0.0186 (2)
H6A	0.425 (3)	1.077 (3)	0.4065 (15)	0.077 (7)*
H6B	0.255 (3)	1.086 (3)	0.4290 (14)	0.069 (6)*
H6C	0.268 (2)	0.968 (2)	0.3306 (13)	0.052 (5)*
C7	0.30068 (15)	0.41217 (14)	0.37623 (8)	0.0185 (2)
H7A	0.201 (2)	0.309 (2)	0.3664 (13)	0.054 (5)*
H7B	0.388 (2)	0.400 (2)	0.4145 (13)	0.053 (5)*
H7C	0.325 (3)	0.409 (3)	0.3160 (15)	0.068 (6)*
C8	0.20401 (13)	0.51302 (13)	0.59214 (7)	0.0150 (2)
C9	0.20687 (16)	0.34153 (14)	0.58796 (8)	0.0202 (2)
H9A	0.1196 (18)	0.2449 (18)	0.5352 (10)	0.025 (4)*
H9B	0.1864 (19)	0.3229 (18)	0.6506 (11)	0.031 (4)*
H9C	0.3194 (19)	0.3413 (17)	0.5768 (10)	0.024 (3)*
C10	0.13290 (13)	0.87315 (13)	0.72905 (7)	0.0140 (2)
C11	0.13272 (13)	0.85723 (14)	0.82151 (8)	0.0168 (2)
H11	0.1558 (18)	0.7698 (18)	0.8352 (9)	0.022 (3)*
C12	0.09668 (14)	0.97454 (14)	0.89422 (8)	0.0201 (2)
H12	0.1010 (18)	0.9640 (18)	0.9589 (10)	0.025 (4)*
C13	0.06252 (14)	1.10730 (15)	0.87670 (8)	0.0209 (2)
H13	0.0429 (18)	1.1944 (17)	0.9304 (10)	0.026 (4)*
C14	0.06191 (14)	1.12117 (14)	0.78412 (8)	0.0188 (2)
H14	0.0400 (18)	1.2165 (18)	0.7725 (10)	0.026 (4)*
C15	0.09546 (13)	1.00400 (13)	0.70950 (7)	0.0159 (2)
H15	0.0939 (17)	1.0137 (16)	0.6435 (10)	0.020 (3)*
C16	0.31614 (13)	0.67883 (12)	0.28381 (7)	0.0135 (2)
C17	0.47296 (13)	0.75326 (13)	0.25873 (7)	0.0160 (2)
H17	0.5705 (17)	0.8175 (17)	0.3081 (10)	0.020 (3)*
C18	0.48821 (13)	0.73679 (13)	0.16198 (7)	0.0163 (2)
H18	0.5959 (19)	0.7913 (18)	0.1471 (10)	0.027 (4)*
C19	0.34573 (13)	0.64654 (12)	0.08963 (7)	0.0147 (2)
C20	0.18917 (13)	0.56965 (13)	0.11409 (7)	0.0166 (2)
H20	0.0915 (19)	0.5081 (18)	0.0624 (11)	0.029 (4)*
C21	0.17423 (13)	0.58490 (13)	0.21035 (7)	0.0158 (2)
H21	0.0619 (17)	0.5258 (17)	0.2258 (9)	0.021 (3)*
C22	0.35412 (14)	0.63421 (13)	−0.01422 (7)	0.0174 (2)
C23	0.53668 (18)	0.69586 (17)	−0.12779 (8)	0.0256 (3)
H23A	0.637 (2)	0.671 (2)	−0.1346 (11)	0.035 (4)*
H23B	0.439 (2)	0.6031 (19)	−0.1725 (11)	0.029 (4)*
C24	0.56473 (17)	0.87103 (18)	−0.13631 (10)	0.0291 (3)
H24A	0.661 (2)	0.966 (2)	−0.0887 (12)	0.045 (5)*
H24B	0.463 (2)	0.898 (2)	−0.1262 (11)	0.038 (4)*
H24C	0.588 (2)	0.874 (2)	−0.2032 (12)	0.039 (4)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0264 (4)	0.0428 (5)	0.0154 (4)	0.0095 (4)	0.0018 (3)	0.0124 (4)
O2	0.0248 (4)	0.0301 (4)	0.0152 (4)	0.0121 (4)	0.0103 (3)	0.0117 (3)
N1	0.0175 (4)	0.0149 (4)	0.0118 (4)	0.0074 (3)	0.0050 (3)	0.0056 (3)
N2	0.0199 (4)	0.0154 (4)	0.0124 (4)	0.0089 (3)	0.0070 (3)	0.0067 (3)
N3	0.0202 (4)	0.0150 (4)	0.0162 (4)	0.0076 (3)	0.0061 (4)	0.0074 (3)
C1	0.0150 (5)	0.0146 (4)	0.0128 (4)	0.0066 (4)	0.0037 (4)	0.0052 (4)
C2	0.0140 (4)	0.0144 (4)	0.0115 (4)	0.0052 (4)	0.0040 (4)	0.0044 (4)
C3	0.0139 (4)	0.0134 (4)	0.0133 (5)	0.0053 (4)	0.0035 (4)	0.0041 (4)
C4	0.0150 (5)	0.0130 (4)	0.0127 (4)	0.0058 (4)	0.0038 (4)	0.0046 (3)
C5	0.0144 (4)	0.0143 (4)	0.0111 (4)	0.0058 (4)	0.0032 (4)	0.0042 (4)
C6	0.0273 (6)	0.0171 (5)	0.0167 (5)	0.0115 (4)	0.0077 (4)	0.0092 (4)
C7	0.0265 (6)	0.0155 (5)	0.0172 (5)	0.0115 (4)	0.0085 (5)	0.0058 (4)
C8	0.0169 (5)	0.0145 (4)	0.0146 (5)	0.0063 (4)	0.0045 (4)	0.0058 (4)
C9	0.0290 (6)	0.0168 (5)	0.0205 (5)	0.0121 (4)	0.0094 (5)	0.0098 (4)
C10	0.0139 (4)	0.0151 (4)	0.0121 (4)	0.0050 (4)	0.0050 (4)	0.0034 (4)
C11	0.0176 (5)	0.0190 (5)	0.0153 (5)	0.0075 (4)	0.0049 (4)	0.0070 (4)
C12	0.0220 (5)	0.0244 (5)	0.0144 (5)	0.0093 (4)	0.0084 (4)	0.0064 (4)
C13	0.0223 (5)	0.0220 (5)	0.0184 (5)	0.0099 (4)	0.0097 (4)	0.0041 (4)
C14	0.0196 (5)	0.0184 (5)	0.0207 (5)	0.0097 (4)	0.0078 (4)	0.0064 (4)
C15	0.0165 (5)	0.0174 (5)	0.0144 (5)	0.0068 (4)	0.0050 (4)	0.0058 (4)
C16	0.0175 (5)	0.0128 (4)	0.0122 (4)	0.0076 (4)	0.0051 (4)	0.0046 (3)
C17	0.0155 (5)	0.0180 (5)	0.0128 (5)	0.0050 (4)	0.0021 (4)	0.0049 (4)
C18	0.0160 (5)	0.0182 (5)	0.0152 (5)	0.0061 (4)	0.0056 (4)	0.0067 (4)
C19	0.0194 (5)	0.0151 (4)	0.0122 (4)	0.0088 (4)	0.0047 (4)	0.0055 (4)
C20	0.0166 (5)	0.0186 (5)	0.0135 (5)	0.0064 (4)	0.0013 (4)	0.0049 (4)
C21	0.0162 (5)	0.0171 (5)	0.0147 (5)	0.0068 (4)	0.0049 (4)	0.0060 (4)
C22	0.0228 (5)	0.0182 (5)	0.0143 (5)	0.0095 (4)	0.0062 (4)	0.0074 (4)
C23	0.0357 (7)	0.0340 (6)	0.0169 (5)	0.0190 (6)	0.0153 (5)	0.0141 (5)
C24	0.0291 (6)	0.0348 (7)	0.0315 (7)	0.0137 (6)	0.0100 (6)	0.0206 (6)

Geometric parameters (Å, º)

O1—C22	1.2073 (13)	C10—C15	1.3943 (14)
O2—C22	1.3396 (14)	C11—C12	1.3879 (15)
O2—C23	1.4547 (13)	C11—H11	0.927 (15)
N1—C1	1.3373 (13)	C12—C13	1.3833 (16)
N1—C5	1.3405 (13)	C12—H12	0.972 (14)
N2—C5	1.3736 (13)	C13—C14	1.3869 (16)
N2—N3	1.3776 (12)	C13—H13	0.996 (14)
N2—C10	1.4174 (13)	C14—C15	1.3916 (14)
N3—C8	1.3200 (13)	C14—H14	0.976 (14)
C1—C2	1.4228 (13)	C15—H15	0.988 (13)
C1—C6	1.4979 (14)	C16—C17	1.3943 (14)
C2—C3	1.3907 (14)	C16—C21	1.3984 (14)
C2—C16	1.4948 (13)	C17—C18	1.3930 (14)
C3—C4	1.4080 (13)	C17—H17	0.953 (13)
C3—C7	1.5009 (14)	C18—C19	1.3916 (14)
C4—C5	1.4027 (13)	C18—H18	0.948 (15)
C4—C8	1.4319 (14)	C19—C20	1.3923 (15)
C6—H6A	0.96 (2)	C19—C22	1.4925 (14)
C6—H6B	0.99 (2)	C20—C21	1.3871 (14)
C6—H6C	0.975 (18)	C20—H20	0.971 (15)
C7—H7A	0.961 (19)	C21—H21	0.993 (14)
C7—H7B	0.97 (2)	C23—C24	1.4999 (18)
C7—H7C	0.91 (2)	C23—H23A	0.975 (17)
C8—C9	1.4913 (15)	C23—H23B	0.965 (15)
C9—H9A	0.988 (14)	C24—H24A	0.983 (17)
C9—H9B	0.984 (15)	C24—H24B	1.006 (17)
C9—H9C	1.001 (15)	C24—H24C	1.008 (16)
C10—C11	1.3919 (14)
C22—O2—C23	117.09 (9)	C10—C11—H11	121.3 (8)
C1—N1—C5	114.70 (8)	C13—C12—C11	121.29 (10)
C5—N2—N3	110.21 (8)	C13—C12—H12	120.7 (8)
C5—N2—C10	131.24 (9)	C11—C12—H12	118.0 (8)
N3—N2—C10	118.55 (8)	C12—C13—C14	119.08 (10)
C8—N3—N2	107.28 (8)	C12—C13—H13	120.5 (8)
N1—C1—C2	123.76 (9)	C14—C13—H13	120.4 (8)
N1—C1—C6	115.23 (9)	C13—C14—C15	120.85 (10)
C2—C1—C6	121.00 (9)	C13—C14—H14	118.7 (8)
C3—C2—C1	120.42 (9)	C15—C14—H14	120.4 (8)
C3—C2—C16	121.38 (9)	C14—C15—C10	119.23 (10)
C1—C2—C16	118.08 (9)	C14—C15—H15	120.6 (8)
C2—C3—C4	116.16 (9)	C10—C15—H15	120.2 (8)
C2—C3—C7	122.03 (9)	C17—C16—C21	119.14 (9)
C4—C3—C7	121.81 (9)	C17—C16—C2	122.16 (9)
C5—C4—C3	118.41 (9)	C21—C16—C2	118.63 (9)
C5—C4—C8	104.69 (9)	C18—C17—C16	120.59 (9)
C3—C4—C8	136.89 (9)	C18—C17—H17	119.5 (8)
N1—C5—N2	126.44 (9)	C16—C17—H17	119.9 (8)
N1—C5—C4	126.36 (9)	C19—C18—C17	119.86 (10)
N2—C5—C4	107.17 (9)	C19—C18—H18	121.3 (8)
C1—C6—H6A	113.6 (14)	C17—C18—H18	118.9 (8)
C1—C6—H6B	114.9 (12)	C18—C19—C20	119.79 (9)
H6A—C6—H6B	106.3 (17)	C18—C19—C22	121.86 (10)
C1—C6—H6C	114.1 (11)	C20—C19—C22	118.32 (9)
H6A—C6—H6C	102.5 (16)	C21—C20—C19	120.33 (9)
H6B—C6—H6C	104.2 (16)	C21—C20—H20	121.4 (9)
C3—C7—H7A	111.7 (11)	C19—C20—H20	118.3 (9)
C3—C7—H7B	110.7 (10)	C20—C21—C16	120.28 (10)
H7A—C7—H7B	105.6 (15)	C20—C21—H21	118.9 (7)
C3—C7—H7C	112.7 (13)	C16—C21—H21	120.8 (7)
H7A—C7—H7C	105.6 (16)	O1—C22—O2	124.06 (10)
H7B—C7—H7C	110.3 (17)	O1—C22—C19	123.73 (10)
N3—C8—C4	110.65 (9)	O2—C22—C19	112.20 (9)
N3—C8—C9	118.86 (9)	O2—C23—C24	110.74 (10)
C4—C8—C9	130.48 (9)	O2—C23—H23A	102.5 (9)
C8—C9—H9A	111.3 (8)	C24—C23—H23A	111.7 (9)
C8—C9—H9B	108.6 (8)	O2—C23—H23B	107.7 (9)
H9A—C9—H9B	109.1 (11)	C24—C23—H23B	112.6 (9)
C8—C9—H9C	110.2 (8)	H23A—C23—H23B	111.1 (13)
H9A—C9—H9C	108.8 (11)	C23—C24—H24A	112.3 (10)
H9B—C9—H9C	108.8 (11)	C23—C24—H24B	111.2 (9)
C11—C10—C15	120.41 (10)	H24A—C24—H24B	107.8 (14)
C11—C10—N2	118.83 (9)	C23—C24—H24C	110.3 (9)
C15—C10—N2	120.76 (9)	H24A—C24—H24C	107.5 (13)
C12—C11—C10	119.11 (10)	H24B—C24—H24C	107.6 (13)
C12—C11—H11	119.6 (8)
C5—N2—N3—C8	−0.46 (11)	N3—N2—C10—C11	14.94 (14)
C10—N2—N3—C8	−179.60 (9)	C5—N2—C10—C15	16.86 (17)
C5—N1—C1—C2	1.16 (15)	N3—N2—C10—C15	−164.22 (9)
C5—N1—C1—C6	−178.18 (9)	C15—C10—C11—C12	−0.73 (16)
N1—C1—C2—C3	−4.27 (16)	N2—C10—C11—C12	−179.90 (9)
C6—C1—C2—C3	175.04 (10)	C10—C11—C12—C13	−0.57 (17)
N1—C1—C2—C16	171.81 (9)	C11—C12—C13—C14	1.01 (17)
C6—C1—C2—C16	−8.88 (14)	C12—C13—C14—C15	−0.16 (17)
C1—C2—C3—C4	3.15 (14)	C13—C14—C15—C10	−1.11 (16)
C16—C2—C3—C4	−172.79 (9)	C11—C10—C15—C14	1.55 (16)
C1—C2—C3—C7	−176.98 (10)	N2—C10—C15—C14	−179.30 (9)
C16—C2—C3—C7	7.08 (15)	C3—C2—C16—C17	−101.45 (12)
C2—C3—C4—C5	0.50 (14)	C1—C2—C16—C17	82.51 (13)
C7—C3—C4—C5	−179.37 (10)	C3—C2—C16—C21	81.68 (13)
C2—C3—C4—C8	178.72 (11)	C1—C2—C16—C21	−94.36 (11)
C7—C3—C4—C8	−1.15 (18)	C21—C16—C17—C18	0.96 (15)
C1—N1—C5—N2	−179.15 (9)	C2—C16—C17—C18	−175.89 (9)
C1—N1—C5—C4	2.93 (15)	C16—C17—C18—C19	0.53 (16)
N3—N2—C5—N1	−177.42 (9)	C17—C18—C19—C20	−1.52 (15)
C10—N2—C5—N1	1.58 (18)	C17—C18—C19—C22	176.35 (9)
N3—N2—C5—C4	0.83 (11)	C18—C19—C20—C21	1.01 (16)
C10—N2—C5—C4	179.82 (10)	C22—C19—C20—C21	−176.93 (9)
C3—C4—C5—N1	−3.85 (16)	C19—C20—C21—C16	0.50 (15)
C8—C4—C5—N1	177.41 (10)	C17—C16—C21—C20	−1.47 (15)
C3—C4—C5—N2	177.91 (9)	C2—C16—C21—C20	175.49 (9)
C8—C4—C5—N2	−0.83 (11)	C23—O2—C22—O1	2.20 (16)
N2—N3—C8—C4	−0.09 (11)	C23—O2—C22—C19	−177.20 (8)
N2—N3—C8—C9	−179.35 (9)	C18—C19—C22—O1	−169.52 (11)
C5—C4—C8—N3	0.58 (11)	C20—C19—C22—O1	8.38 (16)
C3—C4—C8—N3	−177.80 (11)	C18—C19—C22—O2	9.89 (14)
C5—C4—C8—C9	179.73 (11)	C20—C19—C22—O2	−172.21 (9)
C3—C4—C8—C9	1.3 (2)	C22—O2—C23—C24	94.70 (12)
C5—N2—C10—C11	−163.98 (10)

Hydrogen-bond geometry (Å, º)

Cg2, Cg3 and Cg4 are the centroids of the N1/C1–C5, C10–C15 and C16–C21 rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
C15—H15···N1	0.988 (13)	2.385 (13)	3.0225 (14)	121.6 (10)
C6—H6A···Cg2^i	0.96 (2)	2.79 (3)	3.6483 (15)	149.5 (17)
C18—H18···Cg3^i	0.948 (15)	2.558 (16)	3.4209 (14)	151.4 (11)
C23—H23A···Cg4^ii	0.975 (17)	2.910 (17)	3.6135 (17)	129.7 (13)

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